The disclosure relates to a method of forming an electrode for a lithium-ion electrochemical cell.
Electrochemical cells or batteries are useful for converting chemical energy into electrical energy, and may be described as primary or secondary. Primary batteries are generally non-rechargeable, whereas secondary batteries are readily rechargeable and may be restored to a full charge after use. As such, secondary batteries may be useful for applications such as powering electronic devices, tools, machinery, and vehicles.
One type of secondary battery, a lithium-ion secondary battery, may include a negative electrode or anode, a positive electrode or cathode, and a separator disposed between the positive and negative electrodes. The negative electrode may be formed from a material that is capable of incorporating and releasing lithium ions during charging and discharging of the lithium-ion secondary battery. During charging of the lithium-ion secondary battery, lithium ions may move from the positive electrode to the negative electrode and embed, e.g., by intercalation, insertion, substitutional solid solution strengthening, or other means, in the material. Conversely, during battery discharge, lithium ions may be released from the material and move from the negative electrode to the positive electrode.
A method of forming an electrode for a lithium-ion electrochemical cell includes mixing together a conductive filler component, an active material component, and a binder solution that includes a binder component and a solvent to disperse the conductive filler component and the active material component within the binder solution and form a slurry. The method also includes casting the slurry onto a current collector to form a wet workpiece. In addition, the method includes submersing the wet workpiece in a bath that includes a non-solvent to thereby contact the non-solvent and the solvent, induce a phase inversion, and form a wet electrode composition. Submersing and inducing the phase inversion includes forming a liquid-like polymer lean phase and a solid-like polymer rich phase in the wet electrode composition as the non-solvent enters the slurry. The method further includes drying the wet electrode composition to form an electrode composition disposed on the current collector and thereby form the electrode.
In one aspect, drying the wet electrode may form the electrode composition having a first surface and a second surface spaced apart from and parallel to the first surface. The electrode composition may define: a plurality of channels therein each extending between the first surface and the second surface in a first direction that is generally perpendicular to the first surface and each configured for lithium ion transport between the first surface and the second surface; and a plurality of pores between the first surface and the second surface and adjacent to the plurality of channels.
In another aspect, drying may include removing the liquid-like polymer lean phase from the wet electrode composition.
In a further aspect, submersing may include soaking the slurry in the non-solvent and drying may include removing the liquid-like polymer lean phase to thereby define the plurality of channels.
In yet another aspect, submersing may form a continuous solid-like polymer rich phase in the wet electrode composition.
In an additional aspect, the method may further include, prior to drying the wet electrode composition, subjecting the wet electrode composition to a vacuum at a temperature of from 20° C. to 150° C.
In one aspect, drying the wet electrode composition may include pyrolyzing the wet electrode composition at from 350° C. to 950° C. in a nitrogen atmosphere.
In another aspect, mixing may include blending together the conductive filler component, the active material component, and the binder solution for from 3 minutes to 10 minutes.
In a further aspect, the method may further include, after mixing and prior to casting, remixing the slurry.
In yet another aspect, the method may further include, after mixing, resting the wet workpiece for from 0.1 minutes to 4 minutes in air.
In an additional aspect, the method may further include, after drying, calendaring the first surface to modify a porosity of the electrode.
A method of forming an electrode for a lithium-ion electrochemical cell includes mixing together a conductive filler component, an active material component, and a binder solution that includes a binder component and a solvent to disperse the conductive filler component and the active material component within the binder solution and form a slurry. The method also includes casting the slurry onto a current collector to form a wet workpiece. In addition, the method includes drying the wet workpiece to thereby form an electrode composition. The electrode composition has a first surface and a second surface spaced apart from and parallel to the first surface. After drying, the method includes defining: a plurality of channels within the electrode composition each extending between the first surface and the second surface in a first direction that is generally perpendicular to the first surface and each configured for lithium ion transport between the first surface and the second surface; and a plurality of pores between the first surface and the second surface and adjacent to the plurality of channels.
In one aspect, defining may include laser etching the electrode composition.
In another aspect, defining may include additively manufacturing the electrode composition.
In a further aspect, defining may include 3D printing the electrode composition.
In yet another aspect, defining may include calendaring and puncturing the electrode composition.
In an additional aspect, the method may further include, prior to drying the wet workpiece, subjecting the wet workpiece to a vacuum at a temperature of from 20° C. to 150° C.
In one aspect, drying the wet workpiece may include pyrolyzing the wet workpiece at from 350° C. to 950° C. in a nitrogen atmosphere.
In another aspect, mixing may include blending together the conductive filler component, the active material component, and the binder solution for from 3 minutes to 10 minutes.
In a further aspect, the method may include, after mixing and prior to casting, remixing the slurry.
The above features and advantages and other features and advantages of the present disclosure will be readily apparent from the following detailed description of the preferred embodiments and best modes for carrying out the present disclosure when taken in connection with the accompanying drawings and appended claims.
Referring to the Figures, wherein like reference numerals refer to like elements, an electrode 10 for a lithium-ion electrochemical cell 12 is shown generally in
As such, the electrode 10, lithium-ion electrochemical cell 12, and method 14 may be useful for vehicular applications such as, but not limited to, automobiles, buses, forklifts, motorcycles, bicycles, trains, trams, trolleys, spacecraft, airplanes, farming equipment, earthmoving or construction equipment, cranes, transporters, boats, and the like. Alternatively, the electrode 10, lithium-ion electrochemical cell 12, and method 14 may be useful for non-vehicular applications such as household and industrial power tools, residential appliances, electronic devices, computers, and the like. By way of a non-limiting example, the electrode 10, lithium-ion electrochemical cell 12, and method 14 may be useful for powertrain applications for non-autonomous, autonomous, or semi-autonomous vehicle applications.
Referring now to
Therefore, the device 16 or secondary battery module may be useful for automotive applications, such as for a plug-in hybrid electric vehicle (PHEV). For example, the secondary battery module may be a lithium-ion secondary battery module. Further, although not shown, a plurality of secondary battery modules may be combined to form a secondary battery or pack. That is, the secondary battery module may be connected to one or more other secondary battery modules to form the secondary battery. By way of example, the secondary battery module may be sufficiently sized to provide sufficient voltage for powering a hybrid electric vehicle (HEV), an electric vehicle (EV), a plug-in hybrid electric vehicle (PHEV), and the like, e.g., approximately 300 to 400 Volts or more, depending on the required application. Alternatively, although not shown, the device 16 may be a vehicle and may include a plurality of lithium-ion electrochemical cells 12.
Further, as shown in
Referring again to
Referring now to
As described with reference to
As described with continued reference to
The binder component 28 may include a polyimide. The binder component 28 may be dispersed in the solvent, such as, but not limited to, N-methyl-2-pyrrolidone to form the binder solution. Although the solvent is removed from the electrode 10, 110 during subsequent processing as set forth below, the binder component 28 may bind or glue the electrode 10, 110 together and may provide mechanical stability to electrical contact points between the conductive filler component 24, e.g., single wall carbon nanotubes, and the active material component 26. Suitable compounds, polymer binders, or polymer precursors may include, but are not limited to, nitrogen-containing compounds and polymers such as polyimides, polyamic acid, phenolic resins, epoxy resins, polyethyleneimines, polyacrylonitrile, melamine, cyanuric acid, polyamides, polyvinylidene fluoride, and combinations thereof. Suitable solvents may include, but are not limited to, N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, methanol, ethanol, isopropanol, acetone, water, and combinations thereof.
In one specific embodiment, the binder component 28 may include a polyimide, the conductive filler component 24 may include carbon, and the active material component 26 may include silicon, e.g., silicon nanoparticles and silicon micron-sized particles.
As set forth in more detail below, the electrode 10, 110 includes a current collector 34 and an electrode composition 132 disposed on the current collector 34. For the electrode 10, 110, the binder component 28 may be present in the electrode composition 132 in a first amount; the conductive filler component 24 may be present in the electrode composition 132 in a second amount; and the active material component 26 may be present in the electrode composition 132 in a third amount that is greater than the first amount and the second amount. For example, the binder component 28 may be present in the electrode composition 132 in an amount of from 3 parts by weight to 40 parts by weight, or from 10 parts by weight to 30 parts by weight, or from 20 parts by weight to 25 parts by weight, based on 100 parts by weight of the electrode composition 132. The conductive filler component 24 may be present in the electrode composition 132 in an amount of from 2 parts by weight to 50 parts by weight, or from 10 parts by weight to 40 parts by weight, or from 30 parts by weight to 35 parts by weight, based on 100 parts by weight of the electrode composition 132. The active material component 26 may be present in the electrode composition 132 in an amount of from 30 parts by weight to 95 parts by weight, or from 40 parts by weight to 80 parts by weight, or from 50 parts by weight to 60 parts by weight, based on 100 parts by weight of the electrode composition 132. At amounts outside the aforementioned ranges, the electrode 10, 110 may not exhibit the excellent energy density, operating life, power performance, and charging speed of the claimed embodiments.
Referring again to
The current collector 34 may be a suitable copper matrix. For example, the current collector 34 may be a solid sheet formed from copper. Alternatively, the current collector 34 may be a foil formed from copper and may define a plurality of perforations or slits therein. Alternatively, the current collector 34 may be a woven mesh made from copper. In other embodiments, the current collector 34 may be a copper foam. In other embodiments, the current collector 34 may be a nickel or stainless steel or aluminum foil.
Alternatively, in some instances, the method 14 may include, after mixing 22 and prior to casting 36, remixing 122 (
Additionally, the method 14 may further include, after mixing 22, resting 40 the wet workpiece 38 for from 0.1 minutes to 4 minutes in air. For example, resting 40 the wet workpiece 38 in air may allow the slurry 30 to settle and spread along the current collector 34.
Referring again to
In particular, submersing 42 and inducing the phase inversion includes forming a liquid-like polymer lean phase and a solid-like polymer rich phase in the wet electrode composition 32 as the non-solvent 46 enters the slurry 30. As set forth in more detail below, the phase inversion process may be specifically useful for generating a favorable arrangement of pores 48 (
Referring again to
Further, drying 60 may include removing the liquid-like polymer lean phase from the wet electrode composition 32. More specifically, during drying 60, the non-solvent 46 may be removed from the wet electrode composition 32 to thereby define a plurality of channels 54 (
In particular, submersing 42 may include soaking the slurry 30 in the non-solvent 46 and drying 60 may include removing the liquid-like polymer lean phase to thereby define the plurality of channels 54. That is, once the liquid-like polymer lean phase and the solid-like polymer rich phase are formed during rinsing or soaking in the bath 44 (
Referring now to
In particular, the plurality of channels 54 may form a channel network 56 within the electrode composition 132 between the first surface 50 and the second surface 52 that is configured to minimize a travel distance 58 of lithium ions between the first surface 50 and the second surface 52. Such minimized travel distance 58 enables fast charging and excellent energy and power performance of the lithium-ion electrochemical cell 12. In one example, each of the plurality of channels 54 may extend tortuously between the first surface 50 and the second surface 52. That is, each of the plurality of channels 54 may bend or curve through the electrode composition 132 from the first surface 50 to the second surface 52. However, each of the plurality of channels 54 may also exhibit a minimized tortuosity to enable efficient lithium ion transport. Further, the plurality of channels 54 may be disposed generally parallel to one another and generally perpendicular to the first surface 50 and the second surface 52 to also enable efficient lithium ion transport.
In addition, each of the plurality of pores 48 may be arranged adjacent to a lithium transport tunnel, i.e., one of the plurality of channels 54. For example, the plurality of pores 48 may be arranged adjacent to an entirety of and/or an entrance to or exit from to one of the plurality of channels 54 defined within the electrode composition 132. As such, the plurality of pores 48 may be randomly arranged or located between the first surface 50 and the second surface 52 to promote excellent lithium ion transport.
In some instances, the method 14 may also include, after drying 60 at from room temperature to about 150° C., calendaring 64 the first surface 50 and/or the second surface 52 to modify a porosity of the electrode composition 132 and electrode 10, 110. For example, calendaring 64 may include pressing the electrode 10, 110 between two rollers (not shown) in a continuous process to smooth the first surface 50 and/or the second surface 52 and optimize the porosity of the electrode 10, 110. Similarly, the method 14 may include sanding or buffing the first surface 50 and/or the second surface 52 to remove any compacted material that may block or alter a shape of individual ones of the plurality of pores 48. The rollers may be formed from, for example, polytetrafluoroethylene-impregnated hard-anodized aluminum, polytetrafluoroethylene-coated brass, polytetrafluoroethylene-coated copper, polytetrafluoroethylene-coated stainless steel, polytetrafluoroethylene-coated nickel, polytetrafluoroethylene-coated nickel alloys, and combinations thereof. Calendaring 64 may therefore harden, flatten, and further dry the electrode composition 132.
Referring now to
For example, drying 60 the wet workpiece 38 may include first heat treating the wet workpiece 38 from at from room temperature to about 150° C., and then pyrolyzing at from 350° C. to 950° C., or from 475° C. to 925° C., or at about 800° C. in a nitrogen or inert environment to form the electrode 10, 110. In addition, as shown in
In addition, the method 114 also includes, after drying 60, defining 66: the plurality of channels 54 within the electrode composition 132 each extending between the first surface 50 and the second surface 52 in the first direction 51 that is generally perpendicular to the first surface 50 and each configured for lithium ion transport between the first surface 50 and the second surface 52; and the plurality of pores 48 between the first surface 50 and the second surface 52 and adjacent to the plurality of channels 54 to thereby form the electrode 10, 110.
For example, the plurality of pores 48 and/or channels 54 may be defined within the electrode composition 132 by laser etching the electrode composition 132, 3D printing the electrode composition 132, puncturing the electrode composition 132, and combinations thereof. That is, in one non-limiting embodiment, defining 66 may include laser etching the electrode composition 132 to define the plurality of channels 54 and/or pores 48 therein. Stated differently, defining 66 may include performing a subtractive manufacturing process on the electrode composition 132 to remove material and thereby define the plurality of channels 54 and/or pores 48.
Alternatively or additionally, defining 66 may include additively manufacturing the electrode composition 132. That is, in one non-limiting embodiment, defining 66 may include iteratively adding material to the current collector 34 to form the electrode composition 132 and define the plurality of channels 54 and/or pores 48 therein. For example, defining 66 may include 3D printing the electrode composition 132 to thereby define the plurality of channels 54 and/or pores 48.
Further, alternatively or additionally, defining 66 may include calendaring and puncturing the electrode composition 132. That is, in one non-limiting embodiment, defining 66 may include first calendaring 64 the first surface 50 and/or the second surface 52 and then puncturing the first surface 50 and/or second surface 52 to define the plurality of pores 48 between the first and/or second surfaces 50, 52 and define the plurality of channels 54 within the electrode composition 132. For example, calendaring 64 may include pressing the electrode composition 132 between two rollers to smooth the first surface 50 and/or the second surface 52 before puncturing the surfaces 50, 52 with a needle or trocar to define the plurality of pores 48 and channels 54.
Therefore, the electrode 10, 110 and lithium-ion electrochemical cell 12 exhibit excellent energy density, operating life, performance, and charging speed. In particular, submersing 42 the wet workpiece 38 into the bath 44 and inducing the phase inversion process described above and/or defining 66 the plurality of pores 48 and channels 54 after the wet workpiece 38 is dried provides the electrode 10, 110 and lithium-ion electrochemical cell 12 with enhanced performance and fast charging capabilities by minimizing the travel distance 58 of lithium ions through the electrode composition 132 during operation of the lithium-ion electrochemical cell 12. Further, the method 14 is an economical and efficient process to form the electrode 10, 110. In particular, the method 14 may be performed continuously. Therefore, the electrode 10, 110 and lithium-ion electrochemical cell 12 may be economical in terms of manufacturing time and cost and may be scalable to mass production manufacturing operations.
While the best modes for carrying out the disclosure have been described in detail, those familiar with the art to which this disclosure relates will recognize various alternative designs and embodiments for practicing the disclosure within the scope of the appended claims.
This application is a continuation of U.S. patent application Ser. No. 16/686,398, filed on Nov. 18, 2019, the disclosure of which is hereby incorporated by reference in its entirety.
Number | Date | Country | |
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Parent | 16686398 | Nov 2019 | US |
Child | 16686659 | US |