CN104900419B - Use CNTs@SiO2@Ni/Al LDH core shell structures are the ultracapacitor of positive electrode - Google Patents
Use CNTs@SiO2@Ni/Al LDH core shell structures are the ultracapacitor of positive electrode Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 42
- 239000011258 core-shell material Substances 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052681 coesite Inorganic materials 0.000 title claims description 20
- 229910052906 cristobalite Inorganic materials 0.000 title claims description 20
- 229910052682 stishovite Inorganic materials 0.000 title claims description 20
- 229910052905 tridymite Inorganic materials 0.000 title claims description 20
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 15
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 15
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 15
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003990 capacitor Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- -1 battery diaphragm Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
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- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910002706 AlOOH Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 4
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- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
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- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical group CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000011244 liquid electrolyte Substances 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 12
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- 238000002360 preparation method Methods 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
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- 238000004146 energy storage Methods 0.000 description 6
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- 239000004698 Polyethylene Substances 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910002065 alloy metal Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
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- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AGLSQWBSHDEAHB-UHFFFAOYSA-N azane;boric acid Chemical compound N.OB(O)O AGLSQWBSHDEAHB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
CNTs@SiO are used the invention discloses one kind2@Ni/Al LDH core shell structures are the ultracapacitor of positive electrode, including plus plate current-collecting body, positive electrode, battery diaphragm, electrolyte, negative material and negative current collector, positive electrode is the CNT with high conductivity as core, nickel aluminum hydrotalcite is shell, and silica is the composite with 3-D nano, structure that connecting layer is formed, with specific surface area and very strong electro-chemical activity very high.Ultracapacitor of the invention has the extremely short discharge and recharge time, and high power density and energy density, long service life, energy density can reach 100Wh/kg.
Description
Technical field
The invention belongs to energy storage field, it is related to three using a kind of CNT silica nickel aluminum hydrotalcite core shell structure
Dimensional nano structure material is the asymmetric ultracapacitor of positive pole.
Background technology
Under normal circumstances, according to the difference of energy storage mechanism, ultracapacitor is divided into two types：One class is referred to as double
Electric layer capacitor, abbreviation EDLC, electric double layer capacitance is caused by the oriented alignment of electronics or ion in electrode/electrolyte interface
Produced by the face-off of electric charge.To an electrode/electrolyte system, can be in the electrode and the electrolyte of ionic conduction of electronic conduction
Electric double layer is formed on interface.Another kind of is faraday's capacitor (FS), is called pseudocapacitor, is also pseudocapacitors, faraday's electricity
The charge storage mechanisms of container are then on the two-dimentional or quasi- two-dimensional space in electrode surface or body phase, to carry out electrode active material
Underpotential deposition, there is the chemisorbed/desorption or redox reaction of high reversible, thus produce electric with electrode charge
The relevant electric capacity in position.Because the generation mechanism of two kinds of electric capacity is different, and the latter is with the generation of charge transfer process, institute
It is referred to as pseudo capacitance with by the electric capacity caused by redox.Be can be seen that from the energy storage mechnism of above ultracapacitor
It is a kind of novel energy storage component between General Physics capacitor and secondary cell.This novel energy storage component is stored
Energy ratio General Physics capacitor it is order of magnitude greater more than, while maintain again physical capacitor release energy it is fireballing
Advantage, this obviously can make up battery (such as plumbic acid, ni-mh, lithium electricity) very slow shortcoming of release electric energy speed.In addition, in phase
In the case of same electrode area, double layer capacitor is compared with pseudocapacitors, and the capacitance of the latter is bigger more than 10 times than the former.
As typical fake capacitance material, nickel aluminum hydrotalcite（Ni/Al-LDH）With theoretical capacity is high, electrochemical oxidation also
The features such as former activity high, cheap, environmentally friendly and unique layer structure and be widely studied.With other materials phase
Than its unique layer structure can allow almost all of active material to participate in surface electrochemistry reaction, be redox reaction
Larger specific surface area is provided, and with good stability.
In order to further improve the chemical property of material, Ni/Al-LDH is combined with CNT, helps to carry
The capacitance and cycle performance of composite high.CNT has that specific surface area is big, electric conductivity for electrode of super capacitor
The excellent performance such as good, chemical resistance is strong, operating potential window is wide, quality is small, utilization rate is high.By liquid phase method, carbon is received
Nanotube surface is modified, and on the one hand the modified CNT in surface can provide ratio high for the growth in situ of Ni/Al-LDH
Surface area.For example in patent of invention, Lei Xiaodong et al.（Application for a patent for invention number：201410174751.5）Disclose nickel aluminium
Hydrotalcite/CNT/nickel multilevel hierarchy film and its preparation method and application, by synthesizing nickel aluminium nickel in foam nickel base
Aluminum hydrotalcite film, then grows CNT on nickel aluminium nickel aluminum hydrotalcite film, then prepares nickel on the carbon nanotubes again
The three-dimensional multistage structural membrane material of aluminium nickel aluminum hydrotalcite.Comparing specific surface area high is obtained, but in the preparation method, mistake
Journey is complicated, cracks acetylene gas by high temperature and carbon pipe is prepared in nickel foam, and the technical process is for nickel foam as substrate
Electrochemistry aspect application for, large-scale production difficulty it is big.Still further aspect, not referred in above invention can obtain many
Big energy density, and energy density is a most important index of the ultracapacitor as stored energy application.Therefore exploitation one
Kind of mild condition, be adapted to large-scale industrial production with CNT/nickel aluminum hydrotalcite composite as positive electrode, with height
Energy density it is significant to ultracapacitor.
The content of the invention
It is an object of the present invention to provide a kind of simple and practical method, changed on CNT prepared by commercial
Property, nickel aluminium nickel aluminum hydrotalcite is then prepared on the carbon nanotubes, very big specific surface area can be obtained, especially, prepare
Super electrical equipment device can obtain energy density very high.
The technical scheme is that：Use CNTs@SiO2@Ni/Al-LDH core shell structures are the super electricity of positive electrode
Container, including plus plate current-collecting body, positive electrode, battery diaphragm, electrolyte, negative material and negative current collector, wherein positive pole material
Material is CNTs@SiO2@LDH core shell structures（Hereinafter referred to as CNTs@SiO2@LDH）Three-dimensional nanometer material.
CNTs in the present invention refers to CNT, and Ni/Al-LDH refers to nickel aluminum hydrotalcite.
In the present invention, CNTs@SiO2@Ni/Al-LDH Core-shell structure materials with the CNT of high conductivity as core, nickel aluminium
Hydrotalcite is shell, and silica is the composite with 3-D nano, structure that connecting layer is formed.
Further, in the present invention, the plus plate current-collecting body is：Nickel foil, Copper Foil, aluminium foil, stainless steel foil, metal alloy material
Material paper tinsel, nickel foam or other foam metals, stainless (steel) wire or other wire nettings etc..
Further, in the present invention, the battery diaphragm is polyethylene（Polyethylene, PE）, polypropylene
（Polypropylene, PP）And other TPO barrier films.
Further, the present invention in, the electrolyte be aqueous electrolyte, organic electrolyte and il electrolyte,
Wherein aqueous electrolyte is potassium hydroxide aqueous solution, and the mixing of the single saline solution such as aqueous sodium persulfate solution or various salt is water-soluble
Liquid；Organic electrolyte is propene carbonate, ethylene carbonate, dissolving or scattered five fluorination in the organic solvent such as diethyl carbonate
It is clear, lithium hexafluoro phosphate, tetraethyl tetrafluoro boric acid amine, the material such as methyl triethyl group tetrafluoro boric acid amine；Il electrolyte is 1-
Methyl -3- ethyl imidazol(e) chlorides, 1- ethyl-3-methylimidazoles, N- trimethyl-N- hexyls ammonium two（Trimethyl fluoride sulfonyl）Imines
Deng material.
Further, in the present invention, the negative material is activated carbon, CNT, Graphene and other porous carbons
The mixing material of material or various carbon materials.
Further, in the present invention, the negative current collector is nickel foil, Copper Foil, aluminium foil, stainless steel foil, metal alloy material
Material paper tinsel, nickel foam or other foam metals, stainless (steel) wire or other wire nettings etc..
CNTs@SiO in the present invention2@Ni/Al-LDH Core-shell structure materials are prepared in the following manner：
1) a certain amount of CNT, cetyl trimethylammonium bromide are taken（CTAB）In container, ethanol, deionization are added
Water forms mixed solution, and above-mentioned mixed solution is carried out ultrasonically treated to obtain carbon nano-tube solution A；
2) NaOH, tetraethyl orthosilicate (TEOS) are added in solution A, after being stirred under room temperature condition, is centrifuged or is filtered
Take, wash product with ethanol and dry, finally give the powder B of cleaning；
3) by the dispersion of a certain amount of aluminium isopropoxide in deionized water, after stirring, HNO is added dropwise3Regulation solution ph
It is 1 ~ 8, and after continuing to stir, solution system is cooled to room temperature, after can obtain AlOOH colloidal sols after moisture evaporation；
4）Dried AlOOH is ground, deionized water is added, stirring and flow back 1-24 hours can obtain
Solution C；
5) a certain amount of solution C is taken, product centrifugation or filtering, alcohol are washed, product is dried by powder B mixing after stirring
Can obtain material powder D afterwards；
6) powder D is dispersed in the deionized water for having dissolved urea, solution E is obtained after stirring；
7) to dropwise addition Ni (NO in solution E3)2, and after constantly stirring, above-mentioned solution system is transferred to reactor
In, 50-250 DEG C of hydro-thermal reaction or water-bath or oil bath are reacted 1-48 hour, product is centrifuged after the completion of question response or
Person is filtered, and product is alternately washed repeatedly with deionized water and ethanol, after being dried under the conditions of 20-100 DEG C of products therefrom, just be can obtain
The 3-D nano, structure positive electrode of CNT titanium dioxide tantnickel aluminium nickel aluminum hydrotalcite core shell structure；
Further, step 1）In CNT and CTAB quality than scope be 1:1 to 1:100；Step 2）In
NaOH concentration control is controlled in 0.001-5000mmol/L in 0.01-5000mmol/L, tetraethyl orthosilicate concentration；Step 3）In
The quality of aluminium isopropoxide and deionized water be (1-100) than scope:100, step 5）In when taking solution C and powder B and mixing, often
The scope of 1g powder B mixed solution Cs is 100-1000ml；Step 5）In urea concentration range be 0.1-5mol/L；Step
6）In urea concentration range be 0.1-5mol/L.
The present invention has advantages below compared with prior art：
1）CNTs@SiO2@Ni/Al-LDH composite material of core-shell structure possesses nanometer while with high-specific surface area
The high electrochemical activity of structural material, can greatly increase specific capacity；
2）After carbon nano tube surface forms shell, CNT forms the branch of high surface area to nickel aluminum hydrotalcite two-dimensional nano piece
Timbering material, improves its mechanical stability, and the cycle charge discharge electric life of material is greatly increased；
3）CNT can turn into the cushion of volumetric expansion and contraction during redox reaction, so that effectively
Stability of material in charge and discharge process is improved, material circulation performance is greatly improved；
4）Because CNT has excellent electric conductivity, quick " electron transport passage " can be formed, so as to greatly enhance
The electric conductivity of electrode active material, improves its chemical property；
5）The easy agglomeration of CNT is overcome, the bigger serface of CNT is also given full play of, with
Obtain specific capacity higher.
6）The core shell structure has abundant effective apearture, is beneficial to the immersion of electrolyte in electrochemical reaction, nickel aluminium water
Talcum is rendered as two-dimensional nano sheet structure also for redox reaction provides more favourable place, can obtain energy higher
Density.
Thus, based on CNTs@SiO2The ultracapacitor that@Ni/Al-LDH core shell structures are proposed will obtain following breakthrough：
1）The extremely short discharge and recharge time.The swift electron passage that CNT is constituted, the electronics for producing fake capacitance effect
Collector can be efficiently quickly transferred to and form discharge current, ultracapacitor can realize energy input and the output of moment；
2）High power density and energy density.The CNTs@SiO of this Project design2@Ni/Al-LDH core shell structure materials
When material is used as super capacitor anode material, ultracapacitor power density and energy density are greatly improved.This is caused
The ultracapacitor directly replaces secondary cell to be applied to powerful occasion to be possibly realized, change ultracapacitor in electricity
Secondary role present situation is only played during the stored energy applications such as electrical automobile, power station energy storage；
3）Long service life；
4）Energy density can reach 100Wh/kg.
Brief description of the drawings
Fig. 1 is with CNT@silica@nickel aluminium nickel aluminum hydrotalcites as positive electrode material prepared by the present invention
Asymmetric Supercapacitor energy density changing trend diagram under different current densities；
Fig. 2 is non-right as positive electrode with CNT@silica@nickel aluminium nickel aluminum hydrotalcites prepared by the present invention
Claim the cycle life figure of ultracapacitor；
Fig. 3 is the 3-D nano, structure material of CNT@silica@nickel aluminium nickel aluminum hydrotalcites prepared by the present invention
Electron scanning micrograph；
Fig. 4 is supercapacitor structures schematic diagram of the invention, wherein, 1 is plus plate current-collecting body, and 2 is CNT@bis-
Silica@nickel aluminium nickel aluminum hydrotalcite positive poles, 3 is electrode diaphragm, and 4 is negative material, and 5 is negative current collector.
Specific embodiment
Embodiment 1
CNT@silica@nickel aluminium nickel aluminum hydrotalcites (CNTs@SiO2@Ni/Al-LDH) core shell structure positive pole material
Prepared by material, its preparation process is as follows：
1) weigh CNT and CTAB powder state addition ethanol and deionized water in container in container, then up,
Wherein, the mass ratio of CNT and CTAB is 1:1 to 1:The 100 pairs of above-mentioned mixed solutions carry out ultrasonically treated, obtain carbon nanometer
Pipe solution A；
2) take solution A add NaOH, tetraethyl orthosilicate (TEOS), wherein, NaOH concentration control in 0.01-5000mmol/
L, after the control of tetraethyl orthosilicate concentration stirs under 0.001-5000Mmol/L, room temperature condition, centrifugation, ethanol washes product
And dry, finally give the powder B of cleaning.
3) by aluminium isopropoxide dispersion in deionized water, mass ratio is (1-100):100, stirred under the conditions of 10-100 DEG C
After uniform, HNO is added dropwise in upward System Solution3Regulation solution ph is 1 ~ 8, after continuing to stir, solution system is cooled down
To room temperature, after can obtain AlOOH colloidal sols after moisture evaporation.Dried AlOOH is ground, deionized water, 10- is added
Backflow can obtain solution C in 1-24 hours after being stirred under the conditions of 100 DEG C.
4) solution C and powder B mixing, the solution C per 1g powder B mixing 100-1000ml are taken, and after stirring 1-48 hours
Product is centrifuged or filtering, alcohol are washed, product is dried at room temperature for can obtain material powder D.
5) powder D is dispersed in the deionized water for having dissolved urea, the concentration range of urea is 0.1-5mol/L, stirring
Solution E is obtained after uniform.
6) to dropwise addition Ni (NO in solution E3)2, Ni (NO3)2Concentration in mixed solution is controlled in 0.1-3mol/L, it
After continue to stir after, above-mentioned solution system is transferred in reactor, 50-250 DEG C of hydro-thermal reaction or water-bath or
Person's oil bath is reacted 1-48 hours, and product is centrifuged or is filtered after the completion of question response, and alternately product is washed with deionized water and ethanol
Repeatedly, after being dried under the conditions of 20-100 DEG C of products therefrom, CNT@silica@nickel aluminum hydrotalcite core shell structures are obtained
Three-dimensional nanometer material.
Fig. 3 is CNT@silica@nickel aluminium nickel aluminum hydrotalcite (the CNTs@SiO2@Ni/Al- prepared by the present invention
LDH) the scanning of materials electron micrograph of electrode material.
The preparation method of super capacitor of the invention is：
1）With the CNTs@SiO for preparing2The three-dimensional nanometer material of@Ni/Al-LDH core shell structures is active material, acetylene black
Used as conductive agent, polytetrafluoroethylene (PTFE) is binding agent, is dispersed in absolute ethyl alcohol according to the ︰ 5 of 75 ︰ of mass ratio 20, ultrasonic 30 min
It is allowed to be coated onto in foamed nickel current collector after being well mixed, 80 °C are vacuum dried 12 hours, will under 10 MPa pressure
Electrode compressing tablet 30 seconds.
2）The electrode for completing is immersed at the activation being electrolysed for 12 hours in the potassium hydroxide electrolyte of 6 M
Reason.
3) using activated carbon as negative material, mix according to activated carbon and the ︰ 5 of PTFE mass ratioes 95, and add water and ethanol
Underflow shape is made into, coating slurry is prepared into negative pole after drying in nickel foam using tablet press machine compacting flakiness.
4）Space cells barrier film and crimp coiled between positive pole and negative pole, and be soaked in the KOH electrolyte of 6mol/L
12h。
5）It is packaged into ultracapacitor.
Embodiment 2
The device architecture for being assembled is as shown in figure 4, the assembling of wherein positive electrode and plus plate current-collecting body is to prepare
CNTs@SiO2The three-dimensional nanometer material of@Ni/Al-LDH core shell structures, nano-graphene and the ︰ 5 of binding agent 75 ︰ in mass ratio 20 are mixed
It is coated on after conjunction on nickel foil collector, coating thickness is 20 μm.The assembling of negative material and negative current collector is by active carbon materials
Material is coated on nickel foil collector, and coating thickness is 20 μm.It is positioned over after the positive pole of assembling and negative pole electrode diaphragm are separated
Soaked in KOH electrolyte, be finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 3
The device architecture for being assembled is as shown in figure 4, the assembling of wherein positive electrode and plus plate current-collecting body is to prepare
CNTs@SiO2The ︰ 5 of the three-dimensional nanometer material of@Ni/Al-LDH core shell structures, CNT and binding agent 85 ︰ in mass ratio 10 mix
After be coated on stainless steel foil collector, coating thickness be 30 μm.The assembling of negative material and negative current collector is by activated carbon
Material is coated on nickel foil collector, and coating thickness is 30 μm.The positive pole and negative pole electrode diaphragm that will be assembled are placed after separating
Soaked in KOH electrolyte, be finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 4
The device architecture for being assembled is as shown in figure 4, the assembling of wherein positive electrode and plus plate current-collecting body is CNTs@SiO2@
The three-dimensional nanometer material of Ni/Al-LDH core shell structures, Graphene and 15 ︰ of binding agent 80 ︰ in mass ratio 5 are coated on Copper Foil after mixing
On collector, coating thickness is 10 μm.The assembling of negative material and negative current collector is that active carbon material is coated on into Copper Foil collection
On fluid, coating thickness is 10 μm.Methyl triethyl group tetrafluoro is positioned over after the positive pole of assembling and negative pole electrode diaphragm are separated
Soaked in amine borate electrolyte, be finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 5
The device architecture for being assembled is as shown in figure 4, the assembling of wherein positive electrode and plus plate current-collecting body is to prepare
CNTs@SiO2The three-dimensional nanometer material of@Ni/Al-LDH core shell structures, carbon black and 15 ︰ of binding agent 80 ︰ in mass ratio 5 are applied after mixing
It is overlying on dilval metal foil collector, coating thickness is 50 μm.The assembling of negative material and negative current collector is by activity
Carbon material is coated on dilval metal foil collector, and coating thickness is 50 μm.Will assemble positive pole and negative pole electrode every
Film soaks during KOH electrolyte is positioned over after separating, and is finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 6
The device architecture for being assembled is as shown in figure 4, the assembling of wherein positive electrode and plus plate current-collecting body is to prepare
CNTs@SiO2The three-dimensional nanometer material of@Ni/Al-LDH core shell structures, CNT and the ︰ 5 of binding agent 75 ︰ in mass ratio 20 mix
After be coated on dilval metal foil collector, coating thickness be 40 μm.The assembling of negative material and negative current collector be by
Active carbon material is coated on dilval metal foil collector, and coating thickness is 40 μm.By the positive pole for assembling and negative pole electricity consumption
Pole barrier film soaks during KOH electrolyte is positioned over after separating, and is finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 7
The device architecture for being assembled is as shown in figure 4, the assembling of wherein positive electrode and plus plate current-collecting body is to prepare
CNTs@SiO2The three-dimensional nanometer material of@Ni/Al-LDH core shell structures, carbon black and 15 ︰ of binding agent 80 ︰ in mass ratio 5 are applied after mixing
It is overlying on nickel alumin(i)um alloy metal foil collector, coating thickness is 20 μm.The assembling of negative material and negative current collector is by activity
Carbon material is coated on nickel alumin(i)um alloy metal foil collector, and coating thickness is 20 μm.Will assemble positive pole and negative pole electrode every
Film soaks during methyl triethyl group tetrafluoro boric acid amine electrolyte is positioned over after separating, and is finally assembled into battery.
Preparation flow is similar to Example 1.
The present invention is exactly, for the problem for overcoming current super capacitor energy density relatively low, to propose that one kind uses CNTs@
SiO2@LDH composite material of core-shell structure is the new construction and preparation method of the ultracapacitor of positive electrode.The method is a kind of
Brand-new invention, can obtain energy density higher, good cyclical stability, extremely short charging interval.The positive electrode：
CNTs@SiO2@LDH composite material of core-shell structure is the three-dimensional manometer nucleocapsid with nickel aluminum hydrotalcite as shell with CNT as core
Structure, wherein SiO2It is connecting layer, the composite material of core-shell structure is designated as：CNTs@SiO2@LDH.The CNTs@SiO of preparation2@LDH
On the one hand 3-D nano, structure material avoids the reunion of the stacking and CNTs between LDH two-dimensional nano thin slices；On the other hand,
Space between nano flake is conducive to the immersion of electrolyte.Additionally, the great specific surface area of three-dimensional structure material, can be oxidation
Reduction reaction provides more favourable environment, and high energy density can be obtained as super capacitor anode material, overcomes existing
There is the low density shortcoming of super capacitor energy, while the ultracapacitor also characteristic with quick charge, can contract significantly
The short charging interval, in addition, CNTs@SiO2It is good that the good mechanical stability of@LDH composites can have ultracapacitor
Cyclical stability.
Embodiment described above only expresses the specific embodiment of the application, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the application protection domain can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, on the premise of technical scheme design is not departed from, various modifications and improvements can be made, these belong to this
The protection domain of application.
Claims (7)
1. CNTs@SiO are used2@Ni/Al-LDH core shell structures are the ultracapacitor of positive electrode, including plus plate current-collecting body, just
Pole material, battery diaphragm, electrolyte, negative material and negative current collector, it is characterised in that positive electrode is CNTs@SiO2@
The three-dimensional nanometer material of Ni/Al-LDH core shell structures, CNTs@SiO2@Ni/Al-LDH core shell structures are with the carbon nanometer of high conductivity
Guan Weihe, nickel aluminum hydrotalcite is shell, and silica is the composite with three-dimensional structure that connecting layer is formed, CNTs SiO2@
Ni/Al-LDH Core-shell structure materials are prepared in the following manner：
1) a certain amount of CNT, cetyl trimethylammonium bromide are taken in container, adds ethanol, deionized water to form mixing
Solution, carries out ultrasonically treated obtaining carbon nano-tube solution A to above-mentioned mixed solution；
2) NaOH, tetraethyl orthosilicate (TEOS) are added in solution A, after being stirred under room temperature condition, is centrifuged or leaching, used
Ethanol is washed product and is dried, and finally gives the powder B of cleaning；
3) by the dispersion of a certain amount of aluminium isopropoxide in deionized water, after stirring, HNO is added dropwise3Regulation solution ph is 1 ~ 8,
And after continuing to stir, solution system is cooled to room temperature, after after moisture evaporation i.e. can obtain AlOOH colloidal sols；
4）Dried AlOOH is ground, deionized water is added, stirring and flow back 1-24 hours can obtain solution
C；
5) a certain amount of solution C is taken, powder B mixing is washed product centrifugation or filtering, alcohol after stirring, after product is dried i.e.
Can obtain material powder D；
6) powder D is dispersed in the deionized water for having dissolved urea, solution E is obtained after stirring；
7) to dropwise addition Ni (NO in solution E3)2, and after constantly stirring, above-mentioned solution system is transferred in reactor, 50-
250 DEG C of hydro-thermal reactions or water-bath or oil bath are reacted 1-48 hours, and product is centrifuged or is filtered after the completion of question response, are used
Deionized water and ethanol alternately wash product repeatedly, after being dried under the conditions of 20-100 DEG C of products therefrom, just can obtain CNTs@SiO2@
The 3-D nano, structure positive electrode of Ni/Al-LDH Core-shell structure materials.
2. use CNTs@SiO according to claim 12@Ni/Al-LDH core shell structures are the super capacitor of positive electrode
Device, it is characterised in that step 1）In CNT and cetyl trimethylammonium bromide quality than scope be 1:1 to 1:
100；Step 2）In NaOH concentration control in 0.01-5000mmol/L, tetraethyl orthosilicate concentration is controlled in 0.001-
5000mmol/L；Step 3）In the quality of aluminium isopropoxide and deionized water be (1-100) than scope:100, step 5）In take it is molten
It is 100-1000ml per the scope of 1g powder B mixed solution Cs when liquid C and powder B mixes；Step 6）In urea concentration model
It is 0.1-5mol/L to enclose.
3. use CNTs@SiO according to claim 12@Ni/Al-LDH core shell structures are the super capacitor of positive electrode
Device, it is characterised in that the plus plate current-collecting body is：Nickel foil, Copper Foil, aluminium foil, metal alloy compositions paper tinsel, foam metal or metal
Net.
4. use CNTs@SiO according to claim 12@Ni/Al-LDH core shell structures are the super capacitor of positive electrode
Device, it is characterised in that battery diaphragm is TPO barrier film.
5. use CNTs@SiO according to claim 12@Ni/Al-LDH core shell structures are the super capacitor of positive electrode
Device, it is characterised in that electrolyte is aqueous electrolyte, organic electrolyte or il electrolyte, wherein aqueous electrolyte is
The mixed aqueous solution of single saline solution or various salt；Organic electrolyte is propene carbonate, ethylene carbonate, diethyl carbonate
Middle dissolving or the clear, lithium hexafluoro phosphate of scattered five fluorination, tetraethyl tetrafluoro boric acid amine or methyl triethyl group tetrafluoro boric acid amine；Ion
Liquid electrolyte is 1- methyl -3- ethyl imidazol(e)s chloride, 1- ethyl-3-methylimidazoles or N- trimethyl-N- hexyls ammonium two（Three
Methyl fluoride sulphonyl）Imines.
6. use CNTs@SiO according to claim 12@Ni/Al-LDH core shell structures are the super capacitor of positive electrode
Device, it is characterised in that institute's negative material is the mixing material of one or more in activated carbon, CNT or Graphene.
7. use CNTs@SiO according to claim 12@Ni/Al-LDH core shell structures are the super capacitor of positive electrode
Device, it is characterised in that negative current collector is nickel foil, Copper Foil, aluminium foil, metal alloy compositions paper tinsel, foam metal or wire netting.
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| CN105869918B (en) * | 2016-04-06 | 2018-07-06 | 江苏中天科技股份有限公司 | A kind of ultracapacitor based on carbon nanomaterial and preparation method thereof |
| CN106158417A (en) * | 2016-08-22 | 2016-11-23 | 电子科技大学 | A kind of sheet nickel aluminum hydrotalcite nano material is the preparation method of the ultracapacitor of positive pole |
| CN107785177B (en) * | 2016-08-30 | 2020-09-22 | 横店集团东磁股份有限公司 | Bromide capacitor positive electrode slurry and preparation method thereof |
| CN107785179B (en) * | 2016-08-31 | 2020-09-29 | 横店集团东磁股份有限公司 | Preparation method of bromide capacitor positive plate |
| CN106450221B (en) * | 2016-11-11 | 2019-01-11 | 深圳市鑫永丰科技有限公司 | One kind silicon-carbon composite cathode material containing aluminium and preparation method thereof |
| CN109225228B (en) * | 2018-10-10 | 2021-04-27 | 河北大学 | Nickel-based core-shell structure nano catalyst and preparation method and application thereof |
| CN109767928B (en) * | 2018-12-18 | 2021-03-19 | 武汉纽赛儿科技股份有限公司 | Synthetic method and application of fluorine-doped carbon-coated silicon oxide nanoparticle @ carbon nanotube composite material |
| CN112908711A (en) * | 2021-02-04 | 2021-06-04 | 广州金立电子有限公司 | Production process of capacitor |
| CN113096966A (en) * | 2021-04-16 | 2021-07-09 | 广德天运新技术股份有限公司 | High-specific-capacity supercapacitor electrode material based on silicon dioxide and preparation method thereof |
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