Silicon nanowire structure embedded in nickel silicide nanowires for lithium-based battery anodes

Abstract

The present invention provides a silicon nanowire structure embedded in nickel silicide nanowires for lithium-based battery anodes and anodes including the same. In particular, a Si nanowire structure embedded in NiSi.sub.x nanowires according to the present invention may provide a solution to a problem, such as disconnection of Si nanowires from a current collector shown when the Si nanowires are expanded by alloying with Li or contracted during the use of a battery, and the like, by flexibly embedding the Si nanowires in the NiSi.sub.x nanowires.

Claims

1. A method for manufacturing a Si nanowire structure embedded in NiSi.sub.x nanowires, the method comprising: depositing a Ni thin film on a substrate; obtaining Si nanowires by an etching process; dispersing the Si nanowires in a suspension solution; providing the suspension solution comprising the Si nanowires on the substrate coated with the Ni thin film; loading the Si nanowires on the substrate coated with the Ni thin film into a chemical vapor deposit (CVD) reactor; and growing the NiSi.sub.x nanowires by preforming a CVD process.

2. The method of claim 1, wherein the CVD process is performed by introducing H.sub.2 and SiH.sub.4 into the CVD reactor.

3. The method of claim 1, wherein the substrate is a Cu substrate or a steel-use-stainless (SUS) substrate.

4. The method of claim 1, wherein the substrate is a current collector of an anode.

5. The method of claim 1, wherein in the obtaining of Si nanowires by an etching process, the Si nanowires are obtained from a crystalline Si wafer or a crystalline Si powder.

6. The method of claim 1, wherein in the obtaining of Si nanowires, the etching process is a metal-assisted chemical etching.

7. The method of claim 1, wherein the suspension solution is an alcohol-based suspension solution.

8. The method of claim 1, wherein the Si nanowires in the suspension solution is provided on the substrate coated with the Ni thin film by a dropping method.

9. The method of claim 1, wherein in the growing of the NiSi.sub.x nanowires by introducing H.sub.2 and SiH.sub.4 into the CVD reactor to perform a CVD process, H.sub.2 and SiH.sub.4 are introduced into the CVD reactor at a rate in a range from about 350 to about 450 sccm and a rate in a range from about 0.5 to about 1.5 sccm, respectively, and at a pressure in a range from about 40 to about 60 mTorr.

10. The method of claim 1, wherein the growing of the NiSi.sub.x nanowires by performing the CVD process is performed at a temperature in a range from about 300 to about 500 C. and a pressure in a range from about 10.sup.5 to about 10.sup.7 Torr.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other features of the present invention will now be described in detail with reference to exemplary embodiments thereof illustrated the accompanying drawings which are given hereinbelow by way of illustration only, and thus are not limitative of the present invention, and wherein:

(2) FIG. 1 (a) schematically illustrates an exemplary Si nanowire structure embedded in NiSi.sub.x nanowires before lithiation occurs according to an exemplary embodiment of the present invention, and FIG. 1 (b) schematically illustrates an exemplary modified Si nanowires structure after lithiation occurs;

(3) FIGS. 2 (a) and 2 (b) are a cross-sectional structural view and a plan view, respectively, which schematically illustrate exemplary Si nanowires on the substrate coated with Ni by NiSi.sub.x nanowires before CVD according to an exemplary embodiment of the present invention;

(4) FIGS. 3 (a) and 3 (b) are a cross-sectional schematic view and a plan view, respectively, which schematically illustrate an exemplary Si nanowire structure embedded in NiSi.sub.x nanowires according to an exemplary embodiment of the present invention;

(5) FIG. 4 is a diagram illustrating exemplary processes of a method for manufacturing a Si nanowire structure embedded in NiSi.sub.x nanowires according to an exemplary embodiment of the present invention;

(6) FIG. 5 is a graph illustrating a general ageing curve for exemplary anodes including the Si nanowire structure embedded in NiSi.sub.x nanowires manufactured by the method according to an exemplary embodiment of the present invention; and

(7) FIG. 6 is a graph illustrating a change in charging-discharging cycle capacity for the conventional anode manufactured by a method according to Comparative Example.

(8) Reference numerals set forth in the Drawings includes reference to the following elements as further discussed below:

(9) TABLE-US-00001 110: substrate 120: Ni thin film 130: Si nanowire 140: NiSi.sub.x nanowire

(10) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various exemplary features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.

(11) In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.

DETAILED DESCRIPTION

(12) It is understood that the term vehicle or vehicular or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g., fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.

(13) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. As used herein, the term and/or includes any and all combinations of one or more of the associated listed items.

(14) Unless specifically stated or obvious from context, as used herein, the term about is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. About can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term about.

(15) Hereinafter reference will now be made in detail to various exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.

(16) Hereinafter, an exemplary embodiment of the present invention will be described in more detail as follows.

(17) The present invention relates to a Si nanowire structure deposited on a Ni thin film and embedded in NiSi.sub.x nanowires, and provides an anode structure which may fix Si nanowires etched on a current collector, and a method of manufacturing the Si nanowire structure.

(18) The Si nanowire structure embedded in NiSi.sub.x nanowires according to an exemplary embodiment of the present invention may be formed on a substrate. In particular, the substrate may be, but not limited to, a Cu substrate or a steel-use-stainless (SUS) substrate. In an exemplary embodiment, the substrate may be a current collector of an anode, without limitation. In an exemplary embodiment, a Ni thin film may be coated on the substrate by deposition. In particular, the thickness of the Ni thin film may be, but not limited to, in a range from about 200 to about 500 nm. In another exemplary embodiment, a Ni foam may also be used instead of the Ni thin film. In addition, the Si nanowires may be obtained by an etching process.

(19) In an exemplary embodiment, the Si nanowire structure embedded in NiSi.sub.x nanowires may be formed on the substrate. Particularly, the embedded structure may be obtained by loading the Si nanowires into a CVD reactor after a desired amount of the Si nanowires are provided on a substrate coated with a Ni thin film, and growing the NiSi.sub.x nanowires by performing a CVD process while introducing H.sub.2 and SiH.sub.4 therein.

(20) In an exemplary embodiment, the method of manufacturing the Si nanowire structure embedded in NiSi.sub.x nanowires may include: preparing a substrate; depositing a Ni thin film on the substrate; obtaining Si nanowires by an etching process; dispersing the Si nanowires in a suspension solution; providing the suspension solution including the Si nanowires on the substrate coated with the Ni thin film; loading the Si nanowires and the substrate coated with the Ni thin film into a CVD reactor after a desired amount of the Si nanowires are provided on the substrate coated with the Ni thin film; and growing the NiSi.sub.x nanowires while introducing H.sub.2 and SiH.sub.4 into the CVD reactor to perform a CVD process.

(21) According to an exemplary embodiment of the present invention, the Si nanowires may be obtained by an individual etching of a crystalline Si wafer or a crystalline Si powder, without limitation. In particular, the Si nanowires may be obtained from the crystalline Si wafer or the crystalline Si powder, without limitation, by a metal-assisted chemical etching.

(22) Subsequently, the obtained Si nanowires may be dispersed in a suspension solution. In particular, the suspension solution may be an alcohol-based solution. The alcohol-based suspension solution may include, without limitation, ethyl alcohol, or alcohol-based component such as 99.9% ethyl alcohol. In addition, the suspension solution including Si nanowires may be prepared by dispersing the Si nanowires in the suspension solution at room temperature.

(23) Further, in an exemplary embodiment of the present invention, the Si nanowires in the suspension solution may be provided on the substrate coated with the Ni thin film, without limitation, by a dropping method. In addition, the process of providing of the solution including the Si nanowires on the substrate coated with the Ni thin film may continue until the desired amount of the Si nanowires is provided on the substrate coated with the Ni thin film.

(24) The Si nanowires may be loaded into a chemical vapor deposit (CVD) reactor after the desired amount of the Si nanowires are provided on the substrate coated with the Ni thin film. When the desired amount of Si nanowires required for a current collector substrate are provided, Si nanowires and substrate coated with Ni thin film may be loaded into the CVD reactor for growth of NiSi.sub.x nanowires. In an exemplary embodiment, the NiSi.sub.x nanowires may be grown by introducing H.sub.2 and SiH.sub.4 into the CVD reactor to perform a CVD process. In particular, at a pressure in a range from about 40 to about 60 mTorr, H.sub.2 and SiH.sub.4 may be introduced into the CVD reactor at a rate in a range from about 350 to about 450 sccm and a rate in a range from about 0.5 to about 1.5 sccm, respectively. In addition, the process of growing NiSi.sub.x in the CVD reactor may be performed at a temperature in a range from about 300 C. to about 500 C. and a pressure in a range from about 10.sup.5 Torr to about 10.sup.7 Torr.

(25) The NiSi.sub.x nanowires in which the Si nanowires are embedded may connect the Si nanowires on a current collector, and may readily withstand a change in volume of the Si nanowires, particularly, during alloying and de-alloying with Li as an elastic binder.

(26) In an exemplary embodiment of the present invention, an anode for a lithium secondary battery may be manufactured by using the Si nanowire structure embedded in NiSi.sub.x nanowires which may be manufactured according an exemplary embodiment as described above. The anode including the Si nanowire structure embedded in NiSi.sub.x nanowires according an exemplary embodiment of to the present invention may include: a substrate; a Ni thin film deposited on the substrate; Si nanowires deposited on the Ni thin film; and NiSi.sub.x nanowires embedding the Si nanowires while being deposited on the Ni thin film.

(27) In FIG. 1, the Si nanowire structures embedded in NiSi.sub.x nanowires according to an exemplary embodiment of the present invention are illustrated. Before the lithiation occurs as shown in FIG. 1 (a), a Si nanowire 130 on a Ni thin film 120 on a substrate 110 may be embedded in a SiNi.sub.x nanowire 140. After the lithiation occurs as shown in FIG. 1(b), the elastic NiSi.sub.x nanowires may keep supporting Si nanowires, thereby providing both electrical contact and adhesion properties on a current collector. FIGS. 1 (a) and 1 (b) illustrate modified forms of the Si nanowire structures embedded in NiSi.sub.x nanowires, without limitation, according to various exemplary embodiments of the present invention.

(28) FIG. 1 (a) illustrates an exemplary Si nanowire structure embedded in NiSi.sub.x nanowires before the lithiation occurs. FIG. 1 (b) illustrates an exemplary modified form of FIG. 1 (a) after the lithiation occurs. Since the elastic SiNi.sub.x nanowires keep supporting the Si nanowires while maintaining the state of being embedded even after the lithiation, both electrical contact and adhesion properties may be provided on a current collector.

(29) FIG. 1 further illustrates cross-sectional forms of a shape in which the Ni thin film 120 is formed by depositing a Ni film on the substrate 110, and the NiSi.sub.x nanowire 140 grown under the flow of SiH.sub.4 while being embedded with the Si nanowire 130 is randomly arranged. In detail, an orientation in which the NiSi.sub.x nanowire 140 is grown and arranged on the substrate 110 is illustrated, and the NiSi.sub.x nanowire 140 is grown from the Ni thin film 120 deposited on the substrate. According to an exemplary embodiment, the NiSi.sub.x nanowire 140 may be grown under the flow of SiH.sub.4 in the CVD reactor. The NiSi.sub.x nanowire 140 may be grown at a random angle with respect to the plane of the substrate 110, or the NiSi.sub.x nanowire 140 may not be vertical to the plane. In this respect, the NiSi.sub.x nanowire 140 may be grown on the Si nanowire 130 already disposed on the Ni thin film 120. Accordingly, as illustrated in FIG. 1, the NiSi.sub.x nanowire 140 may be embedded with the Si nanowire 130.

(30) FIGS. 2 (a) and 2 (b) are a cross-sectional structural view and a plan view, respectively, which schematically illustrate exemplary orientations of Si nanowires before being embedded on the substrate coated with Ni by NiSi.sub.x nanowires. In FIG. 2, an exemplary Si nanowire structure as in FIG. 1 may be formed when the Si nanowire 110 is formed on a substrate coated with Ni, and NiSi.sub.x nanowires are grown thereon.

(31) FIGS. 3 (a) and 3 (b) are a cross-sectional schematic view and a plan view, respectively, which schematically illustrate an exemplary Si nanowire structure, in which the NiSi.sub.x nanowire 140 is embedded with the Si nanowire 130 on the substrate 110 according to an exemplary embodiment of the present invention. FIG. 3 further illustrates exemplary NiSi.sub.x nanowires 140 which may be randomly grown after Si nanowires 130 are deposited on the substrate coated with Ni. Since the NiSi.sub.x nanowire 140 is long and flexible, the NiSi.sub.x nanowire 140 may provide a kind of elastic contact with respect to the Si nanowire 130, and have a structure which may withstand the volume expansion of the Si nanowire when alloyed with Li during the operation of a lithium secondary battery.

(32) As described above, the Si nanowire structure according to various exemplary embodiments of the present invention may provide a solution to the problem, such as disconnection of Si nanowires from a current collector shown when the Si nanowires are expanded by alloying with Li or contracted during the use of a battery, and the like, since the Si nanowires may exhibit improved performance of maintaining about 75% of the original capacity even after 250 times of charging-discharging cycles, and further, NiSi.sub.x nanowires may be flexibly embedded with Si nanowires.

(33) Hereinafter, the present invention will be described in detail with reference to an Example, and the present invention is not limited thereto.

(34) The present Example is not a comprehensive overview of all the possible Examples, and is not even intended to identify the core element among all the elements or cover the scope of all the Examples. The present Example is for providing a concept by using an Example in a simplified form as an exemplary embodiment for the detailed description.

EXAMPLES

(35) The following examples illustrate the invention and are not intended to limit the same.

(36) A Si nanowire structure embedded in NiSi.sub.x nanowires may be manufactured by a process illustrated in FIG. 4.

(37) In an exemplary embodiment, the method of manufacturing may include: preparing a substrate in step 410; depositing a Ni thin film on the substrate in step 420; obtaining Si nanowires by an etching process in step 430; dispersing the Si nanowires in a suspension solution in step 440; providing the suspension solution including the Si nanowires on the substrate coated with the Ni thin film in step 450; loading the Si nanowires and the substrate coated with the Ni thin film into a CVD reactor after a desired amount of Si nanowires are provided on the substrate coated with the Ni thin film in step 460; and growing the NiSi.sub.x nanowires by performing a CVD process while introducing H.sub.2 and SiH.sub.4 into the CVD reactor in step 470.

(38) A substrate may be prepared in step 410. The substrate may be a current collector of an anode by using an SUS substrate. The Ni thin film may be deposited on the substrate in step 420. In particular, the thickness of the Ni thin film may be about 200 nm. In step 430, the Si nanowires may be obtained by the etching process. In particular, the Si nanowires may be obtained individually by using a metal-assisted chemical etching on a crystalline Si wafer.

(39) In step 440, the Si nanowires obtained after the etching may be dispersed in the suspension solution. As of the suspension solution, an alcohol-based suspension may be used. When the Si nanowires are dispersed in an alcohol-based liquid suspension solution, for instance, 99% ethyl alcohol, the wires may be mixed in the solution. When the suspension solution including the Si nanowires may be dropped on the substrate in the subsequent step, the wires may remain on the substrate and be randomly distributed on the substrate as the solution is evaporated.

(40) In step 450, the suspension solution including Si nanowires may be provided by, but not limited to, a dropping method. A dropper may be used to perform the dropping method. The Si nanowires provided on the substrate may be randomly disposed. When the Si nanowires are dispersed in the suspension solution, and then the suspension solution including the Si nanowires is dropped on the substrate by dropping, Si nanowires may be randomly distributed on the substrate, and the solution is evaporated.

(41) In step 460, when a desired amount of the Si nanowires are provided on the substrate coated with the Ni thin film, and the Si nanowires and the substrate coated with the Ni thin film may be loaded into the CVD reactor. A typical type of CVD reactor may be used without limitation.

(42) In step 470, the NiSi.sub.x may grow into the CVD reactor, at a pressure of about 50 mTorr, and, H.sub.2 and SiH.sub.4 may be introduced at a rate of about 400 sccm and about 1 sccm, respectively, into the CVD reactor. In particular, the growing of the NiSi.sub.x nanowires by performing the CVD process may be performed at a temperature of about 400 C. and a pressure of about 10.sup.6 Torr. The NiSi.sub.x nanowires may be randomly grown by using the CVD process, and be embedded with the Si nanowires. After the CVD process is completed and the temperature drops to less than about 50 C., the sample may be unloaded from the CVD reactor, and used as an anode for a lithium secondary battery.

(43) In another exemplary embodiment, instead of using slurry in the process, nickel silicide (NiSi.sub.x) may be grown after the deposition of Si nanowires etched on a current collector coated with Ni. The NiSi.sub.x nanowires grown after the Si nanowires are provided may be formed and embedded with the Si nanowires, thereby attaching the Si nanowires on the current collector. Thus, the NiSi.sub.x nanowires may provide a structure to serve as an elastic binder.

TEST EXAMPLES

(44) For an anode including a Si nanowire structure in which the NiSi.sub.x nanowires are embedded according to the Example, a performance of an exemplary lithium secondary battery in which the anode is applied is evaluated. For the evaluation, a half-cell arrangement may be used for various electrochemical tests, and an anode electrode on one side and pure metallic Li as an opposite electrode may be used. For the above-prepared half-cell, a capacity test and a safety test may be prepared in a glove box filled with an Ar gas while keeping the humidity and oxygen contents less than about 1.0 ppm. The cell may be manufactured by using two cylindrical stainless steel electrodes having a diameter of about 14 mm and PTFE Swagelok parts.

(45) For an electrolyte of a lithium secondary battery, a solution of about 1.15 M lithium hexafluorophosphate (LiPF.sub.6) in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) at a ratio of 3:7 (vol %), respectively, may be used as the electrolyte.

(46) The electrochemical property of the electrode may be measured by varying charging-discharging rates by a battery tester system (BioLogic VSP). The galvanostatic cycling for evaluation of the service life as shown in FIG. 5 may be measured at a voltage window from 2.0 to 0 V for Li/Li+.

(47) As a result, the ageing curve is provided in FIG. 5. Therefore, the Si nanowires according to an exemplary embodiment of the Example may maintain about 75% of the original capacity even after about 250 times of the charging-discharging cycles.

COMPARATIVE EXAMPLES

(48) For comparison, the charging-discharging cycle capacity of the electrode manufactured by a convention method is illustrated in FIG. 6. The convention electrode is a negative electrode including a silicon powder having a size of about 100 nm size, in an amount of about 60 wt %, a binder, for instance PVDF of about 20 wt %, and carbon black of about 20 wt %. The capacity measured from the exemplary conventional anode rapidly decreases without withstanding the volume expansion occurring after a first cycle.

(49) Various modifications of the exemplary embodiments will be obvious to the person with ordinary skill in the art of the present invention, and general principles defined herein may be applied to other exemplary embodiments without departing from the scope of the present invention. Therefore, the present invention is not limited to the exemplary embodiment suggested herein, and is to be interpreted in the broadest scope, which is consistent with the principles and novel features suggested herein.

(50) The present invention provides a technology which may be applied to an anode of a lithium secondary battery, and may be applied to improve the structure of Si nanowires of the anode.

(51) The invention has been described in detail with reference to exemplary embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.