CN105047420A - Porous nickel-based carbon fiber composite material and preparation method and purpose thereof - Google Patents
Porous nickel-based carbon fiber composite material and preparation method and purpose thereof Download PDFInfo
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- CN105047420A CN105047420A CN201510300879.6A CN201510300879A CN105047420A CN 105047420 A CN105047420 A CN 105047420A CN 201510300879 A CN201510300879 A CN 201510300879A CN 105047420 A CN105047420 A CN 105047420A
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Abstract
The invention provides a porous nickel-based carbon fiber material and a preparation method and purpose thereof. The composite material structurally comprises a carbon fiber cloth layer, a porous nano nickel metal film layer and a nickel hydroxide layer from inside to outside successively. A nano nickel metal film is deposited on a carbon fiber cloth substrate, the nano nickel metal film is converted into a porous nano nickel metal film, nickel at the surface layer of the porous nano nickel metal film is oxidized to nickel hydroxide, and thus, the porous nickel-based carbon fiber material is obtained. The material is characterized by being light and flexible and large is the specific surface area, can be used as electrode material of a super capacitor, has obvious characteristic of fake capacitance, is high in capacity and stability, can be applied to the field of energy storage, and is wide in application prospects.
Description
Technical field
The invention belongs to energy storage material field, relate to a kind of porous Ni-base carbon fibre composite and its production and use.
Background technology
Along with fast development that is wearable and portable electronic products, the flexible energy storage material of provided power supply is had higher requirement, the feature such as the high and cycle performance of lightweight, flexibility, specific capacity is excellent that requires it to have.Conventional energy storage mode has battery and ultracapacitor two kinds, relative to battery, ultracapacitor can provide charge/discharge rates, higher power density and outstanding cycle performance faster, and than conventional electrochemical capacitor, there is higher energy density, ultracapacitor is a kind of a kind of novel energy-storing mode between battery and generic electrochemical capacitor.
Ultracapacitor is mainly divided into two classes, double electric layer capacitor and pseudocapacitors.The electric double layer that double electric layer capacitor mainly utilizes electrode to be formed in the electrolytic solution carries out storage and the release of electric charge, so require that electrode material has very high specific area and the conductivity of excellence; Fake capacitance is the varying chemical valency utilizing transition metal oxide, carries out electric charge deposit in the reaction of the surface of material generation oxidation chemistry.Double electric layer capacitor common electrode material is material with carbon element, such as carbon fiber, porous carbon, carbon nano-tube and Graphene etc.Carbon cloth (CC) has high specific area, suppleness and high conductivity, be a kind of double electric layers supercapacitor material of excellence, but its ratio capacitance is lower, causes its use to be restricted.The excellent fake capacitance material that nickel hydroxide and nickel oxide are environmental friendliness, specific capacity is high, but their conductivity is poor, cannot reach its theoretical specific capacity in real use procedure, and especially in high power charging-discharging situation, the decay of its capacity is even more serious.In order to overcome the shortcoming of its poorly conductive, often itself and high conductivity material are carried out compound, such as porous carbon, conducting polymer or nano metal particles etc.
Nanoporous (Nanoporous) metal material is the functional material that a class has obvious pore character, as fake capacitance electrode material, nano-pore metal material not only has large internal surface area, high porosity, and be beneficial to the transmission of electrolyte intermediate ion, be beneficial to and improve electric capacity high rate performance.At present, the preparation method of nano porous metal focuses mostly in block body stephanoporate metal material, and the normal preparation method adopted has powder metallurgic method, de-alloyage, oblique incidence sedimentation, By Colloidal Template Method etc.Such as (the H.J.Qiu such as ChenM.W, J.L.Kang, M.W.Chen.etal.Fabricationoflarge-scalenanoporousnickelwi thatunableporesizeforenergystorage.JournalofPowerSources, 247 (2014) 896 ~ 905) Ni, Mn are become ingot by electric arc melting, then 50 microns are cold-rolled to, prepare nickel porous by corroding de-alloying, and be used successfully to the preparation of electrode material for super capacitor.The technics comparing of this preparation porous Ni is complicated, and is difficult to be prepared into flexible capacitor electrode material, more cannot carry out compound with carbon cloth.
Therefore, expect in this area the advantage of fake capacitance material and carbon cloth to be combined, obtain the electrode material for super capacitor of excellent performance.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of porous Ni-base carbon fibre composite and its production and use.
For reaching this goal of the invention, the present invention by the following technical solutions:
On the one hand, the invention provides a kind of porous Ni-base carbon fibre composite, the structure of described porous Ni-base carbon fibre composite is followed successively by carbon fibre cloth layer from the inside to the outside, porous nano thin nickel metal film layer and hydroxide nickel dam.
In one embodiment of the invention, the structure of described porous Ni-base carbon fibre composite is on the side of carbon fibre cloth layer, deposit porous nano thin nickel metal film layer, and porous nano thin nickel metal film layer has hydroxide nickel dam.
In another embodiment of the invention, the structure of described porous Ni-base carbon fibre composite is all deposit porous nano thin nickel metal film layer in the both sides of carbon fibre cloth layer, and the porous nano thin nickel metal film layer of carbon cloth both sides all has hydroxide nickel dam.
Fake capacitance material and nanoporous nickel metal and nickel hydroxide and electric double layer capacitance material carbon cloth combine by porous Ni-base carbon fibre composite of the present invention, make it simultaneously in conjunction with the advantage of fake capacitance material and electric double layer capacitance material, there are high-specific surface area, excellent ratio capacitance and cycle performance etc.
In porous Ni-base carbon fibre composite of the present invention, in the area of carbon cloth, the load capacity of nickel metal is 0.3-0.5mg/cm
2, the load capacity of such as nickel metal is 0.3mg/cm
2, 0.32mg/cm
2, 0.34mg/cm
2, 0.36mg/cm
2, 0.38mg/cm
2, 0.4mg/cm
2, 0.42mg/cm
2, 0.44mg/cm
2, 0.45mg/cm
2, 0.47mg/cm
2, 0.48mg/cm
2, 0.49mg/cm
2or 0.5mg/cm
2.
Preferably, in the area of carbon cloth, the load capacity of nickel hydroxide is 0.1-0.3mg/cm
2, the load capacity of such as nickel hydroxide is 0.1mg/cm
2, 0.12mg/cm
2, 0.14mg/cm
2, 0.16mg/cm
2, 0.18mg/cm
2, 0.2mg/cm
2, 0.23mg/cm
2, 0.25mg/cm
2, 0.27mg/cm
2, 0.28mg/cm
2, 0.29mg/cm
2or 0.3mg/cm
2.
On the other hand, the invention provides the preparation method of the porous Ni-base carbon fibre composite described in first aspect, described method is: at carbon cloth deposited on substrates nano nickel metallic film, then nano nickel metallic film is converted into porous nano thin nickel metal film, finally the top layer nickel of porous nickel metal film is oxidized to nickel hydroxide and obtains described porous Ni-base carbon fibre composite.
The present invention passes through at carbon cloth deposited on substrates nano nickel metallic film, nickel and carbon cloth are closely linked, then nano nickel metallic film is converted into porous nickel metal film, make that there is pore space structure, increase the specific area of material, the top layer nickel of porous nickel metal film is oxidized to nickel hydroxide, fake capacitance material nickel hydroxide and porous nickel metal film and carbon cloth are combined, defining internal layer is carbon fibre cloth layer, carbon cloth external sediment has porous nano thin nickel metal film layer, there is outside porous nano thin nickel metal film layer the porous Ni-base carbon fibre composite of hydroxide nickel dam.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, describedly to be realized by magnetically controlled sputter method at deposited on substrates nano nickel metallic film.
Preferably, describedly nano nickel metallic film is converted into porous nickel metal film is realized by wet corrosion technique.
Preferably, the described top layer nickel by porous nickel metal film is oxidized to nickel hydroxide and is realized by electrochemical oxidation method.
The present invention utilizes magnetron sputtering nickel deposited metallic film on carbon cloth, and because nickel and material with carbon element have very strong active force, the carbon fiber cloth material of what this depositing operation obtained deposit nickel metal has very high stability.And thin nickel metal film is grown to column crystal growth in sputter deposition process, this column crystal metallic film film intercrystalline corrosion speed in wet corrosion technique is then parallel to substrate direction can be greater than perpendicular to substrate direction, therefore can form pore space structure, thus on carbon cloth, obtain the nickel film of porous.Then adopt electrochemical oxidation method that top layer nickel is oxidized to nickel hydroxide, thus fake capacitance material nickel hydroxide and carbon cloth are combined, make prepared porous Ni-base carbon fibre composite combining hydrogen oxidation nickel and carbon cloth and metallic nickel at ratio capacitance, the advantage of the aspect such as specific area and conductivity, obtains a kind of porous Ni-base carbon fibre composite of function admirable.
Preferably, the preparation method of porous Ni-base carbon fibre composite of the present invention comprises the following steps:
(1) adopt carbon cloth as substrate, using metallic nickel as sputtering target material, carry out sputtering sedimentation, plated metal nickel film on carbon cloth;
(2) carbon cloth depositing metal nickel film step (1) obtained immerses in acid solution, takes out, and residual acid is removed in cleaning, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film step (2) obtained is as work electrode, using aqueous slkali as electrolyte, by cyclic voltammetry, top layer nickel is converted into nickel hydroxide, obtains described porous Ni-base carbon fibre composite.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, step (1) described carbon cloth through cleaning and drying steps, then will put into sputter deposition chamber before sputtering sedimentation.
Preferably, described cleaning is by carbon cloth difference ultrasonic cleaning 10-50min in acetone and absolute ethyl alcohol, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min or 50min, then deionized water rinsing 3-10 time is used, such as 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times.
Preferably, described drying is heat drying 8-24h at 110-150 DEG C.Such as, baking temperature can be 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C or 150 DEG C; Drying time can be 8h, 9h, 10h, 11h, 12h, 14h, 16h, 18h, 20h, 22h, 23h or 24h.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, the parameter of step (1) described sputtering sedimentation is: background vacuum is 1 × 10
-5-9 × 10
-5pa, is preferably 6 × 10
-5pa; Sputtering power is direct current 80-120W, is preferably 105W; Sputtering pressure is 0.2-1.5Pa, is preferably 0.5Pa; Sputtering time is 1-3h, is preferably 2h; Depositing temperature is 20-50 DEG C, is preferably room temperature.
Such as, in sputtering sedimentation, background vacuum can be 1 × 10
-5pa, 2 × 10
-5pa, 3 × 10
-5pa, 4 × 10
-5pa, 5 × 10
-5pa, 6 × 10
-5pa, 7 × 10
-5pa, 8 × 10
-5pa or 9 × 10
-5pa, is preferably 6 × 10
-5pa; Sputtering power can be direct current 80W, 85W, 90W, 95W, 100W, 105W, 110W, 115W or 120W, is preferably 105W; Sputtering pressure can be 0.2Pa, 0.3Pa, 0.4Pa, 0.5Pa, 0.6Pa, 0.8Pa, 1.0Pa, 1.1Pa, 1.2Pa, 1.3Pa, 1.4Pa or 1.5Pa, is preferably 0.5Pa; Sputtering time can be 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h or 3h, is preferably 2h; Depositing temperature can be 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C, is preferably 25 DEG C.
Step of the present invention (1), for magnetically controlled sputter method is at deposited on substrates nano nickel metallic film, makes nickel and carbon cloth be combined with each other.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, step (2) described acid is the combination of any one or at least two kinds in hydrochloric acid, sulfuric acid or nitric acid.
Preferably, the molar concentration of step (2) described acid solution is 1-5mol/L, such as 1mol/L, 1.3mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.3mol/L, 2.5mol/L, 2.8mol/L, 3mol/L, 3.2mol/L, 3.4mol/L, 3.6mol/L, 3.8mol/L, 4mol/L, 4.2mol/L, 4.4mol/L, 4.6mol/L, 4.8mol/L or 5mol/L, be preferably 2.5mol/L.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, step (2) the described time of being immersed in acid solution by the carbon cloth depositing metal nickel film is 100-500s, such as 100s, 130s, 150s, 180s, 200s, 220s, 250s, 270s, 300s, 330s, 350s, 380s, 400s, 430s, 450s, 480s or 500s, be preferably 200-300s.
Preferably, step (2) described cleaning utilizes plasma water to carry out.
Step (2) is corroded the metallic film obtained in carbon-point fiber cloth by sputtering sedimentation for utilizing wet corrosion technique, because metal nickel film intercrystalline corrosion speed is parallel to substrate direction can be greater than perpendicular to substrate direction, therefore pore space structure can be formed.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, step (3) described alkali is NaOH and/or potassium hydroxide.
Preferably, the molar concentration of step (3) described aqueous slkali is 0.5-3mol/L, such as 0.5mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.2mol/L, 2.4mol/L, 2.6mol/L, 2.8mol/L or 3mol/L, be preferably 1mol/L.
In the preparation method of porous Ni-base carbon fibre composite of the present invention, the speed of sweeping of step (3) described cyclic voltammetry is 5-50mVs
-1, such as 5mVs
-1, 8mVs
-1, 10mVs
-1, 15mVs
-1, 20mVs
-1, 25mVs
-1, 30mVs
-1, 35mVs
-1, 40mVs
-1, 45mVs
-1or 50mVs
-1, be preferably 10mVs
-1.
Preferably, the circulation number of turns of step (3) described cyclic voltammetry is 30-80 circle, and such as 30 circles, 35 circles, 40 circles, 45 circles, 50 circles, 55 circles, 60 circles, 65 circles, 70 circles, 75 circles or 80 circles, be preferably 60 circles.
Step make use of electrochemistry three-electrode system in (3), by cyclic voltammetry, top layer nickel is converted into nickel hydroxide, the metal nickel film of internal layer does not react in the process, therefore containing nickel hydroxide and metallic nickel in the composite material obtained, both can ensure that material had height ratio capacity, can ensure again that material had excellent electric conductivity.
As the preferred technical solution of the present invention, the preparation method of described porous Ni-base carbon fibre composite comprises the following steps:
(1) adopt carbon cloth as substrate, cleaning, sputter deposition chamber is put in drying, using metallic nickel as sputtering target material, carries out sputtering sedimentation, plated metal nickel film on carbon cloth, and wherein the parameter of sputtering sedimentation is: background vacuum is 1 × 10
-5-9 × 10
-5pa, sputtering power is direct current 80-120W, and sputtering pressure is 0.2-1.5Pa, and sputtering time is 1-3h, and depositing temperature is 20-50 DEG C;
(2) it is in the acid solution of 1-5mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, takes out after 100-500s, and residual acid is removed in cleaning, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the aqueous slkali of 0.5-3mol/L as electrolyte, sweeping speed for 5-50mVs
-1under, by cyclic voltammetry circulation 30-80 circle, top layer nickel is converted into nickel hydroxide, obtains described porous Ni-base carbon fibre composite.
As further preferred technical scheme, the preparation method of described porous Ni-base carbon fibre composite comprises the following steps:
(1) adopt carbon cloth as substrate, cleaning, sputter deposition chamber is put in drying, using metallic nickel as sputtering target material, carries out sputtering sedimentation, plated metal nickel film on carbon cloth, and wherein the parameter of sputtering sedimentation is: background vacuum is 6 × 10
-5pa, sputtering power is direct current 105W, and sputtering pressure is 0.5Pa, and sputtering time is 2h, and depositing temperature is 25 DEG C;
(2) it is in the acid solution of 2.5mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, takes out after 200-300s, and residual acid is removed in cleaning, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the aqueous slkali of 1mol/L as electrolyte, sweeping speed for 10mVs
-1under, by cyclic voltammetry circulation 60 circle, top layer nickel is converted into nickel hydroxide, obtains described porous Ni-base carbon fibre composite.
The porous Ni-base carbon fibre composite that the present invention prepares combines the advantage of fake capacitance material metal nickel, nickel hydroxide and electric double layer capacitance material carbon cloth, there is very high specific area, excellent ratio capacitance and cycle performance, it is a kind of composite electrode material for super capacitor of excellence, can be used as electrode material, be applied to the fields such as electric automobile, flexible electronic product and wearable electronic product.
Relative to prior art, the present invention has following beneficial effect:
The structure of porous Ni-base carbon fibre composite of the present invention is followed successively by carbon fibre cloth layer, porous nano thin nickel metal film layer and hydroxide nickel dam from the inside to the outside.The present invention passes through at deposited on substrates nano nickel metallic film, and then just nano nickel metallic film is converted into porous nickel metal film, finally the top layer nickel of porous nickel metal film is oxidized to nickel hydroxide and obtains described porous Ni-base carbon fibre composite.Preparation method is simple, and cost is low.Gained composite material has the features such as lightweight, flexibility, bigger serface, and as electrode material for super capacitor, there is discharge platform in the discharge curve of capacitor, present obvious fake capacitance feature, is 0.8Ag in current density
-1time, the specific discharge capacity of capacitor can reach 1820Fg
-1, area ratio capacity can reach 118mFcm
-2, there is the feature of high power capacity, and after circulation 3000 times, capacity can keep 86% of initial capacity, prove that this capacitor electrode material has excellent stability.Fake capacitance material and carbon cloth combine by this porous Ni-base carbon fibre composite, are the electrode material for super capacitor of a kind of high power capacity, high stability, can be applied to energy storage field, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the carbon cloth depositing metal nickel film in the embodiment of the present invention 1, and A figure scale is 20 μm, and B figure scale is 500nm;
Fig. 2 is the SEM figure of the nickel porous carbon fibre material obtained after acid corrosion in the embodiment of the present invention 1, and A figure scale is 10 μm, and B figure scale is 500nm;
Fig. 3 is the SEM figure of the end product porous Ni-base carbon fibre composite obtained after electrochemical oxidation in the embodiment of the present invention 1, and A figure scale is 1 μm, and B figure scale is 500nm;
Fig. 4 is the X-ray photoelectron spectroscopic analysis figure of porous Ni-base carbon fibre composite prepared by the embodiment of the present invention 1, and wherein A figure is the 2p track spectrogram of nickel, and B figure is the 1s track spectrogram of oxygen;
Fig. 5 is the porous Ni-base carbon fibre composite prepared by the embodiment of the present invention 1 discharge curve of ultracapacitor under different current density as electrode material;
Fig. 6 is the porous Ni-base carbon fibre composite prepared by the embodiment of the present invention 1 as the specific capacity of the ultracapacitor of electrode material with the change curve of current density;
Fig. 7 is that the porous Ni-base carbon fibre composite prepared by the embodiment of the present invention 1 ultracapacitor as electrode material is at current density 20Ag
-1under cycle performance test result figure.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
embodiment 1
In the present embodiment, be prepared by the following method porous Ni-base carbon fibre composite, specifically comprise the following steps:
(1) adopt carbon cloth as substrate, by carbon cloth difference ultrasonic cleaning 30min in acetone and absolute ethyl alcohol, then deionized water rinsing is used 5 times, then at 120 DEG C, put into sputter deposition chamber after heat drying 12h, using metallic nickel as sputtering target material, carry out sputtering sedimentation, wherein the parameter of sputtering sedimentation is: background vacuum is 6 × 10
-5pa, sputtering power is direct current 105W, and sputtering pressure is 0.5Pa, and sputtering time is 2h, and depositing temperature is 25 DEG C;
(2) it is in the hydrochloric acid solution of 2.5mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, take out after 270s, carry out cleaning with a large amount of plasma water and remove residual hydrochloric acid, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the potassium hydroxide solution of 1mol/L as electrolyte, sweeping speed for 10mVs
-1under, by cyclic voltammetry circulation 60 circle, top layer nickel is converted into nickel hydroxide, obtains porous Ni-base carbon fibre composite.
The product of application scanning electron microscope (HitachiS4800) to step each in embodiment 1 characterizes, Fig. 1 is the SEM figure depositing the carbon cloth of metal nickel film that step (1) obtains, deposited nickel film smooth surface can be found out, crystal grain is tiny and even, owing to having very strong adhesion between nickel and material with carbon element, prepared thin nickel metal film can closely wrap up carbon cloth fiber.Fig. 2 is the SEM figure of the nickel porous carbon fibre material that step (2) obtains after acid corrosion, as seen from the figure, after acid corrosion, nickel film still can be combined with carbon cloth fibre compact, the phenomenon do not come off occurs, find out from enlarged drawing B figure, be there is the nano aperture structure of gully shape in the nickel film of otherwise smooth, this nano aperture structure is beneficial to the specific area improving nickel film, is also beneficial to the ion-exchange of electrolyte in electrochemical reaction process after acid corrosion.The SEM figure of the end product porous Ni-base carbon fibre composite that Fig. 3 obtains after being through electrochemical oxidation, as seen from the figure, after electrochemical oxidation, nickel film surface defines the nickel hydroxide material of lamellar structure, and is filled into inside hole.Material outermost layer is made to form nickel hydroxide material layer.
X-ray photoelectron spectroscopy (ESCALab250) is utilized to carry out X-ray photoelectron spectroscopic analysis to porous Ni-base carbon fibre composite prepared by embodiment 1, result as shown in Figure 4, A figure is the 2p track spectrogram of nickel, two main peaks lay respectively at 855.7eV and 873.3eV, poor 17.6eV between the two, this is typical nickel hydroxide feature; B figure is the 1s track spectrogram of oxygen, and main peak is positioned at 531.3eV, for O-H in conjunction with energy.Therefore can judge to have nickel hydroxide on porous Ni-base carbon fibre composite surface.
In addition, obtaining the load capacity of nickel metal on carbon cloth by mensuration is 0.42mg/cm
2, the load capacity of nickel hydroxide is 0.21mg/cm
2.
Porous Ni-base carbon fibre composite embodiment 1 prepared is as electrode of super capacitor, using 1M metabisulfite solution as electrolyte, glass fabric is barrier film, loads in the Swagelok type battery tester of bipolar electrode, make symmetrical ultracapacitor, test capacitors performance.The discharge curve of this capacitor that test obtains under different current density as shown in Figure 5; Under different current density, area specific capacity and specific discharge capacity are as shown in Figure 6; At current density 20Ag
-1under cycle performance as shown in Figure 7.
As can be seen from Figure 5, there is obvious land regions in the discharge curve of this capacitor, illustrate that this porous Ni-base carbon fibre composite has obvious fake capacitance feature.As can be seen from Figure 6, be 0.8Ag in current density
-1time, specific discharge capacity can reach 1820Fg
-1, area ratio capacity can reach 118mFcm
-2, there is the feature of high power capacity.Show by testing (Fig. 7) to the cycle life of the capacitor made, after circulation 3000 times, capacity can keep 86% of initial capacity, proves that this capacitor electrode material has excellent stability.
embodiment 2
In the present embodiment, be prepared by the following method porous Ni-base carbon fibre composite, specifically comprise the following steps:
(1) adopt carbon cloth as substrate, by carbon cloth difference ultrasonic cleaning 10min in acetone and absolute ethyl alcohol, then deionized water rinsing is used 10 times, then at 110 DEG C, put into sputter deposition chamber after heat drying 24h, using metallic nickel as sputtering target material, carry out sputtering sedimentation, wherein the parameter of sputtering sedimentation is: background vacuum is 1 × 10
-5pa, sputtering power is direct current 80W, and sputtering pressure is 1Pa, and sputtering time is 3h, and depositing temperature is 20 DEG C;
(2) it is in the hydrochloric acid solution of 1mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, take out after 200s, carry out cleaning with a large amount of plasma water and remove residual hydrochloric acid, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the potassium hydroxide solution of 0.5mol/L as electrolyte, sweeping speed for 20mVs
-1under, by cyclic voltammetry circulation 40 circle, top layer nickel is converted into nickel hydroxide, obtains porous Ni-base carbon fibre composite.
Show through the sign identical with embodiment 1 and test, porous Ni-base carbon fibre composite prepared by the present embodiment has nano aperture structure, specific area is large, the metallic nickel film surface of material defines the nickel hydroxide material of lamellar structure, and the load capacity obtaining nickel metal is after measured 0.38mg/cm
2, the load capacity of nickel hydroxide is 0.15mg/cm
2.The porous Ni-base carbon fibre composite that embodiment 2 obtains has obvious fake capacitance feature, is 0.8Ag in current density
-1time, specific discharge capacity can reach 1790Fg
-1, area ratio capacity can reach 112mFcm
-2, there is the feature of high power capacity.By showing the cycle life test of the capacitor made, after circulation 3000 times, capacity can keep 86.5% of initial capacity, proves that this capacitor electrode material has excellent stability.
embodiment 3
In the present embodiment, be prepared by the following method porous Ni-base carbon fibre composite, specifically comprise the following steps:
(1) adopt carbon cloth as substrate, by carbon cloth difference ultrasonic cleaning 50min in acetone and absolute ethyl alcohol, then deionized water rinsing is used 3 times, then at 130 DEG C, put into sputter deposition chamber after heat drying 20h, using metallic nickel as sputtering target material, carry out sputtering sedimentation, wherein the parameter of sputtering sedimentation is: background vacuum is 4 × 10
-5pa, sputtering power is direct current 100W, and sputtering pressure is 1.5Pa, and sputtering time is 1h, and depositing temperature is 30 DEG C;
(2) it is in the sulfuric acid solution of 4mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, take out after 300s, carry out cleaning with a large amount of plasma water and remove residual sulfuric acid, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the sodium hydroxide solution of 2mol/L as electrolyte, sweeping speed for 30mVs
-1under, by cyclic voltammetry circulation 80 circle, top layer nickel is converted into nickel hydroxide, obtains porous Ni-base carbon fibre composite.
Show through the sign identical with embodiment 1 and test, porous Ni-base carbon fibre composite prepared by the present embodiment has nano aperture structure, specific area is large, the metallic nickel film surface of material defines the nickel hydroxide material of lamellar structure, and the load capacity obtaining nickel metal is after measured 0.45mg/cm
2, the load capacity of nickel hydroxide is 0.3mg/cm
2.The porous Ni-base carbon fibre composite that embodiment 3 obtains has obvious fake capacitance feature, is 0.8Ag in current density
-1time, specific discharge capacity can reach 1800Fg
-1, area ratio capacity can reach 115mFcm
-2, there is the feature of high power capacity.By showing the cycle life test of the capacitor made, after circulation 3000 times, capacity can keep 86.8% of initial capacity, proves that this capacitor electrode material has excellent stability.
embodiment 4
In the present embodiment, be prepared by the following method porous Ni-base carbon fibre composite, specifically comprise the following steps:
(1) adopt carbon cloth as substrate, by carbon cloth difference ultrasonic cleaning 40min in acetone and absolute ethyl alcohol, then deionized water rinsing is used 7 times, then at 150 DEG C, put into sputter deposition chamber after heat drying 8h, using metallic nickel as sputtering target material, carry out sputtering sedimentation, wherein the parameter of sputtering sedimentation is: background vacuum is 9 × 10
-5pa, sputtering power is direct current 120W, and sputtering pressure is 0.8Pa, and sputtering time is 2h, and depositing temperature is 50 DEG C;
(2) it is in the hydrochloric acid solution of 5mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, take out after 100s, carry out cleaning with a large amount of plasma water and remove residual hydrochloric acid, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the sodium hydroxide solution of 3mol/L as electrolyte, sweeping speed for 50mVs
-1under, by cyclic voltammetry circulation 30 circle, top layer nickel is converted into nickel hydroxide, obtains porous Ni-base carbon fibre composite.
Show through the sign identical with embodiment 1 and test, porous Ni-base carbon fibre composite prepared by the present embodiment has nano aperture structure, specific area is large, the metallic nickel film surface of material defines the nickel hydroxide material of lamellar structure, and the load capacity obtaining nickel metal is after measured 0.3mg/cm
2, the load capacity of nickel hydroxide is 0.1mg/cm
2.The porous Ni-base carbon fibre composite that embodiment 4 obtains has obvious fake capacitance feature, is 0.8Ag in current density
-1time, specific discharge capacity can reach 1780Fg
-1, area ratio capacity can reach 110mFcm
-2, there is the feature of high power capacity.By showing the cycle life test of the capacitor made, after circulation 3000 times, capacity can keep 86.5% of initial capacity, proves that this capacitor electrode material has excellent stability.
embodiment 5
In the present embodiment, be prepared by the following method porous Ni-base carbon fibre composite, specifically comprise the following steps:
(1) adopt carbon cloth as substrate, by carbon cloth difference ultrasonic cleaning 30min in acetone and absolute ethyl alcohol, then deionized water rinsing is used 8 times, then at 120 DEG C, put into sputter deposition chamber after heat drying 10h, using metallic nickel as sputtering target material, carry out sputtering sedimentation, wherein the parameter of sputtering sedimentation is: background vacuum is 7 × 10
-5pa, sputtering power is direct current 110W, and sputtering pressure is 1Pa, and sputtering time is 1h, and depositing temperature is 25 DEG C;
(2) it is in the salpeter solution of 1mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, take out after 500s, carry out cleaning with a large amount of plasma water and remove residual nitric acid, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the potassium hydroxide solution of 2mol/L as electrolyte, sweeping speed for 5mVs
-1under, by cyclic voltammetry circulation 70 circle, top layer nickel is converted into nickel hydroxide, obtains porous Ni-base carbon fibre composite.
Show through the sign identical with embodiment 1 and test, porous Ni-base carbon fibre composite prepared by the present embodiment has nano aperture structure, specific area is large, the metallic nickel film surface of material defines the nickel hydroxide material of lamellar structure, and the load capacity obtaining nickel metal is after measured 0.5mg/cm
2, the load capacity of nickel hydroxide is 0.26mg/cm
2.The porous Ni-base carbon fibre composite that embodiment 5 obtains has obvious fake capacitance feature, is 0.8Ag in current density
-1time, specific discharge capacity can reach 1760Fg
-1, area ratio capacity can reach 114mFcm
-2, there is the feature of high power capacity.By showing the cycle life test of the capacitor made, after circulation 3000 times, capacity can keep 85.8% of initial capacity, proves that this capacitor electrode material has excellent stability.
embodiment 6
In the present embodiment, be prepared by the following method porous Ni-base carbon fibre composite, specifically comprise the following steps:
(1) adopt carbon cloth as substrate, by carbon cloth difference ultrasonic cleaning 20min in acetone and absolute ethyl alcohol, then deionized water rinsing is used 5 times, then at 120 DEG C, put into sputter deposition chamber after heat drying 15h, using metallic nickel as sputtering target material, carry out sputtering sedimentation, wherein the parameter of sputtering sedimentation is: background vacuum is 3 × 10
-5pa, sputtering power is direct current 95W, and sputtering pressure is 0.2Pa, and sputtering time is 2h, and depositing temperature is 30 DEG C;
(2) it is in the hydrochloric acid solution of 2.5mol/L that the carbon cloth depositing metal nickel film step (1) obtained immerses molar concentration, take out after 240s, carry out cleaning with a large amount of plasma water and remove residual hydrochloric acid, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film that step (2) is obtained as work electrode, with molar concentration be the potassium hydroxide solution of 1mol/L as electrolyte, sweeping speed for 20mVs
-1under, by cyclic voltammetry circulation 50 circle, top layer nickel is converted into nickel hydroxide, obtains porous Ni-base carbon fibre composite.
Show through the sign identical with embodiment 1 and test, porous Ni-base carbon fibre composite prepared by the present embodiment has nano aperture structure, specific area is large, the metallic nickel film surface of material defines the nickel hydroxide material of lamellar structure, and the load capacity obtaining nickel metal is after measured 0.40mg/cm
2, the load capacity of nickel hydroxide is 0.2mg/cm
2.The porous Ni-base carbon fibre composite that embodiment 6 obtains has obvious fake capacitance feature, is 0.8Ag in current density
-1time, specific discharge capacity can reach 1780Fg
-1, area ratio capacity can reach 120mFcm
-2, there is the feature of high power capacity.By showing the cycle life test of the capacitor made, after circulation 3000 times, capacity can keep 85.7% of initial capacity, proves that this capacitor electrode material has excellent stability.
Applicant states, the present invention illustrates porous Ni-base carbon fibre composite of the present invention and its production and use by above-described embodiment, but the present invention is not limited to above-described embodiment, does not namely mean that the present invention must rely on above-described embodiment and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a porous Ni-base carbon fibre composite, is characterized in that, the structure of described porous Ni-base carbon fibre composite is followed successively by carbon fibre cloth layer from the inside to the outside, porous nano thin nickel metal film layer and hydroxide nickel dam.
2. porous Ni-base carbon fibre composite according to claim 1, is characterized in that, in the area of carbon cloth, the load capacity of nickel metal is 0.3-0.5mg/cm
2;
Preferably, in the area of carbon cloth, the load capacity of nickel hydroxide is 0.1-0.3mg/cm
2.
3. the preparation method of porous Ni-base carbon fibre composite according to claim 1 and 2, it is characterized in that, described method is: at carbon cloth deposited on substrates nano nickel metallic film, then nano nickel metallic film is converted into porous nano thin nickel metal film, finally the top layer nickel of porous nickel metal film is oxidized to nickel hydroxide and obtains described porous Ni-base carbon fibre composite.
4. preparation method according to claim 3, is characterized in that, is describedly realized by magnetically controlled sputter method at deposited on substrates nano nickel metallic film;
Preferably, describedly nano nickel metallic film is converted into porous nickel metal film is realized by wet corrosion technique;
Preferably, the described top layer nickel by porous nickel metal film is oxidized to nickel hydroxide and is realized by electrochemical oxidation method.
5. the preparation method according to claim 3 or 4, is characterized in that, said method comprising the steps of:
(1) adopt carbon cloth as substrate, using metallic nickel as sputtering target material, carry out sputtering sedimentation, plated metal nickel film on carbon cloth;
(2) carbon cloth depositing metal nickel film step (1) obtained immerses in acid solution, takes out, and residual acid is removed in cleaning, metal nickel film is converted into porous nickel metal film;
(3) take calomel electrode as reference electrode, platinized platinum is to electrode, the carbon cloth depositing porous-metal nickel film step (2) obtained is as work electrode, using aqueous slkali as electrolyte, by cyclic voltammetry, top layer nickel is converted into nickel hydroxide, obtains described porous Ni-base carbon fibre composite.
6. preparation method according to claim 5, is characterized in that, step (1) described carbon cloth through cleaning and drying steps, then will put into sputter deposition chamber before sputtering sedimentation;
Preferably, described cleaning is by carbon cloth difference ultrasonic cleaning 10-50min in acetone and absolute ethyl alcohol, then uses deionized water rinsing 3-10 time;
Preferably, described drying is heat drying 8-24h at 110-150 DEG C.
7. the preparation method according to claim 5 or 6, is characterized in that, the parameter of step (1) described sputtering sedimentation is: background vacuum is 1 × 10
-5-9 × 10
-5pa, is preferably 6 × 10
-5pa; Sputtering power is direct current 80-120W, is preferably 105W; Sputtering pressure is 0.2-1.5Pa, is preferably 0.5Pa; Sputtering time is 1-3h, is preferably 2h; Depositing temperature is 20-50 DEG C, is preferably 25 DEG C.
8. the preparation method according to any one of claim 5-7, is characterized in that, step (2) described acid is the combination of any one or at least two kinds in hydrochloric acid, sulfuric acid or nitric acid;
Preferably, the molar concentration of step (2) described acid solution is 1-5mol/L, is preferably 2.5mol/L;
Preferably, step (2) the described time of being immersed in acid solution by the carbon cloth depositing metal nickel film is 100-500s, is preferably 200-300s;
Preferably, step (2) described cleaning utilizes plasma water to carry out.
9. the preparation method according to any one of claim 5-8, is characterized in that, step (3) described alkali is NaOH and/or potassium hydroxide;
Preferably, the molar concentration of step (3) described aqueous slkali is 0.5-3mol/L, is preferably 1mol/L.
Preferably, the speed of sweeping of step (3) described cyclic voltammetry is 5-50mVs
-1, be preferably 10mVs
-1;
Preferably, the circulation number of turns of step (3) described cyclic voltammetry is 30-80 circle, is preferably 60 circles.
10. the purposes of the Ni-based carbon fibre composite in hole according to claim 1 and 2, is characterized in that, the Ni-based carbon fibre composite in described hole is used as electrode material, is applied to electric automobile, flexible electronic product and wearable electronic product scope.
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| CN112002564A (en) * | 2020-08-26 | 2020-11-27 | 郑州航空工业管理学院 | Electrode material of super capacitor, preparation method and application |
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