ABSTRACT
Abstract
In an example of a method for enhancing the performance of a silicon-based negative electrode, the silicon-based negative electrode is pre-lithiated in an electrolyte including a lithium salt dissolved in a solvent mixture of dimethoxyethane (DME) and fluoroethylene carbonate (FEC). The DME and FEC are present in a volume to volume ratio ranging from 10 to 1 to 1 to 10. The pre-lithiation forms a stable solid electrolyte interface layer on an exposed surface of the negative electrode.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/941,068, filed Feb. 18, 2014, which is incorporated by reference herein in its entirety.
BACKGROUND
Secondary, or rechargeable, lithium-sulfur batteries or lithium ion 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 a method for enhancing the performance of a silicon-based negative electrode, the silicon-based negative electrode is pre-lithiated in an electrolyte including a lithium salt dissolved in a solvent mixture of dimethoxyethane (DME) and fluoroethylene carbonate (FEC). The DME and FEC are present in a volume to volume ratio ranging from 10 to 1 to 1 to 10. The pre-lithiation forms a stable solid electrolyte interface layer on an exposed surface of the silicon-based negative electrode.
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.
FIG. 1 is a schematic, perspective view of an example of a silicon-sulfur battery showing a charging and discharging state, the battery including an electrolyte according to an example of the present disclosure;
FIG. 2 is a schematic, perspective view of an example of a lithium ion battery showing a discharging state, the battery including an example of the pre-lithiated negative electrode disclosed herein;
FIG. 3 is a graph illustrating the capacity (mAh/g s , left Y-axis labeled âCâ) vs. cycle number (X-axis labeled â#â) and the Coulombic efficiency (%, right Y-axis labeled â%â) vs. cycle number (X-axis labeled â#â) for an example silicon-sulfur battery with an example of a pre-lithiated negative electrode disclosed herein, and a comparative example silicon-sulfur battery with a comparative pre-lithiated negative electrode; and
FIG. 4 is a graph illustrating the specific capacity based on sulfur (mAh/g, left Y-axis labeled âY 1 â) vs. cycle number (X-axis labeled â#â) and the Coulombic efficiency (right Y-axis labeled âY 2 â) vs. cycle number (X-axis labeled â#â) for an example silicon-sulfur battery with an example of an electrolyte including a lithium salt additive as disclosed herein, and a comparative example silicon-sulfur battery with an unmodified electrolyte (i.e., no lithium salt additive).
DETAILED DESCRIPTION
Lithium-sulfur and lithium ion 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. 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 the negative electrode active material for either a lithium-sulfur battery or a lithium ion battery include silicon or silicon alloys. When the lithium-sulfur battery includes silicon or a silicon alloy as the active material, the battery may be referred to as a silicon-sulfur battery or a silicon(lithium) sulfur battery.
Silicon or a silicon alloy may be a desirable material for the negative electrode of a lithium-sulfur or lithium ion battery, at least in part because of its high theoretical capacity (e.g., 4200 mAh/g). Moreover, a solid electrolyte interphase (SEI) layer may form on exposed surface(s) of the silicon-based negative electrode, and this layer can desirably affect the cell performance. Generally, the SEI layer forms from i) electrolyte components decomposing when exposed to low voltage potential, and ii) the electrolyte decomposition products depositing on the exposed surfaces of the silicon-based negative electrode. It is desirable that the SEI layer be formed in a controlled environment so that an electronically insulating layer with a desirable thickness is obtained. In theory, the SEI covers the negative electrode surface and blocks electrons from diffusing out of the negative electrode, which would otherwise inevitably consume the electrolyte by electrochemical reduction. Furthermore, the SEI layer can impart kinetic stability to the electrolyte against further reductions in subsequent cycles. The SEI is also typically ionically conducting and thus allows Li-ions to travel across the layer. Overall, the SEI should contribute to good cycling of the battery.
While silicon and silicon alloy(s) have high theoretical capacity advantages, the use of silicon or the silicon alloy may also result in the battery having a poor life cycle. For example, silicon and silicon alloy(s) may exhibit large volume expansion and contraction during charging/discharging of the battery. Extreme volume expansion and contraction can cause the negative electrode material to fracture, decrepitate, or otherwise mechanically degrade, which results in a loss of electrical contact and poor life cycling. Additionally, the extreme volume expansion and contraction of the silicon or silicon alloy can also damage unstable SEI layer(s) and expose portions of the underlying silicon/silicon alloy to additional electrolyte. This can cause further decomposition of the electrolyte at the exposed portions, resulting in the formation of additional SEI layer(s). Continuous breaking and formation of the SEI layer can irreversibly trap lithium in the SEI layer, can consume the electrolyte, and/or can undesirably thicken the SEI layer.
An example of the electrolyte disclosed herein may be used to pre-lithiate a silicon-based negative electrode and to form a stable SEI layer on a surface thereof. By âstableâ, it is meant that the formed SEI layer is relatively resistant to decomposition when exposed to migrating, diffusing, or shuttling lithium-polysulfide intermediates (LiS x , where x is 2<x<8) from the sulfur-based positive electrode during the silicon-sulfur battery discharge process. Lithium-polysulfide intermediates generated at the sulfur-based positive electrode are generally soluble in the battery electrolyte, and can migrate to the silicon-based negative electrode where they react with the negative electrode in a parasitic fashion to generate lower-order lithium-polysulfide intermediates. These lithium-polysulfide intermediates diffuse back to the positive electrode and regenerate the higher forms of lithium-polysulfide intermediates. As a result, a shuttle effect takes place in the battery. Furthermore, these polysulfide intermediate anions are a strong Lewis base due to their electron rich characteristic, and thus will attack chemicals having electron withdrawing group(s), such as carbonyl groups. However, the stable SEI layer disclosed herein, which is formed using the pre-litiation electrolyte disclosed herein, remains intact when exposed to lithium-polysulfide intermediates, and thus consumes less of the electrolyte and acts as a barrier layer that keeps the lithium-polysulfide intermediates from reaching the silicon-based negative electrode. Additionally, it is believed that the stable SEI layer is more tolerant of the silicon or silicon alloy volume expansion. Overall the use of the pre-lithiation electrolyte disclosed herein can contribute to an improved battery life cycle.
Another example of the electrolyte disclosed herein may be used during the cycling of the silicon-sulfur battery. This electrolyte includes additive(s) that can further contribute to the stability of the SEI layer during battery operation.
As noted above, one of the electrolytes disclosed herein is a pre-lithiation electrolyte that is used to pre-lithiate an example of the silicon-based negative electrode ( reference numeral 12 in FIG. 1 ) and to form an SEI layer ( reference numeral 19 in FIG. 1 and FIG. 2 ) on exposed surface(s) of the silicon-based negative electrode 12 . The pre-lithiation electrolyte solution disclosed herein may be included in a pre-lithiation kit with the silicon-based negative electrode 12 . As will be described in further detail below, pre-lithiation adds active Li + into the silicon-based negative electrode 12 , and renders it suitable for use in a lithium based battery.
The pre-lithiation electrolyte and the process for forming and pre-lithiating the silicon-based negative electrode 12 will now be described. FIG. 1 will be referenced throughout the discussion.
The pre-lithiation electrolyte includes a lithium salt. As examples, the lithium salt may be LiPF 6 , LiAlCl 4 , LiI, LiBr, LiSCN, LiB(C 6 H 5 ) 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , LiBF 4 , LiClO 4 , LiN(CF 3 SO 2 ) 2 (LiTFSI), LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiN(FSO 2 ) 2 (LiFSI), LiPF 3 (C 2 F 5 ) 3 (LiFAP), LiPF 4 (CF 3 ) 2 , LiPF 3 (CF 3 ) 3 , etc. In an example, the lithium salt in the pre-lithiation electrolyte is 1M LiPF 6 .
The lithium salt is dissolved in a solvent mixture of dimethoxyethane (DME) and fluoroethylene carbonate (FEC). The volume to volume ratio of the solvents (DME to FEC) ranges from 10 to 1 to 1 to 10. In an example, the volume to volume ratio of DME to FEC is 3 to 1. It has been found that using FEC as a co-solvent forms the desirable SEI layer 19 on the exposed surface(s) of the silicon-based negative electrode 12 during the pre-lithiation process. The FEC is active and readily decomposes during pre-lithiation to form the SEI layer 19 .
Prior to pre-lithiating the silicon-based negative electrode 12 , the electrode 12 is purchased or fabricated. In an example, fabrication of the electrode 12 involves dispersing the silicon or silicon alloy, a conducting carbon, and a binder at a certain ratio into an organic solvent or water. The dispersion may be mixed to obtain a homogeneous solution. The solution may then be doctor blade coated (or otherwise deposited) onto a copper or other suitable negative-side current collector.
The silicon-based negative electrode 12 includes any silicon-based lithium host material (i.e., active material) that can sufficiently undergo lithium alloying and intercalating with copper, or another suitable current collector, functioning as the negative terminal 12 a . Examples of the silicon 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 silicon-based negative electrode 12 may also include the previously mentioned polymer binder material to structurally hold the silicon active material together. Example binders include polyvinylidene fluoride (PVdF), 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, poly(acrylamide-co-diallyl dimethyl ammonium chloride), polyethylene oxide (PEO), or polyimide (PI). Other suitable binders include polyvinyl alcohol (PVA), sodium alginate, or other water-soluble binders.
Still further, the silicon-based negative electrode 12 may also include the previously mentioned conductive carbon material. The conductive carbon may be a high surface area carbon, such as acetylene black (i.e., carbon black), and is included to ensure electron conduction between the silicon active material and, for example, a negative-side current collector (reference numeral 12 a in FIG. 1 ). Other examples of suitable conductive fillers, which may be used alone or in combination with carbon black, include graphene, graphite, carbon nanotubes, and/or carbon nanofibers. One specific example of a combination of conductive fillers is carbon black and carbon nanofibers.
The silicon-based negative electrode 12 may include about 40% by weight to about 90% by weight (i.e., 90 wt %) of the silicon active material. The negative electrode 12 may include from 0% by weight to about 30% by weight of the conductive filler. Additionally, the negative electrode 12 may include 0% by weight to about 20% by weight of the polymer binder. In an example, the silicon-based negative electrode 12 includes about 70 wt % of the silicon active material, about 15 wt % of the conductive carbon material, and about 15 wt % of the polymer binder material. As briefly des
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/941,068, filed Feb. 18, 2014, which is incorporated by reference herein in its entirety.
BACKGROUND
Secondary, or rechargeable, lithium-sulfur batteries or lithium ion 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 a method for enhancing the performance of a silicon-based negative electrode, the silicon-based negative electrode is pre-lithiated in an electrolyte including a lithium salt dissolved in a solvent mixture of dimethoxyethane (DME) and fluoroethylene carbonate (FEC). The DME and FEC are present in a volume to volume ratio ranging from 10 to 1 to 1 to 10. The pre-lithiation forms a stable solid electrolyte interface layer on an exposed surface of the silicon-based negative electrode.
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.
FIG. 1 is a schematic, perspective view of an example of a silicon-sulfur battery showing a charging and discharging state, the battery including an electrolyte according to an example of the present disclosure;
FIG. 2 is a schematic, perspective view of an example of a lithium ion battery showing a discharging state, the battery including an example of the pre-lithiated negative electrode disclosed herein;
FIG. 3 is a graph illustrating the capacity (mAh/g s , left Y-axis labeled âCâ) vs. cycle number (X-axis labeled â#â) and the Coulombic efficiency (%, right Y-axis labeled â%â) vs. cycle number (X-axis labeled â#â) for an example silicon-sulfur battery with an example of a pre-lithiated negative electrode disclosed herein, and a comparative example silicon-sulfur battery with a comparative pre-lithiated negative electrode; and
FIG. 4 is a graph illustrating the specific capacity based on sulfur (mAh/g, left Y-axis labeled âY 1 â) vs. cycle number (X-axis labeled â#â) and the Coulombic efficiency (right Y-axis labeled âY 2 â) vs. cycle number (X-axis labeled â#â) for an example silicon-sulfur battery with an example of an electrolyte including a lithium salt additive as disclosed herein, and a comparative example silicon-sulfur battery with an unmodified electrolyte (i.e., no lithium salt additive).
DETAILED DESCRIPTION
Lithium-sulfur and lithium ion 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. 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 the negative electrode active material for either a lithium-sulfur battery or a lithium ion battery include silicon or silicon alloys. When the lithium-sulfur battery includes silicon or a silicon alloy as the active material, the battery may be referred to as a silicon-sulfur battery or a silicon(lithium) sulfur battery.
Silicon or a silicon alloy may be a desirable material for the negative electrode of a lithium-sulfur or lithium ion battery, at least in part because of its high theoretical capacity (e.g., 4200 mAh/g). Moreover, a solid electrolyte interphase (SEI) layer may form on exposed surface(s) of the silicon-based negative electrode, and this layer can desirably affect the cell performance. Generally, the SEI layer forms from i) electrolyte components decomposing when exposed to low voltage potential, and ii) the electrolyte decomposition products depositing on the exposed surfaces of the silicon-based negative electrode. It is desirable that the SEI layer be formed in a controlled environment so that an electronically insulating layer with a desirable thickness is obtained. In theory, the SEI covers the negative electrode surface and blocks electrons from diffusing out of the negative electrode, which would otherwise inevitably consume the electrolyte by electrochemical reduction. Furthermore, the SEI layer can impart kinetic stability to the electrolyte against further reductions in subsequent cycles. The SEI is also typically ionically conducting and thus allows Li-ions to travel across the layer. Overall, the SEI should contribute to good cycling of the battery.
While silicon and silicon alloy(s) have high theoretical capacity advantages, the use of silicon or the silicon alloy may also result in the battery having a poor life cycle. For example, silicon and silicon alloy(s) may exhibit large volume expansion and contraction during charging/discharging of the battery. Extreme volume expansion and contraction can cause the negative electrode material to fracture, decrepitate, or otherwise mechanically degrade, which results in a loss of electrical contact and poor life cycling. Additionally, the extreme volume expansion and contraction of the silicon or silicon alloy can also damage unstable SEI layer(s) and expose portions of the underlying silicon/silicon alloy to additional electrolyte. This can cause further decomposition of the electrolyte at the exposed portions, resulting in the formation of additional SEI layer(s). Continuous breaking and formation of the SEI layer can irreversibly trap lithium in the SEI layer, can consume the electrolyte, and/or can undesirably thicken the SEI layer.
An example of the electrolyte disclosed herein may be used to pre-lithiate a silicon-based negative electrode and to form a stable SEI layer on a surface thereof. By âstableâ, it is meant that the formed SEI layer is relatively resistant to decomposition when exposed to migrating, diffusing, or shuttling lithium-polysulfide intermediates (LiS x , where x is 2<x<8) from the sulfur-based positive electrode during the silicon-sulfur battery discharge process. Lithium-polysulfide intermediates generated at the sulfur-based positive electrode are generally soluble in the battery electrolyte, and can migrate to the silicon-based negative electrode where they react with the negative electrode in a parasitic fashion to generate lower-order lithium-polysulfide intermediates. These lithium-polysulfide intermediates diffuse back to the positive electrode and regenerate the higher forms of lithium-polysulfide intermediates. As a result, a shuttle effect takes place in the battery. Furthermore, these polysulfide intermediate anions are a strong Lewis base due to their electron rich characteristic, and thus will attack chemicals having electron withdrawing group(s), such as carbonyl groups. However, the stable SEI layer disclosed herein, which is formed using the pre-litiation electrolyte disclosed herein, remains intact when exposed to lithium-polysulfide intermediates, and thus consumes less of the electrolyte and acts as a barrier layer that keeps the lithium-polysulfide intermediates from reaching the silicon-based negative electrode. Additionally, it is believed that the stable SEI layer is more tolerant of the silicon or silicon alloy volume expansion. Overall the use of the pre-lithiation electrolyte disclosed herein can contribute to an improved battery life cycle.
Another example of the electrolyte disclosed herein may be used during the cycling of the silicon-sulfur battery. This electrolyte includes additive(s) that can further contribute to the stability of the SEI layer during battery operation.
As noted above, one of the electrolytes disclosed herein is a pre-lithiation electrolyte that is used to pre-lithiate an example of the silicon-based negative electrode ( reference numeral 12 in FIG. 1 ) and to form an SEI layer ( reference numeral 19 in FIG. 1 and FIG. 2 ) on exposed surface(s) of the silicon-based negative electrode 12 . The pre-lithiation electrolyte solution disclosed herein may be included in a pre-lithiation kit with the silicon-based negative electrode 12 . As will be described in further detail below, pre-lithiation adds active Li + into the silicon-based negative electrode 12 , and renders it suitable for use in a lithium based battery.
The pre-lithiation electrolyte and the process for forming and pre-lithiating the silicon-based negative electrode 12 will now be described. FIG. 1 will be referenced throughout the discussion.
The pre-lithiation electrolyte includes a lithium salt. As examples, the lithium salt may be LiPF 6 , LiAlCl 4 , LiI, LiBr, LiSCN, LiB(C 6 H 5 ) 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , LiBF 4 , LiClO 4 , LiN(CF 3 SO 2 ) 2 (LiTFSI), LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiN(FSO 2 ) 2 (LiFSI), LiPF 3 (C 2 F 5 ) 3 (LiFAP), LiPF 4 (CF 3 ) 2 , LiPF 3 (CF 3 ) 3 , etc. In an example, the lithium salt in the pre-lithiation electrolyte is 1M LiPF 6 .
The lithium salt is dissolved in a solvent mixture of dimethoxyethane (DME) and fluoroethylene carbonate (FEC). The volume to volume ratio of the solvents (DME to FEC) ranges from 10 to 1 to 1 to 10. In an example, the volume to volume ratio of DME to FEC is 3 to 1. It has been found that using FEC as a co-solvent forms the desirable SEI layer 19 on the exposed surface(s) of the silicon-based negative electrode 12 during the pre-lithiation process. The FEC is active and readily decomposes during pre-lithiation to form the SEI layer 19 .
Prior to pre-lithiating the silicon-based negative electrode 12 , the electrode 12 is purchased or fabricated. In an example, fabrication of the electrode 12 involves dispersing the silicon or silicon alloy, a conducting carbon, and a binder at a certain ratio into an organic solvent or water. The dispersion may be mixed to obtain a homogeneous solution. The solution may then be doctor blade coated (or otherwise deposited) onto a copper or other suitable negative-side current collector.
The silicon-based negative electrode 12 includes any silicon-based lithium host material (i.e., active material) that can sufficiently undergo lithium alloying and intercalating with copper, or another suitable current collector, functioning as the negative terminal 12 a . Examples of the silicon 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 silicon-based negative electrode 12 may also include the previously mentioned polymer binder material to structurally hold the silicon active material together. Example binders include polyvinylidene fluoride (PVdF), 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, poly(acrylamide-co-diallyl dimethyl ammonium chloride), polyethylene oxide (PEO), or polyimide (PI). Other suitable binders include polyvinyl alcohol (PVA), sodium alginate, or other water-soluble binders.
Still further, the silicon-based negative electrode 12 may also include the previously mentioned conductive carbon material. The conductive carbon may be a high surface area carbon, such as acetylene black (i.e., carbon black), and is included to ensure electron conduction between the silicon active material and, for example, a negative-side current collector (reference numeral 12 a in FIG. 1 ). Other examples of suitable conductive fillers, which may be used alone or in combination with carbon black, include graphene, graphite, carbon nanotubes, and/or carbon nanofibers. One specific example of a combination of conductive fillers is carbon black and carbon nanofibers.
The silicon-based negative electrode 12 may include about 40% by weight to about 90% by weight (i.e., 90 wt %) of the silicon active material. The negative electrode 12 may include from 0% by weight to about 30% by weight of the conductive filler. Additionally, the negative electrode 12 may include 0% by weight to about 20% by weight of the polymer binder. In an example, the silicon-based negative electrode 12 includes about 70 wt % of the silicon active material, about 15 wt % of the conductive carbon material, and about 15 wt % of the polymer binder material. As briefly described above, the solution formed from a dispersion of these materials may be made and cast onto the negative-side current collector (e.g., copper) and dried to form the silicon-based negative electrode 12 .
The silicon-based negative electrode 12 may then be pre-lithiated using a lithium-silicon half cell method. More specifically, the LiâSi half cell is assembled using the silicon-based negative electrode 12 , which is soaked in the pre-lithiation electrolyte previously described. A voltage potential is applied to the half cell, which causes the FEC in the pre-lithiation electrode to decompose. The decomposition product deposits on the exposed surface(s) 13 of the silicon-based negative electrode 12 to form the SEI layer 19 . The decomposition product may be LiF, Li 2 CO 3 , Li x PF y O z , F-replaced Lithium Ethylene Di Carbonate (F-LEDC), an unsaturated polyolefin, etc. The voltage potential is applied for a time sufficient to form the SEI layer 19 . The time that the voltage potential is applied may range from about 1 hour to about 100 hours. In an example, the voltage potential is applied for about 20 hours. In an example, when a higher current is used, the exposure time may be shorter. Similarly, when a lower current is used, the exposure time may be longer. The SEI layer 19 may have a thickness of about 10 nm or less.
In another example, the silicon-based negative electrode 12 may be pre-lithiated by short circuiting lithium-silicon having the previously described pre-lithiation electrolyte positioned therebetween. This may be accomplished for a time period ranging from about 1 hour to about 24 hours.
During pre-lithiation, lithium ions are dissolved (or de-plated or stripped) from lithium metal of the LiâSi half cell and are alloyed with silicon by an electrochemical reaction with the pre-lithiation electrolyte (which can conduct the lithium ions). The lithium ions can alloy with the silicon-based active material, thereby lithiating the silicon-based negative electrode 12 .
When pre-lithiation is complete, the lithiated silicon-based negative electrode 12 having the SEI layer 19 formed thereon may be rinsed to remove any remaining pre-lithiation electrolyte, and then may be used in either a lithium ion battery 30 or a silicon- sulfur battery 10 .
When used in a lithium-sulfur battery or a silicon- sulfur battery 10 , the lithiated silicon-based negative electrode 12 disclosed herein may be paired with a positive electrode 14 formed from any sulfur-based active material that can sufficiently undergo lithium alloying and dealloying with aluminum, or another suitable current collector, functioning as the positive terminal of the battery 10 . In an example, the sulfur based active material may be a sulfur-carbon composite. In an example, the weight ratio of S to C in the positive electrode 14 ranges from 1:9 to 8:1.
The positive electrode 14 may also include a polymer binder material to structurally hold the sulfur-based active material together. The polymer binder material may be made of at least one of 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 polyvinyl alcohol (PVA), sodium alginate, or other water-soluble binders.
Still further, the positive electrode 14 may include a conductive carbon material. In an example, the conductive carbon material is a high surface area carbon, such as acetylene black (i.e., carbon black) or activated carbon. Other examples of suitable conductive fillers, which may be used alone or in combination with carbon black, include graphene, graphite, carbon nanotubes, and/or carbon nanofibers. One specific example of a combination of conductive fillers is carbon black and carbon nanofibers.
The positive electrode 14 may include about 40% by weight to about 90% by weight (i.e., 90 wt %) of the sulfur-based active material. The positive electrode 14 may include 0% by weight to about 30% by weight of the conductive filler. Additionally, the positive electrode 14 may include 0% by weight to about 20% by weight of the polymer binder. In an example, the positive electrode 14 includes about 80 wt % of the sulfur-based active material, about 10 wt % of the conductive carbon material, and about 10 wt % of the polymer binder material.
The silicon- sulfur battery 10 will now be discussed in more detail. As shown in FIG. 1 , the silicon- sulfur battery 10 includes the positive-side current collector 14 a and the previously mentioned negative-side current collector 12 a positioned in contact with the positive electrode 14 and the silicon-based negative electrode 12 , respectively, to collect and move free electrons to and from an external circuit 24 . The positive-side current collector 14 a may be formed from aluminum or any other appropriate electrically conductive material. The negative-side current collector 12 a may be formed from copper or any other appropriate electrically conductive material.
It is to be understood that the silicon- sulfur battery 10 may include the pre-lithiated silicon-based negative electrode 12 having the SEI layer 19 formed thereon.
Also, as shown in FIG. 1 , the silicon- sulfur battery 10 includes the pre-lithiated silicon-based negative electrode 12 (having the SEI layer 19 formed thereon) and the sulfur-based positive electrode 14 separated by a porous separator 16 .
The porous separator 16 may be formed, e.g., from a polyolefin. 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 may be polyethylene (PE), polypropylene (PP), a blend of PE and PP, or multi-layered structured porous films of PE and/or PP. Commercially available porous separators 16 include single layer polypropylene membranes, such as CELGARD 2400 and CELGARD 2500 from Celgard, LLC (Charlotte, N.C.). It is to be understood that the porous separator 16 may be coated or treated, or uncoated or untreated. For example, the porous separator 16 may or may not be coated or include any surfactant treatment thereon.
In other examples, the porous separator 16 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, polyolefin copolymers, 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) and ZENITE® (DuPont, Wilmington, Del.)), polyaramides, polyphenylene oxide, and/or combinations thereof. It is believed that another example of a liquid crystalline polymer that may be used for the porous separator 16 is poly(p-hydroxybenzoic acid). In yet another example, the porous separator 16 may be chosen from a combination of the polyolefin (such as PE and/or PP) and one or more of the other polymers listed above.
The porous separator 16 may be a single layer or may be a multi-layer (e.g., bilayer, trilayer, etc.) 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 16 . As another example, however, multiple discrete layers of similar or dissimilar polyolefins and/or polymers may be assembled into the separator 16 . 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 16 . Further, the polyolefin (and/or other polymer) layer, and any other optional polymer layers, may further be included in the separator 16 as a fibrous layer to help provide the separator with appropriate structural and porosity characteristics. Still other suitable separators 16 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 16 .
The porous separator 16 operates as an electrical insulator (preventing the occurrence of a short), a mechanical support, and a barrier to prevent physical contact between the two electrodes
12 , 14 . The porous separator 16 also ensures passage of lithium ions (identified by the Li + ) through an electrolyte 18 filling its pores.
As shown in FIG. 1 , each of the silicon-based negative electrode 12 (including the SEI layer 19 ), the positive electrode 14 , and the porous separator 16 are soaked in the battery electrolyte 18 . In the examples disclosed herein, the battery electrolyte 18 (not to be confused with the previously described pre-lithiation electrolyte) consists of lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and/or LiPF 6 , a solvent mixture of dimethoxyethane (DME) and 1,3-dioxolane (DIOX), a lithium salt additive selected from the group consisting of LiBF 2 (C 2 O 4 ) (LiODFB), LiPF 6 , and/or LiB(C 2 O 4 ) 2 , and optionally LiNO 3 .
The lithium salt additive is included in a small amount, ranging from about 0.1 wt % to about 10 wt % of a total wt % of the electrolyte solution. It is believed that the small amount of the lithium salt additive disclosed herein can effectively increase the battery cycling performance and Coulombic efficiency. The lithium salt additive may contribute to the formation of a stable SEI layer 19 .
It is to be understood that when LiPF 6 is present in the battery electrolyte 18 , the electrolyte solution also consists of a Lewis base to stabilize the LiPF 6 . Examples of suitable Lewis bases include dimethylacetamide (DMAc) and tributylamine (TBA). The Lewis base may be present in an amount ranging from about 0.1 wt % and about 5 wt %.
The battery electrolyte 18 disclosed herein enhances the performance of the silicon-sulfur full cell. One specific example of the battery electrolyte 18 includes from about 0.1 M to about 0.5 M LiNO 3 plus from about 0.1 M to about 1 M LiTFSI and from about 0.1 M to about 1 M LiPF 6 in dimethoxyethane (DME):1,3-dioxolane (DIOX) (v:v=10:1 to 1:10), and from about 0.1 M to about 0.5 M LiODFB as a lithium salt additive. This example battery electrolyte 18 may or may not include a trace amount (from about 0.1 wt % to about 3 wt %) DMAc or TBA as a PF 5 scavenger. This electrolyte system can effectively improve the columbic efficiency of a prepared silicon-sulfur full cell, although it is believed that the low Coloumbic efficiency for silicon-sulfur full cell may be further enhanced.
The silicon- sulfur battery 10 also includes the interruptible external circuit 24 that connects the positive electrode 14 and the negative electrode 12 . The silicon- sulfur battery 10 may also support a load device 26 that can be operatively connected to the external circuit 24 . The load device 26 receives a feed of electrical energy from the electric current passing through the external circuit 24 when the silicon- sulfur battery 10 is discharging. While the load device 26 may be any number of known electrically-powered devices, a few specific examples of a power-consuming load device include an electric motor for a hybrid vehicle or an all-electrical vehicle, a laptop computer, a cellular phone, and a cordless power tool. The load device 26 may also, however, be a power-generating apparatus that charges the silicon- sulfur battery 10 for purposes of storing energy. For instance, the tendency of windmills and solar panels to variably and/or intermittently generate electricity often results in a need to store surplus energy for later use.
The silicon- sulfur battery 10 can include a wide range of other components that, while not depicted here, are nonetheless known to skilled artisans. For instance, the silicon- sulfur battery 10 may include a casing, gaskets, terminals, tabs, and any other desirable components or materials that may be situated between or around the positive electrode 14 and the silicon-based negative electrode 12 for performance-related or other practical purposes. Moreover, the size and shape of the silicon- sulfur battery 10 , as well as the design and chemical make-up of its main components, may vary depending on the particular application for which it is designed. Battery-powered automobiles and hand-held consumer electronic devices, for example, are two instances where the silicon- sulfur battery 10 would most likely be designed to different size, capacity, and power-output specifications. The silicon- sulfur battery 10 may also be connected in series and/or in parallel with other similar silicon- sulfur batteries 10 to produce a greater voltage output and current (if arranged in parallel) or voltage (if arranged in series) if the load device 26 so requires.
The silicon- sulfur battery 10 can generate a useful electric current during battery discharge (shown by reference numeral 20 in FIG. 1 ). During discharge, the chemical processes in the battery 10 include lithium (Li + ) dissolution from the negative electrode 12 and incorporation of the lithium cations into alkali metal polysulfide salts (i.e., Li 2 S n , such as Li 2 S 8 , Li 2 S 6 , Li 2 S 4 , Li 2 S 2 , and Li 2 S) in the positive electrode 14 . As such, polysulfides are formed (sulfur is reduced) within the positive electrode 14 in sequence while the battery 10 is discharging. The chemical potential difference between the positive electrode 14 and the negative electrode 12 (ranging from approximately 1.5 to 3.0 volts, depending on the exact chemical make-up of the electrodes 12 , 14 ) drives electrons produced by the dissolution of lithium at the negative electrode 12 through the external circuit 24 towards the positive electrode 14 . The resulting electric current passing through the external circuit 24 can be harnessed and directed through the load device 26 until the lithium in the negative electrode 12 is depleted and the capacity of the silicon- sulfur battery 10 is diminished.
The silicon- sulfur battery 10 can be charged or re-powered at any time by applying an external power source to the silicon- sulfur battery 10 to reverse the electrochemical reactions that occur during battery discharge. During charging (shown at reference numeral 22 in FIG. 1 ), lithium alloying to the negative electrode 12 takes place and sulfur formation within the positive electrode 14 takes place. The connection of an external power source to the silicon- sulfur battery 10 compels the otherwise non-spontaneous oxidation of lithium at the positive electrode 14 to produce electrons and lithium ions. The electrons, which flow back towards the negative electrode 12 through the external circuit 24 , and the lithium ions (Li + ), which are carried by the electrolyte 18 across the separator 16 back towards the negative electrode 12 , reunite at the negative electrode 12 and replenish it with lithium for consumption during the next battery discharge cycle 20 . The external power source that may be used to charge the silicon- sulfur battery 10 may vary depending on the size, construction, and particular end-use of the silicon- sulfur battery 10 . Some suitable external power sources include a battery charger plugged into an AC wall outlet and a motor vehicle alternator.
Referring now to FIG. 2 , when the pre-lithiated silicon-based negative electrode 12 herein is used in a lithium ion battery 30 , any known separator 16 , current collector(s), etc. may be used with the pre-lithiated silicon-based negative electrode 12 and an appropriate positive electrode 14 â². It is to be understood that the porous separator 16 used in the lithium ion battery 30 may be the same type of porous separator 16 that is described in FIG. 1 for the silicon- sulfur battery 10 . In addition, the negative-side current collector 12 a and positive-side current collector 14 a described herein for the silicon-<fig
CLAIMS
Claims ( 14 )
What is claimed is:
1. A method for enhancing performance of a silicon-based negative electrode, the method comprising:
pre-lithiating the silicon-based negative electrode in an electrolyte including a lithium salt dissolved in a solvent mixture consisting of dimethoxyethane (DME) and fluoroethylene carbonate (FEC) present in a volume to volume ratio ranging from 10 to 1 to 1 to 10, thereby forming a stable solid electrolyte interface layer on an exposed surface of the silicon-based negative electrode.
2. The method as defined in claim 1 wherein the silicon-based negative electrode includes an active material selected from silicon or a silicon alloy.
3. The method as defined in claim 1 wherein pre-lithiation is accomplished by:
incorporating the silicon-based negative electrode into a half cell;
soaking the silicon-based negative electrode in the electrolyte; and
exposing the silicon-based negative electrode to a voltage potential for a time sufficient to form the stable solid electrolyte interface layer.
4. The method as defined in claim 1 wherein pre-lithiation is accomplished by:
incorporating the silicon-based negative electrode into a half cell with a lithium-based counter electrode;
soaking the silicon-based negative electrode in the electrolyte; and
short circuiting the half cell.
5. The method as defined in claim 1 wherein the lithium salt is selected from the group consisting of LiPF 6 , LiAlCl 4 , LiI, LiBr, LiSCN, LiB(C 6 H 5 ) 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , LiBF 4 , LiClO 4 , LiN(CF 3 SO 2 ) 2 (LiTFSI), LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiN(FSO 2 ) 2 (LiFSI), LiPF 3 (C 2 F 5 ) 3 (LiFAP), LiPF 4 (CF 3 ) 2 , LiPF 3 (CF 3 ) 3 and combinations thereof.
6. The method as defined in claim 1 wherein the stable solid electrolyte interface layer remains intact when exposed to lithium-polysulfide intermediates.
7. The method as defined in claim 1 wherein the stable solid electrolyte interface layer has a thickness of less than or equal to about 10 nm.
8. An electrolyte for pre-lithiating a silicon-based negative electrode, the electrolyte consisting of:
a lithium salt; and
a solvent mixture consisting of dimethoxyethane (DME) and fluoroethylene carbonate (FEC) present in a volume to volume ratio ranging from 10 to 1 to 1 to 10.
9. The electrolyte as defined in claim 8 wherein the lithium salt is selected from the group consisting of LiPF 6 , LiAlCl 4 , LiI, LiBr, LiSCN, LiB(C 6 H 5 ) 4 , LiAsF 6 , LiCF 3 SO 3 , LiPF 4 (C 2 O 4 ) (LiFOP), LiNO 3 , LiBF 4 , LiClO 4 , LiN(CF 3 SO 2 ) 2 (LiTFSI), LiB(C 2 O 4 ) 2 (LiBOB), LiBF 2 (C 2 O 4 ) (LiODFB), LiN(FSO 2 ) 2 (LiFSI), LiPF 3 (C 2 F 5 ) 3 (LiFAP), LiPF 4 (CF 3 ) 2 , LiPF 3 (CF 3 ) 3 and combinations thereof.
10. A method for enhancing performance of a silicon-sulfur battery including a negative electrode and an electrolyte, the method comprising:
adding to the electrolyte a lithium salt additive selected from the group consisting of LiBF 2 (C 2 O 4 ) (LiODFB), LiPF 6 , and combinations thereof,
wherein an amount of lithium salt additive added to the electrolyte is greater than or equal to about 0.1 wt % to less than or equal to about 10 wt % of a total wt % of the electrolyte,
wherein the electrolyte consisting of lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), LiPF 6 , or combinations thereof in a solvent mixture of dimethoxyethane (DME) and 1,3-dioxolane (DIOX), optionally LiNO 3 , and optionally a Lewis base when LiPF 6 is present, and
wherein the lithium salt additive forms a stable solid electrolyte interface layer on a surface of the negative electrode,
wherein the stable solid electrolyte interface layer has a thickness of less than or equal to about 10 nm, and
wherein the silicon-sulfur battery has a specific capacity of greater than 800 mAh/g for more than 80 cycles of the silicon-sulfur battery.
11. A silicon-sulfur battery, comprising:
a negative electrode including a silicon-based active material;
a positive electrode including a sulfur-based active material;
a separator positioned between the negative electrode and the positive electrode; and
an electrolyte solution soaking each of the positive electrode, the negative electrode, and the separator, the electrolyte solution consisting of:
lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), LiPF 6 , or combinations thereof;
a solvent mixture of dimethoxyethane (DME) and 1,3-dioxolane (DIOX);
a lithium salt additive selected from the group consisting of LiBF 2 (C 2 O 4 ) (LiODFB), LiPF 6 , or combinations thereof, the lithium salt additive present in an amount ranging from about 0.1 wt % to about 10 wt % of a total wt % of the electrolyte solution; and
optionally LiNO 3 ; and
when LiPF 6 is present, the electrolyte solution also consists of a Lewis base,
wherein the lithium salt additive forms a stable solid electrolyte interface layer on a surface of the negative electrode,
wherein the stable solid electrolyte interface layer has a thickness of less than or equal to about 10 nm, and
wherein the silicon-sulfur battery has a specific capacity of greater than 800 mAh/g for more than 80 cycles of the silicon-sulfur battery.
12. The silicon-sulfur battery as defined in claim 11 wherein the LiPF 6 is the lithium salt additive, and wherein the Lewis base is selected from the group consisting of dimethylacetamide (DMAc) and tributylamine (TBA).
13. The silicon-sulfur battery as defined in claim 12 wherein the Lewis base is present in an amount ranging from about 0.1 wt % and about 5 wt % of the total wt % of the electrolyte solution.
14. A pre-lithiation kit, comprising:
a negative electrode including a silicon-based active material; and
an electrolyte solution for pre-lithiating the negative electrode, the electrolyte solution including a lithium salt dissolved in a solvent mixture consisting of dimethoxyethane (DME) and fluoroethylene carbonate (FEC) present in a volume to volume ratio ranging from 10 to 1 to 1 to 10.
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