CN107622878A - Preparation method of nano-porous gold/manganese dioxide composite electrode material - Google Patents
Preparation method of nano-porous gold/manganese dioxide composite electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano-porous gold/manganese dioxide composite electrode material, which comprises the following steps: (1) taking Au35Ag65Dealloying the alloy film to prepare a nano porous gold film; (2) treating the nano-porous gold film by adopting an atomic layer deposition method, and using Mn (thd)3And ozone as precursor, the reaction temperature is controlled at 150-250 ℃, and the reaction is carried out by Mn (thd)3Pulse, N2Cleaning, O3Pulse sum N2And cleaning, and depositing for 500-5000 cycles in such a way, and uniformly depositing manganese dioxide on the inner surface and the outer surface of the nano porous gold film to obtain the nano porous gold/manganese dioxide composite electrode material. The composite electrode material has good specific capacitance characteristic, controllable structure and stable performance.
Description
Technical field
The invention belongs to the preparing technical field of nano material, and in particular to a kind of nano-porous gold/manganese dioxide is compound
The preparation method of electrode material.
Background technology
Ultracapacitor(Supercapacitor)It is a kind of new energy storage device, has that energy storage density is big, output work
Rate is high, operating temperature range is wide, the features such as having extended cycle life, and can carry out fast charging and discharging, can be preferably to energy
The utilization and storage of progress.High performance electrode is the important directions for lifting performance of the supercapacitor.Metal oxide materials have
There is very high theoretical fake capacitance capacity to turn into and improve the preferable electrode material of electrochemical capacitance performance.And as the allusion quotation of base metal oxide
Section bar material, it is very high that manganese dioxide possesses theoretical bulking value(1370F/g), price is low, amount it is big be easy to get with it is environment-friendly etc. a variety of excellent
Point.But because the electric conductivity of manganese dioxide is poor, mechanical stability is not high, it is difficult to reaches higher bulking value.Therefore, from height
Electric conductivity, the material of bigger serface can effectively improve the performance of electrode as the collector of manganese dioxide electrode.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided one kind has good specific capacitance special
The preparation method of property, structure-controllable and nano-porous gold/manganese dioxide composite electrode material of stable performance.
In order to solve the above technical problems, the present invention uses following technical scheme:
A kind of preparation method of nano-porous gold/manganese dioxide composite electrode material, comprises the following steps:
(1)Prepare nanoporous gold thin film:
Take Au35Ag65Alloy firm carries out de- Alloying Treatment, obtains the nanoporous gold thin film with nano-porous structure;
(2)Prepare nano-porous gold/manganese dioxide composite electrode material
By step(1)Obtained nanoporous gold thin film is handled using Atomic layer deposition method, with Mn (thd)3And ozone
For presoma, reaction temperature is controlled at 150 DEG C~250 DEG C, is evacuated to 0.6Torr~2Torr, Mn (thd)3Pulse 0.5s~
5s, N2Clean 5s~15s, O3Pulse 0.01s~0.05s, N215s~30s is cleaned, so deposits 500~5000 circulations,
The surfaces externally and internally uniform deposition manganese dioxide of nanoporous gold thin film, after the completion of deposition, it is multiple to obtain nano-porous gold/manganese dioxide
Composite electrode material.
In the preparation method of above-mentioned nano-porous gold/manganese dioxide composite electrode material, it is preferred that the step(1)
In, the process of the de- Alloying Treatment is as follows:By Au35Ag65Alloy firm be placed at room temperature concentration for 12mol/L~
30min~120min is handled in 16mol/L salpeter solution, obtains nanoporous gold thin film.
In the preparation method of above-mentioned nano-porous gold/manganese dioxide composite electrode material, it is preferred that the step(1)
In, after obtaining nanoporous gold thin film, first cleaned with deionized water, then with washes of absolute alcohol, then the nanometer of cleaning is more
Hole gold thin film is dried standby at room temperature.
In the preparation method of above-mentioned nano-porous gold/manganese dioxide composite electrode material, it is preferred that the step(1)
In, the average pore size of nanoporous gold thin film is 30nm~60nm.
In the preparation method of above-mentioned nano-porous gold/manganese dioxide composite electrode material, it is preferred that the step(2)
In, the thickness of nano-porous gold/manganese dioxide composite electrode material is 105nm~150nm.
In the present invention, Mn (thd)3Refer to three(2,2,6,6- tetramethyl -3,5- heptadione)Manganese.
The innovative point of the present invention is:
The present invention is successfully prepared with good ratio using de- Alloying Treatment and the synergistic function of Atomic layer deposition method
Nano-porous gold/manganese dioxide composite electrode material of capacitance characteristic and structure-controllable.In the prior art, the system of electrode material
Standby is mostly to use electrochemical deposition method, and electrochemical deposition method is generally by controlling electrochemical deposition parameter(As solution concentration,
Temperature, mixing speed and current density(Overpotential)Size etc.), to control nucleation and growth pattern(Such as continuous nucleation, instantaneously
Nucleation, two-dimensional growth, three dimensional growth), it is final to control pattern and crystal structure, electrochemical deposition manganese dioxide, for nucleation
The particle diameter of nano particle is difficult to control, it is more difficult to accomplishes to be nucleated everywhere equal in magnitude, and nano particle is easily reunited, so as to influence to sink
Long-pending uniformity, the manganese dioxide for depositing to obtain tend to carry out petal-like preferential growth, to the space availability ratio of substrate compared with
It is low, so as to influence specific capacitance performance.Applicant is screened by largely testing with method, and finishing screen selects Atomic layer deposition method
The defects of to overcome prior art, ald utilize Mn (thd)3And O3In the change of substrate surface alternately monolayer
Absorption and reaction are learned, the deposition of manganese dioxide is limited to the growth of monoatomic layer from technological principle, by controlling reaction temperature
The parameters such as degree, the number circulated can accomplish the accurate control to manganese bioxide coated growth, make coating uniform controllable.Due to heavy
The manganese dioxide that product obtains is good for the shape-retaining ability of substrate, has three-dimensional porous structure, higher specific surface area ensure that superior
Capacitive property.Atomic layer deposition method is used for surface modification field, the even electrode for being used to study battery in the prior art
Performance, but from improvement capacitive property is not used for, the present invention is innovatively combined using Atomic layer deposition method with de- Alloying Treatment,
So that the capacitive property of the electrode material prepared is largely increased.
Compared with prior art, the advantage of the invention is that:
The present invention uses nano-porous gold as collector, with the manganese bioxide coated preparation of method uniform deposition of ald
Electrode material for super capacitor.The manganese bioxide coated even structure obtained by ald, there is three-dimensional porous structure.
Electrode material provided by the invention deposits to obtain using Atomic layer deposition method, can be by controlling the presoma of ald
Species and deposition parameter adjust its specific capacitance characteristic thickness, crystal formation, composition of the material that controls to obtain etc., are allowed to have
Standby higher specific capacitance, the volume ratio performance of electrode material can also be improved.
Brief description of the drawings
Fig. 1 is the SEM image of nanoporous gold thin film prepared by the embodiment of the present invention 1.
Fig. 2 is the SEM image of nano-porous gold/manganese dioxide composite electrode prepared by the embodiment of the present invention 1.
Fig. 3 is the TEM image of nano-porous gold/manganese dioxide composite electrode prepared by the embodiment of the present invention 3.
Fig. 4 is the SEM image of nano-porous gold/manganese dioxide composite electrode prepared by comparative example 1.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Material and instrument employed in following examples are commercially available.
A kind of preparation method of nano-porous gold/manganese dioxide composite electrode material, comprises the following steps:
(1)Prepare nanoporous gold thin film
From Au35Ag65Alloy firm(That is atomic ratio 7: 13), alloy firm is intercepted into appropriate size, at room temperature by alloy firm
It is 12M-16M to be placed in concentration(M is mol/L)Salpeter solution in, carry out de- Alloying Treatment 30-120 points using chemical method
Clock, so as to which the nanoporous gold thin film with nano-porous structure be made.The nanoporous gold thin film is with de- alloying time
And de- alloying corrosive liquid concentration change and there is different pore diameter ranges, average pore size is generally in 30nm~60nm scopes
It is interior, show the level under different technology conditions.Obtained nanoporous gold thin film is first cleaned with deionized water, Ran Houyong
Washes of absolute alcohol, then it is standby by 12h is dried under the nano-porous gold film room temperature of cleaning.
(2)Prepare nano-porous gold/manganese dioxide composite electrode material
By step(1)Obtained nanoporous gold thin film is placed in atomic layer deposition apparatus, is existed using the method for ald
Nanoporous gold thin film surfaces externally and internally uniform deposition layered manganese oxide.With Mn (thd)3It is presoma with ozone, reaction temperature
Control is evacuated to 6 × 10 at 150 DEG C~250 DEG C-1Torr~2Torr.First, Mn (thd)3Pulse 0.5s~5s, N2Cleaning
5s~15s, ensure Mn (thd)3It is uniform in nano-porous gold diffusion into the surface, then O3Pulse 0.01s~0.05s, N2Gas cleans
15s~30s, according to Mn (thd)3Pulse-nitrogen cleaning-ozone purge-nitrogen cleaning is a circulation, so deposits 500-
5000 circulations, finally can uniformly deposit one layer of manganese dioxide in the surfaces externally and internally of nano-porous gold.Deposition is completed
Nano-porous gold/manganese dioxide composite electrode material film of three-dimensional structure is obtained, thickness is 105nm~150nm.
Embodiment 1:
A kind of preparation method of nano-porous gold/manganese dioxide composite electrode material of the invention, comprises the following steps:
(1)Prepare nanoporous gold thin film:From the Au that thickness is 100nm35Ag65Alloy firm(Atomic ratio), it is cut into
1×1cm2Size, alloy firm is placed in the salpeter solution that concentration is 16M takes off Alloying Treatment 30 minutes at room temperature, taken off and close
After aurification terminates, nanoporous gold thin film is obtained.By film by deionized water cleaning 30min, it is clear to change deionized water repetition
Wash 4 times, then with washes of absolute alcohol, be dried at room temperature for after cleaning up 12 hours it is standby, obtained nano-porous gold is thin
Film microscopic appearance is as shown in figure 1, the average pore size of nanoporous gold thin film is 30nm.
(2)Prepare nano-porous gold/manganese dioxide composite electrode material:By step(1)Dried nano-porous gold is thin
Film is put into the reaction chamber of conventional atomic layer depositing device, is passed through nitrogen, flow 20sccm, line temperature is heated into 150 DEG C,
Reaction chamber is heated to 186 DEG C(That is reaction temperature), Mn (thd)3Presoma bottle is heated to 133 DEG C, is evacuated to 6 × 10-1Torr。
Drive before being turned off under body bottle hand-operated valve state, Mn (thd)3Pulse 1s, nitrogen cleaning 5s, repetitive cycling to pressure pulse disappear,
Complete degasification.Open presoma bottle hand-operated valve, Mn (thd)3Pulse 2s, nitrogen cleaning 10s, ozone purge 0.03s(Ozone concentration
15vol.%, flow 400sccm), nitrogen cleaning 20s, according to Mn (thd)3Pulse-nitrogen cleaning-ozone purge-nitrogen cleaning
For a circulation, 1000 circulations are so repeated, in nano-porous gold surfaces externally and internally one layer of manganese dioxide of uniform deposition, are obtained
The nano-porous gold that thickness is about 110nm/manganese dioxide composite electrode material film, the microcosmic shape of the combination electrode material film
Looks are as shown in Figure 2.After tested, the specific capacitance of the nano-porous gold/manganese dioxide composite electrode material film is 560Fg-1。
Embodiment 2:
A kind of preparation method of nano-porous gold/manganese dioxide composite electrode material of the invention, comprises the following steps:
(1)Prepare nanoporous gold thin film:
From the Au that thickness is 100nm35Ag65Alloy firm(Atomic ratio), it is cut into 2 × 1cm2Size, it will close at room temperature
Gold thin film, which is placed in the salpeter solution that concentration is 12M, takes off Alloying Treatment 90 minutes, after de- alloying terminates, obtains nanoporous
Gold thin film, film is then clear with absolute ethyl alcohol by deionized water cleaning 30min, replacing deionized water repeated washing 4 times
Wash, be dried at room temperature for after cleaning up 12 hours it is standby, the average pore size of nanoporous gold thin film is 50nm.
(2)Prepare nano-porous gold/manganese dioxide composite electrode material:Dried nanoporous gold thin film is put into original
The reaction chamber of sublayer depositing device, nitrogen is passed through, flow 20sccm, line temperature is heated to 150 DEG C, reaction chamber is heated to
246 DEG C, Mn (thd)3Presoma bottle is heated to 133 DEG C, is evacuated to 6 × 10-1Torr.Body bottle hand-operated valve state is driven before being turned off
Under, Mn (thd)3Pulse 1s, nitrogen cleaning 5s, repetitive cycling to pressure pulse disappear, and complete degasification.It is manual to open presoma bottle
Valve, Mn (thd)3Pulse 2s, nitrogen cleaning 10s, ozone purge 0.03s(Ozone concentration 15vol.%, flow 400sccm), nitrogen
20s is cleaned, so repeats 2000 circulations, in nanoporous gold surface one layer of manganese dioxide of uniform deposition, obtaining thickness is about
120nm nano-porous gold/manganese dioxide composite electrode film.After tested, the nano-porous gold/manganese dioxide composite electrode material
The specific capacitance for expecting film is 672Fg-1。
Embodiment 3:
A kind of preparation method of nano-porous gold/manganese dioxide composite electrode material of the invention, comprises the following steps:
(1)Prepare nanoporous gold thin film:
From the Au that thickness is 100nm35Ag65Alloy firm(Atomic ratio), it is cut into 1 × 1cm2Size, it will close at room temperature
Gold thin film, which is placed in the salpeter solution that concentration is 16M, takes off Alloying Treatment 120 minutes, and after de- alloying terminates, it is more to obtain nanometer
Hole gold thin film, film is then clear with absolute ethyl alcohol by deionized water cleaning 30min, replacing deionized water repeated washing 4 times
Wash, be dried at room temperature for after cleaning up 12 hours, obtain nanoporous gold thin film, the average pore size of nanoporous gold thin film is
60nm。
(2)Prepare nano-porous gold/manganese dioxide composite electrode material:Dried nanoporous gold thin film is put into original
Sublayer deposition reaction chamber, nitrogen is passed through, flow 20sccm, line temperature is heated to 150 DEG C, reaction chamber is heated to 246 DEG C, Mn
(thd)3Presoma bottle is heated to 133 DEG C, is evacuated to 6 × 10-1Torr.Drive before being turned off under body bottle hand-operated valve state, Mn
(thd)3Pulse 1s, nitrogen cleaning 5s, repetitive cycling to pressure pulse disappear, and complete degasification.Open presoma bottle hand-operated valve, Mn
(thd)3Pulse 2s, nitrogen cleaning 10s, ozone purge 0.03s(Ozone concentration 15vol.%, flow 400sccm), nitrogen cleaning
20s, so repeats 5000 circulations, and one layer of manganese dioxide is uniformly deposited in nanoporous gold surface, and it is 150nm's to obtain thickness
Nano-porous gold/manganese dioxide composite electrode film.The transmission electron microscope pattern of the combination electrode material film as shown in figure 3, by
Scheme visible, have one layer of manganese dioxide in nano-porous gold surface uniform deposition.After tested, the nano-porous gold/manganese dioxide is multiple
The specific capacitance of composite electrode material film is 640 Fg-1。
Comparative example 1:
Nano-porous gold/the manganese dioxide composite electrode prepared using anodic deposition method, its microscopic appearance is as shown in figure 4, than electricity
Hold for 432 Fg-1.Compared with existing electrochemical deposition method, nano-porous gold/manganese dioxide composite electrode material of the invention
Film is evenly controllable, and specific capacitance significantly improves.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention.Though
So the present invention is disclosed as above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from the Spirit Essence of the present invention and technical scheme, all using in the methods and techniques of the disclosure above
Appearance makes many possible changes and modifications to technical solution of the present invention, or is revised as the equivalent embodiment of equivalent variations.Therefore,
Every content without departing from technical solution of the present invention, the technical spirit according to the present invention is to made for any of the above embodiments any simple
Modification, equivalent substitution, equivalence changes and modification, still fall within technical solution of the present invention protection in the range of.
Claims (5)
1. a kind of preparation method of nano-porous gold/manganese dioxide composite electrode material, comprises the following steps:
(1)Prepare nanoporous gold thin film:
Take Au35Ag65Alloy firm carries out de- Alloying Treatment, obtains the nanoporous gold thin film with nano-porous structure;
(2)Prepare nano-porous gold/manganese dioxide composite electrode material
By step(1)Obtained nanoporous gold thin film is handled using Atomic layer deposition method, with Mn (thd)3It is with ozone
Presoma, reaction temperature are controlled at 150 DEG C~250 DEG C, are evacuated to 0.6Torr~2Torr, Mn (thd)3Pulse 0.5s~
5s, N2Clean 5s~15s, O3Pulse 0.01s~0.05s, N215s~30s is cleaned, so deposits 500~5000 circulations,
The surfaces externally and internally uniform deposition manganese dioxide of nanoporous gold thin film, after the completion of deposition, it is multiple to obtain nano-porous gold/manganese dioxide
Composite electrode material.
2. the preparation method of nano-porous gold/manganese dioxide composite electrode material according to claim 1, its feature exist
In the step(1)In, the process of the de- Alloying Treatment is as follows:By Au35Ag65Alloy firm is placed in concentration at room temperature
30min~120min is handled in 12mol/L~16mol/L salpeter solution, obtains nanoporous gold thin film.
3. the preparation method of nano-porous gold/manganese dioxide composite electrode material according to claim 1 or 2, its feature
It is, the step(1)In, after obtaining nanoporous gold thin film, first cleaned with deionized water, then with washes of absolute alcohol,
It will be dried again under the nano-porous gold film room temperature of cleaning standby.
4. the preparation method of nano-porous gold/manganese dioxide composite electrode material according to claim 1 or 2, its feature
It is, the step(1)In, the average pore size of nanoporous gold thin film is 30nm~60nm.
5. the preparation method of nano-porous gold/manganese dioxide composite electrode material according to claim 1 or 2, its feature
It is, the step(2)In, the thickness of nano-porous gold/manganese dioxide composite electrode material is 105nm~150nm.
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