Patent Application
20240039002
The information provided in this section is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.
The present disclosure relates to battery cells, and more particularly to lithium battery cells with reduced dendrite formation.
Electric vehicles (EVs) such as battery electric vehicles (BEVs), hybrid vehicles, and/or fuel cell vehicles include one or more electric machines and a battery system including one or more battery cells, modules and/or packs. A power control system is used to control power to/from the battery system during charging, propulsion and/or regeneration. If the battery cells include anode electrodes or cathode electrodes that use lithium as the active material, dendrite formation can occur. Dendrites may reduce performance and/or cause short circuits.
A battery cell includes a first current collector and a cathode electrode arranged adjacent to the first current collector and including lithium active material. A separator is arranged adjacent to the cathode electrode. The battery cell includes a second current collector. A porous conductive layer is arranged on the second current collector between the second current collector and the separator.
In other features, the porous conductive layer comprises conductive material mixed in a polymer. The polymer comprises polyvinylidene difluoride. The conductive material is selected from a group consisting of stainless-steel particles, copper (Cu), carbon nanofibers, carbon particles, carbon nanotubes including electrodeposited Cu, nickel (Ni), gold (Au) particles, silver (Ag) particles, brass particles, and platinum (Pt) particles. The polymer comprises less than or equal to 30% by weight of the porous conductive layer.
In other features, the conductive material has a nominal size in a predetermined range from 1 micron to 100 microns. The porous conductive layer has a nominal thickness in a predetermined range from 1 micron to 100 microns. The porous conductive layer comprises conductive polymer foam and an adhesive layer attaching the conductive polymer foam to the second current collector.
In other features, electrolyte comprises ionic liquid electrolyte. The porous conductive layer comprises a foam layer including conductive material mixed with conductive polymer and an adhesive layer connecting the foam layer to the second current collector. The foam layer comprises greater than 50% by weight of the foam layer.
A battery cell comprises a first current collector and a cathode electrode arranged adjacent to the first current collector and including lithium active material. A separator is arranged adjacent to the cathode electrode. An anode electrode includes lithium active material. A porous conductive layer is arranged on a first surface of the anode electrode facing the separator. A second current collector is arranged adjacent to the anode electrode.
In other features, the porous conductive layer comprises conductive material and polymer. The polymer comprises polyvinylidene difluoride. The conductive material is selected from a group consisting of stainless-steel particles, copper (Cu), carbon nanofibers, carbon particles, carbon nanotubes including electrodeposited Cu, nickel (Ni), gold (Au) particles, silver (Ag) particles, brass particles, and platinum (Pt) particles. The polymer comprises less than or equal to 30% by weight of the porous conductive layer.
In other features, the conductive material has a nominal size in a predetermined range from 1 micron to 100 microns. The porous conductive layer has a nominal thickness in a predetermined range from 1 micron to 100 microns. The porous conductive layer comprises polymer mixed with conductive material.
In other features, the porous conductive layer comprises conductive polymer foam and an adhesive layer between the conductive polymer foam and the second current collector. Electrolyte comprises ionic liquid electrolyte. The porous conductive layer comprises conductive polymer foam and conductive material. An adhesive layer is arranged between the conductive polymer foam and the second current collector.
Further areas of applicability of the present disclosure will become apparent from the detailed description, the claims and the drawings. The detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the disclosure.
The present disclosure will become more fully understood from the detailed description and the accompanying drawings, wherein:
In the drawings, reference numbers may be reused to identify similar and/or identical elements.
The present disclosure relates to battery cells with an electrically conductive framework provided by a porous conductive layer that mitigates lithium (Li) dendrite formation in either lithium metal or anodeless battery cells.
In some examples, the porous conductive layer includes a mixture of conductive materials such as metal particles and/or polymer, a mixture of conductive polymer and conductive materials, and/or conductive polymer foam including cell cores. The conductive materials are disordered in that they are located in random locations within the polymer or polymer foam. The porous conductive layer can be made using a slurry coating or a polymer foaming process that creates foam cell cores. The porous conductive layer provides pores or foam cell cores for lithium ions to deposit during charging. The disordered locations of lithium ions in the pores reduce the formation of dendrites that may cause short circuits.
A battery cell according to the present disclosure includes a plurality of cathodes, a plurality of separators, a plurality of anodes (for battery cells with anodes), and a plurality of current collectors. In anodeless battery cells, a porous conductive layer is arranged on the current collectors facing the separator to emulate the anodes. For battery cells with anodes, the porous conductive layer is arranged on the anode layer facing the separator. In some examples, the porous conductive layer is made using an electrode casting method (slurry including conductive metal particles, polymer and solvent applied to the current collectors). In other examples, the porous conductive layer is made using polymer foam and conductive material.
In other examples, the porous conductive layer is made using a polymer foaming process with a conductive polymer. In some examples, an ionic liquid is used in combination with the conductive polymer to improve compatibility and prevent unwanted reactions and/or dissolving of the conductive polymer in electrolyte.
In the description below,
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The separator 22 may include, in certain instances, a microporous polymeric separator including a polyolefin. The polyolefin may be a homopolymer (derived from a single monomer constituent) or a heteropolymer (derived from more than one monomer constituent), which may be either linear or branched. If a heteropolymer is derived from two monomer constituents, the polyolefin may assume any copolymer chain arrangement, including those of a block copolymer or a random copolymer. Similarly, if the polyolefin is a heteropolymer derived from more than two monomer constituents, it may likewise be a block copolymer or a random copolymer. In certain aspects, the polyolefin may be polyethylene (PE), polypropylene (PP), or a blend of PE and PP, or multi-layered structured porous films of PE and/or PP. Commercially available polyolefin porous membranes 26 include CELGARD® 2500 (a monolayer polypropylene separator) and CELGARD® 2320 (a trilayer polypropylene/polyethylene/polypropylene separator) available from Celgard LLC.
the separator 22 may further include one or more of a ceramic coating layer and a heat-resistant material coating. The ceramic coating layer and/or the heat-resistant material coating may be disposed on one or more sides of the separator 22. The material forming the ceramic layer may be selected from the group consisting of: alumina (Al2O3), silica (SiO2), and combinations thereof. The heat-resistant material may be selected from the group consisting of: Nomex, Aramid, and combinations thereof.
When the separator 22 is a microporous polymeric separator, it may be a single layer or a multi-layer laminate, which may be fabricated from either a dry or wet process. For example, in certain instances, a single layer of the polyolefin may form the entire separator 22. In other aspects, the separator 22 may be a fibrous membrane having an abundance of pores extending between the opposing surfaces and may have an average thickness of less than a millimeter, for example. As another example, however, multiple discrete layers of similar or dissimilar polyolefins may be assembled to form the microporous polymer separator 22. The separator 22 may also comprise other polymers in addition to the polyolefin such as, but not limited to, polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), a polyamide, polyimide, poly(amide-imide) copolymer, polyetherimide, and/or cellulose, or any other material suitable for creating the required porous structure. The polyolefin layer, and any other optional polymer layers, may further be included in the separator 22 as a fibrous layer to help provide the separator 22 with appropriate structural and porosity characteristics. In certain aspects, the separator 22 may also be mixed with a ceramic material or its surface may be coated in a ceramic material. For example, a ceramic coating may include alumina (Al2O3), silicon dioxide (SiO2), titania (TiO2) or combinations thereof. Various conventionally available polymers and commercial products for forming the separator 22 are contemplated, as well as the many manufacturing methods that may be employed to produce such a microporous polymer separator 22.
The anodeless battery cell 50 is anodeless since it does not initially include an anode layer including active material such as lithium. A porous conductive layer 52 is arranged on a surface of the current collector 26 facing the separator 22. The porous conductive layer 52 is initially free of active material such as lithium. After charging, the lithium ions travel from the cathode and randomly deposit in pores of the porous conductive layer 52 as shown by arrows. As a result, dendrite formation is reduced.
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The porous conductive layer 52 is arranged on the current collector 26 facing the separator 22. In some examples, the porous conductive layer 52 is applied to or cast on the current collector 26 in the form of a slurry including the polymer 54, the conductive material 56 and a solvent. In some examples, the solvent may be fully or partially removed by heating the current collector and the porous conductive layer 52. In some examples, the polymer comprises <=≤30% by weight of the solid mixture. In some examples, the polymer comprises polyvinylidene difluoride (PVDF), although other polymers can be used.
In some examples, the conductive material in the porous conductive layer 52 comprise metal particles. The conductive material in the porous conductive layer 52 does not initially include active material such as lithium. In some examples, the metal particles are selected from a group consisting of stainless-steel particles, copper (Cu), carbon nanofibers, carbon particles, carbon nanotubes including electrodeposited Cu, nickel (Ni), gold (Au) particles, silver (Ag) particles, brass particles, and platinum (Pt) particles. In some examples, the particles have a nominal size in a predetermined range from 1 micron to 100 microns. In some examples, the porous conductive layer has a nominal thickness in a predetermined range from 1 micron to 100 microns. After charging, the lithium ions travel from the cathode and randomly deposit in pores of the porous conductive layer 52. As a result, dendrite formation is reduced.
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In some examples, conductive polymer is selected from a group consisting of polypyrrole (PPY), polyaniline (PANI), polythiophene (PT), PSS (poly(3,4-ethylenedioxythiophene)polystyrene sulfonate) (PEDOT), copper(II) phthalocyanine (CuPc) doped PPY formed by using copper(II) phthalocyanine tetrasulfanate salts (CuPcTs) to cross-link PPY PF-COONa (sodium poly(9, 9-bis(3-propanoate) fluorine), and sodium alginate grafted poly(3, 4-propylened ioxythiophene (SA-PProDOT).
In some examples, ionic liquid electrolyte can be used with the conductive polymer for compatibility. In some examples, the ionic liquid electrolyte is selected from a group consisting of cation or anion electrolytes. In some examples, the cation electrolytes are selected from a group consisting of imidazolium, pyrrolidinium, and piperidinium. In some examples, imidazolium is selected from a group consisting of 3-ethyl-1-methyl-1H-imidazol-3-ium, 3-allyl-1-methyl-1H-imidazol-3-ium, and 3-butyl-1-methyl-1H-imidazol-3-ium. In some examples, pyrrolidinium is selected from a group consisting of 1-butyl-1-methylpyrrolidin-1-ium, 1-methyl-1-propylpyrrolidin-1-ium, 1-2-methoxyethyl)-1-methylpyrrolidin-1-ium, and 1-methyl-1-pentylpyrrolidin-1-ium. In some examples, piperidinium is selected from a group consisting of 1-methyl-1-propylpiperidin-1-ium and 1-butyl-1methylpiperidin-1-ium.
In some examples, the anion electrolytes are selected from a group consisting of bis(fluorosulfonyl)amide and bis((trifluoromethyl)sulfonyl) amide.
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At 522, melt viscosity is increased and/or surfactant is added to form a stable foam layer. At 526, the foam layer (corresponding to the porous conductive layer) is attached to a current collector or anode electrode using an adhesive layer. At 530, battery cells are assembled using the current collector with the porous conductive layer. In other words, one or more current collectors with the porous conductive layers are combined with one or more cathode electrodes, current collectors, anodes (
In some examples, the blowing agent for the foaming process is selected from a group consisting of water, air, nitrogen, carbon dioxide, pentane, hexane, dichloroethane, freon and/or combinations thereof. In some examples, the solvent is an organic solvent. In some examples, the solvent is selected from a group consisting of acetone, NMP, ethanol, methanol, isopropanol, acetonitrile and/or combinations thereof.
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The foregoing description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. The broad teachings of the disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent upon a study of the drawings, the specification, and the following claims. It should be understood that one or more steps within a method may be executed in different order (or concurrently) without altering the principles of the present disclosure. Further, although each of the embodiments is described above as having certain features, any one or more of those features described with respect to any embodiment of the disclosure can be implemented in and/or combined with features of any of the other embodiments, even if that combination is not explicitly described. In other words, the described embodiments are not mutually exclusive, and permutations of one or more embodiments with one another remain within the scope of this disclosure.
Spatial and functional relationships between elements (for example, between modules, circuit elements, semiconductor layers, etc.) are described using various terms, including “connected,” “engaged,” “coupled,” “adjacent,” “next to,” “on top of,” “above,” “below,” and “disposed.” Unless explicitly described as being “direct,” when a relationship between first and second elements is described in the above disclosure, that relationship can be a direct relationship where no other intervening elements are present between the first and second elements, but can also be an indirect relationship where one or more intervening elements are present (either spatially or functionally) between the first and second elements. As used herein, the phrase at least one of A, B, and C should be construed to mean a logical (A OR B OR C), using a non-exclusive logical OR, and should not be construed to mean “at least one of A, at least one of B, and at least one of C.”
In the figures, the direction of an arrow, as indicated by the arrowhead, generally demonstrates the flow of information (such as data or instructions) that is of interest to the illustration. For example, when element A and element B exchange a variety of information but information transmitted from element A to element B is relevant to the illustration, the arrow may point from element A to element B. This unidirectional arrow does not imply that no other information is transmitted from element B to element A. Further, for information sent from element A to element B, element B may send requests for, or receipt acknowledgements of, the information to element A.
