KR20160136550A - Method of manufacturing a nano metal oxide particle having a hollow structure - Google Patents
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- C01B13/322—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process of elements or compounds in the solid state
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Abstract
Description
More particularly, the present invention relates to a hollow structure capable of being applied to a conductive paste, a magnetic material, a catalyst, an electrode, and the like used in various fields such as a secondary battery, a medical device, To a process for producing nano-metal oxide particles.
Electrical properties such as high energy density, high dielectric constant, and high charge discharge characteristics are essential elements of lithium ion batteries in the use of next-generation electric vehicles and energy storage devices.
In order to improve the electrical characteristics, various cathodes of lithium secondary batteries having various types and shapes have been studied through various synthetic methods. Of these, spherical metal oxide particles having a hollow structure are intensively illuminated. Particularly, nano-metal oxide particles having a nano-sized hollow structure have advantages of high specific surface area and short conversion distance of lithium. In addition, it is possible to effectively suppress the electrode efficiency reduction due to the volume expansion of the electrode during the charge and discharge of the lithium ion.
Further, when the hollow nano-metal oxide particles are used as an electrode material, a high energy density of the electrode material can be expected due to efficient interaction between the material and lithium.
On the other hand, the spray drying process is widely applied in industrial chemistry, pharmaceuticals, biotechnology, and food industry as a process capable of obtaining fine powder by evaporating and drying instantaneously by contacting a liquid sample with a hot air stream by spraying and dripping .
Particularly, products such as powdered milk, instant soup, coffee, detergents and dyestuffs are produced through a spray drying process. The spray drying process is advantageous in that a large amount of powder can be produced within a short time.
However, since it is difficult to control the shape and size distribution of the produced particles, it is difficult to apply it to synthesis of electronic material powder requiring nano size narrow particle size distribution condition.
Particularly, nano-metal oxides (for example, Mn x O y, N x O y, Fe O x, C x O y, Co O x, etc.) used as typical electronic materials have been developed in various process technologies for synthesizing nano metal oxide particles having a hollow structure as a next- come. However, the conventional method is complicated in process, and its application in industries requiring mass production due to low yield is extremely limited.
(Patent Document 1) Korean Patent Laid-Open Publication No. 10-2014-0143713
It is an object of the present invention to provide a method for producing nano-metal oxide particles having a hollow structure capable of producing a large number of hollow nano metal oxide particles through simplified processes.
In order to accomplish the above object, in a method of manufacturing a nano-metal oxide particle having a hollow structure according to embodiments of the present invention, a spray drying process using a solution of a metal oxide precursor, a carbonizable organic material, and a solvent is performed To form a composite powder. The composite powder is subjected to a first heat treatment step in a reducing gas atmosphere to form a carbon matrix composite comprising carbonized carbon particles from the organic material in the composite powder and metal particles reduced from the metal oxide particles in the composite powder. Thereafter, the carbon matrix composite is subjected to a second heat treatment process using a kirkendall diffusion effect under an oxidizing atmosphere to form hollow nano metal oxide particles from the carbon matrix composite.
In one embodiment of the present invention, the metal oxide precursor may be composed of metal acetate, nitrate, chloride, hydroxide, carbonate, or oxide.
In one embodiment of the present invention, the carbonizable organic material is selected from the group consisting of sucrose, dextrin, citric acid, ethyleneglycol, polyethyleneglycol, polyvinylpyrrolidone (PVP), polyethylenedioxythiophene (PEDOT), polyacrylonitrile (polyvinyl alcohol), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinylacetate, polystyrene, polyvinylchloride, polyetherimide, polybenzimidasol, caprolactone, PA-6, polytrimethylenetetraphthalate (PTT), poly D, L-lactic acid (PDLA), polycarbonate, polydioxanone, polyglicolide or dextran.
In one embodiment of the present invention, the solvent is selected from the group consisting of water, ethanol, methanol, isopropanol, DCM, methylene chloride, acetic acid, acetonitrile, DMA, N-dimethylacetamide, , tetrahydrofuran, formic acid, pyridine, aceton, acetonitrile, chloroform, ethyl acetate or trifluoroethanol.
In one embodiment of the present invention, the metal oxide precursor contained in the solution may have a concentration of at least 0.001 M and a saturation solubility of the metal oxide precursor.
In one embodiment of the present invention, the inlet and outlet of the jetting portion used in the spray drying process may be adjusted to a temperature in the range of 50 to 500 ° C.
In one embodiment of the present invention, the first heat treatment step may be performed in a single gas of air, nitrogen, and hydrogen, or in a mixed gas atmosphere in which hydrogen and argon are mixed.
In one embodiment of the present invention, the first heat treatment process may be performed at a temperature ranging from 10 to 1,500 ° C.
In one embodiment of the present invention, the second heat treatment process may be performed in an atmosphere of air or oxygen.
In one embodiment of the present invention, the second heat treatment may be performed at a temperature ranging from 100 to 1,500 ° C.
In one embodiment of the present invention, in the second heat treatment step, the surface portion of the metal particles contained in the carbon matrix composite is oxidized to form surface-oxidized metal oxide particles in the carbon matrix, The inside of the metal oxide particles is oxidized through the above-described Kerken diffusion process to form hollow metal oxide particles in the carbon matrix, and carbon is removed from the carbon matrix composite to form hollow metal oxide particles dispersed with each other .
In the present invention, hollow metal oxide particles can be produced in large quantities through a simplified manufacturing process such as a spray drying process and a ketene diffusion process. Accordingly, when the hollow metal oxide particle is applied to an electrode material due to hollows present therein, the hollow metal oxide particles can effectively receive the charge and discharge characteristics, that is, the mechanical stress applied to the electrode during the charge and discharge of the secondary battery.
In addition, the nano-sized hollow metal oxide particles effectively suppress the cohesion of the metal oxide particles during the discharge process so that the electrode containing the hollow metal oxide particles can maintain its structure and electrical characteristics continuously do.
Meanwhile, since the nano-sized hollow metal oxide particles are easily synthesized by using the composite powder having various compositions by applying the spray drying process, the metal oxide material having a hollow structure or the ceramic-metal oxide material having various compositions have. Thus, hollow metal oxide particles can be applied to various fields such as a multilayer ceramic capacitor, a secondary battery, a medical instrument, a catalyst, and the like. In addition, the hollow metal oxide particles synthesized in the present invention can be applied to various fields due to their properties such as improved oxidation resistance and stability.
Also, the composition and shape of the hollow metal oxide particles can be changed through control of the composition of the material forming the solution, the concentration of the carbonizable organic substance, the inlet temperature and the outlet temperature of the injection part used in the spray drying process, and the heat treatment temperature, The concentration of the powder material to be dissolved in the solution, the reduction temperature, the particle size and the thickness of the cells formed by controlling the oxidation temperature can be controlled.
In addition, the Kirkendall diffusion effect is applied to a mass-production spray-drying process, which simplifies the process and has the technology to mass-produce hollow spherical nano powder.
Since the hollow nano-metal oxide powder of hollow structure can effectively accommodate mechanical stress during charging and discharging due to the formation of hollow therein, it effectively suppresses the re-agglomeration due to nano-powdering of metal oxide particles during charging and discharging, And electrical characteristics can be maintained continuously. Therefore, hollow spherical metal oxide particles are very ideal as an electrode material of a lithium secondary battery and can be applied to oxides of various transition metals.
1 is a view for explaining a reaction mechanism for forming SnO 2 particles having a hollow structure according to an embodiment of the present invention.
2 is a scanning electron microscope (SEM) photograph showing a composite powder composed of tin oxalate [C 2 O 4 Sn] and PVP (polyvinylpyrrolidone) synthesized by a spray drying process according to Synthesis Example 1.
3 is a graph showing the results of thermal analysis (TG) on the composite powder of FIG.
4 is a graph showing the XRD analysis results of the composite powder of FIG.
5 is a scanning electron microscope (SEM) photograph showing a carbon matrix composite composed of low-crystalline Sn particles and carbon particles produced through a first heat treatment step in a reducing gas atmosphere after synthesis according to Synthesis Example 1.
6A and 6B are transmission electron microscope (TEM) photographs showing the carbon matrix composite of FIG.
7 is a graph showing line profiling results of the carbon matrix composite of FIG.
FIG. 8 is an element mapping image of tin, oxygen, and carbon included in the carbon matrix composite of FIG.
FIG. 9 is a scanning electron microscope (SEM) photograph showing SnO 2 particles of a hollow structure formed through a second heat treatment process on a carbon matrix composite synthesized according to Synthesis Example 2. FIG.
10 is a transmission electron microscope (TEM) photograph showing SnO 2 particles of the hollow structure of FIG.
FIGS. 11A, 11B, and 11C are high-resolution transmission micrographs showing SnO 2 particles of the hollow structure of FIG.
12 is a photograph showing a SAED pattern of SnO 2 particles of the hollow structure of FIG.
13 is a photograph showing the results of thermal analysis of SnO 2 particles of the hollow structure of FIG. 9 in an air atmosphere.
FIG. 14 is an element mapping image of tin, oxygen, and carbon contained in SnO 2 particles of the hollow structure of FIG. 9; FIG.
15 is a graph showing the XRD analysis results of SnO 2 particles of the hollow structure of FIG.
16 is a graph showing the results of thermal analysis of SnO 2 particles of the hollow structure of FIG. 9 in an air atmosphere.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the accompanying drawings, the sizes and the quantities of objects are shown enlarged or reduced from the actual size for the sake of clarity of the present invention.
The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprise", "comprising", and the like are intended to specify that there is a feature, step, function, element, or combination of features disclosed in the specification, Quot; or " an " or < / RTI > combinations thereof.
On the other hand, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
According to the method of manufacturing a nano-metal oxide particle having a hollow structure according to embodiments of the present invention, a spray-drying process using a solution of a metal oxide precursor, a carbonizable organic material, and a solvent is first performed to form a composite powder. Thereafter, the composite powder is subjected to a first heat treatment step in a reducing gas atmosphere to form a carbon matrix composite comprising carbonized carbon particles from the organic material in the composite powder and metal particles reduced from the metal oxide particles in the composite powder do. Thereafter, the carbon matrix composite is subjected to a second heat treatment process using a kirkendall diffusion effect under an oxidizing atmosphere to form hollow nano metal oxide particles from the carbon matrix composite.
More particularly, the composite powder is first formed by a spray drying process using a solution of a metal oxide precursor, a carbonizable organic compound, and a solvent. That is, according to the spray drying process, a solution comprising a metal oxide precursor, a carbonizable organic substance, and a solvent is prepared. Thereafter, the solution is injected through the injection part to generate droplets. The droplets are then dried to form composite powders. This allows a large amount of composite powders to be formed through a simplified spray drying process.
Examples of the metal oxide precursor include acetate, nitrate, chloride, hydroxide, carbonate, oxide, or a mixed salt thereof.
The carbonizable organic material may be selected from the group consisting of sucrose, dextrin, citric acid, ethyleneglycol, polyethyleneglycol, PVP (polyvinylpyrrolidone), PEDOT (polyethylenedioxythiophene), PAN (polyacrylonitrile), polyacrylic acid (PAA), polyvinylalcohol (PVA), polymethyl methacrylate , Polyvinylidene fluoride (PVDF), polyvinylacetate (PV), polystyrene, polyvinylchloride, polyetherimide, polybenzimidasol, polyethyleneoxide, poly-caprolactone (PCL), polyamide -6), polytrimethylenetetraphthalate (PTT), PDLA (poly D, L-lactic acid), polycarbonate, polydioxanone, polyglicolide, dextran or mixtures thereof.
The solvent may be selected from the group consisting of water, ethanol, methanol, isopropanol, DCM, methylene chloride, acetic acid, acetonitrile, DMA, m-cresol, toluene, tetrahydrofuran, formic acid, , Acetonitrile, chloroform, ethyl acetate, trifluoroethanol, or mixtures thereof.
According to an embodiment of the present invention, the metal oxide precursor contained in the solution may have a concentration of not less than 0.01 M and a saturation solubility of the precursor forming the hollow metal oxide particles.
On the other hand, the concentration of the organic substance in the solution can be adjusted so that the organic substance can have a concentration ranging from 10 to 300% by weight based on the hollow nano-metal oxide particles to be finally produced.
According to an embodiment of the present invention, the inlet of the jetting portion into which the solution is introduced may be maintained at a temperature in the range of 50 to 500 ° C. On the other hand, the outlet of the injection part can be maintained at a temperature in the range of 50 to 500 ° C.
Thereafter, the composite powder is subjected to a first heat treatment step in a reducing gas atmosphere to form a carbon matrix composite from the composite powder.
At this time, the first heat treatment process may be performed in a single gas of air, nitrogen, and hydrogen, or in a mixed gas atmosphere in which hydrogen and argon are mixed.
The first heat treatment may be performed at a temperature ranging from 10 to 1,500 ° C. Through the first heat treatment step, the organic material contained in the composite powder is carbonized so that the carbon particles have a carbon matrix shape, and each of the metal oxide particles in the composite powder is reduced and dispersed in the carbon matrix as metal particles.
If the carbon matrix is not formed, there is a problem that the metal oxide particles aggregate and have a bulk state. Therefore, the carbonized carbon matrix can inhibit mutual aggregation of the metal particles.
Thereafter, the carbon matrix composite is subjected to a second heat treatment process using a kirkendall diffusion effect under an oxidizing atmosphere to form hollow nano metal oxide particles from the carbon matrix composite.
Here, the second heat treatment process may be performed in an atmosphere of air or oxygen. The second heat treatment may be performed at a temperature ranging from 100 to 1,500 ° C.
Describing the detailed process of the second heat treatment process, surface oxidized metal oxide particles are first formed in the carbon matrix by oxidizing the surface portion of the metal particles contained in the carbon matrix composite. Thereafter, the interior of the surface oxidized metal oxide particles is oxidized through the Kerken diffusion process to form hollow metal oxide particles in the carbon matrix.
At this time, a hollow is formed due to the difference in the diffusion speed between the different minerals due to the Kirkendall diffusion effect. That is, in the Kirkendall effect, the diffusion rate at which the metal cations are diffused toward the surface of the surface oxidized metal oxide particles is lower than the diffusion rate at which oxygen ions are diffused from the outside toward the center of the surface oxidized metal oxide high. Accordingly, as the additional metal oxide particles on the surface of the surface-oxidized metal oxide formed at the same time by being a plurality of public grow by interlocking therein preliminary core cell (Sn @ SnO 2) is formed as an intermediate product.
The difference between the diffusion rate of the metal cation and the diffusion rate of the oxygen ion is related to the ion radius. That is, the metal cations have ionic radii (Sn 2+ = 93 pm, Sn 4+ = 69 pm) smaller than the ionic radius of oxygen (140 pm). Therefore, the cavity formed by the Kirkendall diffusion effect is generated from the interface where the metal and the metal oxide are in contact with each other, and the generated pluralities of the cavities grow by bonding with each other. As a result, A hollow is formed inside the particle.
Subsequently, the carbon is removed from the carbon matrix composite to form mutually dispersed hollow metal oxide particles. Wherein the carbon may be removed from the carbon matrix composite by burning the carbon.
The nanostructured metal oxide particles produced according to embodiments of the present invention may have an average particle size in the range of 0.1 to 5000 nm. In addition, the nano-metal oxide particles having a hollow structure may have a shell in the range of 0.01 to 1000 nm.
The composition of the hollow nano metal oxide particles may be selected from the group consisting of SnO 2 , SnO 2 -TiO 2 , Fe 2 O 3 , Co 3 O 4 , LiNi 0.5 Mn 1.5 O 4 , WO 3 , CoMn 2 O 4 , ZnCo 2 O 4 , CuCo 2 O 4, LiMn 2 O 4, NiCo 2 O 4, Li 4 Ti 5 O 12, Li 4 Ti 5 O 12 -
1 is a view for explaining a reaction mechanism for forming SnO 2 particles having a hollow structure according to an embodiment of the present invention.
Referring to Fig. 1, Synthesis Example 1, Synthesis Example 2, and Example 1 will be described as follows.
Synthesis Example 1: Single-component hollow SnO 2 Composite Powder Synthesis Consisting of
A composite powder in which SnO 2 hollow is formed as the most basic Sn-based material as a cathode of a lithium secondary battery was synthesized. A composite powder composed of SnO 2 hollowed by a spray drying process under various conditions was prepared by varying the concentration of the starting solution, the kind and amount of the organic material added to the solution, the inlet and outlet temperatures during the drying process, and the like.
Sn oxalate was used as the metal oxide precursor as a raw material of the Sn component. As possible organic materials are carbonized PVP (Polyvinylpyrrolidone): it was used (M w 1,300,000). Distilled water was used as a solvent.
More specifically, the starting solution is PVP of Sn oxalate, and Xg Xg of: was prepared by dissolving the (M w 1,300,000) in distilled water. The prepared solution is supplied to the reactor chamber after dropletization through the injection part. Thereafter, the inlet of the jetting portion to form the jetted droplet was dried in a reaction chamber maintained at 300 ° C and the outlet was maintained at 250 ° C, and the composite powder was collected in a collector.
2 is a scanning electron microscope (SEM) photograph showing a composite powder composed of tin oxalate [C 2 O 4 Sn] and PVP (polyvinylpyrrolidone) synthesized by a spray drying process according to Synthesis Example 1. Figure 3 is a graph showing the results of thermal analysis (TG) on the composite powder of Figure 1; 4 is a graph showing the XRD analysis results of the composite powder of FIG.
Referring to FIG. 2, it can be confirmed that a composite powder having pores composed of Sn oxalate and PVP is formed as a powder synthesized by a spray drying process.
Referring to FIG. 3, the result of thermal analysis of the synthesized composite powder is shown in FIG. 3, and the amount of pyrolyzed PVP added during the production of the solution can be confirmed through weight reduction in the air.
Referring to FIG. 4, it can be confirmed that low-
Synthesis Example 2: Carbon matrix composite synthesis
The composite powder formed according to Synthesis Example 1 was subjected to a first heat treatment step in a reducing atmosphere to synthesize a carbon matrix composite. The first heat treatment step was performed in a reducing atmosphere at 500 DEG C for 5 hours.
5 is a scanning electron microscope (SEM) photograph showing a carbon matrix composite composed of low-crystalline Sn particles and carbon particles produced through a first heat treatment step in a reducing gas atmosphere after synthesis according to Synthesis Example 1. 6A and 6B are transmission electron microscope (TEM) photographs showing the carbon matrix composite of FIG.
5, 6A, and 6B, it is possible to confirm a form in which Sn metal particles are precipitated in the carbon matrix through a first heat treatment process in a reducing atmosphere with respect to the synthesized composite powder. At this time, Sn nanoparticles having a size of 100 to 200 nm can be identified.
7 is a graph showing line profiling results of the carbon matrix composite of FIG.
Referring to FIG. 7, it is possible to confirm the Sn phase after reduction through the phase analysis result. In addition, line profiling analysis of the particles contained in the carbon support confirmed that the particle component is Sn.
FIG. 8 is an element mapping image of tin, oxygen, and carbon included in the carbon matrix composite of FIG.
Referring to FIG. 8, Sn present in the carbon support is identified through a mapping image of elements of tin, oxygen, and carbon.
Example 1: Formation of hollow nano-metal oxide particles
The carbon matrix composite formed in Synthesis Example 2 was subjected to a second heat treatment process at 400 캜 for 5 hours in an oxidizing atmosphere to form hollow nano metal oxide particles in the carbon matrix. Thereafter, the carbon remaining in the carbon matrix was burned to remove hollow nano-metal oxide particles.
FIG. 9 is a scanning electron microscope (SEM) photograph showing SnO 2 particles of a hollow structure formed through a second heat treatment process on a carbon matrix composite synthesized according to Synthesis Example 2. FIG. 10 is a transmission electron microscope (TEM) photograph showing SnO 2 particles of the hollow structure of FIG.
9 and 10, hollow spherical nano-metal oxide particles were formed through a second heat treatment process in air on the carbon matrix composite formed according to Synthesis Example 1. As shown in FIG.
11A, 11B and 11C are high resolution transmission microscope photographs showing SnO 2 particles of the hollow structure of FIG.
Referring to FIGS. 11A, 11B, and 11C, a high-resolution photograph was observed using a transmission microscope having a high resolution. As a result, it can be confirmed that SnO 2 particles having a hollow structure are uniformly dispersed. The average size of the hollow metal oxide particles composed of SnO 2 is 150 nm and the average shell thickness is 30 nm.
12 is a photograph showing a SAED pattern of SnO 2 particles of the hollow structure of FIG.
Referring to FIG. 12, in the high-resolution TEM photograph, a clear crystal plane of 0.34 nm is observed, which corresponds to the (110) plane of SnO 2 . As a result, analysis of the SAED pattern revealed a specific ring pattern of SnO 2 .
13 is a photograph showing the results of thermal analysis of SnO 2 particles of the hollow structure of FIG. 9 in an air atmosphere.
Referring to FIG. 13, it can be confirmed from the result of thermal analysis in an air atmosphere that carbon exists in the structure after reduction.
FIG. 14 is an element mapping image of tin, oxygen, and carbon contained in SnO 2 particles of the hollow structure of FIG. 9; FIG.
Referring to FIG. 14, tin and oxygen are uniformly distributed in the structure and the carbon is pyrolyzed and removed through the result of the element mapping.
15 is a graph showing the XRD analysis results of SnO 2 particles of the hollow structure of FIG.
Referring to FIG. 15, through the first heat treatment process of the reduction process and the second heat treatment process subsequent to the oxidation process, SnO 2 is produced in the hollow nano metal oxide particles from the Sn metal particles through the X-ray diffraction analysis result Can be confirmed.
16 is a graph showing the results of thermal analysis of SnO 2 particles of the hollow structure of FIG. 9 in an air atmosphere.
Referring to FIG. 16, it can be confirmed that carbon is not present in the structure through the result of thermal analysis in an air atmosphere.
Synthesis Example 3: Single-component hollow nano NiO particle synthesis
NiO particles were prepared by a spray drying process under the same production conditions as in Synthesis Example 1, except that the composition of the powder was changed from iron to nickel.
Synthesis Example 4: Single-component hollow nano-Co 3 O 4 Particle synthesis
Co 3 O 4 particles were prepared by a spray drying process in the same manner as in Synthesis Example 1, except that the composition of the powder was changed from iron to cobalt.
Synthesis Example 5: Single component hollow nanoporous WO 3 Particle synthesis
WO 3 particles were prepared by a spray drying process in the same manner as in Synthesis Example 1, except that the composition of the powder was changed from iron to tungsten.
Synthesis Example 5: Single component hollow nano Y 2 O 3 Particle synthesis
Y 2 O 3 particles were prepared by a spray drying process in the same manner as in Synthesis Example 1, except that the composition of the powders was changed from iron to iridium.
Synthesis Example 6: Single component hollow nano TiO 2 Particle synthesis
TiO 2 particles were prepared by a spray drying process in the same manner as in Synthesis Example 1 except that the composition of the powder was changed from iron to titanium.
Synthesis Example 7 Synthesis of Single Component Hollow Nano CuO Particles
CuO particles were prepared by a spray drying process in the same manner as in Synthesis Example 1, except that the composition of the powders was changed from iron to copper.
Synthesis Example 8: Multicomponent hollow nano-SnO 2 -TiO 2 Particle synthesis
Particles composed of hollow nano metal oxides of various compositions were prepared by an electrospinning process in the same manner as in Synthesis Example 1 except that tin and titania were used as the powder composition.
Synthesis Example 9: Multicomponent hollow nano-Fe 2 O 3 -CuO Particle synthesis
Particles composed of hollow nano metal oxides of various compositions were prepared by an electrospinning process in the same manner as in Synthesis Example 1 except that tin and titania were used as the powder composition.
Synthesis Example 10: Multicomponent hollow nano-SnO 2 -CuO Particle synthesis
Particles composed of hollow nano metal oxides of various compositions were prepared by an electrospinning process in the same manner as in Synthesis Example 1 except that tin and titania were used as the powder composition.
Synthesis Example 11: Multicomponent hollow nano-SnO 2 -Co 3 O 4 Particle synthesis
Particles composed of hollow nano metal oxides of various compositions were prepared by an electrospinning process in the same manner as in Synthesis Example 1 except that tin and titania were used as the powder composition.
On the other hand, nano metal oxide particles having a hollow structure can be easily formed through the processes described in Synthesis Example 2 and Example 1 using the composite powder formed in Synthesis Examples 3 to 11.
Accordingly, when the Kirkendall effect is applied to a spray-drying process capable of mass production, the metal oxide powder having a hollow structure as described above can be controlled to have a diameter of several tens of microns (占 퐉) at a size of several nanometers and has a high specific surface area, Gas sensors, and high specific surface area hollow nano-sized metal oxide particles required in the medical field.
More specifically, in the present invention, by controlling the inlet temperature and outlet temperature of the injection part and the kind and amount of the organic substance added to the starting solution by using the spray drying process, the solution is injected to generate droplets, Thereby forming a composite powder of a metal oxide composite structure. Thereafter, the low-crystalline metal oxide particles in the composite powder are reduced to metal particles in a reducing gas atmosphere, and the reduced metal particles are oxidized to metal oxide particles again in an oxidizing atmosphere.
In this case, the dense metal particles formed during the reduction are changed into hollow nano-metal oxide particles by the difference in ion diffusion rate between two adjacent materials due to the Kirkendall effect, and ultimately, metal oxide particles having hollow structure and nano- .
Metal oxide particles having a hollow structure according to embodiments of the present invention can be used as a negative electrode material for a secondary battery. The metal oxide particles such as tin oxide, iron oxide, nickel oxide, tin oxide-copper oxide, tin oxide-nickel oxide, tin oxide-iron oxide and the like have relatively high volume expansion characteristics. At this time, the metal oxide particles having a hollow structure are formed with hollows as a space for compensating for volume expansion, thereby solving the problem of application as a cathode material. Thus, when spherical hollow particles having a nano size are used as the electrode material, a space for compensating the volume expansion during the charging and discharging process can be secured, thereby effectively overcoming the nanoization problem of the powder due to the volume expansion of the electrode can do. In addition, during the discharge process, the metal oxide particles maintain a spherical shape continuously, so that a high energy density can be expected when used as a cathode material.
On the other hand, the present invention can be applied to various fields such as multilayer ceramic capacitors, medical instruments, catalysts, and the like, by using hollow spherical nano-sized metal oxide particles having various compositions.
Claims (11)
Performing a first heat treatment process on the composite powder in a reducing gas atmosphere to form a carbon matrix composite comprising carbonized carbon particles from the organic material in the composite powder and metal particles reduced from the metal oxide particles in the composite powder; ; And
Performing a second heat treatment process on the carbon matrix composite using an effect of a kirkendall diffusion under an oxidizing atmosphere to form hollow nano metal oxide particles from the carbon matrix composite, Oxide particles.
Wherein the metal oxide precursor is at least one selected from the group consisting of metal acetate, nitrate, chloride, hydroxide, carbonate and oxide. Wherein the method comprises the steps of:
Oxidizing the surface portion of the metal particles contained in the carbon matrix composite to form surface oxidized metal oxide particles in the carbon matrix;
Oxidizing the surface oxidized metal oxide particles through the Kerken diffusion process to form hollow metal oxide particles in the carbon matrix; And
And removing carbon from the carbon matrix composite to form mutually dispersed hollow metal oxide particles.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107399738A (en) * | 2017-08-11 | 2017-11-28 | 中国科学院合肥物质科学研究院 | A kind of method that magnetic field modulation Kinkendal Effect prepares hollow/mesoporous nanostructured materials |
| KR20200109975A (en) * | 2019-03-15 | 2020-09-23 | 충북대학교 산학협력단 | Nanocomposite, electrode composition comprising the same and manufactuaring method therefor |
| KR20210048052A (en) * | 2019-10-23 | 2021-05-03 | 한국과학기술연구원 | Hollow porous nanoparticles and a preparation method thereof |
| WO2021261334A1 (en) * | 2020-06-23 | 2021-12-30 | 国立大学法人静岡大学 | Nanoparticles for detecting or quantifying target substance and production method therefor, and method for detecting or quantifying target substance |
-
2015
- 2015-05-20 KR KR1020150070144A patent/KR20160136550A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107399738A (en) * | 2017-08-11 | 2017-11-28 | 中国科学院合肥物质科学研究院 | A kind of method that magnetic field modulation Kinkendal Effect prepares hollow/mesoporous nanostructured materials |
| KR20200109975A (en) * | 2019-03-15 | 2020-09-23 | 충북대학교 산학협력단 | Nanocomposite, electrode composition comprising the same and manufactuaring method therefor |
| KR20210048052A (en) * | 2019-10-23 | 2021-05-03 | 한국과학기술연구원 | Hollow porous nanoparticles and a preparation method thereof |
| WO2021261334A1 (en) * | 2020-06-23 | 2021-12-30 | 国立大学法人静岡大学 | Nanoparticles for detecting or quantifying target substance and production method therefor, and method for detecting or quantifying target substance |
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