CN107369563A - A kind of preparation method of nickel sulphide particles/cellulose base composite carbon aerogel material - Google Patents
A kind of preparation method of nickel sulphide particles/cellulose base composite carbon aerogel material Download PDFInfo
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- CN107369563A CN107369563A CN201610315966.3A CN201610315966A CN107369563A CN 107369563 A CN107369563 A CN 107369563A CN 201610315966 A CN201610315966 A CN 201610315966A CN 107369563 A CN107369563 A CN 107369563A
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- Prior art keywords
- cellulose
- nickel
- carbon aerogels
- cellulose base
- preparation
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 100
- 239000001913 cellulose Substances 0.000 title claims abstract description 96
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 65
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 title abstract description 6
- 235000010980 cellulose Nutrition 0.000 claims abstract description 99
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005864 Sulphur Substances 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 239000004964 aerogel Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000017 hydrogel Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 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 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000000203 mixture Substances 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
- 238000003756 stirring Methods 0.000 claims description 3
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000008104 plant cellulose Substances 0.000 claims description 2
- 239000004627 regenerated cellulose Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 235000015110 jellies Nutrition 0.000 claims 1
- 239000008274 jelly Substances 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000007096 poisonous effect Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 35
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing 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
- H01G11/30—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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
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- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of nickel sulphide particles/cellulose base composite carbon aerogel material.The compound carbon aerogels of nickel sulfide/cellulose base of the present invention are using one or more celluloses, nickel salt, sulphur source as raw material；Its preparation process includes：By cellulose dissolution into cellulose concentrated solution, then through sol-gel process, Freeze Drying Technique preparation cellulose aerogels；Handled by high temperature cabonization and cellulose base carbon aerogels are prepared；By a step solvent-thermal method on cellulose base carbon aerogels growth in situ nickel sulphide particles.The present invention uses the cheap cellulose of wide material sources, cost as precursor, use without poisonous and harmful reagent, the obtained compound carbon aerogels of nickel sulphide particles/cellulose base have the characteristics that nickel sulphide particles be evenly distributed, high-specific surface area, high conductivity, be a kind of electrode material of the preferably new energy devices such as ultracapacitor, lithium ion battery.
Description
Technical field
The invention belongs to transient metal sulfide-carbon aerogels technical field, and in particular to a kind of nickel sulfide
Particle/cellulose base composite carbon aerogel material and preparation method thereof.
Background technology
Aeroge is a kind of porous gel-like with three-dimensional net structure using gas as decentralized medium
Material, porosity are generally 80~99.8%, and specific surface area is generally 200~1000m2g-1, density
Typically smaller than 0.1g cm-3.The first aeroge-silica airsetting is prepared from Kistler in 1931
Since glue, occur polymer aerogel, carbon aerogels and other aeroges in succession.In recent years,
Carbon aerogels are due to high porosity, low-density, high-specific surface area, high conductivity, structure-controllable
And stability it is good the advantages that, obtained extensive concern and application.High porosity and high-specific surface area
The advantages that cause carbon aerogels to show strong adsorption capacity, adsorbent, catalyst carrier etc. have
Have broad application prospects；The advantages that high-specific surface area, high conductivity, structure-controllable, stability are good
Allow electrode material of the carbon aerogels as energy storage device.
Carbon aerogels because its have higher specific surface area, good electric conductivity and heat endurance and by
For preparing electrode material, but carbon aerogels specific capacity is relatively low, and prepares the conventional of this carbon aerogels
One of raw material formaldehyde is a kind of toxic gas, can be had a negative impact to environment and human health.Therefore,
Carbon aerogels are restricted in use.
The content of the invention
Present invention the shortcomings that be directed to above-mentioned carbon aerogels, there is provided a kind of preparation process environmental protection, preparation cost compared with
The low compound carbon aerogels of nickel sulphide particles/cellulose base, with and its preparation method and application.
The present invention provides a kind of preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base, using one
Walk solvent-thermal method growth in situ nickel sulphide particles, its preparing raw material on cellulose base carbon aerogels skeleton
Composition includes：One or more celluloses, aqueous slkali, nickel salt, sulphur source, are comprised the following steps that：
(1) cellulose is scattered in aqueous slkali, obtains translucent cellulose concentrated solution；
(2) cellulose concentrated solution is transferred in mould, heated in the water-bath of 50~120 DEG C of temperature
3~6h, obtain alkaline fiber hydrogel；
(3) alkaline fiber hydrogel is soaked into 12~72h in deionized water, obtains cellulose water
Gel；
(4) it is solid in freezing by cellulose aquagel, is then freeze-dried in freeze drier,
Sublimation drying is 12~72h, obtains cellulose aerogels；
(5) cellulose aerogels are subjected to high temperature cabonization, obtain cellulose base carbon aerogels；
(6) nickel salt, sulphur source are dissolved in appropriate solvent, it is molten that the mixing containing nickel source and sulphur source is prepared
Liquid；
(7) the cellulose base carbon aerogels being prepared and the mixed solution containing nickel source and sulphur source are existed
By 6~24h of solvent thermal reaction at 100~220 DEG C, nickel sulfide/fiber is obtained after scrubbed, dry
The plain compound carbon aerogels of base.
Further, the aqueous slkali is the mixed solution of sodium hydroxide/urea.
Preferably, described cellulose concentrated solution is prepared by following steps：Cellulose is first scattered in hydrogen-oxygen
To change the mixed solution of sodium/urea, then solution is placed in refrigerator and freezed, cryogenic temperature is -18~10 DEG C,
Then quick stirring a period of time, cellulose concentrated solution is obtained.
Preferably, sodium hydroxide accounts for mixed solution gross weight in described sodium hydroxide/urea mixed solution
5~10%, urea accounts for the 10~15% of mixed solution gross weight.
Further, described cellulose includes plant cellulose, bacteria cellulose, regenerated cellulose, institute
The cellulose solid content for the cellulose concentrated solution stated is 1~5%.
Further, the high temperature cabonization process described in step (5), is that cellulose aerogels are placed in into pipe
In formula stove, under nitrogen atmosphere, the heating schedule is controlled to be：From room temperature to 500 DEG C of 80~150min of heating；
From 500~800 DEG C of 20~50min of heating；From 800~1000 DEG C of 30~60min of heating, insulation
80~150min, obtain cellulose base carbon aerogels.
Further, the nickel salt described in step (6) is selected from nickel nitrate, nickel sulfate, nickel chloride, acetic acid
Nickel, the concentration of described nickel salt is 5~50mg mL-1.
Further, the sulphur source described in step (6) is thiocarbamide or vulcanized sodium, described sulphur source it is dense
Spend for 5~20mg mL-1.
The present invention also provides a kind of in situ on cellulose base carbon aerogels skeleton using a step solvent-thermal method
Grow the compound carbon aerogels of nickel sulphide particles/cellulose base of nickel sulphide particles, its preparing raw material composition bag
Include：One or more celluloses, aqueous slkali, nickel salt, thiocarbamide.
The present invention also provide a kind of compound carbon aerogels of nickel sulphide particles/cellulose base as ultracapacitor,
The application of the ideal electrode material of the new energy devices such as lithium ion battery, dye-sensitized cell.
The beneficial effects of the present invention are：
(1) mentality of designing of the present invention is ingenious, and it is main to use cheap, green cellulose
Raw material, it is multiple that the preparation process that use is simple and environmentally-friendly, easily operated directly constructs nickel sulfide/cellulose base
Close carbon aerogels.
(2) nickel sulphide particles point on the compound carbon aerogels skeleton of nickel sulphide particles/cellulose base prepared by
Cloth uniformly and size uniformity, the capacity of carbon aerogels is improved using the high specific capacity of nickel sulfide, so as to
Significantly optimization composite chemical property, become prepare high-performance super capacitor, lithium from
The ideal electrode material of the new energy devices such as sub- battery, dye-sensitized cell.
Brief description of the drawings
Fig. 1 a are the scanning electron microscope (SEM) photograph of cellulose base carbon aerogels prepared in the present invention；
Fig. 1 b are the scanning electron microscope (SEM) photograph of the compound carbon aerogels of nickel sulfide/cellulose base prepared in the present invention.
Embodiment
With reference to instantiation, the present invention is described in further detail.It should be understood that these are implemented
Example is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that reading
After the content that the present invention lectures, those skilled in the art can make various changes or modification to the present invention,
These equivalent form of values equally fall within the application appended claims limited range.
Embodiment 1
20g sodium hydroxides are completely dissolved in 80g deionized waters, are configured to 20wt% hydroxide
Sodium solution；30g urea is substantially soluble in 70g deionized waters, is configured to 30wt% urea liquid.
Wherein sodium hydroxide can also be replaced by other alkaline matters, such as potassium hydroxide, lithium hydroxide.
19g 20wt% sodium hydroxide is taken to add 2g bacteriums after being mixed with 19g 30wt% urea liquids
Cellulose, and be transferred in refrigerator and freezed, cooling temperature range is -18~10 DEG C.After freezing
Bacterial fibers/sodium hydroxide/urea/water mixed liquid stirs rapidly, makes cellulose dissolution, obtains bacterial fibers
The concentrated solution of element.
The cellulose concentrated solution of gained is poured into mould, in water-soluble middle heating a period of time, obtains alkali
Property cellulose aquagel.Wherein heating-up temperature be 50~120 DEG C, preferably 60~90 DEG C, the heat time
For 1~10 hour, preferred position 2~6 hours.Alkaline fiber hydrogel is soaked in deionized water again
12~72 hours, obtain cellulose aquagel.
It is then cold under 10~20Pa vacuums by the cellulose aquagel of gained liquid nitrogen snap frozen
It is lyophilized dry 12~72 hours, preferably 24~28 hours, obtain cellulose aerogels.
Resulting cellulose aerogels are placed in tube furnace, heating is controlled under nitrogen protection atmosphere
Program, i.e. room temperature to 500 DEG C heating 80~150min；500~800 DEG C of 20~50min of heating, insulation
80~120min, obtain cellulose base carbon aerogels.
600mg nickel nitrates and 300mg thiocarbamides is taken it is completely dissolved in 30mL N, N- diformazans by ultrasound
In base formamide, 25mg cellulose base carbon aerogels are placed in above-mentioned solution, place 1h.Wherein,
Nickel nitrate can be replaced by other nickel salts, such as nickel sulfate, nickel chloride, nickel acetate etc..Thiocarbamide also may be used
To be replaced by other sulphur sources such as vulcanized sodium, potassium sulfide.N,N-dimethylformamide can also by water,
DMAC N,N' dimethyl acetamide, water/N,N-dimethylformamide, water/DMAC N,N' dimethyl acetamide equal solvent generation
Replace.
The mixed solution of carbon aerogels and nickel nitrate/thiocarbamide is poured into 50mL water heating kettles, and by hydro-thermal
Kettle is placed in 100~220 DEG C of baking ovens and is incubated 6~24 hours.After reaction terminates, by nickel sulfide/fibre of gained
Respectively washing 3 times of the compound carbon aerogels ethanol of plain base and deionized water are tieed up, and are done in 80~100 DEG C of baking ovens
Dry 6~24 hours, finally give the compound carbon aerogels of nickel sulfide/cellulose base.
Embodiment 2
10g sodium hydroxides are completely dissolved in 90g deionized waters, are configured to 10wt% hydroxide
Sodium solution；20g urea is substantially soluble in 80g deionized waters, is configured to 20wt% urea liquid.
99g 10wt% sodium hydroxide is taken to add 2g strings after being mixed with 99g 20wt% urea liquids
Element, and be transferred in refrigerator and freezed, cooling temperature range is -18~10 DEG C.Nickel sulfide/cellulose base
Compound carbon aerogels prepare other processes with embodiment 1.
Embodiment 3
15g sodium hydroxides are completely dissolved in 85g deionized waters, are configured to 15wt% hydroxide
Sodium solution；25g urea is substantially soluble in 75g deionized waters, is configured to 25wt% urea liquid.
49g 15wt% sodium hydroxide is taken to add 2g bacterial fibers after being mixed with 49g 25wt% urea liquids
Element, and be transferred in refrigerator and freezed, cooling temperature range is -18~10 DEG C.Nickel sulfide/cellulose base
Compound carbon aerogels prepare other processes with embodiment 1.
Embodiment 4
The preparation process of cellulose base carbon aerogels is the same as embodiment 1.
The quality of nickel nitrate and thiocarbamide is changed to 1500mg and 600mg respectively, remaining with embodiment 1,
The compound carbon aerogels of nickel sulfide/cellulose base can be prepared.
Embodiment 5
The preparation process of cellulose base carbon aerogels is the same as embodiment 1.
The quality of nickel nitrate and thiocarbamide is changed to 150mg and 150mg respectively, remaining with embodiment 1,
The compound carbon aerogels of nickel sulfide/cellulose base can be prepared.
The survey of the chemical property of the compound carbon aerogels of nickel sulfide/cellulose base obtained in embodiment 1-5
Test result is shown in table 1.As a result show the nickel sulfide that is obtained by preparation method provided by the present invention/
The compound carbon aerogels of cellulose base have preferable chemical property, be it is a kind of preferably ultracapacitor,
The electrode material of the new energy devices such as lithium ion battery.
Table 1:The chemical property of the compound carbon aerogels of nickel sulfide/cellulose base obtained in embodiment 1-5
Fig. 1 a and Fig. 1 b be respectively the cellulose base carbon aerogels prepared in the embodiment of the present invention 1 and
The scanning electron microscope (SEM) photograph of the compound carbon aerogels of nickel sulfide/cellulose base.SEM test result is shown：Using
Inside cellulose base carbon aerogels prepared by sol-gel process, Freeze Drying Technique and high temperature cabonization process
The aperture of hole is 10~20 μm.And nickel sulphide particles/cellulose base carbon gas prepared in the present invention
Solidifying upper nickel sulphide particles are evenly distributed, and uniform particle diameter, are 2~5 μm.SEM test result is more
Add the nickel sulfide/cellulose base composite carbon for intuitively showing to obtain using preparation method provided by the present invention
Aeroge is the new energy devices such as high-performance super capacitor, lithium ion battery, dye-sensitized cell
Ideal electrode material.
Claims (10)
1. a kind of preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base, it is characterised in that using one
Solvent-thermal method growth in situ nickel sulphide particles on cellulose base carbon aerogels skeleton are walked, it prepares former
Material composition includes：One or more celluloses, aqueous slkali, nickel salt, sulphur source, are comprised the following steps that：
(1) cellulose is scattered in aqueous slkali, obtains translucent cellulose concentrated solution；
(2) cellulose concentrated solution is transferred in mould, heated in the water-bath of 50~120 DEG C of temperature
3~6h, obtain alkaline fiber hydrogel；
(3) alkaline fiber hydrogel is soaked into 12~72h in deionized water, obtains cellulose water
Gel；
(4) it is solid by cellulose aquagel freezing, is then freeze-dried in freeze drier, it is cold
Jelly drying time is 12~72h, obtains cellulose aerogels；
(5) cellulose aerogels are subjected to high temperature cabonization, obtain cellulose base carbon aerogels；
(6) nickel salt, sulphur source are dissolved in appropriate solvent, it is molten that the mixing containing nickel source and sulphur source is prepared
Liquid；
(7) the cellulose base carbon aerogels being prepared and the mixed solution containing nickel source and sulphur source are existed
By 6~24h of solvent thermal reaction at 100~220 DEG C, it is scrubbed, dry after obtain nickel sulfide/
The compound carbon aerogels of cellulose base.
2. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 1,
It is characterized in that the aqueous slkali is the mixed solution of sodium hydroxide/urea.
3. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 2,
It is characterized in that described cellulose concentrated solution is prepared by following steps：Cellulose is first scattered in hydrogen
The mixed solution of sodium oxide molybdena/urea, then solution is placed in refrigerator and freezed, cryogenic temperature is -18~10
DEG C, then quick stirring a period of time, obtain cellulose concentrated solution.
4. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 2,
It is characterized in that sodium hydroxide accounts for mixed solution gross weight in described sodium hydroxide/urea mixed solution
The 5~10% of amount, urea accounts for the 10~15% of mixed solution gross weight.
5. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 1,
It is characterized in that described cellulose includes plant cellulose, bacteria cellulose, regenerated cellulose, institute
The cellulose solid content for the cellulose concentrated solution stated is 1~5%.
6. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 1,
It is characterized in that the high temperature cabonization process described in step (5), is that cellulose aerogels are placed in into pipe
In formula stove, under nitrogen atmosphere, the heating schedule is controlled to be：From room temperature to 500 DEG C of heatings 80~150
min；From 500~800 DEG C of 20~50min of heating；Heat up 30~60min from 800~1000 DEG C,
80~150min is incubated, obtains cellulose base carbon aerogels.
7. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 1,
It is characterized in that the nickel salt described in step (6) is selected from nickel nitrate, nickel sulfate, nickel chloride, acetic acid
Nickel, the concentration of described nickel salt is 5~50mg mL-1。
8. the preparation method of the compound carbon aerogels of nickel sulphide particles/cellulose base according to claim 1,
It is characterized in that the sulphur source described in step (6) is thiocarbamide or vulcanized sodium, described sulphur source it is dense
Spend for 5~20mg mL-1。
9. the nickel sulphide particles that the preparation method in a kind of 1-8 according to claim described in any one obtains/
The compound carbon aerogels of cellulose base.
A kind of 10. compound carbon aerogels conduct of nickel sulphide particles/cellulose base according to described in claim 9
The ideal electrode material of the new energy devices such as ultracapacitor, lithium ion battery, dye-sensitized cell
Application.
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