CN104900419B - Use CNTs@SiO2@Ni/Al LDH core shell structures are the ultracapacitor of positive electrode - Google Patents

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

Use CNTs@SiO2@Ni/Al-LDH core shell structures are the ultracapacitor of positive electrode

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.