US20230352653A1 - Method and system for pulverization mitigation additives for silicon dominant anodes - Google Patents
Method and system for pulverization mitigation additives for silicon dominant anodes Download PDFInfo
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- US20230352653A1 US20230352653A1 US18/214,053 US202318214053A US2023352653A1 US 20230352653 A1 US20230352653 A1 US 20230352653A1 US 202318214053 A US202318214053 A US 202318214053A US 2023352653 A1 US2023352653 A1 US 2023352653A1
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 41
- 239000010703 silicon Substances 0.000 title claims abstract description 41
- 239000000654 additive Substances 0.000 title abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 38
- 238000010298 pulverizing process Methods 0.000 title abstract description 16
- 230000000116 mitigating effect Effects 0.000 title abstract description 10
- 239000011149 active material Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002482 conductive additive Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 11
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- 230000008569 process Effects 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000006138 lithiation reaction Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
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- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
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- 150000003624 transition metals Chemical class 0.000 claims description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
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- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
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- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- aspects of the present disclosure relate to energy generation and storage. More specifically, certain embodiments of the disclosure relate to a method and system for pulverization mitigation additives for silicon dominant anodes.
- a system and/or method for pulverization mitigation additives for silicon dominant anodes substantially as shown in and/or described in connection with at least one of the figures, as set forth more completely in the claims.
- FIG. 1 is a diagram of a battery, in accordance with an example embodiment of the disclosure.
- FIG. 2 A is a flow diagram of a lamination process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure.
- FIG. 2 B is a flow diagram of a direct coating process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure.
- FIG. 3 illustrates anode active material layers on a current collector after multiple cycles, in accordance with an example embodiment of the disclosure.
- FIG. 4 illustrates an anode active material layer with conductive structural additives, in accordance with an example embodiment of the disclosure.
- FIG. 1 is a diagram of a battery with silicon-dominant anodes, in accordance with an example embodiment of the disclosure.
- a battery 100 comprising a separator 103 sandwiched between an anode 101 and a cathode 105 , with current collectors 107 A and 107 B.
- a load 109 coupled to the battery 100 illustrating instances when the battery 100 is in discharge mode.
- the term “battery” may be used to indicate a single electrochemical cell, a plurality of electrochemical cells formed into a module, and/or a plurality of modules formed into a pack.
- FIG. 1 is a very simplified example merely to show the principle of operation of a lithium ion cell. Examples of realistic structures are shown to the right in FIG. 1 , where stacks of electrodes and separators are utilized, with electrode coatings typically on both sides of the current collectors.
- the stacks may be formed into different shapes, such as a coin cell, cylindrical cell, or prismatic cell, for example.
- the anode 101 and cathode 105 may comprise the electrodes, which may comprise plates or films within, or containing, an electrolyte material, where the plates may provide a physical barrier for containing the electrolyte as well as a conductive contact to external structures.
- the anode/cathode plates are immersed in electrolyte while an outer casing provides electrolyte containment.
- the anode 101 and cathode 105 are electrically coupled to the current collectors 107 A and 107 B, which comprise metal or other conductive material for providing electrical contact to the electrodes as well as physical support for the active material in forming electrodes.
- the separator 103 is generally a film material, made of an electrically insulating polymer, for example, that prevents electrons from flowing from anode 101 to cathode 105 , or vice versa, while being porous enough to allow ions to pass through the separator 103 .
- the separator 103 , cathode 105 , and anode 101 materials are individually formed into sheets, films, or active material coated foils.
- the separator 103 is a sheet and generally utilizes winding methods and stacking in its manufacture.
- the anodes, cathodes, and current collectors may comprise films.
- the battery 100 may comprise a solid, liquid, or gel electrolyte.
- the separator 103 preferably does not dissolve in typical battery electrolytes such as compositions that may comprise: Ethylene Carbonate (EC), Fluoroethylene Carbonate (FEC), Propylene Carbonate (PC), Dimethyl Carbonate (DMC), Ethyl Methyl Carbonate (EMC), Diethyl Carbonate (DEC), etc. with dissolved LiBF 4 , LiAsF 6 , LiPF 6 , and LiClO 4 etc.
- the separator 103 may be wet or soaked with a liquid or gel electrolyte.
- the separator 103 does not melt below about 100 to 120° C., and exhibits sufficient mechanical properties for battery applications.
- a battery, in operation, can experience expansion and contraction of the anode and/or the cathode.
- the separator 103 can expand and contract by at least about 5 to 10% without failing, and may also be flexible.
- the separator 103 may be sufficiently porous so that ions can pass through the separator once wet with, for example, a liquid or gel electrolyte. Alternatively (or additionally), the separator may absorb the electrolyte through a gelling or other process even without significant porosity.
- the porosity of the separator 103 is also generally not too porous to allow the anode 101 and cathode 105 to transfer electrons through the separator 103 .
- the anode 101 and cathode 105 comprise electrodes for the battery 100 , providing electrical connections to the device for transfer of electrical charge in charge and discharge states.
- the anode 101 may comprise silicon, carbon, or combinations of these materials, for example.
- Typical anode electrodes comprise a carbon material that includes a current collector such as a copper sheet. Carbon is often used because it has excellent electrochemical properties and is also electrically conductive.
- Anode electrodes currently used in rechargeable lithium-ion cells typically have a specific capacity of approximately 200 milliamp hours per gram. Graphite, the active material used in most lithium ion battery anodes, has a theoretical energy density of 372 milliamp hours per gram (mAh/g).
- silicon has a high theoretical capacity of 4200 mAh/g.
- silicon may be used as the active material for the cathode or anode.
- Silicon anodes may be formed from silicon composites, with more than 50% silicon or more by weight in the anode material on the current collector, for example.
- the anode 101 and cathode 105 store the ion used for separation of charge, such as lithium.
- the electrolyte carries positively charged lithium ions from the anode 101 to the cathode 105 in discharge mode, as shown in FIG. 1 for example, and vice versa through the separator 105 in charge mode.
- the movement of the lithium ions creates free electrons in the anode 101 which creates a charge at the positive current collector 1078 .
- the electrical current then flows from the current collector through the load 109 to the negative current collector 107 A.
- the separator 103 blocks the flow of electrons inside the battery 100 , allows the flow of lithium ions, and prevents direct contact between the electrodes.
- the anode 101 releases lithium ions to the cathode 105 via the separator 103 , generating a flow of electrons from one side to the other via the coupled load 109 .
- the materials selected for the anode 101 and cathode 105 are important for the reliability and energy density possible for the battery 100 .
- the energy, power, cost, and safety of current Li-ion batteries need to be improved in order to, for example, compete with internal combustion engine (ICE) technology and allow for the widespread adoption of electric vehicles (EVs).
- High energy density, high power density, and improved safety of lithium-ion batteries are achieved with the development of high-capacity and high-voltage cathodes, high-capacity anodes and functionally non-flammable electrolytes with high voltage stability and interfacial compatibility with electrodes.
- materials with low toxicity are beneficial as battery materials to reduce process cost and promote consumer safety.
- the performance of electrochemical electrodes is largely dependent on the robustness of electrical contact between electrode particles, as well as between the current collector and the electrode particles.
- the electrical conductivity of silicon anode electrodes may be manipulated by incorporating conductive additives with different morphological properties. Carbon black (SuperP), vapor grown carbon fibers (VGCF), and a mixture of the two have previously been incorporated separately into the anode electrode resulting in improved performance of the anode.
- the synergistic interactions between the two carbon materials may facilitate electrical contact throughout the large volume changes of the silicon anode during charge and discharge.
- State-of-the-art lithium-ion batteries typically employ a graphite-dominant anode as an intercalation material for lithium.
- Silicon-dominant anodes offer improvements compared to graphite-dominant Li-ion batteries. Silicon exhibits both higher gravimetric (3579 mAh/g vs. 372 mAh/g for graphite) and volumetric capacities (2194 mAh/L vs. 890 mAh/L for graphite).
- silicon-based anodes have a low lithiation/delithiation voltage plateau at about 0.3-0.4V vs. Li/Li+, which allows it to maintain an open circuit potential that avoids undesirable Li plating and dendrite formation.
- SEI solid electrolyte interphase
- a solution to enhance the electrical conductivity of Li-ion battery anodes and cathodes is to introduce conductive structural additives to the anode active material layer.
- the additives may comprise materials that are stronger than the binder materials, able to withstand the expansion and contraction caused by the lithiation of the silicon, providing a structural and electrical connection between cracked regions of the active material layer.
- the materials may comprise long filaments (1D), such as carbon nanotubes, for example, planar sheets (2D), such as graphene, or chunks of material (3D).
- Two primary benefits of adding conductive additives to anodes and cathodes are improved particle-to-particle conductivity and improved particle-to-current-collector conductivity. These additives maintain conductive pathways for electrons, minimizing capacity loss in electrode active materials and, thus, enhancing the overall performance of Li-ion batteries.
- FIG. 2 A is a flow diagram of a lamination process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure.
- This process employs a high-temperature pyrolysis process on a substrate, layer removal, and a lamination process to adhere the active material layer to a current collector.
- the raw electrode active material is mixed in step 201 .
- the active material may be mixed, e.g., a binder/resin (such as PI, PAI), solvent, and conductive structural additives.
- the additives may comprise conductive materials that also provide structural continuity between cracks in the anode following multiple cycles.
- the materials may comprise carbon nanotubes/fibers, graphene sheets, metal polymers, metals, semiconductors, and/or metal oxides, for example.
- the additives may comprise 1D filaments with one dimension at least 4 ⁇ , at least 10 ⁇ , or at least 20 ⁇ that of the other two dimensions, 2D sheets or mesh with two dimensions at least 4 ⁇ , at least 10 ⁇ , or at least 20 ⁇ that of the other dimension, or 3D structures with one dimension at least 20 ⁇ , at least 10 ⁇ , or at least 4 ⁇ that of the other two, where none of the dimensions are of nanoscale size.
- Silicon powder with a 5-30 ⁇ m particle size may then be dispersed in polyamic acid resin (15% solids in N-Methyl pyrrolidone (NMP)) at, e.g., 1000 rpm for, e.g., 10 minutes, and then the conjugated carbon/NMP slurry may be added and dispersed at, e.g., 2000 rpm for, e.g., 10 minutes to achieve a slurry viscosity within 2000-4000 cP and a total solid content of about 30%.
- NMP N-Methyl pyrrolidone
- the slurry may be coated on a substrate.
- the slurry may be coated onto a Polyester, polyethylene terephthalate (PET), or Mylar film at a loading of, e.g., 2-4 mg/cm 2 and then in step 205 undergo drying to an anode coupon with high Si content and less than 15% residual solvent content.
- This may be followed by an optional calendering process in step 207 , where a series of hard pressure rollers may be used to finish the film/substrate into a smoothed and denser sheet of material.
- the green film may then be removed from the PET, where the active material may be peeled off the polymer substrate, the peeling process being optional for a polypropylene (PP) substrate, since PP can leave ⁇ 2% char residue upon pyrolysis.
- the peeling may be followed by a pyrolysis step 211 where the material may be heated to >900 C but less than 1250 C for 1-3 hours, cut into sheets, and vacuum dried using a two-stage process (120° C. for 15 h, 220° C. for 5 h).
- the dry film may be thermally treated at, e.g., 1100-1200° C. to convert the polymer matrix into carbon.
- the electrode material may be laminated on a current collector.
- a current collector For example, a 5-20 ⁇ m thick copper foil may be coated with polyamide-imide with a nominal loading of, e.g., 0.2-0.6 mg/cm 2 (applied as a 6 wt % varnish in NMP and dried for, e.g., 12-18 hours at, e.g., 110° C. under vacuum).
- the anode coupon may then be laminated on this adhesive-coated current collector.
- the silicon-carbon composite film is laminated to the coated copper using a heated hydraulic press.
- An example lamination press process comprises 30-70 seconds at 300° C. and 3000-5000 psi, thereby forming the finished silicon-composite electrode.
- the process described above is one example process that represents a composite with fabrication steps including pyrolysis and lamination.
- Another example scenario comprises a direct coating process in which an anode slurry is directly coated on a copper foil using a binder such as CMC, SBR, Sodium Alginate, PAI, PI and mixtures and combinations thereof.
- the process in this example comprises: direct coat active material on a current collector, dry, calender, heat treatment.
- an anode slurry is coated on a current collector with residual solvent followed by a calendaring process for densification followed by pyrolysis ( ⁇ 500-800 C) such that carbon precursors are partially or completely converted into glassy carbon.
- Pyrolysis can be done either in roll form or after punching. If done in roll form, the punching is done after the pyrolysis process.
- an anode slurry may be coated on a current collector with low residual solvent followed by a calendaring process for densification followed by removal of residual solvent.
- the conductive structural additives such as might be added in step 201 or 221 may comprise between 1 and 40% by weight of the anode composition, with between 50% and 99% silicon by weight.
- the fibrous (1 D) particles may have an aspect ratio of at least 4, but may be higher than 10, higher than 20, or higher than 40, for example, and may comprise a tubular or fiber-like conductive structure with nanoscale size in two-dimensions, where carbon-based examples comprise carbon nanotubes, carbon nanofibers (CNF), and vapor grown carbon fibers (VGCP).
- Other fibrous structures are possible, such as metals, metal polymers, metal oxides
- the 2D carbon structures may have an average dimension in the micron scale in each of the two non-nanoscale dimensions that is at least 4 ⁇ that in the thickness direction, for example, and may be at least 20 ⁇ larger, or at least 40 ⁇ larger in the lateral directions as compared to the thickness direction.
- Graphene sheets are an example of conductive carbon additives, while other 2D structures are possible, such as “wire” meshes of metal or metal polymers, for example.
- the active material may comprise 3D conductive structural additives, where the material is not limited to nanoscale in any one dimension.
- one dimension of the structure may be at least 4 ⁇ , at least 10 ⁇ , or at least 20 ⁇ that of the other two dimensions, where none of the dimensions are of nanoscale size.
- 3D conductive structural additives may be “chunks” of carbon, metal, metal polymer, or semiconductors.
- the anode active material layer fabricated with the carbon additive described above may comprise 20 to 95% silicon and in yet another example scenario may comprise 50 to 95% silicon by weight.
- FIG. 2 B is a flow diagram of a direct coating process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure.
- This process comprises physically mixing the active material, conductive additive, and binder together, and coating it directly on a current collector.
- This example process comprises a direct coating process in which an anode or cathode slurry is directly coated on a copper foil using a binder such as CMC, SBR, Sodium Alginate, PAI, PI and mixtures and combinations thereof.
- a binder such as CMC, SBR, Sodium Alginate, PAI, PI and mixtures and combinations thereof.
- the active material may be mixed, e.g., a binder/resin (such as PI, PAI), solvent, and conductive and structural additive.
- the additives may comprise conductive materials that also provide structural continuity between cracks in the anode following multiple cycles.
- the materials may comprise carbon nanotubes/fibers, graphene sheets, metal polymers, metals, semiconductors, and/or metal oxides, metal/carbon nanofiber or metal/carbon nanotube composites, carbon nanowire bundles, for example.
- Silicon powder with a 5-30 ⁇ m particle size may then be dispersed in polyamic acid resin (15% solids in N-Methyl pyrrolidone (NMP)) at, e.g., 1000 rpm for, e.g., 10 minutes, and then the conjugated carbon/NMP slurry may be added and dispersed at, e.g., 2000 rpm for, e.g., 10 minutes to achieve a slurry viscosity within 2000-4000 cP and a total solid content of about 30%.
- NMP N-Methyl pyrrolidone
- cathode active materials may be mixed in step 221 , where the active material may comprise lithium cobalt oxide (LCO), lithium iron phosphate, lithium nickel cobalt manganese oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium nickel manganese spinel, or similar materials or combinations thereof, mixed with a binder as described above for the anode active material.
- LCO lithium cobalt oxide
- NMC lithium nickel cobalt manganese oxide
- NCA lithium nickel cobalt aluminum oxide
- LMO lithium manganese oxide
- lithium nickel manganese spinel lithium nickel manganese spinel
- the slurry may be coated on a copper foil.
- cathode active materials may be coated on a foil material, such as aluminum, for example.
- the active material layer may undergo a drying in step 225 resulting in reduced residual solvent content.
- An optional calendering process may be utilized in step 227 where a series of hard pressure rollers may be used to finish the film/substrate into a smoother and denser sheet of material.
- the foil and coating proceeds through a roll press for lamination.
- the active material may be pyrolyzed by heating to 500-1000° C. such that carbon precursors are partially or completely converted into glassy carbon.
- the pyrolysis step may result in an anode active material having silicon content greater than or equal to 50% by weight, where the anode has been subjected to heating at or above 400 degrees Celsius.
- Pyrolysis can be done either in roll form or after punching in step 231 . If done in roll form, the punching is done after the pyrolysis process.
- the formed electrode may be perforated with a punching roller, for example. The punched electrodes may then be sandwiched with a separator and electrolyte to form a cell.
- the cell may be subjected to a formation process, comprising initial charge and discharge steps to lithiate the anode, with some residual lithium remaining, and the cell capacity may be assessed.
- FIG. 3 illustrates anode active material layers on a current collector after multiple cycles, in accordance with an example embodiment of the disclosure.
- the scanning electron microscope (SEM) images show two anodes at different magnifications, with the top two rows being top-down images of the surface of the anode active material layer and the bottom row being cross-sectional images of the anode active material layers on both sides of a metal current collector.
- the cross-sectional view shows active material layers 301 A- 301 D on current collectors 303 A and 303 B, while the top two rows show top views of the active material layers 301 A and 301 B.
- the active material layers 301 A- 301 D do not include the conductive structural additives described above.
- the active material layers 301 A- 301 D become cracked after multiple charge/discharge cycles, 200 cycles in this example, where pulverization occurs due to expansion and contraction due to lithiation/delithiation of the silicon during cycling. This results in voids or cracks 305 and islands 307 , where the large number of cracks/voids and islands shown in the images precludes labeling each incidence of these structures.
- cracks 305 may cause mirror image surfaces in adjacent islands 307 where, for example, a depression in one island results in an extension in an adjacent island.
- the cracks 305 in the active material layers 301 A- 301 D may range from sub-micron size to several microns across, as shown by the various dimensions shown in the SEM images, and even above 10 microns for higher cycle numbers.
- the cracks 305 may extend partway through the thickness of the active material layers 301 A- 301 D or may extend all the way down to the current collectors 303 A or 303 B.
- the expansion and contraction of the active material layers may result in islands 307 of the active material layers 301 A- 301 D separated by the cracks, where the islands 307 may be as small as sub-micron size and as large as tens of microns.
- Spatial separation between islands of active material layer may result in reduced cell capacity since electron flow may be inhibited by increased resistance or even open circuit conditions for some portions. This may be mitigated by conductive structural additives in the active material layer, as discussed further with respect to FIG. 4 . These additives may extend across the cracks between islands, thereby providing both a structural connection that mitigates further pulverization, as well as a conductive path between islands, stabilizing impedance and reducing the cycle loss of the cell.
- FIG. 4 illustrates an anode active material layer with conductive structural additives, in accordance with an example embodiment of the disclosure.
- an anode 400 comprising an active material layer 401 on a current collector 403 .
- the active material layer 401 may comprise cracks 405 and islands 407 with pulverization mitigation additives 409 .
- the cracks 405 and islands 407 may be formed by expansion and contraction of the active material layer 401 during formation and/or normal cycling from lithiation and delithiation of the cell in which the anode 400 is integrated.
- the cracks 405 may cause mirror image surfaces in adjacent islands 407 where, for example, a depression in one island results in an extension in an adjacent island, as illustrated by the “Mirrored Surfaces” label in FIG. 4 .
- the active material layer 401 is shown as partially transparent to show the extent of the additives 409 as being throughout the layer, and the density and size of the additives are merely examples.
- the additives 409 are large enough that a least a portion of the additives extend from within islands 407 and bridge across the cracks 405 .
- the additives 409 may comprise metal, carbon nanotubes/fibers, graphene sheets, metal polymers, semiconductors, and/or metal oxides, graphene sheets, metal polymers, metals, semiconductors, and/or metal oxides, metal/carbon nanofiber or metal/carbon nanotube composites, carbon nanowire bundles.
- the additives 409 may comprise filaments, sheets, 3D structures with one dimension larger than the other two, or a combination thereof.
- the conductive additives 409 extend between the islands 407 thereby providing a conductive channel between the islands and also provides a mechanical connection to mitigate further pulverization.
- Metals may comprise copper, nickel, stainless steel, tungsten, or other high strength metals.
- the additives 409 may comprise a metal with a lower melting point, such as gallium, indium, or other metal, metal alloy, or eutectic, as long as it does not adversely react with other materials in the active material layer 401 or the current collector 403 .
- the lower melting point metal may melt during operation of the cell and fill in cracks formed by expansion and contraction, solidifying again after the cell returns to near room-temperature, providing a low impedance coupling between the islands as well as a thermal path for heat. This melting/solidifying may repeat with each thermal cycle, improving the cycle retention.
- the additives 409 may comprise strain-absorbing structures, such as flexible conductors comprising metal polymers, for example, where the additives 409 continue to bridge gaps between islands 407 in the active material layers during lithiation/delithiation expansion/contraction cycles.
- the additives comprise coil-like structures for strain-absorbing and providing conductivity between islands 407 , the coil-like structures comprising coiled/twisted metal or carbon nanotubes, for example.
- the additives 409 may comprise 2D structures, such as conductive mesh or graphene sheets, indicated by the regular hexagon patterns in the figure.
- Conductive mesh may comprise metal or metal polymer, for example.
- the mesh or sheets have lateral dimensions that are large enough to bridge any cracks in the active material layer 401 , extending up to several tens of microns, for example.
- the additives 409 may comprise 3D structures, such as a cylindrical or rectangular shape with a length that is at least 4 ⁇ , at least 10 ⁇ , or at least 20 ⁇ that of the other dimensions, where none of the dimensions are nanoscale size.
- the additives 409 may comprise a metal foam with dimensions large enough to extend from within an island 407 across a crack 405 to another of the islands 407 . This may provide improved electrical conductivity but also provides structural resistance to pulverization, where active material may be within and external to the conductive metal foam structure, thereby embedding the foam. This embedding of additives 409 provides enhanced structure and improved conductivity.
- the additives 409 may comprise blocks of conductive material with one dimension large enough to bridge any crack 405 that may form in the active material layer 401 .
- the additives 409 may comprise a conductive polymer in fiber, sheet, or cylindrical/rectangular form, that may be embedded within active material layer 401 , where the conductive material is capable of withstanding the processing and operational temperatures encountered by the anode 400 .
- the anode may comprise an active material.
- the active material may comprise an electrode comprising a metal current collector and an active material layer on the current collector.
- the active material layer may comprise islands of material separated by cracks, where the islands may comprise silicon, pyrolyzed binder, and conductive additives, and wherein at least a portion of the additives may bridge the cracks of the active material layer.
- the conductive additives may comprise between 1% and 40% of the active material layer.
- the active material layer may comprise between 20% to 95% silicon.
- the conductive additives may comprise carbon nanotubes and/or graphene sheets.
- the conductive additives may comprise metal.
- the metal may comprise one or more of: gallium, indium, copper, aluminum, lead, tin, nickel.
- the metal may comprises a transition metal.
- the conductive additives may comprise one or more semiconductors.
- the conductive additives may comprise long narrow filaments with an aspect ratio of 20 or greater.
- the cracks may form after one or more formation processes and/or one or more lithiation/delithiation cycles of a battery incorporating the electrode.
- circuits and circuitry refer to physical electronic components (i.e. hardware) and any software and/or firmware (“code”) which may configure the hardware, be executed by the hardware, and or otherwise be associated with the hardware.
- code software and/or firmware
- a particular processor and memory may comprise a first “circuit” when executing a first one or more lines of code and may comprise a second “circuit” when executing a second one or more lines of code.
- and/or means any one or more of the items in the list joined by “and/or”.
- x and/or y means any element of the three-element set ⁇ (x), (y), (x, y) ⁇ .
- x and/or y means “one or both of x and y”.
- x, y, and/or z means any element of the seven-element set ⁇ (x), (y), (z), (x, y), (x, z), (y, z), (x, y, z) ⁇ .
- x, y and/or z means “one or more of x, y and z”.
- the term “exemplary” means serving as a non-limiting example, instance, or illustration.
- the terms “e.g.,” and “for example” set off lists of one or more non-limiting examples, instances, or illustrations.
- a battery, circuitry or a device is “operable” to perform a function whenever the battery, circuitry or device comprises the necessary hardware and code (if any is necessary) or other elements to perform the function, regardless of whether performance of the function is disabled or not enabled (e.g., by a user-configurable setting, factory trim, configuration, etc.).
Abstract
Systems and methods for pulverization mitigation additives for silicon dominant anodes may include an electrode including a metal current collector and an active material layer on the current collector. The active material layer may include islands of material separated by cracks, with the islands including, at least, silicon and conductive additives. At least a portion of the additives may extend from within the islands and bridge the cracks of the active material layer. The conductive additives may form a structure providing electrical conductivity between a first island and a second island, or between at least one island and the metal current collector. The additives may include between 1% and 40% of the active material layer. The active material layer may include between 20% to 95% silicon. The conductive additives may include carbon nanotubes and/or graphene sheets.
Description
- This patent application is a continuation of U.S. patent application Ser. No. 17/172,049 filed on Feb. 9, 2021, now issued U.S. Pat. No. 11,688,848. The above identified application is hereby incorporated herein by reference in its entirety.
- Aspects of the present disclosure relate to energy generation and storage. More specifically, certain embodiments of the disclosure relate to a method and system for pulverization mitigation additives for silicon dominant anodes.
- Conventional approaches for battery anodes may be costly, cumbersome, and/or inefficient—e.g., they may be complex and/or time consuming to implement, and may limit battery lifetime.
- Further limitations and disadvantages of conventional and traditional approaches will become apparent to one of skill in the art, through comparison of such systems with some aspects of the present disclosure as set forth in the remainder of the present application with reference to the drawings.
- A system and/or method for pulverization mitigation additives for silicon dominant anodes, substantially as shown in and/or described in connection with at least one of the figures, as set forth more completely in the claims.
- These and other advantages, aspects and novel features of the present disclosure, as well as details of an illustrated embodiment thereof, will be more fully understood from the following description and drawings.
-
FIG. 1 is a diagram of a battery, in accordance with an example embodiment of the disclosure. -
FIG. 2A is a flow diagram of a lamination process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure. -
FIG. 2B is a flow diagram of a direct coating process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure. -
FIG. 3 illustrates anode active material layers on a current collector after multiple cycles, in accordance with an example embodiment of the disclosure. -
FIG. 4 illustrates an anode active material layer with conductive structural additives, in accordance with an example embodiment of the disclosure. -
FIG. 1 is a diagram of a battery with silicon-dominant anodes, in accordance with an example embodiment of the disclosure. Referring toFIG. 1 , there is shown abattery 100 comprising aseparator 103 sandwiched between ananode 101 and acathode 105, withcurrent collectors load 109 coupled to thebattery 100 illustrating instances when thebattery 100 is in discharge mode. In this disclosure, the term “battery” may be used to indicate a single electrochemical cell, a plurality of electrochemical cells formed into a module, and/or a plurality of modules formed into a pack. Furthermore, thebattery 100 shown inFIG. 1 is a very simplified example merely to show the principle of operation of a lithium ion cell. Examples of realistic structures are shown to the right inFIG. 1 , where stacks of electrodes and separators are utilized, with electrode coatings typically on both sides of the current collectors. The stacks may be formed into different shapes, such as a coin cell, cylindrical cell, or prismatic cell, for example. - The development of portable electronic devices and electrification of transportation drive the need for high performance electrochemical energy storage. Small-scale (<100 Wh) to large-scale (>10 KWh) devices primarily use lithium-ion (Li-ion) batteries over other rechargeable battery chemistries due to their high-performance.
- The
anode 101 andcathode 105, along with thecurrent collectors anode 101 andcathode 105 are electrically coupled to thecurrent collectors - The configuration shown in
FIG. 1 illustrates thebattery 100 in discharge mode, whereas in a charging configuration, theload 109 may be replaced with a charger to reverse the process. In one class of batteries, theseparator 103 is generally a film material, made of an electrically insulating polymer, for example, that prevents electrons from flowing fromanode 101 tocathode 105, or vice versa, while being porous enough to allow ions to pass through theseparator 103. Typically, theseparator 103,cathode 105, andanode 101 materials are individually formed into sheets, films, or active material coated foils. Sheets of the cathode, separator and anode are subsequently stacked or rolled with theseparator 103 separating thecathode 105 andanode 101 to form thebattery 100. In some embodiments, theseparator 103 is a sheet and generally utilizes winding methods and stacking in its manufacture. In these methods, the anodes, cathodes, and current collectors (e.g., electrodes) may comprise films. - In an example scenario, the
battery 100 may comprise a solid, liquid, or gel electrolyte. Theseparator 103 preferably does not dissolve in typical battery electrolytes such as compositions that may comprise: Ethylene Carbonate (EC), Fluoroethylene Carbonate (FEC), Propylene Carbonate (PC), Dimethyl Carbonate (DMC), Ethyl Methyl Carbonate (EMC), Diethyl Carbonate (DEC), etc. with dissolved LiBF4, LiAsF6, LiPF6, and LiClO4 etc. Theseparator 103 may be wet or soaked with a liquid or gel electrolyte. In addition, in an example embodiment, theseparator 103 does not melt below about 100 to 120° C., and exhibits sufficient mechanical properties for battery applications. A battery, in operation, can experience expansion and contraction of the anode and/or the cathode. In an example embodiment, theseparator 103 can expand and contract by at least about 5 to 10% without failing, and may also be flexible. - The
separator 103 may be sufficiently porous so that ions can pass through the separator once wet with, for example, a liquid or gel electrolyte. Alternatively (or additionally), the separator may absorb the electrolyte through a gelling or other process even without significant porosity. The porosity of theseparator 103 is also generally not too porous to allow theanode 101 andcathode 105 to transfer electrons through theseparator 103. - The
anode 101 andcathode 105 comprise electrodes for thebattery 100, providing electrical connections to the device for transfer of electrical charge in charge and discharge states. Theanode 101 may comprise silicon, carbon, or combinations of these materials, for example. Typical anode electrodes comprise a carbon material that includes a current collector such as a copper sheet. Carbon is often used because it has excellent electrochemical properties and is also electrically conductive. Anode electrodes currently used in rechargeable lithium-ion cells typically have a specific capacity of approximately 200 milliamp hours per gram. Graphite, the active material used in most lithium ion battery anodes, has a theoretical energy density of 372 milliamp hours per gram (mAh/g). In comparison, silicon has a high theoretical capacity of 4200 mAh/g. In order to increase volumetric and gravimetric energy density of lithium-ion batteries, silicon may be used as the active material for the cathode or anode. Silicon anodes may be formed from silicon composites, with more than 50% silicon or more by weight in the anode material on the current collector, for example. - In an example scenario, the
anode 101 andcathode 105 store the ion used for separation of charge, such as lithium. In this example, the electrolyte carries positively charged lithium ions from theanode 101 to thecathode 105 in discharge mode, as shown inFIG. 1 for example, and vice versa through theseparator 105 in charge mode. The movement of the lithium ions creates free electrons in theanode 101 which creates a charge at the positive current collector 1078. The electrical current then flows from the current collector through theload 109 to the negativecurrent collector 107A. Theseparator 103 blocks the flow of electrons inside thebattery 100, allows the flow of lithium ions, and prevents direct contact between the electrodes. - While the
battery 100 is discharging and providing an electric current, theanode 101 releases lithium ions to thecathode 105 via theseparator 103, generating a flow of electrons from one side to the other via the coupledload 109. When the battery is being charged, the opposite happens where lithium ions are released by thecathode 105 and received by theanode 101. - The materials selected for the
anode 101 andcathode 105 are important for the reliability and energy density possible for thebattery 100. The energy, power, cost, and safety of current Li-ion batteries need to be improved in order to, for example, compete with internal combustion engine (ICE) technology and allow for the widespread adoption of electric vehicles (EVs). High energy density, high power density, and improved safety of lithium-ion batteries are achieved with the development of high-capacity and high-voltage cathodes, high-capacity anodes and functionally non-flammable electrolytes with high voltage stability and interfacial compatibility with electrodes. In addition, materials with low toxicity are beneficial as battery materials to reduce process cost and promote consumer safety. - The performance of electrochemical electrodes, while dependent on many factors, is largely dependent on the robustness of electrical contact between electrode particles, as well as between the current collector and the electrode particles. The electrical conductivity of silicon anode electrodes may be manipulated by incorporating conductive additives with different morphological properties. Carbon black (SuperP), vapor grown carbon fibers (VGCF), and a mixture of the two have previously been incorporated separately into the anode electrode resulting in improved performance of the anode. The synergistic interactions between the two carbon materials may facilitate electrical contact throughout the large volume changes of the silicon anode during charge and discharge.
- State-of-the-art lithium-ion batteries typically employ a graphite-dominant anode as an intercalation material for lithium. Silicon-dominant anodes, however, offer improvements compared to graphite-dominant Li-ion batteries. Silicon exhibits both higher gravimetric (3579 mAh/g vs. 372 mAh/g for graphite) and volumetric capacities (2194 mAh/L vs. 890 mAh/L for graphite). In addition, silicon-based anodes have a low lithiation/delithiation voltage plateau at about 0.3-0.4V vs. Li/Li+, which allows it to maintain an open circuit potential that avoids undesirable Li plating and dendrite formation. While silicon shows excellent electrochemical activity, achieving a stable cycle life for silicon-based anodes is challenging due to silicon's large volume changes during lithiation and delithiation. Silicon regions may lose electrical contact from the anode as large volume changes coupled with its low electrical conductivity separate the silicon from surrounding materials in the anode.
- In addition, the large silicon volume changes exacerbate solid electrolyte interphase (SEI) formation, which can further lead to electrical isolation and, thus, capacity loss. Expansion and shrinkage of silicon particles upon charge-discharge cycling causes pulverization of silicon particles, which increases their specific surface area. As the silicon surface area changes and increases during cycling, SEI repeatedly breaks apart and reforms. The SEI thus continually builds up around the pulverizing silicon regions during cycling into a thick electronic and ionic insulating layer. This accumulating SEI increases the impedance of the electrode and reduces the electrode electrochemical reactivity, which is detrimental to cycle life.
- A solution to enhance the electrical conductivity of Li-ion battery anodes and cathodes is to introduce conductive structural additives to the anode active material layer. The additives may comprise materials that are stronger than the binder materials, able to withstand the expansion and contraction caused by the lithiation of the silicon, providing a structural and electrical connection between cracked regions of the active material layer. The materials may comprise long filaments (1D), such as carbon nanotubes, for example, planar sheets (2D), such as graphene, or chunks of material (3D). Two primary benefits of adding conductive additives to anodes and cathodes are improved particle-to-particle conductivity and improved particle-to-current-collector conductivity. These additives maintain conductive pathways for electrons, minimizing capacity loss in electrode active materials and, thus, enhancing the overall performance of Li-ion batteries.
-
FIG. 2A is a flow diagram of a lamination process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure. This process employs a high-temperature pyrolysis process on a substrate, layer removal, and a lamination process to adhere the active material layer to a current collector. - The raw electrode active material is mixed in
step 201. In the mixing process, the active material may be mixed, e.g., a binder/resin (such as PI, PAI), solvent, and conductive structural additives. For example, the additives may comprise conductive materials that also provide structural continuity between cracks in the anode following multiple cycles. The materials may comprise carbon nanotubes/fibers, graphene sheets, metal polymers, metals, semiconductors, and/or metal oxides, for example. The additives may comprise 1D filaments with one dimension at least 4×, at least 10×, or at least 20× that of the other two dimensions, 2D sheets or mesh with two dimensions at least 4×, at least 10×, or at least 20× that of the other dimension, or 3D structures with one dimension at least 20×, at least 10×, or at least 4× that of the other two, where none of the dimensions are of nanoscale size. Silicon powder with a 5-30 μm particle size, for example, may then be dispersed in polyamic acid resin (15% solids in N-Methyl pyrrolidone (NMP)) at, e.g., 1000 rpm for, e.g., 10 minutes, and then the conjugated carbon/NMP slurry may be added and dispersed at, e.g., 2000 rpm for, e.g., 10 minutes to achieve a slurry viscosity within 2000-4000 cP and a total solid content of about 30%. - In
step 203, the slurry may be coated on a substrate. In this step, the slurry may be coated onto a Polyester, polyethylene terephthalate (PET), or Mylar film at a loading of, e.g., 2-4 mg/cm2 and then instep 205 undergo drying to an anode coupon with high Si content and less than 15% residual solvent content. This may be followed by an optional calendering process instep 207, where a series of hard pressure rollers may be used to finish the film/substrate into a smoothed and denser sheet of material. - In
step 209, the green film may then be removed from the PET, where the active material may be peeled off the polymer substrate, the peeling process being optional for a polypropylene (PP) substrate, since PP can leave ˜2% char residue upon pyrolysis. The peeling may be followed by apyrolysis step 211 where the material may be heated to >900 C but less than 1250 C for 1-3 hours, cut into sheets, and vacuum dried using a two-stage process (120° C. for 15 h, 220° C. for 5 h). The dry film may be thermally treated at, e.g., 1100-1200° C. to convert the polymer matrix into carbon. - In
step 213, the electrode material may be laminated on a current collector. For example, a 5-20 μm thick copper foil may be coated with polyamide-imide with a nominal loading of, e.g., 0.2-0.6 mg/cm2 (applied as a 6 wt % varnish in NMP and dried for, e.g., 12-18 hours at, e.g., 110° C. under vacuum). The anode coupon may then be laminated on this adhesive-coated current collector. In an example scenario, the silicon-carbon composite film is laminated to the coated copper using a heated hydraulic press. An example lamination press process comprises 30-70 seconds at 300° C. and 3000-5000 psi, thereby forming the finished silicon-composite electrode. - The process described above is one example process that represents a composite with fabrication steps including pyrolysis and lamination. Another example scenario comprises a direct coating process in which an anode slurry is directly coated on a copper foil using a binder such as CMC, SBR, Sodium Alginate, PAI, PI and mixtures and combinations thereof. The process in this example comprises: direct coat active material on a current collector, dry, calender, heat treatment.
- In a direct coating process, an anode slurry is coated on a current collector with residual solvent followed by a calendaring process for densification followed by pyrolysis (˜500-800 C) such that carbon precursors are partially or completely converted into glassy carbon. Pyrolysis can be done either in roll form or after punching. If done in roll form, the punching is done after the pyrolysis process.
- In another example of a direct coating process, an anode slurry may be coated on a current collector with low residual solvent followed by a calendaring process for densification followed by removal of residual solvent.
- In an example scenario, the conductive structural additives, such as might be added in
step - The 2D carbon structures may have an average dimension in the micron scale in each of the two non-nanoscale dimensions that is at least 4× that in the thickness direction, for example, and may be at least 20× larger, or at least 40× larger in the lateral directions as compared to the thickness direction. Graphene sheets are an example of conductive carbon additives, while other 2D structures are possible, such as “wire” meshes of metal or metal polymers, for example.
- Furthermore, the active material may comprise 3D conductive structural additives, where the material is not limited to nanoscale in any one dimension. In a 3D additive example, one dimension of the structure may be at least 4×, at least 10×, or at least 20× that of the other two dimensions, where none of the dimensions are of nanoscale size. Examples of 3D conductive structural additives may be “chunks” of carbon, metal, metal polymer, or semiconductors.
- In another example scenario, the anode active material layer fabricated with the carbon additive described above may comprise 20 to 95% silicon and in yet another example scenario may comprise 50 to 95% silicon by weight.
-
FIG. 2B is a flow diagram of a direct coating process for forming a silicon anode with pulverization mitigation additives, in accordance with an example embodiment of the disclosure. This process comprises physically mixing the active material, conductive additive, and binder together, and coating it directly on a current collector. This example process comprises a direct coating process in which an anode or cathode slurry is directly coated on a copper foil using a binder such as CMC, SBR, Sodium Alginate, PAI, PI and mixtures and combinations thereof. - In
step 221, the active material may be mixed, e.g., a binder/resin (such as PI, PAI), solvent, and conductive and structural additive. For example, the additives may comprise conductive materials that also provide structural continuity between cracks in the anode following multiple cycles. The materials may comprise carbon nanotubes/fibers, graphene sheets, metal polymers, metals, semiconductors, and/or metal oxides, metal/carbon nanofiber or metal/carbon nanotube composites, carbon nanowire bundles, for example. Silicon powder with a 5-30 μm particle size, for example, may then be dispersed in polyamic acid resin (15% solids in N-Methyl pyrrolidone (NMP)) at, e.g., 1000 rpm for, e.g., 10 minutes, and then the conjugated carbon/NMP slurry may be added and dispersed at, e.g., 2000 rpm for, e.g., 10 minutes to achieve a slurry viscosity within 2000-4000 cP and a total solid content of about 30%. - Furthermore, cathode active materials may be mixed in
step 221, where the active material may comprise lithium cobalt oxide (LCO), lithium iron phosphate, lithium nickel cobalt manganese oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium manganese oxide (LMO), lithium nickel manganese spinel, or similar materials or combinations thereof, mixed with a binder as described above for the anode active material. - In
step 223, the slurry may be coated on a copper foil. Similarly, cathode active materials may be coated on a foil material, such as aluminum, for example. The active material layer may undergo a drying instep 225 resulting in reduced residual solvent content. An optional calendering process may be utilized instep 227 where a series of hard pressure rollers may be used to finish the film/substrate into a smoother and denser sheet of material. Instep 227, the foil and coating proceeds through a roll press for lamination. - In
step 229, the active material may be pyrolyzed by heating to 500-1000° C. such that carbon precursors are partially or completely converted into glassy carbon. The pyrolysis step may result in an anode active material having silicon content greater than or equal to 50% by weight, where the anode has been subjected to heating at or above 400 degrees Celsius. Pyrolysis can be done either in roll form or after punching instep 231. If done in roll form, the punching is done after the pyrolysis process. In instances where the current collector foil is not pre-punched/pre-perforated, the formed electrode may be perforated with a punching roller, for example. The punched electrodes may then be sandwiched with a separator and electrolyte to form a cell. Instep 233, the cell may be subjected to a formation process, comprising initial charge and discharge steps to lithiate the anode, with some residual lithium remaining, and the cell capacity may be assessed. -
FIG. 3 illustrates anode active material layers on a current collector after multiple cycles, in accordance with an example embodiment of the disclosure. The scanning electron microscope (SEM) images show two anodes at different magnifications, with the top two rows being top-down images of the surface of the anode active material layer and the bottom row being cross-sectional images of the anode active material layers on both sides of a metal current collector. - The cross-sectional view shows active material layers 301A-301D on
current collectors active material layers cracks 305 andislands 307, where the large number of cracks/voids and islands shown in the images precludes labeling each incidence of these structures. As these pulverized sections, orislands 307, may become detached from adjacent material and even detached from thecollector adjacent islands 307 where, for example, a depression in one island results in an extension in an adjacent island. - The
cracks 305 in the active material layers 301A-301D may range from sub-micron size to several microns across, as shown by the various dimensions shown in the SEM images, and even above 10 microns for higher cycle numbers. In addition, thecracks 305 may extend partway through the thickness of the active material layers 301A-301D or may extend all the way down to thecurrent collectors islands 307 of the active material layers 301A-301D separated by the cracks, where theislands 307 may be as small as sub-micron size and as large as tens of microns. - Spatial separation between islands of active material layer may result in reduced cell capacity since electron flow may be inhibited by increased resistance or even open circuit conditions for some portions. This may be mitigated by conductive structural additives in the active material layer, as discussed further with respect to
FIG. 4 . These additives may extend across the cracks between islands, thereby providing both a structural connection that mitigates further pulverization, as well as a conductive path between islands, stabilizing impedance and reducing the cycle loss of the cell. -
FIG. 4 illustrates an anode active material layer with conductive structural additives, in accordance with an example embodiment of the disclosure. Referring toFIG. 4 , there is shown ananode 400 comprising anactive material layer 401 on acurrent collector 403. Theactive material layer 401 may comprisecracks 405 andislands 407 withpulverization mitigation additives 409. Thecracks 405 andislands 407 may be formed by expansion and contraction of theactive material layer 401 during formation and/or normal cycling from lithiation and delithiation of the cell in which theanode 400 is integrated. Thecracks 405 may cause mirror image surfaces inadjacent islands 407 where, for example, a depression in one island results in an extension in an adjacent island, as illustrated by the “Mirrored Surfaces” label inFIG. 4 . Theactive material layer 401 is shown as partially transparent to show the extent of theadditives 409 as being throughout the layer, and the density and size of the additives are merely examples. Theadditives 409 are large enough that a least a portion of the additives extend from withinislands 407 and bridge across thecracks 405. - The
additives 409 may comprise metal, carbon nanotubes/fibers, graphene sheets, metal polymers, semiconductors, and/or metal oxides, graphene sheets, metal polymers, metals, semiconductors, and/or metal oxides, metal/carbon nanofiber or metal/carbon nanotube composites, carbon nanowire bundles. Theadditives 409 may comprise filaments, sheets, 3D structures with one dimension larger than the other two, or a combination thereof. Theconductive additives 409 extend between theislands 407 thereby providing a conductive channel between the islands and also provides a mechanical connection to mitigate further pulverization. Metals may comprise copper, nickel, stainless steel, tungsten, or other high strength metals. In another example scenario, theadditives 409 may comprise a metal with a lower melting point, such as gallium, indium, or other metal, metal alloy, or eutectic, as long as it does not adversely react with other materials in theactive material layer 401 or thecurrent collector 403. The lower melting point metal may melt during operation of the cell and fill in cracks formed by expansion and contraction, solidifying again after the cell returns to near room-temperature, providing a low impedance coupling between the islands as well as a thermal path for heat. This melting/solidifying may repeat with each thermal cycle, improving the cycle retention. - In another example, the
additives 409 may comprise strain-absorbing structures, such as flexible conductors comprising metal polymers, for example, where theadditives 409 continue to bridge gaps betweenislands 407 in the active material layers during lithiation/delithiation expansion/contraction cycles. In one example, the additives comprise coil-like structures for strain-absorbing and providing conductivity betweenislands 407, the coil-like structures comprising coiled/twisted metal or carbon nanotubes, for example. - In yet another example, the
additives 409 may comprise 2D structures, such as conductive mesh or graphene sheets, indicated by the regular hexagon patterns in the figure. Conductive mesh may comprise metal or metal polymer, for example. The mesh or sheets have lateral dimensions that are large enough to bridge any cracks in theactive material layer 401, extending up to several tens of microns, for example. - In another example scenario, the
additives 409 may comprise 3D structures, such as a cylindrical or rectangular shape with a length that is at least 4×, at least 10×, or at least 20× that of the other dimensions, where none of the dimensions are nanoscale size. In another example, theadditives 409 may comprise a metal foam with dimensions large enough to extend from within anisland 407 across acrack 405 to another of theislands 407. This may provide improved electrical conductivity but also provides structural resistance to pulverization, where active material may be within and external to the conductive metal foam structure, thereby embedding the foam. This embedding ofadditives 409 provides enhanced structure and improved conductivity. In addition, theadditives 409 may comprise blocks of conductive material with one dimension large enough to bridge anycrack 405 that may form in theactive material layer 401. - In another example scenario, the
additives 409 may comprise a conductive polymer in fiber, sheet, or cylindrical/rectangular form, that may be embedded withinactive material layer 401, where the conductive material is capable of withstanding the processing and operational temperatures encountered by theanode 400. - In an example embodiment of the disclosure, a method and system is described for pulverization mitigation additives for silicon dominant anodes. The anode may comprise an active material. The active material may comprise an electrode comprising a metal current collector and an active material layer on the current collector. The active material layer may comprise islands of material separated by cracks, where the islands may comprise silicon, pyrolyzed binder, and conductive additives, and wherein at least a portion of the additives may bridge the cracks of the active material layer.
- The conductive additives may comprise between 1% and 40% of the active material layer. The active material layer may comprise between 20% to 95% silicon. The conductive additives may comprise carbon nanotubes and/or graphene sheets. The conductive additives may comprise metal. The metal may comprise one or more of: gallium, indium, copper, aluminum, lead, tin, nickel. The metal may comprises a transition metal. The conductive additives may comprise one or more semiconductors. The conductive additives may comprise long narrow filaments with an aspect ratio of 20 or greater. The cracks may form after one or more formation processes and/or one or more lithiation/delithiation cycles of a battery incorporating the electrode.
- As utilized herein the terms “circuits” and “circuitry” refer to physical electronic components (i.e. hardware) and any software and/or firmware (“code”) which may configure the hardware, be executed by the hardware, and or otherwise be associated with the hardware. As used herein, for example, a particular processor and memory may comprise a first “circuit” when executing a first one or more lines of code and may comprise a second “circuit” when executing a second one or more lines of code. As utilized herein, “and/or” means any one or more of the items in the list joined by “and/or”. As an example, “x and/or y” means any element of the three-element set {(x), (y), (x, y)}. In other words, “x and/or y” means “one or both of x and y”. As another example, “x, y, and/or z” means any element of the seven-element set {(x), (y), (z), (x, y), (x, z), (y, z), (x, y, z)}. In other words, “x, y and/or z” means “one or more of x, y and z”. As utilized herein, the term “exemplary” means serving as a non-limiting example, instance, or illustration. As utilized herein, the terms “e.g.,” and “for example” set off lists of one or more non-limiting examples, instances, or illustrations. As utilized herein, a battery, circuitry or a device is “operable” to perform a function whenever the battery, circuitry or device comprises the necessary hardware and code (if any is necessary) or other elements to perform the function, regardless of whether performance of the function is disabled or not enabled (e.g., by a user-configurable setting, factory trim, configuration, etc.).
- While the present invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from its scope. Therefore, it is intended that the present invention not be limited to the particular embodiment disclosed, but that the present invention will include all embodiments falling within the scope of the appended claims.
Claims (24)
1-21. (canceled)
22. A battery electrode, the electrode comprising:
a metal current collector; and
an active material layer on the current collector;
wherein the active material layer comprises islands of material separated by cracks, the islands comprising silicon and conductive additives;
wherein at least a portion of the conductive additives extend from within the islands and bridge the cracks of the active material layer; and
wherein the conductive additives form a structure providing electrical conductivity between a first island and a second island, or between at least one island and the metal current collector.
23. The electrode according to claim 22 , wherein the conductive additives comprise between 1% and 40% of the active material layer.
24. The electrode according to claim 22 , wherein the active material layer comprises between 20% to 95% silicon.
25. The electrode according to claim 22 , wherein the conductive additives comprise carbon nanotubes and/or graphene sheets.
26. The electrode according to claim 22 , wherein the conductive additives comprise metal.
27. The electrode according to claim 26 , wherein the metal comprises one or more of: gallium, indium, copper, aluminum, lead, tin, nickel.
28. The electrode according to claim 26 , wherein the metal comprises a transition metal.
29. The electrode according to claim 22 , wherein the conductive additives comprise one or more semiconductors.
30. The electrode according to claim 22 , wherein the conductive additives comprise long narrow filaments with an aspect ratio of 20 or greater.
31. The electrode according to claim 22 , wherein the cracks form after one or more formation processes and/or one or more lithiation/delithiation cycles of a battery incorporating the electrode.
32. The electrode according to claim 22 , wherein islands adjacent to a particular crack have mirror image surfaces facing the particular crack.
33. A method of forming an electrode, the method comprising:
providing a metal current collector; and
providing an active material layer on the current collector;
wherein the active material layer comprises islands of material separated by cracks, the islands comprising silicon and conductive additives;
wherein at least a portion of the conductive additives extend from within the islands and bridge the cracks of the active material layer; and
wherein the conductive additives form a structure providing electrical conductivity between a first island and a second island, or between at least one island and the metal current collector.
34. The method according to claim 33 , wherein the conductive additives comprise between 1% and 40% of the active material layer.
35. The method according to claim 33 , wherein the active material layer comprises between 20% to 95% silicon.
36. The method according to claim 33 , wherein the conductive additives comprise carbon nanotubes and/or graphene sheets.
37. The method according to claim 33 , wherein the conductive additives comprise metal.
38. The method according to claim 37 , wherein the metal comprises one or more of: gallium, indium, copper, aluminum, lead, tin, nickel.
39. The method according to claim 37 , wherein the metal comprises a transition metal.
40. The method according to claim 33 , wherein the conductive additives comprise one or more semiconductors.
41. The method according to claim 33 , wherein the conductive additives comprise long narrow filaments with an aspect ratio of 20 or greater.
42. The method according to claim 33 , wherein the cracks form after one or more formation processes and/or one or more lithiation/delithiation cycles of a battery incorporating the electrode.
43. The method according to claim 33 , wherein islands adjacent to a particular crack have mirror image surfaces facing the particular crack.
44. A battery, the battery comprising:
a battery comprising a cathode, an electrolyte, and an anode comprising a metal current collector and an active material layer on the current collector;
wherein the active material layer comprises: islands of material separated by cracks, the islands comprising silicon and conductive additives;
wherein at least a portion of the conductive additives extend from within the islands and bridge the cracks of the active material layer; and
wherein the conductive additives form a structure providing electrical conductivity between a first island and a second island, or between at least one island and the metal current collector.
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