ABSTRACT
Abstract
An example of a negative electrode includes silicon nanoparticles having a carbon coating thereon. The carbon coating has an oxygen-free structure including pentagon rings. The negative electrode with the silicon nanoparticles having the carbon coating thereon may be incorporated into a lithium-based battery. In an example of a method, silicon nanoparticles are provided. A carbon precursor is applied on the silicon nanoparticles. The carbon precursor is an oxygen-free, fluorene-based polymer. Then the silicon nanoparticles are heated in an inert gas atmosphere to form the carbon coating on the silicon nanoparticles. The carbon coating formed on the silicon nanoparticles has an oxygen-free structure including pentagon rings.
Description
Secondary, or rechargeable, lithium-based 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
An example of a negative electrode includes silicon nanoparticles having a carbon coating thereon. The carbon coating has an oxygen-free structure including pentagon rings. The negative electrode, with the silicon nanoparticles having the carbon coating thereon, may be incorporated into a lithium-based battery. The lithium-based battery also includes a positive electrode and a microporous polymer separator soaked in an electrolyte solution. The microporous polymer separator is disposed between the positive electrode and the negative electrode.
In an example of a method, silicon nanoparticles are provided. A carbon precursor is applied on the silicon nanoparticles. The carbon precursor is an oxygen-free, fluorene-based polymer. Then the silicon nanoparticles are heated in an inert gas atmosphere to form a carbon coating on the silicon nanoparticles. The carbon coating formed on the silicon nanoparticles has an oxygen-free structure including pentagon rings.
BRIEF DESCRIPTION OF THE DRAWINGS
Features 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.
FIG. 1 is a schematic view of an example of a silicon nanoparticle having a carbon coating thereon;
FIG. 2 is a schematic, cross-sectional view of an example of a negative electrode, including an example of the carbon coated silicon nanoparticles disclosed herein, on a current collector;
FIG. 3 is a schematic, cross-sectional view of another example of a negative electrode, including an example of the carbon coated silicon nanoparticles disclosed herein, on a current collector;
FIG. 4 is a schematic, cross-sectional view of an example of a lithium sulfur battery that has a negative electrode including an example of the carbon coated silicon nanoparticles disclosed herein;
FIG. 5 is a cross-sectional, schematic view of an example of a lithium ion battery that has a negative electrode including an example of the carbon coated silicon nanoparticles disclosed herein; and
FIG. 6 is a graph illustrating the capacity retention (Y axis) versus the cycle number (X axis) of three comparative batteries and an example battery with a negative electrode including an example of the carbon coated silicon nanoparticles disclosed herein.
DETAILED DESCRIPTION
Lithium-based batteries generally operate by reversibly passing lithium ions between a negative electrode (sometimes called an anode) and a positive electrode (sometimes called a cathode). The negative and positive electrodes are situated on opposite sides of a porous polymer separator soaked with an electrolyte solution that is suitable for conducting the lithium ions. During charging, lithium ions are inserted (e.g., intercalated, alloyed, etc.) into the negative electrode, and during discharging, lithium ions are extracted from the negative electrode. Each of the electrodes is also associated with respective current collectors, which are connected by an interruptible external circuit that allows an electric current to pass between the negative and positive electrodes. Examples of lithium-based batteries include a lithium sulfur battery (i.e., includes a sulfur based positive electrode paired with a lithiated negative electrode) and a lithium ion battery (i.e., includes a lithium-based positive electrode paired with a negative electrode or a non-lithium positive electrode paired with a lithiated negative electrode).
Silicon nanoparticles may be used as the active material for a negative electrode. Fully lithiated silicon (Li 4.4 Si) has a high gravimetric capacity of about 2010 mAh and a high volumetric capacity of about 2400 mAh, e.g., as compared to lithiated graphite (LiC 6 ), which has a gravimetric capacity of about 340 mAh and a volumetric capacity of about 712 mAh. However, silicon has a high volume expansion of V Si :V Li4.4Si =1:4.0, which means approximately 300% volume expansion (e.g., as compared to silicon suboxide, which may have a volume expansion of V SiOx :V (Li4Si+Li4SiO4) =1:2.3, which means approximately 130% volume expansion). The high volume expansion of silicon may result in electrode fracture and loss of electrical contact and electrode integrity. Silicon also has a low electrical conductivity of about 1.5Ã10 â3 S/m, e.g., as compared to carbon, which may have electrical conductivity greater than 10 3 S/m. Additionally, a silicon electrode may have a poor cycle life and active surface solid-electrolyte interphase (SEI) formation, which may cause continuous electrolyte consumption and lithium loss.
Silicon nanoparticles may be coated with carbon to mitigate the high volume expansion, low electrical conductivity, poor cycle life, and active surface SEI formation of silicon electrodes. If the carbon coating has oxygen rich surface functional groups, these functional groups may consume active lithium and electrolyte, which may result in low efficiency and cycle life. A carbon coating with oxygen rich surface functional groups may be formed when oxygen rich carbon precursors are used, such as resorcinol-formaldehyde or glucose. Oxygen can be removed from the carbon coating by heating at a high temperature (e.g., greater than 1,000° C.). Additionally, the carbon coating precursors may be heated to increase the electrical conductivity of the carbon coating. However, heating at temperatures higher than about 850° C. may result in the formation of a silicon carbide (SiC) layer between the carbon coating that is formed and the silicon nanoparticles on which the carbon coating is formed. Silicon carbide is an insulator of both electrons and lithium ions, and thus, the formation of a silicon carbide layer may deleteriously affect the electrochemical performance of the carbon coated silicon nanoparticles.
In the negative electrode
24 , 24 â² (see FIGS. 2 and 3 ) disclosed herein, coated nanoparticles 10 are included as an active material. The coated nanoparticles 10 are made up of silicon nanoparticles 12 having a carbon coating 14 thereon. FIG. 1 schematically illustrates one coated nanoparticle 10 , including one silicon nanoparticle 12 with the carbon coating 14 thereon. The carbon coating 14 has an oxygen-free structure including pentagon rings 16 .
The method disclosed herein uses an oxygen-free, fluorene-based polymer as a carbon precursor and heats the silicon nanoparticles 12 (with the carbon precursor applied thereon) in an inert gas atmosphere. The method forms the oxygen-free carbon coating 14 on the silicon nanoparticles 12 without having to heat the coating 14 to a temperature greater than 850° C. Thus, a silicon carbide layer is not formed in the coated nanoparticles 10 .
Additionally, the oxygen-free, fluorene-based polymer is able to develop electrical conductivity at a relatively low temperature. In an example of the method, the silicon nanoparticles 12 , with the carbon precursor applied thereon, are heated at a temperature ranging from about 650° C. to about 750° C.
Further, the oxygen-free, fluorene-based polymer contains pentagon rings, which causes the carbon coating 14 to include pentagon rings 16 . The presence of the pentagon rings 16 in the carbon coating 14 may give rise to curvatures 20 in the carbon coating 14 , which effectively resist the volume expansion of silicon. In some examples, the oxygen-free, fluorene-based polymer includes an allyl group, which may cross-link the polymer and render a strong electron conducting network throughout the carbon coating 14 .
The method for forming the coated nanoparticles 10 includes providing the silicon nanoparticles 12 . The silicon nanoparticles 12 provided may have a particle size ranging from about 30 nm to about 100 nm.
The method also includes applying the carbon precursor on the silicon nanoparticles 12 . Applying the carbon precursor may be accomplished by mixing the carbon precursor, the silicon nanoparticles 12 , and a solvent to form a slurry, and drying the slurry. In an example, the carbon precursor, the silicon nanoparticles 12 , and the solvent are mixed by a planetary centrifugal mixer, e.g., a THINKY® Mixer for about 20 minutes. In another example, the slurry is dried in a hood over night (e.g., 12 hours), followed by drying the mixture at 60° C. under vacuum for about 12 hours.
The silicon nanoparticles 12 may be present in the slurry in an amount ranging from about 10 wt % to about 50 wt % (based on the total wt % of the slurry). In an example, the silicon nanoparticles 12 make up about 31.25 wt % of the slurry.
The carbon precursor may be present in the slurry in an amount ranging from about 1 wt % to about 10 wt % (based on the total wt % of the slurry). In an example, the carbon precursor is about 6.25 wt % of the slurry.
In an example, the weight ratio of the carbon precursor to silicon nanoparticles 12 in the slurry is 1:5.
As mentioned above, the carbon precursor is an oxygen-free, fluorene-based polymer. Examples of suitable oxygen-free, fluorene-based polymers include polymers formed (e.g., via a condensation reaction) from the following monomer(s): (i) 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester
and (ii) 2,7-dibromofluorene
or a modified 2,7-dibromofluorene monomer (e.g., having an allyl group attached to the 9,9â² position). Other examples of monomer (i) include 9,9-Dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester
9,9-Didodecylfluorene-2,7-diboronic acid
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Secondary, or rechargeable, lithium-based 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
An example of a negative electrode includes silicon nanoparticles having a carbon coating thereon. The carbon coating has an oxygen-free structure including pentagon rings. The negative electrode, with the silicon nanoparticles having the carbon coating thereon, may be incorporated into a lithium-based battery. The lithium-based battery also includes a positive electrode and a microporous polymer separator soaked in an electrolyte solution. The microporous polymer separator is disposed between the positive electrode and the negative electrode.
In an example of a method, silicon nanoparticles are provided. A carbon precursor is applied on the silicon nanoparticles. The carbon precursor is an oxygen-free, fluorene-based polymer. Then the silicon nanoparticles are heated in an inert gas atmosphere to form a carbon coating on the silicon nanoparticles. The carbon coating formed on the silicon nanoparticles has an oxygen-free structure including pentagon rings.
BRIEF DESCRIPTION OF THE DRAWINGS
Features 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.
FIG. 1 is a schematic view of an example of a silicon nanoparticle having a carbon coating thereon;
FIG. 2 is a schematic, cross-sectional view of an example of a negative electrode, including an example of the carbon coated silicon nanoparticles disclosed herein, on a current collector;
FIG. 3 is a schematic, cross-sectional view of another example of a negative electrode, including an example of the carbon coated silicon nanoparticles disclosed herein, on a current collector;
FIG. 4 is a schematic, cross-sectional view of an example of a lithium sulfur battery that has a negative electrode including an example of the carbon coated silicon nanoparticles disclosed herein;
FIG. 5 is a cross-sectional, schematic view of an example of a lithium ion battery that has a negative electrode including an example of the carbon coated silicon nanoparticles disclosed herein; and
FIG. 6 is a graph illustrating the capacity retention (Y axis) versus the cycle number (X axis) of three comparative batteries and an example battery with a negative electrode including an example of the carbon coated silicon nanoparticles disclosed herein.
DETAILED DESCRIPTION
Lithium-based batteries generally operate by reversibly passing lithium ions between a negative electrode (sometimes called an anode) and a positive electrode (sometimes called a cathode). The negative and positive electrodes are situated on opposite sides of a porous polymer separator soaked with an electrolyte solution that is suitable for conducting the lithium ions. During charging, lithium ions are inserted (e.g., intercalated, alloyed, etc.) into the negative electrode, and during discharging, lithium ions are extracted from the negative electrode. Each of the electrodes is also associated with respective current collectors, which are connected by an interruptible external circuit that allows an electric current to pass between the negative and positive electrodes. Examples of lithium-based batteries include a lithium sulfur battery (i.e., includes a sulfur based positive electrode paired with a lithiated negative electrode) and a lithium ion battery (i.e., includes a lithium-based positive electrode paired with a negative electrode or a non-lithium positive electrode paired with a lithiated negative electrode).
Silicon nanoparticles may be used as the active material for a negative electrode. Fully lithiated silicon (Li 4.4 Si) has a high gravimetric capacity of about 2010 mAh and a high volumetric capacity of about 2400 mAh, e.g., as compared to lithiated graphite (LiC 6 ), which has a gravimetric capacity of about 340 mAh and a volumetric capacity of about 712 mAh. However, silicon has a high volume expansion of V Si :V Li4.4Si =1:4.0, which means approximately 300% volume expansion (e.g., as compared to silicon suboxide, which may have a volume expansion of V SiOx :V (Li4Si+Li4SiO4) =1:2.3, which means approximately 130% volume expansion). The high volume expansion of silicon may result in electrode fracture and loss of electrical contact and electrode integrity. Silicon also has a low electrical conductivity of about 1.5Ã10 â3 S/m, e.g., as compared to carbon, which may have electrical conductivity greater than 10 3 S/m. Additionally, a silicon electrode may have a poor cycle life and active surface solid-electrolyte interphase (SEI) formation, which may cause continuous electrolyte consumption and lithium loss.
Silicon nanoparticles may be coated with carbon to mitigate the high volume expansion, low electrical conductivity, poor cycle life, and active surface SEI formation of silicon electrodes. If the carbon coating has oxygen rich surface functional groups, these functional groups may consume active lithium and electrolyte, which may result in low efficiency and cycle life. A carbon coating with oxygen rich surface functional groups may be formed when oxygen rich carbon precursors are used, such as resorcinol-formaldehyde or glucose. Oxygen can be removed from the carbon coating by heating at a high temperature (e.g., greater than 1,000° C.). Additionally, the carbon coating precursors may be heated to increase the electrical conductivity of the carbon coating. However, heating at temperatures higher than about 850° C. may result in the formation of a silicon carbide (SiC) layer between the carbon coating that is formed and the silicon nanoparticles on which the carbon coating is formed. Silicon carbide is an insulator of both electrons and lithium ions, and thus, the formation of a silicon carbide layer may deleteriously affect the electrochemical performance of the carbon coated silicon nanoparticles.
In the negative electrode
24 , 24 â² (see FIGS. 2 and 3 ) disclosed herein, coated nanoparticles 10 are included as an active material. The coated nanoparticles 10 are made up of silicon nanoparticles 12 having a carbon coating 14 thereon. FIG. 1 schematically illustrates one coated nanoparticle 10 , including one silicon nanoparticle 12 with the carbon coating 14 thereon. The carbon coating 14 has an oxygen-free structure including pentagon rings 16 .
The method disclosed herein uses an oxygen-free, fluorene-based polymer as a carbon precursor and heats the silicon nanoparticles 12 (with the carbon precursor applied thereon) in an inert gas atmosphere. The method forms the oxygen-free carbon coating 14 on the silicon nanoparticles 12 without having to heat the coating 14 to a temperature greater than 850° C. Thus, a silicon carbide layer is not formed in the coated nanoparticles 10 .
Additionally, the oxygen-free, fluorene-based polymer is able to develop electrical conductivity at a relatively low temperature. In an example of the method, the silicon nanoparticles 12 , with the carbon precursor applied thereon, are heated at a temperature ranging from about 650° C. to about 750° C.
Further, the oxygen-free, fluorene-based polymer contains pentagon rings, which causes the carbon coating 14 to include pentagon rings 16 . The presence of the pentagon rings 16 in the carbon coating 14 may give rise to curvatures 20 in the carbon coating 14 , which effectively resist the volume expansion of silicon. In some examples, the oxygen-free, fluorene-based polymer includes an allyl group, which may cross-link the polymer and render a strong electron conducting network throughout the carbon coating 14 .
The method for forming the coated nanoparticles 10 includes providing the silicon nanoparticles 12 . The silicon nanoparticles 12 provided may have a particle size ranging from about 30 nm to about 100 nm.
The method also includes applying the carbon precursor on the silicon nanoparticles 12 . Applying the carbon precursor may be accomplished by mixing the carbon precursor, the silicon nanoparticles 12 , and a solvent to form a slurry, and drying the slurry. In an example, the carbon precursor, the silicon nanoparticles 12 , and the solvent are mixed by a planetary centrifugal mixer, e.g., a THINKY® Mixer for about 20 minutes. In another example, the slurry is dried in a hood over night (e.g., 12 hours), followed by drying the mixture at 60° C. under vacuum for about 12 hours.
The silicon nanoparticles 12 may be present in the slurry in an amount ranging from about 10 wt % to about 50 wt % (based on the total wt % of the slurry). In an example, the silicon nanoparticles 12 make up about 31.25 wt % of the slurry.
The carbon precursor may be present in the slurry in an amount ranging from about 1 wt % to about 10 wt % (based on the total wt % of the slurry). In an example, the carbon precursor is about 6.25 wt % of the slurry.
In an example, the weight ratio of the carbon precursor to silicon nanoparticles 12 in the slurry is 1:5.
As mentioned above, the carbon precursor is an oxygen-free, fluorene-based polymer. Examples of suitable oxygen-free, fluorene-based polymers include polymers formed (e.g., via a condensation reaction) from the following monomer(s): (i) 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester
and (ii) 2,7-dibromofluorene
or a modified 2,7-dibromofluorene monomer (e.g., having an allyl group attached to the 9,9â² position). Other examples of monomer (i) include 9,9-Dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester
9,9-Didodecylfluorene-2,7-diboronic acid
or 9,9-Dihexylfluorene-2,7-diboronic acid
and other examples of monomer (ii) include
2,7-Dibromo-9,9-dimethyl-9H- fluorene 2,7-Dibromo-9,9-diallyl-9H-fluorene
9,9-Didodecyl-2,7-dibromofluorene
and 9,9-Dihexyl-2,7-dibromofluorene
Any of monomer (i) (or another like monomer) may be reacted with any of monomer (ii) to form the oxygen-free, fluorene-based polymers disclosed herein. As another example, 9,9-Didodecylfluorene-2,7-diboronic acid may be reacted with 2,7-Dibromo-9,9-diallyl-9H-fluorene.
While not being bound to any theory, it is believed that use of the oxygen-free, fluorene-based polymer as the carbon precursor allows the structure of the carbon coating 14 to be oxygen-free without being exposed to heating at high temperatures (e.g., greater than 1000° C.). Thus, the use of the oxygen-free, fluorene-based polymer contributes to the ability of the carbon coating 14 to mitigate the high volume expansion, low electrical conductivity, poor cycle life, and active surface SEI formation of silicon electrodes, without consuming active lithium and electrolyte or forming an electrically insulating silicon carbide layer.
As also mentioned above, in some examples, the oxygen-free, fluorene-based polymer includes an allyl group. As an example, the two protons on the five-membered ring structure (9,9â² position) of 2,7-dibromofluorene are acidic and can be modified with allyl groups. When they are present, allyl groups in the oxygen-free, fluorene-based polymer may crosslink the polymer. The crosslinked polymer may form a strong electron conducting network in the carbon coating 14 . The crosslinked polymer may also be resistant to softening during the heat treatment (which will be discussed below). If the polymer does soften or melt, the carbon coating 14 formed may be insufficiently porous and have a high electrical resistance.
The solvent may be present in the slurry in an amount ranging from about 50 wt % to about 80 wt % (based on the total wt % of the slurry). In an example, the solvent makes up about 62.5 wt % of the slurry. An example of the solvent includes chlorobenzene, dichlorobenzene, etc.
In one specific example, the carbon precursor is applied on the silicon nanoparticles 12 by mixing 1 g of the carbon precursor, 5 g of the silicon nanoparticles 12 , and 10 g of chlorobenzene with a THINKY® Mixer to form a slurry. In this example, the slurry may then be dried in a hood.
In some examples, the method may include synthesizing the carbon precursor prior to applying the carbon precursor on the silicon nanoparticles 12 . In an example, the carbon precursor may be synthesized by stirring a mixture including fluorene-based monomers (i) and (ii), a catalyst, and a solvent. In an example, the mixture may be stirred in an inert (e.g., argon) gas atmosphere. In another example, the mixture may be vigorously stirred for about 72 hours at 70° C. in tetrahydrofuran (THF).
The fluorene-based monomer(s) may be present in the mixture in an amount ranging from about 2 wt % to about 50 wt % (based on the total wt % of the mixture). In an example, the fluorene-based monomer makes up about 30 wt % of the mixture. As mentioned above, an example of the fluorene-based monomer includes 2,7-dibromofluorene (or a modified version thereof), used in combination with 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester at a 1:1 molar ratio. It is to be understood that when an oxygen-containing, fluorene-based monomer is used to synthesize the oxygen-free, fluorene-based polymer, the oxygen will become part of a removable byproduct and will not be present in the synthesized polymer.
While some examples of the fluorene-based monomers are disclosed herein, it is to be understood that any fluorene-based monomers may be used that, when reacted via a condensation reaction, will form an oxygen-free fluorene-based polymer.
The catalyst may be present in the mixture in an amount ranging from about 0.01 wt % to about 1 wt % (based on the total wt % of the mixture). In an example, the catalyst makes up about 0.035 wt % of the mixture. An example of the catalyst includes tetrakis(triphenylphosphine)palladium(0) ((PPh 3 ) 4 Pd(0)). Other palladium catalysts may also be used.
The solvent may be present in the mixture in an amount ranging from about 30 wt % to about 95 wt % (based on the total wt % of the mixture). In an example, the solvent makes up about 80 wt % of the mixture. Examples of the solvent include tetrahydrofuran (THF), toluene, dimethyl ether (DME), diethyl ether (DEE), and the like.
After the carbon precursor is synthesized, it is to be understood that the mixture has been altered, and at least includes the oxygen-free, fluorene-based polymer, which is the carbon precursor. At least some solvent may also be present in the altered mixture.
After the carbon precursor is synthesized, the carbon precursor may then be removed from the mixture using any suitable separation technique. For example, the carbon precursor may be removed by vacuum filtration, centrifugal force, or any other suitable means. The carbon precursor may be washed multiple times with deionized water during and/or after the separation of the carbon precursor from the altered mixture. It may be desirable to wash the carbon precursor with deionized water before it is applied to the silicon nanoparticles 12 .
After the carbon precursor is separated from the altered mixture and washed, the carbon precursor may be dried at a temperature ranging from about 60° C. to about 100° C. for a time period ranging from about 6 hours to about 24 hours. The drying of the precursor may also be under vacuum.
In one specific example, the carbon precursor is synthesized by refluxing, with vigorously stirring, 1.72 g of 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester, 1.0 g 2,7-dibromofluorene, 20 mg (PPh 3 ) 4 Pd(0), 50 g THF, and 5 mL of a 2 M Na 2 CO 3 solution for about 72 hours in an inert gas atmosphere. In this example, the carbon precursor may then be filtered, washed by water, and dried under vacuum at 60° C. overnight (i.e., for 12 hours). The oxygen atoms from 9,9-dioctylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester are present in a byproduct (Na 2 CO 3 âBO 2 C 3 H 6 ) which is soluble in THF and therefore, removed during filtering.
After the carbon precursor is applied on the silicon nanoparticles 12 , the method includes heating the silicon nanoparticles 12 (with the carbon precursor thereon) to form the carbon coating 14 on the silicon nanoparticles 12 . In addition to forming the carbon coating 14 , the heating also causes the carbon coating 14 to develop electrical conductivity. In an example, the silicon nanoparticles 12 (with the carbon precursor thereon) are heated at a temperature ranging from about 650° C. to about 750° C. for a time period ranging from about 1 hour to about 10 hours. In another example, the silicon nanoparticles 12 (with the carbon precursor thereon) are heated at a temperature of 720° C. for a time period ranging from about 1 hour to about 10 hours.
The heating of the silicon nanoparticles 12 may be performed in an inert gas atmosphere. In some examples of the method, the silicon nanoparticles 12 may be purged with an inert gas prior to being heated to form the carbon coating 14 . In one such example, the silicon nanoparticles 12 with the carbon precursor applied thereon may be purged with argon gas after being placed in a closed system (e.g., a furnace) and prior to being heated. While not being bound to any theory, it is believed that heating in an inert gas atmosphere and/or purging the silicon nanoparticles 12 with an inert gas may help the structure of the carbon coating 14 to remain oxygen-free at a heating temperature ranging from about 650° C. to about 750° C. The oxygen-free structure of the carbon coating 14 allows the carbon coating 14 to mitigate the high volume expansion, low electrical conductivity, poor cycle life, and active surface SEI formation of silicon electrodes, without consuming active lithium and electrolyte or forming an electrically insulating silicon carbide layer.
As shown in FIG. 1 , the structure of the carbon coating 14 , in addition to being oxygen-free, includes pentagon rings 16 . In some examples, the structure of the carbon coating 14 further includes heptagon rings 18 . The presence of the pentagon rings 16 and/or the heptagon rings 18 in the structure of the carbon coating 14 may give rise to curvatures 20 in the carbon coating 14 . While not being bound to any theory, it is believed that the presence of these curvatures 20 in the carbon coating 14 may help the coating 14 resist the volume expansion of silicon.
As shown in FIG. 1 , the carbon coating 14 may have pores 22 . When the silicon nanoparticles 12 are heated to form the carbon coating 14 , the carbon precursor may release small molecule gases (e.g., hydrogen gas, water vapor, and carbon dioxide). These small molecule gases form pores 22 in the carbon coating 14 . When the carbon coated silicon nanoparticles 10 are incorporated into the negative electrode
24 , 24 â² (see FIGS. 2 and 3 ) of a battery, the electrolyte may fill the pores 22 and allow lithium ions to be conducted to and from the silicon nanoparticles 12 .
As mentioned above, the presence of allyl groups in in the oxygen-free, fluorene-based polymer may affect the porosity of the carbon coating 14 . Allyl groups may promote the crosslinking of the oxygen-free, fluorene-based polymer, and crosslinking may prevent the polymer from softening or melting during the heating of the silicon nanoparticles 12 . Polymer melting or softening may cause the carbon coating 14 to be insufficiently porous. If the carbon coating 14 is insufficiently porous, too few lithium ions will be conducted to and from the silicon nanoparticles 12 .
The pores 22 of the carbon coating 14 may be any shape (e.g., circular, elongated, or irregularly shaped). The pores 22 of the carbon coating 14 may also be any size. In an example, 80% of the pores 22 in the carbon coating 14 are meso-sized (i.e., from about 2 nm to about 50 nm in diameter). In another example, the average diameter of the pores 22 ranges from 2 nm to 50 nm. In still another example, the pore volume may range from about 0.1 cm 3 /g to about 0.5 cm 3 /g.
The carbon coating 14 may also have a surface area ranging from about 50 m 2 /g to about 300 m 2 /g. If the surface area of the carbon coating 14 is too high (e.g., greater than 1,000 m 2 /g), a large amount of active lithium may be consumed to form SEI. The surface area of the carbon coating 14 may be affected by the number of pores 22 in the coating 14 , the size of the pores 22 in the coating 14 , and the thickness of the coating 14 . In an example, the carbon coating 14 may have a thickness ranging from about 1 nm to about 10 nm.
After obtaining the coated nanoparticles 10 (i.e., silicon nanoparticles 12 having the carbon coating 14 thereon), the carbon coated silicon nanoparticle 10 may be added, as an active material, to a negative electrode composition to form a negative electrode
24 , 24 â² for use in a lithium-based battery. An example of the method for preparing a negative electrode
24 , 24 â² of a lithium-based battery 400 , 500 (see FIGS. 4 and 5 ) will now be discussed in reference to FIGS. 2 and 3 . FIG. 2 depicts an example of a negative electrode 24 including the carbon coated silicon nanoparticles 10 as an active material, a binder 26 , and a conductive filler 28 , on a support 30 . FIG. 3 depicts an example of a negative electrode 24 â² including the carbon coated silicon nanoparticles 10 as an active material, a binder 26 , a conductive filler 28 , and an additional active material 32 , on a support 30 .
In examples of preparing the negative electrode 24 , the carbon coated silicon nanoparticles 10 are dry mixed with the conductive filler 28 . In examples of preparing the negative electrode 24 â², the carbon coated silicon nanoparticles 10 are dry mixed with the additional active material 32 and the conductive filler 28 . In some instances, the binder 26 is also dry mixed with the
other components
10 , 28 or 10 , 28 , 32 . A solvent may then be added to the dry mixture. In other instances, the binder 26 and solvent are mixed together, and then added to the dry
mixed components
10 , 28 or 10 , 28 , 32 . As will be discussed in more detail below, the solvent may be deionized water or an organic solvent, depending on the binder 26 selected to form a dispersion or mixture.
The additional active material 32 , included in the negative electrode 24 â², may be any lithium host active material that may be incorporated into the negative electrode 24 â² using a slurry coating method and that can sufficiently undergo lithium intercalation and deintercalation, or lithium alloying and dealloying, or lithium insertion and deinsertion, while copper or another current collector 30 functions as the negative terminal of the electrochemical cell/battery. Examples of the lithium host active material include graphite or silicon-based materials. Further examples include tin, alloys of tin, antimony, and alloys of antimony. Graphite exhibits favorable lithium intercalation and deintercalation characteristics, is relatively non-reactive, and can store lithium in quantities that produce a relatively high energy density. Commercial forms of graphite that may be used to fabricate the additional active material 32 of the negative electrode 24 â² are available from, for example, Timcal Graphite & Carbon (Bodio, Switzerland), Lonza Group (Basel, Switzerland), or Superior Graphite (Chicago, Ill.). Examples of the silicon-based active material include crystalline silicon, amorphous silicon, silicon oxide (SiO x ), silicon alloys (e.g., SiâSn), etc. The silicon active material may be in the form of a powder, particles, etc. ranging from nano-size to micro-size.
The carbon coated silicon nanoparticles 10 , alone or in combination with the additional active material 32 may be intermingled with the binder 26 and the conductive filler 28 . The binder 26 may be used to structurally hold the carbon coated silicon nanoparticles 10 , the conductive filler 28 , and/or the additional active material 32 together. Some examples of suitable binders 26 include polyvinylidene fluoride (PVdF), polyethylene oxide (PEO), an ethylene propylene diene monomer (EPDM) rubber, carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), styrene-butadiene rubber carboxymethyl cellulose (SBR-CMC), polyacrylic acid (PAA), cross-linked polyacrylic acid-polyethylenimine, polyimide, or any other suitable binder material. Examples of the still other suitable binders 26 include polyvinyl alcohol (PVA), sodium alginate, or other water-soluble binders.
The conductive filler 28 may be a conductive carbon material. The conductive carbon may be a high surface area carbon, such as acetylene black or another carbon material (e.g., Super P). Other examples of suitable conductive fillers 28 include graphene, graphite, carbon nanotubes, and/or carbon nanofibers. The conductive filler 28 ensures electron conduction between the negative-side current collector 30 and the carbon coated silicon nanoparticles 10 and/or the additional active material 32 .
In an example of the method for making the negative electrode 24 , the carbon coated silicon nanoparticles 10 are mixed with the binder 26 and the conductive filler 28 . In an example of the method for making the negative electrode 24 â², the carbon coated silicon nanoparticles 10 are mixed with the binder 26 , the conductive filler 28 , and the additional active material 32 . In either of these examples, all of the components may be manually mixed by dry-grinding. After all the components are ground together, the ground components are combined with water or organic solvent (depending on the binder 26 used) to form the dispersion/mixture. In an example, the solvent is a polar aprotic solvent. Examples of suitable polar aprotic solvents include dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylsulfoxide (DMSO), or another Lewis base, or combinations thereof. When a water soluble binder, such as sodium alginate, is used, the solvent may be water.
The dispersion/mixture may be mixed by milling. Milling aids in transforming the dispersion/mixture into a coatable slurry. Low-shear milling or high-shear milling may be used to mix the dispersion/mixture. The dispersion/mixture milling time ranges from about 10 minutes to about 20 hours depending on the milling shear rate. In an example, a rotator mixer is used for about 20 minutes at about 2000 rpm to mill the dispersion/mixture.
The carbon coated silicon nanoparticles 10 may be present in the dispersion/mixture in an amount ranging from about 5 wt % to about 95 wt % (based on total solid wt % of the dispersion/mixture). When the additional active material 32 is not present in the dispersion/mixture, the carbon coated silicon nanoparticles 10 may be present in a greater amount (e.g., an amount ranging from about 50 wt % to about 95 wt %) as the coated nanoparticles function as the sole active material. When the additional active material 32 is present in the dispersion/mi
CLAIMS
Claims ( 20 )
What is claimed is:
1. A negative electrode, comprising silicon nanoparticles having a carbon coating thereon, the carbon coating having an oxygen-free structure including pentagon rings, and including a plurality of pores, wherein a pore volume of the carbon coating ranges from about 0.1 cm 3 /g to about 0.5 cm 3 /g.
2. The negative electrode as defined in claim 1 wherein the oxygen-free structure further includes heptagon rings.
3. The negative electrode as defined in claim 1 wherein the carbon coating has a surface area ranging from about 50 m 2 /g to about 300 m 2 /g.
4. The negative electrode as defined in claim 1 wherein the negative electrode further comprises:
a binder mixed with the silicon nanoparticles having the carbon coating thereon; and
a conductive filler mixed with the silicon nanoparticles having the carbon coating thereon.
5. The negative electrode as defined in claim 4 wherein:
the silicon nanoparticles having the carbon coating thereon are present in an amount ranging from about 5 wt % to about 95 wt % based on a total wt % of the negative electrode;
the binder is present in an amount ranging from about 1 wt % to about 20 wt % based on the total wt % of the negative electrode; and
the conductive filler is present in an amount ranging from about 1 wt % to about 20 wt % based on the total wt % of the negative electrode.
6. The negative electrode as defined in claim 4 wherein the negative electrode further comprises an active material selected from the group consisting of graphite, tin, alloys of tin, antimony, alloys of antimony, crystalline silicon, amorphous silicon, silicon oxide, and silicon alloys, and wherein the active material is mixed with the silicon nanoparticles having the carbon coating thereon.
7. The negative electrode as defined in claim 6 wherein:
the silicon nanoparticles having the carbon coating thereon are present in an amount ranging from about 5 wt % to about 75 wt % based on a total wt % of the negative electrode;
the binder is present in an amount ranging from about 1 wt % to about 20 wt % based on the total wt % of the negative electrode;
the conductive filler is present in an amount ranging from about 1 wt % to about 20 wt % based on the total wt % of the negative electrode; and
the active material is present in an amount ranging from about 50 wt % to about 95 wt % based on a total wt % of the negative electrode.
8. The negative electrode as defined in claim 1 wherein the silicon nanoparticles having the carbon coating thereon have a particle size ranging from about 30 nm to about 100 nm.
9. The negative electrode as defined in claim 1 wherein the carbon coating has a thickness ranging from about 1 nm to about 10 nm.
10. The negative electrode as defined in claim 1 about 80% of the pores of the plurality of pores are meso-sized.
11. A lithium-based battery, comprising:
a negative electrode, including silicon nanoparticles having a carbon coating thereon, the carbon coating having an oxygen-free structure including pentagon rings, and including a plurality of pores, wherein a pore volume of the carbon coating ranges from about 0.1 cm 3 /g to about 0.5 cm 3 /g;
a positive electrode; and
a microporous polymer separator soaked in an electrolyte solution, the microporous polymer separator being disposed between the positive electrode and the negative electrode.
12. The lithium-based battery as defined in claim 11 wherein the electrolyte solution is 1M LiPF 6 -DMC:FEC with dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) at a volume ratio of 4:1.
13. The lithium-based battery as defined in claim 12 wherein one of:
the lithium-based battery has a loading of the silicon nanoparticles having the carbon coating thereon of about 1.5 mg/cm 2 , and a stable cycling performance for about 300 cycles; or
the lithium-based battery has a loading of the silicon nanoparticles having the carbon coating thereon of about 0.5 mg/cm 2 , and a stable cycling performance for about 1,000 cycles.
14. A method, comprising:
providing silicon nanoparticles;
applying a carbon precursor on the silicon nanoparticles, the carbon precursor being an oxygen-free, fluorene-based polymer; and
then heating the silicon nanoparticles in an inert gas atmosphere, thereby forming a carbon coating on the silicon nanoparticles, the carbon coating having an oxygen-free structure including pentagon rings, and including a plurality of pores, wherein a pore volume of the carbon coating ranges from about 0.1 cm 3 /g to about 0.5 cm 3 /g.
15. The method as defined in claim 14 wherein the oxygen-free, fluorene-based polymer includes an allyl group.
16. The method as defined in claim 14 wherein the applying of the carbon precursor on the silicon nanoparticles is accomplished by:
mixing the carbon precursor, the silicon nanoparticles, and a solvent to form a slurry; and
drying the slurry.
17. The method as defined in claim 14 wherein a weight ratio of the carbon precursor to silicon nanoparticles is 1:5.
18. The method as defined in claim 14 wherein the heating of the silicon nanoparticles is accomplished at a temperature ranging from about 650° C. to about 750° C. for a time period ranging from about 1 hour to about 10 hours.
19. The method as defined in claim 14 , further comprising:
dry mixing the silicon nanoparticles having the carbon coating thereon into a mixture, the mixture including a conductive filler;
adding a binder and a solvent to the mixture;
mixing the mixture to form a slurry;
depositing the slurry onto a support; and
drying the slurry.
20. The method as defined in claim 19 , further comprising adding an active material to the mixture, the active material being selected from the group consisting of graphite, tin, alloys of tin, antimony, alloys of antimony, crystalline silicon, amorphous silicon, silicon oxide, and silicon alloys.
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