Methods involving use of nitrogen-containing plasma to treat liquid electrolyte lithium-ion cathode materials
12015142 ยท 2024-06-18
Inventors
Cpc classification
H01M4/505
ELECTRICITY
Y02E60/10
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
H01M4/1391
ELECTRICITY
H01M4/525
ELECTRICITY
H01M4/0471
ELECTRICITY
H01M10/0525
ELECTRICITY
International classification
H01M4/1391
ELECTRICITY
H01M10/0525
ELECTRICITY
H01M4/505
ELECTRICITY
H01M4/525
ELECTRICITY
Abstract
Systems and methods related to manufacturing of Lithium-Ion cells and Lithium-Ion cell cathode materials are disclosed. In one exemplary implementation, there is provided a method of using a Nitrogen-containing plasma to treat the Lithium-Ion cell cathode materials. Moreover, the method may include treating the cathode materials before and/or after coating the cathode materials on a metal foil.
Claims
1. A method of fabricating a Lithium-ion cell, the method comprising: coating a cathode powder on a metal foil to produce a cathode-coated metal foil; wherein the cathode powder comprises one or more cathode active materials; wherein the cathode powder contains Lithium, Nickel, and Oxygen and the one or more cathode active materials have a chemical formula of Li(Ni.sub.xMn.sub.yCo.sub.zAl.sub.w)O.sub.2, wherein 0.6?x?0.95, 0.02?y?0.2, 0?z?0.2, 0?w?0.1, and the Lithium is not lithium excess; drying, by one or more dryer chambers, the cathode-coated metal foil, wherein each of the one or more dryer chambers is configured with a header, a solvent exhaust collection and a recovery system; exposing, by at least one plasma chamber, the cathode-coated metal foil with treating material comprising nitrogen containing plasma having a nitrogen-containing reactive gas that reacts with the one or more cathode active materials to incorporate Nitrogen into the Lithium-ion cell's cathode, wherein the plasma is a near-atmospheric pressure plasma source ranging from about 0.5 to about 1.5 atmospheres pressure; calendering or rolling the cathode-coated metal foil treated to incorporate the Nitrogen; and placing the cathode-coated foil, treated to incorporate the Nitrogen, in a receptacle with a liquid electrolyte, to yield the Lithium-ion cell.
2. The method of claim 1 wherein the nitrogen-containing reactive gas consists essentially of N.sub.2.
3. The method of claim 1 wherein the nitrogen-containing reactive gas consists essentially of NH.sub.3.
4. The method of claim 1 wherein the nitrogen-containing reactive gas comprises one or more of N.sub.2/O.sub.2, air, N.sub.2/NF.sub.3, N.sub.2/NF.sub.3/O.sub.2, N.sub.2/NH.sub.3, and/or N.sub.2/NH.sub.3/O.sub.2.
5. The method of claim 1 wherein x=0.6, y=0.2, z=0.2, and w=0.
6. The method of claim 1 wherein x=0.8, y=0.1, z=0.1, and w=0.
7. The method of claim 1 wherein 0.9<x?0.95, 0.02?y?0.1, 0?z?0.1, and w=0.
8. The method of claim 1 wherein 0.6?x?0.95, 0.02?y?0.2, 0?z?0.2, and 0<w?0.1.
9. The method of claim 1 wherein the nitrogen-containing reactive gas comprises N.sub.2/O.sub.2.
10. The method of claim 9 wherein x=0.6, y=0.2, z=0.2, and w=0.
11. The method of claim 9 wherein x=0.8, y=0.1, z=0.1, and w=0.
12. The method of claim 9 wherein 0.9<x?0.95, 0.02?y?0.1, 0?z?0.1, and w=0.
13. The method of claim 9 wherein 0.6?x?0.95, 0.02?y?0.2, 0?z?0.2, and 0<w?0.1.
14. The method of claim 11, wherein the nitrogen-containing reactive gas consists essentially of N.sub.2/O.sub.2.
15. The method of claim 1 wherein the cathode powder is applied onto the metal foil as a slurry that fills regions of the metal foil.
16. The method of claim 15, wherein the nitrogen-containing reactive gas consists essentially of N.sub.2.
17. The method of claim 16, wherein x=0.8, y=0.1, z=0.1, and w=0.
18. The method of claim 1 further comprising: mixing the cathode powder to form a slurry that is coated on the metal foil to produce the cathode-coated metal foil.
19. The method of claim 9 wherein the cathode powder is applied onto the metal foil as a slurry that fills regions of the metal foil.
20. The method of claim 19 wherein x=0.8, y=0.1, z=0.1, and w=0.
21. The method of claim 19 wherein 0.6?x?0.95, 0.02?y?0.2, 0?z?0.2, and 0<w?0.1.
22. The method of claim 9 further comprising: mixing the cathode powder to form a slurry that is coated on the metal foil to produce the cathode-coated metal foil.
23. The method of claim 22 wherein x=0.8, y=0.1, z=0.1, and w=0.
24. The method of claim 22 wherein 0.6?x?0.95, 0.02?y?0.2, 0?z?0.2, and 0<w?0.1.
25. The method of claim 1, wherein the nitrogen-containing reactive gas consists essentially of N.sub.2/O.sub.2.
26. The method of claim 25, wherein the cathode powder is applied onto the metal foil as a slurry that fills regions of the metal foil.
27. The method of claim 25, further comprising: mixing the cathode powder to form a slurry that is coated on the metal foil to produce the cathode-coated metal foil.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Various embodiments of the present disclosure can be further explained with reference to the attached drawings, wherein like structures are referred to by like numerals throughout the several views. The drawings shown are not necessarily to scale, with emphasis instead generally being placed upon illustrating the principles of the present disclosure. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ one or more illustrative embodiments.
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
DETAILED DESCRIPTION OF CERTAIN ILLUSTRATIVE IMPLEMENTATIONS
(11) Various detailed embodiments of the present disclosure, taken in conjunction with the accompanying figures, are disclosed herein. However, it is to be understood that the disclosed embodiments are merely illustrative. In addition, each of the examples given in connection with the various embodiments of the present disclosure is intended to be illustrative, and not restrictive.
(12) Throughout the specification, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise. The phrases in one embodiment and in some embodiments as used herein do not necessarily refer to the same embodiment(s), though it may. Furthermore, the phrases in another embodiment and in some other embodiments as used herein do not necessarily refer to a different embodiment, although it may. Thus, as described below, various embodiments may be readily combined, without departing from the scope or spirit of the present disclosure.
(13) While other aspects are involved, the present disclosure focuses on the manufacturing process of the cathode for Lithium-ion cells. As explained in more detail, below, and consistent with the disclosed technology, systems and methods herein involving innovative utilization and/or incorporation of Nitrogen into Lithium-ion battery cathode materials are disclosed, such as for Nickel-rich (Ni-rich) cathodes, and the like. Further, implementations of the disclosed technology and innovations herein do not add significant costs to the manufacture of Lithium ion (Li-ion) batteries. In addition, such incorporation of nitrogen into the Ni-rich cathode materials make it less sensitive to atmospheric moisture. Accordingly, consistent with aspects herein, the overall cost of building and operating Lithium-ion cell factories using the Nickel-rich (e.g., greater than or equal to 50% Nickel, as atomic ratio of cathode metallic elements) cathode materials is reduced. Further, unlike other existing methods of incorporating nitrogen (see, e.g., Background), systems and methods involving the plasma exposure components/features disclosed herein take a much shorter period of time to complete and can easily be incorporated into the Li-ion cell manufacturing flow.
(14) Turning to implementations herein, one example of cathode materials consistent with the disclosed technology may be NMC532 (Ni.sub.0.5Mn.sub.0.3Co.sub.0.2). Here, in such example(s), while the full composition of the cathode material is approximately denoted as Li (Ni.sub.0.5Mn.sub.0.3Co.sub.0.2)O.sub.2, typically only the active cathode material composition (NMC532) is used to denote the cathode material composition. In the rest of this invention disclosure, such shorthand notations for Li-ion cell cathode materials will be adopted. For this particular composition, i.e., NMC532, the Nickel (Ni) forms 50% of the active cathode material and Manganese (Mn) forms 30% of the active cathode material and Cobalt (Co) forms 20% of the active cathode material. Other materials with higher Nickel composition are also within the scope of the disclosed technology, including but not limited to NMC622 (Ni.sub.0.6Mn.sub.0.2Co.sub.0.2), with 60% Nickel composition of the active cathode material, NMC811 (Ni.sub.0.8Mn.sub.0.1Co.sub.0.1), as well as LNO (Lithium Nickel Oxide) with greater than 95% Nickel composition of the active cathode materials. Further, other materials with higher Nickel composition are also within the scope of the disclosed technology, including, e.g., NCA (Ni.sub.0.8Co.sub.0.15Al.sub.0.05) as well as NCA materials with even higher Nickel composition than 80%, such as NCMA (NiCoMnAl), etc.
(15) Referring next to
(16) Next, the step of exposing or treating the coated cathode foil to a nitrogen-containing plasma may be performed, at 304. Here, in step 304, the plasma source gas may be any nitrogen-containing gas or gases. According to embodiments herein, such Nitrogen-containing gas could be or include N.sub.2 or NH.sub.3 or NF.sub.3 or NO or N.sub.2O or other nitrogen containing gases. Other gases such as air or oxygen could also be mixed with the nitrogen containing gases for the plasma. In some implementations, for example, this plasma could be pure N.sub.2 or combination of N.sub.2/O.sub.2 in any percentage including air (e.g., approximately 80% N.sub.2, approximately 20% O.sub.2, or the like). Other gases, such as NH.sub.3 (ammonia), NF.sub.3, or a combination of gases such as N.sub.2/NF.sub.3 or N.sub.2/NH.sub.3 or N.sub.2/O.sub.2/NH.sub.3 or N.sub.2/O.sub.2/NF.sub.3 can be used as the nitrogen source gas for the plasma treatment. In an alternative embodiment, a multi-step plasma treatment process can be employed. For example, one step with N.sub.2/O.sub.2 could be used, followed by another step with N.sub.2/NF.sub.3 or N.sub.2/NH.sub.3. This is only an example of a multi-step process, but many other multi-step plasma treatment combinations are possible. According to various embodiments herein, the plasma frequency may be between about 13 MHz to about 5000 MHz (i.e. 5 GHz). Further, in some embodiments, the plasma may be set in a more narrow range of frequency, such as between about 800 MHz to about 2500 MHz (i.e. 2.5 GHz). Further, in some even more specific embodiments, plasma frequencies such as 915 MHz or 2450 MHz may be utilized.
(17) After the treatment with the nitrogen-containing plasma, at 304, one or more optional steps of (further) drying the coated cathode foil may be performed, at 305. After such stages, an optional step of cooling down the foil may be employed. Next, a step of calendering or winding the cathode foil may be performed, at 306, and, notably, this step of calendering may be done at normal atmospheric or room conditions, i.e., without certain special environmental (gas or air) requirements or restrictions that are otherwise needed for existing technologies. Moreover, in some embodiments, the cathode foil may be wound or otherwise bundled with the other layers of the Li-ion cell at or after such stage. In particular, throughout such steps of processing the foil, advantageously, the humidity (relative humidity) of room air, when utilizing the present innovations, may range from about 5% to about 35%. More specifically, the humidity can be controlled between about 10% to about 30%, and, further, in some specific embodiments, between about 20% and about 30%. Such humidity levels are significantly higher than the requirements of existing techniques, and thus reduce the technical requirements, complexities and/or costs of manufacture of Li-ion cells. Finally, one or more additional steps may be performed, at 307, in continuing with various additional, known Lithium-ion cell manufacturing process steps, as per the standard processes used by Li-ion cell manufacturers.
(18)
(19) Moreover, as also shown in
(20) In step 401 of
(21) Overall, as similar with the embodiment of
(22)
(23)
(24)
(25)
(26)
(27) Various embodiments may be configured such that cathode active materials/metals of different compositions are utilized to coat metal foils. For example, such cathode active material may comprise, substantially comprise or consist of NMC532 (Ni.sub.0.5Mn.sub.0.3Co.sub.0.2). In another example, cathode active materials may comprise, substantially comprise or consist of NMC622 (Ni.sub.0.6Mn.sub.0.2Co.sub.0.2). In yet another example, cathode active materials may comprise, substantially comprise or consist of NMC811 (Ni.sub.0.8Mn.sub.0.1Co.sub.0.1). In still yet another example, cathode active materials may comprise, substantially comprise or consist of LNO (Lithium Nickel Oxide with Nickel >90%). In another example, cathode active materials may comprise, substantially comprise or consist of NCA (Ni.sub.0.8Co.sub.0.15Al.sub.0.05) or with NCA with Nickel concentration above 0.8. In yet another example, cathode active materials may comprise, substantially comprise or consist of NMCA, with Nickel, Manganese, Cobalt and Aluminum. In one example, cathode active materials may comprise, substantially comprise or consist of Magnesium at a concentration of less than about 3%, or less than 3%.
(28) Various embodiments may be also configured such that nitrogen containing gas of different composition are utilized to treat coated metal foils and/or cathode powder. For example, such nitrogen containing gas may comprise, substantially comprise, or consists of N2. In another example, the nitrogen containing gas may comprise, substantially comprise, or consists of NH3 (Ammonia). In yet another example, the nitrogen containing gas may comprise, substantially comprise, or consists of one or both of N2 and/or O2, or of N2 and O2. In still yet another example, the nitrogen containing gas may comprise, substantially comprise, or consists of NF3 (Nitrogen trifluoride). In another example, the nitrogen containing gas may comprise, substantially comprise, or consists of a combination of N2/O2 or air or N2/NF3 or N2/NF3/O2 or N2/NH3 or N2/NH3/O2.
(29) In various embodiments, the plasma may be generated via any suitable technique. For example, the plasma may be generated using a remote plasma source. For another example, the plasma may be generated using a low-pressure plasma source. For yet another example, the plasma may be generated using a near-atmospheric pressure (e.g., ranging from about 0.5 to about 1.5 atmospheres pressure) plasma source.
(30) Unless the context clearly requires otherwise, throughout the description, the words comprise, comprising, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in a sense of including, but not limited to. Words using the singular or plural number also include the plural or singular number respectively. Additionally, the words herein, hereunder, above, below, and words of similar import refer to this application as a whole and not to any particular portions of this application. When the word or is used in reference to a list of two or more items, that word covers all of the following interpretations of the word: any of the items in the list, all of the items in the list and any combination of the items in the list.
(31) Other implementations of the inventions will be apparent to those skilled in the art from consideration of the specification and practice of the innovations disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the inventions being indicated by the present disclosure and claims and various associated principles of related patent doctrine.