JP2016162805A - Carbon fiber aggregate with layered manganese oxide carried thereon and production method thereof - Google Patents
Carbon fiber aggregate with layered manganese oxide carried thereon and production method thereof Download PDFInfo
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- carbon fiber
- manganese oxide
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 180
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 91
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 90
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000003990 capacitor Substances 0.000 claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- 239000002759 woven fabric Substances 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 abstract description 16
- 238000010586 diagram Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 65
- 229910052799 carbon Inorganic materials 0.000 description 53
- 239000004744 fabric Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000012286 potassium permanganate Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 150000002697 manganese compounds Chemical class 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XTCNADHUPNOYJX-UHFFFAOYSA-M [Mn+].C(C(=O)[O-])(=O)[O-].[NH4+] Chemical compound [Mn+].C(C(=O)[O-])(=O)[O-].[NH4+] XTCNADHUPNOYJX-UHFFFAOYSA-M 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
【課題】本発明の課題は、電気化学キャパシタ等に使用できる、容量が大きく急速充放電が可能であり、機械的な柔軟性と強度に優れる電極材料及びその製造方法、並びに容量が大きく急速充放電が可能であり、機械的な柔軟性と強度に優れる電極及び電気化学キャパシタを提供することにある。【解決手段】表面に層状マンガン酸化物が担持された炭素繊維集合体であり、前記層状マンガン酸化物がマンガンを含む化合物の電気分解により炭素繊維集合体の表面に担持されたことを特徴とする束状、織布状又は不織布状の炭素繊維集合体。【選択図】図１An object of the present invention is to provide an electrode material which can be used for an electrochemical capacitor or the like and which has a large capacity and can be rapidly charged/discharged and which is excellent in mechanical flexibility and strength, and a method for producing the same, and a large capacity and rapid charging. An object of the present invention is to provide an electrode and an electrochemical capacitor capable of discharging and having excellent mechanical flexibility and strength. A layered manganese oxide is supported on the surface, and the layered manganese oxide is supported on the surface of the carbon fiber aggregate by electrolysis of a compound containing manganese. A bundle, a woven fabric, or a non-woven fabric-like carbon fiber aggregate. [Selection diagram] Figure 1
Description
本発明は、表面に層状マンガン酸化物が担持された炭素繊維集合体及びその製造方法並びに前記炭素繊維集合体を備える電極及び該電極を備える電気化学キャパシタに関する。 The present invention relates to a carbon fiber aggregate having a layered manganese oxide supported on its surface, a method for producing the same, an electrode including the carbon fiber aggregate, and an electrochemical capacitor including the electrode.
近年、二次電池の代替、ハイブリッド自動車等の補助電源、太陽光発電のエネルギーバッファ等に用いるデバイスとして、大容量でありながらパワー密度が高く急速充放電が可能でサイクル安定性が高いとの特徴を有する電気化学キャパシタが注目されている。また、最近では、電子機器等に対するフレキシブル化、ウェアラブル化の要求から、電池のフレキシブル化が求められており、フレキシブルな電極の必要性が高まってきている。このような状況下、上記の特徴を有する電気化学キャパシタをフレキシブル化することが検討され、電気化学キャパシタに用いることができるフレキシブルな電極の開発が要請されている。 In recent years, as a device used for substituting for secondary batteries, auxiliary power sources for hybrid vehicles, etc., energy buffers for solar power generation, etc., it has features of high capacity, high power density, rapid charge / discharge, and high cycle stability. Electrochemical capacitors having the following attention have been drawn. In recent years, there has been a demand for flexible batteries due to demands for flexible and wearable electronic devices, and the need for flexible electrodes has been increasing. Under such circumstances, it has been studied to make the electrochemical capacitor having the above characteristics flexible, and development of a flexible electrode that can be used for the electrochemical capacitor is demanded.
電気化学キャパシタは、その蓄電メカニズムによって大きく２つに分けられる。一つは、イオンを物理的に吸脱着させることにより電荷を蓄える電気二重層キャパシタ、もう一つは速く可逆なレドックス反応により電荷を蓄える擬似キャパシタ（レドックスキャパシタ）である。電気二重層キャパシタでは、活性炭、カーボンナノチューブ、グラフェン等の炭素材料が電極活物質として使用されている。そして電極は、これらの電極活物質に導電材とバインダーを混合し、この混合物からなるシートを集電体に接着する方法や、この混合物を含むペーストや分散液を金属箔等の集電体に塗布する方法により作製されている（特許文献１）。しかし、このように作製された電極は、絶縁性物質であるバインダーを含むことによる内部抵抗の増加、電極活物質と集電体の界面抵抗等により速度特性が著しく妨げられ、内部抵抗を下げるためのカーボンブラック等の導電材のために電極活物質の配合割合が低くなりキャパシタ容量の減少を招くなどの問題点があった。さらに、上記の方法では、フレキシブルな電極を作製することは難しかった。 Electrochemical capacitors are roughly divided into two types depending on the storage mechanism. One is an electric double layer capacitor that stores charges by physically absorbing and desorbing ions, and the other is a pseudo capacitor (redox capacitor) that stores charges by a fast and reversible redox reaction. In the electric double layer capacitor, a carbon material such as activated carbon, carbon nanotube, graphene or the like is used as an electrode active material. The electrode is prepared by mixing a conductive material and a binder with these electrode active materials, and bonding a sheet made of the mixture to the current collector, or applying a paste or dispersion containing the mixture to a current collector such as a metal foil. It is produced by a coating method (Patent Document 1). However, the electrode manufactured in this manner has an increased internal resistance due to the inclusion of a binder that is an insulating material, and the speed characteristics are significantly hindered by the interface resistance between the electrode active material and the current collector, thereby reducing the internal resistance. The conductive material such as carbon black has a problem in that the mixing ratio of the electrode active material is lowered and the capacitance of the capacitor is reduced. Furthermore, it has been difficult to produce a flexible electrode by the above method.
一方、他の炭素材料として、従来から様々な分野で用いられている炭素繊維がある。炭素繊維とは、有機繊維のプレカーサーを加熱炭素化処理して得られる、質量比で９０％以上が炭素で構成される繊維のことである（JIS L0204-2:2010）。しかし、炭素繊維は、比キャパシタンスが、活性炭、カーボンナノチューブ、グラフェン等に比べて著しく小さいため、電気二重層キャパシタの電極活物質として使用することはできなかった。最近、炭素繊維でできたカーボンクロスを賦活処理して、単位面積あたりのキャパシタンスを高めたことが報告されているが、まだ満足する特性は得られていない（非特許文献１）。 On the other hand, as other carbon materials, there are carbon fibers conventionally used in various fields. The carbon fiber is a fiber obtained by heating and carbonizing an organic fiber precursor and having a mass ratio of 90% or more of carbon (JIS L0204-2: 2010). However, since the specific capacitance of carbon fiber is significantly smaller than that of activated carbon, carbon nanotube, graphene, etc., it cannot be used as an electrode active material for an electric double layer capacitor. Recently, it has been reported that a carbon cloth made of carbon fiber is activated to increase the capacitance per unit area, but satisfactory characteristics have not yet been obtained (Non-patent Document 1).
また、電気化学キャパシタのもう一つの方式である擬似キャパシタでは、酸化ルテニウム、酸化マンガン、酸化ニッケル等の金属酸化物、ポリアセチレン、ポリアニリン、ポリピロール、ポリチオフェン等の導電性高分子などの炭素材料とは異なる材料が電極活物質として検討されている。本発明者らも、二次電池やキャパシタに用いることができる層状マンガン酸化物を電気化学的に製造する方法（特許文献２及び３）や、層状マンガン酸化物を用いた光電極（特許文献４）を提案している。しかしながら、擬似キャパシタにおいても、フレキシブルな電極やデバイスは得られていなかった。 In addition, the pseudo-capacitor, which is another type of electrochemical capacitor, is different from carbon materials such as metal oxides such as ruthenium oxide, manganese oxide and nickel oxide, and conductive polymers such as polyacetylene, polyaniline, polypyrrole and polythiophene. Materials are being investigated as electrode active materials. The present inventors have also electrochemically produced a layered manganese oxide that can be used in secondary batteries and capacitors (Patent Documents 2 and 3), and a photoelectrode using the layered manganese oxide (Patent Document 4). ). However, flexible electrodes and devices have not been obtained even in pseudo capacitors.
本発明の課題は、電気化学キャパシタ等に使用できる、容量が大きく急速充放電が可能であり、機械的な柔軟性と強度に優れる電極材料及びその製造方法、並びに容量が大きく急速充放電が可能であり、機械的な柔軟性と強度に優れる電極及び電気化学キャパシタを提供することにある。 The problem of the present invention is that it can be used for an electrochemical capacitor or the like, has a large capacity and can be rapidly charged and discharged, and has an electrode material excellent in mechanical flexibility and strength, its manufacturing method, and a large capacity and capable of rapid charge and discharge It is an object of the present invention to provide an electrode and an electrochemical capacitor excellent in mechanical flexibility and strength.
本発明者らは、電気化学キャパシタ等に使用できるフレキシブルな電極を作製することを目指して開発を開始した。そして、導電性が高く、機械的な柔軟性と強度に優れながらも、比キャパシタンスが小さいため、従来は電気化学キャパシタの電極材料として用いられてこなかった炭素繊維に着目した。本発明者らは、電気化学キャパシタの性能は、電極活物質の性能だけではなくセルとしての性能を考える必要があり、電極活物質の単位質量あたりの指標で、電極へのローディング量が多くなると使用効率が低下するため、ローディング量が少ない方が大きな値を示す傾向にある比キャパシタンスよりも、電極の単位面積あたりのキャパシタンスを重視して開発を進めた。こうして検討を重ねたところ、炭素繊維を束状、織布状、不織布状等の集合体とし、その表面に層状マンガン酸化物を電気化学的処理により担持させ、炭素繊維の集合体と層状マンガン酸化物を複合化することにより、単位面積あたりのキャパシタンスを非常に大きくできることを見いだした。このようにして得られた炭素繊維と層状マンガン酸化物の複合体は、導電材やバインダーを用いる必要はなく、導電性及び機械的な柔軟性と強度に優れるため、必ずしも集電体を必要とせずに、それ自体をフレキシブルな電極として使用することも可能であることを見いだしたものである。 The present inventors have started development with the aim of producing a flexible electrode that can be used in an electrochemical capacitor or the like. The inventors have focused on carbon fibers that have not been conventionally used as electrode materials for electrochemical capacitors because of their high conductivity and excellent mechanical flexibility and strength, but low specific capacitance. The inventors of the present invention need to consider not only the performance of the electrode active material but also the performance of the cell as the performance of the electrochemical capacitor, and it is an index per unit mass of the electrode active material. Since the efficiency of use decreased, the development pertains to the capacitance per unit area of the electrode rather than the specific capacitance, which tends to show a larger value when the loading amount is smaller. As a result of repeated investigations, carbon fibers were assembled into bundles, woven fabrics, nonwoven fabrics, etc., and layered manganese oxide was supported on the surface by electrochemical treatment, and the carbon fiber aggregates and layered manganese oxidation were supported. It was found that the capacitance per unit area can be greatly increased by compounding objects. The composite of carbon fiber and layered manganese oxide thus obtained does not require the use of a conductive material or binder, and is excellent in conductivity and mechanical flexibility and strength. Therefore, a current collector is not necessarily required. It has also been found that it can be used as a flexible electrode.
すなわち、本発明は以下に示す事項により特定されるものである。
（１）表面に層状マンガン酸化物が担持された炭素繊維集合体であり、前記層状マンガン酸化物がマンガンを含む化合物の電気分解により炭素繊維集合体の表面に担持されたことを特徴とする束状、織布状又は不織布状の炭素繊維集合体。
（２）賦活処理された表面に層状マンガン酸化物が担持されたことを特徴とする上記（１）記載の炭素繊維集合体。
（３）賦活処理が、炭素繊維集合体を酸化処理し、その後還元処理する処理であることを特徴とする上記（２）記載の炭素繊維集合体。
（４）上記（１）〜（３）のいずれかに記載の炭素繊維集合体を備えることを特徴とする電極。
（５）上記（４）記載の電極、電解質層及び対極を備えることを特徴とする電気化学キャパシタ。
（６）束状、織布状又は不織布状の炭素繊維集合体を、２価のマンガンイオン又は過マンガン酸イオンを含む溶液中に浸漬し、前記溶液中の２価のマンガンイオンを電気化学的に酸化することにより、又は過マンガン酸イオンを電気化学的に還元することにより、炭素繊維集合体の表面に層状マンガン酸化物を析出させることを特徴とする表面に層状マンガン酸化物が担持された束状、織布状又は不織布状の炭素繊維集合体の製造方法。
That is, the present invention is specified by the following items.
(1) A carbon fiber aggregate having a layered manganese oxide supported on the surface, wherein the layered manganese oxide is supported on the surface of the carbon fiber aggregate by electrolysis of a compound containing manganese. , Woven or non-woven carbon fiber aggregate.
(2) The carbon fiber aggregate as described in (1) above, wherein a layered manganese oxide is supported on the activated surface.
(3) The carbon fiber aggregate according to (2) above, wherein the activation treatment is a treatment in which the carbon fiber aggregate is oxidized and then reduced.
(4) An electrode comprising the carbon fiber assembly according to any one of (1) to (3) above.
(5) An electrochemical capacitor comprising the electrode according to (4), an electrolyte layer, and a counter electrode.
(6) A bundle, woven fabric, or nonwoven fabric of carbon fiber aggregates is immersed in a solution containing divalent manganese ions or permanganate ions, and the divalent manganese ions in the solution are electrochemically treated. The layered manganese oxide was supported on the surface, characterized in that the layered manganese oxide was deposited on the surface of the carbon fiber aggregate by oxidizing it to an oxygen or electrochemically reducing permanganate ions A method for producing a bundle, woven fabric, or nonwoven fabric of carbon fibers.
本発明によると、単位面積あたりのキャパシタンスが大きく、急速充放電が可能であり、機械的な柔軟性と強度に優れる電極材料、電極及び電気化学キャパシタを提供することができる。また、本発明の製造方法によると、炭素繊維集合体の表面に、バインダー等を必要とせずに層状マンガン酸化物を均一に担持させることができ、その担持量を調整することができるので、単位面積あたりのキャパシタンスが大きく、急速充放電が可能であり、機械的な柔軟性と強度に優れる電極材料を製造することができる。 ADVANTAGE OF THE INVENTION According to this invention, the capacitance per unit area is large, rapid charge / discharge is possible, and the electrode material, electrode, and electrochemical capacitor which are excellent in mechanical flexibility and intensity | strength can be provided. Further, according to the production method of the present invention, the layered manganese oxide can be uniformly supported on the surface of the carbon fiber aggregate without requiring a binder, and the amount supported can be adjusted. An electrode material having a large capacitance per area, capable of rapid charge and discharge, and excellent in mechanical flexibility and strength can be manufactured.
本発明の炭素繊維集合体は、表面に層状マンガン酸化物が担持されたことを特徴とする束状、織布状又は不織布状の炭素繊維集合体である。本発明における炭素繊維は、炭素繊維であれば特に限定されるものではないが、例えば、ＰＡＮ（ポリアクリロニトリル）系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維等を挙げることができる。本発明における炭素繊維集合体は、炭素繊維を束状、織布状又は不織布状の形態にしたものである。本発明における束状の炭素繊維集合体は、炭素繊維を集合させて束状の形態にしたものであれば特に限定されるものではないが、例えば、炭素繊維の長繊維の原糸（単繊維）の束、炭素繊維の短繊維の原糸をステープル紡績により糸としたもの等を挙げることができ、一般にフィラメント、トウ、ステープルなどと呼ばれるものを使用することができる。本発明における織布状の炭素繊維集合体は、炭素繊維を集合させて織布状の形態にしたものであれば特に限定されるものではないが、例えば、炭素繊維の長繊維の束を織ったもの、炭素繊維の短繊維をステープル紡績により糸としたものを織ったもの等を挙げることができ、一般にカーボンクロスと呼ばれるものを使用することができる。また、本発明における不織布状の炭素繊維集合体は、炭素繊維を集合させて不織布状の形態にしたものであれば特に限定されるものではないが、例えば、炭素繊維を積層したもの、ニードルパンチ加工をしたもの等を挙げることができ、フェルト状、マット状及びペーパー状のものも含まれる。 The carbon fiber aggregate of the present invention is a bundle, woven or non-woven carbon fiber aggregate characterized in that layered manganese oxide is supported on the surface. The carbon fiber in the present invention is not particularly limited as long as it is a carbon fiber, and examples thereof include PAN (polyacrylonitrile) -based carbon fiber, pitch-based carbon fiber, and rayon-based carbon fiber. The carbon fiber aggregate in the present invention is obtained by forming carbon fibers into a bundle, woven fabric, or nonwoven fabric. The bundle of carbon fiber aggregates in the present invention is not particularly limited as long as the carbon fibers are aggregated into a bundle form. For example, a carbon fiber long fiber yarn (single fiber) ), A carbon fiber staple yarn made by staple spinning, and the like, and generally called filaments, tows, staples, and the like can be used. The woven fabric-like carbon fiber aggregate in the present invention is not particularly limited as long as the carbon fibers are aggregated into a woven fabric shape. For example, a woven bundle of carbon fibers is woven. And those obtained by weaving carbon fiber staple fibers made by staple spinning, and the like, and generally called carbon cloth can be used. In addition, the non-woven carbon fiber aggregate in the present invention is not particularly limited as long as the carbon fibers are aggregated to form a non-woven form. Processed ones can be mentioned, and felts, mats and papers are also included.
本発明における層状マンガン酸化物は、マンガン酸化物の層が形成され、各層の間に間隙があるものであれば特に限定されるものではないが、例えば、バーネサイト型層状マンガン酸化物等を挙げることができる。バーネサイト型層状マンガン酸化物は、マンガンを中心とし頂点に６つの酸素を配置したＭｎＯ６で示される八面体構造が、互いに頂点と稜を共有して広がった層を形成し、その層が積み重なった層状化合物であり、Ｍｎ３＋／Ｍｎ４＋の混合原子価をもつマンガン酸化物（ＭｎＯ２）である。本発明における層状マンガン酸化物は、一つの層の厚みとその次の層との間の間隔を加えた値（層間距離）が、物理化学的及び機械的安定性の観点から０．４〜５ｎｍが好ましく、０．５〜３ｎｍが更に好ましく、０．７〜１．５ｎｍがより好ましい。また、本発明においては、層状マンガン酸化物が炭素繊維集合体の少なくとも表面に担持されていればよく、さらに炭素繊維集合体の内部に担持されていてもよい。ここで、表面に担持とは、層状マンガン酸化物が炭素繊維集合体の表面に付着していればよく、要求されるキャパシタ特性を発現できれば必ずしも表面全体に付着していなくてもよいが、キャパシタ特性を向上させる観点から、炭素繊維集合体の表面に均一に担持されていることが好ましい。また表面を被覆するように担持されていることが好ましい。本発明においては、層状マンガン酸化物の担持量は、要求されるキャパシタ特性に合わせて調製することができ、特に限定されるものではないが、キャパシタ特性を向上させる観点から、３ｍｇ／ｃｍ２以上が好ましく、４ｍｇ／ｃｍ２以上が更に好ましく、９ｍｇ／ｃｍ２以上がより好ましい。 The layered manganese oxide in the present invention is not particularly limited as long as a layer of manganese oxide is formed and there is a gap between each layer. For example, a birnessite type layered manganese oxide may be mentioned. Can do. The birnessite-type layered manganese oxide has an octahedral structure represented by MnO 6 in which six oxygens are arranged at the apex centering on manganese, forming a layer that spreads sharing apexes and edges, and the layers are stacked. It is a layered compound and is a manganese oxide (MnO 2 ) having a mixed valence of Mn 3+ / Mn 4+ . The layered manganese oxide according to the present invention has a value (interlayer distance) obtained by adding a thickness between one layer and the next layer (interlayer distance) from the viewpoint of physicochemical and mechanical stability. Is preferable, 0.5-3 nm is still more preferable, and 0.7-1.5 nm is more preferable. In the present invention, the layered manganese oxide may be supported on at least the surface of the carbon fiber aggregate, and may be further supported on the inside of the carbon fiber aggregate. Here, “supported on the surface” means that the layered manganese oxide only needs to adhere to the surface of the carbon fiber aggregate, and may not necessarily adhere to the entire surface as long as the required capacitor characteristics can be expressed. From the viewpoint of improving the characteristics, it is preferable that the carbon fiber aggregate is uniformly supported on the surface. Moreover, it is preferable to carry | support so that the surface may be coat | covered. In the present invention, the loading amount of the layered manganese oxide can be adjusted according to the required capacitor characteristics, and is not particularly limited. However, from the viewpoint of improving the capacitor characteristics, 3 mg / cm 2 or more. Is preferably 4 mg / cm 2 or more, more preferably 9 mg / cm 2 or more.
層状マンガン酸化物を白金板等の平板な基体上に担持させると、層状マンガン酸化物は、基体上に水平方向に担持される。このため、電気化学キャパシタ等の電極として用いようとした場合、電気化学的に利用されるのは、マンガン酸化物の外表面のみとなり、マンガン酸化物の層間は利用されない。一方、本発明の場合、炭素繊維を集合させて束状、織布状又は不織布状の形態としているため、炭素繊維自身の曲面に加え、集合体を構成する炭素繊維の間に炭素繊維同士により形成される窪みや凹凸がある。この炭素繊維集合体上にマンガン化合物の電気分解により層状マンガン酸化物を析出させると、析出したマンガン酸化物上にマンガン酸化物が成長するため、層状マンガン酸化物が一定方向に平面的に並ぶのではなく、三次元的にランダムに配向して担持されると考えられる。そのため、本発明の炭素繊維集合体は、マンガン酸化物の外表面だけでなく層間も電気化学的に利用されることにより、イオン拡散が速く大きなキャパシタ応答性が得られると考えられる。また、層状マンガン酸化物が水平方向に重なって担持された場合、電気化学的に利用されるのは、積層されたマンガン酸化物の表面部分のみであり、下方にあるマンガン酸化物は利用されないため、マンガン酸化物の担持量を増やしてもキャパシタンスは一定以上増加しない。これに対し、本発明の炭素繊維集合体においては、層状マンガン酸化物が三次元的にランダムに配向して担持され、その外表面だけでなく層間の内表面も電気化学的に利用できることにより、担持されたマンガン酸化物を有効に利用でき、マンガン酸化物の担持量を増加させることにより、単位面積当たりのキャパシタンスを増加させることができるものと考えられる。さらに、本発明の炭素繊維集合体は、炭素繊維を束状、織布状又は不織布状の集合体として用いているので、導電性が高く、機械的な柔軟性と強度に優れ、また大面積化も可能となるので、フレキシブルな電極用の電極材料及び電極として好適である。水熱処理により層状マンガン酸化物を析出させる方法もあるが、水熱処理による反応は、過マンガン酸イオンと炭素間の酸化還元反応により反応が進行するため、マンガン酸化物上にマンガン酸化物は形成されず、本発明とはマンガン酸化物の担持状態が異なる。 When the layered manganese oxide is supported on a flat substrate such as a platinum plate, the layered manganese oxide is supported horizontally on the substrate. For this reason, when it is going to be used as an electrode of an electrochemical capacitor or the like, only the outer surface of the manganese oxide is used electrochemically, and the interlayer of the manganese oxide is not used. On the other hand, in the case of the present invention, since the carbon fibers are aggregated to form a bundle, a woven fabric, or a nonwoven fabric, in addition to the curved surface of the carbon fibers themselves, the carbon fibers between the carbon fibers constituting the aggregate There are depressions and irregularities that are formed. When a layered manganese oxide is deposited on the carbon fiber aggregate by electrolysis of a manganese compound, the manganese oxide grows on the deposited manganese oxide, so that the layered manganese oxide is arranged in a plane in a certain direction. Instead, it is considered that the particles are supported while being randomly oriented three-dimensionally. Therefore, it is considered that the carbon fiber aggregate of the present invention is used not only in the outer surface of the manganese oxide but also in the interlayer electrochemically, so that the ion diffusion is fast and a large capacitor response can be obtained. In addition, when the layered manganese oxide is supported in the horizontal direction, only the surface portion of the stacked manganese oxide is used electrochemically, and the underlying manganese oxide is not used. Even if the amount of manganese oxide supported is increased, the capacitance does not increase beyond a certain level. On the other hand, in the carbon fiber aggregate of the present invention, the layered manganese oxide is supported in three-dimensional random orientation, and not only the outer surface but also the inner surface between layers can be used electrochemically. It is considered that the supported manganese oxide can be used effectively, and the capacitance per unit area can be increased by increasing the supported amount of manganese oxide. Furthermore, the carbon fiber assembly of the present invention uses carbon fibers as a bundle, woven fabric, or non-woven fabric assembly, so it has high conductivity, excellent mechanical flexibility and strength, and a large area. Therefore, it is suitable as a flexible electrode material and electrode. There is also a method of depositing layered manganese oxide by hydrothermal treatment, but the reaction by hydrothermal treatment proceeds by a redox reaction between permanganate ions and carbon, so that manganese oxide is formed on the manganese oxide. In addition, the supported state of manganese oxide is different from that of the present invention.
本発明の炭素繊維集合体は、マンガンを含む化合物の電気分解により炭素繊維集合体の表面に層状マンガン酸化物を析出させて担持させる電気化学的方法により製造される。前記電気化学的方法としては、例えば、２価のマンガンイオンを電気化学的に酸化することにより、層状マンガン酸化物をアノード側に析出させる方法（以下、アノード電解法ともいう。）、過マンガン酸イオンを電気化学的に還元することにより、層状マンガン酸化物をカソード側に析出させる方法（以下、カソード電解法ともいう。）等が挙げられる。また、２価のマンガンイオン又は過マンガン酸イオンの存在する溶液中には、アルカリ金属イオンを共存させることが好ましい。アノード電解法において使用されるマンガン化合物は、電解液に可溶な２価のマンガン化合物であれば特に限定されず、例えば、硫酸マンガン、塩化マンガン、硝酸マンガン、炭酸マンガン等の無機酸の塩、蓚酸マンガンアンモニウム、蓚酸マンガンカリウム等の有機マンガン化合物などを挙げることができる。なかでも電気分解による層状マンガン酸化物の析出のしやすさや、入手の容易性等から硫酸マンガンを好適に例示できる。カソード電解法において使用されるマンガン化合物は、特に限定されず、例えば、過マンガン酸塩を挙げることができ、過マンガン酸塩としては、過マンガン酸のアルカリ金属塩、アルカリ土類金属塩等を挙げることができる。なかでも、ナトリウム塩又はカリウム塩を好適に例示できる。本発明の炭素繊維集合体は、上記マンガン化合物が溶解した溶液中に炭素繊維集合体を浸漬し、アノード電解法の場合は、炭素繊維集合体をアノード電極として用い、カソード電解法の場合は、炭素繊維集合体をカソード電極として用い、対極に白金電極等を用いて電気分解を行うことにより、炭素繊維集合体上に層状マンガン酸化物を析出させることにより製造することができる。本発明の炭素繊維集合体を製造する方法としては、使用するマンガン酸化物の取扱いの容易さ、電気分解による析出のコントロールの容易さの観点からアノード電解法が好ましい。水熱処理により層状マンガン酸化物を析出させる方法もあるが、水熱処理による反応は、過マンガン酸イオンと炭素間の酸化還元反応により反応が進行するため、本発明のように層状マンガン酸化物を炭素繊維集合体の表面に定量的にコントロールして担持させることはできない。また、水熱処理法の場合、炭素表面での反応のため、表面が完全に被覆されると反応が自己停止し、層状マンガン酸化物の析出量を増やすことはできない。 The carbon fiber aggregate of the present invention is produced by an electrochemical method in which a layered manganese oxide is deposited and supported on the surface of the carbon fiber aggregate by electrolysis of a compound containing manganese. Examples of the electrochemical method include a method of depositing a layered manganese oxide on the anode side by electrochemically oxidizing divalent manganese ions (hereinafter also referred to as an anode electrolysis method), permanganic acid. Examples include a method of depositing layered manganese oxide on the cathode side by electrochemically reducing ions (hereinafter also referred to as a cathode electrolysis method). In addition, it is preferable that alkali metal ions coexist in the solution in which divalent manganese ions or permanganate ions are present. The manganese compound used in the anode electrolysis method is not particularly limited as long as it is a divalent manganese compound that is soluble in the electrolytic solution. For example, a salt of an inorganic acid such as manganese sulfate, manganese chloride, manganese nitrate, manganese carbonate, Examples thereof include organic manganese compounds such as manganese ammonium oxalate and potassium potassium oxalate. Among these, manganese sulfate can be suitably exemplified from the easiness of precipitation of the layered manganese oxide by electrolysis and the availability. The manganese compound used in the cathode electrolysis method is not particularly limited, and examples thereof include permanganate. Examples of the permanganate include alkali metal salts of alkaline manganese salts, alkaline earth metal salts, and the like. Can be mentioned. Especially, a sodium salt or potassium salt can be illustrated suitably. The carbon fiber aggregate of the present invention is obtained by immersing the carbon fiber aggregate in a solution in which the manganese compound is dissolved. In the case of the anode electrolysis method, the carbon fiber aggregate is used as an anode electrode. It can be produced by depositing a layered manganese oxide on a carbon fiber aggregate by performing electrolysis using a carbon fiber aggregate as a cathode electrode and a platinum electrode or the like as a counter electrode. As a method for producing the carbon fiber aggregate of the present invention, an anode electrolysis method is preferable from the viewpoint of easy handling of the manganese oxide to be used and easy control of deposition by electrolysis. There is also a method of depositing layered manganese oxide by hydrothermal treatment, but the reaction by hydrothermal treatment proceeds by a redox reaction between permanganate ions and carbon, so that the layered manganese oxide is carbonized as in the present invention. It cannot be supported on the surface of the fiber assembly in a quantitatively controlled manner. Further, in the case of the hydrothermal treatment method, since the reaction is on the carbon surface, the reaction self-stops when the surface is completely covered, and the amount of deposited layered manganese oxide cannot be increased.
本発明の炭素繊維集合体は、賦活処理された表面に層状マンガン酸化物が担持されていることが好ましい。炭素材料における賦活処理とは、炭素材料に細孔又は凹凸を付与する処理をいう。本発明における賦活処理は、特に限定されるものではないが、例えば、ガス賦活法、薬品賦活法等を挙げることができる。ガス賦活法とは、水蒸気、二酸化炭素、空気、酸素、燃焼ガス等を用いて高温で炭素材料と反応させ、炭素材料中の揮発成分や炭素原子をガス化する方法であり、薬品賦活法とは、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸リチウム等のアルカリ金属化合物、塩化カルシウム、塩化マグネシウム、塩化亜鉛等の脱水性の塩、リン酸、硫酸、硝酸等の酸などの薬品を用いて賦活処理する方法であり、本発明における賦活処理は、これら一般的に行われる賦活方法によることができる。また、薬品を用いて賦活処理する方法として、炭素繊維を酸化処理し、その後還元処理する方法を挙げることができる。使用する酸化剤や還元剤は、特に限定されるものではないが、酸化剤としては、例えば、硫酸、硝酸、硫酸と硝酸の混合物、過マンガン酸カリウム等を挙げることができ、還元剤としては、例えば、ヒドラジン、水素化ホウ素ナトリウム、アンモニア等を挙げることができる。具体的には、炭素繊維を、硫酸、硝酸及び過マンガン酸カリウムを含む溶液中で酸化処理し、その後、ヒドラジンガス、続いてアンモニアガスを用いて２段階で還元処理する方法や、炭素繊維を、硫酸、硝酸及び過マンガン酸カリウムを含む溶液中で酸化処理し、その後、水素化ホウ素ナトリウムを溶解した溶液中で還元処理する方法を挙げることができる。水素化ホウ素ナトリウムはヒドラジンよりも還元力が強く、１段階で炭素繊維の還元処理ができるため、炭素繊維を、硫酸、硝酸及び過マンガン酸カリウムを含む溶液中で酸化処理し、その後、水素化ホウ素ナトリウム溶液中で還元処理する方法が好ましい。炭素繊維集合体の表面が賦活処理されることにより、炭素繊維集合体を構成する炭素繊維の表面に細孔や凹凸が形成され、層状マンガン酸化物が、より一層、三次元的にランダムに配向して担持されるため、更にキャパシタ応答性を大きくでき、単位面積当たりのキャパシタンスを増加させることができる。本発明においては、炭素繊維を束状、織布状又は不織布状の集合体にした後に賦活処理を行ってもよく、賦活処理した炭素繊維を束状、織布状又は不織布状の形態にしてもよい。 The carbon fiber aggregate of the present invention preferably has a layered manganese oxide supported on the surface subjected to activation treatment. The activation treatment in the carbon material refers to a treatment for imparting pores or irregularities to the carbon material. The activation treatment in the present invention is not particularly limited, and examples thereof include a gas activation method and a chemical activation method. The gas activation method is a method of reacting with a carbon material at a high temperature using water vapor, carbon dioxide, air, oxygen, combustion gas, etc., and gasifying volatile components and carbon atoms in the carbon material. Are alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, dehydrating salts such as calcium chloride, magnesium chloride, zinc chloride, phosphoric acid, sulfuric acid, nitric acid, etc. In the present invention, the activation treatment can be carried out by these generally used activation methods. Moreover, as a method of activating treatment using chemicals, a method of oxidizing carbon fiber and then reducing it can be mentioned. Although the oxidizing agent and reducing agent to be used are not particularly limited, examples of the oxidizing agent include sulfuric acid, nitric acid, a mixture of sulfuric acid and nitric acid, potassium permanganate, and the like. Examples thereof include hydrazine, sodium borohydride, ammonia and the like. Specifically, carbon fiber is oxidized in a solution containing sulfuric acid, nitric acid, and potassium permanganate, and then reduced in two steps using hydrazine gas and then ammonia gas, An oxidation treatment in a solution containing sulfuric acid, nitric acid and potassium permanganate, followed by a reduction treatment in a solution in which sodium borohydride is dissolved can be mentioned. Sodium borohydride has stronger reducing power than hydrazine and can reduce carbon fiber in one step. Therefore, carbon fiber is oxidized in a solution containing sulfuric acid, nitric acid and potassium permanganate, and then hydrogenated. A method of reducing treatment in a sodium boron solution is preferred. By activating the surface of the carbon fiber aggregate, pores and irregularities are formed on the surface of the carbon fiber constituting the carbon fiber aggregate, and the layered manganese oxide is further randomly oriented in three dimensions. Therefore, the capacitor response can be further increased, and the capacitance per unit area can be increased. In the present invention, the carbon fibers may be bundled, woven or nonwoven, and the activation treatment may be performed, and the activated carbon fibers may be bundled, woven or nonwoven. Also good.
本発明の電極は、本発明の炭素繊維集合体を備えていれば特に限定されない。本発明の炭素繊維集合体をそのまま電極として用いてもよく、本発明の炭素繊維集合体を他の導電性シート、導電板等に固定して電極としてもよい。本発明の電気化学キャパシタは、本発明の電極、電解質層及び対極を備えていれば特に限定されない。本発明における電解質層を形成する電解質は、特に限定されないが、例えば、硫酸水溶液等の水系の電解質、ＴＥＡＢＦ４（ホウフッ化テトラエチルアンモニウム）／ＰＣ（プロピレンカーボネート）、ＬｉＰＦ６／ＥＣ（エチレンカーボネート）＋ＤＥＣ（ジエチルカーボネート）等の有機系の電解質、イオン液体などを挙げることができる。また、本発明における対極は、特に限定されず、アルミニウム、ステンレス、導電性樹脂等の一般的に電極として用いられるものを用いることができる。本発明の電気化学キャパシタは、本発明の電極と対極との間に電解質層を形成することにより製造することができる。 The electrode of the present invention is not particularly limited as long as it includes the carbon fiber assembly of the present invention. The carbon fiber aggregate of the present invention may be used as an electrode as it is, or the carbon fiber aggregate of the present invention may be fixed to another conductive sheet, a conductive plate or the like as an electrode. The electrochemical capacitor of the present invention is not particularly limited as long as it includes the electrode, the electrolyte layer, and the counter electrode of the present invention. The electrolyte forming the electrolyte layer in the present invention is not particularly limited. For example, an aqueous electrolyte such as an aqueous sulfuric acid solution, TEABF 4 (tetraethylammonium borofluoride) / PC (propylene carbonate), LiPF 6 / EC (ethylene carbonate) + DEC Examples thereof include organic electrolytes such as (diethyl carbonate), ionic liquids, and the like. Moreover, the counter electrode in this invention is not specifically limited, What is generally used as an electrode, such as aluminum, stainless steel, and a conductive resin, can be used. The electrochemical capacitor of the present invention can be produced by forming an electrolyte layer between the electrode of the present invention and a counter electrode.
硫酸２０ｍｌに硝酸１０ｍｌをゆっくりと加え、室温になるまで放冷し、放冷後の混酸に過マンガン酸カリウム３ｇを溶解させた。カーボンクロス（商品名カーボンクロス・テフロン処理なし(EC-CC1-060)、東陽テクニカ(Electrochem社in USA)社製）を、得られた溶液に浸漬し、溶液を撹拌しながら３５℃で３時間保持した。その後、蒸留水１００ｍｌを加え、さらに３時間保持した。さらに、過酸化水素を、溶液が透明になり、泡が発生しなくなるまで加えた。その後、浸漬したカーボンクロスを溶液から取り出し、蒸留水で洗浄した。次に、洗浄したカーボンクロスを、水酸化ホウ素ナトリウム０．５ｇを溶かした０．１Ｍ水酸化ナトリウム水溶液中に浸漬し、９０℃で３時間還流した。その後、浸漬したカーボンクロスを溶液から取り出し、蒸留水で洗浄した。このようにしてカーボンクロスを賦活処理した後、５０ｍＭ塩化カリウムを含む２ｍＭ硫酸マンガン水溶液にカーボンクロスを浸漬し、対極として白金板を用いて、＋１．０Ｖ vs Ａｇ／ＡｇＣｌ sat．ＫＣｌでアノード電解して、カーボンクロス上に層状マンガン酸化物を析出させ担持させた(担持量：０．４４ｍｇ／ｃｍ２、４．２７ｍｇ／ｃｍ２）。 To 20 ml of sulfuric acid, 10 ml of nitric acid was slowly added and allowed to cool to room temperature, and 3 g of potassium permanganate was dissolved in the mixed acid after cooling. Carbon cloth (trade name: Carbon cloth without Teflon treatment (EC-CC1-060), manufactured by Toyo Technica (Electrochem in USA)) is immersed in the resulting solution, and the solution is stirred at 35 ° C. for 3 hours. Retained. Thereafter, 100 ml of distilled water was added and held for another 3 hours. In addition, hydrogen peroxide was added until the solution became clear and no bubbles were generated. Thereafter, the immersed carbon cloth was taken out of the solution and washed with distilled water. Next, the washed carbon cloth was immersed in a 0.1 M sodium hydroxide aqueous solution in which 0.5 g of sodium borohydride was dissolved, and refluxed at 90 ° C. for 3 hours. Thereafter, the immersed carbon cloth was taken out of the solution and washed with distilled water. After the carbon cloth was activated in this manner, the carbon cloth was immersed in a 2 mM manganese sulfate aqueous solution containing 50 mM potassium chloride, and a platinum plate was used as a counter electrode, and +1.0 V vs Ag / AgCl sat. Anodic electrolysis with KCl was performed to deposit and support layered manganese oxide on the carbon cloth (supported amount: 0.44 mg / cm 2 , 4.27 mg / cm 2 ).
電解酸化の際の通過電気量の条件以外は、実施例１と同じにして、層状マンガン酸化物の担持量の異なるカーボンクロスを得た(担持量：０．９３ｍｇ／ｃｍ２、１．７２ｍｇ／ｃｍ２、２．５２ｍｇ／ｃｍ２、４．２７ｍｇ／ｃｍ２、９．７５ｍｇ／ｃｍ２、１３．０ｍｇ／ｃｍ２)。 Except for the conditions for the amount of electricity passed during electrolytic oxidation, the same procedure as in Example 1 was carried out to obtain carbon cloth having a different amount of layered manganese oxide supported (supported amount: 0.93 mg / cm 2 , 1.72 mg / cm 2, 2.52mg / cm 2, 4.27mg / cm 2, 9.75mg / cm 2, 13.0mg / cm 2).
実施例１と同じ賦活処理を行ったカーボンクロスを、５０ｍＭ塩化カリウムを含む２ｍＭ過マンガン酸カリウム水溶液に浸漬し、対極として白金板を用いて、０Ｖ vs Ａｇ／ＡｇＣｌ sat．ＫＣｌでカソード電解して、カーボンクロス上に層状マンガン酸化物を析出させ担持させた(担持量：０．２４ｍｇ／ｃｍ２）。 The carbon cloth subjected to the same activation treatment as in Example 1 was immersed in a 2 mM aqueous potassium permanganate solution containing 50 mM potassium chloride, and a platinum plate was used as a counter electrode, and 0 V vs Ag / AgCl sat. Cathodic electrolysis with KCl was performed to deposit and support layered manganese oxide on the carbon cloth (supported amount: 0.24 mg / cm 2 ).
［比較例１］
白金板を、５０ｍＭ塩化カリウムを含む２ｍＭ硫酸マンガン水溶液に浸漬し、対極として白金板を用いて、＋１．０Ｖ vs Ａｇ／ＡｇＣｌ sat．ＫＣｌでアノード電解し、白金板上に層状マンガン酸化物を析出させた(担持量：０．４４ｍｇ／ｃｍ２）。
[Comparative Example 1]
A platinum plate is immersed in a 2 mM manganese sulfate aqueous solution containing 50 mM potassium chloride, and a platinum plate is used as a counter electrode, and +1.0 V vs Ag / AgCl sat. Anode electrolysis was performed with KCl to deposit a layered manganese oxide on a platinum plate (supported amount: 0.44 mg / cm 2 ).
［比較例２］
実施例１と同じ賦活処理を行ったカーボンクロスを、５ｍＭ過マンガン酸カリウム水溶液に浸漬し、オートクレーブ中で、１２０℃で１２時間保持して、カーボンクロス上に層状マンガン酸化物を析出させ担持させた(担持量：２．０ｍｇ／ｃｍ２）。なお、実施例１〜３並びに比較例１及び２で析出した層状マンガン酸化物は、バーネサイト型層状マンガン酸化物であった。
[Comparative Example 2]
The carbon cloth subjected to the same activation treatment as in Example 1 was immersed in a 5 mM potassium permanganate aqueous solution and held at 120 ° C. for 12 hours in an autoclave to deposit and support layered manganese oxide on the carbon cloth. (Supported amount: 2.0 mg / cm 2 ). In addition, the layered manganese oxide deposited in Examples 1 to 3 and Comparative Examples 1 and 2 was a birnessite type layered manganese oxide.
実施例１で得られた層状マンガン酸化物が担持されたカーボンクロス（担持量：０．４４ｍｇ／ｃｍ２）、比較例１で得られた層状マンガン酸化物が担持されたカーボンクロスを、それぞれ電極としてそのまま用いて、０．５Ｍ硫酸ナトリウム水溶液中でサイクリックボルタンメトリーを行った。その結果を図１に示す（図中、実施例１で得られたカーボンクロスをMnO2/A-CC、比較例１で得られたカーボンクロスをMnO2/Pt plateと表示した）。図１では、担持されたマンガン酸化物そのものの性質を比較するため、電流密度はマンガン酸化物の単位質量あたりの値として見積もっている。図１からわかるとおり、層状マンガン酸化物を担持したカーボンクロスは、層状マンガン酸化物を担持した白金板に比べてはるかに大きなキャパシタ応答を示している。比キャパシタは、それぞれ２３１Ｆ／ｇ（MnO2/A-CC）、４Ｆ／ｇ（MnO2/Pt plate）と見積もられる。 The carbon cloth carrying the layered manganese oxide obtained in Example 1 (loading amount: 0.44 mg / cm 2 ) and the carbon cloth carrying the layered manganese oxide obtained in Comparative Example 1 were respectively used as electrodes. As it was, and cyclic voltammetry was performed in a 0.5 M aqueous sodium sulfate solution. The results are shown in FIG. 1 (in the figure, the carbon cloth obtained in Example 1 is indicated as MnO 2 / A-CC, and the carbon cloth obtained in Comparative Example 1 is indicated as MnO 2 / Pt plate). In FIG. 1, in order to compare the properties of the supported manganese oxide itself, the current density is estimated as a value per unit mass of the manganese oxide. As can be seen from FIG. 1, the carbon cloth carrying the layered manganese oxide shows a much larger capacitor response than the platinum plate carrying the layered manganese oxide. The specific capacitors are estimated to be 231 F / g (MnO 2 / A-CC) and 4 F / g (MnO 2 / Pt plate), respectively.
実施例１で得られたカーボンクロス（担持量：４．２７ｍｇ／ｃｍ２）、並びに比較例２で得られたカーボンクロスを、それぞれ電極としてそのまま用いて、０．５Ｍ硫酸ナトリウム水溶液中でサイクリックボルタンメトリーを行った。その結果を図２に示す（図中、実施例１で得られたカーボンクロスをAnodic-MnO2、比較例２で得られたカーボンクロスをH.T.-MnO2と表示した）。また、実施例１における賦活処理後のカーボンクロスと、実施例１で用いたものと同じ種類のカーボンクロスを、アセトンに浸漬させ１５分間超音波洗浄し、その後エタノールに浸漬させて１５分間超音波洗浄して脱脂を行ったものを電極としてそのまま用いて、０．５Ｍ硫酸ナトリウム水溶液中でサイクリックボルタンメトリーを行った。その結果を図３に示す（図中、賦活処理したものをActivated-CC、脱脂処理のみのものをUntreated-CCと表示した）。図２及び図３からわかるとおり、実施例１で得られた電気化学的に層状マンガン酸化物が担持されたカーボンクロスは、賦活処理や脱脂処理したカーボンクロスに比べて、はるかに大きな電流応答を示している。また、比較例２で得られた水熱処理により層状マンガン酸化物が担持されたカーボンクロスに比べても優れた電流応答を示している。さらに、掃引速度に対する単位面積あたりのキャパシタをプロットしたものを図４に示す。図４からわかるとおり、実施例１の電気化学的に層状マンガン酸化物が担持されたカーボンクロスは、層状マンガン酸化物を担持しないカーボンクロスや水熱処理により層状マンガン酸化物が担持されたカーボンクロスに比べて、いずれの掃引速度においても単位面積あたりのキャパシタンスが増加している。また、図５で示されるように、実施例３で得られたカーボンクロスは、マンガン酸化物の担持量が極めて少ないにもかかわらず、賦活処理したカーボンクロスに比べて、大きなキャパシタ応答を示し（図５（ａ））、いずれの掃引速度においても単位面積あたりのキャパシタンスが増加している（図５（ｂ））。 Using the carbon cloth obtained in Example 1 (supported amount: 4.27 mg / cm 2 ) and the carbon cloth obtained in Comparative Example 2 as an electrode, they were cyclic in a 0.5 M aqueous sodium sulfate solution. Voltammetry was performed. The results are shown in FIG. 2 (in the figure, the carbon cloth obtained in Example 1 is indicated as Anodic-MnO 2 and the carbon cloth obtained in Comparative Example 2 is indicated as HT-MnO 2 ). In addition, the carbon cloth after the activation treatment in Example 1 and the same type of carbon cloth as used in Example 1 were immersed in acetone and ultrasonically cleaned for 15 minutes, and then immersed in ethanol and ultrasonicated for 15 minutes. The washed and degreased one was used as an electrode as it was, and cyclic voltammetry was performed in a 0.5 M aqueous sodium sulfate solution. The results are shown in FIG. 3 (in the figure, the activated treatment is indicated as Activated-CC, and the degreasing treatment only is indicated as Untreated-CC). As can be seen from FIGS. 2 and 3, the carbon cloth carrying the electrochemically layered manganese oxide obtained in Example 1 has a much larger current response than the activated or degreased carbon cloth. Show. In addition, the current response superior to that of the carbon cloth supporting the layered manganese oxide by the hydrothermal treatment obtained in Comparative Example 2 is shown. Further, FIG. 4 shows a plot of capacitors per unit area against the sweep speed. As can be seen from FIG. 4, the carbon cloth in which the layered manganese oxide is electrochemically supported in Example 1 is divided into the carbon cloth in which the layered manganese oxide is not supported and the carbon cloth in which the layered manganese oxide is supported by hydrothermal treatment. In comparison, the capacitance per unit area increases at any sweep speed. Further, as shown in FIG. 5, the carbon cloth obtained in Example 3 showed a large capacitor response compared to the activated carbon cloth despite the extremely small amount of manganese oxide supported ( 5A), the capacitance per unit area increases at any sweep speed (FIG. 5B).
実施例１で得られたカーボンクロス（層状マンガン酸化物の担持量：０．９３ｍｇ／ｃｍ２、１．７２ｍｇ／ｃｍ２、２．５２ｍｇ／ｃｍ２、４．２７ｍｇ／ｃｍ２、９．７５ｍｇ／ｃｍ２、１３．０ｍｇ／ｃｍ２）をそれぞれ用いて、掃引速度の違いによる比キャパシタンスを測定した結果を図６に示す。また、掃引速度の違いによる単位面積あたりのキャパシタンスを測定した結果を図７に示す。図６からわかるように、低掃引速度において、比キャパシタンスは、ローディング量が１．７２ｍｇ／ｃｍ２で最大となり、それ以降はローディング量が増加するにつれ低下した。これは、マンガン酸化物に一般的にみられる傾向で。１．７２ｍｇ／ｃｍ２を境に、マンガン酸化物の電気化学的利用効率が低下することを表している。一方、単位面積あたりのキャパシタンスでみると、図７からわかるように、本発明の炭素繊維集合体は、ローディング量の増加に伴いキャパシタンスは増加した。そして、２ｍＶ／ｓの掃引速度において、最大１２００ｍＦの単位面積あたりのキャパシタンスが得られた。 Carbon cloth obtained in Example 1 (supported amount of layered manganese oxide: 0.93 mg / cm 2 , 1.72 mg / cm 2 , 2.52 mg / cm 2 , 4.27 mg / cm 2 , 9.75 mg / cm 2 , 13.0 mg / cm 2 ), and the specific capacitance due to the difference in sweep speed is measured. FIG. Moreover, the result of having measured the capacitance per unit area by the difference in sweep speed is shown in FIG. As can be seen from FIG. 6, at a low sweep rate, the specific capacitance reached its maximum when the loading amount was 1.72 mg / cm 2 , and thereafter decreased as the loading amount increased. This is a tendency commonly seen in manganese oxide. It represents that the electrochemical utilization efficiency of manganese oxide decreases at a boundary of 1.72 mg / cm 2 . On the other hand, in terms of the capacitance per unit area, as can be seen from FIG. 7, the capacitance of the carbon fiber assembly of the present invention increased as the loading amount increased. A maximum capacitance per unit area of 1200 mF was obtained at a sweep rate of 2 mV / s.
本発明の炭素繊維集合体は、単位面積あたりのキャパシタンスが大きく、キャパシタ応答性に優れ、高い導電性と優れた機械的な柔軟性と強度を有するため、フレキシブルな電極の材料として好適である。特に、電気化学キャパシタ用の電極材料、電極として好適であり、本発明の炭素繊維集合体を用いると、容量が大きく、急速充放電可能で、フレキシブルな電気化学キャパシタを作製することができる。 The carbon fiber assembly of the present invention is suitable as a flexible electrode material because it has a large capacitance per unit area, excellent capacitor response, high conductivity, and excellent mechanical flexibility and strength. In particular, it is suitable as an electrode material and electrode for an electrochemical capacitor. When the carbon fiber assembly of the present invention is used, a flexible electrochemical capacitor having a large capacity and capable of rapid charge / discharge can be produced.
Claims (6)
A bundle, woven fabric, or non-woven carbon fiber assembly is immersed in a solution containing divalent manganese ions or permanganate ions, and the divalent manganese ions in the solution are electrochemically oxidized. , Or by electrochemically reducing permanganate ions, and depositing layered manganese oxide on the surface of the carbon fiber aggregate, a bundle of layered manganese oxide supported on the surface, A method for producing a woven or non-woven carbon fiber assembly.
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| CN106531476A (en) * | 2016-12-29 | 2017-03-22 | 湖北文理学院 | Preparation method of metal oxide/ carbon composite material |
| CN110581028A (en) * | 2019-08-30 | 2019-12-17 | 浙江工业大学 | A kind of preparation method of manganese dioxide/carbon-based flexible electrode material |
| CN112863890A (en) * | 2019-11-27 | 2021-05-28 | 中南大学 | Method for electrochemically activating commercial carbon cloth through volt-ampere cycle |
| JP2021107307A (en) * | 2019-12-27 | 2021-07-29 | 株式会社ナカボーテック | Manganese oxide and method for producing the same, and electrode using the manganese oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106531476A (en) * | 2016-12-29 | 2017-03-22 | 湖北文理学院 | Preparation method of metal oxide/ carbon composite material |
| CN106531476B (en) * | 2016-12-29 | 2018-10-02 | 湖北文理学院 | A kind of preparation method of metal oxide/carbon composite |
| CN110581028A (en) * | 2019-08-30 | 2019-12-17 | 浙江工业大学 | A kind of preparation method of manganese dioxide/carbon-based flexible electrode material |
| CN112863890A (en) * | 2019-11-27 | 2021-05-28 | 中南大学 | Method for electrochemically activating commercial carbon cloth through volt-ampere cycle |
| JP2021107307A (en) * | 2019-12-27 | 2021-07-29 | 株式会社ナカボーテック | Manganese oxide and method for producing the same, and electrode using the manganese oxide |
| JP7479027B2 (en) | 2019-12-27 | 2024-05-08 | 株式会社ナカボーテック | Electrode for cathodic protection, manganese oxide and its manufacturing method |
| CN114561794A (en) * | 2022-01-27 | 2022-05-31 | 北京工业大学 | Nano-scale Cu based on aldehyde removal and antibiosis2O-MnO2Preparation method of bimetal oxide |
| CN114561794B (en) * | 2022-01-27 | 2023-09-19 | 北京工业大学 | A preparation method for nanoscale Cu2O-MnO2 bimetal oxide based on aldehyde removal and antibacterial properties |
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