LITHIUM- AND MANGANESE-RICH POSITIVE ACTIVE MATERIAL COMPOSITIONS

Abstract

An active material for positive electrodes may include a compound represented by the formula Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b where M is Co, Cr or a combination thereof, NW +6 , Ta +5 , V +5 or a combination thereof, 0 ≤ a ≤ 0.02, 0 ≤ b ≤ 0.1, 0 ≤ c ≤ 0.1, 0 ≤ x ≤ 0.1, and 0 ≤ y ≤ 0.04. A positive electrode may contain the positive electrode active material. A battery may contain the positive electrode.

Description

FIELD OF TECHNOLOGY

[0001] In at least one aspect, active materials for positive electrodes for lithium-ion batteries are provided. GENERAL STATE OF THE ART

[0002] A lithium- and manganese-rich (LMR) positive electrode active material has been considered as a promising next-generation cathode material due to its high gravimetric energy density compared to currently used nickel-cobalt-manganese (NCM) and nickel-cobalt-aluminum (NCA) materials. SUMMARY

[0003] In at least one aspect, a positive electrode active material is provided. The positive electrode active material includes a compound represented by the formula Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b (1) where M is Co, Cr or a combination thereof, NW +6 , Ta +5 , V+5 or a combination thereof, 0 ≤ a ≤ 0.02, 0 ≤ b ≤ 0.1, 0 < c < 0.01, 0 ≤ x ≤ 0.1 and 0 ≤ y ≤ 0.04.

[0004] In another aspect, a positive electrode for a lithium-ion battery is provided. The positive electrode includes a positive electrode active material comprising a compound represented by the chemical formula Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x - y N y O (2-b) F b where M is Co, Cr or a combination thereof, NW +6 , Ta +5 , V +5 or a combination thereof, 0 ≤ a ≤ 0.02, 0 ≤ b ≤ 0.1, 0 < c < 0.01, 0 ≤ x ≤ 0.1 and 0 ≤ y ≤ 0.04.

[0005] In another aspect, a rechargeable lithium-ion battery is provided that includes at least one lithium-ion battery cell. Each lithium-ion battery cell includes a positive electrode comprising a compound represented by the formula Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b shown, a negative electrode including a negative electrode active material, and an electrolyte, wherein M is Co, Cr or a combination thereof, NW +6 , Ta +5 , V +5 or a combination thereof, 0 ≤ a ≤ 0.02, 0 ≤ b ≤ 0.1, 0 < c < 0.01, 0 ≤ x ≤ 0.1, 0 ≤ y ≤ 0.04. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] For a fuller understanding of the nature, objects, and advantages of the present disclosure, reference should be made to the following detailed description taken in conjunction with the following drawings, in which like reference numerals designate like elements and in which: Fig. 1A is a schematic cross-sectional view of a positive electrode including a cathode active material on a single side of a current collector; Fig. Figure 1B is a schematic cross-sectional view of a positive electrode including a cathode active material on both sides of a current collector. Fig. Figure 2 is a schematic cross-sectional view of a battery cell showing the positive electrode of Fig. 1A includes; and Fig. 3 is a schematic cross-sectional view of a battery pack containing the battery cells of Fig. 2 includes. DETAILED DESCRIPTION

[0007] Reference will now be made in more detail to presently preferred compositions, embodiments, and methods of the present invention, illustrating the best modes presently known to the inventors for carrying out the invention. The figures are not necessarily to scale. It should be understood, however, that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed in this specification 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.

[0008] Furthermore, unless expressly stated otherwise in the examples or elsewhere, all numerical quantities in this specification indicating amounts of material or reaction and / or use conditions are to be understood as modified by the word "about" in describing the broadest scope of the invention. In general, reaction within the stated numerical limits is 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.), then that substituent is attributed to a more general chemical structure that includes the given structure; percent, "parts of," and ratios are by weight; the term "polymer" includes "oligomer," "copolymer," "terpolymer," and the like.Molecular weights provided for any polymers refer to the weight average molecular weight unless otherwise indicated; a description of a group or class of materials as suitable or preferred for a particular purpose in connection with the invention means that mixtures of any two or more of the members of the group or class are equally suitable or preferred; a description of components in chemical terms refers to the components at the time of addition to any combination indicated in the description and does not necessarily preclude chemical interactions between the components of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses of the same abbreviation herein and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation.and, unless expressly stated to the contrary, the measurement of a property is determined by the same technique referred to above or below for the same property.;

[0009] It should be noted that the singular forms "a," "an," and "the" used in the description and the appended claims include plural references unless the context clearly indicates otherwise. For example, a reference to a component in the singular is intended to include a plurality of components.

[0010] As used in this specification, the term "about" means that the amount or value in question may be the specifically stated value or some other value close to it. In general, the term "about," when denoting a particular value, is intended to denote a range within + / - 5% of the value. As an example, the phrase "about 100" denotes a range of 100 + / - 5, i.e., the range from 95 to 105. In general, when the term "about" is used, it can be expected that similar results or effects can be obtained according to the invention within a range of + / - 5% of the stated value. In the present context, the term "and / or" means that either all or only one of the elements of this group may be present. For example, "A and / or B" means "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 not present, i.e.,i.e. “only A, but not B”.

[0011] 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 in this specification is used only for the purpose of describing specific embodiments of the present invention and is not intended to be limiting in any way.

[0012] The term "comprising" is synonymous with "including," "having," "containing," or "characterized by." These terms are inclusive and open-ended and do not exclude additional, unstated elements or process steps. The phrase "consisting of" excludes any element, step, or ingredient not recited in the claim. When this phrase appears in a body section of a claim, rather than immediately following the preamble, it limits only the element recited in that section; other elements are not excluded from the claim as a whole. The phrase "consisting essentially of" limits the scope of a claim to the recited materials or steps, plus those that do not substantially 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 indicate that an object is formed from a material. With respect to the phrases "comprising," "consisting of," and "consisting essentially of," when any of these three phrases are used herein, the presently disclosed and claimed subject matter may include the use of any of the other two phrases. The phrase "one or more" means "at least one," and the phrase "at least one" means "one or more." The phrases "one or more" and "at least one" include "plurality" as a subset. When refined, "one or more" includes "two or more." The phrases "essentially," "generally," or "about" may be used in this specification to describe disclosed or claimed embodiments.The term "substantially" may modify a value or relative property disclosed or claimed in the present disclosure. In such cases, "substantially" may mean that the value or relative property it modifies is within ± 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, or 10% of the value or relative property.

[0013] It is also understood that integer ranges explicitly include all intermediate 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. Likewise, if an arbitrary range is required, intermediate numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be used 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.

[0014] When referring to a numerical quantity, the expression "less than" in one refinement includes a lower non-inclusive limit that is 5 percent of the number specified after "less than." For example, "less than 20" includes a lower non-inclusive limit of 1. Therefore, this refinement, "less than 20," includes a range between 1 and 20. In another refinement, the expression "less than" includes a lower non-inclusive limit that is, in ascending order of preference, 20 percent, 10 percent, 5 percent, or 1 percent of the number specified after "less than."

[0015] The term “positive electrode” refers to a battery cell electrode from which current flows when the lithium-ion battery cell or battery is discharged. Sometimes a “positive electrode” is referred to as a “cathode.” The term “negative electrode” refers to a battery cell electrode into which current flows when the lithium-ion battery cell is discharged. Sometimes a “negative electrode” is referred to as an “anode.” The term “cell” or “battery cell” refers to an electrochemical cell made from at least one positive electrode, at least one negative electrode, an electrolyte, and a separator membrane. The term “battery” or “battery pack” refers to an electrical storage device made from at least one battery cell. In an improvement, a “battery” or “battery pack” is an electrical storage device made from a plurality of battery cells.The term "specific capacity" refers to the capacity per unit mass of the active anode. Specific capacity is expressed in milliampere-hours / gram (mAh / g).

[0016] There are intrinsic problems with current LMR material compositions, such as voltage drop 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.

[0017] The present disclosure provides compositions for lithium-manganese-rich (LMR) cathodes used in lithium-ion batteries. Performance issues associated with conventional LMR compositions can include voltage drop during cycling, reduced rate capability over consecutive cycles, and poor cycling performance. These issues can be mitigated by optimizing the LMR composition.

[0018] In one embodiment of this disclosure, the LMR composition is optimized to have a lower Li content (Li2MnO3) than conventional compositions. This modification improves cycling performance, power performance, and rate capability by enhancing the voltage drop and electronic and ionic conductivity of the LMR. However, it is recognized that a lower Li content typically results in lower capacity than conventional LMR.

[0019] To address this potential capacity reduction, the LMR composition is further modified to incorporate more nickel (Ni) with an optimized content of cobalt (Co) or chromium (Cr), with a focus on cobalt. This modified composition series increases the capacity of Ni and Co by controlling the average oxidation state of the Ni ion. An optimized Co content also supports the enhancement of electronic and ionic conductivity.

[0020] In one embodiment, the general formula of the new LMR composition is Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b where M can be Co, Cr or a combination thereof and NW +6 , Ta +5 , V +5or a combination thereof. The average oxidation state of the Ni ion is controlled to 2.0. The average oxidation state of the Mn ion is controlled by controlling the F (fluorine) doping content between 3.7 and 4.0, where "b" is again a value between 0 and 0.1.

[0021] In the LMR composition Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b represents F, the Li 1,1 in the formula, represents an optimized lithium content that promotes cycling, reduces voltage drop, and increases power performance. The configuration also allows for near-maximum actual capacity to be achieved by manipulating the amounts of Ni 3+ and Co 3+ -ions within the composition.

[0022] An optimal co 3+-content within this formula also serves to enhance electronic conductivity and performance. In this composition, the Co 3+ content is further limited to between 0 and 0.06, a constraint that helps balance performance metrics such as capacity and power against production. This formula also allows for a wider range of increase achieved by the increased integration of Mn 3+ This is achieved by F - -doping, which effectively lowers the oxidation state of Mn, resulting in an increase in the presence of Mn 3+ -ions.

[0023] A higher initial Coulomb efficiency (ICE), resulting in increased discharge capacity, is another notable advantage. This increased ICE is associated with better structural stability after initial charging, due to a strong metal-fluoride (Me-F) bond in the composition. Additionally, the increased Mn 3+ -content further increases the electronic conductivity. With respect to the Mn 3+ -content and the ICE, this adaptation shows enhancements compared to previously known compositions.

[0024] In another embodiment, the general formula of the new LMR composition is Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b where M can be Co or Cr or a combination thereof and NW +6 , Ta +5 , V +5or a combination thereof. Here, "x" is a variable value between 0 and 0.1, which defines the proportion of M in the composition. The average oxidation state of the Ni ion is controlled at 2, while the average oxidation state of the manganese (Mn) ion is controlled between 3.7 and 4.0 by controlling the fluorine (F) doping content "b," which ranges between 0 and 0.1.

[0025] The LMR composition Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b , which begins with F - -doping has several advantages. It has been found that Li 1,1 an optimized Li content to achieve a good cycle, a good voltage drop and a good power performance. The maximum actual capacity is determined in the composition Li 1,1 by controlling the level of Ni 3+ and Co 3+ In addition, the optimized Co3+ -content increases electronic conductivity, which leads to better performance.

[0026] A limited co 3+ -content, between 0 and 0.1, is advantageous in controlling performance, i.e., capacity and power. A larger increase range is associated with a higher integration of Mn 3+ accessible, since F - can lower the Mn oxidation state. A higher initial Coulombic efficiency (ICE) can lead to higher discharge capacity because better structural stability is achieved after the first charge due to a strong metal-fluoride bond (Me-F bond). In addition, higher Mn 3+ the electronic conductivity. A higher Mn 3+ -Salary and a higher ICE lead to an overall increase in performance.

[0027] With reference to Fig. 1 provides a schematic of a positive electrode including a positive electrode active material. The positive electrode 10 includes a positive electrode active material layer 12 disposed over and typically contacting a positive electrode current collector 14. Typically, the positive electrode current collector 14 is a metal plate or metal foil composed of a metal such as aluminum, copper, platinum, zinc, titanium, and the like. Currently, aluminum is most commonly used for the positive electrode current collector. The positive electrode active material is represented by Formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y O (2-b) F b (1) where: M is Co, Cr or a combination thereof; NW +6 , Ta + ', V +s or a combination thereof; 0 ≤ a ≤ 0.02; 0 < b < 0.01; 0 ≤ c ≤ 0.1; 0 < x < 0.1; and 0 ≤ y ≤ 0.04.

[0028] A specific active electrode composition can be Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y O (2-b) F b where M can be Co, Cr or a combination thereof and NW +6 , Ta +5 , V +5 or a combination thereof. The average oxidation state of the Mn ion is controlled to 2. The average oxidation state of the Mn ion is controlled by controlling the F doping content between 3.7 and 4.0, where "b" is again a value between 0 and 0.1.

[0029] Another LMR composition is called Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y O (2-b) F b where M can be Co or Cr or a combination thereof and NW +6 , Ta +5 , V +5 or a combination thereof and NW+6 , Ta +5 , V +5 or a combination thereof. Here, "x" is a variable value between 0 and 0.1, which defines the proportion of M in the composition.

[0030] The average oxidation state of the Ni ion is controlled to 2.0, while the average oxidation state of the manganese (Mn) ion is controlled between 3.7 and 4.0 by controlling the fluorine (F) doping content “b”, which is between 0 and 0.1.

[0031] With reference to Fig. 2 is a schematic representation of a rechargeable lithium-ion battery cell in which the positive electrode is made of Fig. 1. The battery cell 20 includes the positive electrode 10, as described above, a negative electrode 22, and a separator 24 disposed between the positive electrode and the negative electrode. The negative electrode 22 includes a negative electrode current collector 26 and a negative active material layer 28 disposed over and typically in contact with the negative electrode current collector 26. Typically, the negative electrode current collector 26 is a metal plate or metal foil composed of a metal such as aluminum, copper, platinum, zinc, titanium, and the like. Currently, copper is most commonly used for the negative electrode current collector 26. The battery cell 20 is immersed in an electrolyte 30 enclosed by the battery cell casing 32. The electrolyte 30 is imbibed into the separator 24.In other words, the separator 24 contains the electrolyte, which allows lithium ions to move between the negative and positive electrodes. The electrolyte 30 includes a non-aqueous organic solvent and a lithium salt. The non-aqueous organic solvent serves as a medium for transferring ions involved in the electrochemical reaction of a battery. Advantageously, the battery cell 20 can have a specific capacity of more than 150 mAh / g.

[0032] With reference to Fig. 3 is a schematic of a rechargeable lithium-ion battery in which the positive electrode is made of Fig. 1 and the battery cells from Fig. 2 are integrated. The rechargeable lithium-ion battery 40 includes at least one battery cell of the embodiment in Fig. 2. Typically, a rechargeable lithium-ion battery 40 includes at least one battery cell 20 i the design of Fig. 2. Each of the lithium-ion battery cells 20 iincludes the positive electrode 10, which includes the compound represented by formula 1, the negative electrode 22, which includes a negative active material, and the electrolyte 30, where i is an integer designation for each battery cell. The designation i ranges from 1 to nmax, where nmax is the total number of battery cells in the rechargeable lithium-ion battery 40. The electrolyte 30 includes a non-aqueous organic solvent and a lithium salt. The non-aqueous organic solvent serves as a medium for transferring ions involved in the electrochemical reaction of a battery. The plurality of battery cells can be wired in series, parallel, or a combination thereof. The voltage output from the battery 40 is provided via the connection terminals 42 and 44.Advantageously, the rechargeable lithium-ion battery 40 may have a specific capacity of more than 150 mAh / g for each battery cell therein.

[0033] With reference to the Fig. 2 and Fig. 3, the separator 24 physically separates the negative electrode 22 from the positive electrode 10, thereby preventing a short circuit while allowing the transport of lithium ions for charging and discharging. Therefore, the separator 24 may be composed of any material suitable for this purpose. Examples of suitable materials from which the separator 24 may be composed include, but are not limited to, polytetrafluoroethylene (e.g., TEFLON). ®), glass fiber, polyester, polyethylene, polypropylene, and combinations thereof. The separator 24 can be in the form of either a woven or a nonwoven fabric. The separator 24 can be in the form of a nonwoven or a woven fabric. For example, a polyolefin-based polymer separator, such as polyethylene and / or polypropylene, is typically used for a lithium-ion battery. To ensure heat resistance or mechanical strength, a coated separator includes a ceramic coating, or a polymer material can be used.

[0034] With reference to the Fig. 2 and Fig. 3, the electrolyte 30 includes a lithium salt dissolved in the non-aqueous organic solvent. Therefore, the electrolyte 30 includes lithium ions that can intercalate into the positive electrode active material during discharge and into the anode active material during charge. Examples of lithium salts include, but are not limited to, LiPF6, LiBF4, LiSbF6, LiAsF6, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiCl, LiI, LiB(C2O4)2, and combinations thereof. In a further development, the electrolyte includes the lithium salt in an amount of about 0.1 M to about 2.0 M.

[0035] With further reference to the Fig. 2 and Fig. 3, the electrolyte comprises a non-aqueous organic solvent and a lithium salt. The non-aqueous organic solvent advantageously serves as a medium for transferring ions, and in particular lithium ions, that participate in the electrochemical reaction of a battery. Suitable non-aqueous organic solvents include carbonate-based solvents, ester-based solvents, ether-based solvents, ketone-based solvents, alcohol-based solvents, aprotic solvents, and combinations thereof. Examples of carbonate-based solvents include, but are not limited to, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl methyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and combinations thereof.Examples of ester-based solvents include, but are not limited to, methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and combinations thereof. Examples of ether-based solvents include, but are not limited to, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like, and the ketone-based solvent may include cyclohexanone and the like. Examples of alcohol-based solvents include, but are not limited to, methanol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and the like. Examples of the aprotic solvent include, but are not limited to, nitriles such as R-CN (where R is a linear, branched, or cyclic C). 2-20-hydrocarbon, which may include a double bond, an aromatic ring, or an ether bond), amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, and the like. Advantageously, the non-aqueous organic solvent may be used alone. In other variations, mixtures of the non-aqueous organic solvent may be used. Such mixtures are typically formulated to optimize battery performance. In one improvement, a carbonate-based solvent is prepared by mixing a cyclic carbonate and a linear carbonate. In one variation, the electrolyte 30 may further include vinylene carbonate or an ethylene carbonate-based compound to increase battery life.

[0036] With reference to the Fig. 1, Fig. 2 and Fig. 3, the negative electrode and the positive electrode can be manufactured by methods known to those skilled in the art of lithium-ion batteries. Typically, an active material (e.g., the positive or negative active material) is mixed with a conductive material and a binder in a solvent (e.g., N-methylpyrrolidone) to form an active material composition, and the composition is applied to a current collector. The electrode manufacturing process is well known and thus will not be described in detail in this specification. The solvent includes, among others, N-methylpyrrolidone and the like.

[0037] With reference to the Fig. 1, Fig. 2 and Fig. 3, the positive electrode active material layer 12 includes the positive electrode active material represented by Formula 1, a binder, and a conductive material. The binder can enhance the bonding properties of the positive electrode active material particles to each other and to the positive electrode current collector 14. Examples of suitable binders include, but are not limited to, polyvinyl alcohol, carboxylmethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, a styrene-butadiene rubber, an acrylate-styrene-butadiene rubber, an epoxy resin, nylon, and the like, and combinations thereof. The conductive material provides electrical conductivity to the positive electrode 10.Examples of suitable electrically conductive materials include, but are not limited to, natural graphite, synthetic graphite, carbon black, acetylene black, Ketjen black, carbon fibers, copper, metal powders, metal fibers, and combinations thereof. Examples of metal powders and metal fibers are composed of nickel, aluminum, silver, and the like.

[0038] With reference to the Fig. 1, Fig. 2 and Fig.3, the negative active material layer 26 includes a negative active material, a binder, and optionally a conductive material. The negative active materials used in this document may be those negative materials known to those skilled in the art of lithium-ion batteries. Negative active materials include, but are not limited to, carbon-based negative electrode active materials, silicon-based negative electrode active materials, and combinations thereof. A suitable carbon-based negative active material may include graphite and graphene. A suitable silicon-based negative active material may include at least one selected from silicon, silicon oxide, silicon oxide coated with conductive carbon on the surface, and silicon (Si) coated with conductive carbon on the surface. For example, silicon oxide may be represented by the formula SiO zwhere z is 0.09 to 1.1. Mixtures of carbon-based negative active materials or silicon-based negative active materials can also be used for the negative active material.

[0039] The negative electrode binder enhances the bonding properties of the negative active material particles to each other and to a current collector. The binder can be a non-aqueous binder, an aqueous binder, or a combination thereof.

[0040] Examples of non-aqueous binders may include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamide-imide, polyimide, or a combination thereof. Aqueous binders may be rubber-based binders or polymer resin binders. Examples of rubber-based binders include, but are not limited to, styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluororubber, and combinations thereof.Examples of polymer resin binders include, but are not limited to, polyethylene, polypropylene, ethylene-propylene copolymer, polyethylene oxide, polyvinylpyrrolidone, epichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, ethylene-propylene-diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, a polyester resin, an acrylic resin, a phenolic resin, an epoxy resin, polyvinyl alcohol, and combinations thereof.

[0041] Although exemplary embodiments are described above, these embodiments are not intended to describe all possible forms of the invention. Rather, the terms used in the description are terms 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. Moreover, the features of various implementing embodiments may be combined to form further embodiments of the invention.

[0042] According to the present invention, there is provided a positive electrode active material for lithium-ion batteries comprising a compound represented by the chemical formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b (1) where M is Co, Cr or a combination thereof; NW +6 , Ta +5 , V +5 or a combination thereof; 0 ≤ a ≤ 0.02; 0 < c < 0.01; 0 ≤ x ≤ 0.1; 0 ≤ y ≤ 0.04; and 0 ≤ b ≤ 0.1.

[0043] According to one embodiment, a = 0 and c = 0.01.

[0044] According to one embodiment, a = 0.1 and c = 0.

[0045] According to one embodiment, the average oxidation state of Mn is controlled between 3.7 and 4.0.

[0046] According to the present invention, a positive electrode for a lithium-ion battery, the positive electrode is provided as having a positive electrode active material comprising a compound represented by the chemical formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b (1) where M is Co, Cr or a combination thereof; NW +6 , Ta +5 , V +5 or a combination thereof; 0 ≤ a ≤ 0.02; 0 < c < 0.01; 0 ≤ x ≤ 0.1; 0 ≤ y ≤ 0.04; and 0 ≤ b ≤ 0.1.

[0047] According to one embodiment, a = 0 and c = 0.01.

[0048] According to one embodiment, a = 0.1 and c = 0.

[0049] According to one embodiment, the average oxidation state of Mn is between 3.7 and 4.0.

[0050] According to the present invention, there is provided a rechargeable lithium-ion battery comprising at least one lithium-ion battery cell, each lithium-ion battery cell including a positive electrode comprising a positive electrode active material as represented by Formula 1.

[0051] According to the present invention, there is provided a rechargeable lithium-ion battery comprising at least one lithium-ion battery cell, each lithium-ion battery cell including: a positive electrode comprising a positive electrode active material as represented by the formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y N y O (2-b) F b (1) where M is Co, Cr or a combination thereof; NW +6 , Ta +5 , V +5or a combination thereof; 0 ≤ a ≤ 0.02; 0 < c < 0.01; 0 ≤ x ≤ 0.1; 0 ≤ y ≤ 0.04; 0 ≤ b ≤ 0.1; a negative electrode including a negative active material; and an electrolyte.

[0052] According to one embodiment, the active material for positive electrodes is a = 0 and c = 0.01.

[0053] According to one embodiment, the active material for positive electrodes is a = 0.1 and c = 0.

[0054] According to one embodiment, the average oxidation state of the positive electrode active material of Mn is between 3.7 and 4.0.

[0055] According to one embodiment, the at least one lithium-ion battery cell is a plurality of battery cells.

[0056] According to one embodiment, each battery cell further includes a separator interposed between the positive electrode and the negative electrode.

[0057] According to one embodiment, each battery cell has a specific capacity of more than 150 mAh / g.

Claims

[1] Active material for positive electrodes for lithium-ion batteries, comprising a compound represented by the general formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y O (2-b) F b (1) where: M is Co, Cr or a combination thereof; NW +6 , Ta + ', V +s or a combination thereof; 0 ≤ a ≤ 0.02; 0 < c < 0.01; 0 ≤ x ≤ 0.1; 0 ≤ y ≤ 0.04; and 0 ≤ b ≤ 0.

1. [2] The positive electrode active material according to claim 1, wherein a = 0 and c = 0.

01. [3] The positive electrode active material according to claim 1, wherein a = 0.1 and c = 0. [4] The positive electrode active material according to claim 1, wherein the average oxidation state of Mn is controlled between 3.7 and 4.

0. [5] A positive electrode for a lithium-ion battery, wherein the positive electrode comprises a positive electrode active material comprising a compound represented by chemical formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y O (2-b) F b (1) where: M is Co, Cr or a combination thereof; NW +6 , Ta + ', V +s or a combination thereof; 0 ≤ a ≤ 0.02; 0 < c < 0.01; 0 ≤ x ≤ 0.1; 0 ≤ y ≤ 0.04; and 0 ≤ b ≤ 0.

1. [6] A positive electrode according to claim 5, wherein a = 0 and c = 0.

01. [7] A positive electrode according to claim 5, wherein a = 0.1 and c = 0. [8] The positive electrode according to claim 5, wherein the average oxidation state of Mn is between 3.7 and 4.

0. [9] A rechargeable lithium-ion battery comprising at least one lithium-ion battery cell, each lithium-ion battery cell comprising: a positive electrode comprising a positive electrode active material as represented by Formula 1. [10] A rechargeable lithium-ion battery comprising at least one lithium-ion battery cell, each lithium-ion battery cell comprising: a positive electrode comprising a positive electrode active material as represented by Formula 1: Li (1,1+a) Mn (0,51+c) Ni (0,38-x) M x-y O (2-b) F b (1) where: M is Co, Cr or a combination thereof; NW +6 , Ta + ', V +s or a combination thereof; 0 ≤ a ≤ 0.02; 0 < c < 0.01; 0 ≤ x ≤ 0.1; 0 ≤ y ≤ 0.04; 0 ≤ b ≤ 0.1; a negative electrode containing a negative active material; and an electrolyte. [11] A rechargeable lithium-ion battery according to claim 10, wherein the positive electrode active material a = 0 and c = 0.

01. [12] A rechargeable lithium-ion battery according to claim 10, wherein the positive electrode active material a = 0.1 and c = 0. [13] A rechargeable lithium-ion battery according to claim 10, wherein the average oxidation state of Mn of the positive electrode active material is between 3.7 and 4.

0. [14] A rechargeable lithium-ion battery according to claim 10, wherein the at least one lithium-ion battery cell is a plurality of battery cells. [15] A rechargeable lithium-ion battery according to claim 10, wherein each battery cell further includes a separator interposed between the positive electrode and the negative electrode.

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