ABSTRACT
Abstract
In an example of the method disclosed herein, SiO x (0<x<2) particles are combined with a lithium metal. The SiO x (0<x<2) particles and the lithium metal are caused to react to form lithium oxide nanoparticles in a silicon matrix. At least some of the lithium oxide nanoparticles are removed from the silicon matrix to form porous silicon particles.
Description
BACKGROUND
Secondary, or rechargeable, lithium ion batteries or lithium-sulfur batteries are often used in many stationary and portable devices, such as those encountered in the consumer electronic, automobile, and aerospace industries. The lithium class of batteries has gained popularity for various reasons, including a relatively high energy density, a general nonappearance of any memory effect when compared to other kinds of rechargeable batteries, a relatively low internal resistance, and a low self-discharge rate when not in use. The ability of lithium batteries to undergo repeated power cycling over their useful lifetimes makes them an attractive and dependable power source.
SUMMARY
In an example of the method disclosed herein, the SiO x (0<x<2) particles are combined with a lithium metal. The SiO x (0<x<2) particles and the lithium metal are caused to react to form lithium oxide nanoparticles in a silicon matrix. The lithium oxide nanoparticles are removed from the silicon matrix to form porous silicon particles.
BRIEF DESCRIPTION OF THE DRAWINGS
Features and advantages of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.
FIGS. 1A, 1B and 1E-1G are schematic and partially cross-sectional diagrams which together illustrate one example of a method for forming a negative electrode active material;
FIGS. 1C-1G are schematic and partially cross-sectional diagrams which together illustrate another example of a method for forming a negative electrode active material;
FIGS. 2A-2D are schematic and partially cross-sectional diagrams which together illustrate yet another example of a method for forming a negative electrode active material;
FIG. 3 is a cross-sectional view of an example of a negative electrode on a current collector;
FIG. 4 is a perspective schematic view of an example of a lithium ion battery, including an example of the negative electrode disclosed herein;
FIG. 5 is a perspective schematic view of an example of a lithium-sulfur battery, including an example of the negative electrode disclosed herein;
FIGS. 6A-6C are transmission electron microscope (âTEMâ) images, taken at magnifications of 36K, 20K, and 230K respectively, of the SiO x (0<x<2) particles ( FIG. 6A ), the porous silicon particles formed via an example of the method disclosed herein ( FIG. 6B ), and the porous silicon particles of FIG. 6B using a scalar bar of 100 nm; and
FIG. 7 is a graph exhibiting the cycling stability, in terms of capacity retention and efficiency, of a coin cell including a negative electrode formed with an example of the porous silicon particles disclosed herein and of a comparative coin cell including a negative electrode formed with SiO x (0<x<2) powder.
DETAILED DESCRIPTION
The high theoretical capacity (e.g., 4200 mAh/g) of silicon renders it desirable for use as a negative electrode active material in lithium-based batteries. However, it has been found that negative electrode active materials (e.g., silicon particles) with high specific capacities also have large volume expansion and contraction during charging/discharging of the lithium-based battery. The large volume change (e.g., about 400%) experienced by the negative electrode active material during charging/discharging causes the negative electrode active material to fracture, decrepitate, or otherwise mechanically degrade, which results in a loss of electrical contact and poor life cycling. Poor cycling performance often includes a large capacity fade, which may result from the breakdown of contact between the negative electrode active material and conductive fillers in the negative electrode due to the large volume change.
The examples of the methods disclosed herein form silicon-based negative electrode active materials that can improve the cycling performance of the negative electrode and battery in which the materials are used. In particular, the cycling performance is improved as a result of pores that are formed within the silicon-based negative electrode active materials. These pores provide space that can accommodate the volume expansion of the silicon, and thus can reduce the stress on the silicon. It is believed that the pores within the silicon particles contribute to a reduction in fracturing, decrepitating, or mechanical degradation that would otherwise lead to the capacity fading during the charging and discharging process.
In examples of the methods disclosed herein, it is to be understood that no hydrofluoric acid is used to generate the silicon-based negative electrode active materials. Hydrofluoric acid (HF) is a corrosive contact poison. Without hydrofluoric acid, the methods disclosed herein do not involve risks associated with hydrofluoric acid, and are relatively cost effective (e.g., since specialized equipment for handling hydrofluoric acid is not necessary).
In one example of the method disclosed herein, a silicon matrix may be formed using an electrochemical cell to partially lithiate SiO x (0<x<2) particles. The lithiation reaction forms a by-product in the silicon matrix, which may be removed from the silicon matrix to form porous silicon. In another example of the method disclosed herein, the SiO x (0<x<2) particles may be mixed with a lithium metal and heated to generate the silicon matrix. Heating causes a reaction which results in the formation of a by-product in the silicon matrix, which may be removed from the silicon matrix to form porous silicon.
In the examples of the method disclosed herein, the term âmatrixâ refers to a surrounding medium or structure. More particularly, the matrix is silicon that is formed from a reaction that involves the SiO x (0<x<2) particles. The matrix may have any shape, including that of spherical particles, non-spherical particles, etc.
Also in the examples of the method disclosed herein, the SiO x (0<x<2) particles may be silicon monoxide, silicon suboxide, or combinations thereof.
Referring now to FIGS. 1A-1G , different examples (labeled as â 1 â and â 2 â) of forming the different active materials
10 , 10 â² are shown. It is to be understood that both active materials
10 , 10 â² may be used as the active material (alone or in combination) in the negative electrode.
One example of the method is shown in FIGS. 1A, 1B, 1E and 1F (labeled â 1 â). This example of the method may also include an additional step, including a coating process as shown in FIG. 1G . This example of the method involves an electrochemical cell 11 . Generally, the electrochemical cell 11 includes a working electrode 21 (shown in phantom in FIG. 1B ), an electrolyte solution 14 , a reference electrode 19 , and a counter electrode (which, in this example, is lithium metal 16 ). In some instances, a separator (not shown) may also be used in the electrochemical cell 11 .
In the example shown in FIGS. 1A and 1B , the SiO x (0<x<2) particles 12 are added to a current collector container 18 . It is to be understood that the SiO x (0<x<2) particles 12 are in electrical contact with the current collector container 18 . For example, when the SiO x (0<x<2) particles 12 are positioned on the bottom of the current collector container 18 , the particles 12 and container 18 are in contact with each other, and when a voltage potential is applied to the container 18 , the particles 12 and the container 18 are in electrical contact with each other. The combination of the current collector container 18 and the SiO x (0<x<2) particles 12 forms the working electrode 21 .
The current collector container 18 receives and transports electrons from an external circuit 15 (shown in FIG. 1B ) to the SiO x (0<x<2) particles 12 , thereby facilitating the reduction of the SiO x (0<x<2) particles 12 to form the silicon matrix 12 â². In an example, the current collector container 18 may be an electrically conductive metal container. In some examples, the current collector container 18 may be a copper container, copper foil, or a copper cup. In some other examples, the metal of the current collector container 18 may be a container, foil or cup selected from nickel, titanium, platinum, gold, silver, aluminum, magnesium, vanadium, and alloys thereof. While aluminum and magnesium may be used, these materials may not be selected in order to avoid side reactions (e.g., with the lithium metal 16 ) during the lithiation of the SiO x (0<x<2) particles 12 .
As shown in FIG. 1A , the SiO x (0<x<2) particles 12 are combined with the lithium metal 16 in the electrochemical cell 11 . In an example, pure lithium may be used as the lithium metal 16 . In this example, the lithium metal 16 is the counter electrode, and is combined with the SiO x (0<x<2) particles 12 in the electrolyte solution 14 . It is to be understood that when combined with each other in the electrolyte solution 14 , the SiO x (0<x<2) particles 12 and the lithium metal 16 are positioned so that they are not physically contacting one another. In addition, the lithium metal 16 also does not physically contact the current collector container 18 . As such, there is a gap between the working electrode 21 and the counter electrode/ lithium metal 16 .
As previously mentioned, the electrochemical cell <
BACKGROUND
Secondary, or rechargeable, lithium ion batteries or lithium-sulfur batteries are often used in many stationary and portable devices, such as those encountered in the consumer electronic, automobile, and aerospace industries. The lithium class of batteries has gained popularity for various reasons, including a relatively high energy density, a general nonappearance of any memory effect when compared to other kinds of rechargeable batteries, a relatively low internal resistance, and a low self-discharge rate when not in use. The ability of lithium batteries to undergo repeated power cycling over their useful lifetimes makes them an attractive and dependable power source.
SUMMARY
In an example of the method disclosed herein, the SiO x (0<x<2) particles are combined with a lithium metal. The SiO x (0<x<2) particles and the lithium metal are caused to react to form lithium oxide nanoparticles in a silicon matrix. The lithium oxide nanoparticles are removed from the silicon matrix to form porous silicon particles.
BRIEF DESCRIPTION OF THE DRAWINGS
Features and advantages of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.
FIGS. 1A, 1B and 1E-1G are schematic and partially cross-sectional diagrams which together illustrate one example of a method for forming a negative electrode active material;
FIGS. 1C-1G are schematic and partially cross-sectional diagrams which together illustrate another example of a method for forming a negative electrode active material;
FIGS. 2A-2D are schematic and partially cross-sectional diagrams which together illustrate yet another example of a method for forming a negative electrode active material;
FIG. 3 is a cross-sectional view of an example of a negative electrode on a current collector;
FIG. 4 is a perspective schematic view of an example of a lithium ion battery, including an example of the negative electrode disclosed herein;
FIG. 5 is a perspective schematic view of an example of a lithium-sulfur battery, including an example of the negative electrode disclosed herein;
FIGS. 6A-6C are transmission electron microscope (âTEMâ) images, taken at magnifications of 36K, 20K, and 230K respectively, of the SiO x (0<x<2) particles ( FIG. 6A ), the porous silicon particles formed via an example of the method disclosed herein ( FIG. 6B ), and the porous silicon particles of FIG. 6B using a scalar bar of 100 nm; and
FIG. 7 is a graph exhibiting the cycling stability, in terms of capacity retention and efficiency, of a coin cell including a negative electrode formed with an example of the porous silicon particles disclosed herein and of a comparative coin cell including a negative electrode formed with SiO x (0<x<2) powder.
DETAILED DESCRIPTION
The high theoretical capacity (e.g., 4200 mAh/g) of silicon renders it desirable for use as a negative electrode active material in lithium-based batteries. However, it has been found that negative electrode active materials (e.g., silicon particles) with high specific capacities also have large volume expansion and contraction during charging/discharging of the lithium-based battery. The large volume change (e.g., about 400%) experienced by the negative electrode active material during charging/discharging causes the negative electrode active material to fracture, decrepitate, or otherwise mechanically degrade, which results in a loss of electrical contact and poor life cycling. Poor cycling performance often includes a large capacity fade, which may result from the breakdown of contact between the negative electrode active material and conductive fillers in the negative electrode due to the large volume change.
The examples of the methods disclosed herein form silicon-based negative electrode active materials that can improve the cycling performance of the negative electrode and battery in which the materials are used. In particular, the cycling performance is improved as a result of pores that are formed within the silicon-based negative electrode active materials. These pores provide space that can accommodate the volume expansion of the silicon, and thus can reduce the stress on the silicon. It is believed that the pores within the silicon particles contribute to a reduction in fracturing, decrepitating, or mechanical degradation that would otherwise lead to the capacity fading during the charging and discharging process.
In examples of the methods disclosed herein, it is to be understood that no hydrofluoric acid is used to generate the silicon-based negative electrode active materials. Hydrofluoric acid (HF) is a corrosive contact poison. Without hydrofluoric acid, the methods disclosed herein do not involve risks associated with hydrofluoric acid, and are relatively cost effective (e.g., since specialized equipment for handling hydrofluoric acid is not necessary).
In one example of the method disclosed herein, a silicon matrix may be formed using an electrochemical cell to partially lithiate SiO x (0<x<2) particles. The lithiation reaction forms a by-product in the silicon matrix, which may be removed from the silicon matrix to form porous silicon. In another example of the method disclosed herein, the SiO x (0<x<2) particles may be mixed with a lithium metal and heated to generate the silicon matrix. Heating causes a reaction which results in the formation of a by-product in the silicon matrix, which may be removed from the silicon matrix to form porous silicon.
In the examples of the method disclosed herein, the term âmatrixâ refers to a surrounding medium or structure. More particularly, the matrix is silicon that is formed from a reaction that involves the SiO x (0<x<2) particles. The matrix may have any shape, including that of spherical particles, non-spherical particles, etc.
Also in the examples of the method disclosed herein, the SiO x (0<x<2) particles may be silicon monoxide, silicon suboxide, or combinations thereof.
Referring now to FIGS. 1A-1G , different examples (labeled as â 1 â and â 2 â) of forming the different active materials
10 , 10 â² are shown. It is to be understood that both active materials
10 , 10 â² may be used as the active material (alone or in combination) in the negative electrode.
One example of the method is shown in FIGS. 1A, 1B, 1E and 1F (labeled â 1 â). This example of the method may also include an additional step, including a coating process as shown in FIG. 1G . This example of the method involves an electrochemical cell 11 . Generally, the electrochemical cell 11 includes a working electrode 21 (shown in phantom in FIG. 1B ), an electrolyte solution 14 , a reference electrode 19 , and a counter electrode (which, in this example, is lithium metal 16 ). In some instances, a separator (not shown) may also be used in the electrochemical cell 11 .
In the example shown in FIGS. 1A and 1B , the SiO x (0<x<2) particles 12 are added to a current collector container 18 . It is to be understood that the SiO x (0<x<2) particles 12 are in electrical contact with the current collector container 18 . For example, when the SiO x (0<x<2) particles 12 are positioned on the bottom of the current collector container 18 , the particles 12 and container 18 are in contact with each other, and when a voltage potential is applied to the container 18 , the particles 12 and the container 18 are in electrical contact with each other. The combination of the current collector container 18 and the SiO x (0<x<2) particles 12 forms the working electrode 21 .
The current collector container 18 receives and transports electrons from an external circuit 15 (shown in FIG. 1B ) to the SiO x (0<x<2) particles 12 , thereby facilitating the reduction of the SiO x (0<x<2) particles 12 to form the silicon matrix 12 â². In an example, the current collector container 18 may be an electrically conductive metal container. In some examples, the current collector container 18 may be a copper container, copper foil, or a copper cup. In some other examples, the metal of the current collector container 18 may be a container, foil or cup selected from nickel, titanium, platinum, gold, silver, aluminum, magnesium, vanadium, and alloys thereof. While aluminum and magnesium may be used, these materials may not be selected in order to avoid side reactions (e.g., with the lithium metal 16 ) during the lithiation of the SiO x (0<x<2) particles 12 .
As shown in FIG. 1A , the SiO x (0<x<2) particles 12 are combined with the lithium metal 16 in the electrochemical cell 11 . In an example, pure lithium may be used as the lithium metal 16 . In this example, the lithium metal 16 is the counter electrode, and is combined with the SiO x (0<x<2) particles 12 in the electrolyte solution 14 . It is to be understood that when combined with each other in the electrolyte solution 14 , the SiO x (0<x<2) particles 12 and the lithium metal 16 are positioned so that they are not physically contacting one another. In addition, the lithium metal 16 also does not physically contact the current collector container 18 . As such, there is a gap between the working electrode 21 and the counter electrode/ lithium metal 16 .
As previously mentioned, the electrochemical cell 11 also may include the electrolyte solution 14 . The electrolyte solution may be added to the current collector container 18 to neutralize the positive and negative charges that form around the working electrode 21 and counter electrode/ lithium metal 16 . In an example, the electrolyte solution 14 may be selected from any electrolyte solution that includes a lithium ion or lithium salt. Some examples of the electrolyte solution 14 include an ether based solvent and a lithium salt dissolved in the ether based solvent. Some examples of the ether based solvent may be 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, tetraethylene glycol dimethyl ether (TEGDME), polyethylene glycol dimethyl ether (PEGDME), and combinations thereof. Some examples of the lithium salt may be LiClO 4 , LiAlCl 4 , LiI, LiBr, LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiSCN, LiBF 4 , LiB(C 6 H 5 ) 4 , LiAsF 6 , LiCF 3 SO 3 , LiN(FSO 2 ) 2 (LIFSI), LiN(CF 3 SO 2 ) 2 (LITFSI), LiPF 6 , LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , and mixtures thereof.
In some other examples, the electrolyte solution 14 may be an organic based solvent and a lithium salt dissolved in the organic based solvent. Some examples of the organic based solvent may be carbonates, linear carbonates, aliphatic carboxylic esters, γ-lactones, chain structure ethers, cyclic ethers, and combinations thereof. Any of the previously listed lithium salts may be used with the organic based solvent.
In some instances, the electrochemical cell 11 includes a separator positioned between the working electrode 21 and the counter electrode/ lithium metal 16 . A separator (not shown in FIGS. 1A and 1B ) may be used to prevent physical contact of the working electrode 21 and counter electrode/ lithium metal 16 in the electrochemical cell 11 .
Some examples of the separator include a polyolefin membrane. The polyolefin may be a homopolymer (derived from a single monomer constituent) or a heteropolymer (derived from more than one monomer constituent), and may be either linear or branched. If a heteropolymer derived from two monomer constituents is employed, the polyolefin may assume any copolymer chain arrangement, including those of a block copolymer or a random copolymer. The same holds true if the polyolefin is a heteropolymer derived from more than two monomer constituents. As examples, the polyolefin membrane may be formed of polyethylene (PE), polypropylene (PP), a blend of PE and PP, or multi-layered structured porous films of PE and/or PP.
In other examples, the separator may be formed from another polymer chosen from polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamides (Nylons), polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK), polyethersulfones (PES), polyimides (PI), polyamide-imides, polyethers, polyoxymethylene (e.g., acetal), polybutylene terephthalate, polyethylenenaphthenate, polybutene, acrylonitrile-butadiene styrene copolymers (ABS), polystyrene copolymers, polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), polysiloxane polymers (such as polydimethylsiloxane (PDMS)), polybenzimidazole (PBI), polybenzoxazole (PBO), polyphenylenes (e.g., PARMAX⢠(Mississippi Polymer Technologies, Inc., Bay Saint Louis, Miss.)), polyarylene ether ketones, polyperfluorocyclobutanes, polytetrafluoroethylene (PTFE), polyvinylidene fluoride copolymers and terpolymers, polyvinylidene chloride, polyvinylfluoride, liquid crystalline polymers (e.g., VECTRAN⢠(Hoechst AG, Germany), ZENITE® (DuPont, Wilmington, Del.), poly(p-hydroxybenzoic acid), polyaramides, polyphenylene oxide, and/or combinations thereof. In yet another example, the separator may be chosen from a combination of the polyolefin (such as PE and/or PP) and one or more of the polymers listed above.
The separator may contain a single layer or a multi-layer laminate fabricated from either a dry or wet process. For example, a single layer of the polyolefin and/or other listed polymer may constitute the entirety of the separator. As another example, however, multiple discrete layers of similar or dissimilar polyolefins and/or polymers may be assembled into the separator. In one example, a discrete layer of one or more of the polymers may be coated on a discrete layer of the polyolefin to form the separator. Further, the polyolefin (and/or other polymer) layer, and any other optional polymer layers, may further be included in the separator as a fibrous layer to help provide the separator with appropriate structural and porosity characteristics. Still other suitable separators include those that have a ceramic layer attached thereto, and those that have ceramic filler in the polymer matrix (i.e., an organic-inorganic composite matrix). In still other instances, a ceramic membrane, such as Al 2 O 3 , Si 3 N 4 , and SiC, itself may be used as the separator.
The electrochemical cell 11 may further include the reference electrode 19 . The reference electrode 19 may be used to monitor the amount of current being applied to the electrochemical cell 11 . By connecting the reference electrode 19 to a potentiostat 13 in the electrochemical cell 11 , the reference electrode 19 is capable of measuring the amount of current being applied to the electrochemical cell 11 . The reference electrode 19 measures the voltage (i.e., potential difference) between the working electrode 21 and the reference electrode 19 . In an example, the voltage may be applied and maintained in an amount ranging from about 0.2 volts (V) to about 0.8 volts (V) versus the Li/Li + reference electrode 19 . The voltage may be applied and maintained for a time ranging from about 1 minute to about 100 hours. It is believed that the amount of time the voltage is applied to the electrochemical cell 11 depends, in part, on the SiO x (0<x<2) particle 12 size and the diffusion rate of the lithium ions. In addition, the amount of time the voltage is applied is inversely proportional to the intensity of the current. In an example, the time for holding the voltage may be determined by measuring the initial current when the voltage is applied, and then stopping the voltage application when the current is 1/100 th of the initially measured current.
Referring now to FIG. 1B , an external circuit 15 may be connected to the working electrode 21 (i.e., the current collector container 18 in contact with the SiO x (0<x<2) particles 12 ), the counter electrode/ lithium metal 16 , and the reference electrode 19 . The external circuit 15 is used to connect the working electrode 21 , the reference electrode 19 , and to the counter electrode/ lithium metal 16 . It is to be understood that the three electrodes (i.e., the counter electrode/ lithium metal 16 , the working electrode 21 , and the reference electrode 19 ) are connected to the potentiostat 13 . The reference electrode 19 maintains the same potential even if some current is flowing through it. In this electrochemical cell 11 , the potential difference between working electrode 21 and reference electrode 19 is registered or controlled, while the current flows mainly between the working electrode 21 and the counter electrode/ lithium metal 16 . The external circuit 15 may be operatively connected to the potentiostat 13 , which applies the voltage, and supplies the electrical current, from a power supply (not shown).
The current resulting from the voltage application causes lithium ions to dissolve (or de-plate) from the counter electrode/ lithium metal 16 . These ions are carried through the electrolyte solution 14 towards the working electrode 21 . The lithium ions are alloyed with the SiO x (0<x<2) particles 12 by a conversion reaction with the electrolyte. This reaction lithiates the SiO x (0<x<2) particles 12 . It is believed that a reduction reaction may occur between the SiO x (0<x<2) particles 12 and the lithium ions to form the silicon matrix 12 â² (shown in FIG. 1E ). More particularly, the reduction reaction reduces the SiO x (0<x<2) particles 12 to form the silicon matrix 12 â², and the lithium ions react with the oxygen to form lithium oxide nanoparticles 16 â² within the silicon matrix 12 â² (shown in FIG. 1E ). As such, the silicon matrix 12 â² includes lithium oxide nanoparticles 16 â² therein. During the reduction of the SiO x (0<x<2) particles 12 , the following reaction (I) may occur:
SiO x +2Li + âSi+Li 2 Oââ(I)
In some instances, an oxidation reaction, shown as reaction (II), may also occur:
SiO x +Li + +Li 2 OâLi 2 SiO 3 ââ(II)
As the voltage application continues, the lithium oxide 16 â² may react with the SiO x (0<x<2) particles 12 and the lithium ions to form lithium silicate nanoparticles 16 â³. Whether reaction (II) occurs depends, in part, on the amount of the SiO x (0<x<2) particles 12 used in the electrochemical cell 11 and the amount of time the voltage is applied to the electrochemical cell 11 .
Referring now to FIG. 1E , after the voltage has been applied for a suitable time, the silicon matrix 12 â² may be formed with lithium oxide nanoparticles 16 â² and, in some instances, lithium silicate nanoparticles 16 â³ therein.
The silicon matrix 12 â² having lithium oxide nanoparticles 16 â² and, in some instances, lithium silicate nanoparticles 16 â³ therein may be exposed to a removal process that extracts or otherwise remove the lithium oxide nanoparticles 16 â² and, in some instances, the lithium silicate nanoparticles 16 â³ from the silicon matrix 12 â². This removal process generates the porous silicon particles 12 â³, as shown in FIG. 1F . Examples of the removal process are discussed further hereinbelow.
Another example of the method is shown in FIGS. 1C, 1D, 1E and 1F (labeled â 2 â). This example of the method may also include an additional step, including a coating process as shown in FIG. 1G . This example of the method involves another electrochemical cell 11 â². Generally, the electrochemical cell 11 â² includes the working electrode 21 â², the electrolyte solution 14 , the reference electrode 19 , and the counter electrode (which, in this example, is also lithium metal 16 ). In some instances, the separator (not shown) may also be used in the electrochemical cell 11 â².
In the example shown in FIGS. 1C and 1D , the SiO x (0<x<2) particles 12 are added to a porous current collector 18 â². The SiO x (0<x<2) particles 12 are positioned within pores of the porous current collector 18 â². When the SiO x (0<x<2) particles 12 are positioned within the pores of the porous current collector 18 â², the particles 12 and porous current collector 18 â² are in contact with each other, and when a voltage potential is applied to the porous current collector 18 â², the particles 12 and the porous current collector 18 â² are in electrical contact with each other. The porous current collector 18 â² with the SiO x (0<x<2) particles 12 therein functions as the working electrode 21 â².
It is to be understood that the electrolyte solution 14 , the reference electrode 19 , the lithium metal 16 , and the separator may be the same materials as previously described in reference to FIG. 1A . Furthermore, the electrolyte solution 14 , the reference electrode 19 , the lithium metal 16 , and the separator when used, may be incorporated in the electrochemical cell 11 â² in the same manner as the electrochemical cell 11 described in FIG. 1A . In this example, it is to be understood that the container 20 of the electrochemical cell is not a current collector and is some non-conductive material (e.g., a non-conductive polymer, glass, etc.).
The porous current collector 18 â² receives and transports electrons from an external circuit 15 (shown in FIG. 1D ) to the SiO x (0<x<2) particles 12 within the porous current collector 18 â², thereby reducing the SiO x (0<x<2) particles 12 to form the silicon matrix 12 â². In an example, the porous current collector 18 â² may be a conductive porous metal. Some examples of the conductive porous metal include porous copper, nickel, titanium, platinum, gold, silver, aluminum, magnesium, vanadium, or alloys thereof. As noted above, aluminum and magnesium may not be used in order to avoid side reactions with the lithium metal 16 . In an example, the porous current collector 18 â² is porous copper.
Referring to FIG. 1D , an external circuit 15 may be connected to the working electrode 21 â² (i.e., the porous current collector 18 â² with the SiO x (0<x<2) particles 12 therein), the counter electrode/ lithium metal 16 , and the reference electrode 19 as previously described in reference to FIG. 1B . In this example, the external circuit 15 may also be operatively connected to the potentiostat 13 , which applies the voltage, and supplies the electrical current, from a power supply (not shown).
The current resulting from the voltage application causes the lithium ions to react with the SiO x (0<x<2) particles 12 as previously described in FIG. 1B . The same reaction(s) (I), (II) occur that result in the formation of the silicon matrix 12 â², the lithium oxide nanoparticles 16 â², and, in some instances, the lithium silicate nanoparticles 16 â³, as shown in FIG. 1E .
In another example, not shown in FIGS. 1A-1E , a two electrode cell configuration may be used. In the two electrode cell configuration, the counter electrode/ lithium metal 16 may also function as the reference electrode 19 . The voltage may be measured at the counter electrode/ lithium metal 16 as previously described in reference to FIGS. 1B and 1D using a potentiostat 13 .
The silicon matrix 12 â² having the lithium oxide nanoparticles 16 â², and, in some instances, the lithium silicate nanoparticles 16 â³ therein may be removed from the electrochemical cell and exposed to additional processing.
Referring now to FIG. 1F (which may be used in both methods 1 and 2 ), at least some of the lithium oxide nanoparticles 16 â² may be removed from the silicon matrix 12 â². When present, at least some of the lithium silicate nanoparticles 16 â³ may or may not be removed. In an example, the silicon matrix 12 â² includes lithium oxide nanoparticles 16 â² alone, and the removal process may involve exposure to water and/or ethanol. In another example, the silicon matrix 12 â² includes both lithium oxide nanoparticles 16 â² and lithium silicate nanoparticles 16 â³, and the removal process may involve exposure to water and/or ethanol. In still another example, the silicon matrix 12 â² includes both lithium oxide nanoparticles 16 â² and lithium silicate nanoparticles 16 â³, and the removal process may involve exposure to water and/or ethanol, and then exposure to a diluted acid. In yet a further example, the silicon matrix 12 â² includes both lithium oxide nanoparticles 16 â² and lithium silicate nanoparticles 16 â³, and the removal process may involve exposure to a diluted acid.
In an example, at least some of the nanoparticles 16 â² are removed from the silicon matrix 12 â² by exposing the silicon matrix 12 â² to deionized water, ethanol, or a combination thereof. In an example, the amount of liquid (water and/or ethanol) used for removal may be present in a ratio of at least 1:1 of the liquid to the SiO x (0<x<2) particles 12 . In some inst
CLAIMS
Claims ( 20 )
What is claimed is:
1. A method for forming a porous material, the method comprising:
combining SiO x (0<x<2) particles with a lithium metal;
causing the SiO x (0<x<2) particles and the lithium metal to react to form lithium oxide nanoparticles in a silicon matrix; and
removing at least some of the lithium oxide nanoparticles from the silicon matrix, thereby forming porous silicon particles.
2. The method as defined in claim 1 wherein the causing results in lithium silicate nanoparticles to form in the silicon matrix;
and the removing further includes removing at least some of the lithium silicate nanoparticles from the silicon matrix.
3. The method as defined in claim 2 wherein the removing of at least some of the lithium oxide nanoparticles and the removing of at least some of the lithium silicate nanoparticles includes any of:
i) exposing the silicon matrix to deionized water, ethanol, or a combination thereof, thereby leaching at least some of the lithium oxide nanoparticles from the silicon matrix; and
exposing the silicon matrix to a diluted acid, thereby etching at least some of the lithium silicate nanoparticles from the silicon matrix and forming a dispersion containing the porous silicon particles, wherein the diluted acid is selected from the group consisting of HCl, H 2 SO 4 , HNO 3 , H 3 PO 4 , and combinations thereof; or
ii) exposing the silicon matrix to a diluted acid, thereby etching at least some of the lithium oxide nanoparticles and at least some of the lithium silicate nanoparticles from the silicon matrix and forming a dispersion containing the porous silicon particles, wherein the diluted acid is selected from the group consisting of HCl, H 2 SO 4 , HNO 3 , H 3 PO 4 , and combinations thereof;
and wherein the method further comprises isolating the porous silicon particles using centrifugation or ultrasonic waves.
4. The method as defined in claim 1 wherein the causing includes applying a voltage, ranging from about 0.2 volts to 0.8 volts versus a Li/Li + reference electrode, to an electrochemical cell including an electrolyte solution, the lithium metal as a counter electrode, and a current collector, wherein the SiO x (0<x<2) particles and the current collector are in electrical contact to form a working electrode, thereby lithiating the SiO x (0<x<2) particles to form the lithium oxide nanoparticles in the silicon matrix.
5. The method as defined in claim 4 wherein:
the current collector is selected from the group consisting of a metal container, metal foil, and a metal cup, wherein the metal of the container, the foil, or the cup is selected from the group consisting of copper, nickel, titanium, platinum, gold, silver, magnesium, aluminum, vanadium, and alloys thereof; and
the current collector includes the electrolyte solution, the lithium metal as the counter electrode, the reference electrode, and the SiO x (0<x<2) particles therein.
6. The method as defined in claim 4 wherein:
the current collector is a porous structure selected from the group consisting of copper, nickel, titanium, platinum, gold, silver, aluminum, magnesium, vanadium, and alloys thereof; and
the working electrode is formed by introducing the SiO x (0<x<2) particles into the porous structure;
and the method further comprises placing the working electrode into the electrolyte solution with the lithium metal as the counter electrode.
7. The method as defined in claim 4 wherein the electrochemical cell further includes a separator positioned between the working electrode and the counter electrode.
8. The method as defined in claim 4 wherein the voltage is applied for a time ranging from about 1 minute to about 100 hours.
9. The method as defined in claim 4 wherein the Li/Li + reference electrode and the counter electrode are a single counter/reference electrode.
10. The method as defined in claim 1 wherein the combining includes mixing the SiO x (0<x<2) particles with the lithium metal at a ratio of the SiO x (0<x<2) particles to the lithium metal being 1:2X where X is equal to x of the SiO x (0<x<2) particles; and wherein the causing includes heating the SiO x (0<x<2) particles and the lithium metal to a temperature greater than 100° C.
11. The method as defined in claim 1 wherein the removing of the lithium oxide nanoparticles includes any of:
i) exposing the silicon matrix to deionized water, ethanol, or a combination thereof, thereby leaching at least some of the lithium oxide nanoparticles from the silicon matrix and forming a dispersion containing the porous silicon particles; or
ii) exposing the silicon matrix to a diluted acid, thereby etching at least some of the lithium oxide nanoparticles from the silicon matrix and forming the dispersion containing the porous silicon particles, wherein the diluted acid is selected from the group consisting of HCl, Hâ 2 SO 4 , HNO 3 , H 3 PO 4 , and combinations thereof;
and wherein the method further comprises isolating the porous silicon particles using centrifugation or ultrasonic waves.
12. The method as defined in claim 1 , further comprising applying an electrically conductive coating to the porous silicon particles, wherein the electrically conductive coating is selected from the group consisting of a graphitic carbon coating and a nitride based coating.
13. The method as defined in claim 12 wherein the electrically conductive coating is applied using chemical vapor deposition or atomic layer deposition.
14. The method as defined in claim 1 , further comprising:
forming a lithium battery negative electrode including:
the porous silicon particles as a negative electrode active material of the lithium battery negative electrode;
a binder; and
a conductive material; and
applying a conductive coating to a surface of the lithium battery negative electrode.
15. The method as defined in claim 1 wherein no hydrofluoric acid is used during the method of forming the porous material.
16. The method as defined in claim 1 , further comprising adding the porous silicon particles as a negative electrode active material to a negative electrode dispersion.
17. The method as defined in claim 16 , further comprising:
applying the negative electrode dispersion to a current collector; and
removing any solvent from the negative electrode dispersion to form a lithium battery negative electrode on the current collector.
18. The method as defined in claim 17 , further comprising incorporating the lithium battery negative electrode into a lithium ion battery or a lithium-sulfur battery.
19. The method as defined in claim 18 wherein the lithium-sulfur battery further includes:
a sulfur-based positive electrode; and
an other electrolyte solution, the other electrolyte solution including an ether based solvent and a lithium salt dissolved in the ether based solvent, the ether based solvent being selected from the group consisting of 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1-2-diethoxyethane, ethoxymethoxyethane, tetraethylene glycol dimethyl ether (TEGDME), polyethylene glycol dimethyl ether (PEGDME), and combinations thereof; and the lithium salt being selected from the group consisting of LiClO 4 , LiAlCl 4 , LiI, LiBr, LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiSCN, LiBF 4 , LiB(C 6 H 5 ) 4 , LiAsF 6 , LiCF 3 SO 3 , LiN(FSO 2 ) 2 (LIFSI), LiN(CF 3 SO 2 ) 2 (LITFSI), LiPF 6 , LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , and mixtures thereof.
20. The method as defined in claim 18 wherein the lithium ion battery further includes:
a lithium-based positive electrode; and
an other electrolyte solution, the other electrolyte solution including an organic based solvent and a lithium salt dissolved in the organic based solvent, the organic based solvent being selected from the group consisting of carbonates, linear carbonates, aliphatic carboxylic esters, γ-lactones, chain structure ethers, cyclic ethers, and combinations thereof, and the lithium salt being selected from the group consisting of LiClO 4 , LiAlCl 4 , LiI, LiBr, LiSCN, LiBF 4 , LiB(C 6 H 5 ) 4 , LiCF 3 SO 3 , LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiAsF 6 , LiPF 6 , LITFSI, LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , and combinations thereof.
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