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Electrochemical cell for lithium-based batteries — GM Global Technology Operations LLC (US10593988B2)

GM Global Technology Operations LLC · Google Patents

Google Patents · Patents · License: Open Access

patent, google patents, intellectual property, US10593988B2, GM Global Technology Operations LLC, Xingcheng Xiao, en, 2020

ABSTRACT

Abstract

An electrochemical cell is formed. The cell includes a non-lithium negative electrode in contact with a lithium ion permeable negative electrode current collector, and a positive electrode disposed in contact with a lithium ion permeable positive electrode current collector. The non-lithium negative electrode and the positive electrode are lithium ion permeable. The cell also has a lithium source electrode including lithium ions. A respective microporous polymer separator is disposed between the lithium source electrode and each of the negative and positive electrodes; or a first separator is disposed between the lithium source electrode and one of the negative and positive electrodes, and a second separator is disposed between the negative and positive electrodes. An electrolyte is introduced into the electrochemical cell. A voltage potential is applied across the electrochemical cell to pre-lithiate any of the non-lithium negative electrode and positive electrode with lithium ions from the lithium source electrode.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 13/923,354, filed Jun. 20, 2013, which is incorporated by reference herein in its entirety.

BACKGROUND

Secondary, or rechargeable, 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

An electrochemical cell is formed. The electrochemical cell includes a non-lithium negative electrode disposed in contact with a lithium ion permeable negative electrode current collector. Also, the electrochemical cell includes a positive electrode disposed in contact with a lithium ion permeable positive electrode current collector. The non-lithium negative electrode and the positive electrode are lithium ion permeable. The electrochemical cell also has a lithium source electrode including lithium ions. A respective microporous polymer separator is disposed between the lithium source electrode and each of the non-lithium negative electrode and the positive electrode; or a first microporous polymer separator is disposed between the lithium source electrode and one of the non-lithium negative electrode and the positive electrode, and a second microporous polymer separator is disposed between the non-lithium negative electrode and the positive electrode. An electrolyte is introduced into the electrochemical cell. A voltage potential is applied across the electrochemical cell to pre-lithiate any of the non-lithium negative electrode and the positive electrode with lithium ions from the lithium source electrode.

Examples of the electrochemical cell disclosed herein may form a lithium ion battery or a lithium sulfur battery.

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 cross-sectional view of an example of an electrochemical cell disclosed herein;

FIG. 2 is a cross-sectional view of another example of the electrochemical cell disclosed herein;

FIG. 3 is a cross-sectional view of an example of the electrochemical cell disclosed herein including two sub-cells within the electrochemical cell;

FIG. 4 is a cross-sectional view of another example of the electrochemical cell disclosed herein including two sub-cells within the electrochemical cell;

FIG. 5 is a schematic illustration of the structure of an electrochemical test cell that includes lithiated positive and negative electrodes;

FIG. 6 includes three graphs respectively illustrating the difference in voltage over time for three different pairs of electrodes; and

FIG. 7 includes five graphs respectively illustrating the impedance of one of the electrodes from the electrochemical test cell of FIG. 5 vs. the impedance of another one of the electrodes from the electrochemical test cell of FIG. 5 .

DETAILED DESCRIPTION

The 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 microporous 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. Additionally, a reference electrode may be introduced into the lithium-based battery to monitor the state of charge of the positive electrode, the negative electrode, or both electrodes.

In some instances, prior to forming a functional lithium-based battery, the negative electrode is pre-lithiated by adding the negative electrode to a half-cell soaked in an electrolyte. A voltage potential is applied to the half-cell to complete the pre-lithiation of the negative electrode. When the negative electrode is pre-lithiated in a half-cell, additional manufacturing steps are included to form the lithium-based battery. The additional steps include removing the negative electrode from the half-cell, and then cleaning, drying, and placing the negative electrode into a lithium-based battery that includes the other components described above. The additional steps to form the full cell may increase the cost of production, and may also reduce the life cycling of the lithium-based battery by exposing the negative electrode to moisture or oxygen gas in the air. The negative electrode may also be damaged during the cleaning and drying process prior to being inserted into the full electrochemical cell.

Moreover, during the additional steps to form the lithium-based battery, moving the negative electrode to the battery may be difficult. This may be due, in part, to deformation of the negative electrode from the large volume expansion of the negative electrode active material during the pre-lithiation. It has been found that negative electrode active materials (e.g., silicon particles) with high specific capacities also have large volume expansion during pre-lithiation (i.e., the initial charging) of the negative electrode in the half-cell. The large volume change (e.g., about 300%) experienced by the negative electrode active material during the pre-lithiation causes the negative electrode active material to expand. The expansion of the negative electrode active material may cause the negative electrode to deform. As an example, the deformation may change the curvature of the negative electrode. The altered curvature of the negative electrode may render the electrode more difficult to transfer into the lithium-based battery.

To form examples of the electrochemical cell herein, the method includes forming an electrochemical cell that may be pre-lithiated in-situ to form a lithium ion or lithium sulfur battery. The electrochemical cell includes a non-lithium negative electrode and a positive electrode, which are lithium ion permeable. At the outset of the method (i.e., prior to pre-lithiation), in some instances, the electrodes do not include lithium. Due, in part, to the lithium ion permeability of the non-lithium electrodes, in-situ pre-lithiation can occur. The in-situ pre-lithiation eliminates the need to perform any additional manufacturing steps to form the full electrochemical cell (e.g., the lithium-based battery). By eliminating any additional manufacturing steps, the life cycle of the lithium-based battery may be extended, in part because it is not exposed to oxygen gas or moisture in the air. Additionally, the in-situ pre-lithiation eliminates the previously mentioned cleaning and drying processes that may be performed after pre-lithiating in a half-cell, and thus eliminates the possibility of deformation resulting therefrom.

In an example of the method disclosed herein, an electrochemical cell 10 may be formed. An example of the electrochemical cell 10 that may be formed is shown in FIG. 1 . In this example, the electrochemical cell 10 includes non-lithium negative electrode 12 in contact with a lithium ion permeable negative electrode current collector 14 . The electrochemical cell 10 also includes a positive electrode 20 , 20 â² in contact with a lithium ion permeable positive electrode current collector 22 . The electrochemical cell 10 further includes a lithium source electrode 16 with first and second microporous polymer separators

18 A, 18 B disposed between the lithium source electrode 16 and each of the non-lithium negative electrode 12 and the positive electrode 20 , 20 â².

In an example, the non-lithium negative electrode 12 includes a non-lithium containing negative active material. The non-lithium containing negative active material does not contain lithium. In an example, the negative active material may be selected from the group consisting of graphite or another electron-conducting carbon, coke, soft carbons, hard carbons, amorphous carbon, silicon, aluminum, tin, or alloys of Si, Al, and/or Sn, a silicon-carbon composite, silicon oxide (e.g., SiO x x<2), tin oxide, and titanium oxide. Some examples of electron-conducting carbon include natural graphites, such as flaky graphite, plate-like graphite, and other types of graphite; high-temperature sintered carbon products obtained, for example, from petroleum coke, coal coke, celluloses, saccharides, and mesophase pitch; artificial graphites, including pyrolytic graphite; carbon blacks, such as acetylene black, furnace black, Ketjen black, channel black, lamp black, and thermal black; asphalt pitch, coal tar, active carbon, mesophase pitch, and polyacetylenes.

It is to be understood that the non-lithium negative electrode 12 is lithium ion permeable. This permeability is due, in part to the negative active material, which, while not being formed of lithium, is permeable to lithium ions. Additionally, the non-lithium negative electrode 12 may be porous, and the pores may allow lithium ions to permeate the negative electrode 12 .

The non-lithium negative electrode 12 may further include a binder and a conductive filler. The binder may be included to aid in adhering the negative active material together as well as to aid in the adhesion of the non-lithium negative electrode 12 to the lithium ion permeable negative electrode current collector 14 . The choice of binder material may vary widely so long as it is inert with respect to the other materials in the negative electrode 12 . Some examples of the binder used in the non-lithium negative electrode 12 may include polytetrafluoroethylenes, 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, acrylates, methacrylates, divinyl ethers, or any other suitable binder material known to skilled artisans. Other suitable binders include polyvinyl alcohol (PVA), sodium alginate, or other water-soluble binders.

The conductive filler may be included to ensure electron conduction between the lithium ion permeable negative electrode current collector 14 and the negative active material. Some examples of the conductive filler may be a high surface area carbon, such as acetylene black (i.e., carbon black). Other examples of suitable conductive fillers include graphene, graphite, carbon nanotubes, activated carbon fibers, non-activated carbon fibers, metal flakes, metal powders, metal fibers, carbon fabrics, metal mesh, and electrically conductive polymers. In yet another example, a combination of conductive fillers is used, such as carbon black and carbon nanofibers.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 13/923,354, filed Jun. 20, 2013, which is incorporated by reference herein in its entirety.

BACKGROUND

SUMMARY

Examples of the electrochemical cell disclosed herein may form a lithium ion battery or a lithium sulfur battery.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of an example of an electrochemical cell disclosed herein;

FIG. 2 is a cross-sectional view of another example of the electrochemical cell disclosed herein;

FIG. 3 is a cross-sectional view of an example of the electrochemical cell disclosed herein including two sub-cells within the electrochemical cell;

FIG. 4 is a cross-sectional view of another example of the electrochemical cell disclosed herein including two sub-cells within the electrochemical cell;

FIG. 5 is a schematic illustration of the structure of an electrochemical test cell that includes lithiated positive and negative electrodes;

FIG. 6 includes three graphs respectively illustrating the difference in voltage over time for three different pairs of electrodes; and

DETAILED DESCRIPTION

18 A, 18 B disposed between the lithium source electrode 16 and each of the non-lithium negative electrode 12 and the positive electrode 20 , 20 â².

The non-lithium containing negative electrode 12 may be formed by applying a slurry of the electrode components to the lithium ion permeable negative electrode current collector 14 , then drying the slurry to form the non-lithium containing negative electrode 12 . In an example, the slurry of electrode components is applied to both sides of the lithium ion permeable negative current collector 14 . In another example, the slurry may be applied to one side, and may penetrate the pores of the current collector 14 to substantially coat the other side of the current collector 14 . In either example, it is to be understood that the slurry of electrode components may also substantially fill the pores of the lithium ion permeable negative electrode current collector 14 as well as coat the sides.

In an example, the lithium ion permeable negative electrode current collector 14 may be formed from copper mesh, nickel mesh, porous carbon paper (e.g., made up of nanofibers, nanotubes, fibers, and/or graphene), or any other appropriate electrically conductive material. It is to be understood that the negative electrode current collector 14 may be in any form that allows lithium ions to pass through the current collector 14 . As examples, the lithium ion permeable negative electrode current collector 14 may be in the form of a foam, grid, net, woven fiber, honeycomb, patterned holes on metal foil, perforated holes on metal foil, metallized plastic film, expanded metal grid, metal wool, micro-truss, woven carbon fabric, woven carbon mesh, non-woven carbon mesh, carbon felt, or combinations thereof. The current collector 14 may have an average pore size ranging from about 1 nm to about 10 Î¼m. The current collector 14 may be characterized by an average pore-to-surface ratio or porosity ranging from about 0.1% to about 99.9%. In an example, the average pore-to-surface ratio or porosity is at least 10%. The lithium ion permeable negative electrode current collector 14 that is selected should be lithium ion permeable and capable of collecting and moving free electrons to and from an external circuit connected thereto.

An example of the positive electrode 20 , 20 â² includes a positive active material, a binder, and a conductive filler. The binder and conductive filler of the positive electrode 20 , 20 â² may be selected from the same examples of binder and conductive filler described herein for the non-lithium negative electrode 12 .

In some examples, the positive electrode 20 may be formed from a non-lithium containing positive active material that may function as the positive electrode for a lithium ion battery. One common class of known non-lithium positive active materials suitable for the positive electrode 20 includes layered transitional metal oxides. Some specific examples of the positive active materials include manganese oxide (Mn 2 O 4 ), cobalt oxide (CoO 2 ), a nickel-manganese oxide spinel, a layered nickel-manganese-cobalt oxide, or an iron polyanion oxide, such as iron phosphate (FePO 4 ) or iron fluorophosphate (FePO 4 F), or vanadium oxide (V 2 O 5 ). A non-lithium positive electrode 20 may be desirable when the positive electrode 20 is the electrode 20 to be pre-lithiated using the example methods disclosed herein.

In some other examples, the positive electrode active material for the lithium ion battery may be a lithium-containing active material. In these instances, the positive electrode is not pre-lithiated, but rather includes some amount of lithium less than the total capacity of the positive electrode (e.g., from about 10% to about 50% of the total capacity). A lithium-based positive electrode may help compensate for lithium loss resulting from the formation of a solid electrolyte interphase (SEI) layer and/or other side reaction.

Some examples of lithium-containing active material for the lithium ion battery positive electrode include spinel lithium manganese oxide (LiMn 2 O 4 ), lithium cobalt oxide (LiCoO 2 ), a nickel-manganese oxide spinel (Li(Ni 0.5 Mn 1.5 )O 2 ), or a layered nickel-manganese-cobalt oxide (having a general formula of xLi 2 MnO 3 .(1âx)LiMO 2 or (M is composed of any ratio of Ni, Mn and/or Co). A specific example of the layered nickel-manganese-cobalt oxide includes (xLi 2 MnO 3 .(1âx)Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 ). Other suitable lithium active materials include Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 , Li x+y Mn 2ây O 4 (LMO, 0<x<1 and 0<y<0.1), or a lithium iron polyanion oxide, such as lithium iron phosphate (LiFePO 4 ) or lithium iron fluorophosphate (Li 2 FePO 4 F). Still other lithium-based active materials may also be utilized, such as LiNi x M 1âx O 2 (M is composed of any ratio of Al, Co, and/or Mg, for example, lithium nickel cobalt aluminum oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) or NCA), aluminum stabilized lithium manganese oxide spinel (e.g., Li x Al 0.05 Mn 0.95 O 2 ), lithium vanadium oxide (LiV 2 O 5 ), Li 2 MSiO 4 (M is composed of any ratio of Co, Fe, and/or Mn), and any other high efficiency lithium nickel-manganese-cobalt material (e.g., NMC or LiNiMnCoO 2 ). By âany ratioâ it is meant that any element may be present in any amount. So, for example, M could be Al, with or without Co and/or Mg, or any other combination of the listed elements.

In another example, the positive electrode 20 â² may be formed from a non-lithium containing positive active material that may function as the positive electrode for a lithium sulfur battery. In this example, the non-lithium containing positive active material may be sulfur-based active material. In an example, the sulfur-based active material is a sulfur-carbon composite. In an example, the sulfur-carbon composite has a weight ratio of S to C that ranges from 1:9 to 9:1. Some other examples of the sulfur-based active material include S 8 , copper sulfide, or iron sulfide.

In yet another example, the positive electrode 20 â² may be formed from a lithium containing active material. The lithium containing active material may be a lithium sulfur-based active material, such as a lithium sulfur-carbon composite. In another example, the lithium containing sulfur-based active material may be Li 2 S 8 , Li 2 S 6 , Li 2 S 4 , Li 2 S 2 , or Li 2 S.

It is to be understood that the positive electrode 20 , 20 â² is lithium ion permeable. This permeability is due, in part to the positive active material, which is permeable to lithium ions. Additionally, the positive electrode 20 , 20 â² may be porous, and the pores may allow lithium ions to permeate the positive electrode 20 , 20 â².

The positive electrode 20 , 20 â² may be formed by applying a slurry of the components to the lithium ion permeable positive electrode current collector 22 , and then drying the slurry to form the non-lithium containing positive electrode 20 , 20 â². In an example, the slurry of electrode components is applied to both sides of the lithium ion permeable positive current collector 22 . In another example, the slurry may be applied to one side, and may penetrate the pores of the current collector 14 to substantially coat the other side of the current collector 14 . In either example, it is to be understood that the slurry of electrode components may also substantially fill the pores of the lithium ion permeable positive electrode current collector 22 as well as coat the sides.

In an example, the lithium ion permeable positive electrode current collector 22 may be formed from aluminum mesh, nickel mesh, porous carbon paper (e.g., made up of nanofibers, nanotubes, fibers, and/or graphene), or any other appropriate electrically conductive material. It is to be understood that the lithium ion permeable positive electrode current collector 22 may be in any form that allows lithium ions to pass through the current collector 22 . As examples, the lithium ion permeable positive electrode current collector 22 may be in the form of a foam, grid, net, woven fiber, honeycomb, patterned holes on metal foil, perforated holes on metal foil, metallized plastic film, expanded metal grid, metal wool, micro-truss, woven carbon fabric, woven carbon mesh, non-woven carbon mesh, carbon felt, or combinations thereof. The current collector 22 may have an average pore size ranging from about 1 nm to about 10 Î¼m. The current collector 22 may be characterized by an average pore-to-surface ratio or porosity ranging from about 0.1% to about 99.9%. In an example, the average pore-to-surface ratio or porosity is at least 10%. The lithium ion permeable positive electrode current collector 22 that is selected should be lithium ion permeable and capable of collecting and moving free electrons to and from an external circuit connected thereto.

In the example shown in FIG. 1 , the electrochemical cell 10 has two microporous polymer separators

18 A, 18 B. The microporous polymer separators

18 A, 18 B operate as both an electrical insulator and a mechanical support. One microporous polymer separator 18 A is sandwiched between the non-lithium negative electrode 12 and the lithium source electrode 16 . The other microporous polymer separator 18 B is sandwiched between the positive electrode 20 , 20 â² and the lithium source electrode 16 . The microporous polymer separators

18 A, 18 B prevent physical contact between each of the two electrodes 12 , 20 , 20 â² and the reference electrode 16 , and the occurrence of a short circuit. In addition to providing a physical barrier between the electrodes 12 , 20 , 20 â², 16 , the microporous polymer separators

18 A, 18 B ensure passage of lithium ions (identified by Li + 28 ) and related anions (not shown) through an electrolyte solution 30 (discussed in greater detail below) filling their pores. This helps ensure that the electrochemical cell 10 functions properly.

Each of the microporous polymer separators

18 A, 18 B may be any suitable material. In an example, the separators

18 A, 18 B may be a polyolefin membrane. The polyolefin may be a homopolymer (derived from a single monomer constituent) or a heteropolymer (derived from more than one monomer constituent), and may be either linear or branched. If a heteropolymer derived from two monomer constituents is employed, the polyolefin may assume any copolymer chain arrangement, including those of a block copolymer or a random copolymer. The same holds true if the polyolefin is a heteropolymer derived from more than two monomer constituents. As examples, the polyolefin membrane may be formed of polyethylene (PE), polypropylene (PP), a blend of PE and PP, or multi-layered structured porous films of PE and/or PP.

In other examples, the microporous polymer separator

18 A, 18 B may be formed from another polymer chosen from polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamides (Nylons), polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK), polyethersulfones (PES), polyimides (PI), polyamide-imides, polyethers, polyoxymethylene (e.g., acetal), polybutylene terephthalate, polyethylenenaphthenate, polybutene, acrylonitrile-butadiene styrene copolymers (ABS), polystyrene copolymers, polymethylmethacrylate (PMMA), polyvinyl chloride (PVC), polysiloxane polymers (such as polydimethylsiloxane (PDMS)), polybenzimidazole (PBI), polybenzoxazole (PBO), polyphenylenes (e.g., PARMAXâ¢ (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., VECTRANâ¢ (Hoechst AG, Germany), ZENITEÂ® (DuPont, Wilmington, Del.), poly(p-hydroxybenzoic acid), polyaramides, polyphenylene oxide, and/or combinations thereof. In yet another example, the microporous polymer separator 18 may be chosen from a combination of the polyolefin (such as PE and/or PP) and one or more of the polymers listed above.

The microporous polymer separators

18 A, 18 B may contain a single layer or a multi-layer laminate fabricated from either a dry or wet process. For example, a single layer of the polyolefin and/or other listed polymer may constitute the entirety of the microporous polymer separator

18 A, 18 B. As another example, however, multiple discrete layers of similar or dissimilar polyolefins and/or polymers may be assembled into the microporous polymer separator

18 A, 18 B. 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 microporous polymer separator

18 A, 18 B. Further, the polyolefin (and/or other polymer) layer, and any other optional polymer layers, may further be included in the microporous polymer separator

18 A, 18 B as a fibrous layer to help provide the microporous polymer separator

18 A, 18 B with appropriate structural and porosity characteristics. Still other suitable microporous polymer separators

18 A, 18 B 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).

The lithium source electrode 16 may first be used to provide a source of lithium ions 28 during pre-lithiation of the non-lithium negative electrode 12 , the positive electrode 20 , 20 â², or both electrodes 12 , 20 , 20 â² separately. In one example, a voltage potential (which may be varied while current remains constant) is applied between the reference electrode 16 and the non-lithium negative electrode 12 during pre-lithiation of the non-lithium negative electrode 12 . In this example, the lithium ions 28 flow from the source electrode 16 to the non-lithium negative electrode 12 during pre-lithiation (discussed further below). The flow of lithium ions 28 to the negative electrode 12 causes the negative electrode 12 to become lithiated, and thus provides an initial charged state for the electrochemical cell 10 once pre-lithiation is complete. During pre-lithiation, it is to be understood that the amount of lithium added to the non-lithium negative electrode 12 does not exceed 110% of the capacity of the non-lithium negative 12 . Lithiating beyond the capacity of the negative electrode 12 may be desirable to compensate for irreversible lithium loss during battery cycling. The electrochemical cell 10 may then be discharged, so that the lithium ions in the negative electrode 12 are driven toward the positive electrode 20 , 20 , which becomes lithiated.

When pre-lithiating the non-lithium negative electrode 12 (or during the first few battery cycles), a solid electrolyte interface (SEI) layer may form. Formation of the SEI layer typically results in loss of lithium from the positive electrode 20 , 20 , in part because lithium from this electrode 20 , 20 â² may be partially consumed (e.g., up to 10% lithium loss) during the SEI formation. In the examples disclosed herein however, the lithium source electrode 16 is utilized to compensate the lithium loss due to SEI formation. One or more components in the electrolyte are active and readily decompose during pre-lithiation or the first few cycles. When the voltage potential is applied to the cell during the pre-lithiation process or the first few cycles, at least some component in the electrolyte is decomposed and reacts with lithium from the lithium source electrode 16 . The decomposition product deposits on the exposed surface(s) of the negative electrode 12 to form the SEI layer. Examples of the decomposition product may be LiF, Li 2 CO 3 , LiO, Li x PF y O z , F-replaced Lithium Ethylene Di Carbonate (F-LEDC), an unsaturated polyolefin, etc. In this example, the lithium source electrode 16 compensates for the irreversibly lithium loss from the positive electrode 20 , 20 â².

In another example, a voltage potential (which may be varied while current remains constant) is applied between the reference electrode 16 and the positive electrode 20 , 20 â² during pre-lithiation. In this example, the lithium ions 28 flow from the source electrode 16 to the positive electrode 20 , 20 â² during pre-lithiation (discussed further below). The flow of lithium ions 28 to the positive electrode 20 , 20 â² causes the positive electrode 20 , 20 â² to become lithiated, and thus provides an initial discharged state for the electrochemical cell 10 once pre-lithiation is complete. During pre-lithiation, it is to be understood that the amount of lithium added to the positive electrode 20 , 20 â² does not exceed 110% of the capacity of the positive electrode 20 , 20 â². Lithiating beyond the capacity of the negative electrode 12 may be desirable to compensate for irreversible lithium loss during battery cycling. The electrochemical cell 10 may then be charged, so that the lithium ions in the positive electrode 20 , 20 â² are driven toward the non-lithium negative electrode 12 , which becomes lithiated. When the positive electrode 20 , 20 â² is to be pre-lithiated, the active material utilized in the positive electrode 20 , 20 â² may be the non-lithium positive electrode active materials.

In yet another example, a voltage potential (which may be varied while current remains constant) is applied between the reference electrode 16 and the non-lithium negative electrode 12 or the positive electrode 20 , 20 â² to partially pre-lithiate the electrode 12 or 20 , 20 â². After one of the electrodes 12 or 20 , 20 is partially pre-lithiated, then the voltage potential is applied between the lithium source electrode 16 and the other electrode 20 , 20 â² or 12 to partially pre-lithiate the other electrode 20 , 20 â² or 12 (discussed in further detail below). The flow of lithium ions 28 into the respective electrodes separately causes each electrode 12 , 20 , 20 â² to become partially pre-lithiated, and thus provides an initial partial charged/partial discharged state for the electrochemical cell 10 once partial pre-lithiation is complete. When partial lithiation of both electrode 12 and 20 , 20 â² is utilized, it is to be understood that the total percentage of lithiation in both electrodes 12 , 20 , 20 â² does not exceed 110% of the capacity of either electrode 12 , 20 , 20 â². The electrochemical cell 10 may then be charged or discharged, so that the lithium ions in the electrode 12 , 20 , 20 â² move into the other electrode 20 , 20 â² or 12 which becomes fully lithiated.

In an example, the lithium source electrode 16 may be selected from the group consisting of lithium metal; lithiated carbon; a lithium-silicon alloy; a lithium-aluminum alloy; a lithium-tin alloy; lithium-metal oxides having a formula LiMO 2 , where M is selected from the group consisting of Co, Ni, Mn, and combinations thereof; lithium-metal oxides having a formula LiM 2 O 4 , where M is selected from the group consisting of Mn, Ti, and combinations thereof; lithium-metal oxides having a formula LiM x Mâ² 2âx O 4 , where M and Mâ² are independently selected from the group consisting of Mn and Ni and 0.1<x<0.9; lithium-metal phosphates having a formula LiMPO 4 , where M is selected from the group consisting of Fe, Mn, Co, and combinations thereof; and combinations thereof.

While not shown in the figures, it is to be understood that the lithium source electrode 16 may be positioned in contact with a suitable current collector, such as copper foil. In some instances, when the lithium source electrode 16 is positioned in between two or more electrodes or sub-cells, the current collector of the lithium source electrode 16 may be lithium ion permeable as previously disclosed herein. As examples, the lithium source electrode 16 may be a mesh, a cloth, a net made of similar metals or non-metals (e.g., graphene, carbon nanofiber paper, carbon cloth, etc.

The lithium source electrode 16 may be rather large in terms of its âprojected area,â which means the geometric area of the surface as projected toward the negative electrode 12 or

CLAIMS

Claims ( 20 )

What is claimed is:

1. A method, comprising:

forming an electrochemical cell, including:

at least one non-lithium negative electrode in contact with a lithium ion permeable negative electrode current collector, the at least one non-lithium negative electrode having a first side and an opposing second side, wherein the at least one non-lithium negative electrode is lithium ion permeable;

at least one positive electrode in contact with a lithium ion permeable positive electrode current collector, the at least one positive electrode having a first side and an opposing second side, wherein the positive electrode is lithium ion permeable;

a lithium source electrode including lithium ions in an amount ranging from about 10% to about 50% greater than the lithium ion capacity of the at least one non-lithium negative electrode or the at least one positive electrode, the lithium source electrode having a first side and an opposing second side and a projected area that is at least 20% of the area of the at least one non-lithium negative electrode or the at least one positive electrode; and

one of:

i) a first polymer separator disposed between the first side of the lithium source electrode and one of the at least one non-lithium negative electrode and a second polymer separator disposed between the second side of the lithium source electrode and one of the at least one positive electrode; or

ii) a first microporous polymer separator disposed between the lithium source electrode and the first side of a first of the at least one non-lithium negative electrode, a second microporous polymer separator disposed between the second side of the first non-lithium negative electrode and a first side of a first of the at least one positive electrode, a third microporous polymer separator disposed between the second side of the first positive electrode and the first side of a second of the at least one non-lithium negative electrode, and a fourth microporous polymer separator disposed between the second side of the second non-lithium negative electrode and the first side of a second of the at least one positive electrode;

introducing an electrolyte into the electrochemical cell;

applying a voltage potential across the electrochemical cell, thereby pre-lithiating any of the non-lithium negative electrode and the positive electrode with lithium ions from the lithium source electrode, and forming a rechargeable lithium-based battery;

cycling the battery through discharge and charge cycles; and

then, relithiating any of the non-lithium negative electrode and the positive electrode with lithium ions from the lithium source electrode.

2. The method as defined in claim 1 wherein:

the non-lithium negative electrode is pre-lithiated and the voltage potential ranges from about 0.005V to about 2.0V; or

the positive electrode is pre-lithiated and the voltage potential ranges from about 1.5V to about 5.0V.

3. The method as defined in claim 1 wherein the electrochemical cell is selected from the group consisting of a pouch cell, a cylindrical cell, and a coin cell and is not opened after the pre-lithiating.

4. The method as defined in claim 1 wherein the at least one non-lithium negative electrode includes a negative active material, a binder, and a conductive filler, and wherein the negative active material is selected from the group consisting of graphite, amorphous carbon, silicon, a silicon alloy, silicon oxide, a silicon-carbon composite, tin oxide, and titanium oxide.

5. The method as defined in claim 1 wherein the at least one positive electrode includes a positive active material, a binder, and a conductive filler, and wherein:

the positive active material is a non-lithium containing active material selected from the group consisting of sulfur, vanadium oxide, manganese oxide, cobalt oxide, a manganese-nickel-oxide spinel, copper sulfide, iron sulfide, a layered nickel-manganese-cobalt oxide, and an iron polyanion oxide; or

the at least one positive electrode includes a lithium containing positive active material selected from the group consisting of LiMn 2 O 4 , Li(Ni 0.5 Mn 1.5 )O 2 , Li(Ni 1/3 Mn 1/3 Co 1/3 )O 4 , LiCoO 2 , LiNi x M 1âx O 2 (M is composed of any ratio of Al, Co, and Mg), LiFePO 4 , Li 2 MSiO 4 (M=Co, Fe, Mn), xLi 2 MnO 3 .(1âx)LiMO 2 (M is composed of any ratio of Ni, Mn and Co), Li x+y Mn 2ây O 4 (0<x<1, 0<y<0.1), and a high efficiency lithium nickel-manganese-cobalt oxide material.

6. The method as defined in claim 1 wherein the lithium ion permeable negative electrode current collector is selected from the group consisting of a copper mesh, a nickel mesh, and a porous carbon paper, and the lithium ion permeable positive electrode current collector is selected from the group consisting of an aluminum mesh, a nickel mesh, and a porous carbon paper.

7. The method as defined in claim 1 , further comprising controlling a mass of the lithium ions in the lithium source electrode, wherein the mass of the lithium ions in the lithium source electrode ranges from about 10% to about 50% greater than a mass of lithium used to pre-lithiate the any of the non-lithium negative electrode and the positive electrode with lithium ions.

8. The method as defined in claim 1 wherein the method forms a rechargeable lithium-based battery, and where the method further comprises using the lithium source electrode as a reference electrode in the battery to monitor electrode potential.

9. The method as defined in claim 1 wherein the relithiating is of the at least one non-lithium negative electrode, and the relithiating involves applying a relithiation voltage potential across the lithium source electrode and the at least one non-lithium negative electrode.

10. The method as defined in claim 1 wherein the relithiating is of the at least one positive electrode, and the relithiating involves applying a relithiation voltage potential across the lithium source electrode and the at least one positive electrode.

11. A method, comprising:

forming an electrochemical cell, including:

at least one lithium source electrode including lithium ions in an amount ranging from about 10% to about 50% greater than the lithium ion capacity of the at least one non-lithium negative electrode or the at least one positive electrode, the at least one lithium source electrode having a first side and an opposing second side and a projected area that is at least 20% of the area of the at least one non-lithium negative electrode or the at least one positive electrode; and

one of:

i) a first polymer separator disposed between a first of the at least one lithium source electrode and the first side of the at least one non-lithium negative electrode, a second polymer separator disposed between the second side of the least one non-lithium negative electrode and the first side of the at least one positive electrode, and a third polymer separator disposed between the second side of the at least one positive electrode and a second of the at least one lithium source electrode; or

ii) a first polymer separator disposed between a first of the at least one non-lithium negative electrode and a first side of a first of the at least one positive electrode, a second polymer separator disposed between a second side of the first of the at least one positive electrode and the first side of the at least one lithium source electrode, a third polymer separator disposed between the second side of the at least one lithium source electrode and a first side of a second of the at least one non-lithium negative electrode, and a fourth polymer separator disposed between a second side of the second of the at least one non-lithium negative electrode and a second of the at least one positive electrode;

introducing an electrolyte into the electrochemical cell;

applying a voltage potential across the electrochemical cell, thereby pre-lithiating any of the at least one non-lithium negative electrode and the at least one positive electrode with lithium ions from the at least one lithium source electrode, and forming a rechargeable lithium-based battery;

cycling the battery through discharge and charge cycles; and

then, relithiating any of the at least one non-lithium negative electrode and the at least one positive electrode with lithium ions from the at least one lithium source electrode.

12. The method as defined in claim 11 , wherein the lithium ion permeable negative electrode current collector and the a lithium ion permeable positive electrode current collector are capable of collecting and moving free electrons to and from an external circuit connected to the electrochemical cell.

13. The method as defined in claim 11 , comprises forming an electrochemical cell including the first polymer separator disposed between the first of the at least one lithium source electrode and the first side of the at least one non-lithium negative electrode, the second polymer separator disposed between the second side of the least one non-lithium negative electrode and the first side of the at least one positive electrode, and the third polymer separator disposed between the second side of the at least one positive electrode and the second of the at least one lithium source electrode.

14. The method as defined in claim 11 , comprises forming an electrochemical cell including the first polymer separator disposed between the first of the at least one non-lithium negative electrode and the first side of the first of the at least one positive electrode, the second polymer separator disposed between the second side of the first of the at least one positive electrode and the first side of the at least one lithium source electrode, the third polymer separator disposed between the second side of the at least one lithium source electrode and the first side of the second of the at least one non-lithium negative electrode, and the fourth polymer separator disposed between the second side of the second of the at least one non-lithium negative electrode the second of the at least one positive electrode.

15. An electrochemical cell comprising:

a lithium source electrode including lithium ions in an amount ranging from about 10% to about 50% greater than the lithium ion capacity of the at least one non-lithium negative electrode or the at least one positive electrode, and having a projected area that is at least 20% of the area of the at least one non-lithium negative electrode or the at least one positive electrode; and

one of:

i) a first polymer separator disposed between a first side of the lithium source electrode and the at least one non-lithium negative electrode, and a second polymer separator disposed between the second side of the lithium source electrode and the at least one positive electrode; or

ii) a first microporous polymer separator disposed between the lithium source electrode and a first side of a first of the at least one non-lithium negative electrode, a second microporous polymer separator disposed between a second side of the first of the at least one non-lithium negative electrode and a first side of a first of the at least one positive electrode, a third microporous polymer separator disposed between a second side of the first of the at least one positive electrode and a first side of a second of the at least one non-lithium negative electrode, and a fourth microporous polymer separator disposed between a second side of the second of the least one non-lithium negative electrode and a first side of a second of the at least one positive electrode.

16. The electrochemical cell as defined in claim 15 , wherein the at least one non-lithium negative electrode includes a negative active material, a binder, and a conductive filler, and wherein the negative active material is selected from the group consisting of graphite, amorphous carbon, silicon, a silicon alloy, silicon oxide, a silicon-carbon composite, tin oxide, and titanium oxide.

17. The electrochemical cell as defined in claim 15 , wherein the at least one positive electrode includes a positive active material, a binder, and a conductive filler, and wherein:

the positive active material is a non-lithium containing active material selected from the group consisting of sulfur, copper sulfide, iron sulfide, vanadium oxide, manganese oxide, cobalt oxide, a manganese-nickel-oxide spinel, a layered nickel-manganese-cobalt oxide, and an iron polyanion oxide; or

the at least one positive electrode includes a lithium containing positive active material selected from the group consisting of LiMn 2 O 4 , Li(Ni 0.5 Mn 1.5 )O 2 , Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 , LiCoO 2 , LiNi x M 1âx O 2 (M is composed of any ratio of Al, Co, and Mg), LiFePO 4 , Li 2 MSiO 4 (M=Co, Fe, Mn), xLi 2 MnO 3 .(1âx)LiMO 2 (M is composed of any ratio of Ni, Mn and Co), Li x+y Mn 2ây O 4 (0<x<1, 0<y<0.1), and a high efficiency lithium nickel-manganese-cobalt oxide material.

18. The electrochemical cell as defined in claim 15 , wherein the lithium source electrode is selected from the group consisting of lithium metal; lithiated carbon; a lithium-silicon alloy; a lithium-aluminum alloy; a lithium-tin alloy; lithium-metal oxides having a formula LiMO 2 , wherein M is selected from the group consisting of Co, Ni, Mn, and combinations thereof; lithium-metal oxides having a formula LiM 2 O 4 , wherein M is selected from the group consisting of Mn, Ti, and combinations thereof; lithium-metal oxides having a formula LiMxMâ² 2âx O 4 , wherein M and Mâ² are independently selected from the group consisting of Mn and Ni and 0.1<x<0.9; lithium-metal phosphates having a formula LiMPO 4 , wherein M is selected from the group consisting of Fe, Mn, Co, and combinations thereof; and combinations thereof.

19. The electrochemical cell as defined in claim 15 , comprising the first polymer separator disposed between the first side of the lithium source electrode and the at least one non-lithium negative electrode, and the second polymer separator disposed between the second side of the lithium source electrode and the positive electrode.

20. The electrochemical cell as defined in claim 15 , comprising the first microporous polymer separator disposed between the lithium source electrode and the first side of the first of the at least one non-lithium negative electrode, the second microporous polymer separator disposed between the second side of the first of the at least one non-lithium negative electrode and the first side of the first of the at least one positive electrode, the third microporous polymer separator disposed between the second side of the first of the at least one positive electrode and the first side of the second of the at least one non-lithium negative electrode, and the fourth microporous polymer separator disposed between the second side of the second of the least one non-lithium negative electrode and the first side of the second of the at least one positive electrode.

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