CN111748794A - Manganese dioxide nano composite film material and preparation method thereof - Google Patents
Manganese dioxide nano composite film material and preparation method thereof Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
Abstract
The invention discloses a manganese dioxide nano composite film material and a preparation method thereof, the manganese dioxide nano composite film material comprises a polyurethane template, an atomic layer deposition equipment reaction chamber and a precursor source conveying pipeline, the atomic layer deposition equipment reaction chamber is connected with the precursor source conveying pipeline, one end of a precursor source container is connected with a high-purity nitrogen source, the other end of the precursor source container is connected with the reaction chamber, the atomic layer deposition equipment reaction chamber is also connected with a nitrogen inlet, a reaction precursor and a byproduct outlet thereof, the polyurethane template is placed in the atomic layer deposition equipment reaction chamber, by means of the atomic layer deposition method, a manganese dioxide nano film material is deposited on the surface of polyurethane through atomic layer deposition to prepare an electrode with excellent electrochemical activity, a nano manganese dioxide composite film is prepared, and an oxide with good conductivity and a metal film are compounded, the conductivity of the material is fully improved, the electrochemical performance is further improved, the preparation process is environment-friendly, and the preparation cost is low.
Description
Technical Field
The invention relates to the technical field of metal oxides, in particular to a manganese dioxide nano composite film material and a preparation method thereof.
Background
With the development of science and technology and the progress of society, portable electronic devices gradually enter the lives of people, and the research on the devices also becomes a hotspot in the scientific research field. Manganese dioxide is a more classical pseudocapacitance material, and has become a hot field of research due to the advantages of high specific capacitance, capability of performing rapid and reversible redox reaction, no toxicity, no harm, environmental friendliness, low price and abundant reserves. Most of the current research on the capacitance of manganese dioxide focuses on bulk and powder materials. However, the non-conductivity of manganese dioxide limits its application in the field of supercapacitors.
Disclosure of Invention
The invention aims to provide a manganese dioxide nano composite film material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: the utility model provides a manganese dioxide nanometer composite film material, includes polyurethane template, atomic layer deposition equipment reaction chamber, precursor source conveying line, atomic layer deposition equipment reaction chamber is connected with precursor source conveying line, and precursor source conveying line includes precursor source container and the valve of control precursor source, and multiple precursor source can be placed to precursor source container, and the reaction source can be oxidizing source or reducing source, and high-purity nitrogen source is connected to precursor source container one end, and atomic layer deposition equipment reaction chamber still connects nitrogen gas inlet and reaction precursor and by-product outlet, the inside polyurethane template that places of atomic layer deposition equipment reaction chamber.
Further, the reaction chamber of the atomic layer deposition equipment is also connected with a manganese source precursor container.
Further, the reaction chamber of the atomic layer deposition equipment is also connected with a zinc source precursor container, an aluminum source precursor container or a nickel source precursor container.
The invention provides another technical scheme: a preparation method of manganese dioxide nano composite film material comprises the following steps:
s1: manganese oxide film deposited on polyurethane template by utilizing atomic layer deposition method
Placing the polyurethane template into a reaction chamber of atomic layer deposition equipment, wherein the temperature of the reaction chamber of the atomic layer deposition equipment is set to be 150-250 ℃;
s2: introducing high-purity nitrogen into a manganese source precursor container, wherein the flow of the high-purity nitrogen is 10-100sccm, then the high-purity nitrogen carries manganese source precursor pulses to enter a reaction chamber of the atomic layer deposition equipment and is chemically adsorbed on the surface of a polyurethane template, and meanwhile, the temperature of the manganese source precursor is controlled to be 50-100 ℃, the pulse time is 500-1000ms, and the reaction time is 5-10 s;
s3: after the polyurethane template surface is subjected to reaction and adsorption saturation, purging the reaction chamber of the atomic layer deposition equipment for 10-100s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber of the atomic layer deposition equipment;
s4: the oxygen source precursor container is pulsed into a reaction chamber of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container reacts with a manganese source precursor chemically adsorbed on the surface of the polyurethane template in S2;
s5: after the second half reaction is finished, cleaning the cavity for 20-50s by using inert gas nitrogen, and purging redundant reaction precursors and byproducts out of the reaction cavity until a deposition cycle is finished, and after the set cycle number is finished, finishing the deposition process of the manganese oxide film, and controlling the proportion of manganese oxide by setting different cycle numbers;
s6: a film of another oxide or metal may continue to be deposited on top of the manganese oxide film to form a composite film.
Further, the other oxide film in S6 includes at least one of an aluminum oxide-zinc oxide composite film or a nickel film.
Further, the thickness of the manganese dioxide is nanometer.
Further, depositing an aluminum oxide and zinc oxide composite film on the manganese oxide film by utilizing an atomic layer deposition method, wherein the aluminum oxide composite step comprises the following steps:
step 1: firstly, an aluminum source precursor is pulsed into a reaction chamber of atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and simultaneously, the temperature of the aluminum source precursor is controlled to be 20 ℃ and the pulse time is controlled to be 20-50 ms;
step 2: after the surface of the manganese oxide film is subjected to reaction and adsorption saturation, purging the reaction chamber of the atomic layer deposition equipment for 10-50s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber of the atomic layer deposition equipment;
and step 3: the oxygen source precursor container is pulsed into a reaction chamber of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container reacts with the aluminum source precursor chemically adsorbed on the surface of the manganese oxide film in the step 1;
and 4, step 4: after the second half reaction is finished, cleaning the cavity for 20-50s by using inert gas nitrogen, and purging redundant reaction precursors and byproducts out of the reaction cavity until a deposition cycle is finished, and after the set cycle number is finished, finishing the deposition process of the alumina film, wherein the proportion of alumina can be controlled by controlling the cycle number;
the zinc oxide composite compounding method comprises the following steps:
step 1: firstly, a zinc source precursor is pulsed into a reaction chamber of atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and meanwhile, the temperature of the aluminum source precursor is controlled to be 20 ℃ and the pulse time is 20-50 ms;
step 2: purging the atomic layer deposition equipment reaction chamber for 10-50s by using inert gas N2, and purging redundant reaction precursors out of the atomic layer deposition equipment reaction chamber;
and step 3: the oxygen source precursor container is pulsed into a reaction chamber of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container reacts with the zinc source precursor in the step 1;
and 4, step 4: after the second half reaction is finished, the cavity is cleaned for 20-50s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle number is finished, the deposition process of the zinc oxide film is finished, and the proportion of zinc oxide can be controlled by controlling the cycle number.
Further, the step of compounding the nickel simple substance film on the manganese oxide film is as follows:
the first step is as follows: depositing a nickel film on the manganese oxide film by utilizing an atomic layer deposition method to form a composite film;
the second step is that: introducing high-purity nitrogen into a nickel source precursor container, wherein the flow of the high-purity nitrogen is 10-100sccm, then the high-purity nitrogen carries nickel source precursor pulses to enter a reaction chamber of atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide thin film, and meanwhile, the temperature of the nickel source precursor is controlled to be 50-100 ℃, the pulse time is 1-10s, and the reaction time is 5-10 s;
the third step: after the surface of the manganese oxide film is subjected to reaction and adsorption saturation, purging the reaction chamber of the atomic layer deposition equipment for 10-100s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber of the atomic layer deposition equipment;
the fourth step: the reducing precursor container is pulsed into a reaction chamber of the atomic layer deposition equipment, and the pulse time is 100-;
the fifth step: after the second half reaction is finished, the cavity is cleaned for 20-50s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle times are finished, the deposition process of the simple substance nickel is finished, and the proportion of the nickel film is controlled by controlling the cycle deposition times.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the manganese dioxide nano composite film material and the preparation method thereof, disclosed by the invention, the manganese dioxide nano composite film material is compounded on the conductive substrate by an atomic layer deposition method, and the regulation and control of the appearance and the structure of the manganese dioxide nano film material on the surface of the polyurethane material are realized by controlling the cycle number of atomic layer deposition.
2. The manganese dioxide nano composite film material and the preparation method thereof provided by the invention have the advantages that the polyurethane template is used as a matrix, an electrode with excellent electrochemical activity is prepared by depositing the manganese dioxide nano film material on the surface of polyurethane through atomic layer deposition by virtue of the porous structure of the polyurethane template, meanwhile, the appearance and the thickness of the manganese oxide nano film material are regulated and controlled by fully utilizing the cycle frequency of the atomic layer deposition, the deposition of manganese dioxide and other composite films on the polyurethane template can be realized, the nano-grade manganese dioxide composite film is prepared, the conductivity of the nano-grade manganese dioxide composite film is fully improved by compounding an oxide with good conductivity and a metal film, the electrochemical performance is further improved, the preparation process is environment-friendly, and the preparation cost is low.
Drawings
FIG. 1 is a schematic structural diagram of embodiments 1 and 4 of the present invention;
fig. 2 is a schematic structural diagram of embodiments 2 and 3 of the present invention.
In the figure: 1. a polyurethane template; 2. an atomic layer deposition equipment reaction chamber; 3. precursor source delivery line.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A manganese dioxide nano composite film material comprises a polyurethane template 1, an atomic layer deposition device reaction chamber 2 and a precursor source conveying pipeline 3, wherein the atomic layer deposition device reaction chamber 2 is connected with the precursor source conveying pipeline 3, the precursor source conveying pipeline 3 comprises a precursor source container and a valve for controlling the precursor source, the precursor source container can be used for containing a manganese source and other precursor sources, the reaction sources can be oxidizing sources (such as water, oxygen, ozone, plasma oxygen, hydrogen peroxide and the like) and reducing sources (such as formaldehyde, hydrazine, plasma hydrogen, plasma ammonia and the like), one end of the precursor source container is connected with a high-purity nitrogen source, the deposition device reaction chamber 2 is further connected with a nitrogen inlet and a reaction precursor and a byproduct outlet, and the polyurethane template 1 is placed inside the atomic layer deposition device reaction chamber 2.
Example 1
Referring to fig. 1, a manganese dioxide nanocomposite film material includes a polyurethane template 1, an atomic layer deposition apparatus reaction chamber 2, and a manganese source precursor container, where the atomic layer deposition apparatus reaction chamber 2 is connected to the manganese source precursor container, the manganese source precursor container is used to provide manganese, the manganese source precursor container is connected to a high-purity nitrogen source, the manganese source precursor is blown into the atomic layer deposition apparatus reaction chamber 2 by the high-purity nitrogen, the atomic layer deposition apparatus reaction chamber 2 is further connected to a nitrogen inlet, a reaction precursor outlet and a byproduct outlet, and is used to discharge the reaction precursor and the byproduct, a polyurethane template 1 is placed inside the atomic layer deposition apparatus reaction chamber 2, and a manganese dioxide film is composited on the polyurethane template 1.
A preparation method of manganese dioxide nano composite film material comprises the following steps:
step 1: depositing manganese oxide film on polyurethane template 1 by utilizing atomic layer deposition method
Placing the polyurethane template 1 into a reaction chamber 2 of the atomic layer deposition equipment, setting the temperature of the reaction chamber 2 of the atomic layer deposition equipment to be 150 ℃, and after the required temperature is reached, realizing the thickness controllability of the manganese dioxide nano-scale film by utilizing an atomic layer deposition mode;
step 2: introducing high-purity nitrogen into a manganese source precursor container, wherein the flow rate of the high-purity nitrogen is 10sccm, then introducing the high-purity nitrogen carrying manganese source precursor pulse into an atomic layer deposition equipment reaction chamber 2, and carrying out chemical adsorption on the surface of a polyurethane template 1, and simultaneously controlling the temperature of the manganese source precursor to be 50 ℃, the pulse time to be 500ms and the reaction time to be 5 s;
and step 3: after the polyurethane template 1 is subjected to surface reaction and adsorption saturation, the time for purging the reaction chamber 2 of the atomic layer deposition equipment by using inert gas N2 is 10s, and redundant reaction precursors are purged out of the reaction chamber 2 of the atomic layer deposition equipment;
and 4, step 4: the oxygen source precursor container is pulsed into a reaction chamber 2 of the atomic layer deposition equipment, and the pulse time is 10ms, so that the oxygen source precursor container reacts with the manganese source precursor chemically adsorbed on the surface of the polyurethane template 1 in the step 2;
and 5: after the second half reaction is finished, cleaning the cavity for 20s by using inert gas nitrogen, and purging redundant reaction precursors and byproducts out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle times are finished, the deposition process of the manganese dioxide film is finished, the proportion of manganese oxide can be controlled by setting different cycle times, and the prepared manganese dioxide nano film material has better conductivity, higher mass specific capacitance and volume specific capacitance, and is an ideal electrode material of a super capacitor;
example 2
Referring to fig. 2, a manganese dioxide nano composite thin film material includes a polyurethane template 1, an atomic layer deposition apparatus reaction chamber 2, and an aluminum source precursor container, where the atomic layer deposition apparatus reaction chamber 2 is connected to the aluminum source precursor container, the aluminum source precursor container is used to provide aluminum, the aluminum source precursor container is connected to a high purity nitrogen source, the aluminum source precursor is blown into the atomic layer deposition apparatus reaction chamber 2 by the high purity nitrogen, the atomic layer deposition apparatus reaction chamber 2 is further connected to a nitrogen inlet, a reaction precursor outlet and a byproduct outlet thereof for discharging the reaction precursor and the byproduct thereof, the polyurethane template 1 is placed inside the atomic layer deposition apparatus reaction chamber 2, and an aluminum oxide thin film is composited on the polyurethane template 1.
A preparation method of manganese dioxide nano composite film material comprises the following steps:
step 1: firstly, an aluminum source precursor is pulsed into a reaction chamber 2 of the atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and meanwhile, the temperature of the aluminum source precursor is controlled to be 20 ℃ and the pulse time is controlled to be 20 ms;
step 2: after the manganese oxide film surface is saturated in reaction and adsorption, purging the atomic layer deposition equipment reaction chamber 210s by using inert gas N2, and purging redundant reaction precursors out of the atomic layer deposition equipment reaction chamber 2;
and step 3: the oxygen source precursor container is pulsed into a reaction chamber 2 of the atomic layer deposition equipment, and the pulse time is 10ms, so that the oxygen source precursor container reacts with the aluminum source precursor chemically adsorbed on the surface of the manganese oxide film in the step 1;
and 4, step 4: after the second half reaction is finished, the cavity is cleaned for 20s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle number is finished, the deposition process of the alumina film is finished, and the proportion of alumina can be controlled by controlling the cycle number.
Example 3.
Referring to fig. 2, a manganese dioxide nanocomposite thin film material includes a polyurethane template 1, an atomic layer deposition apparatus reaction chamber 2, and a zinc source precursor container, where the atomic layer deposition apparatus reaction chamber 2 is connected to the zinc source precursor container, the zinc source precursor container is used to provide zinc, the zinc source precursor container is connected to a high purity nitrogen source, the zinc source precursor is blown into the atomic layer deposition apparatus reaction chamber 2 by the high purity nitrogen, the atomic layer deposition apparatus reaction chamber 2 is further connected to a nitrogen inlet, a reaction precursor and a byproduct outlet, and is used to discharge the reaction precursor and the byproduct, a polyurethane template 1 is placed inside the atomic layer deposition apparatus reaction chamber 2, and a zinc oxide composite thin film is formed on the polyurethane template 1.
A preparation method of manganese dioxide nano composite film material comprises the following steps:
step 1: firstly, a zinc source precursor is pulsed into a reaction chamber 2 of the atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and meanwhile, the temperature of the zinc source precursor is controlled to be 20 ℃ and the pulse time is controlled to be 20-50 ms;
step 2: purging the atomic layer deposition device reaction chamber 210-50s with an inert gas N2 to purge excess reaction precursor out of the atomic layer deposition device reaction chamber 2;
and step 3: the oxygen source precursor container is pulsed into a reaction chamber 2 of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container reacts with the zinc source precursor in the step 1;
and 4, step 4: after the second half reaction is finished, the cavity is cleaned for 20-50s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle number is finished, the deposition process of the zinc oxide film is finished, and the proportion of zinc oxide can be controlled by controlling the cycle number.
Example 4
Referring to fig. 1, a manganese dioxide nano composite thin film material includes a polyurethane template 1, an atomic layer deposition apparatus reaction chamber 2, and a nickel source precursor container, where the atomic layer deposition apparatus reaction chamber 2 is connected to the nickel source precursor container, the nickel source precursor container is used to provide elemental nickel, the nickel source precursor container is connected to a high-purity nitrogen source, the nickel source precursor is blown into the atomic layer deposition apparatus reaction chamber 2 by the high-purity nitrogen, the atomic layer deposition apparatus reaction chamber 2 is further connected to a nitrogen inlet, a reaction precursor outlet and a byproduct outlet, and is used to discharge the reaction precursor and the byproduct, a polyurethane template 1 is placed inside the atomic layer deposition apparatus reaction chamber 2, and a nickel thin film is composited on the polyurethane template 1.
A preparation method of manganese dioxide nanometer composite film material is disclosed, wherein the step of compounding a nickel simple substance film on a manganese oxide film comprises the following steps:
the first step is as follows: depositing a nickel film on the manganese oxide film by utilizing an atomic layer deposition method to form a composite film;
the second step is that: introducing high-purity nitrogen into a nickel source precursor container, wherein the flow of the high-purity nitrogen is 10-100sccm, then the high-purity nitrogen carries nickel source precursor pulses to enter a reaction chamber 2 of the atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide thin film, and meanwhile, the temperature of the nickel source precursor is controlled to be 50-100 ℃, the pulse time is 1-10s, and the reaction time is 5-10 s;
the third step: after the reaction and adsorption on the surface of the manganese oxide film are saturated, purging the reaction chamber 210 of the atomic layer deposition equipment for 100s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber 2 of the atomic layer deposition equipment;
the fourth step: the reducing precursor container is pulsed into a reaction chamber 2 of the atomic layer deposition equipment, and the pulse time is 100-;
the fifth step: after the second half reaction is finished, the cavity is cleaned for 20-50s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle times are finished, the deposition process of the simple substance nickel is finished, and the proportion of the nickel film is controlled by controlling the cycle deposition times.
The manganese dioxide nano-thin film materials prepared in examples 1 to 4 were characterized by using a Scanning Electron Microscope (SEM), an X-ray diffractometer (XRD) and an electrochemical workstation according to the morphology and structure of the manganese oxide nano-thin film material and the manganese dioxide nano-composite thin film material prepared in the present invention and the electrochemical properties of the electrode material used as a supercapacitor.
In summary, the manganese dioxide nano composite film material and the preparation method thereof provided by the invention realize the composition of the manganese dioxide nano composite film material on the conductive substrate by the atomic layer deposition method, and realize the regulation and control of the appearance and the structure of the manganese dioxide nano film material on the surface of the polyurethane material by controlling the cycle number of atomic layer deposition, the invention takes the polyurethane template 1 as a matrix, and prepares the electrode with excellent electrochemical activity by depositing the manganese dioxide nano film material on the surface of the polyurethane by the atomic layer deposition by virtue of the porous structure of the polyurethane template, and simultaneously fully utilizes the cycle number of the atomic layer deposition to regulate and control the appearance and the thickness of the manganese oxide nano film material, and can realize the deposition of manganese dioxide and other composite films on the polyurethane template 1 to prepare the nano-scale manganese dioxide composite film, and compound oxides with good conductivity and metal films to fully improve the conductivity of the nano-scale manganese dioxide composite, and the electrochemical performance is further improved, the preparation process is environment-friendly, and the preparation cost is low.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The utility model provides a manganese dioxide nanometer composite film material, includes polyurethane template (1), atomic layer deposition equipment reaction chamber (2), precursor source pipeline (3), its characterized in that, atomic layer deposition equipment reaction chamber (2) are connected with precursor source pipeline (3), precursor source pipeline (3) include precursor source container and the valve of control precursor source, multiple precursor source can be placed to precursor source container, the reaction source can be oxidizing source or reducing source, high-purity nitrogen source is connected to precursor source container one end, atomic layer deposition equipment reaction chamber (2) still connect nitrogen inlet and reaction precursor and by-product export, atomic layer deposition equipment reaction chamber (2) inside places polyurethane template (1).
2. The manganese dioxide nanocomposite thin film material according to claim 1, wherein a manganese source precursor container is further connected to the atomic layer deposition apparatus reaction chamber (2).
3. The manganese dioxide nanocomposite thin film material according to claim 1, wherein the atomic layer deposition equipment reaction chamber (2) is further connected with a zinc source precursor container, an aluminum source precursor container or a nickel source precursor container.
4. A method for preparing manganese dioxide nanocomposite thin film material according to claims 1-3, comprising the steps of:
s1: depositing a manganese oxide film on a polyurethane template (1) by means of an atomic layer deposition method
Putting the polyurethane template (1) into a reaction chamber (2) of the atomic layer deposition equipment, wherein the temperature of the reaction chamber (2) of the atomic layer deposition equipment is set to be 150-250 ℃;
s2: introducing high-purity nitrogen into a manganese source precursor container, wherein the flow rate of the high-purity nitrogen is 10-100sccm, then the high-purity nitrogen carries manganese source precursor pulses to enter a reaction chamber (2) of the atomic layer deposition equipment and is chemically adsorbed on the surface of a polyurethane template (1), and meanwhile, the temperature of the manganese source precursor is controlled to be 50-100 ℃, the pulse time is 500-1000ms, and the reaction time is 5-10 s;
s3: after the surface of the polyurethane template (1) is saturated in reaction and adsorption, purging the reaction chamber (2) of the atomic layer deposition equipment for 10-100s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber (2) of the atomic layer deposition equipment;
s4: the oxygen source precursor container is pulsed into a reaction chamber (2) of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container reacts with a manganese source precursor chemically adsorbed on the surface of the polyurethane template (1) in S2;
s5: after the second half reaction is finished, cleaning the cavity for 20-50s by using inert gas nitrogen, and purging redundant reaction precursors and byproducts out of the reaction cavity until a deposition cycle is finished, and after the set cycle number is finished, finishing the deposition process of the manganese oxide film, and controlling the proportion of manganese oxide by setting different cycle numbers;
s6: a film of another oxide or metal may continue to be deposited on top of the manganese oxide film to form a composite film.
5. The method of claim 4, wherein the other oxide film of S6 comprises at least one of an aluminum oxide-zinc oxide composite film or a nickel film.
6. The method of claim 4, wherein the thickness of the manganese dioxide is nanometer.
7. The method for preparing manganese dioxide nano composite film material according to claim 5, depositing aluminum oxide and zinc oxide composite film on the manganese oxide film by using atomic layer deposition method, wherein the step of aluminum oxide composite is as follows:
step 1: firstly, an aluminum source precursor is pulsed into a reaction chamber (2) of the atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and meanwhile, the temperature of the aluminum source precursor is controlled to be 20 ℃ and the pulse time is controlled to be 20-50 ms;
step 2: after the surface of the manganese oxide film is subjected to reaction and adsorption saturation, purging the reaction chamber (2) of the atomic layer deposition equipment for 10-50s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber (2) of the atomic layer deposition equipment;
and step 3: the oxygen source precursor container is pulsed into a reaction chamber (2) of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container reacts with the aluminum source precursor chemically adsorbed on the surface of the manganese oxide film in the step 1;
and 4, step 4: after the second half reaction is finished, cleaning the cavity for 20-50s by using inert gas nitrogen, and purging redundant reaction precursors and byproducts out of the reaction cavity until a deposition cycle is finished, and after the set cycle number is finished, finishing the deposition process of the alumina film, wherein the proportion of alumina can be controlled by controlling the cycle number;
the zinc oxide composite compounding method comprises the following steps:
step 1: firstly, a zinc source precursor is pulsed into a reaction chamber (2) of the atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and meanwhile, the temperature of the aluminum source precursor is controlled to be 20 ℃ and the pulse time is 20-50 ms;
step 2: purging the atomic layer deposition equipment reaction chamber (2) for 10-50s by using inert gas N2, and blowing excessive reaction precursor out of the atomic layer deposition equipment reaction chamber (2);
and step 3: the oxygen source precursor container is pulsed into a reaction chamber (2) of the atomic layer deposition equipment, and the pulse time is 10-50ms, so that the oxygen source precursor container and the zinc source precursor in the step (1) react;
and 4, step 4: after the second half reaction is finished, the cavity is cleaned for 20-50s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle number is finished, the deposition process of the zinc oxide film is finished, and the proportion of zinc oxide can be controlled by controlling the cycle number.
8. The method for preparing manganese dioxide nano composite film material according to claim 5, wherein the step of compounding the nickel simple substance film on the manganese oxide film comprises:
the first step is as follows: depositing a nickel film on the manganese oxide film by utilizing an atomic layer deposition method to form a composite film;
the second step is that: introducing high-purity nitrogen into a nickel source precursor container, wherein the flow rate of the high-purity nitrogen is 10-100sccm, then the high-purity nitrogen carries nickel source precursor pulses to enter a reaction chamber (2) of the atomic layer deposition equipment and is chemically adsorbed on the surface of a manganese oxide film, and meanwhile, the temperature of the nickel source precursor is controlled to be 50-100 ℃, the pulse time is 1-10s, and the reaction time is 5-10 s;
the third step: after the surface of the manganese oxide film is subjected to reaction and adsorption saturation, purging the reaction chamber (2) of the atomic layer deposition equipment for 10-100s by using inert gas N2, and purging redundant reaction precursors out of the reaction chamber (2) of the atomic layer deposition equipment;
the fourth step: the reducing precursor container is pulsed into a reaction chamber (2) of the atomic layer deposition equipment, and the pulse time is 100-;
the fifth step: after the second half reaction is finished, the cavity is cleaned for 20-50s by using inert gas nitrogen, redundant reaction precursors and byproducts thereof are flushed out of the reaction cavity, so that a deposition cycle is finished, and after the set cycle times are finished, the deposition process of the simple substance nickel is finished, and the proportion of the nickel film is controlled by controlling the cycle deposition times.
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