CN105489389A - Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof - Google Patents
Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN105489389A CN105489389A CN201610041587.XA CN201610041587A CN105489389A CN 105489389 A CN105489389 A CN 105489389A CN 201610041587 A CN201610041587 A CN 201610041587A CN 105489389 A CN105489389 A CN 105489389A
- Authority
- CN
- China
- Prior art keywords
- nickel
- composite material
- cobalt
- doping
- alkali
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002023 wood Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000428 dust Substances 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007772 electrode material Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 239000003990 capacitor Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 7
- 229910001453 nickel ion Inorganic materials 0.000 claims description 7
- 241000219000 Populus Species 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- QVCGXRQVUIKNGS-UHFFFAOYSA-L cobalt(2+);dichloride;hydrate Chemical compound O.Cl[Co]Cl QVCGXRQVUIKNGS-UHFFFAOYSA-L 0.000 claims description 2
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 claims description 2
- HGGYAQHDNDUIIQ-UHFFFAOYSA-L dichloronickel;hydrate Chemical compound O.Cl[Ni]Cl HGGYAQHDNDUIIQ-UHFFFAOYSA-L 0.000 claims description 2
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 claims description 2
- LKNLEKUNTUVOML-UHFFFAOYSA-L nickel(2+);sulfate;hydrate Chemical compound O.[Ni+2].[O-]S([O-])(=O)=O LKNLEKUNTUVOML-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910021392 nanocarbon Inorganic materials 0.000 description 4
- -1 nickel hydroxide cobalt compound Chemical class 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 239000000758 substrate Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- H01G11/84—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
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- 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)
- Carbon And Carbon Compounds (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention provides a carbon/nickel-cobalt layered double hydroxide composite material which is prepared according to the following method that carbonization treatment is performed on raw material wood powder under the atmosphere of nitrogen; then the carbonized product is uniformly mixed with alkali and water, and most of the water of the mixture is heated and evaporated and then activation treatment is performed so that alkali activated charcoal powder is prepared; the alkali activated charcoal powder is added in a nitrogen doped solution, and hydrothermal reaction is performed ultrasonic uniform mixing so that nitrogen doped activated charcoal powder is prepared; the nitrogen doped activated charcoal powder is added in deionized water, and the mixed solution of nickel salt and cobalt salt is added after dispersion; an alkali solution is added after temperature rising and stirring, and heat preservation and stirring reaction is continued; and then the reaction solution is post-treated so that the finished product is obtained. Low-cost, environment-friendly, renewable and easily obtaining wood material acts as the raw material to prepare carbon material used for manufacturing of the carbon/nickel-cobalt layered double hydroxide composite material used for a supercapacitor so that the cost advantage is obvious. Besides, stability of the composite material can be enhanced by the nitrogen doped feature of the carbon material in the composite material so that capacitance output capability of the composite material can be enhanced.
Description
(1) technical field
The present invention relates to a kind of electrode material for super capacitor and preparation method thereof, be specifically related to a kind of low cost carbon/nickel cobalt layered double-hydroxide composite material taking wood powder as raw material and prepare, this composite material can be used as electrode material for super capacitor.
(2) background technology
Ultracapacitor is a kind of new electric energy energy storage device, has the advantage that energy density is high and power density is large concurrently.In the various assembly of ultracapacitor, electrode material is the key factor affecting ultracapacitor performance and production cost.Based on charge-storage mechanism, electrode material for super capacitor is divided into Electric double-layer capacitor material and Faraday pseudo-capacitance material (also claiming redox capacitance material) usually.In recent years, to the continuous pursuit of high performance electrode material, hybrid supercapacitor electrode material is developed rapidly.Compound electrode material is usually organically combined by Electric double-layer capacitor material and fake capacitance material and is formed (Nat.Mater., 2008,7,845-854.).Compare with fake capacitance material with single Electric double-layer capacitor material, benefit from the dual contribution (NanoLett. of Electric double-layer capacitor and fake capacitance, 2011,11,2905-2911.), compound electrode material has higher capacitive property usually, be usually expressed as the significantly lifting (ACSNano of ratio capacitance, energy density or power density, 2010,4,4403-4411.; ACSNano, 2010,4,5835-5842.).The composite material that material with carbon element (providing Electric double-layer capacitor) and metal (hydrogen) oxide material (providing fake capacitance) are compounded to form is current the most typical hybrid supercapacitor electrode material (Adv.Funct.Mater., 2014,24,2938-2946.; Adv.Mater., 2014,26,4173-4178.; Chem.Soc.Rev., 2013,42,3088-3113.).
In recent years, layered metal double-hydroxide is subject to more research and pays close attention to (Adv.EnergyMater., 2014,4,1301240. because having more outstanding capacitive property compared to common metal hydroxide; Adv.Funct.Mater., 2014,24,4831-4842.).Material with carbon element and layered metal double-hydroxide compound are prepared study hotspot (Adv.Mater., 2014,26, the 4173-4178. that electrode material has become current super capacitor area; Adv.Funct.Mater., 2014,24,2938-2946.).In this composite material, material with carbon element, except the Electric double-layer capacitor of contribution self, is also of value to the electric transmission of surface attachment layered metal double-hydroxide to current collector, makes it fully contribute self fake capacitance.Layered double-hydroxide then forms various nanostructure using carbon skeleton as substrate growth in situ, reduces self aggregation, improves electrolyte contacts, improves electric capacity and effectively contributes.Although nanocarbon/metal layered double-hydroxide hybrid supercapacitor electrode material relies on the advantage of its uniqueness, extremely study concern, but at present for the preparation of the material with carbon element of nanocarbon/metal layered double-hydroxide combination electrode material, as nanoporous carbon (Template synthesis), carbon nano-tube, Graphene etc., in manufacture or there is the problems such as complicated process of preparation, cost are relatively high, raw material resources are deficient, limit the suitability for industrialized production application of this composite material.Therefore, seek cheap renewable resource as raw material, adopt relatively green straightforward procedure to prepare material with carbon element, and make it to be applied to that to prepare in nanocarbon/metal layered double-hydroxide compound be that this hybrid supercapacitor electrode material can reduce costs the key point realizing suitability for industrialized production application.
Timber is that a kind of environmental protection is renewable, abundance, the biomass resource that cheap, carbon content is high, prepares electrode of super capacitor material with carbon element because being used as raw material.Such as, the researcher of state-run research institute of Spain can reach 308F/g (BiomassBioenerg.2012,46,145.) by using phosphoric acid and the NaOH porous carbon materials capacitive property that step by step prepared by high-temperature activation wood-curing waste.The high-sequential of room temperature acidifying three-dimensional macropore wood-based material with carbon element is used for electrode of super capacitor by Illinois, USA university research personnel, obtains the capacitive property (Electrochim.Acta2013,113,481.) of 115F/g.The activated carbon fiber prepared by Liquefied wood is used for electrode material for super capacitor by the outstanding teach problem group of Zhao Guang of Beijing Forestry University, and performance reaches as high as 280F/g (J.Mater.Chem.A2014,2,11706.).The researcher of Univ Utah USA have studied the capacitive property of various wood raw material carbonized product, reaches as high as 320F/g (ECSSolidStateLett.2014,3, M25.).But, up to the present not yet there is report timber derived carbon material being used for nanocarbon/metal layered double-hydroxide compound and preparing, the correlative study more not having N doping to activate wooden carbon/nickel cobalt layered double-hydroxide compound to prepare.
(3) summary of the invention
The object of this invention is to provide a kind of low cost, electrode material for super capacitor that performance is outstanding and preparation method thereof, for the efficiency utilization of renewable timber resources on electrode material for super capacitor provides significant reference.Due to timber be that a kind of proliferative speed is fast, output is large, cost is low, the biomass resource of renewable, environmental protection, the present invention is using wood powder as raw material, through carbonization, alkali activation, nitrogen-doping, obtained N doping activates wooden carbon dust, then wooden carbon dust surface chemistry nickel deposited cobalt layered hydroxide is activated at gained N doping, obtained carbon/nickel cobalt layered double-hydroxide composite finished product.This preparation method utilizes N doping feature to improve composite material electric capacity fan-out capability, and what utilize timber low cost, reproducible feature reduction composite material manufactures cost.This electrode material preparation method promises to be the effective way of development low-cost and high-performance electrode material for super capacitor.
For achieving the above object, the present invention adopts following technical scheme:
A kind of carbon/nickel cobalt layered double-hydroxide composite material, described composite material prepares as follows:
(1) wood powder carbonization: under nitrogen protection, raw material wood powder carries out carbonization treatment 1 ~ 3h at 700 ~ 900 DEG C, obtains carbonized product;
(2) wooden carbon dust alkali activation: the carbonized product that step (1) is obtained and alkali, water take mass ratio as 1:2 ~ 7:2 ~ 9 Homogeneous phase mixing, then gained mixture being placed in content that 80 ~ 100 DEG C of baking ovens are heated to mixture water is 10% ~ 30% (i.e. gained mixture in an oven heating evaporation fall the water of 70% ~ 90%) initially adding the water yield, obtain gluey slurry, then gained glue slurry carries out activation processing 1 ~ 3h in 700 ~ 900 DEG C under nitrogen protection, after activation processing, gained activation material neutralizes through acid, deionized water washing is to neutral, be placed in the dry 12 ~ 24h of 80 ~ 100 DEG C of vacuum drying chambers again, obtained alkali activates wooden carbon dust,
Described alkali is NaOH or potassium hydroxide;
(3) wooden carbon dust nitrogen-doping is activated: the alkali that step (2) obtains is activated wooden carbon dust and adds in N doping solution, mix prior to the ultrasonic 30 ~ 40min of 30 ~ 40KHz, hydro-thermal reaction 12 ~ 24h is carried out again in 120 ~ 180 DEG C, be cooled to room temperature afterwards, reactant liquor obtains solid product through centrifugal or filtration, by gained solid product water and ethanol washing extremely neutrality, then be placed in the dry 12 ~ 24h of 80 ~ 100 DEG C of vacuum drying chambers, obtain N doping and activate wooden carbon dust;
The mass ratio that described alkali activates wooden carbon dust and N doping solution is 1:40 ~ 70; Described N doping solution is aqueous solution of urea or ammonia spirit, and described concentration of aqueous solution of urea is 60 ~ 120g/L, and described ammonia spirit concentration is 10 ~ 40g/L;
(4) preparation of carbon/nickel cobalt layered double-hydroxide composite material: the N doping that step (3) obtains is activated wooden carbon dust and adds in deionized water, obtain dispersion liquid in the ultrasonic 50 ~ 60min of 30 ~ 40KHz; Under room temperature, magnetic agitation, in gained dispersion liquid, add the mixed solution of nickel salt and cobalt salt, be then warming up to 80 ~ 90 DEG C, insulated and stirred 30 ~ 40min; Then add aqueous slkali, continue insulated and stirred 50 ~ 70min; Be cooled to room temperature afterwards, reactant liquor obtains solid product through centrifugal or filtration, by gained solid product water and ethanol washing extremely neutrality, then be placed in the dry 12 ~ 24h of 80 ~ 100 DEG C of vacuum drying chambers, obtain described carbon/nickel cobalt layered double-hydroxide composite material;
Described N doping activates the mixed solution of wooden carbon dust and deionized water, nickel salt and cobalt salt, the mass ratio of aqueous slkali is 1:400 ~ 600:250 ~ 400:250 ~ 450; In the mixed solution of described nickel salt and cobalt salt, nickel ion concentration is 15 ~ 35mmol/L, and concentration of cobalt ions is 15 ~ 35mmol/L; Described aqueous slkali is the aqueous solution of NaOH, potassium hydroxide, hexa or urea, and the concentration of described aqueous slkali is 0.15 ~ 1.25mol/L.
In the present invention, described raw material wood powder is the conventional wood powder of commercially available acquisition, and its granularity is 70 ~ 200 orders usually, the ash content of coal≤5%, moisture≤5%; Further, preferably described raw material wood powder is poplar (Classification system: Populus) powder.
Preparation method of the present invention, in step (1), described carbonization treatment is carried out usually in temperature programmed control tube furnace, and programming rate is 1 ~ 5 DEG C/min.
In step (2), the mass ratio of preferred described carbonized product and alkali, water is 1:4 ~ 5:5 ~ 7.Described activation processing is carried out usually in temperature programmed control tube furnace, and programming rate is 1 ~ 5 DEG C/min.The acid that described acid neutralization uses is 5wt% ~ 10wt% hydrochloric acid or 5wt% ~ 10wt% sulfuric acid.
In step (3), the mass ratio that preferred described alkali activates wooden carbon dust and N doping solution is 1:50 ~ 60.In preferred described aqueous solution of urea, the concentration of urea is 70 ~ 100g/L; In preferred described ammonia spirit, ammonia density is 15 ~ 30g/L.The temperature of preferred described hydro-thermal reaction is 140 ~ 160 DEG C, and the reaction time is 16 ~ 20h.The container recommending hydro-thermal reaction is stainless steel hydrothermal reaction kettle.
In step (4), described nickel salt can be nickel nitrate, nickel nitrate hydrate, nickel chloride, nickel chloride hydrate, nickelous sulfate or nickel sulfate hydrate.Described cobalt salt can be cobalt nitrate, cobalt nitrate hydrate, cobalt chloride, cobalt chloride hydrate, cobaltous sulfate or cobaltous sulfate hydrate.Preferred described N doping activates the mixed solution of wooden carbon dust and deionized water, nickel salt and cobalt salt, the mass ratio of aqueous slkali is 1:450 ~ 550:300 ~ 370:300 ~ 400.In the mixed solution of preferred described nickel salt and cobalt salt, nickel ion concentration is 20 ~ 30mmol/L, and concentration of cobalt ions is 20 ~ 30mmol/L.The concentration of preferred described aqueous slkali is 0.25 ~ 1mol/L.
Carbon/nickel cobalt layered double-hydroxide composite material prepared by the inventive method has good electrochemical capacitance performance, can be used as electrode material for super capacitor.
Advantage of the present invention is as follows:
(1) making of material with carbon element for electrochemical capacitance carbon/nickel cobalt layered double-hydroxide composite material is prepared using the timber of cheapness, environmental protection, renewable, easy acquisition as raw material, compared to using some performances outstanding but expensive material with carbon element (as Graphene, carbon nano-tube, fullerene etc.), the inventive method has obvious cost advantage;
(2) in composite material of the present invention, the N doping feature of material with carbon element can reinforced composite stability, improves composite material electric capacity fan-out capability.
(4) embodiment
For a better understanding of the present invention, be further detailed below by specific embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1
(1) carbide wood carbon dust is prepared
By Poplar Powder (manufacturer: Chemical Co., Ltd. of Long Youmu nation; size: 100 orders; the ash content of coal≤5%; moisture≤5%) 80g is placed in temperature programmed control tube furnace; under nitrogen protection, temperature is risen to 800 DEG C with the speed of 2 DEG C/min from room temperature, and in the removing in 1.5 hours of this temperature, there is volatile organic matter carbonized solid residue simultaneously.Namely brownish black carbide wood carbon dust 25g is obtained after temperature is down to room temperature.
(2) the wooden carbon dust of preparation activation
Carbonized product 10g step (1) prepared mixes with potassium hydroxide 40g, water 50mL (mass ratio 1:4:5), the content being heated to water in mixture after stirring in 100 DEG C of baking ovens is 22% (i.e. gained mixture in an oven heating evaporation fall 39g water) initially adding the water yield, obtains black glue slurry.Then this black glue slurry is proceeded in tube furnace, under nitrogen protection, temperature is risen to 800 DEG C with the speed of 2 DEG C/min from room temperature, and this temperature 1.5 hours with abundant activated carbon material.Take out sample after being cooled to room temperature, by the salt acid elution (50mL × 3) of sample mass fraction 6% obtained, be then washed with distilled water to pH neutrality.The sample obtained after dry 24 hours, can obtain black and activate wooden carbon dust 2.8g in the vacuum drying chamber of 100 DEG C.
(3) the wooden carbon dust of the nitrogen co-doped activation of phosphorus is prepared
Taking activation wood carbon dust, 25g deionized water and 2.5g concentrated ammonia liquor (28% content) prepared by 0.5g step (2) respectively with electronic balance adds in conical flask, at room temperature in 35KHz ultrasonic disperse 35 minutes.Afterwards, mixture is moved in 100mL polytetrafluoroethyllining lining high pressure water heating kettle, react 20 hours in 150 DEG C of high temperature ovens under sealing.After being cooled to room temperature, with water and ethanol by centrifugal for gained solid product or filtration washing to neutral.Afterwards, solid sample is placed in vacuum drying chamber 100 DEG C of dryings 24 hours, black N doping can be obtained and activate wooden carbon dust 0.21g.
(4) carbon/nickel cobalt layered double-hydroxide compound is prepared
Take with electronic balance N doping that 0.06g step (3) obtains respectively and activate wooden carbon dust and 30g deionized water adds in 100mL three-neck flask, at room temperature within 55 minutes, obtain uniform dispersion in 35KHz ultrasonic disperse.Afterwards, under room temperature, magnetic agitation, in above-mentioned dispersion liquid, in 60 minutes, at the uniform velocity add the mixed solution (concentration of nickel ion and cobalt ions is 25mmol/L) of 20mL nickel nitrate and cobalt nitrate, be then warming up to 85 DEG C, insulated and stirred 35 minutes.Then, 85 DEG C, in mixed solution, in 4 hours, at the uniform velocity add the NaOH solution of 20mL1mol/L under magnetic agitation, be then incubated 60 minutes.After being cooled to room temperature, with water and ethanol by centrifugal for gained solid product or filtration washing to neutral.Afterwards, solid sample is placed in vacuum drying chamber 90 DEG C of dryings 24 hours, namely obtains 0.12g N doping wood carbon/nickel hydroxide cobalt compound.
(5) carbon/nickel cobalt layered double-hydroxide compound electrochemical property test
Carbon/nickel cobalt layered double-hydroxide composite powder the 0.0160g of preparation is mixed with acetylene black 0.0030g, polytetrafluoroethylene 0.0010g (mass ratio 80:15:5), obtain homogeneous slurry with fine the milling of a small amount of water (0.1mL), utilize tablet press machine to be pressed onto by slurry on nickel foam current collector and be prepared into electrode.Before carrying out electrochemical properties test, electrode needs vacuum degassing 5 hours in 1MKOH solution.Platinum electrode and saturated calomel electrode are used separately as electrode and reference electrode.By three-electrode system, at ambient temperature, in 1MKOH electrolyte, electrochemical workstation (CHI660E, Shanghai Chen Hua equipment company) is utilized to carry out constant current charge-discharge test (charging/discharging voltage scope 0 ~ 0.5V) to preparing electrode.
According to formula C
s=I × △ t/ (△ V × m), can calculate based on charging and discharging curve and prepare sample ratio capacitance value C corresponding under different charging and discharging currents density
s.Wherein △ t (s) represents discharge time, and I (A) represents discharging current, and △ V (V) represents the potential change of discharge process, and m (g) represents the quality of active material in electrode.Result shows, under 1A/g current density, the ratio capacitance (638F/g) of the N doping wood carbon/nickel cobalt layered double-hydroxide compound of preparation activates wooden carbon (206F/g) and nickel cobalt layered double-hydroxide (490F/g) far above one-component N doping, and higher than the ratio capacitance (530F/g) of the wooden carbon that do not adulterate/nickel cobalt layered double-hydroxide compound.In addition, gained compound has excellent cyclical stability, circulate to keep after 1000 times 83% initial ratio capacitance.
Above data illustrate, carbon/nickel cobalt layered double-hydroxide composite material prepared by the inventive method has excellent electrochemical capacitance performance, is potential electrode material for super capacitor candidate.
Embodiment 2
(1) carbide wood carbon dust is prepared
By Poplar Powder (manufacturer: Chemical Co., Ltd. of Long Youmu nation; size: 100 orders; the ash content of coal≤5%; moisture≤5%) 80g is placed in temperature programmed control tube furnace; under nitrogen protection, temperature is risen to 900 DEG C with the speed of 3 DEG C/min from room temperature, and in the removing in 1 hour of this temperature, there is volatile organic matter carbonized solid residue simultaneously.Namely brownish black carbide wood carbon dust 22g is obtained after temperature is down to room temperature.
(2) the wooden carbon dust of preparation activation
Carbonized product 10g step (1) prepared mixes with NaOH 45g, water 50mL (mass ratio 1:4.5:5), the content being heated to water in mixture after stirring in 90 DEG C of baking ovens is 25% (i.e. gained mixture in an oven heating evaporation fall 37.5g water) initially adding the water yield, obtains black glue slurry.Then this black glue slurry is proceeded in tube furnace, under nitrogen protection, temperature is risen to 900 DEG C with the speed of 3 DEG C/min from room temperature, and this temperature 1 hour with abundant activated carbon material.Take out sample after being cooled to room temperature, by the salt acid elution (50mL × 3) of sample mass fraction 8% obtained, be then washed with distilled water to pH neutrality.The sample obtained after dry 20 hours, can obtain black and activate wooden carbon dust 3.0g in the vacuum drying chamber of 90 DEG C.
(3) the wooden carbon dust of the nitrogen co-doped activation of phosphorus is prepared
Taking activation wood carbon dust, 25g deionized water and 2.5g urea prepared by 0.5g step (2) respectively with electronic balance adds in conical flask, at room temperature in 35KHz ultrasonic disperse 40 minutes.Afterwards, mixture is moved in 100mL polytetrafluoroethyllining lining high pressure water heating kettle, react 12 hours in 180 DEG C of high temperature ovens under sealing.After being cooled to room temperature, with water and ethanol by centrifugal for gained solid product or filtration washing to neutral.Afterwards, solid sample is placed in vacuum drying chamber 90 DEG C of dryings 24 hours, black N doping can be obtained and activate wooden carbon dust 0.23g.
(4) carbon/nickel cobalt layered double-hydroxide compound is prepared
Take with electronic balance N doping that 0.06g step (3) obtains respectively and activate wooden carbon dust and 35g deionized water adds in 100mL three-neck flask, at room temperature within 60 minutes, obtain uniform dispersion in 35KHz ultrasonic disperse.Afterwards, under room temperature, magnetic agitation, in above-mentioned dispersion liquid, in 70 minutes, at the uniform velocity add the mixed solution (concentration of nickel ion and cobalt ions is 30mmol/L) of 20mL nickelous sulfate and cobaltous sulfate, be then warming up to 90 DEG C, insulated and stirred 30 minutes.Then, 90 DEG C, in mixed solution, in 4.5 hours, at the uniform velocity add the urea liquid of 20mL1mol/L under magnetic agitation, be then incubated 60 minutes.After being cooled to room temperature, with water and ethanol by centrifugal for gained solid product or filtration washing to neutral.Afterwards, solid sample is placed in vacuum drying chamber 95 DEG C of dryings 24 hours, namely obtains 0.13g N doping wood carbon/nickel hydroxide cobalt compound.
(5) gained carbon/nickel hydroxide cobalt composite material powder electrochemical property test step is with embodiment 1.Result shows, under 1A/g current density, the ratio capacitance (650F/g) of the N doping wood carbon/nickel cobalt layered double-hydroxide compound of preparation activates wooden carbon (190F/g) and nickel cobalt layered double-hydroxide (502F/g) far above one-component N doping, and higher than the ratio capacitance (540F/g) of the wooden carbon that do not adulterate/nickel cobalt layered double-hydroxide compound.In addition, gained composite material has excellent cyclical stability, circulate to keep after 1000 times 85% initial ratio capacitance.
Embodiment 3
(1) carbide wood carbon dust is prepared
By Poplar Powder (manufacturer: Chemical Co., Ltd. of Long Youmu nation; size: 100 orders; the ash content of coal≤5%; moisture≤5%) 80g is placed in temperature programmed control tube furnace; under nitrogen protection, temperature is risen to 700 DEG C with the speed of 1 DEG C/min from room temperature, and in the removing in 2 hours of this temperature, there is volatile organic matter carbonized solid residue simultaneously.Namely brownish black carbide wood carbon dust 25g is obtained after temperature is down to room temperature.
(2) the wooden carbon dust of preparation activation
Carbonized product 10g step (1) prepared mixes with potassium hydroxide 45g, water 60mL (mass ratio 1:4.5:6), the content being heated to water in mixture after stirring in 100 DEG C of baking ovens is 20% (i.e. gained mixture in an oven heating evaporation fall 48g water) initially adding the water yield, obtains black glue slurry.Then this black glue slurry is proceeded in tube furnace, under nitrogen protection, temperature is risen to 700 DEG C with the speed of 1 DEG C/min from room temperature, and this temperature 2 hours with abundant activated carbon material.Take out sample after being cooled to room temperature, by the salt acid elution (50mL × 3) of sample mass fraction 10% obtained, be then washed with distilled water to pH neutrality.The sample obtained after dry 12 hours, can obtain black and activate wooden carbon dust 3.2g in the vacuum drying chamber of 100 DEG C.
(3) the wooden carbon dust of the nitrogen co-doped activation of phosphorus is prepared
Taking activation wood carbon dust, 25g deionized water and 2.5g concentrated ammonia liquor (28% content) prepared by 0.5g step (2) respectively with electronic balance adds in conical flask, at room temperature in 35KHz ultrasonic disperse 40 minutes.Afterwards, mixture is moved in 100mL polytetrafluoroethyllining lining high pressure water heating kettle, react 24 hours in 120 DEG C of high temperature ovens under sealing.After being cooled to room temperature, with water and ethanol by centrifugal for gained solid product or filtration washing to neutral.Afterwards, solid sample is placed in vacuum drying chamber 100 DEG C of dryings 12 hours, black N doping can be obtained and activate wooden carbon dust 0.20g.
(4) carbon/nickel cobalt layered double-hydroxide compound is prepared
Take with electronic balance N doping that 0.06g step (3) obtains respectively and activate wooden carbon dust and 30g deionized water adds in 100mL three-neck flask, at room temperature within 60 minutes, obtain uniform dispersion in 35KHz ultrasonic disperse.Afterwards, under room temperature, magnetic agitation, in above-mentioned dispersion liquid, in 60 minutes, at the uniform velocity add the mixed solution (concentration of nickel ion and cobalt ions is 20mmol/L) of 20mL nickel chloride and cobalt chloride, be then warming up to 90 DEG C, insulated and stirred 35 minutes.Then, 90 DEG C, in mixed solution, in 4 hours, at the uniform velocity add the potassium hydroxide solution of 20mL1mol/L under magnetic agitation, be then incubated 60 minutes.After being cooled to room temperature, with water and ethanol by centrifugal for gained solid product or filtration washing to neutral.Afterwards, solid sample is placed in vacuum drying chamber 100 DEG C of dryings 18 hours, namely obtains 0.15g N doping wood carbon/nickel hydroxide cobalt compound.
(5) gained carbon/nickel hydroxide cobalt composite material powder electrochemical property test step is with embodiment 1.Result shows, under 1A/g current density, the ratio capacitance (663F/g) of the N doping wood carbon/nickel cobalt layered double-hydroxide compound of preparation activates wooden carbon (210F/g) and nickel cobalt layered double-hydroxide (511F/g) far above one-component N doping, and higher than the ratio capacitance (562F/g) of the wooden carbon that do not adulterate/nickel cobalt layered double-hydroxide compound.In addition, gained composite material has excellent cyclical stability, circulate to keep after 1000 times 81% initial ratio capacitance.
Claims (10)
1. carbon/nickel cobalt layered double-hydroxide composite material, it is characterized in that, described composite material prepares as follows:
(1) wood powder carbonization: under nitrogen protection, raw material wood powder carries out carbonization treatment 1 ~ 3h at 700 ~ 900 DEG C, obtains carbonized product;
(2) wooden carbon dust alkali activation: the carbonized product that step (1) is obtained and alkali, water take mass ratio as 1:2 ~ 7:2 ~ 9 Homogeneous phase mixing, then gained mixture being placed in the content that 80 ~ 100 DEG C of baking ovens are heated to mixture water is initially add the water yield 10% ~ 30%, obtain gluey slurry, then gained glue slurry carries out activation processing 1 ~ 3h in 700 ~ 900 DEG C under nitrogen protection, after activation processing, gained activation material neutralizes through acid, deionized water washing is to neutral, be placed in the dry 12 ~ 24h of 80 ~ 100 DEG C of vacuum drying chambers again, obtained alkali activates wooden carbon dust,
Described alkali is NaOH or potassium hydroxide;
(3) wooden carbon dust nitrogen-doping is activated: the alkali that step (2) obtains is activated wooden carbon dust and adds in N doping solution, mix prior to the ultrasonic 30 ~ 40min of 30 ~ 40KHz, hydro-thermal reaction 12 ~ 24h is carried out again in 120 ~ 180 DEG C, be cooled to room temperature afterwards, reactant liquor obtains solid product through centrifugal or filtration, by gained solid product water and ethanol washing extremely neutrality, then be placed in the dry 12 ~ 24h of 80 ~ 100 DEG C of vacuum drying chambers, obtain N doping and activate wooden carbon dust;
The mass ratio that described alkali activates wooden carbon dust and N doping solution is 1:40 ~ 70; Described N doping solution is aqueous solution of urea or ammonia spirit, and described concentration of aqueous solution of urea is 60 ~ 120g/L, and described ammonia spirit concentration is 10 ~ 40g/L;
(4) preparation of carbon/nickel cobalt layered double-hydroxide composite material: the N doping that step (3) obtains is activated wooden carbon dust and adds in deionized water, obtain dispersion liquid in the ultrasonic 50 ~ 60min of 30 ~ 40KHz; Under room temperature, magnetic agitation, in gained dispersion liquid, add the mixed solution of nickel salt and cobalt salt, be then warming up to 80 ~ 90 DEG C, insulated and stirred 30 ~ 40min; Then add aqueous slkali, continue insulated and stirred 50 ~ 70min; Be cooled to room temperature afterwards, reactant liquor obtains solid product through centrifugal or filtration, by gained solid product water and ethanol washing extremely neutrality, then be placed in the dry 12 ~ 24h of 80 ~ 100 DEG C of vacuum drying chambers, obtain described carbon/nickel cobalt layered double-hydroxide composite material;
Described N doping activates the mixed solution of wooden carbon dust and deionized water, nickel salt and cobalt salt, the mass ratio of aqueous slkali is 1:400 ~ 600:250 ~ 400:250 ~ 450; In the mixed solution of described nickel salt and cobalt salt, nickel ion concentration is 15 ~ 35mmol/L, and concentration of cobalt ions is 15 ~ 35mmol/L; Described aqueous slkali is the aqueous solution of NaOH, potassium hydroxide, hexa or urea, and the concentration of described aqueous slkali is 0.15 ~ 1.25mol/L.
2. composite material as claimed in claim 1, it is characterized in that, described raw material wood powder is Poplar Powder.
3. composite material as claimed in claim 1, is characterized in that, in step (2), the mass ratio of described carbonized product and alkali, water is 1:4 ~ 5:5 ~ 7.
4. composite material as claimed in claim 1, it is characterized in that, in step (3), the mass ratio that described alkali activates wooden carbon dust and N doping solution is 1:50 ~ 60.
5. composite material as claimed in claim 1, it is characterized in that, in step (3), in described aqueous solution of urea, the concentration of urea is 70 ~ 100g/L; In described ammonia spirit, ammonia density is 15 ~ 30g/L.
6. composite material as claimed in claim 1, it is characterized in that, in step (4), described nickel salt is nickel nitrate, nickel nitrate hydrate, nickel chloride, nickel chloride hydrate, nickelous sulfate or nickel sulfate hydrate; Described cobalt salt is cobalt nitrate, cobalt nitrate hydrate, cobalt chloride, cobalt chloride hydrate, cobaltous sulfate or cobaltous sulfate hydrate.
7. composite material as claimed in claim 1, it is characterized in that, in step (4), described N doping activates the mixed solution of wooden carbon dust and deionized water, nickel salt and cobalt salt, the mass ratio of aqueous slkali is 1:450 ~ 550:300 ~ 370:300 ~ 400.
8. composite material as claimed in claim 1, it is characterized in that, in step (4), in the mixed solution of described nickel salt and cobalt salt, nickel ion concentration is 20 ~ 30mmol/L, and concentration of cobalt ions is 20 ~ 30mmol/L.
9. composite material as claimed in claim 1, it is characterized in that, in step (4), the concentration of described aqueous slkali is 0.25 ~ 1mol/L.
10. carbon/nickel cobalt layered double-hydroxide composite material as claimed in claim 1 is as the application of electrode material for super capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610041587.XA CN105489389B (en) | 2016-01-21 | 2016-01-21 | Carbon/nickel cobalt layered double-hydroxide composite and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610041587.XA CN105489389B (en) | 2016-01-21 | 2016-01-21 | Carbon/nickel cobalt layered double-hydroxide composite and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105489389A true CN105489389A (en) | 2016-04-13 |
| CN105489389B CN105489389B (en) | 2017-11-17 |
Family
ID=55676310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610041587.XA Expired - Fee Related CN105489389B (en) | 2016-01-21 | 2016-01-21 | Carbon/nickel cobalt layered double-hydroxide composite and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105489389B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105931854A (en) * | 2016-06-14 | 2016-09-07 | 常州大学 | Nickel-cobalt double hydroxide/nitrogenous carbon nanohorn composite material used for supercapacitor and preparation method for composite material |
| CN106683890A (en) * | 2016-11-01 | 2017-05-17 | 浙江农林大学 | Carbon/manganese oxide composite material, preparation method thereof and application thereof |
| CN106847530A (en) * | 2017-02-27 | 2017-06-13 | 四川大学 | A kind of nickel cobalt base-carbon nano tube combination electrode material and preparation method thereof |
| CN107293408A (en) * | 2017-06-01 | 2017-10-24 | 大连理工大学 | A kind of nickel cobalt hydroxide/nitrogenous activated carbon composite electrode material and preparation method thereof |
| CN108479700A (en) * | 2018-04-13 | 2018-09-04 | 南昌大学 | A kind of preparation method for Cr VI and the porous carbon composite material of methyl orange eutectoid content |
| CN108492998A (en) * | 2018-03-21 | 2018-09-04 | 青海民族大学 | A kind of preparation method of cobalt nickel double-hydroxide/carbosphere combination electrode material |
| CN108837803A (en) * | 2018-06-28 | 2018-11-20 | 东北农业大学 | A kind of layered double-hydroxide loads the preparation method of biological carbon composite |
| CN108928874A (en) * | 2018-07-09 | 2018-12-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of modified magnalium inorganic composite flocculant and products thereof and application |
| CN109065900A (en) * | 2018-09-10 | 2018-12-21 | 华南理工大学 | A kind of multilevel structure composite material and its preparation and application |
| CN109243848A (en) * | 2018-10-30 | 2019-01-18 | 武汉大学 | A kind of preparation method of nickeliferous hydrotalcite/carbon nanotube electrode material |
| CN109225232A (en) * | 2018-10-26 | 2019-01-18 | 陕西科技大学 | A kind of elctro-catalyst and preparation method thereof |
| CN109755030A (en) * | 2019-02-08 | 2019-05-14 | 桂林理工大学 | A kind of preparation method and applications of glucosyl group carbon ball/cobalt nickel hydroxide composite material |
| CN110047658A (en) * | 2019-03-15 | 2019-07-23 | 四川大学 | Carbon, electrode material of sulphur codope and preparation method thereof |
| CN111097422A (en) * | 2019-12-09 | 2020-05-05 | 广东省石油与精细化工研究院 | Catalyst for removing formaldehyde and preparation method and application thereof |
| CN113436900A (en) * | 2021-06-28 | 2021-09-24 | 中南林业科技大学 | Nitrogen-doped carbon-based electrode based on nickel-cobalt double hydroxide, preparation method and super capacitor |
| CN114360921A (en) * | 2022-01-14 | 2022-04-15 | 辽宁工程技术大学 | Preparation method of three-dimensional bulk phase core-shell structure activated carbon @ hydroxide composite electrode material |
| CN115274309A (en) * | 2022-07-20 | 2022-11-01 | 煤炭科学研究总院有限公司 | Nickel-cobalt double hydroxide/oxidized active carbon composite material and preparation method thereof |
| CN115881442A (en) * | 2022-12-20 | 2023-03-31 | 福州大学 | Sucrose-based porous carbon composite nickel-iron layered double hydroxide electrode material regulated by surfactant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008235370A (en) * | 2007-03-16 | 2008-10-02 | Canon Inc | Method of manufacturing electrode for storage material and electrode for electrochemical element |
| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN104252970A (en) * | 2014-10-17 | 2014-12-31 | 武汉理工大学 | Co3O4-graphene @ nickel cobalt double hydroxide composite material with three-dimensional network structure, as well as preparation method and application thereof |
-
2016
- 2016-01-21 CN CN201610041587.XA patent/CN105489389B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008235370A (en) * | 2007-03-16 | 2008-10-02 | Canon Inc | Method of manufacturing electrode for storage material and electrode for electrochemical element |
| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN104252970A (en) * | 2014-10-17 | 2014-12-31 | 武汉理工大学 | Co3O4-graphene @ nickel cobalt double hydroxide composite material with three-dimensional network structure, as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JINGWEN ZHAO, ET AL: "Hierarchical NiMn layered double hydroxide/carbon nanotubes architecture with superb energy density for flexible supercapacitors", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| SHUAI YU, ET AL: "Synthesis of wood derived nitrogen-doped porous carbon-polyaniline composites for supercapacitor electrode materials", 《RSC ADVANCES》 * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105931854A (en) * | 2016-06-14 | 2016-09-07 | 常州大学 | Nickel-cobalt double hydroxide/nitrogenous carbon nanohorn composite material used for supercapacitor and preparation method for composite material |
| CN105931854B (en) * | 2016-06-14 | 2018-06-26 | 常州大学 | A kind of ultracapacitor nickel cobalt double-hydroxide/nitrogenous carbon nanohorn composite material and preparation method thereof |
| CN106683890A (en) * | 2016-11-01 | 2017-05-17 | 浙江农林大学 | Carbon/manganese oxide composite material, preparation method thereof and application thereof |
| CN106847530A (en) * | 2017-02-27 | 2017-06-13 | 四川大学 | A kind of nickel cobalt base-carbon nano tube combination electrode material and preparation method thereof |
| CN107293408A (en) * | 2017-06-01 | 2017-10-24 | 大连理工大学 | A kind of nickel cobalt hydroxide/nitrogenous activated carbon composite electrode material and preparation method thereof |
| CN107293408B (en) * | 2017-06-01 | 2019-03-05 | 大连理工大学 | A kind of nickel cobalt hydroxide/nitrogenous activated carbon composite electrode material and preparation method thereof |
| CN108492998A (en) * | 2018-03-21 | 2018-09-04 | 青海民族大学 | A kind of preparation method of cobalt nickel double-hydroxide/carbosphere combination electrode material |
| CN108479700B (en) * | 2018-04-13 | 2020-10-23 | 南昌大学 | Preparation method of porous carbon composite material for co-adsorption of hexavalent chromium and methyl orange |
| CN108479700A (en) * | 2018-04-13 | 2018-09-04 | 南昌大学 | A kind of preparation method for Cr VI and the porous carbon composite material of methyl orange eutectoid content |
| CN108837803A (en) * | 2018-06-28 | 2018-11-20 | 东北农业大学 | A kind of layered double-hydroxide loads the preparation method of biological carbon composite |
| CN108928874A (en) * | 2018-07-09 | 2018-12-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of modified magnalium inorganic composite flocculant and products thereof and application |
| CN109065900A (en) * | 2018-09-10 | 2018-12-21 | 华南理工大学 | A kind of multilevel structure composite material and its preparation and application |
| CN109065900B (en) * | 2018-09-10 | 2021-06-08 | 华南理工大学 | Multilevel structure composite material and preparation and application thereof |
| CN109225232B (en) * | 2018-10-26 | 2021-11-16 | 陕西科技大学 | Electrocatalyst and preparation method thereof |
| CN109225232A (en) * | 2018-10-26 | 2019-01-18 | 陕西科技大学 | A kind of elctro-catalyst and preparation method thereof |
| CN109243848A (en) * | 2018-10-30 | 2019-01-18 | 武汉大学 | A kind of preparation method of nickeliferous hydrotalcite/carbon nanotube electrode material |
| CN109755030A (en) * | 2019-02-08 | 2019-05-14 | 桂林理工大学 | A kind of preparation method and applications of glucosyl group carbon ball/cobalt nickel hydroxide composite material |
| CN110047658A (en) * | 2019-03-15 | 2019-07-23 | 四川大学 | Carbon, electrode material of sulphur codope and preparation method thereof |
| CN111097422A (en) * | 2019-12-09 | 2020-05-05 | 广东省石油与精细化工研究院 | Catalyst for removing formaldehyde and preparation method and application thereof |
| CN111097422B (en) * | 2019-12-09 | 2022-10-21 | 广东省石油与精细化工研究院 | Catalyst for removing formaldehyde and preparation method and application thereof |
| CN113436900A (en) * | 2021-06-28 | 2021-09-24 | 中南林业科技大学 | Nitrogen-doped carbon-based electrode based on nickel-cobalt double hydroxide, preparation method and super capacitor |
| CN113436900B (en) * | 2021-06-28 | 2022-07-15 | 中南林业科技大学 | Nitrogen-doped carbon-based electrode based on nickel-cobalt double hydroxide, preparation method and super capacitor |
| CN114360921A (en) * | 2022-01-14 | 2022-04-15 | 辽宁工程技术大学 | Preparation method of three-dimensional bulk phase core-shell structure activated carbon @ hydroxide composite electrode material |
| CN115274309A (en) * | 2022-07-20 | 2022-11-01 | 煤炭科学研究总院有限公司 | Nickel-cobalt double hydroxide/oxidized active carbon composite material and preparation method thereof |
| CN115274309B (en) * | 2022-07-20 | 2023-09-01 | 煤炭科学研究总院有限公司 | Nickel-cobalt double hydroxide/oxidized active carbon composite material and preparation method thereof |
| CN115881442A (en) * | 2022-12-20 | 2023-03-31 | 福州大学 | Sucrose-based porous carbon composite nickel-iron layered double hydroxide electrode material regulated by surfactant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105489389B (en) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105489389A (en) | Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof | |
| CN105469999B (en) | Bamboo powder is the method that raw material prepares Carbon-based supercapacitor electrode material | |
| Thambidurai et al. | Preparation and electrochemical behaviour of biomass based porous carbons as electrodes for supercapacitors—a comparative investigation | |
| CN110330016A (en) | An a kind of step cooperative development method of anthracite-base porous carbon graphite microcrystal and hole | |
| Li et al. | Activated carbon prepared from lignite as supercapacitor electrode materials | |
| CN106601490A (en) | Preparation method of biomass-based nitrogenous porous carbon, porous carbon prepared by method and use thereof | |
| Wang et al. | H3PO4-assisted synthesis of apricot shell lignin-based activated carbon for capacitors: understanding the pore structure/electrochemical performance relationship | |
| CN104118863B (en) | A kind of ionic liquid activation rice husk prepares the method for porous carbon material for supercapacitor | |
| CN106683890A (en) | Carbon/manganese oxide composite material, preparation method thereof and application thereof | |
| Wang et al. | Biorefining of sugarcane bagasse to fermentable sugars and surface oxygen group-rich hierarchical porous carbon for supercapacitors | |
| Yin et al. | Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review | |
| CN106348295A (en) | Preparation method of walnut shell active carbon | |
| Lai et al. | Ultralong-life supercapacitors using pyridine-derived porous carbon materials | |
| CN103803550B (en) | A kind of preparation method of asphalt based active carbon | |
| Sinha et al. | Activated carbon as electrode materials for supercapacitors | |
| Wang et al. | Eco-friendly preparation of biomass-derived porous carbon and its electrochemical properties | |
| Zou et al. | Engineering of N, P co-doped hierarchical porous carbon from sugarcane bagasse for high-performance supercapacitors and sodium ion batteries | |
| CN105244503A (en) | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material | |
| CN104409219A (en) | Preparation method for hexagonal manganese dioxide nanosheet material and application of hexagonal manganese dioxide nanosheet material as electrode material of supercapacitor | |
| CN104124446A (en) | Graphite/Li3VO4 lithium ion battery composite negative electrode material and preparation method thereof | |
| Yang et al. | Towards high-performance supercapacitors with cellulose-based carbon for zinc-ion storage | |
| Zhang et al. | Three-dimension in-situ nitrogen doping porous cellulosic biomass-based carbon aerogel for electrocatalytic CO2 reduction | |
| CN104401991A (en) | Method for preparing activated carbon with high specific surface area by using conyza canadensis | |
| CN104681307B (en) | A kind of preparation method of the common supported active carbon resistance rod of oxygen, nitrogen | |
| Liu et al. | Modulating pore nanostructure coupled with N/O doping towards competitive coal tar pitch-based carbon cathode for aqueous Zn-ion storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171117 Termination date: 20200121 |