CN110923646A - Composite carbon film and its preparation method and application - Google Patents
Composite carbon film and its preparation method and application Download PDFInfo
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Abstract
本发明提供了一种复合型碳薄膜及其制备方法和应用。所述复合型碳薄膜的制备方法包括如下步骤有：将碳靶材和能量密度贡献主体元素靶材在真空条件下进行磁控溅射处理，在基体上生长复合型碳薄膜层。本发明复合型碳薄膜的制备方法一方面赋予制备的复合型薄膜的比表面积增大，可以保护活性物质，防止其聚集和破裂；另一方面能稳定碳与活性物质电子传输，又可以减少和阻止电解液与能量密度贡献主体之间的不可逆副反应，减少固体电解质膜(SEI)的产生；另外，形成的碳硅复合型薄膜不仅可以防止电解质的进入和进一步与纳米级氧化物接触，还可以减轻锂化过程氧化物上的应变；其次，其条件易控，有效保证生长的复合型碳薄膜化学性能稳定，效率高。
The invention provides a composite carbon film and a preparation method and application thereof. The preparation method of the composite carbon film includes the following steps: performing magnetron sputtering treatment on the carbon target and the energy density contributing main element target under vacuum conditions, and growing the composite carbon film layer on the substrate. On the one hand, the preparation method of the composite carbon film of the present invention increases the specific surface area of the prepared composite film, which can protect the active material and prevent it from agglomerating and breaking; Prevent irreversible side reactions between the electrolyte and the energy density contributing host, reducing the generation of solid electrolyte membrane (SEI); in addition, the formed carbon-silicon composite film can not only prevent the entry of electrolyte and further contact with nanoscale oxides, but also It can reduce the strain on the oxide during the lithiation process; secondly, the conditions are easy to control, which effectively ensures that the grown composite carbon film has stable chemical properties and high efficiency.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a composite carbon film and a preparation method and application thereof.
Background
Lithium batteries are one of the most potential energy storage systems today and have been widely used due to their advantages of safety, high capacity, high energy density, low cost, long cycle life, high operating voltage, etc. For example, lithium batteries have been widely used in a variety of electronic products as a portable new energy source due to their portable characteristics. Among them, the performance of the electrode material directly determines the performance of the lithium ion battery.
Currently, the research direction of the negative electrode material for lithium ion batteries is developing towards the power type battery material with high specific capacity, high multiplying power, high cycle performance and high safety performance.
However, the volume expansion of the silicon negative electrode is high in the charging and discharging processes of the battery, so that the pulverization of the material is easily caused, and the electric contact with a current collector is lost, so that the cycle performance of the silicon negative electrode is rapidly reduced; silicon is used as a semiconductor material, the conductivity is much lower than that of a graphite cathode, the irreversible degree in the lithium ion de-intercalation process is large, the first coulombic efficiency of the silicon-based cathode material is low, the normal capacity exertion of the battery is influenced, the volume change of an active substance in the circulation process can cause structural damage, and the problems can be improved by adding carbon.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a composite carbon film and a preparation method thereof, so as to solve the technical problems of low efficiency and low capacity of the conventional silicon coulombs.
The invention also aims to provide an electrode plate and application thereof, so as to solve the technical problems of charge-discharge cycle and unsatisfactory high-rate performance of the conventional silicon electrode plate.
In order to achieve the object of the present invention, in one aspect of the present invention, a method for preparing a composite carbon thin film is provided. The preparation method of the composite carbon film comprises the following steps:
and carrying out magnetron sputtering treatment on the carbon target material and the energy density contribution main element target material under a vacuum condition, and growing a composite carbon film layer on the substrate.
In another aspect of the present invention, a composite carbon film is provided. The composite carbon film is prepared according to the preparation method of the invention.
In yet another aspect of the present invention, an electrode sheet is provided. The electrode plate is prepared by the preparation method; wherein the substrate is a current collector.
In still another aspect of the invention, the invention provides an application of the electrode plate in a lithium ion battery or a super capacitor.
Compared with the prior art, the preparation method of the composite carbon film directly adopts the magnetron sputtering method to deposit and form the carbon target material and the energy density contribution main element target material. Thus, the nanometer energy density contribution main body element is embedded in the carbon matrix, so that on one hand, the specific surface area of the prepared composite film is increased, the existence of lithium ions is facilitated, the volume change can be adjusted, the active substance can be protected, and the aggregation and the fracture of the active substance can be prevented; on the other hand, the electronic transmission of carbon and active materials can be stabilized, irreversible side reactions between the electrolyte and an energy density contribution body can be reduced and prevented, and the generation of a Solid Electrolyte Interface (SEI) is reduced; in addition, the formed composite carbon film can not only prevent the electrolyte from entering and further contacting with the nano-scale oxide, but also relieve the strain on the oxide in the lithiation process; and secondly, a film layer is grown by adopting a magnetron sputtering method, the conditions are easy to control, the chemical property stability of the grown composite carbon film is effectively ensured, the efficiency is high, and the method is suitable for industrial large-scale production.
The electrode plate of the invention is formed by directly growing on the current collector by using the preparation method of the invention. And the composite carbon film layer contained in the electrode plate can effectively prevent the electrolyte from directly contacting with the nano-scale energy density contribution main body elements, can reduce and prevent irreversible side reactions between the electrolyte and the energy density contribution main body, reduces the generation of a Solid Electrolyte Interface (SEI), improves the cycling stability of the electrode, reduces the stress of periodic volume change, and stabilizes the structural stability in the lithium ion intercalation/deintercalation process, thereby endowing the electrode plate with good cycling reversibility, keeping higher specific capacity, having large multiplying power performance and high safety performance.
Because the electrode plate has the advantages, the lithium ion battery containing the electrode plate has high lithium ion conduction rate, high structural stability and high capacity retention rate, the lithium ion battery has high first charge-discharge efficiency, and the lithium ion battery or the super capacitor has high rate performance, good safety performance and good cycle performance, the cycle life is prolonged, and the safety performance is high. The super capacitor containing the electrode slice has small internal resistance, fast charge and discharge and excellent energy storage property.
Drawings
Fig. 1 is a coulomb efficiency chart of a lithium ion battery containing a composite carbon thin film electrode material obtained in the seventh embodiment of the present invention;
FIG. 2 is a diagram of cycle performance of a lithium ion battery containing a composite carbon thin film electrode material obtained in example seven of the present invention;
fig. 3 is a comparison graph of the first charge-discharge curves at 150mA/g of the lithium ion battery made of the composite carbon thin film electrode material provided in the eighth, ninth, tenth, eleventh, and twelfth embodiments of the present invention; wherein, curve 1 is the first charge and discharge curve of the lithium ion battery obtained in example eight, curve 2 is the first charge and discharge curve of the lithium ion battery obtained in example nine, curve 3 is the first charge and discharge curve of the lithium ion battery obtained in example ten, curve 4 is the first charge and discharge curve 1 of the lithium ion battery obtained in example eleven, and curve 5 is the first charge and discharge curve of the lithium ion battery obtained in example twelve;
FIG. 4 is a 3000mah/g cycle performance diagram of a lithium ion battery containing the composite carbon thin film electrode material obtained in example VII of the present invention;
fig. 5 is a comparison graph of the charge and discharge capacities of the lithium ion battery made of the composite carbon film electrode material obtained in the seventh embodiment of the present invention and a pure carbon film.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide a method for preparing a composite carbon film. The preparation method of the composite carbon film comprises the following steps:
and carrying out magnetron sputtering treatment on the carbon target material and the energy density contribution main element target material under a vacuum condition, and growing a composite carbon film layer on the substrate.
In the magnetron sputtering treatment process, the energy density contribution main element target material dopes the carbon target material, so that a film layer which takes carbon as a matrix and takes the energy density contribution main element as a doping element grows on the matrix, and a larger surface area is formed in the composite carbon film for accommodating lithium ions, so that the interface resistance of the composite carbon film is remarkably reduced, and meanwhile, the carbon matrix contained in the composite carbon film can effectively prevent the electrolyte from being in direct contact with the nanoscale energy density contribution main element, so that irreversible side reactions between the electrolyte and the energy density contribution main element can be reduced and prevented, the generation of a solid electrolyte film (SEI) is reduced, the stress of periodic volume change is reduced, and the structural stability in the lithium ion embedding/removing process is maintained.
Thus, in an embodiment, the energy density contributing host element target comprises at least one elemental or alloy target of silicon, tin, titanium, vanadium, aluminum, gold, silver, copper, molybdenum, cobalt, manganese, titanium oxide, manganese oxide, tin oxide, vanadium oxide or at least one compound target of silicon, tin, titanium, vanadium, aluminum, gold, silver, copper, molybdenum, cobalt, manganese, titanium oxide, manganese oxide, tin oxide, vanadium oxide. In a specific embodiment, each target should be a high purity target material, such as a corresponding ceramic target material with a purity of 99.999%. The elements contained in the target material of the energy density contribution main body element have high energy density contribution characteristics, can form larger surface area for accommodating lithium ions, thereby obviously reducing the internal resistance of the composite carbon film, and has high stability of electrochemical reaction under the action of a carbon matrix.
In one embodiment, the sputtering power of the magnetron sputtering process satisfies: the ratio of the power of sputtering the carbon target material to the power of sputtering the energy density to the power of the main element target material is 10: 1-1: 10. In a specific embodiment, the power ratio of sputtering the carbon target to sputtering the energy density contributing host element target is between 4:1 and 1: 4. The energy density in the composite carbon film is controlled to contribute to the doping content of the main element by controlling the sputtering power ratio of the two targets, namely, the internal resistance and the corresponding electrochemical performance of the composite carbon film are optimized by indirectly optimizing the doping content of the main element contributed by the energy density.
In another embodiment, the temperature of the substrate is controlled to be 200 ℃ to 800 ℃ during the sputtering process; the sputtering atmosphere is at least one of nitrogen and argon or a mixed gas atmosphere thereof. When two or more gases are used, the volume ratio of the mixed gas can be adjusted as required. Wherein, the purity of nitrogen and argon can be 99.998%. The spacing between the substrate and the target is preferably 30-90mm, in particular 60 mm. The quality of the growing composite carbon film is ensured and improved by controlling the temperature of the matrix and the high-purity inert environment, so that the electrochemical performance of the composite carbon film is ensured and improved.
In addition, under the conditions of the co-sputtering process, the sputtering time can be controlled to control the thickness of the grown carbon-silicon composite thin film, such as but not limited to 50nm-10 μm, such as 0.1-10 μm, and specifically such as 1 μm.
The carbon target material in each embodiment of the preparation method can be directly used as an existing carbon target material. In a particular embodiment, the carbon target should be pure.
In an embodiment, the substrate in each of the above embodiments is a negative electrode current collector of a chemical power source. In a particular embodiment, the substrate may be a stainless steel substrate.
Therefore, the preparation method of the composite carbon film directly adopts the co-sputtering method to deposit and form the carbon target material and the energy density contribution main element target material. Thus, the composite carbon film which is deposited and grown takes carbon as a substrate, namely a film framework support, and the nanometer energy density contribution main element is taken as a doping element to be doped in the carbon as the substrate, so that a larger surface area is formed in the composite carbon film for accommodating lithium ions, and the composite carbon film has the characteristics of small interface resistance, large surface area and the like and has the characteristic of high capacity which can well exert the energy density contribution main element. The composite carbon film with the characteristics can effectively prevent the direct contact of the electrolyte and the elements of the nano-scale energy density contribution main body, reduce and prevent irreversible side reactions between the electrolyte and the energy density contribution main body, generate a Solid Electrolyte Interphase (SEI), relieve the stress of periodic volume change, keep the structural stability in the lithium ion embedding/extracting process, and simultaneously, the grown composite carbon film has good high-rate performance, explosion-proof and fire-proof performance and good safety performance. And the preparation method adopts a co-sputtering method to grow and form the film layer, the conditions are easy to control, the chemical property stability of the grown composite carbon film is effectively ensured, the efficiency is high, and the preparation method is suitable for industrial large-scale production.
Correspondingly, based on the preparation method of the composite carbon film, the embodiment of the invention also provides the composite carbon film. The composite carbon film is prepared by the preparation method of the composite carbon film. Thus, since the composite carbon is prepared by the above-described method for preparing a composite carbon thin film, the composite carbon thin film has the characteristics as described above: the interface resistance is small, the surface area is large, and the conductivity is good; and the characteristic composite carbon film can effectively prevent the direct contact of the electrolyte and the nano-scale energy density contribution main body elements, reduce and prevent irreversible side reactions between the electrolyte and the energy density contribution main body, reduce the generation of a Solid Electrolyte Interphase (SEI), relieve the stress of periodic volume change, keep the structural stability in the lithium ion intercalation/deintercalation process, and meanwhile, the grown composite carbon film has good large-rate performance and good safety performance.
On the other hand, the embodiment of the invention also provides an electrode plate. The electrode plate comprises a current collector, wherein a composite carbon film layer is combined on the surface of the current collector, and the composite carbon film layer is formed by growing on the current collector according to the preparation method. Among them, the current collector is preferably a negative electrode current collector due to the composite type carbon thin film grown according to the above-described preparation method. Such as but not limited to a stainless steel substrate. The grown composite carbon film can be controlled to be 50nm-10 μm, 0.1-10 μm, specifically 1um, but not limited thereto. Therefore, the electrode plate has small internal resistance, and the contained composite carbon film can effectively prevent the direct contact between the electrolyte and the nano-scale energy density contribution main body elements, reduce and prevent the irreversible side reaction between the electrolyte and the energy density contribution main body, reduce the generation of a Solid Electrolyte Interface (SEI), relieve the stress of periodic volume change and maintain the structural stability in the lithium ion intercalation/deintercalation process.
The electrode plate provided by the embodiment of the invention has the advantages, so that the electrode plate is applied to the preparation of a lithium ion battery or a super capacitor. When the electrode sheet is used in a lithium ion battery, the lithium ion battery naturally includes necessary components, such as a cell formed of a positive electrode, a negative electrode, and a separator. Wherein the negative electrode is the electrode sheet described above. The other components may be conventional components contained in conventional lithium ion batteries. Therefore, the lithium ion battery has high first charge-discharge efficiency, high rate performance, good safety performance, good cycle performance, long cycle life and high safety performance. When the electrode sheet is applied to a supercapacitor, the supercapacitor naturally includes necessary components, such as electrode sheets, which are the electrode sheets described above. Therefore, the super capacitor has small internal resistance, quick charge and discharge, excellent energy storage performance, good cycle performance, long cycle life and high safety performance.
The composite carbon film of the present invention, its preparation method and application, etc. are illustrated by a plurality of specific examples.
This embodiment A
The embodiment provides a composite carbon film and a preparation method thereof. The composite carbon film is prepared according to a method comprising the following steps:
s11: uniformly scattering a carbon substrate in a tray by using a copper tray with the diameter of 70mm as the tray of the powder target, and performing unidirectional dry pressing by using a 5-ton unidirectional press machine to obtain the carbon target;
s12: the carbon target prepared in step S11 and a commercially available silicon ceramic target having a purity of 99.999% were used as a sputtering source, and the substrate target pitch was 50mm at 1.0X 10 on a copper foil-2Preparing a C-Si composite film with the thickness of 1um by adopting a power ratio of C to Si being 1 to 1 in a high-purity argon atmosphere in millibar; during deposition, the substrate was maintained at 300 ℃.
Example two
The embodiment provides a composite carbon film and a preparation method thereof. The composite carbon film is prepared according to a method comprising the following steps:
s11: weighing a certain amount of carbon powder, adding 5% polyvinyl alcohol, stirring until the powder has certain viscosity, then putting the powder into a metal mold, increasing the pressure to the design pressure at a pressure increasing speed of 50MPa/min, maintaining the pressure for a period of time, then relieving the pressure at a speed of 30MPa/min, and taking out the powder from the metal mold to obtain a biscuit; putting the biscuit into a muffle furnace, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 5h, then heating to 950 ℃ at the speed of 5 ℃/min, and preserving heat for 10h to obtain the carbon-based ceramic target;
s12: using the carbon-based ceramic target prepared in the step S11 and a purchased nickel ceramic target with the purity of 99.999 percent as a sputtering source, wherein the substrate target distance is 50mm on a copper foil and is 1.0 multiplied by 10-2Preparing a C-Ni composite film with the thickness of 1um by adopting a power ratio co-sputtering method of C: Ni-4: 1 in a high-purity nitrogen atmosphere in millibar; during deposition, the substrate was maintained at 400 ℃.
EXAMPLE III
The embodiment provides a composite carbon film and a preparation method thereof. The composite carbon film is prepared according to a method comprising the following steps:
s11: uniformly scattering carbon powder in a tray by using a copper tray with the diameter of 70mm as the tray of the powder target, and performing unidirectional dry pressing by using a 5-ton unidirectional press machine to obtain the carbon powder target;
s12: the carbon powder target prepared in step S11 and a commercially available tin ceramic target having a purity of 99.999% were used as a sputtering source, and a substrate target pitch of 50mm was set at 1.0X 10 on a copper foil-2Preparing a C-Sn composite film with the thickness of 1um by adopting a power ratio of 1: 4C: Sn in a high-purity ammonia atmosphere in millibar; during deposition, the substrate was maintained at 200 ℃.
Example four
The embodiment provides a composite carbon film and a preparation method thereof. The composite carbon film is prepared according to a method comprising the following steps:
s11: weighing a certain amount of lithium carbonate powder, adding 5% polyvinyl alcohol, stirring until the powder has certain viscosity, then putting the powder into a metal mold, increasing the pressure to the design pressure at the pressure increasing speed of 50MPa/min, maintaining the pressure for a period of time, then releasing the pressure at the speed of 30MPa/min, and taking out the powder from the metal mold to obtain a biscuit; putting the biscuit into a muffle furnace, heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 5h, then heating to 950 ℃ at the speed of 5 ℃/min, and preserving heat for 10h to obtain a lithium carbonate ceramic target;
s12: the lithium carbonate ceramic target prepared in step S11 and a commercially available carbon ceramic target having a purity of 99.999% were used as a sputtering source on a copper foil at a substrate target pitch of 50mm at 1.0X 10-2In a high-purity argon atmosphere in mbar, using Li2CO3Preparation of Li with thickness of 1um by power ratio co-sputtering method of-C-4: 12CO3-C composite film; during deposition, the substrate was maintained at 300 ℃.
EXAMPLE five
The embodiment provides a composite carbon film and a preparation method thereof. The composite carbon film is prepared according to a method comprising the following steps:
s11: uniformly scattering lithium carbonate powder in a tray which is a copper tray with the diameter of 70mm and is used as a powder target, and carrying out unidirectional dry pressing by using a 5-ton unidirectional press machine to obtain a lithium carbonate powder target;
s12: the lithium carbonate powder target prepared in step S11With a commercially available zinc ceramic target of 99.999% purity as a sputtering source, on a copper foil, a substrate target distance of 50mm at 1.0X 10-2In a mixed atmosphere of high-purity nitrogen and oxygen in millibar, Li is adopted2CO3Preparation of 1um thick Li by power ratio co-sputtering method of Zn 2:12CO3-a Zn composite film; during deposition, the substrate was maintained at 500 ℃.
EXAMPLE six
The embodiment provides a composite carbon film and a preparation method thereof. The composite carbon film is prepared according to a method comprising the following steps:
s11: uniformly scattering lithium carbonate powder in a tray by using a copper tray with the diameter of 70mm as a tray of the powder target, and performing unidirectional dry pressing by using a 5-ton unidirectional press machine to obtain a lithium carbonate powder target;
s12: the lithium carbonate powder target prepared in step S11 and a commercially available cobalt ceramic target having a purity of 99.999% were used as a sputtering source on a 304 stainless steel substrate of Japan, the substrate target distance was 60mm at 1.0X 10-2In a mixed atmosphere of high purity ammonia and oxygen in millibar, using (LCO/LO)2) Co-1: 2 power ratio Co-sputtering method for preparing (LCO/LO) with thickness of 1um2) -a Co composite film; during deposition, the substrate was maintained at 700 ℃.
Comparative example 1
This comparative example provides a composite carbon film and a method of making the same. The composite carbon film is prepared according to a method comprising the following steps:
s11: uniformly scattering lithium manganate mixed powder in a tray by using a copper tray with the diameter of 70mm as the tray of the powder target, and carrying out unidirectional dry pressing by using a 5-ton unidirectional press machine to obtain the lithium manganate powder target;
s12: the prepared lithium carbonate powder target is used as a sputtering source, and the target distance of the substrate on a stainless steel substrate is 40mm and is 1.0 multiplied by 10-2Sputtering under the mixed atmosphere of high-purity argon and oxygen in millibar to prepare LCO/LO with the thickness of 1um2A film; during deposition, the substrate was maintained at 300 ℃.
Comparative example No. two
The present comparative example provides a pure carbon thin film and a method of preparing the same. The carbon film is prepared according to a method comprising the following steps:
s11: a carbon target having a purity of 99.999% was purchased as a sputtering source, and the substrate target distance was 50mm on a Japanese 304 stainless steel substrate at 1.0X 10-2Preparing a C film with the thickness of 1um by sputtering in the atmosphere of high-purity argon in millibar; during deposition, the substrate was maintained at 300 ℃.
Seven to twelve examples and three to four comparative examples
A lithium ion battery was assembled by using the stainless steel substrate containing a composite type carbon thin film provided in each of the first to sixth examples as a positive electrode and the stainless steel substrate containing a thin film provided in the first and second comparative examples as a positive electrode, respectively, as follows:
a button cell is assembled by using a lithium sheet as a film electrode, an electrolyte concentration of 1mol/L and a propylene microporous film as a diaphragm of the cell in a glove box filled with argon.
Each lithium ion battery was subjected to the following relevant electrochemical test conditions: the charge-discharge voltage is 0.01V-3V.
Relevant electrochemical test results for each lithium ion battery:
the lithium ion battery provided by the seventh embodiment has a first discharge specific capacity of 1310mah/g and a charge specific capacity of 1900mah/g at a rate of 150 mA/g. In addition, the charging and discharging curves of the first turn, the 50 th turn and the 100 th turn of the lithium ion battery provided by the seventh embodiment at 150mA/g are shown in fig. 4. The cycle performance curve at 1300mA/g is shown in FIG. 2, and the coulombic efficiency curve at 1300mA/g is shown in FIG. 1.
In the lithium ion battery provided in the eighth embodiment, the first discharge specific capacity is 988mah/g and the discharge specific capacity is 952mah/g at a rate of 150 mA/g.
In the case of the lithium ion battery provided in the ninth embodiment, the first discharge specific capacity is 1039mah/g and the discharge specific capacity is 1007mah/g at a rate of 150 mA/g.
The first discharge specific capacity of the lithium ion battery provided in the tenth embodiment is 1033mah/g and the discharge specific capacity is 999mah/g at a rate of 150 mA/g.
When the lithium ion battery provided by the eleventh embodiment is at a rate of 150mA/g, the first discharge specific capacity is 932mah/g, and the discharge specific capacity is 912 mah/g.
The lithium ion battery provided in the twelfth embodiment has a first discharge specific capacity of 1148mah/g and a discharge specific capacity of 885mah/g at a rate of 150 mA/g.
And when the lithium ion battery provided by the fourth comparative example is at the rate of 150mA/g, the first discharge specific capacity is 210mah/g, and the discharge specific capacity is 199 mah/g.
In addition, the first charge and discharge curve of the lithium ion battery provided in the eight to twelve examples at 150mA/g is shown in fig. 3. The charge-discharge capacity ratio of the lithium ion battery with the composite carbon film electrode material obtained in the seventh embodiment of the invention and the pure carbon film obtained in the fourth comparative embodiment is shown in fig. 5.
The charge and discharge performance of the lithium ion batteries provided in the seventh to twelfth examples and the charge and discharge performance of the lithium ion batteries provided in the third to fourth comparative examples are known to be obviously superior to that of the lithium ion batteries with a single silicon electrode and that of the lithium ion batteries with a single carbon electrode, wherein the lithium ion batteries with the composite carbon films provided in the first to sixth examples are provided in the sixth examples. Therefore, the relevant electrochemical test results of the lithium ion batteries show that the lithium ion batteries have high first charge and discharge efficiency, good cycle performance and stable charge and discharge performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
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