CN106531454A - Ageing-resistant cobaltosic oxide nanowire carbon aerogel composite supercapacitor positive electrode material and preparation method thereof - Google Patents
Ageing-resistant cobaltosic oxide nanowire carbon aerogel composite supercapacitor positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN106531454A CN106531454A CN201611245038.0A CN201611245038A CN106531454A CN 106531454 A CN106531454 A CN 106531454A CN 201611245038 A CN201611245038 A CN 201611245038A CN 106531454 A CN106531454 A CN 106531454A
- Authority
- CN
- China
- Prior art keywords
- parts
- carbon aerogels
- appropriate amount
- positive electrode
- ageing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 43
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000032683 aging Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000002070 nanowire Substances 0.000 title abstract description 4
- 239000002131 composite material Substances 0.000 title abstract 2
- 239000007774 positive electrode material Substances 0.000 title abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 7
- 235000013877 carbamide Nutrition 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007780 powder milling Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000007581 slurry coating method Methods 0.000 claims description 3
- ZCCKUOITFYNSQG-UHFFFAOYSA-N styrene;hydrate Chemical compound O.C=CC1=CC=CC=C1 ZCCKUOITFYNSQG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 2
- 239000011148 porous material Substances 0.000 abstract 2
- 239000008098 formaldehyde solution Substances 0.000 abstract 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
Classifications
-
- 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
- H01G11/24—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
-
- 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
-
- 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
- H01G11/32—Carbon-based
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an ageing-resistant cobaltosic oxide nanowire carbon aerogel composite supercapacitor positive electrode material formed by the following materials in parts by weight: 35-38 parts of resorcinol, 70-76 parts of formaldehyde solution, appropriate amount of sodium carbonate, appropriate amount of acetone, appropriate amount of carbon black, appropriate amount of sodium carboxymethylcellulose, appropriate amount of butadiene styrene rubber, appropriate amount of deionized water, appropriate amount of 14-15mol/LKOH concentrated solution, 10-12 parts of hydrated cobalt chloride, 56-60 parts of urea, 1.2-1.3 parts of cerium nitrate, 1.2-1.5 parts of nickel foam, 15-18 parts of glycol and 3-4 parts of citric acid. According to the method, cobaltosic oxide nanowires are generated in pores of the carbon aerogel by using the hydrated cobalt chloride and the urea, so that a specific capacitance of the capacitor is improved, and good electric power storage performance is maintained; the cerium nitrate, the glycol and the citric acid are used for modifying the nickel foam so as to form nano cerium oxide in the pores of the nickel foam, and thus electric power storage and ageing resistance of the electrode material are improved.
Description
Technical field
The present invention relates to capacitor anode field of material technology, more particularly to a kind of ageing-resistant cobaltosic oxide nano line carbon
Aeroge hybrid supercapacitor positive electrode and preparation method thereof.
Background technology
Ultracapacitor is one of most promising electrical source of power of Developing, with having extended cycle life, power density it is big,
Assembling mode is simple, the features such as run safer, it is adaptable to electric automobile and hybrid vehicle power supply, portable instrument equipment with
And the back-up source of emergency set etc..But with the continuous development of energy storage technology, ultracapacitor is for high-energy-density, high ratio
The performance requirement more and more higher of power.Electrode material is one of critical component of ultracapacitor energy storage, and the carbon of commercialization at present
Electrode material is mainly activated carbon, there is low electric conductivity, aperture uncontrollability due to activated carbon, specific surface area utilization rate is low asks
Topic, therefore it is increasingly urgent to prepare the nanoporous carbon materials of excellent properties.Carbon aerogels are used as a kind of nanoporous carbon materials, quilt
It is considered a kind of excellent electrode material for super capacitor, with specific surface area height, pore-size distribution is controllable, density is adjustable, conductive
Property the characteristic such as good, attract widespread attention at aspects such as storing up electricity, hydrogen storages.Carbon aerogels are by the U.S. earliest in 1989
Resorcinol is mixed by LawrenceLivermore National Laboratories PEKALA with formaldehyde, in Na2CO3Under catalyst action, Jing
Supercritical drying prepares RF aeroges, and carbon aerogels have been obtained after carbonization.It is due to industrialization demand, dry using cheap normal pressure
Dry technology prepares carbon aerogels and obtains successfully, it might even be possible to prepares the RF and carbon aerogel films of loose structure, is greatly reduced
Preparation cost.In order to improve the chemical property of carbon aerogels ultracapacitor, regulation activating process is taken to improve carbon airsetting
The pore-size distribution of glue, the method for specific surface area, can increase the capacitance of carbon silica aerogel electrode material, including soak time
With active rate etc..Improve carbon aerogels specific surface area and improving the conventional method of chemical property there are KOH wet chemicals to activate
And CO2Physical activation method, it is therefore an objective to which pore-creating is obtaining the carbon aerogels of more high-specific surface area.In order to further improve carbon aerogels
Specific surface area and specific capacitance, can also use CO2With two step activation methods of KOH.Match somebody with somebody with catalyst herein by optimization presoma
Carbon aerogels of good performance are prepared than parameter, the carbon aerogels for being obtained is activated using 3 kinds of activating process, studied
Impacts of the different activating process to carbon aerogels specific surface area and specific capacitance.
Carbon aerogels have the advantages that many materials are difficult to reach, but due to using binding agent, the stability of electrode is poor,
Electrical conductivity is relatively low, and energy density is low, and power density is low, needs to improve, in addition it is also necessary to improve the ageing-resistant performance of positive electrode.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of ageing-resistant cobaltosic oxide nano line carbon
Aeroge hybrid supercapacitor positive electrode and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of ageing-resistant cobaltosic oxide nano line carbon aerogels hybrid supercapacitor positive electrode, by the original of following weight portion
Material is made：Resorcinol 35-38, formalin 70-76, appropriate sodium carbonate, acetone in proper, appropriate white carbon black, carboxymethyl cellulose
Appropriate sodium, appropriate butadiene-styrene rubber, appropriate deionized water, 14-15mol/LKOH concentrated solutions are appropriate, hydrated cobalt chloride 10-12, carbamide
56-60, cerous nitrate 1.2-1.3, nickel foam 1.2-1.5, ethylene glycol 15-18, citric acid 3-4.
The preparation method of the ageing-resistant cobaltosic oxide nano line carbon aerogels hybrid supercapacitor positive electrode, bag
Include following steps：
（1）By mol ratio for 1: 2 resorcinol and formaldehyde be dissolved in deionized water, add sodium carbonate liquor, uniform stirring 2-
2.3h, resorcinol are 1500 with the mol ratio of sodium carbonate, and Solute mass fraction is 30-32%, and solution sealing is placed in baking oven,
Process at 30 DEG C 1 day, then process 1 day at 50 DEG C, then process 3 days at 90 DEG C, obtain wet gel, then fully replaced with acetone
Wet gel, carries out constant pressure and dry, in N2Protection is lower to be carbonized, then mixes with KOH concentrated solutions, is vacuum dried, in N2It is warming up under protection
900 DEG C of process 2-3 hours, cooling are washed, are dried, obtain carbon aerogels；
（2）Hydrated cobalt chloride, carbamide are added in deionized water, is stirred to dissolving and is obtained solution, cobalt chloride concentration is
0.04mol/L, urea concentration are 0.2mol/L, by volume carbon aerogels：Solution=1:2-2.5 adds carbon aerogels, is put into dry
In dry case, 8-9 hours are reacted at 94-97 DEG C, carbon aerogels are taken out, is dried at 45-48 DEG C, then is placed in muffle furnace
2-2.5 hours are processed at 250-260 DEG C, natural cooling obtains modified carbon aerogels；
（3）Cerous nitrate is mixed with the deionized water of 8-9 weight portions, ethylene glycol, citric acid mix homogeneously is added, in 85-
4-5 hours are stirred at 87 DEG C, is dried at 110-114 DEG C, 2-2.3 hours are calcined at 700-740 DEG C, is ground, is obtained
Powder,
（4）By carbon aerogels: white carbon black: sodium carboxymethyl cellulose: butadiene-styrene rubber=84: 10: 1: 5 weighings, send into ball mill ball milling
0.5-0.7h, adds water and butadiene-styrene rubber, powder, and ball milling 2-2.3h obtains slurry again, and slurry coating machine is equably applied
Cloth on aluminium foil of the thickness for 20-22 μm is dried at 85-90 DEG C, obtains positive electrode.
Negative material proportioning is MCMB: white carbon black: sodium carboxymethyl cellulose: butadiene-styrene rubber=90: 6: 2: 2, prepare
Technique is identical with positive plate, after obtaining uniform sizing material, is uniformly coated on the Copper Foil that thickness is 12-13 μm, 85-90 DEG C of baking
It is dry.The positive/negative plate for obtaining is washed into the rectangle of the disk and 35mm × 40mm of a diameter of 13mm respectively, powder at lug is scraped off,
Pole piece is compacted with tablet machine；LiPF6 of the electrolyte for 1mol/L.
It is an advantage of the invention that：The present invention generates four oxidations three in carbon aerogels hole using hydrated cobalt chloride, carbamide
Cobalt nanowire so that the specific capacitance of capacitor is raised, carbon aerogels are difficult to subside, and increase discharge and recharge number of times, keep good storage
Electrical property；Nickel foam is modified by using cerous nitrate, ethylene glycol, citric acid, is defined in the hole of nickel foam
Nano-cerium oxide, improves electric power storage and the resistance to ag(e)ing of electrode material.
Specific embodiment
A kind of ageing-resistant cobaltosic oxide nano line carbon aerogels hybrid supercapacitor positive electrode, by following weight portion
（Kilogram）Raw material make：Resorcinol 35, formalin 70, appropriate sodium carbonate, acetone in proper, appropriate white carbon black, carboxymethyl are fine
The plain sodium of dimension is appropriate, appropriate butadiene-styrene rubber, appropriate deionized water, 14mol/LKOH concentrated solutions in right amount, hydrated cobalt chloride 10, carbamide
56th, cerous nitrate 1.2, nickel foam 1.2, ethylene glycol 15, citric acid 3.
The preparation method of the ageing-resistant cobaltosic oxide nano line carbon aerogels hybrid supercapacitor positive electrode, bag
Include following steps：
（1）By mol ratio for 1: 2 resorcinol and formaldehyde be dissolved in deionized water, add sodium carbonate liquor, uniform stirring 2h,
Resorcinol is 1500 with the mol ratio of sodium carbonate, and Solute mass fraction is 30%, solution sealing is placed in baking oven, at 30 DEG C
Reason 1 day, then processes 1 day at 50 DEG C, then processes 3 days at 90 DEG C, obtain wet gel, then fully replace wet gel with acetone,
Constant pressure and dry is carried out, in N2Protection is lower to be carbonized, then mixes with KOH concentrated solutions, is vacuum dried, in N2It is warming up under protection at 900 DEG C
Reason 2 hours, cooling are washed, are dried, obtain carbon aerogels；
（2）Hydrated cobalt chloride, carbamide are added in deionized water, is stirred to dissolving and is obtained solution, cobalt chloride concentration is
0.04mol/L, urea concentration are 0.2mol/L, by volume carbon aerogels：Solution=1:2 add carbon aerogels, are put into drying baker
In, react 8 hours at 94 DEG C, take out carbon aerogels, be dried at 45 DEG C, then be placed in muffle furnace and process 2 little at 250 DEG C
When, natural cooling obtains modified carbon aerogels；
（3）Cerous nitrate is mixed with the deionized water of 8 weight portions, ethylene glycol, citric acid mix homogeneously is added, at 85 DEG C
Stirring 4 hours, is dried at 110 DEG C, calcines 2 hours, grind, obtain powder at 700 DEG C,
（4）By carbon aerogels: white carbon black: sodium carboxymethyl cellulose: butadiene-styrene rubber=84: 10: 1: 5 weighings, send into ball mill ball milling
0.5h, adds water and butadiene-styrene rubber, powder, and ball milling 2h obtains slurry again, and slurry coating machine is uniformly coated to thickness
, on 20 μm of aluminium foils, to dry at 85 DEG C, obtaining positive electrode.
Negative material proportioning is MCMB: white carbon black: sodium carboxymethyl cellulose: butadiene-styrene rubber=90: 6: 2: 2, prepare
Technique is identical with positive plate, after obtaining uniform sizing material, is uniformly coated on the Copper Foil that thickness is 12 μm, 85 DEG C of drying.Will
To positive/negative plate be washed into respectively a diameter of 13mm disk and 35mm × 40mm rectangle, scrape off powder at lug, use tabletting
Pole piece is compacted by machine；LiPF6 of the electrolyte for 1mol/L.
The specific capacitance of capacitor made by the electrode material of the embodiment is 308F/g, when electric current density is 20A/g, is followed
Ring 1000 times, specific capacitance maintain the 84.8% of initial specific capacitance, good cycling stability.
Claims (2)
1. a kind of ageing-resistant cobaltosic oxide nano line carbon aerogels hybrid supercapacitor positive electrode, it is characterised in that：By
The raw material of following weight portion is made：Resorcinol 35-38, formalin 70-76, appropriate sodium carbonate, acetone in proper, white carbon black are fitted
Amount, appropriate sodium carboxymethyl cellulose, appropriate butadiene-styrene rubber, appropriate deionized water, 14-15mol/LKOH concentrated solutions are appropriate, hydration
Cobaltous chloride 10-12, carbamide 56-60, cerous nitrate 1.2-1.3, nickel foam 1.2-1.5, ethylene glycol 15-18, citric acid 3-4.
2. ageing-resistant cobaltosic oxide nano line carbon aerogels hybrid supercapacitor positive electrode according to claim 1
Preparation method, it is characterised in that comprise the following steps：
（1）By mol ratio for 1: 2 resorcinol and formaldehyde be dissolved in deionized water, add sodium carbonate liquor, uniform stirring 2-
2.3h, resorcinol are 1500 with the mol ratio of sodium carbonate, and Solute mass fraction is 30-32%, and solution sealing is placed in baking oven,
Process at 30 DEG C 1 day, then process 1 day at 50 DEG C, then process 3 days at 90 DEG C, obtain wet gel, then fully replaced with acetone
Wet gel, carries out constant pressure and dry, in N2Protection is lower to be carbonized, then mixes with KOH concentrated solutions, is vacuum dried, in N2It is warming up under protection
900 DEG C of process 2-3 hours, cooling are washed, are dried, obtain carbon aerogels；
（2）Hydrated cobalt chloride, carbamide are added in deionized water, is stirred to dissolving and is obtained solution, cobalt chloride concentration is
0.04mol/L, urea concentration are 0.2mol/L, by volume carbon aerogels：Solution=1:2-2.5 adds carbon aerogels, is put into dry
In dry case, 8-9 hours are reacted at 94-97 DEG C, carbon aerogels are taken out, is dried at 45-48 DEG C, then is placed in muffle furnace
2-2.5 hours are processed at 250-260 DEG C, natural cooling obtains modified carbon aerogels；
（3）Cerous nitrate is mixed with the deionized water of 8-9 weight portions, ethylene glycol, citric acid mix homogeneously is added, in 85-
4-5 hours are stirred at 87 DEG C, is dried at 110-114 DEG C, 2-2.3 hours are calcined at 700-740 DEG C, is ground, is obtained
Powder,
（4）By carbon aerogels: white carbon black: sodium carboxymethyl cellulose: butadiene-styrene rubber=84: 10: 1: 5 weighings, send into ball mill ball milling
0.5-0.7h, adds water and butadiene-styrene rubber, powder, and ball milling 2-2.3h obtains slurry again, and slurry coating machine is equably applied
Cloth on aluminium foil of the thickness for 20-22 μm is dried at 85-90 DEG C, obtains positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611245038.0A CN106531454A (en) | 2016-12-29 | 2016-12-29 | Ageing-resistant cobaltosic oxide nanowire carbon aerogel composite supercapacitor positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611245038.0A CN106531454A (en) | 2016-12-29 | 2016-12-29 | Ageing-resistant cobaltosic oxide nanowire carbon aerogel composite supercapacitor positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106531454A true CN106531454A (en) | 2017-03-22 |
Family
ID=58338374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611245038.0A Pending CN106531454A (en) | 2016-12-29 | 2016-12-29 | Ageing-resistant cobaltosic oxide nanowire carbon aerogel composite supercapacitor positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106531454A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786120A (en) * | 2019-01-25 | 2019-05-21 | 内蒙古科技大学 | Utilize the method for ionic liquid preparation metal/carbon aeroge composite nano materials |
| CN110364715A (en) * | 2019-07-19 | 2019-10-22 | 深圳职业技术学院 | A kind of lithium ion battery CA/Co3O4The preparation method of/C composite negative pole material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785815A (en) * | 2005-08-28 | 2006-06-14 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN101468795A (en) * | 2007-12-25 | 2009-07-01 | 成都思摩纳米技术有限公司 | Preparation of high specific surface carbon aerogel |
| CN103215104A (en) * | 2013-04-24 | 2013-07-24 | 南京理工大学 | Mixed metal oxide oxygen carrier and preparation method thereof |
| CN103280339A (en) * | 2013-04-12 | 2013-09-04 | 上海大学 | Method for preparing cerium oxide electrode of supercapacitor |
-
2016
- 2016-12-29 CN CN201611245038.0A patent/CN106531454A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785815A (en) * | 2005-08-28 | 2006-06-14 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN101468795A (en) * | 2007-12-25 | 2009-07-01 | 成都思摩纳米技术有限公司 | Preparation of high specific surface carbon aerogel |
| CN103280339A (en) * | 2013-04-12 | 2013-09-04 | 上海大学 | Method for preparing cerium oxide electrode of supercapacitor |
| CN103215104A (en) * | 2013-04-24 | 2013-07-24 | 南京理工大学 | Mixed metal oxide oxygen carrier and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FANG ZHANG等: ""Facile growth of mesoporous Co3O4 nanowire arrays on Ni foam for high performance electrochemical capacitors"", 《JOURNAL OF POWER SOURCES》 * |
| GUANGLIN SUN等: ""Incorporation of homogeneous Co3O4 into a nitrogen-doped carbon aerogel via a facile in situ synthesis method： implications for high performance asymmetric supercapacitors"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786120A (en) * | 2019-01-25 | 2019-05-21 | 内蒙古科技大学 | Utilize the method for ionic liquid preparation metal/carbon aeroge composite nano materials |
| CN110364715A (en) * | 2019-07-19 | 2019-10-22 | 深圳职业技术学院 | A kind of lithium ion battery CA/Co3O4The preparation method of/C composite negative pole material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ke et al. | Boosting lithium storage performance of Si nanoparticles via thin carbon and nitrogen/phosphorus co-doped two-dimensional carbon sheet dual encapsulation | |
| Wang et al. | Polar and conductive iron carbide@ N-doped porous carbon nanosheets as a sulfur host for high performance lithium sulfur batteries | |
| Yu et al. | Facile synthesis of nitrogen-doped carbon nanosheets with hierarchical porosity for high performance supercapacitors and lithium–sulfur batteries | |
| Li et al. | Nitrogen-containing carbon spheres with very large uniform mesopores: the superior electrode materials for EDLC in organic electrolyte | |
| Yang et al. | Sulfur impregnated in a mesoporous covalent organic framework for high performance lithium–sulfur batteries | |
| CN105789571B (en) | Silicon/silicon dioxide nanocomposite of porous carbon ball parcel and its preparation method and application | |
| CN107946086A (en) | It is a kind of using graphene as full carbon resistance rod of ultracapacitor flexible self-supporting of binding agent and preparation method thereof | |
| Kuang et al. | In situ construction of bamboo charcoal derived SiOx embedded in hierarchical porous carbon framework as stable anode material for superior lithium storage | |
| Yan et al. | Boosting chem-insertion and phys-adsorption in S/N co-doped porous carbon nanospheres for high-performance symmetric Li-ion capacitors | |
| Li et al. | CoNi-embedded nitrogen-enriched porous carbon framework for long-life lithium–sulfur batteries | |
| CN106848312A (en) | A kind of modified porous Graphene, modified porous Graphene negative electricity pole piece and preparation method thereof | |
| Jiang et al. | A three-dimensional network structure Si/C anode for Li-ion batteries | |
| Feng et al. | Nitrogen-doped lignin-derived porous carbons for supercapacitors: Effect of nanoporous structure | |
| Liang et al. | Hierarchical nanoarchitectonics of ordered mesoporous carbon from lignin for high-performance supercapacitors | |
| Zhu et al. | Dual-defect site regulation on MOF-derived P-Co 3 O 4@ NC@ O v-NiMnLDH carbon arrays for high-performance supercapacitors | |
| Tang et al. | Enhancement in electrochemical performance of nitrogen-doped hierarchical porous carbon-based supercapacitor by optimizing activation temperature | |
| He et al. | Embedding silicon in biomass-derived porous carbon framework as high-performance anode of lithium-ion batteries | |
| Jing et al. | Facile synthesis of 3D binder-free N-doped carbon nanonet derived from silkworm cocoon for Li–O 2 battery | |
| Ruan et al. | Three-dimensional sp 2 carbon networks prepared by ultrahigh temperature treatment for ultrafast lithium–sulfur batteries | |
| Wu et al. | N-doped hollow carbon nanoparticles encapsulated fibers derived from ZIF-8 self-sacrificed template for advanced lithium–sulfur batteries | |
| Kim et al. | A simple and green approach to develop porous carbons from biomass lignin for advanced asymmetric supercapacitors | |
| CN111825126A (en) | Preparation method of anion-cation co-doped modified MOFs-derived leaf-shaped hollow bimetal hydroxide material | |
| Hoseini et al. | Synthesis of soybean-derived porous carbon as selenium host for high-performance lithium-selenium batteries | |
| Yu et al. | Multi-cavity carbon nanofiber film decorated with Co-N x doped CNTs for lithium–sulfur batteries with high-areal-capacity | |
| CN114702022A (en) | Preparation method and application of hard carbon negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170322 |
|
| WD01 | Invention patent application deemed withdrawn after publication |