Lithium-ion batteries are increasingly used for compact applications, such as wireless ear pods, and compact medical devices, such as pacemakers. These designs require battery electrodes to be wound up into very small spaces with tight radii of curvature (i.e., very tightly wound). In some applications, the inner electrode layers in these wound electrodes may experience a radius of curvature of less than 5 mm. Such tight winding can cause the coating layer of the electrode material to delaminate from the current collector and/or tear the current collector. High energy density lithium-ion cells with thick (i.e., greater than 100 μm) electrodes have higher limits of radii of curvature before such damage occurs than thinner electrodes. These space restrictions mean that thick electrodes cannot be used, as thick electrodes may crack and/or delaminate when the electrodes bend around the small radius of curvature.
During cycling of lithium-ion batteries, lithium ions must homogenously lithiate particles throughout all depths of the electrode in the battery. The ionic conductivity, or ease for lithium ions to travel through a medium, of the electrolyte limits how quickly lithium can travel to and from electrodes during cycling. The tight winding required for small battery applications often prevents the electrolyte from being able to penetrate beyond the surface of the electrode. Thus, there remains a need for thick electrodes to be able to be wound tightly without cracking or delamination and to allow electrolyte to penetrate deep into the electrode roll.
An aspect of the present disclosure is a device including a lithium-ion battery which includes an electrode having a channel, in which the electrode has a length, a width, and a thickness, the channel extends into a first portion of the length of the electrode, the channel extends into a second portion of the width of the electrode, and the channel extends into a third portion of the thickness of the electrode. In some embodiments, the first portion is in the range of about 5 μm to about 50 μm. In some embodiments, the second portion is in the range of about 5 μm to about 50 μm. In some embodiments, the second portion is approximately equivalent to the width of the electrode. In some embodiments, the third portion is in the range of about 5 μm to about 50 μm. In some embodiments, the third portion is about 100 μm or less. In some embodiments, the device also includes an electrolyte, and a portion of the electrolyte is present in the channel.
An aspect of the present disclosure is a method for improving the performance of a lithium-ion battery, and the method includes forming a channel in an electrode of the lithium-ion battery using a laser source configured to emit a beam, in which the beam has a size, the electrode has a length, a width, and a thickness, the channel extends into a first portion of the length of the electrode, the channel extends into a second portion of the width of the electrode, and the channel extends into a third portion of the thickness of the electrode. In some embodiments, the first portion is approximately equivalent to the size of the beam. In some embodiments, the first portion is approximately equivalent to the length. In some embodiments, the second portion is approximately equivalent to the size of the beam. In some embodiments, the second portion is approximately equivalent to the width. In some embodiments, the third portion is approximately equivalent to the size of the beam. In some embodiments, the third portion is less than about 100 μm. In some embodiments, the forming includes pulsing the laser to remove material from the electrode to form the channel. In some embodiments, the method also includes applying an electrolyte to the electrode and during the applying a portion of the electrolyte is present in the channel.
An aspect of the present disclosure is a system for performing laser ablation on an electrode of a lithium-ion battery, and the system includes a laser source configured to emit a beam, a laser optics, and a stage configured to hold the electrode, in which the laser optics is configured to direct the beam to perform laser ablation on the electrode which results a channel on the electrode. In some embodiments, the laser source includes a femtosecond laser. In some embodiments, the laser optics includes a laser mirror, a laser lens, a laser window, a laser filter, ultrafast optics, laser beam expanders, laser beam splitters, a crystal, an isolator, a speckle reducer, and/or a laser prism. In some embodiments, the system includes a gas source, in which the gas source is oriented towards the stage, and the gas source is configured to remove any debris caused by the laser ablation.
Some embodiments of the present disclosure are illustrated in the referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
The embodiments described herein should not necessarily be construed as limited to addressing any of the problems or deficiencies discussed herein. References in the specification to “one embodiment”, “an embodiment”, “an example embodiment”, “some embodiments”, etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
As used herein the term “substantially” is used to indicate that exact values are not necessarily attainable. By way of example, one of ordinary skill in the art will understand that in some chemical reactions 100% conversion of a reactant is possible, yet unlikely. Most of a reactant may be converted to a product and conversion of the reactant may asymptotically approach 100% conversion. So, although from a practical perspective 100% of the reactant is converted, from a technical perspective, a small and sometimes difficult to define amount remains. For this example of a chemical reactant, that amount may be relatively easily defined by the detection limits of the instrument used to test for it. However, in many cases, this amount may not be easily defined, hence the use of the term “substantially”. In some embodiments of the present invention, the term “substantially” is defined as approaching a specific numeric value or target to within 20%, 15%, 10%, 5%, or within 1% of the value or target. In further embodiments of the present invention, the term “substantially” is defined as approaching a specific numeric value or target to within 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, or 0.1% of the value or target.
As used herein, the term “about” is used to indicate that exact values are not necessarily attainable. Therefore, the term “about” is used to indicate this uncertainty limit. In some embodiments of the present invention, the term “about” is used to indicate an uncertainty limit of less than or equal to ±20%, ±15%, ±10%, ±5%, or ±1% of a specific numeric value or target. In some embodiments of the present invention, the term “about” is used to indicate an uncertainty limit of less than or equal to ±1%, ±0.9%, ±0.8%, ±0.7%, ±0.6%, ±0.5%, ±0.4%, ±0.3%, ±0.2%, or ±0.1% of a specific numeric value or target.
The present disclosure relates to utilizing laser ablation to selectively remove regions of active material from lithium-ion battery electrodes during production. In some embodiments, laser ablation may remove a portion of the electrode, forming channels. These channels may improve the radius of curvature of the lithium-ion battery, form patterns on the surface of the electrode to store excess electrolyte, provide improved access to external sources of lithium during pre-lithiation or re-lithiation, and/or lower the tortuosity of electrodes for enhanced ion transfer between electrodes during cycling in prismatic cells and cylindrical cells.
Increasing the thickness of electrodes may increase the energy density of the batteries, but with increasing thickness, the distance that an ion must travel increases, and thus the ability of electrodes to homogenously accept lithium ions is hindered. By milling channels (i.e., micro-holes) in the thick electrode, low tortuosity paths may be provided for lithium ions to reach deeper regions in the electrode more quickly than before, thus reducing lithium concentration gradients and allowing increasingly thick electrodes to operate at a specific discharge rate (or C rate). The present disclosure may remove material with micrometer control to introduce patterns on the electrode to alleviate the stresses of bending.
The electrode 125 shown in
During the manufacturing process of lithium-ion batteries, a critical step is to wet the electrodes with electrolyte. This ensures that there is ionic contact with active materials and that the cell's capacity may be fully accessed during cycling. During extensive cycling, cathodes particles crack and increase the porosity of the cathode which is perceived as irreversible swelling of the cell. This swelling consumes excess electrolyte which traditionally remains present around the perimeter of the electrode. This makes it challenging for the electrolyte to penetrate from the perimeter deep into the electrode. This prevents the electrolyte from being able to fully wet the new surfaces and thus ionic contact loss may occur within the degraded electrode which further exacerbates capacity fade.
The present disclosure includes storing small amounts of electrolyte within the electrode which can be used when needed near the region of storage. This may include introducing micrometer-scale features. The present disclosure includes manufacturing the electrodes with small holes that act as electrolyte wells for when excess electrolyte is needed later in the life of the cell, thus helping extend the life of the cells by prolonging good ionic contact with active material surfaces. In some embodiments, a femtosecond laser may be used to provide the necessary precision to form these wells. An example of an electrolyte well created by laser ablation in a fresh electrode and showing the electrolyte well after cycling is shown in
Next, a channel 205b in the form of a pore or electrolyte well is shown. Similar to channel 205a, the channel 205a does not extend through the full thickness of the electrode 200. The channel 205b may be substantially circular, elliptical, triangular, square, rectangular, trapezoidal, polygonal, or another shape. A plurality of channels 205b may be formed in a pattern or distributed across the surface of an electrode. Various configurations may be used to create channels 205b which enable electrolyte permeation within the electrode and storage of electrolyte in the surface of the electrode, as shown in
Next, a channel 205c is shown in the form of a slice or extended channel. The channel 205c may extend through the width (but not the thickness) of the electrode 200. The channel 205c may be created in a cluster or series of channels 205c. These channels 205c may be spaced based on how the electrode 200 will ultimately be cut, folded, rolled, and/or formed to create the battery. For example, a plurality of channels 205 may be cut in several clusters or series based on where the electrode 200 will be needed to bend in the final battery design. The channels 205c may be substantially straight, and if they are in a cluster or series the channels 205c may be substantially parallel. The formation of the channels 205c may enable the electrode 200 to bend and/or roll as needed to create the battery without cracking. As shown in panel b) of
In some embodiments, the forming 305 may include repeating laser pulses, to “chip” away electrode 200 material, forming a channel 205. The channel 205 may extend through the width of the electrode 200 if it is a location where the electrode 200 will be bent or rolled upon assembly of the lithium-ion battery. The forming 305 may be performed during the manufacture of the lithium-ion battery and may be combined with the manufacture of the electrode 200.
In some embodiments, the method 300 next includes applying 310 an electrolyte to the electrode, resulting in at least a portion of the electrolyte being present in the channel 205. Applying 310 may refer to partial or complete filling of the channel 205 with electrolyte. The applying 310 may be performed during manufacturing of the lithium-ion battery, when electrolyte is applied to the electrode 200. In some embodiments, as a result of the applying 310 the electrolyte may be absorbed into the electrode 200.
In some embodiments, the lithium-ion electrodes may be thick (i.e., greater than about 100 μm) electrodes. In some embodiments, the electrodes may be graphite anodes and/or lithium nickel manganese cobalt oxide (Li1Ni1-x-yMnxCoyO2 or NMC) cathodes for rechargeable lithium-ion battery electrodes. The electrodes may be for use in a jelly roll lithium-ion battery design and may have a significant length which can be wound up to form the battery. In some embodiments, the electrode may be a LiNi0.5Mn0.3Co0.2O2 or NMC532 cathode.
In some embodiments, the electrolyte may include lithium hexafluorophosphate (LiPF6) salt dissolved in organic carbonates, such as ethylene carbonate (EC) with dimethyl carbonate (DMC), propylene carbonate (PC), diethyl carbonate (DEC), and/or ethyl methyl carbonate (EMC).
As used herein, the term “ablation” is used to refer to the removal or destruction of something from an object by vaporization, chipping, erosive processes, or by other means. In the present disclosure, ablation of at least a part of an electrode is performed using a laser to perform the ablation. The laser may burn or cut at least a portion of the electrode, resulting an incision. In some embodiments, the incision may extend through the entire depth of the electrode (i.e., form a hole in the electrode). In some embodiments, the incision may extend only partially into the depth of the electrode (i.e., forming a change in thickness of the electrode at certain locations).
Example 1. A device comprising:
a lithium-ion battery comprising:
the electrode comprises a length, a width, and a thickness,
the channel extends into a first portion of the length of the electrode,
the channel extends into a second portion of the width of the electrode, and
the channel extends into a third portion of the thickness of the electrode.
Example 2. The device of Example 1,
the first portion is in the range of about 5 μm to about 50 μm.
Example 3. The device of Example 1 or 2, wherein:
the first portion is less than the length of the electrode.
Examples 4. The device of Example 1 or 2, wherein:
the first portion is approximately equivalent to the length of the electrode.
Example 5. The device of any of Examples 1-4, wherein:
the second portion is in the range of about 5 μm to about 50 μm.
Example 6. The device of any of Examples 1-5, wherein:
the second portion is approximately less than the width of the electrode.
Example 7. The device of any of Examples 1-5, wherein:
the second portion is approximately equivalent to the width of the electrode.
Example 8. The device of any of Examples 1-7, wherein:
the third portion is in the range of about 5 μm to about 50 μm.
Example 9. The device of any of Example 1-8, wherein:
the third portion is less than the thickness of the electrode.
Example 10. The device of any of Example 1-9, wherein:
the third portion is about 100 μm or less.
Example 11. The device of any of Examples 1-10, further comprising:
an electrolyte.
Example 12. The device of Example 11, wherein:
a portion of the electrolyte is present in the channel.
Example 13. A method for improving the performance of a lithium-ion battery, the method comprising:
forming a channel in an electrode of the lithium-ion battery using a laser source configured to emit a beam; wherein:
the beam comprises a size,
the electrode comprises a length, a width, and a thickness,
the channel extends into a first portion of the length of the electrode,
the channel extends into a second portion of the width of the electrode, and
the channel extends into a third portion of the thickness of the electrode.
Example 14. The method of Example 13, wherein:
the size of the beam comprises approximately 10 μm.
Example 15 The method of Example 13, wherein:
the size of the beam comprises approximately 40 μm.
Example 16. The method of any of Examples 13-15, wherein:
the first portion is approximately equivalent to the size of the beam.
Example 17. The method of any of Examples 13-16, wherein:
the first portion is less than the length.
Example 18. The method of any of Examples 13-16, wherein:
the first portion is approximately equivalent to the length.
Example 19. The method of any of Examples 13-18, wherein:
the second portion is approximately equivalent to the size of the beam.
Example 20. The method of any of Examples 13-19, wherein:
the second portion is approximately less than the width.
Example 21. The method of any of Examples 13-19, wherein:
the second portion is approximately equivalent to the width.
Example 22. The method of any of Examples 13-21, wherein:
the third portion is approximately equivalent to the size of the beam.
Example 23. The method of any of Examples 13-22, wherein:
the third portion is less than the thickness.
Example 24. The method of any of Examples 13-23, wherein:
the third portion is about 100 μm or less.
Example 25. The method of any of Examples 13-24, wherein the forming comprises:
pulsing the laser to remove material from the electrode to form the channel.
Example 26. The method of any of Examples 13-25, further comprising:
applying an electrolyte to the electrode; wherein:
during the applying a portion of the electrolyte is present in the channel.
Example 27. The method of Example 26, wherein:
the portion of the electrolyte is absorbed into the electrode after the applying.
Example 28. The method of any of Examples 13-27, wherein:
the forming is performed using a femtosecond laser.
Example 29. The method of Example 28, wherein:
the femtosecond laser has a pulse-width of approximately 600 fs, an output at 1030 nm, a repetition rate between 100 kHz and 1 MHz, and an average power of 10 MW.
Example 30. A system for performing laser ablation on an electrode of a lithium-ion battery, the system comprising:
a laser source configured to emit a beam;
a laser optics; and
a stage configured to hold the electrode; wherein:
the laser optics is configured to direct the beam to perform laser ablation on the electrode which results a channel on the electrode.
Example 31. The system of Example 30, wherein:
the laser source comprises a femtosecond laser.
Example 32. The system of Example 31, wherein:
the femtosecond laser has a pulse-width of approximately 600 fs, an output at 1030 nm, a repetition rate between 100 kHz and 1 MHz, and an average power of 10 MW.
Example 33. The system of any of Examples 30-32, wherein:
the laser optics comprises at least one of a laser mirror, a laser lens, a laser window, a laser filter, ultrafast optics, laser beam expanders, laser beam splitters, a crystal, an isolator, a speckle reducer, and/or a laser prism.
Example 34. The system of any of Examples 30-33, wherein:
the laser optics comprises a galvo-mirror beam steering assembly.
Example 35. The system of Example 34, wherein:
the galvo-mirror beam steering assembly comprises a f-theta scanning lens.
Example 36. The system of any of Examples 30-35, wherein:
the laser optics comprises a beam steering optics, and
the beam steering optics are coated for 1030 nm.
Example 37. The system of any of Examples 30-36, wherein:
the stage for the battery comprises:
Example 38. The system of any of Examples 30-37, further comprising:
a gas source; wherein:
the gas source is oriented towards the stage, and
the gas source is configured to remove any debris caused by the laser ablation.
Example 39. The system of Example 38, wherein:
the gas source comprises an inert gas.
Example 40. The system of Example 39, wherein:
the inert gas comprises nitrogen.
Example 41. The system of any of Examples 30-40, wherein:
the beam comprises a size,
the electrode comprises a length, a width, and a thickness,
the channel extends into a first portion of the length of the electrode,
the channel extends into a second portion of the width of the electrode, and
the channel extends into a third portion of the thickness of the electrode.
Example 42. The system of Example 41, wherein:
the size of the beam comprises approximately 10 μm.
Example 43. The system of Examples 41 or 42, wherein:
the size of the beam comprises approximately 40 μm.
Example 44. The system of any of Examples 41-43, wherein:
the first portion is approximately equivalent to the size of the beam.
Example 45. The system of any of Examples 41-44, wherein:
the first portion is less than the length of the electrode.
Example 46. The system of any of Examples 41-44, wherein:
the first portion is approximately equivalent to the length of the electrode.
Example 47. The system of any of Examples 41-46, wherein:
the second portion is approximately equivalent to the size of the beam.
Example 48. The system of any of Examples 41-47, wherein:
the second portion is approximately less than the width of the electrode.
Example 49. The system of any of Examples 41-47, wherein:
the second portion is approximately equivalent to the width of the electrode.
Example 50. The system of any of Example 41-49, wherein:
the third portion is approximately equivalent to the size of the beam.
Example 51. The system of any of Example 41-50, wherein:
the third portion is less than the thickness of the electrode.
Example 52. The system of any of Example 41-51, wherein:
the third portion is about 100 μm.
Example 53. The system of any of Examples 41-51, wherein:
the third portion is less than about 100 μm.
Example 54. The system of any of Examples 30-53, further comprising:
an electrolyte.
Example 55. The system of Example 54, wherein:
a portion of the electrolyte is present within the channel.
The foregoing discussion and examples have been presented for purposes of illustration and description. The foregoing is not intended to limit the aspects, embodiments, or configurations to the form or forms disclosed herein. In the foregoing Detailed Description for example, various features of the aspects, embodiments, or configurations are grouped together in one or more embodiments, configurations, or aspects for the purpose of streamlining the disclosure. The features of the aspects, embodiments, or configurations may be combined in alternate aspects, embodiments, or configurations other than those discussed above. This method of disclosure is not to be interpreted as reflecting an intention that the aspects, embodiments, or configurations require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment, configuration, or aspect. While certain aspects of conventional technology have been discussed to facilitate disclosure of some embodiments of the present invention, the Applicants in no way disclaim these technical aspects, and it is contemplated that the claimed invention may encompass one or more of the conventional technical aspects discussed herein. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate aspect, embodiment, or configuration.
This application claims priority to U.S. Provisional Patent Application No. 63/149,466 filed on Feb. 15, 2021, the contents of which are incorporated herein by reference in their entirety.
This invention was made with United States government support under Contract No. DE-AC36-08GO28308 awarded by the U.S. Department of Energy. The United States government has certain rights in this invention.
Number | Date | Country | |
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63149466 | Feb 2021 | US |