ABSTRACT
Abstract
A capacitor-assisted electrode for an electrochemical cell that cycles lithium ions is provided. The capacitor-assisted electrode may include at least two electroactive materials disposed on one or more surfaces of a current collector. A first electroactive material of the at least two electroactive materials may have a first reversible specific capacity and forms a first electroactive material having a first press density. A second electroactive material of the at least two electroactive materials has a second reversible specific capacity and forms a second electroactive material having a second press density. The second reversible specific capacity may be different from the first reversible specific capacity. The second press density may be different from the first press density. One or more capacitor materials may be disposed on or intermingled with one or more of the at least two electroactive materials.
Description
This section provides background information related to the present disclosure which is not necessarily prior art.
The present disclosure relates to capacitor-assisted gradient electrodes, electrochemical cells including capacitor-assisted gradient electrodes, and methods of formation relating thereto.
Advanced energy storage devices and systems are in demand to satisfy energy and/or power requirements for a variety of products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery-assisted systems, hybrid electric vehicles (âHEVsâ), and electric vehicles (âEVsâ). Typical lithium ion batteries include at least two electrodes and an electrolyte and/or separator. One of the two electrodes serves as a positive electrode or cathode and the other electrode serves as a negative electrode or anode. A separator and/or electrolyte may be disposed between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions between the electrodes and, like the two electrodes, may be in solid and/or liquid form and/or a hybrid thereof. In instances of solid-state batteries, which include solid-state electrodes and a solid-state electrolyte, the solid-state electrolyte may physically separate the electrodes so that a distinct separator is not required.
Conventional rechargeable lithium-ion batteries operate by reversibly passing lithium ions back and forth between the negative electrode and the positive electrode. For example, lithium ions may move from the positive electrode to the negative electrode during charging of the battery, and in the opposite direction when discharging the battery. Such lithium-ion batteries can reversibly supply power to an associated load device on demand. More specifically, electrical power can be supplied to a load device by the lithium-ion battery until the lithium content of the negative electrode is effectively depleted. The battery may then be recharged by passing a suitable direct electrical current in the opposite direction between the electrodes.
During discharge, the negative electrode may contain a comparatively high concentration of intercalated lithium, which is oxidized into lithium ions and electrons. Lithium ions may travel from the negative electrode to the positive electrode, for example, through the ionically conductive electrolyte solution contained within the pores of an interposed porous separator. Concurrently, electrons pass through an external circuit from the negative electrode to the positive electrode. Such lithium ions may be incorporated into the material of the positive electrode by an electrochemical reduction reaction. The battery may be recharged or regenerated after a partial or full discharge of its available capacity by an external power source, which reverses the electrochemical reactions that transpired during discharge.
In various instances, however, the lithium-ion battery may experience limited regeneration capabilities, for example as a result of lithium plating on one or more surfaces of the negative electrode, especially during high power and frequent regeneration processes. Some materials, such as hard carbon, may experience improved regeneration capabilities and minimal plating. However, such materials are costly. Accordingly, it would be desirable to develop high-performance electrode designs and methods that enhance intercalation and de-intercalation rates and high-power regeneration capabilities.
SUMMARY
This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
In various aspects, the present disclosure provides a capacitor-assisted electrode for an electrochemical cell that cycles lithium ions. The capacitor-assisted electrode includes at least two electroactive materials disposed on one or more surfaces of a current collector. A first electroactive material of the at least two electroactive materials may have a first reversible specific capacity. A second electroactive material of the at least two electroactive materials may have a second reversible specific capacity. The second reversible specific capacity may be different from the first reversible specific capacity. One or more capacitor materials may be disposed on or intermingled with one or more of the at least two electroactive materials.
In one aspect, the first electroactive material may form a first electroactive material layer. The first electroactive material layer may be disposed adjacent to the one or more surfaces of the current collector. The first electroactive material layer may define a first exposed surface. The second electroactive material may form a second electroactive material layer. The second electroactive material layer may be disposed adjacent to the first exposed surface of the first electroactive material layer.
In one aspect, the first electroactive material layer may have a first press density and the second electroactive material layer may have a second press density. The second press density may be greater than the first press density.
In one aspect, the second reversible specific capacity may be greater than the first reversible specific capacity.
In one aspect, the second electroactive material layer may define a second exposed surface and the at least two electroactive materials may further include a third electroactive material having a third reversible specific capacity. The third electroactive material may forms a third electroactive material layer. The third electroactive material layer may be disposed adjacent to the second exposed surface of the second electroactive material layer.
In one aspect, the first electroactive material layer may have a first press density. The second electroactive material layer may have a second press density. The third electroactive material layer may have a third press density. The third press density may be less than or equal to the second press density. The second press density may be less than or equal to the first press density.
In one aspect, the first press density, the second press density, and the third press density may be each independently greater than or equal to about 2.0 g/cc to less than or equal to about 3.5 g/cc.
In one aspect, the first press density, the second press density, and the third press density may be each independently greater than or equal to about 1.0 g/cc to less than or equal to about 2.0 g/cc.
In one aspect, the third reversible specific capacity may be greater than the second reversible specific capacity. The second reversible specific capacity may be greater than the first reversible specific capacity.
In one aspect, the third reversible specific capacity may be the same as the second reversible specific capacity. The second and third reversible specific capacities may be greater than the first reversible specific capacity.
In one aspect, the second reversible specific capacity may be greater than the third reversible specific capacity. The first reversible specific capacity may be greater than the second reversible specific capacity.
In one aspect, the one or more capacitor materials may be intermingled with the third electroactive material to form the third electroactive material layer.
In one aspect, the one or more capacitor materials may form a capacitor material layer. The capacitor material layer may be disposed adjacent to a third exposed surface of the third electroactive material layer.
In one aspect, the one or more capacitor materials may be selected from the group consisting of: cobalt oxide (Co 3 O 4 ), manganese oxide (MnO 2 ), iridium oxide (IrO 2 ), niobium pentoxide (Nb 2 O 5 ), ruthenium oxide (RuO 2 ), tantalum pentoxide (Ta 2 O 5 ), tin oxide (SnO 2 ), vanadium oxide (V 2 O 5 ), titanium disulfide (TiS 2 ), copper sulfide (CuS), iron sulfide (FeS), activated carbon, graphene, graphite, mesoporous carbon, macroporous carbon, single-walled carbon nanotubes, multi-wailed carbon nanotubes, carbon aerogels, activated carbon fiber cloth, polyaniline, polyacetylene, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene), poly(4-styrenesulfonate), and combinations thereof.
In various other aspects, the present disclosure provides an electrochemical cell that cycles lithium ions. The electrochemical cell that cycles lithium ions includes a first electrode comprising a first electroactive material and a second electrode. The second electrode may include a first layer disposed adjacent to a surface of a current collector; at least one additional layer disposed adjacent to a surface of the first layer; and one or more capacitor materials disposed adjacent to or intermingled with one or more of the first layer and the at least one additional layer. The first layer may have a first reversible specific capacity. The additional layer may have an additional reversible specific capacity that is different from the first reversible specific capacity. The first layer and the at least one additional layer may each include a respective electroactive material.
In one aspect, the at least one additional layer may include a second layer and a third layer. The second layer may be disposed adjacent to the surface of the first layer. The third layer may be disposed adjacent to a surface of the second layer. The second layer may have a second reversible specific capacity. The third layer may have a third reversible specific capacity. The third reversible specific capacity may be greater than the second reversible specific capacity. The second reversible specific capacity may be greater than the first reversible specific capacity.
In one aspect, the first layer may have a first press density. The second layer may have a second press density. The third layer may have a third press density. The second press density maybe greater than the third press density. The first press density may be greater than the second press density. The first layer may include greater than about 0 wt. % to less than or equal to about 100 wt. % of the first electroactive material. The second layer may include greater than about 0 wt. % to less than or equal to about 80 wt. % of a second electroactive material. The third layer may include greater than about 0 wt. % to less than or equal to about 50 wt. % of a third electroactive material.
In one aspect, the first, second, and third electroactive materials may be the same. The one or more capacitor materials may form a first capacitor layer adjacent to a surface of the third electroactive layer.
In one aspect, the one or more capacitor materials may be intermingled with the third layer.
In one aspect, the current collector may be a first current collector and the one or more capacitor materials may be first capacitor materials. The first electrode may include a second layer disposed adjacent to a surface of a second current collector; at least one second additional layer disposed adjacent to a surface of the second layer; and one or more second capacitor materials disposed adjacent or intermingled with one or more of the first layer and the at least one second additional layer. The second layer may have a second reversible specific capacity. The additional layer may have an additional reversible specific capacity that is different from the second reversible specific capacity. The second layer and the at least one second additional layer may each comprise a respective electroactive material.
Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DRAWINGS
The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
FIG. 1 is an example schematic illustration of an electrochemical cell having capacitor-assisted electrodes in accordance with various aspects of the present disclosure;
FIG. 2 A is an example schematic illustration of a capacity-assisted gradient electrode in accordance with various aspects of the present disclosure;
FIG. 2 B is an example schematic illustration of another capacity-assisted gradient electrode in accordance with various aspects of the present disclosure;
FIG. 2 C is an example schematic illustration of another capacity-assisted gradient electrode in accordance with various aspects of the present disclosure;
FIG. 2 D is an example schematic illustration of another capacity-assisted gradient electrode in accordance with various aspects of the present disclosure; and
FIG. 3 is an example schematic illustration of an electrochemical cell having capacitor-assisted gradient electrodes in accordance with various aspects of the present disclosure.
Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION
Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific compositions, components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms âa,â âan,â and âtheâ may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms âcomprises,â âcomprising,â âincluding,â and âhaving,â are inclusive and therefore specify the presence of stated features, elements, compositions, steps, integers, operations, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Although the open-ended term âcomprising,â is to be understood as a non-restrictive term used to describe and claim various embodiments set forth herein, in certain aspects, the term may alternatively be understood to instead be a more limiting and restrictive term, such as âconsisting ofâ or âconsisting essentially ofâ Thus, for any given embodiment reciting compositions, materials, components, elements, features, integers, operations, and/or process steps, the present disclosure also specifically includes embodiments consisting of, or consisting essentially of, such recited compositions, materials, components, elements, features, integers, operations, and/or process steps. In the case of âconsisting of,â the alternative embodiment excludes any additional compositions, materials, components, elements, features, integers, operations, and/or process steps, while in the case of âconsisting essentially of,â any additional compositions, materials, components, elements, features, integ
This section provides background information related to the present disclosure which is not necessarily prior art.
The present disclosure relates to capacitor-assisted gradient electrodes, electrochemical cells including capacitor-assisted gradient electrodes, and methods of formation relating thereto.
Advanced energy storage devices and systems are in demand to satisfy energy and/or power requirements for a variety of products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery-assisted systems, hybrid electric vehicles (âHEVsâ), and electric vehicles (âEVsâ). Typical lithium ion batteries include at least two electrodes and an electrolyte and/or separator. One of the two electrodes serves as a positive electrode or cathode and the other electrode serves as a negative electrode or anode. A separator and/or electrolyte may be disposed between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions between the electrodes and, like the two electrodes, may be in solid and/or liquid form and/or a hybrid thereof. In instances of solid-state batteries, which include solid-state electrodes and a solid-state electrolyte, the solid-state electrolyte may physically separate the electrodes so that a distinct separator is not required.
Conventional rechargeable lithium-ion batteries operate by reversibly passing lithium ions back and forth between the negative electrode and the positive electrode. For example, lithium ions may move from the positive electrode to the negative electrode during charging of the battery, and in the opposite direction when discharging the battery. Such lithium-ion batteries can reversibly supply power to an associated load device on demand. More specifically, electrical power can be supplied to a load device by the lithium-ion battery until the lithium content of the negative electrode is effectively depleted. The battery may then be recharged by passing a suitable direct electrical current in the opposite direction between the electrodes.
During discharge, the negative electrode may contain a comparatively high concentration of intercalated lithium, which is oxidized into lithium ions and electrons. Lithium ions may travel from the negative electrode to the positive electrode, for example, through the ionically conductive electrolyte solution contained within the pores of an interposed porous separator. Concurrently, electrons pass through an external circuit from the negative electrode to the positive electrode. Such lithium ions may be incorporated into the material of the positive electrode by an electrochemical reduction reaction. The battery may be recharged or regenerated after a partial or full discharge of its available capacity by an external power source, which reverses the electrochemical reactions that transpired during discharge.
In various instances, however, the lithium-ion battery may experience limited regeneration capabilities, for example as a result of lithium plating on one or more surfaces of the negative electrode, especially during high power and frequent regeneration processes. Some materials, such as hard carbon, may experience improved regeneration capabilities and minimal plating. However, such materials are costly. Accordingly, it would be desirable to develop high-performance electrode designs and methods that enhance intercalation and de-intercalation rates and high-power regeneration capabilities.
SUMMARY
This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
In various aspects, the present disclosure provides a capacitor-assisted electrode for an electrochemical cell that cycles lithium ions. The capacitor-assisted electrode includes at least two electroactive materials disposed on one or more surfaces of a current collector. A first electroactive material of the at least two electroactive materials may have a first reversible specific capacity. A second electroactive material of the at least two electroactive materials may have a second reversible specific capacity. The second reversible specific capacity may be different from the first reversible specific capacity. One or more capacitor materials may be disposed on or intermingled with one or more of the at least two electroactive materials.
In one aspect, the first electroactive material may form a first electroactive material layer. The first electroactive material layer may be disposed adjacent to the one or more surfaces of the current collector. The first electroactive material layer may define a first exposed surface. The second electroactive material may form a second electroactive material layer. The second electroactive material layer may be disposed adjacent to the first exposed surface of the first electroactive material layer.
In one aspect, the first electroactive material layer may have a first press density and the second electroactive material layer may have a second press density. The second press density may be greater than the first press density.
In one aspect, the second reversible specific capacity may be greater than the first reversible specific capacity.
In one aspect, the second electroactive material layer may define a second exposed surface and the at least two electroactive materials may further include a third electroactive material having a third reversible specific capacity. The third electroactive material may forms a third electroactive material layer. The third electroactive material layer may be disposed adjacent to the second exposed surface of the second electroactive material layer.
In one aspect, the first electroactive material layer may have a first press density. The second electroactive material layer may have a second press density. The third electroactive material layer may have a third press density. The third press density may be less than or equal to the second press density. The second press density may be less than or equal to the first press density.
In one aspect, the first press density, the second press density, and the third press density may be each independently greater than or equal to about 2.0 g/cc to less than or equal to about 3.5 g/cc.
In one aspect, the first press density, the second press density, and the third press density may be each independently greater than or equal to about 1.0 g/cc to less than or equal to about 2.0 g/cc.
In one aspect, the third reversible specific capacity may be greater than the second reversible specific capacity. The second reversible specific capacity may be greater than the first reversible specific capacity.
In one aspect, the third reversible specific capacity may be the same as the second reversible specific capacity. The second and third reversible specific capacities may be greater than the first reversible specific capacity.
In one aspect, the second reversible specific capacity may be greater than the third reversible specific capacity. The first reversible specific capacity may be greater than the second reversible specific capacity.
In one aspect, the one or more capacitor materials may be intermingled with the third electroactive material to form the third electroactive material layer.
In one aspect, the one or more capacitor materials may form a capacitor material layer. The capacitor material layer may be disposed adjacent to a third exposed surface of the third electroactive material layer.
In one aspect, the one or more capacitor materials may be selected from the group consisting of: cobalt oxide (Co 3 O 4 ), manganese oxide (MnO 2 ), iridium oxide (IrO 2 ), niobium pentoxide (Nb 2 O 5 ), ruthenium oxide (RuO 2 ), tantalum pentoxide (Ta 2 O 5 ), tin oxide (SnO 2 ), vanadium oxide (V 2 O 5 ), titanium disulfide (TiS 2 ), copper sulfide (CuS), iron sulfide (FeS), activated carbon, graphene, graphite, mesoporous carbon, macroporous carbon, single-walled carbon nanotubes, multi-wailed carbon nanotubes, carbon aerogels, activated carbon fiber cloth, polyaniline, polyacetylene, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene), poly(4-styrenesulfonate), and combinations thereof.
In various other aspects, the present disclosure provides an electrochemical cell that cycles lithium ions. The electrochemical cell that cycles lithium ions includes a first electrode comprising a first electroactive material and a second electrode. The second electrode may include a first layer disposed adjacent to a surface of a current collector; at least one additional layer disposed adjacent to a surface of the first layer; and one or more capacitor materials disposed adjacent to or intermingled with one or more of the first layer and the at least one additional layer. The first layer may have a first reversible specific capacity. The additional layer may have an additional reversible specific capacity that is different from the first reversible specific capacity. The first layer and the at least one additional layer may each include a respective electroactive material.
In one aspect, the at least one additional layer may include a second layer and a third layer. The second layer may be disposed adjacent to the surface of the first layer. The third layer may be disposed adjacent to a surface of the second layer. The second layer may have a second reversible specific capacity. The third layer may have a third reversible specific capacity. The third reversible specific capacity may be greater than the second reversible specific capacity. The second reversible specific capacity may be greater than the first reversible specific capacity.
In one aspect, the first layer may have a first press density. The second layer may have a second press density. The third layer may have a third press density. The second press density maybe greater than the third press density. The first press density may be greater than the second press density. The first layer may include greater than about 0 wt. % to less than or equal to about 100 wt. % of the first electroactive material. The second layer may include greater than about 0 wt. % to less than or equal to about 80 wt. % of a second electroactive material. The third layer may include greater than about 0 wt. % to less than or equal to about 50 wt. % of a third electroactive material.
In one aspect, the first, second, and third electroactive materials may be the same. The one or more capacitor materials may form a first capacitor layer adjacent to a surface of the third electroactive layer.
In one aspect, the one or more capacitor materials may be intermingled with the third layer.
In one aspect, the current collector may be a first current collector and the one or more capacitor materials may be first capacitor materials. The first electrode may include a second layer disposed adjacent to a surface of a second current collector; at least one second additional layer disposed adjacent to a surface of the second layer; and one or more second capacitor materials disposed adjacent or intermingled with one or more of the first layer and the at least one second additional layer. The second layer may have a second reversible specific capacity. The additional layer may have an additional reversible specific capacity that is different from the second reversible specific capacity. The second layer and the at least one second additional layer may each comprise a respective electroactive material.
Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DRAWINGS
The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
FIG. 1 is an example schematic illustration of an electrochemical cell having capacitor-assisted electrodes in accordance with various aspects of the present disclosure;
FIG. 2 A is an example schematic illustration of a capacity-assisted gradient electrode in accordance with various aspects of the present disclosure;
FIG. 2 B is an example schematic illustration of another capacity-assisted gradient electrode in accordance with various aspects of the present disclosure;
FIG. 2 C is an example schematic illustration of another capacity-assisted gradient electrode in accordance with various aspects of the present disclosure;
FIG. 2 D is an example schematic illustration of another capacity-assisted gradient electrode in accordance with various aspects of the present disclosure; and
FIG. 3 is an example schematic illustration of an electrochemical cell having capacitor-assisted gradient electrodes in accordance with various aspects of the present disclosure.
Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION
Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific compositions, components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms âa,â âan,â and âtheâ may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms âcomprises,â âcomprising,â âincluding,â and âhaving,â are inclusive and therefore specify the presence of stated features, elements, compositions, steps, integers, operations, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Although the open-ended term âcomprising,â is to be understood as a non-restrictive term used to describe and claim various embodiments set forth herein, in certain aspects, the term may alternatively be understood to instead be a more limiting and restrictive term, such as âconsisting ofâ or âconsisting essentially ofâ Thus, for any given embodiment reciting compositions, materials, components, elements, features, integers, operations, and/or process steps, the present disclosure also specifically includes embodiments consisting of, or consisting essentially of, such recited compositions, materials, components, elements, features, integers, operations, and/or process steps. In the case of âconsisting of,â the alternative embodiment excludes any additional compositions, materials, components, elements, features, integers, operations, and/or process steps, while in the case of âconsisting essentially of,â any additional compositions, materials, components, elements, features, integers, operations, and/or process steps that materially affect the basic and novel characteristics are excluded from such an embodiment, but any compositions, materials, components, elements, features, integers, operations, and/or process steps that do not materially affect the basic and novel characteristics can be included in the embodiment.
Any method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed, unless otherwise indicated.
When a component, element, or layer is referred to as being âon,â âengaged to,â âconnected to,â or âcoupled toâ another element or layer, it may be directly on, engaged, connected or coupled to the other component, element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being âdirectly on,â âdirectly engaged to,â âdirectly connected to,â or âdirectly coupled toâ another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., âbetweenâ versus âdirectly between,â âadjacentâ versus âdirectly adjacent,â etc.). As used herein, the term âand/orâ includes any and all combinations of one or more of the associated listed items.
Although the terms first, second, third, etc. may be used herein to describe various steps, elements, components, regions, layers and/or sections, these steps, elements, components, regions, layers and/or sections should not be limited by these terms, unless otherwise indicated. These terms may be only used to distinguish one step, element, component, region, layer or section from another step, element, component, region, layer or section. Terms such as âfirst,â âsecond,â and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first step, element, component, region, layer, or section discussed below could be termed a second step, element, component, region, layer, or section without departing from the teachings of the example embodiments.
Spatially or temporally relative terms, such as âbefore,â âafter,â âinner,â âouter,â âbeneath,â âbelow,â âlower,â âabove,â âupper,â and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially or temporally relative terms may be intended to encompass different orientations of the device or system in use or operation in addition to the orientation depicted in the figures.
Throughout this disclosure, the numerical values represent approximate measures or limits to ranges to encompass minor deviations from the given values and embodiments having about the value mentioned as well as those having exactly the value mentioned. Other than in the working examples provided at the end of the detailed description, all numerical values of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all instances by the term âaboutâ whether or not âaboutâ actually appears before the numerical value. âAboutâ indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by âaboutâ is not otherwise understood in the art with this ordinary meaning, then âaboutâ as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. For example, âaboutâ may comprise a variation of less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and in certain aspects, optionally less than or equal to 0.1%.
In addition, disclosure of ranges includes disclosure of all values and further divided ranges within the entire range, including endpoints and sub-ranges given for the ranges.
Example embodiments will now be described more fully with reference to the accompanying drawings.
The present technology pertains to capacitor-assisted gradient electrodes, electrochemical cells including capacitor-assisted gradient electrodes, and methods of formation relating thereto. For example, capacitor-material coatings or layers disposed on exposed surfaces of an electrode may absorb the regeneration current pulses, for example braking regeneration current during braking regeneration in battery electric vehicles (BEVs). Specific capacity and press density gradients may assist lithium deintercalation and intercalation in respective electrodes. Such electrodes and electrochemical cells integrate capacitors with lithium-ion batteries that may be used in, for example, automotive or other vehicles (e.g., motorcycles, boats), but may also be used in electrochemical cells used in a variety of other industries and applications, such as consumer electronic devices, by way of non-limiting example.
An exemplary and schematic illustration of an electrochemical cell (also referred to as the battery) 20 is shown in FIG. 1 . The battery 20 includes a negative electrode 30 , a positive electrode 40 , and a separator 52 disposed between the electrodes
30 , 40 . As shown, the negative electrode 30 and positive electrode 40 are capacitor-assisted electrodes in accordance with certain aspects of the present disclosure, in that they include both electroactive materials and capacitor materials, such that they function as a hybrid electrode and capacitor. Batteries may incorporate solid-state electrolytes, liquid electrolytes, or semi-solid/gel electrolytes. As shown in FIG. 1 , a separator 52 provides electrical separation and prevents physical contact between the electrodes
30 , 40 . For example, the separator 52 provides a minimal resistance path for internal passage of lithium ions, and in certain instances, related anions, during cycling of the lithium ions. In various aspects, the negative electrode 30 , positive electrode 40 , and/or the separator 52 may each include an electrolyte solution or system 50 .
Any appropriate electrolyte 50 , whether in solid, liquid, or gel form, capable of conducting lithium ions between the electrodes
30 , 40 , may be used in the battery 20 . For example, as shown in FIG. 1 , the electrolyte 50 may be a non-aqueous liquid electrolyte solution that includes a lithium salt dissolved in an organic solvent or a mixture of organic solvents. In certain variations, the separator 52 may be formed of a microporous insulating material, where liquid or semi-solid electrolyte can be imbibed into the pores. While not shown, in various aspects, the liquid electrolyte 50 and separator 52 may be substituted for solid-state electrolyte particles. For example, solid-state electrolyte particles may serve as both ion conductors (e.g., to transport lithium ions) and electrical insulators (e.g., to prevent charge or current from flowing from the negative electrode 30 to the positive electrode 40 ). For example, the separator 52 may be defined by a plurality of solid-state electrolyte particles (not shown). In certain variations, solid-state electrolyte particles (not shown) may also be mixed with electroactive materials
34 , 44 present in the negative and positive electrodes
30 , 40 , respectively.
A negative electrode current collector 32 may be positioned at or near the negative electrode 30 , and a positive electrode current collector 42 may be positioned at or near the positive electrode 40 . The negative electrode current collector 32 and the positive electrode current collector 42 respectively collect and move free electrons to and from an external circuit 22 . For example, an interruptible external circuit 22 and a load device 24 may connect the negative electrode 30 (through the negative electrode current collector 32 ) and the positive electrode 40 (through the positive electrode current collector 42 ). The positive electrode current collector 42 may be a metal foil, metal grid or screen, or expanded metal comprising aluminum or any other appropriate electrically conductive material known to those of skill in the art. The negative electrode current collector 32 may be a metal foil, metal grid or screen, or expanded metal comprising copper or any other appropriate electrically conductive material known to those of skill in the art.
The battery 20 can generate an electric current during discharge by way of reversible electrochemical reactions that occur when the external circuit 22 is closed (to connect the negative electrode 30 and the positive electrode 40 ) and the negative electrode 30 contains a relatively greater quantity of available lithium. The chemical potential difference between the positive electrode 40 and the negative electrode 30 drives electrons produced by the oxidation of inserted lithium at the negative electrode 30 through the external circuit 22 towards the positive electrode 40 . Lithium ions, which are also produced at the negative electrode 30 , are concurrently transferred through the separator 52 towards the positive electrode 40 . The electrons flow through the external circuit 22 and the lithium ions migrate across the separator 52 to the positive electrode 40 , where they may be reacted or intercalated. The electric current passing through the external circuit 22 can be harnessed and directed through the load device 24 until the available lithium in the negative electrode 30 is depleted and the capacity of the battery 20 is diminished.
The battery 20 can be charged or re-energized at any time by connecting an external power source (e.g., charging device) to the battery 20 to reverse the electrochemical reactions that occur during battery discharge. The connection of the external power source to the battery 20 compels the non-spontaneous oxidation of one or more metal elements at the positive electrode 40 to produce electrons and lithium ions. The electrons, which flow back towards the negative electrode 30 through the external circuit 22 , and the lithium ions, which move across the separator 52 back towards the negative electrode 30 , reduce at the negative electrode 30 and replenish it with lithium for consumption during the next battery discharge cycle. As such, each discharge and charge event is considered to be a cycle, where lithium ions are cycled between the positive electrode 40 and the negative electrode 30 .
The external power source that may be used to charge the battery 20 may vary depending on size, construction, and particular end-use of the battery 20 . Some notable and exemplary external power sources include, but are not limited to, AC power sources, such as an AC wall outlet and a motor vehicle alternator. In many battery 20 configurations, each of the negative electrode current collector 32 , the negative electrode 30 , the separator 52 , the positive electrode 40 , and the positive electrode current collector 42 are prepared as relatively thin layers (for example, from several microns to a millimeter or less in thickness) and assembled in layers connected in electrical parallel arrangement to provide a suitable electrical energy and power package. In various other instances, the battery 20 may include electrodes
30 , 40 that are connected in series.
Further, in certain aspects, the battery 20 may include a variety of other components that, while not depicted here, are nonetheless known to those of skill in the art. For instance, the battery 20 may include a casing, gasket, vents, terminal caps, and any other conventional components or materials that may be situated within the battery 20 , including between or around the negative electrode 30 , the positive electrode 40 , and/or the separator 52 , by way of non-limiting example. As noted above, the size and shape of the battery 20 may vary depending on the particular applications for which it is designed. Battery-powered vehicles, hybrid (for example start-stop, microhybrid, and mild-hybrid) internal combustion vehicles, and hand-held consumer electronic devices are three non-limiting examples where the battery 20 would most likely be designed to different size, capacity, and power-output specifications. The battery 20 may also be connected in series or parallel with other similar lithium-ion cells or batteries to produce a greater voltage output, energy, and power if it is required by the load device 24 .
Accordingly, the battery 20 can generate electric current to a load device 24 that can be operatively connected to the external circuit 22 . The load device 24 may be powered fully or partially by the electric current passing through the external circuit 22 when the lithium ion battery 20 is discharging. While the load device 24 may be any number of known electrically-powered devices, a few specific examples of power-consuming load devices include an electric motor for a hybrid vehicle or an all-electric vehicle, a laptop computer, a tablet computer, a cellular phone, and cordless power tools or appliances, by way of non-limiting example. The load device 24 may also be a power-generating apparatus that charges the battery 20 for purposes of storing energy.
With renewed reference to FIG. 1 , the negative and positive electrodes
30 , 40 and/or the separator 52 may each include an electrolyte solution or system 50 . As noted above, the electrolyte 50 may be a non-aqueous liquid electrolyte solution, which may include a lithium salt dissolved in an organic solvent or a mixture of organic solvents. Numerous conventional non-aqueous liquid electrolyte solutions may be employed in the battery 20 .
Appropriate lithium salts generally have inert anions. A non-limiting list of lithium salts that may be dissolved in an organic solvent or a mixture of organic solvents to form the non-aqueous liquid electrolyte solution include lithium hexafluorophosphate (LiPF 6 ); lithium perchlorate (LiClO 4 ), lithium tetrachloroaluminate (LiAlCl 4 ), lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF 4 ), lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )) (LiODFB), lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ), lithium bis-(oxalate)borate (LiB(C 2 O 4 ) 2 ) (LiBOB), lithium tetrafluorooxalatophosphate (LiPF 4 (C 2 O 4 )) (LiFOP), lithium nitrate (LiNO 3 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (LiN(CF 3 SO 2 ) 2 ), lithium fluorosulfonylimide (LiN(FSO 2 ) 2 ) (LiFSI), and combinations thereof. In certain variations, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (LiN(CF 3 SO 2 ) 2 ), lithium fluorosulfonylimide (LiN(FSO 2 ) 2 ) (LiFSI), lithium fluoroalkylphosphate (LiFAP), lithium phosphate (Li 3 PO 4 ), and combinations thereof.
These and other similar lithium salts may be dissolved in a variety of organic solvents, including but not limited to various alkyl carbonates, such as cyclic carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC)), linear carbonates (e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC)), aliphatic carboxylic esters (e.g., methyl formate, methyl acetate, methyl propionate), γ-lactones (e.g., γ-butyrolactone, γ-valerolactone), chain structure ethers (e.g., 1,2-dimethoxyethane (DME), 1-2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran), 1,3-dioxolane (DOL)), sulfur compounds (e.g., sulfolane), and combinations thereof. In various aspects, the electrolyte 50 may include greater than or equal to 1 M to less than or equal to about 2 M concentration of the one or more lithium salts. In certain variations, for example when the electrolyte has a lithium concentration greater than about 2 M or ionic liquids, the electrolyte 50 may include one or more diluters, such as fluoroethylene carbonate (FEC) and/or hydrofluoroether (HFE).
In various aspects, as described above, the electrolyte 50 may be a solid-state electrolyte, where the particles form both the electrolyte 50 and the separator 52 . The solid-state electrolyte may include one or more solid-state electrolyte particles that may comprise one or more polymer-based components, oxide-based particles, sulfide-based particles, halide-based particles, borate-based particles, nitride-based particles, and hydride-based particles. Such a solid-state electrolyte may be disposed in a plurality of layers so as to define a three-dimensional structure. In various aspects, the polymer-based components may be intermingled with a lithium salt so as to act as a solid solvent. In certain variations, the polymer-based components may comprise one or more of polymer materials selected from the group consisting of: polyethylene glycol, polyethylene oxide (PEO), poly(p-phenylene oxide) (PPO), poly(methyl methacrylate) (PMMA), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyvinyl chloride (PVC), and combinations thereof. In one variation, the one or more polymer materials may have an ionic conductivity equal to about 10 4 S/cm.
In various aspects, the oxide-based particles may comprise one or more garnet ceramics, LISICON-type oxides, NASICON-type oxides, and Perovskite-type ceramics. For example, the one or more garnet ceramics may be selected from the group consisting of: Li 6.5 La 3 Zr 1.75 Te 0.25 O 12 , Li 7 La 3 Zr 2 O 12 , Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr 2 O 12 , Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 , Li 6.25 Al 0.25 La 3 Zr 2 O 12 , L 16.75 La 3 Zr 1.75 Nb 0.25 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 , and combinations thereof. The one or more LISICON-type oxides may be selected from the group consisting of: Li 14 Zn(GeO 4 ) 4 , Li 3+x (P 1âx Si x )O 4 (where 0<x<1), Li 3+x Ge x V 1âx O 4 (where 0<x<1), and combinations thereof. The one or more NASICON-type oxides may be defined by LiMMâ²(PO 4 ) 3 , where M and Mâ² are independently selected from Al, Ge, Ti, Sn, Hf, Zr, and La. For example, in certain variations, the one or more NASICON-type oxides may be selected from the group consisting of: Li 1+x Al x Ge 2âx (PO 4 ) 3 (LAGP) (where 0â¤xâ¤2), Li 1+x Al x Ti 2âx (PO 4 ) 3 (LAGP) (where 0â¤xâ¤2), Li 1âx Y x Zr 2âx (PO 4 ) 3 (LYZP) (where 0â¤Xâ¤2), Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , LiTi 2 (PO 4 ) 3 , LiGeTi 2 (PO 4 ) 3 , LiGe 2 (PO 4 ) 3 , LiHf 2 (PO 4 ) 3 , and combinations thereof. The one or more Perovskite-type ceramics may be selected from the group consisting of: Li 3.3 La 0.53 TiO 3 , LiSr 1.65 Zr 1.3 Ta 1.7 O 9 , Li 2xây Sr 1âx Ta y Zr 1ây O 3 (where X=0.75y and 0.60<y<0.75), Li 3/8 Sr 7/16 Nb 3/4 Zr 1/4 O 3 , Li 3x La (2/3âx) TiO 3 (where 0<x<0.25), and combinations thereof. In one variation, the one or more oxide-based materials may have an ionic conductivity greater than or equal to about 10 â5 S/cm to less than or equal to about 10 â1 S/cm.
In various aspects, the sulfide-based particles may include one or more sulfide-based materials selected from the group consisting of: Li 2 SâP 2 S 5 , Li 2 SâP 2 S 5 -MS x (where M is Si, Ge, and Sn and 0â¤xâ¤2), Li 3.4 Si 0.4 P 0.6 S 4 , Li 10 GeP 2 S 11.7 O 0.3 , Li 9.6 P 3 S 12 , Li 7 P 3 S 11 , Li 9 P 3 S 9 O 3 , Li 10.35 Si 1.35 P 1.65 S 12 , Li 9.81 Sn 0.81 P 2.19 S 12 , Li 10 (Si 0.5 Ge 0.5 )P 2 S 12 , Li(Ge 0.5 Sn 0.5 )P 2 S 12 , Li(Si 0.5 Sn 0.5 )P s S 12 , Li 10 GeP 2 S 12 (LGPS), Li 6 PS 5 X (where X is Cl, Br, or I), Li 7 P 2 S 8 I, Li 10.35 Ge 1.35 P 1.65 S 12 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 10 SnP 2 S 12 , Li 10 SiP 2 S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , (1âX)P 2 S 5âX Li 2 S (where 0.5â¤xâ¤0.7), and combinations thereof. In one variation, the one or more sulfide-based materials may have an ionic conductivity greater than or equal to about 10 â7 S/cm to less than or equal to about 1 S/cm.
In various aspects, the halide-based particles may include one or more halide-based materials selected from the group consisting of: Li 2 CdCl 4 , Li 2 MgCl 4 , Li 2 CdI 4 , Li 2 ZnI 4 , Li 3 OCl, LiI, Li 5 ZnI 4 , Li 3 OCl 1âx Br x (where 0<x<1), and combinations thereof. In one variation, the one or more halide-based materials may have an ionic conductivity greater than or equal to about 10 â8 S/cm to less than or equal to about 10 â1 S/cm.
In various aspects, the borate-based particles may include one or more borate-based materials selected from the group consisting of: Li 2 B 4 O 7 , Li 2 Oâ(B 2 O 3 )â(P 2 O 5 ), and combinations thereof. In one variation, the one or more borate-based materials may have an ionic conductivity greater than or equal to about 10 â7 S/cm to less than or equal to about 10 â2 S/cm.
In various aspects, the nitride-based particles may include one or more nitride-based materials selected from the group consisting of: Li 3 N, Li 7 PN 4 , LiSi 2 N 3 , LiPON, and combinations thereof. In one variation, the one or more nitride-based materials may have an ionic conductivity greater than or equal to about 10 â9 S/cm to less than or equal to about 1 S/cm.
In various aspects, the hydride-based particles may include one or more hydride-based materials selected from the group consisting of: Li 3 AlH 6 , LiBH 4 , LiBH 4 âLiX (where X is one of Cl, Br, and I), LiNH 2 , Li 2 NH, LiBH 4 âLiNH 2 , and combinations thereof. In one variation, the one or more hydride-based materials may have an ionic conductivity greater than or equal to about 10 â7 S/cm to less than or equal to about 10 â2 S/cm.
In still fu
CLAIMS
Claims ( 12 )
What is claimed is:
1. A capacitor-assisted electrode for an electrochemical cell that cycles lithium ions comprising:
at least three electroactive material layers disposed on one or more surfaces of a current collector,
wherein a first electroactive material layer of the at least three electroactive material layers has a first reversible specific capacity and is disposed adjacent to the one or more surfaces of the current collector, the first electroactive material layer defines a first exposed surface and comprises a first amount of a first electroactive material;
wherein a second electroactive material layer of the at least three electroactive material layers has a second reversible specific capacity and is disposed adjacent to the first exposed surface of the first electroactive material layer, the second electroactive material layer defines a second exposed surface, the second electroactive material layer comprising a second amount of the first electroactive material, a first amount of a second electroactive material, and a first amount of a third electroactive material, a first combined amount of the second electroactive material and the third electroactive material being greater than the second amount of the first electroactive material, the first amount of the second electroactive material being larger than the first amount of the third electroactive material;
wherein a third electroactive material layer of the at least three electroactive material layers has a third reversible specific capacity and is disposed adjacent to the second exposed surface of the second electroactive material layer, the third electroactive material layer comprising a third amount of the first electroactive material, a second amount of the second electroactive material, and a second amount of the third electroactive material, a second combined amount of the second electroactive material and the third electroactive material being greater than the third amount of the first electroactive material, the second amount of the third electroactive material being larger than the second amount of the second electroactive material;
wherein the third reversible specific capacity is different from the second reversible specific capacity, the second reversible specific capacity is different from the first reversible specific capacity, and the first reversible specific capacity is different from the third reversible specific capacity; and
wherein at least one of the following is true: (i) the third reversible specific capacity is greater than the second reversible specific capacity and the second reversible specific capacity is greater than the first reversible specific capacity and (ii) the second reversible specific capacity is greater than the third reversible specific capacity and the first reversible specific capacity is greater than the second reversible specific capacity; and
one or more capacitor materials disposed on or intermingled with one or more of the at least three electroactive materials.
2. The capacitor-assisted electrode of claim 1 , wherein the second reversible specific capacity is greater than the first reversible specific capacity.
3. The capacitor-assisted electrode of claim 1 , wherein the first electroactive material layer has a first press density, the second electroactive material layer has a second press density, and the second press density is greater than the first press density.
4. The capacitor-assisted electrode of claim 1 , wherein the one or more capacitor materials are intermingled with the third electroactive material to form the third electroactive material layer.
5. The capacitor-assisted electrode of claim 1 , wherein the one or more capacitor materials forms a capacitor material layer disposed adjacent to a third exposed surface of the third electroactive material layer.
6. The capacitor-assisted electrode of claim 1 , wherein the one or more capacitor materials are selected from the group consisting of: cobalt oxide, manganese oxide, iridium oxide, niobium pentoxide, ruthenium oxide, tantalum pentoxide, tin oxide, vanadium oxide, titanium disulfide, copper sulfide, iron sulfide, activated carbon, graphene, graphite, mesoporous carbon, macroporous carbon, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon aerogels, activated carbon fiber cloth, polyaniline, polyacetylene, poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene), poly(4-styrenesulfonate), and combinations thereof.
7. The capacitor-assisted electrode of claim 1 , wherein the first electroactive material layer has a first press density, the second electroactive material layer has a second press density, the third electroactive material layer has a third press density, and the third press density is less than or equal to the second press density and the second press density is less than or equal to the first press density.
8. The capacitor-assisted electrode of claim 7 , wherein the first press density, the second press density, and the third press density are each independently greater than or equal to about 2.0 g/cc to less than or equal to about 3.5 g/cc.
9. The capacitor-assisted electrode of claim 7 , wherein the first press density, the second press density, and the third press density are each independently greater than or equal to about 1.0 g/cc to less than or equal to about 2.0 g/cc.
10. An electrochemical cell that cycles lithium ions comprising:
a first electrode comprising a first electroactive material; and
a second electrode comprising:
a first layer disposed adjacent to a surface of a current collector and comprising a first amount of a second electroactive material, the first layer having a first reversible specific capacity;
a second layer disposed adjacent to a surface of the first layer and comprising the second electroactive material, a third electroactive material, and a fourth electroactive material, the second layer comprising a first combined amount of the third electroactive material and the fourth electroactive material, a second amount of the second electroactive material, a first amount of the third electroactive material, and a first amount of the fourth electroactive material, the first combined amount being greater than the second amount of the second electroactive material, the first amount of the third electroactive material being greater than the first amount of the fourth electroactive material, the second layer having a second reversible specific capacity that is different from the first reversible specific capacity;
a third layer disposed adjacent to a surface of the second layer and comprising the second electroactive material, the third electroactive material, and the fourth electroactive material, the third layer comprising a second combined amount of the third electroactive material and the fourth electroactive material, a third amount of the second electroactive material, a second amount of the third electroactive material, and a second amount of the fourth electroactive material, the second combined amount being greater than the third amount of the second electroactive material, the second amount of the fourth electroactive material being greater than the second amount of the third electroactive material, the third layer having a third reversible specific capacity that is different from both the first reversible specific capacity and the second reversible specific capacity; and
one or more capacitor materials disposed adjacent to or intermingled with one or more of the first layer, the second layer, and the third layer.
11. The electrochemical cell of claim 10 , wherein the one or more capacitor materials are intermingled with the third layer.
12. The electrochemical cell of claim 10 , wherein the first layer has a first press density, the second layer has a second press density, and the third layer has a third press density, and wherein the second press density is greater than the third press density and the first press density is greater than the second press density.
US16/685,389
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