Patent Application
20240421292
In at least one aspect, positive electrode active materials for lithium-ion batteries are provided.
Lithium and Manganese Rich (LMR) positive electrode active material has been considered one of the most promising next-generation cathode materials due to the high gravimetric energy density compared to currently used Nickel Cobal Manganese (NCM) and Nickel Cobalt Aluminum (NCA) materials.
In at least one aspect, a positive electrode active material is provided. The positive electrode active material includes a compound represented by formula 1: Li(1.1+a)Mn(0.51+c)Ni(0.37−x)MxO(2−b)Fb (1) wherein: M is Co, Cr, or a combination thereof, −0.02≤a≤0.02, −0.01≤b≤0.01, 0<x<0.1, and 0<c<0.1.
In another aspect, a positive electrode for a lithium-ion battery is provided. The positive electrode includes a positive electrode active material that includes a compound represented by Chemical Formula 1: Li(1.1+a)Mn(0.51+c)Ni(0.37−x)MxO(2−b)Fb (1), wherein: M is Co, Cr, or a combination thereof, −0.02≤a≤0.02, −0.01≤b≤0.01, 0<x<0.1, and 0<c<0.1.
In another aspect, a rechargeable lithium-ion battery including at least one lithium-ion battery cell is provided. Each lithium-ion battery cell includes a positive electrode comprising a compound represented by formula 1: Li(1.1+a)Mn(0.51+c)Ni(0.37−x)MxO(2−b)Fb (1), wherein: M is Co, Cr, or a combination thereof, −0.02≤a≤0.02, −0.01≤b≤0.01, 0<x<0.1, and 0<c<0.1, a negative electrode including a negative electrode active material, and an electrolyte.
For a further understanding of the nature, objects, and advantages of the present disclosure, reference should be made to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: when a given chemical structure includes a substituent on a chemical moiety (e.g., on an aryl, alkyl, etc.) that substituent is imputed to a more general chemical structure encompassing the given structure; percent, “parts of,” and ratio values are by weight; the term “polymer” includes “oligomer,” “copolymer,” “terpolymer,” and the like; molecular weights provided for any polymers refers to weight average molecular weight unless otherwise indicated; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
As used herein, the term “about” means that the amount or value in question may be the specific value designated or some other value in its neighborhood. Generally, the term “about” denoting a certain value is intended to denote a range within +/−5% of the value. As one example, the phrase “about 100” denotes a range of 100+/−5, i.e. the range from 95 to 105. Generally, when the term “about” is used, it can be expected that similar results or effects according to the invention can be obtained within a range of +/−5% of the indicated value.
As used herein, the term “and/or” means that either all or only one of the elements of said group may be present. For example, “A and/or B” shall mean “only A, or only B, or both A and B”. In the case of “only A”, the term also covers the possibility that B is absent, i.e. “only A, but not B”.
It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
The term “comprising” is synonymous with “including,” “having,” “containing,” or “characterized by.” These terms are inclusive and open-ended and do not exclude additional, unrecited elements or method steps.
The phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
The phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps, plus those that do not materially affect the basic and novel characteristic(s) of the claimed subject matter.
The phrase “composed of” means “including” or “consisting of.” Typically, this phrase is used to denote that an object is formed from a material.
With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” where one of these three terms is used herein, the presently disclosed and claimed subject matter can include the use of either of the other two terms.
The term “one or more” means “at least one” and the term “at least one” means “one or more.” The terms “one or more” and “at least one” include “plurality” and “multiple” as a subset. In a refinement, “one or more” includes “two or more.”
The term “substantially,” “generally,” or “about” may be used herein to describe disclosed or claimed embodiments. The term “substantially” may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such instances, “substantially” may signify that the value or relative characteristic it modifies is within ±0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic.
It should also be appreciated that integer ranges explicitly include all intervening integers. For example, the integer range 1-10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Similarly, the range 1 to 100 includes 1, 2, 3, 4 . . . 97, 98, 99, 100. Similarly, when any range is called for, intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken as alternative upper or lower limits. For example, if the range is 1.1. to 2.1 the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as lower or upper limits.
When referring to a numeral quantity, in a refinement, the term “less than” includes a lower non-included limit that is 5 percent of the number indicated after “less than.” For example, “less than 20” includes a lower non-included limit of 1 in a refinement. Therefore, this refinement of “less than 20” includes a range between 1 and 20. In another refinement, the term “less than” includes a lower non-included limit that is, in increasing order of preference, 20 percent, 10 percent, 5 percent, or 1 percent of the number indicated after “less than.”
The term “positive electrode” means a battery cell electrode from which current flows out when the lithium-ion battery cell or battery is discharged. Sometimes a “positive electrode” is referred to as a “cathode.”
The term “negative electrode” means a battery cell electrode to which current flows in when the lithium-ion battery cell is discharged. Sometimes a “negative electrode” is referred to as an “anode.”
The term “cell” or “battery cell” means an electrochemical cell made of at least one positive electrode, at least one negative electrode, an electrolyte, and a separator membrane.
The term “battery” or “battery pack” means an electric storage device made of at least one battery cell. In a refinement, “battery” or “battery pack” is an electric storage device made of a plurality of battery cells.
The term “specific capacity” means the capacity per unit mass of the anode active. Specific capacity has units of milliamp hours/gram (mAh/g).
There are intrinsic issues with current LMR material compositions such as voltage decay during cycling, rate capability, cycle performance, and volumetric energy density. Accordingly, there is a need for optimized LMR material compositions for positive electrode active materials for lithium-ion batteries with increased rate capability, cell performance, and volumetric energy density.
The present disclosure provides compositions for Lithium Manganese Rich (LMR) cathodes used in lithium-ion batteries. The performance issues inherent to conventional LMR compositions, namely voltage decay during cycling, decreased rate capability over successive cycles, and poor cycle performance. These issues can be mititgated by optimizing the composition of the LMR.
In one embodiment of the disclosure, the LMR composition is optimized to have lower Li content (Li2MnO3) than conventional compositions. This modification betters the cycle performance, power performance, and rate capability by enhancing the voltage decay, and electronic and ionic conductivity of the LMR. However, it is recognized that lower Li content typically results in lower capacity than conventional LMR.
To address this potential reduction in capacity, the LMR composition is further modified to incorporate increased Nickel (Ni) with optimized Cobalt (Co) or Chromium (Cr) content, with Cobalt being the primary focus. This modified composition series increases capacity from Ni and Co by controlling the average oxidation state of the Ni ion. Optimized Co content also assists in enhancing electronic and ionic conductivity.
In one embodiment, the general formula of the new LMR composition is given as Li1.10Mn0.52Ni(0.38−x)MxO(2−b)Fb, where M can be Co, Cr, or a combination thereof. The average oxidation state of the Ni ion is controlled between 2 and 2.15. The average oxidation state of the Mn ion is controlled between 3.8 and 4.0 by controlling the F (fluorine) doping content, where “b” is again a value between 0 and 0.1.
In the LMR composition Li1.10Mn0.52Ni(0.38−x)MxO(2−b)Fb F doping Li1.10 in the formula represents an optimized lithium content that promotes cycling, mitigates voltage decay, and bolsters power performance. The configuration also allows for the attainment of closer to maximum actual capacity by manipulating the amounts of Ni3+ and Co3+ ions within the composition.
Optimal Co3+ content within this formula also serves to enhance electronic conductivity and power capability. In this composition, the Co3+ content is further restricted to between 0 and 0.06, a constraint that helps balance performance metrics such as capacity and power against production. This formula also facilitates a larger slope region, achieved through the heightened incorporation of Mn3+. This is made possible by F− doping, which effectively lowers the oxidation state of Mn, resulting in an increase in the Mn3+ ion presence.
Higher Initial Coulombic Efficiency (ICE), leading to increased discharge capacity, is another notable advantage. This increased ICE is tied to the better structural stability after the initial charge, which can be attributed to strong Metal-Fluoride (Me-F) bonding in the composition. Additionally, the elevated Mn3+ content further augments electronic conductivity. With respect to Mn3+ content and ICE, this adaptation shows enhancements compared to compositions previously known.
In another embodiment the general formula of the new LMR composition is represented as Li1.12Mn0.51Ni(0.37−x)MxO(2−b)Fb, where M can be Co or Cr or a combination thereof. Here, “x” is a variable value between 0 and 0.1, defining the proportion of M in the composition. The average oxidation state of the Ni ion is controlled between 2 and 2.27, while the average oxidation state of the Manganese (Mn) ion is controlled between 3.8 and 4.0 by controlling the fluorine (F) doping content, “b”, which lies between 0 and 0.1.
The LMR composition Li1.12Mn0.51Ni(0.37−x)MxO(2−b)Fb, coupled with F− doping, has several advantages. Li1.12 is found to be an optimized Li content for achieving good cycle, voltage decay, and power performance. Maximum actual capacity is realized in the Li1.12 composition by controlling the contents of Ni3+ and Co3+. Furthermore, optimized Co3+ content betters electronic conductivity, leading to better power capability.
Restricted Co3+ content, between 0 and 0.1, is advantageous in controlling performance meaning capacity and power. A larger slope region is obtainable with a higher incorporation of Mn3+ as F− can lower the Mn oxidation state. Higher Initial Coulombic Efficiency (ICE) can lead to higher discharge capacity, owing to better structural stability after the first charge due to strong Metal-Fluoride (Me-F) bonding. Moreover, higher Mn3+ enhances electronic conductivity. Higher Mn3+ content and higher ICE resulting in an overall increase in performance.
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A specific active electrode composition can be Li1.10Mn0.52Ni(0.38−x)MxO(2−b)Fb, where M can be Co, Cr, or a combination thereof. The average oxidation state of the Ni ion is controlled between 2 and 2.15. The average oxidation state of the Mn ion is controlled between 3.8 and 4.0 by controlling the F doping content, where “b” is again a value between 0 and 0.1.
Another LMR composition is represented as Li1.12Mn0.51Ni(0.37−x)MxO(2−b)Fb, where M can be Co or Cr or a combination thereof. Here, “x” is a variable value between 0 and 0.1, defining the proportion of M in the composition. The average oxidation state of the Ni ion is controlled between 2 and 2.27, while the average oxidation state of the Manganese (Mn) ion is controlled between 3.8 and 4.0 by controlling the fluorine (F) doping content, “b”, which lies between 0 and 0.1.
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The negative electrode binder increases the binding properties of negative active material particles with one another and with a current collector. The binder can be a non-aqueous binder, an aqueous binder, or a combination thereof. Examples of non-aqueous binders may be polyvinylchloride, carboxylated polyvinylchloride, polyvinylfluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide, or a combination thereof. Aqueous binders can be rubber-based binders or polymer resin binders. Examples of rubber-based binders include but are not limited to styrene-butadiene rubbers, acrylated styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, acrylic rubbers, butyl rubbers, fluorine rubbers, and combinations thereof. Examples of polymer resin binders include but are not limited to polyethylene, polypropylene, ethylenepropylene copolymer, polyethyleneoxide, polyvinylpyrrolidone, epichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, ethylenepropylenediene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, a polyester resin, an acrylic resin, a phenolic resin, an epoxy resin, polyvinyl alcohol and combinations thereof.
While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.
