CN101481085A - Nickel protoxide / silicon nano-wire and use thereof for preparing integrated super capacitor electrode material - Google Patents
Nickel protoxide / silicon nano-wire and use thereof for preparing integrated super capacitor electrode material Download PDFInfo
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- CN101481085A CN101481085A CNA2009100459115A CN200910045911A CN101481085A CN 101481085 A CN101481085 A CN 101481085A CN A2009100459115 A CNA2009100459115 A CN A2009100459115A CN 200910045911 A CN200910045911 A CN 200910045911A CN 101481085 A CN101481085 A CN 101481085A
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Abstract
The invention discloses a NiO/SiN wire and a method for preparing an integrated supercapacitor electrode material with high performance by adopting the material. The preparation method comprises the following steps: (1) the SiN wire is taken as a framework, a nickel membrane is sedimented on the SiN wire by the electroless plating technique to produce a nickel-silicon nanometer wire composite; and (2) the produced nickel-silicon nanometer wire composite is subject to rapid thermal annealing oxidation treatment. The invention adopts the advantages of the SiN wire that the scale is small, the specific surface is large, the surface atom has a large amount of nonsaturated bonds, and the tensiometric property is great, and takes the SiN wire as the framework for loading the NiO nanometer structure. The NiO/SiN wire has high specific capacitance, low equivalent essential resistance and good charging and discharging properties, is compatible with the integrated circuit technique and can be used for preparing the integrated supercapacitor electrode material with high performance.
Description
Technical field
The invention belongs to electrochemical capacitor material field, relate to a kind of on silicon nanowires with electroless-plating nickel and thermal oxide annealing preparation nickel protoxide/silicon nanowires (NiO/SiNWs), but and this nickel protoxide/silicon nanowires is used for integrated super capacitor electrode material.
Background technology
Because the yardstick that silicon nanowires has is little, specific area big, there are a large amount of unsaturated linkages in surface atom, has very strong surface-active, can prepare the high performance electrode material for super capacitor of NiO/SiNWs with its skeleton as load NiO nanostructured.
The nano NiO structure is one of known transition metal oxide that can be used as electrode material for super capacitor, though its electrochemical capacitance performance a little less than the RuO material, but its preparation technology is simple, with low cost.
In the prior art, be matrix generally, prepare the active material of transition metal oxides such as manganese oxide, nickel protoxide and ruthenium-oxide thereon as electrode of super capacitor with CNT or activated carbon; Wherein the electrode material for super capacitor based on ruthenium-oxide has best super capacitor characteristic, but it costs an arm and a leg; Be other transition metal oxide electrode material for super capacitor of carrier based on activated carbon or CNT in addition, though can obtain bigger specific area, but because its outside is covered by the surface deposition transition metal oxide fully, cause afflux layer resistance to increase, and active material is difficult to make full use of; Report at carbon nano tube surface deposition nickel protoxide, the nickel protoxide/carbon nano tube structure that can obtain to have higher super capacitor performance, but its preparation method and integrated circuit technology are incompatible.
Super capacitor material with respect to present other transition metal oxides, but NiO has inherent advantage aspect the manufacturing integrated super capacitor energy storage component, because to be widely used, technology maturation prepares on the NiO-Si thin layer technology feasible Ni-Si coating on this basis in integrated circuit; The NiSi phase film that forms behind high annealing on the other hand not only has good alkali resistance solution corrosion ability, but also has the low-resistivity characteristic, with the lattice of Si matching capacity is preferably arranged, the Ni-NiSi layer can be used as the good electrode material current collection layer of silica-based ultracapacitor.
Summary of the invention
The object of the present invention is to provide a kind of nickel protoxide/silicon nanowires (NiO/SiNWs), is skeleton with silicon nanowires (SiNWs), by electroless plating techniques deposition Ni thin layer, adopts the rapid thermal annealing oxidation technology to prepare NiO/SiNWs on its surface then.
Another object of the present invention is but this nickel protoxide/silicon nanowires is used for the preparation integrated super capacitor electrode material.
A kind of nickel protoxide/silicon nanowires provided by the invention (NiO/SiNWs), its preparation method comprises the steps:
(1) is skeleton with the silicon nanowires, on silicon nanowires,, makes nickel-silicon nanowires compound with electroless plating techniques nickel deposited film;
(2) with gained nickel-silicon nanowires compound process rapid thermal annealing oxidation processes.
Silicon nanowires described in the step (1) obtains by the following method: it is 3%～8% hydrofluoric acid preliminary treatment with the quality percentage composition that silicon chip is cleaned the back, and usefulness contains 20mM～35mM silver nitrate and the quality percentage composition is the mixing etching liquid etching of 15%～20% hydrofluoric acid then.
The method with electroless plating techniques nickel deposited film described in the step (1) is, silicon nanowires through the surfactant preliminary treatment, is put into pH and be 8.5～9.5 electroless plating liquid again, reacts 10～30min under 80～90 ℃ of conditions.
The composition of described electroless plating liquid comprises: NiSO
41～2mol/L, buffer (NH
4)
2SO
40.2～0.5mol/L, reducing agent NH
4F 2～3mol/L clamps together agent natrium citricum 0.1～0.4mol/L.
Rapid thermal annealing oxidation processing technique described in the step (2) is to carry out rapid thermal annealing oxidation processes 10～30min under 300 ℃～500 ℃ oxygen atmospheres.
Be preferably under 350 ℃～450 ℃ oxygen atmospheres and carry out rapid thermal annealing oxidation processes 10～30min.
This nickel protoxide/silicon nanowires (NiO/SiNWs) but be used for the preparation integrated super capacitor electrode material.The present invention generates spongiform NiO thin layer again on the basis that utilizes the huge specific area of SiNWs, thereby has increased the efficient of electroactive substance NiO.The yardstick that this method utilizes silicon nanowires to have is little, specific area big, there are a large amount of unsaturated linkages in surface atom, have very strong advantages such as surface-active, with its skeleton, but can prepare high-performance integrated super capacitor electrode material (its final structure is NiO-Ni-NiSi-SiNWs) based on NiO/SiNWs as load NiO nanostructured.
On the other hand, the NiSi phase film that forms after 300～500 ℃ of annealing not only has good alkali resistance solution corrosion ability, but also has the low-resistivity characteristic, with the lattice of Si matching capacity is preferably arranged, the Ni-NiSi layer can be used as the good electrode material current collection layer of silica-based ultracapacitor simultaneously.
Beneficial effect of the present invention is:
Adopt the electrochemistry wet etching to prepare silicon nanowires, this method and ic process compatibility, cost is low;
Adopt electroless method to carry out the metallic nickel deposition on the surface of silicon nanowires, this method technology is simple, technology maturation, and it is even to obtain coating, by the environment temperature of control each constituent concentration of plating bath and reaction, can be controlled the pattern and the thickness of coating;
With electroless plating techniques obtain nickel-silicon nanowires under oxygen atmosphere by carrying out rapid thermal annealing oxidation and annealing in process in RTA (rapid thermal annealing) system, preparation NiO/SiNWs composite nano materials, this structure is as electrode material for super capacitor, higher ratio electric capacity, lower equivalent internal resistance, favorable charge-discharge characteristic are arranged, and and ic process compatibility.Therefore the NiO/SiNWs nano composite structure is more suitable in using in integrated circuit fields than other transition metal oxide super capacitor materials.
Description of drawings
Fig. 1 is SEM photo top view (a) and the partial enlarged drawing (b) of Ni/SiNWs;
Fig. 2 is the SEM partial enlarged drawing of NiO/SiNWs;
Fig. 3 is the EDS spectral line of NiO/SiNWs;
Fig. 4 is the CV characteristic test curve of NiO/SiNWs;
Fig. 5 is the EIS spectral line of NiO/SiNWs.
The specific embodiment
Further set forth the present invention below in conjunction with accompanying drawing, and provide embodiment.
(1). the wet chemical etching is made silicon nanowires (SiNWs)
(a) select the silicon chip of the single-sided polishing of N-type (100 crystal orientation, resistivity 0.06-0.2 Ω cm) for use, cut into 1cm x 1cm print, the RCA standardization program is cleaned; In preliminary treatment 3～5min activating surface in 6% hydrofluoric acid solution at first under the normal temperature and pressure, put into the etching liquid etching 50min that contains 35mM/L silver nitrate and 20% quality percentage composition hydrofluoric acid then.
(b) be the residual silver-colored particle that 30% salpeter solution is removed surface of silicon nanowires with mass concentration, fully clean 70 ℃～80 ℃ dry for standby in drying baker again with deionized water.
Resulting silicon nanowires average diameter～80nm, length is～200 μ m.
(2). electroless deposition nickel thin layer, make nickel-silicon nanowires compound (Ni-SiNWs)
The SiNWs of above-mentioned preparation uses commercially available alkaline electroless nickel plating liquid (to contain NiSO through 0.5% Triton100 solution preliminary treatment 30s then
46H
2O 2mol/L, buffer (NH
4)
2SO
40.2mol/L, reducing agent NH
4F3mol/L clamps together agent natrium citricum 0.2mol/L) carry out Ni layer deposition.Bath pH value is adjusted to 9.5 through 10M ammoniacal liquor, and water-bath keeps reaction 20min in 80 ℃～90 ℃, uses 80 ℃ ± 5 ℃ deionized water rinsings at last and puts into 70 ℃～80 ℃ oven dry of baking oven once more.Its SEM pattern is seen Fig. 1; The surface topography of visible Ni-SiNWs array composite construction among Fig. 1 (a), Fig. 1 (b) has shown the partial enlarged drawing of this structure, can obviously observe its surface and be covered by the skim metal.
(3). nickel protoxide/silicon nanowires composite (NiO/SiNWs) preparation
The Ni/SiNWs of above-mentioned preparation in RTA (rapid thermal annealing system) under the 120mL/min oxygen atmosphere, 400 ℃ of thermal annealing 20min, make NiO/SiNWs, its surface topography is seen Fig. 2, the ESD collection of illustrative plates is seen Fig. 3.We can see that the surface of SiNWs becomes spongy from Fig. 2, and a large amount of folds is arranged, and have therefore further increased the contact area of electroactive substance NiO on the huge surface area of SiNWs again.Ni, O element have covered the SiNWs surface fully as can see from Figure 3.
(4) .NiO/SiNWs electrode electro Chemical parameter testing
The NiO/SiNWs print that makes is welded through the silver slurry with the sub-thread thin copper wire, seal remainder, only stay 1cm with paraffin
2Area as the electrochemical property test working electrode.
Testing equipment is LK3200A, and three-electrode system, Ag/AgCl are reference electrode, and platinized platinum is to electrode, and electrolyte solution is 2M KOH.Cyclic voltammetric under its different scanning rates (CV) test curve is seen Fig. 4, and be as the criterion reversible redox reaction of the reaction of active material NiO and electrolyte on this electrode as can be seen shows good chemical capacitive property.
Its electrochemical impedance spectroscopy (EIS) is seen Fig. 5, reveals typical local charge transfer process at the EIS of this electrode material spectral line table as can be seen, and its equivalence contact internal resistance is about 1.5 Ω, and behind the 3.15Hz, electrode shows tangible faraday's mass transport process, OH
-1Ion enters active material difficulty inner and stored charge and strengthens.
The electrochemical parameter that CV under the 5mV/s sweep speed carries out integral and calculating electricity level is: this material 1cm
2Apparent area when faraday's electrochemical reaction takes place, chemically reactive substance NiO is 0.538mg, reaches 888.76cm with the real contact area of electrolyte
2, the about 0.184C of storing electricity, quality reaches 681.04F/g than electric capacity, and capacitance density is 183.2F/cm
3
Embodiment 2
(1). the wet chemical etching is made silicon nanowires (SiNWs)
(a) select the single-sided polishing silicon chip of N-type (100 crystal orientation, resistivity 0.06-0.2 Ω cm) for use, cut into 1cm x 1cm print, the RCA standardization program is cleaned; In under the normal temperature and pressure in 3% hydrofluoric acid solution preliminary treatment 3～5min activating surface, put into the etching liquid etching 30min that contains 20mM/L silver nitrate and 15% quality percentage composition hydrofluoric acid then.
(b) be the residual silver-colored particle that 35% concentrated nitric acid solution is removed surface of silicon nanowires with mass concentration, fully clean 70 ℃～80 ℃ oven dry in drying baker again with deionized water.
Resulting silicon nanowires average diameter is～200nm length～50 μ m.
(2). electroless deposition nickel thin layer, make nickel-silicon nanowires compound
The SiNWs of above-mentioned preparation uses commercially available alkaline electroless nickel plating liquid (to contain NiSO through 1% neopelex solution preliminary treatment 30s then
46H
2O 1mol/L, buffer (NH
4)
2SO
40.5mol/L, reducing agent NH
4F 2.5mol/L clamps together agent natrium citricum 0.2mol/L) carry out Ni layer deposition.Bath pH value is adjusted to 8.5 through 10M ammoniacal liquor, and water-bath keeps reaction 15min in 80 ℃～90 ℃, uses 80 ℃ ± 5 ℃ left and right sides deionized water rinsings at last and puts into 70 ℃～80 ℃ oven dry of baking oven once more.
(3) .NiO/SiNWs Composite Preparation
The Ni/SiNWs of above-mentioned preparation in RTA (rapid thermal annealing system) under the 120mL/min oxygen atmosphere heat 300 ℃ of thermal annealing 20min, make NiO/SiNWs.
Its electrode electro Chemical parameter testing condition is with embodiment 1, and the electrochemical parameter that the CV under the 5mV/s sweep speed carries out integral and calculating electricity level is: this material 1cm
2Apparent area when faraday's electrochemical reaction takes place, chemically reactive substance NiO is 0.122mg, reaches 72.05cm with the equivalent contact area of electrolyte
2, the about 0.015C of storing electricity, quality reaches 247.95F/g than electric capacity, and capacitance density is 15.2F/cm
3
Embodiment 3
(1). the wet chemical etching is made silicon nanowires (SiNWs)
(a) select the single-sided polishing silicon chip of N-type (100 crystal orientation, resistivity 0.06-0.2 Ω cm) for use, cut into 1cm x 1cm print, the RCA standardization program is cleaned; Preliminary treatment 3～5min activating surface in 5% hydrofluoric acid solution is at normal temperatures and pressures put into then and is contained 25mM/L liquor argenti nitratis ophthalmicus and 15% quality percentage composition hydrofluoric acid solution etching 30min.
(b) be the residual silver-colored particle that 30% concentrated nitric acid solution is removed surface of silicon nanowires with mass concentration, fully clean 70 ℃～80 ℃ oven dry in drying baker again with deionized water.
Resulting silicon nanowires average diameter is～150nm that length is～100 μ m.
(2). electroless deposition nickel thin layer, make nickel-silicon nanowires compound
The SiNWs of above-mentioned preparation uses commercially available alkaline electroless nickel plating liquid (to contain NiSO through 1% neopelex solution preliminary treatment then
46H
2O 1mol/L, buffer (NH
4)
2SO
40.5mol/L, reducing agent NH
4F2.5mol/L clamps together agent natrium citricum 0.2mol/L) carry out Ni layer deposition.Bath pH value is adjusted to 8.5 through 10M ammoniacal liquor, and water-bath keeps reaction 15min in 80 ℃～90 ℃, uses 80 ℃ ± 5 ℃ left and right sides deionized water rinsings at last and puts into 70 ℃～80 ℃ oven dry of baking oven once more.
(3) .NiO/SiNWs Composite Preparation
The Ni/SiNWs of above-mentioned preparation in RTA (rapid thermal annealing system) under the 120mL/min oxygen atmosphere heat 500 ℃ of thermal annealing 20min, make NiO/SiNWs.
Its electrode electro Chemical parameter testing condition is with embodiment 1, and the electrochemical parameter that the CV under the 5mV/s sweep speed carries out integral and calculating electricity level is: this material 1cm
2Apparent area when faraday's electrochemical reaction takes place, the oxide of nickel is that 0.685mg (wherein may contain non-Ni
+ 2Oxide), the equivalent contact area with electrolyte reaches 586.67cm
2, the about 0.118C of storing electricity, quality reaches 345.11F/g than electric capacity, and capacitance density is 118.2F/cm
3
Claims (6)
1. a nickel protoxide/silicon nanowires is characterized in that its preparation method comprises the steps:
(1) is skeleton with the silicon nanowires, on silicon nanowires,, makes nickel-silicon nanowires compound with electroless plating techniques nickel deposited film;
(2) with gained nickel-silicon nanowires compound process rapid thermal annealing oxidation processes.
2. the described a kind of nickel protoxide/silicon nanowires of claim 1 is characterized in that the process conditions of described rapid thermal annealing oxidation processes are: carry out rapid thermal annealing oxidation processes 10～30min under 300 ℃～500 ℃ oxygen atmospheres.
3. the described a kind of nickel protoxide/silicon nanowires of claim 1 is characterized in that the process conditions of described rapid thermal annealing oxidation processes are: carry out rapid thermal annealing oxidation processes 10～30min under 350 ℃～450 ℃ oxygen atmospheres.
4. the described a kind of nickel protoxide/silicon nanowires of claim 1, it is characterized in that, described silicon nanowires preparation method is: after heavily doped polished silicon slice is cleaned, preliminary treatment in 3%～8% hydrofluoric acid solution is again with the mixing etching liquid etching that contains 20mM～35mM silver nitrate and 15%～20% hydrofluoric acid.
5. the described a kind of nickel protoxide/silicon nanowires of claim 1 is characterized in that, described in the step (1) on silicon nanowires the method with electroless plating techniques nickel deposited film be:
Silicon nanowires through the surfactant preliminary treatment, is put into pH and be 8.5～9.5 electroless plating liquid again, under 80～90 ℃ of conditions, react 10～30min;
The composition of described electroless plating liquid comprises: NiSO
41～2mol/L, buffer (NH
4)
2SO
40.2～0.5mol/L, reducing agent NH
4F 2～3mol/L clamps together agent natrium citricum 0.1～0.4mol/L.
6. but the application of the described a kind of nickel protoxide/silicon nanowires of claim 1 aspect the preparation integrated super capacitor electrode material.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973517A (en) * | 2010-10-21 | 2011-02-16 | 东华大学 | Method for preparing low doped porous silicon nanowire array |
| CN105047872A (en) * | 2015-06-26 | 2015-11-11 | 齐齐哈尔大学 | Preparation method of nanometer nickel protoxide-nickel-silicon alloy lithium ion battery negative electrode material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100575550C (en) * | 2008-05-23 | 2009-12-30 | 华东师范大学 | A kind of method of on silicon nanowires, carrying out non-phosphate electroless nickel plating |
| CN101280415A (en) * | 2008-05-29 | 2008-10-08 | 复旦大学 | Nickel plating method for surface of silicon nanowires |
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2009
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973517A (en) * | 2010-10-21 | 2011-02-16 | 东华大学 | Method for preparing low doped porous silicon nanowire array |
| CN105047872A (en) * | 2015-06-26 | 2015-11-11 | 齐齐哈尔大学 | Preparation method of nanometer nickel protoxide-nickel-silicon alloy lithium ion battery negative electrode material |
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