Convention lithium-metal and lithium-ion cells utilize current collectors in the form of metal foils. For example, a positive electrode may be fabricated with an aluminum foil that supports one or two positive active material layers. Metal foils provide mechanical support and electrical conductivity between the active material layers (supported by the foils) and other components of the cell, e.g., an electrode tab that can be welded to the foil. However, only a portion of the total thickness is typically needed for electrical conductivity (even for high-rate applications). The remaining thickness is needed for handling current collectors as standalone structures, e.g., rewinding, deposting active material layers, etc. However, metals are significantly heavier than other materials (e.g., polymers) that are capable of providing the same level of mechanical support. At the same time, these other materials may not be electrically conductive.
Furthermore, excessing thickness (from the electrical conductivity standpoint) is less desirable from safety considerations. For example, lithium dendrite growth can cause a local short circuit between the electrodes while the current collectors provide the electrical pathways to this short circuit. If the current (through one or both current collectors) is not cut to this short circuit, then a more severe thermal event can develop leading to potentially more dangerous conditions in the cell.
One option to mitigate such shorts is to use a polymer base as a part of a current collector. Specifically, a combination of a polymer base and metal layers supported on the polymer base can be used to replace a metal foil. The polymer base provides mechanical support while the metal layers are used for electrical conductivity to and from the active material layers disposed over these metal layers. Unlike metals, polymers have low melting points and would melt at the area of a short circuit of one develops.
However, introducing polymer bases interferes with conventional processing of the current collectors, in particular with the ability to form electrical connections between the current collectors and other components, such as cell tabs. For example, a portion of the current can extend beyond the active material layers and used as electrode tabs. These tabs needs to be interconnected and/or connected to a cell tab. Various forms of welding (e.g., ultrasonic, resistance, and laser) that are conventionally used for connecting foils to electrode tabs may not suitable when current collectors are formed with polymer bases.
What is needed are new current collectors comprising metal grids as well as electrodes and lithium-metal cells comprising such current collectors and methods of fabricating such current collectors, electrodes, and lithium-metal cells
Described herein are current collectors comprising metal grids as well as electrodes and lithium-metal cells comprising such current collectors and methods of fabricating such current collectors, electrodes, and lithium-metal cells. A thin current collector comprises a polymer base and a metal layer positioned on, directly interfaces, and supported by one side of the polymer base. A thin current collector also comprises a metal grid, which directly interfaces and is supported by the edge of the polymer base. The metal grid is electrically coupled to the metal layer, e.g., by overlapping or at least forming an interface with the metal layer. In an electrode that further comprises an active material layer supported on the metal layer, the metal grid extends away from the active material layer. In an electrochemical cell, the metal grid can be connected to the metal grids of other electrodes and/or cell tabs.
Clause 1. An electrochemical cell comprising: an electrode comprising a current collector and an active material layer, wherein: the current collector comprises a polymer base comprising a first side, a second side, and a third side, the first side is opposite the second side and separated from the second side by a thickness of the polymer base, the third side extends between the first side and the second side along the thickness of the polymer base, the current collector further comprises a metal layer disposed on and supported by the first side of the polymer base, the metal layer has a thickness smaller than the thickness of the polymer base, the metal layer is positioned between and directly interfaces both the polymer base and the active material layer, the current collector further comprising a metal grid directly interfacing and supported by the third side of the polymer base thereby forming a polymer base-grid interface with the polymer base, and the metal grid is electrically coupled to the metal layer and extends away from the active material layer.
Clause 2. The electrochemical cell of clause 1, wherein the electrochemical cell is a lithium metal cell.
Clause 3. The electrochemical cell of clause 1, wherein: the electrode is a positive electrode, and the active material layer is a positive active material layer comprising positive active material structures and a positive polymer active layer binder.
Clause 4. The electrochemical cell of clause 3, wherein the metal layer is a positive metal layer comprising aluminum.
Clause 5. The electrochemical cell of clause 1, wherein: the electrode is a negative electrode, and the active material layer is a negative active material layer comprising lithium metal.
Clause 6. The electrochemical cell of clause 5, wherein the metal layer comprises one or more lithium, copper, steel, and nickel.
Clause 7. The electrochemical cell of clause 1, wherein the thickness of the metal layer is at least 5 times smaller than the thickness of the polymer base.
Clause 8. The electrochemical cell of clause 1, wherein: the thickness of the metal layer is less than 2 micrometers, and the thickness of the polymer base is at least 5 micrometers.
Clause 9. The electrochemical cell of clause 1, wherein the composition of the metal layer and the composition of the metal grid is substantially similar.
Clause 10. The electrochemical cell of clause 1, wherein the composition of the metal layer and the composition of the metal grid is different.
Clause 11. The electrochemical cell of clause 1, wherein: the metal layer comprises aluminum, and the metal grid comprises nickel.
Clause 12. The electrochemical cell of clause 1, wherein at least one of the metal layer and the metal grid comprises at least one of aluminum, copper, nickel, titanium, steel, and silver.
Clause 13. The electrochemical cell of clause 1, wherein the polymer base comprises polyethylene terephthalate, polypropylene, polycarbonate, polyethylene, polyimide, ceramic-based polymer, cellulose, nylon, and various polyolefins.
Clause 14. The electrochemical cell of clause 1, wherein the metal layer and the metal grid form a metal layer-grid interface corresponding to a thickness of the metal layer.
Clause 15. The electrochemical cell of clause 14, wherein at least one surface of the metal layer is coplanar with at least one surface of the metal grid.
Clause 16. The electrochemical cell of clause 14, wherein the metal layer-grid interface is formed by a weld seam.
Clause 17. The electrochemical cell of clause 14, wherein the metal layer-grid interface is aligned with the polymer base-grid interface.
Clause 18. The electrochemical cell of clause 1, wherein the metal layer extends past the third side of the polymer base and overlaps with the metal grid forming a meta layer-grid interface.
Clause 19. The electrochemical cell of clause 18, wherein the metal layer-grid interface is substantially perpendicular to the polymer base-grid interface.
Clause 20. The electrochemical cell of clause 1, wherein the meta layer-grid interface extends along at least a portion of a length of the metal grid.
Clause 21. The electrochemical cell of clause 1, wherein the meta layer-grid interface forms by sputtering, soldering, or cathodic-arc depositing the metal layer over the metal grid.
Clause 22. The electrochemical cell of clause 1, wherein the metal grid comprises a pin protruding into the polymer base past the third side.
Clause 23. The electrochemical cell of clause 22, wherein the pin protrudes into the polymer base parallel to the metal layer.
Clause 24. The electrochemical cell of clause 1, wherein the metal grid protrudes past an exterior surface of the metal layer that faces away from the polymer base.
Clause 25. The electrochemical cell of clause 24, wherein a height (H) of the metal grid protruding past the exterior surface of the metal layer is at least 1 micrometer.
Clause 26. The electrochemical cell of clause 24, wherein the metal grid is formed by sputtering, soldering, ultrasonic soldering, or electroplating.
Clause 27. The electrochemical cell of clause 1, further comprising an additional active material layer, wherein: the current collector further comprises an additional metal layer disposed on and supported by the second side of the polymer base, the additional metal layer is positioned between and directly interfaces both the polymer base and the additional active material layer, and the metal grid is electrically coupled to the additional metal layer and extends away from the additional active material layer.
Clause 28. The electrochemical cell of clause 27, wherein the thickness of a stack comprising the metal layer, the polymer base, and the additional metal layer is equal to the thickness of the metal grid.
Clause 29. A current collector comprising: a polymer base comprising a first side, a second side, and a third side, wherein the first side is opposite the second side and separated from the second side by a thickness of the polymer base, and wherein the third side extends between the first side and the second side along the thickness of the polymer base; a metal layer disposed on, directly interfaces, and supported by the first side of the polymer base, wherein the metal layer has a thickness smaller than the thickness of the polymer base; and a metal grid directly interfacing and supported by the third side of the polymer base thereby forming a polymer base-grid interface with the polymer base, wherein the metal grid is electrically coupled to the metal layer.
Clause 30. A method comprising: providing a polymer base comprising a first side, a second side, and a third side, wherein the first side is opposite the second side and separated from the second side by a thickness of the polymer base, and wherein the third side extends between the first side and the second side along the thickness of the polymer base, depositing a metal layer on the first side of the polymer base, wherein the metal layer has a thickness smaller than the thickness of the polymer base; and attaching a metal grid to the third side of the polymer base thereby forming a polymer base-grid interface with the polymer base, wherein the metal grid is electrically coupled to the metal layer.
Clause 31. The method of clause 30, wherein depositing the metal layer comprises puttering, soldering, ultrasonic soldering, or electroplating.
Clause 32. The method of clause 30, wherein attaching the metal grid comprises at least one of: welding the metal grid to the polymer base, adhering the metal grid to the polymer base, inserting a portion of the metal grid into the polymer base, and overlapping a portion of the metal layer with the metal grid.
Clause 33. The method of clause 30, wherein welding the metal grid to the polymer base comprises one of ultrasonic welding, ultrasonic soldering, laser welding, or heat sealing.
Clause 34. The method of clause 30, wherein the metal layer is deposited before attaching the metal grid.
Clause 35. The method of clause 34, wherein attaching the metal grid further comprising welding the metal grid to the metal layer.
Clause 36. The method of clause 30, wherein the metal grid is attached before depositing the metal layer.
Clause 37. The method of clause 36, wherein the metal layer at least partially overlaps with the metal grid.
These and other embodiments are described further below with reference to the figures.
In the following description, numerous specific details are outlined to provide a thorough understanding of the presented concepts. The presented concepts may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the described concepts. While some concepts will be described in conjunction with the specific embodiments, it will be understood that these embodiments are not intended to be limiting.
As noted above, a polymer base can be used as a part of a current collector to mitigate local shorts and to reduce the overall weight of the current collector. Specifically, polymer bases can be operable as fuses, isolating specific areas in an electrode that have experienced short circuits, while the rest of the electrode continues to function. This functionality may be referred to as localized electrode fusing. An additional benefit of polymer bases (instead of metal foils) is weight saving. Specifically, metals are substantially heavier than polymers as shown in the following table comparing the specific gravities of different materials.
As such, replacing most or all metal current collectors with polymer bases provides substantial weight savings thereby potentially increasing the gravimetric capacity of an electrochemical cell as well as improving cell safety.
However, forming electrical connections (e.g., by welding) to a current collector comprising a polymer base is challenging. The polymer base interferes with forming a metal weld nugget by being closely positioned to the weld zone or even being positioned along the path of weld tools. To address this issue, a current collector is equipped with a metal grid that is supported by a polymer base but also extends away from the polymer base. The metal grid is electrically connected to a metal layer that is positioned on the polymer base and that interfaces with the cell's active layer. The metal grid can be connected to one or more other metal grids and/or other components of the cell (e.g., a cell tab extending to a cell terminal).
In some examples, the negative active material layer 131 further comprises negative active material structures 134 (e.g., a lithium metal layer, graphite/silicon active material structures/particles). In more specific examples (e.g., lithium ion cells), the negative active material layer 131 may further comprise a negative active layer polymer binder 136 and/or a negative active layer conductive additive 138.
Electrochemical cell 100 is a lithium metal cell, in which case negative active material layer 131 and additional negative active material layer 132 comprise or are formed substantially from lithium metal. However, other types of cells (e.g., lithium-ion cells) are within the scope.
Additional components of electrochemical cell 100 are presented in
Additional features of positive electrode 110 (comprising positive metal grid 126) and negative electrode 130 (comprising negative metal grid 146) will now be described with reference to
Referring to
Current collector 160 comprises polymer base 170 comprising first side 171, second side 172, and third side 173. First side 171 is opposite second side 172 and separated from second side 172 by the thickness of polymer base 170. For example, the thickness of polymer base 170 can be at least 5 micrometers or, more specifically, at least 10 micrometers. Third side 173 extends between first side 171 and second side 172 along the thickness of polymer base 170 and may be referred to as an edge of polymer base 170
Referring to
Metal layer 161 is positioned between and directly interfaces both polymer base 170 and active material layer 151. Specifically, metal layer 161 is used for electronic conductivity between active material layer 151 and various other components of electrode 150. In some examples, when the material of active material layer 151 is sufficiently conductive (e.g., lithium metal), active material layer 151 and metal layer 161 can have the composition and form the same monolythic structure. A portion of this structure can be used as active material layer 151 (e.g., a portion of lithium metal that is transferred to the positive electrode during the discharge) and another portion remains as metal layer 161. The remaining metal layer 161 effectively serves as a seed for the later deposition of active material layer 151 (during the charge).
In some examples, metal layer 161 has a thickness smaller than the thickness of polymer base 170, e.g., at least 2 times smaller, 5 times smaller, or even 10 times smaller. As such, polymer base 170 can provide the bulk of mechanical support to current collector 160.
For example, the thickness of metal layer 161 is less than 5 micrometers, less than 2 micrometers or even less than 1 micrometer. The thickness of metal layer 161 can be selected based on the electronic conductivity of the materials forming metal layer 161, the size of metal layer 161 (the electron travel distance), and the current carrying capabilities required from metal layer 161 (e.g., thicker metal layers for higher-current applications).
In the same other examples, the thickness of polymer base 170 is at least 5 micrometers, at least about 10 micrometers, or even at least about 15 micrometers. This thickness depends on the material of polymer base 170, the required mechanical support capabilities required from polymer base 170, and the required short-circuit fusing capabilities of polymer base 170.
Current collector 160 further comprises metal grid 166 directly interfacing and supported by third side 173 of polymer base 170 thereby forming polymer base-grid interface 176 with polymer base 170. Metal grid 166 is electrically coupled to metal layer 161 and extends away from active material layer 151. In other words, metal grid 166 does not overlap with active material layer 151, at least in the manner of metal layer 161 which is substantially covered by active material layer 151 in electrode 150. In some examples, most of metal grid 166 does not overlap with active material layer 151. In more specific examples, no portion of metal grid 166 overlaps with active material layer 151.
Various examples of materials suitable for metal grid 166 or metal layer 161 are within the scope such as aluminum, copper, nickel, titanium, steel, and silver. Another example of the material for metal layer 161 is lithium (e.g., when a lithium metal layer is formed directly over polymer base 170).
In some examples, the composition of metal layer 161 and the composition of metal grid 166 is the same or at least substantially similar (e.g., compositional variations are less than 10% by weight). The similarity of the materials can help to join the two components, e.g., by welding, soldering, or other techniques further described below.
In some examples, the composition of metal layer 161 and the composition of metal grid 166 are different. For example, metal layer 161 can be formed from aluminum while metal grid 166 can be formed from nickel.
In some examples, polymer base 170 comprises one or more polyethylene terephthalate, polypropylene, polycarbonate, polyethylene, polyimide (e.g., KAPTON®), ceramic-based polymer, cellulose, nylon, and various polyolefins. A material for polymer base 170 can be selected to ensure shrinkage during heating (e.g., during a local short), which pulls the corresponding portion of metal layer 161 (supported by polymer base 170) from that local short. In other words, in some examples, the material of polymer base 170 shrinks upon heating.
Various forms of integration of metal grid 166 to current collector 160 will now be described with reference to
It should be noted that additional mechanical support to metal grid 166 is provided by polymer base 170, e.g., through polymer base-grid interface 176. This polymer base-grid interface 176 can be formed by various means, e.g., thermal welding, adhesive, and the like.
Additional components of electrochemical cells 100 include electrolyte 190, which can comprise one or more lithium-containing salts 192, one or more solvents 194, and one or more electrolyte additives 196.
Referring to
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In some examples, pin 167 is monolithic with the rest of metal grid 166. Alternatively, pin 167 and the rest of metal grid 166 are separate components (e.g., made from different materials) that are joined together. In some examples, pin 167 interfaces metal layer 161.
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In some examples, method 400 comprises (block 410) providing polymer base 170 comprising first side 171, second side 172, and third side 173. First side 171 is opposite second side 172 and separated from second side 172 by the thickness of polymer base 170. Third side 173 extends between first side 171 and second side 172 along the thickness of polymer base 170.
In some examples, method 400 proceeds with (block 420) depositing metal layer 161 on first side 171 of polymer base 170. Metal layer 161 has a thickness smaller than the thickness of polymer base 170. Various deposition techniques, such as sputtering, are within the scope.
In some examples, method 400 comprises (block 430) attaching metal grid 166 to third side 173 of polymer base 170 thereby forming a polymer base-grid interface 176 with polymer base 170. This grid-attaching operation (block 430) can be performed before or after the metal-layer depositing operation (block 420). For example,
In some examples, the grid-attaching operation (block 430) comprises at least one of (a) welding metal grid 166 to polymer base 170, (b) adhering metal grid 166 to polymer base 170, (c) inserting a portion of metal grid 166 into polymer base 170, and (d) overlapping a portion of metal layer 161 with metal grid 166.
In some examples, method 400 also comprises (block 450) depositing one or more active material layers over corresponding metal layers of current collector 160, (block 460) arranging electrode 150 (formed with current collector 160) with other electrodes (e.g., staking, winding into a jelly roll), and/or (block 470) interconnecting metal grid 166 with other metal grids and/or other components (e.g., cell tabs)
Electrochemical cell 100, e.g., lithium-metal cell, described herein, can be used for various applications, such as ground-based vehicles, boats, aircraft, and spacecraft. For example, aircraft and/or spacecraft use Li-metal batteries as such batteries have significantly higher gravimetric energy density than, e.g., Li-ion batteries. Both aircraft and spacecraft applications require lower mass cells, as additional mass leads to lower payload capacity. For these applications to utilize the maximum amount of their designed capacity, the energy system must be the lowest mass possible. In addition, safety is paramount in both of these applications, as onboard fires while in flight could be mission-critical and cause catastrophic failure of the system. In this scenario, occupants or personnel using the system are not able to simply depart from aircraft and/or spacecraft (e.g., in comparison to ground-based vehicles).
Although the foregoing concepts have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing processes, systems, and apparatuses. Accordingly, the present embodiments are to be considered illustrative and not restrictive.
This application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application 63/380,545, filed on 2022 Oct. 21, which is incorporated herein by reference in its entirety for all purposes.
Number | Date | Country | |
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63380545 | Oct 2022 | US |