DOPED CATHODE ACTIVE MATERIALS AND METHODS THEREOF

Abstract

Doped cathode active materials and methods of manufacture are described that enable energy storage devices with improved performance, including but not limited to improved energy density and capacity retention.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application is a nonprovisional application of and claims priority to U.S. Provisional Patent Application No. 63 / 266,719, entitled "DOPED CATHODE ACTIVE MATERIALS AND METHODS THEREOF," filed on January 12, 2022, and which is incorporated by reference in its entirety for all purposes.

[0002] The present disclosure relates generally to energy storage devices, and more particularly to doped cathode active materials for lithium ion batteries and processes for forming the same. [Background technology]

[0003] Electrochemical energy storage systems are widely used to power electronic, electromechanical, electrochemical, and other useful devices. Lithium-ion batteries are one of the most common examples of electrochemical energy storage systems, and the popularity of lithium-ion batteries is due to their high energy density compared to other electrochemical energy storage systems. Lithium-ion batteries consist of four main components: a cathode electrode, an anode electrode, an electrolyte, and a separator, and much of the success of lithium-ion batteries is due to the development of high energy density electrodes.

[0004] Some cathode electrodes of lithium-ion batteries are made from first row transition metal oxides, and some examples of cathode active materials include lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), and lithium iron phosphate (LFP). However, many cathode active materials have drawbacks when used in lithium-ion batteries, including a significant loss of charge capacity over repeated charge / discharge cycles. Summary of the Invention

[0005] For the purpose of summarizing the present disclosure and the advantages achieved over the prior art, certain objects and advantages of the present disclosure are described herein.Not all such objects or advantages can be achieved in any particular embodiment.Thus, for example, a person skilled in the art will recognize that the present invention can be embodied or implemented to achieve or optimize one or a group of advantages as taught herein, without necessarily achieving other objects or advantages as taught or suggested herein.

[0006] In a first aspect, a doped cathode active material is provided. The doped cathode active material has the formula Li 1+a Tm 1-a-b M b O c and Li(Tm) 2-b M b O c where Tm is a transition metal element, M is a dopant element, a is a value between 0 and 0.3, b is a value between 0 and 0.3, and c is a value between 2 and 4.

[0007] In another aspect, a doped cathode active material is provided. The doped cathode active material has the formula Li 1+a Tm 1-a-b M b O c and Li(Tm) 2-b M b O c where Tm is a transition metal element, M is a dopant element, a is a value between 0 and 0.3, b is a value between 0.001 and 0.3, and c is a value between 2 and 4.

[0008] In some embodiments, the transition metal element is selected from the group consisting of Ni, Mn, Ti, Co, and combinations thereof. In some embodiments, the transition metal element is selected from the group consisting of Ni, Mn, and combinations thereof. In some embodiments, the transition metal element is Ni x Mn 1-xwhere x is a value between 0.4 and 0.8. In some embodiments, the compound has the formula LiNi x Mn 1-x M b O2. In some embodiments, the dopant element is a metal selected from the group consisting of Al, Ca, B, Mg, Ti, Ta, Zr, Mo, W, Y, Co, Na, and combinations thereof. In some embodiments, the dopant element is a metal selected from the group consisting of Al, Ca, Mg, Ti, Ta, Co, and combinations thereof. In some embodiments, the dopant element is a metal selected from the group consisting of Al, Ca, Mg, Ti, Ta, Co, W, Zr, and combinations thereof. In some embodiments, the doped cathode active material has a tap density of at least about 2.24 g / cc. In some embodiments, the doped cathode active material has a tap density of at least about 1 g / cc. In some embodiments, a is a value between 0 and 0.15. In some embodiments, b is a value between 0.001 and 0.08.

[0009] In some embodiments, an electrode film is provided that includes a doped cathode active material. In some embodiments, the electrode film is disposed on a current collector that forms a cathode electrode. In some embodiments, an energy storage device is provided. In some embodiments, the energy storage device includes a cathode electrode, a separator, an anode electrode, an electrolyte, and a housing, where the electrolyte, the cathode electrode, the separator, and the anode electrode are disposed within the housing. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is configured to have at least about 80% discharge capacity retention after 30 cycles at a rate of C / 3. In some embodiments, the operating voltage of the energy storage device is about 4.35V.

[0010] In a second aspect, a method of preparing a doped cathode active material is provided, the method including mixing a transition metal precursor, a dopant material, and a lithium source to form an active material mixture, and heating the active material mixture to form the doped cathode active material.

[0011] In some embodiments, the dopant material comprises a plurality of nanoparticles. In some implementations, the nanoparticles have a D of less than about 100 nm. 50 In some embodiments, the dopant material comprises a plurality of particles. In some implementations, the particles have a D of about 2 μm to about 3 μm. 50 In some embodiments, the particles have a D of about 1 μm to about 5 μm. 50 In some embodiments, the dopant material is selected from the group consisting of metals, metal oxides, metal hydroxides, metal carbonates, metal bicarbonates, and combinations thereof. In some embodiments, the dopant material includes a metal element selected from the group consisting of Al, Ca, B, Mg, Ti, Ta, Zr, Mo, W, Y, Co, Na, and combinations thereof. In some embodiments, the metal element is selected from the group consisting of Al, Ca, Mg, Ti, Ta, Co, Zr, Na, W, Zr, and combinations thereof. In some embodiments, the metal element is selected from the group consisting of Al, Ca, Mg, Ti, Ta, Co, Zr, Na, and combinations thereof. In some embodiments, the dopant material is selected from the group consisting of Al2O3, Ta2O5, TiO2, Co2O3, Ta, Ca(OH)2, NaHCO3, and combinations thereof. In some embodiments, the dopant material is selected from the group consisting of Al2O3, Ta2O5, TiO2, Co2O3, WO x , Ta, Ca(OH)2, NaHCO3, and combinations thereof.

[0012] In some embodiments, the transition metal precursor is a spherical transition metal precursor. In some embodiments, the transition metal precursor is selected from the group consisting of transition metal oxides, transition metal hydroxides, transition metal carbonates, and combinations thereof. In some embodiments, the transition metal precursor comprises a transition metal element selected from the group consisting of Ni, Mn, Ti, Co, and combinations thereof. In some embodiments, the transition metal precursor comprises Ni x Mn 1-x (OH)2, Ni x Mn 1-x CO3, and combinations thereof, where x is 0.5 to 0.7.

[0013] In some embodiments, the lithium source is selected from the group consisting of LiOH.H2O, Li2CO3, and combinations thereof. In some embodiments, the molar ratio of the lithium source:dopant material is about 1:0.005 to about 1:0.1. In some embodiments, the molar ratio of the lithium source:dopant material is about 1:0.0005 to about 1:0.1. In some embodiments, the molar ratio of the transition metal precursor:dopant material is about 1:0.001 to about 1:0.1. In some embodiments, the transition metal precursor and the dopant material are premixed to form a precursor mixture, and the precursor mixture is mixed with the lithium source to form the active material mixture. In some embodiments, the lithium source is a lithium salt. In some embodiments, the lithium salt is selected from the group consisting of LiOH.H2O, Li2CO3, and combinations thereof.

[0014] In some embodiments, the precursor mixture is preheated. In some embodiments, the preheating occurs at a temperature of about 400-600° C. In some embodiments, the precursor mixture is preheated for a period of 3-7 hours. In some embodiments, the preheating occurs in an atmosphere comprising oxygen. In some embodiments, the preheating occurs in air. In some embodiments, the active material mixture is heated at a temperature of about 800-1000° C. In some embodiments, the active material mixture is heated at a temperature of about 700-1000° C. In some embodiments, the active material mixture is heated for a period of 5-15 hours. In some embodiments, the active material mixture is heated for a period of 3-15 hours. In some embodiments, the heating occurs in an atmosphere comprising oxygen. In some embodiments, the heating occurs in air. In some embodiments, the heating occurs under a gas flow.

[0015] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those of ordinary skill in the art from the following detailed description of the preferred embodiments, taken in conjunction with the accompanying figures, although the invention is not limited to any particular preferred embodiment disclosed. [Brief description of the drawings]

[0016] [Figure 1] FIG. 2 is a schematic diagram illustrating a process for forming a doped cathode active material according to some embodiments.

[0017] [Figure 2A] 1 is an SEM image of a doped cathode active material according to some embodiments.

[0018] [Figure 2B] 1A-1D are SEM images of undoped and doped cathode active materials according to some embodiments.

[0019] [Diagram 3]1 is a bar graph illustrating the effect of several dopants on normalized tap density of cathode active materials according to some embodiments.

[0020] [Figure 4] 1 is a bar graph illustrating the effect of several dopants on the normalized energy of a half-cell, according to some embodiments.

[0021] [Diagram 5] 1 is a bar graph illustrating the effect of several dopants on half-cell charge retention, according to some embodiments.

[0022] [Figure 6] 1 is a bar graph showing the effect of different amounts of dopant on first cycle efficiency in half-cell testing, according to some embodiments.

[0023] [Figure 7] 1 is a graph showing the effect of different dopants on the energy loss of a full cell, according to some embodiments. Detailed Description of the Invention

[0024] Various embodiments of doped cathode active materials having improved energy density and capacity retention, and methods of preparing doped cathode active materials are provided herein. Doping of cathode active materials, such as nickel manganese oxide cathode active materials (e.g., about 60% nickel content), can allow for improved electrode capacity and improved electron transport while minimizing the use of expensive elements such as cobalt.

[0025] In certain embodiments, the doped cathode active material comprises lithium (Li), a transition metal element (Tm), a dopant element (M), and oxygen (O). In some embodiments, the doped cathode active material comprises Li 1+a Tm 1-a-b M b O c , Li(Tm) 2-b Mb O c and combinations thereof.

[0026] In certain embodiments, the precursor mixture is formed from a transition metal precursor and a dopant material. In some embodiments, the dopant material is a metal (M), a metal oxide (M y O z ), metal hydroxide (M y (OH) z ), metal carbonates (MCO3), metal bicarbonates (MHCO3), and combinations thereof, where "M" represents a metal and "y" and "z" are values ​​that produce a neutrally charged dopant material. In some embodiments, the dopant material comprises a metal ("M") selected from aluminum (Al), calcium (Ca), boron (B), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), molybdenum (Mo), tungsten (W), yttrium (Y), cobalt (Co), sodium (Na), and combinations thereof.

[0027] In some embodiments, the precursor mixture is mixed with a lithium source and heated to form a doped cathode active material, which exhibits improved tap density. In some embodiments, a cathode electrode is formed from the doped cathode active material, and the cathode electrode is used to form an electrochemical energy storage system, which exhibits improved cycle life and energy density. The use of a dopant material in the cathode active material improves the energy and cycle life of the electrochemical energy storage system. Doped cathode active materials

[0028] The cathode active material may be doped to improve the performance of the cathode electrode. In some embodiments, the cathode active material is based on layered oxides (Li(Tm)O), spinels (Li(Tm)O), lithium-rich materials (Li 1+x (Tm) 1-xO2), and combinations thereof. In some embodiments, "x" is about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.7, 0.75, 0.8, 0.9, or 1, or any range of values ​​therebetween, or is an approximation thereof. For example, in some embodiments, "x" is a number between 0 and 1, between 0 and 0.5, or between 0 and 0.33. For example, a cathode active material as described herein may be doped with a dopant element to form a doped cathode active material. In some embodiments, the doped cathode active material includes lithium (Li), a transition metal element (Tm), a dopant element (M), and oxygen (O). In some embodiments, the doped cathode active material includes Li 1+a Tm 1-a-b M b O c , Li(Tm) 2-b M b O c and combinations thereof.

[0029] In some embodiments, the transition metal element ("Tm") is selected from nickel (Ni), manganese (Mn), titanium (Ti), cobalt (Co), and combinations thereof. In some embodiments, the transition metal element ("Tm") is selected from nickel (Ni), manganese (Mn), cobalt (Co), and combinations thereof. In some embodiments, the transition metal element ("Tm") is selected from nickel (Ni), manganese (Mn), and combinations thereof. In some embodiments, the transition metal element ("Tm") is free or substantially free of cobalt (Co).

[0030] In some embodiments, the dopant element ("M") comprises a metal selected from aluminum (Al), calcium (Ca), boron (B), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), molybdenum (Mo), tungsten (W), yttrium (Y), cobalt (Co), sodium (Na), and combinations thereof. In some embodiments, the dopant element ("M") comprises a metal selected from aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), tungsten (W), cobalt (Co), and combinations thereof. In some embodiments, the dopant element comprises a metal selected from aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), cobalt (Co), and combinations thereof. In some embodiments, the dopant element ("M") comprises a metal selected from aluminum (Al), magnesium (Mg), titanium (Ti), zirconium (Zr), and combinations thereof. In some embodiments, the dopant element ("M") comprises a metal selected from tantalum (Ta), tungsten (W), and combinations thereof. In some embodiments, the doped cathode active material comprises, at least comprises, or at most comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 dopant elements, or any range of values ​​therebetween.

[0031] In some embodiments, "a" is 0, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.12, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, and 0.5, or any range therebetween, or is an approximation thereof. For example, in some embodiments, "a" is a number between 0 and 0.5, between 0 and 0.15, or between 0 and 0.05. In some embodiments, "b" is 0, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, and 0.5, or any range therebetween, or an approximation thereof. For example, in some embodiments, "b" is a number between 0 and 0.5, between 0.001 and 0.3, or between 0.001 and 0.08. In some embodiments, "c" is 1, 2, 3, 4, or 5, or any range therebetween, or an approximation thereof. For example, in some embodiments, "c" is a number between 1 and 4, or between 2 and 4. In some embodiments, "c" is 2 or 4, or about 2 or 4. In some embodiments, the transition metal element comprises 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, or 80 mol% nickel, or any range of values ​​therebetween, or any approximate value thereof. x Mn 1-x Is it Ni? x Mn 1-xIn some embodiments, x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1, or any range therebetween, or an approximation thereof. For example, in some embodiments, "x" is a number between 0 and 0.95, between 0.45 and 0.75, between 0.55 and 0.74, or between 0.6 and 0.7. In some implementations, the doped cathode active material comprises less than about 1 atomic %, 2 atomic %, 3 atomic %, 4 atomic %, 5 atomic %, 6 atomic %, 7 atomic %, 8 atomic %, 10 atomic %, or 15 atomic % cobalt, or an approximation thereof. In some embodiments, the doped cathode active material is free of, or substantially free of, cobalt. In some embodiments, the doped cathode active material is a material having the formula LiNi x Mn 1-x M b Has O2.

[0032] In some embodiments, the doped cathode active material has a tap density of, at least at, or at least about 0.5 g / cc, 0.7 g / cc, 0.8 g / cc, 0.9 g / cc, 1 g / cc, 1.2 g / cc, 1.4 g / cc, 1.6 g / cc, 1.8 g / cc, 2 g / cc, 2.2 g / cc, 2.24 g / cc, 2.4 g / cc, 2.6 g / cc, 2.9 g / cc, 3 g / cc, or any range therebetween. In some embodiments, the doped cathode active material has a tap density of 1 g / cc or 2.24 g / cc, about 1 g / cc or 2.24 g / cc, at least 1 g / cc or 2.24 g / cc, at least about 1 g / cc or 2.24 g / cc.

[0033] In some embodiments, the doped cathode active material is comprised of a plurality of spherical particles. In some embodiments, the spherical particles have a diameter (e.g., D) of 0.1 μm, 0.5 μm, 1 μm, 2 μm, 4 μm, 8 μm, 10 μm, 15 μm, 16 μm, 20 μm, 30 μm, 32 μm, 35 μm, 40 μm, 50 μm, or 60 μm, or any range of values ​​therebetween, or an approximation thereof. 50For example, in some embodiments, the D 50 In some embodiments, the diameter of the spherical particles of the cathode active material is between about 1 μm and about 50 μm. In some embodiments, the smaller particles have a diameter (e.g., D) of 0.005 μm, 0.01 μm, 0.02 μm, 0.04 μm, 0.05 μm, 0.08 μm, 0.10 μm, 0.15 μm, 0.16 μm, 2 μm, 2.40 μm, 2.80 μm, 3.20 μm, 3.60 μm, 4 μm, 4.2 μm, 4.4 μm, 4.5 μm, 4.6 μm, 4.8 μm, 5 μm, or 6 μm, or any range of values ​​therebetween, or approximations thereof. 50 For example, in some embodiments, the smaller particles have a D 50 The diameter is about 0.01 μm to about 5 μm, about 0.01 μm to about 4 μm, about 2 μm to about 3 μm. In some embodiments, the size of the smaller particles can be adjusted by the type and amount of dopant. In some embodiments, the morphology and / or surface area of ​​the cathode active material can be modified by adding a secondary dopant in addition to adding a primary dopant and / or by controlling the amount of the secondary dopant. In some embodiments, by adding a secondary dopant and / or increasing the amount of the secondary dopant in addition to the primary dopant, the smaller particles are more densely packed and sensed.

[0034] Doped cathode active materials may be formed utilizing precursor materials, precursor mixtures, and active material mixtures. In some embodiments, the precursor mixtures are formed from transition metal precursors and dopant materials. In some embodiments, the precursor materials, precursor mixtures, and / or active material mixtures are free of, or substantially free of, cobalt. In some embodiments, the transition metal precursors are spherical transition metal precursors. In some embodiments, the transition metal precursors are metal oxides (Tm p O q ), metal hydroxides (Tm p (OH) q ), metal carbonates (Tm p (CO3)q ), and combinations thereof, where "Tm" represents a transition metal element and "p" and "q" are values ​​that produce a neutrally charged transition metal precursor. In some embodiments, the transition metal precursor comprises a transition metal element ("Tm") selected from nickel (Ni), manganese (Mn), titanium (Ti), cobalt (Co), and combinations thereof. In some embodiments, the transition metal precursor comprises a transition metal element ("Tm") selected from nickel (Ni), manganese (Mn), cobalt (Co), and combinations thereof. In some embodiments, the transition metal element ("Tm") is selected from nickel (Ni), manganese (Mn), and combinations thereof. In some embodiments, the transition metal element ("Tm") is free of or substantially free of cobalt (Co). In some embodiments, the transition metal precursor comprises a transition metal element ("Tm") selected from nickel (Ni), manganese (Mn), and combinations thereof. x Mn 1-r (OH)2, Ni r Mn 1-r CO3, and combinations thereof. In some embodiments, "r" is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1, or any range of values ​​therebetween, or an approximation thereof. For example, in some embodiments, "r" is a number between 0 and 1, between 0.55 and 0.75, between 0.45 and 0.75, or between 0.6 and 0.7. In some embodiments, the precursor mixture comprises 75%, 80%, 85%, 90%, 95%, or 100% by weight of the transition metal precursor, or any range of values ​​therebetween, or an approximation thereof.

[0035] In some embodiments, the dopant material is a metal (M), a metal oxide (M y O z ), metal hydroxide (M y (OH) z), metal carbonates (MCO3), metal bicarbonates (MHCO3), and combinations thereof, where "M" represents a metal element and "y" and "z" are values ​​that produce a neutrally charged dopant material. In some embodiments, "M" is a metal element selected from aluminum (Al), calcium (Ca), boron (B), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), molybdenum (Mo), tungsten (W), yttrium (Y), cobalt (Co), sodium (Na), and combinations thereof. In some embodiments, M is a metal element selected from aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), tungsten (W), cobalt (Co), and combinations thereof. In some embodiments, "M" is a metal element selected from aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), cobalt (Co), and combinations thereof. In some embodiments, "M" is a metal element selected from aluminum (Al), magnesium (Mg), titanium (Ti), zirconium (Zr), and combinations thereof. In some embodiments, "M" is a metal element selected from tantalum (Ta), tungsten (W), and combinations thereof. In some embodiments, the dopant material comprises a metal selected from aluminum (Al), calcium (Ca), boron (B), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), molybdenum (Mo), tungsten (W), yttrium (Y), cobalt (Co), sodium (Na), and combinations thereof. In some embodiments, the dopant material comprises a metal selected from aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), tantalum (Ta), zirconium (Zr), tungsten (W), cobalt (Co), and combinations thereof. In some embodiments, the dopant material comprises a metal selected from aluminum (Al), calcium (Ca), magnesium (Mg), titanium (Ti), cobalt (Co), and combinations thereof.In some embodiments, the dopant material comprises a metal selected from aluminum (Al), magnesium (Mg), titanium (Ti), zirconium (Zr), and combinations thereof. In some embodiments, the dopant material comprises a metal selected from tantalum (Ta), tungsten (W), and combinations thereof. In some embodiments, the dopant material comprises Al2O3, Ta2O5, TiO2, Co2O3, WO. x and combinations thereof. x is tungsten oxide, including, for example, tungsten(III) oxide, tungsten(IV) oxide, tungsten(VI) oxide, tungsten pentoxide, and combinations thereof. In some embodiments, the dopant material is a metal hydroxide, such as NaHCO3, Ca(OH)2, or Mg(OH)2. In some embodiments, the molar ratio of transition metal precursor to dopant material is 1:0.001, 1:0.002, 1:0.005, 1:0.008, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.1, or 1:0.2, or any range of values ​​therebetween or approximations thereof. In some embodiments, the dopant material is a powder. In some embodiments, the powder is a plurality of particles. In some embodiments, the particles are nanoparticles. In some implementations, the nanoparticles have a D of less than about 100 nm. 50 In some embodiments, the particles have a particle size distribution. In some embodiments, the particles are microparticles. In some embodiments, the particles have a D of about 0.5 μm, 1 μm, 1.2 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.8 μm, 2 μm, 2.2 μm, 2.4 μm, 2.5 μm, 2.7 μm, 3 μm, 3.5 μm, 4 μm, 5 μm, 6 μm, or any range therebetween or approximations thereof. 50In some embodiments, the precursor mixture comprises 0%, 1%, 2%, 3%, 5%, 7%, 10%, 15%, 20%, or 25% by weight, or any range of values ​​therebetween, or approximations thereof, of the dopant material. In some embodiments, the precursor mixture comprises 0 mol%, 0.1 mol%, 0.5 mol%, 0.8 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, or 10 mol%, or any range of values ​​therebetween, or approximations thereof, of the dopant material.

[0036] The active material mixture may include a precursor mixture and a lithium source. In some embodiments, the lithium source is a lithium salt. In some embodiments, the lithium salt is selected from LiOH.H2O, Li2CO3, and combinations thereof. In some embodiments, the molar ratio of the lithium source:dopant material is or is about 1:0.0001, 1:0.0005, 1:0.001, 1:0.002, 1:0.005, 1:0.008, 1:0.009, 1:0.01, 1:0.015, 1:0.02, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, 1:0.05, 1:0.1, or 1:0.2, or any range of values ​​therebetween. In some embodiments, the active material mixture comprises 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%, or any range of values ​​therebetween, or approximations thereof, of the lithium source. In some embodiments, the molar ratio of lithium ions in the lithium source to metal ions (including dopant metal ions and transition metal ions) in the precursor mixture is 0.8:1, .085:1, 0.9:1, 1:1, 1:1.001, 1:1.005, 1:1.01, 1:1.05, 1:1.08, 1:1.1, 1:1.15, 1:1.2, 1:1.25, 1:1.28, 1:1.3, 1:1.35, 1:1.4, or any range of values ​​therebetween, or approximations thereof. In some embodiments, the ratio of lithium source to dopant material is based on the intended formula of the doped cathode active material. Formation process of doped cathode active material

[0037] The precursor materials, precursor mixture, and active material mixture are processed to form a doped cathode active material. Figure 1 is a flow chart 100 illustrating an example of a doped cathode active material formation process according to some of the embodiments. A transition metal precursor 102 and a dopant material 104 are provided and combined (e.g., mixed) in process step 106 to form a precursor mixture 108. The precursor mixture 108 is combined (e.g., mixed) with a lithium source 110 in process step 112 to form an active material mixture 114. The active material mixture 114 is heated (e.g., high temperature calcination) in process step 116 to form a doped cathode active material 118.

[0038] In some embodiments, the precursor mixture is preheated after it is formed. In some embodiments, the preheating occurs before the precursor mixture is combined (e.g., mixed) with a lithium source to form the active material mixture. In some embodiments, the preheating occurs at a temperature of 400° C., 420° C., 440° C., 460° C., 480° C., 500° C., 520° C., 540° C., 560° C., 580° C., 600° C., 625° C., 650° C., 700° C., 800° C., or 1000° C., or any range of values ​​therebetween, approximations thereof, at least approximations thereof, or at least approximations thereof. In some embodiments, the preheating occurs in an oxidizing atmosphere or gas, an inert atmosphere or gas, or a reducing atmosphere or gas. In some embodiments, the oxidizing atmosphere is an atmosphere that includes oxygen, such as, for example, air or an oxygen-rich atmosphere. In some embodiments, the oxygen-rich atmosphere includes at least 21% oxygen by volume, at least 23.5% oxygen by volume, or at least 25% oxygen by volume. In some embodiments, the inert atmosphere is an atmosphere containing helium, neon, argon, krypton, xenon, radon, nitrogen, and combinations thereof. In some embodiments, the reducing atmosphere is an atmosphere containing hydrogen, carbon monoxide, hydrogen sulfide, and combinations thereof. In some embodiments, the preheating is performed for a period of time of 0, 1, 2, 3, 4, 5, 7, 10, 11, 12, 15, 17, 19, or 20 hours, or any range of values ​​therebetween, approximations thereof, at least approximations thereof, or at least approximations thereof. In some embodiments, no preheating is performed after forming the precursor mixture.

[0039] In some embodiments, the active material mixture is heated after it is formed. In some embodiments, the heating is at a temperature of 600° C., 650° C., 700° C., 725° C., 750° C., 760° C., 780° C., 800° C., 820° C., 840° C., 850° C., 860° C., 880° C., 900° C., 950° C., 1000° C., 1050° C., 1100° C., 1150° C., or 1200° C., or any range of values ​​therebetween, at or near, at or near the temperature. In some embodiments, the heating of the active material mixture is in an oxidizing atmosphere, an inert atmosphere, or a reducing atmosphere. In some embodiments, the heating temperature is higher than the preheat temperature. In some embodiments, the oxidizing atmosphere is an atmosphere that includes oxygen, such as, for example, air or an oxygen-rich atmosphere. In some embodiments, the oxidizing atmosphere is an oxygen atmosphere or oxygen gas. In some embodiments, the oxygen-rich atmosphere comprises at least 21% oxygen by volume, at least 23.5% oxygen by volume, or at least 25% oxygen by volume. In some embodiments, the inert atmosphere is an atmosphere comprising helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof. In some embodiments, the reducing atmosphere is an atmosphere comprising hydrogen, carbon monoxide, hydrogen sulfide, or a combination thereof. In some embodiments, the heating is performed under a gas flow. In some embodiments, the gas comprises an oxidizing gas, an inert gas, or a reducing gas. In some embodiments, the heating is performed for a period of time of 0, 1, 2, 3, 4, 5, 7, 8, 9, 10, 11, 12, 15, 17, 19, 20, 30, 35, 40, 45, or 50 hours, or any range of values ​​therebetween, approximations thereof, at least approximations thereof, or at least approximations thereof. In some embodiments, the active material mixture is sintered during heating.

[0040] In some embodiments, the process further includes breaking down the doped cathode active material. In some embodiments, breaking down includes a step selected from crushing, grinding, and combinations thereof. In some embodiments, the process includes treating the doped cathode active material. In some embodiments, treating includes a step selected from sieving, washing, filtering, drying, coating, and combinations thereof. Energy Storage Device

[0041] The doped cathode active material can be used to prepare an electrode for an energy storage device. In some embodiments, an electrode film (e.g., a doped electrode film) comprises the doped cathode active material. In some embodiments, an electrode comprises a current collector and an electrode film (e.g., a doped electrode film). In some embodiments, the electrode is a cathode electrode (e.g., a doped cathode electrode).

[0042] In some embodiments, the energy storage device includes a doped cathode active material as described herein. In some embodiments, the energy storage device includes a separator, an anode electrode, a cathode electrode (e.g., a doped cathode electrode), an electrolyte, and a housing, where the electrolyte, separator, anode electrode, and cathode electrode are disposed within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is formed by disposing an electrolyte, separator, anode electrode, and cathode electrode as described herein within the housing, and the separator is disposed between the anode electrode and the cathode electrode. In some embodiments, the energy storage device is a battery. In some embodiments, the energy storage device is a lithium ion battery. In some embodiments, the energy storage device includes an anode electrode sandwiched by two cathode electrodes.

[0043] In some embodiments, the energy storage device is configured to have a discharge capacity retention of, at least about, or at least about 70%, 75%, 80%, 83%, 85%, 90%, 95%, 98% or 99%, or any range of values ​​therebetween, after 30 cycles at a C / 2, C / 3 or C / 5 rate. In some embodiments, the energy storage device is configured to have a charge capacity retention of, at least about, or at least about 70%, 75%, 80%, 83%, 85%, 87%, 90%, 95%, 96%, 97%, 98% or 99%, or any range of values ​​therebetween, after 30 cycles at a C / 2, C / 3 or C / 5 rate. In some embodiments, the energy storage device is configured to have an energy loss of, about, less than, or about 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, or 3%, or any range therebetween, after 200 cycles at a charge rate of C / 2, C / 3, or C / 5. In some embodiments, the energy storage device is configured to have an energy loss of, about, less than, or about 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, or 3%, or any range therebetween, after 200 cycles at a discharge rate of C / 2, C / 3, or C / 5. In some embodiments, the energy storage device is configured to have a first cycle efficiency of, at or near 80%, 82%, 84%, 85%, 87%, 89%, 90%, 92%, 94%, 95%, 96% or 97%, or any range therebetween, at a charge rate of C / 2, C / 3 or C / 5. In some embodiments, the energy storage device is configured to have a first cycle efficiency of, at or near 80%, 82%, 84%, 85%, 87%, 89%, 90%, 92%, 94%, 95%, 96% or 97%, or any range therebetween ...

[0044] In some embodiments, the operating voltage of an energy storage device having a cathode including a doped cathode active material is 4.2V, 4.25V, 4.3V, 4.35V, 4.4V, 4.45V, 4.5V, 4.55V, or 4.6V, or any range of values ​​therebetween, approximations thereof, or at least approximations thereof. In some embodiments, the operating voltage of an energy storage device having a cathode including a doped cathode active material is higher than a normal operating voltage (e.g., 4.2V). The higher operating voltage can increase the energy density and charge and discharge rates of the energy storage device. In some embodiments, the higher operating voltage is at least partially related to the nickel content in the doped cathode active material. In some embodiments, the nickel content is about 40 mol% to about 80 mol% among transition metal elements to achieve a higher than normal operating voltage. EXAMPLES

[0045] Exemplary embodiments of the disclosure, including processes, materials, and / or resulting products, are described in the following examples. Example 1

[0046] 2A is a SEM image of a doped cathode active material according to some embodiments. FIG 2A shows that the doped cathode active material is composed of a plurality of spherical particles. FIG 2A also shows that the spherical particles are aggregates of smaller particles.

[0047] FIG. 2B is a SEM image of cathode active material with no dopant, doped with 1% Ta, doped with 1% Ta and 0.2% W, and doped with 1% Ta and 0.8% W, respectively. As shown in FIG. 2B, the morphology and surface area of ​​the cathode active material can be modified by adding a secondary dopant in addition to the primary dopant and / or controlling the amount of the secondary dopant. From FIG. 2B, it can be seen that the smaller particles that form the spherical particles of the cathode active material become more closely packed and denser with increasing addition and amount of secondary dopant. Example 2

[0048] Doped and undoped cathode active materials were prepared and their tap densities were compared. 0.65 Mn 0.35 The (OH2)2 transition metal precursor was mixed with 1 mol% TiO2 (i.e., 1 mol% Ti) or 1 mol% Co2O3 (i.e., 1 mol% Co) dopant material in a molar ratio of 1:0.009 to form a precursor mixture, and undoped transition metal precursors were also prepared. Some of the precursor mixtures were prebaked at about 500°C in air or O2 for 3 hours, and some of the precursor mixtures were not prebaked. The prebaked precursor mixtures, the unprebaked precursor mixtures, or the undoped transition metal precursor were mixed with a Li2CO3 lithium source in a molar ratio of 1:0.009 to form an active material mixture. The active material mixtures were heated at 880-940°C for 5-15 hours (e.g., 10 hours) under air or O2 flow. The heated active material mixture is ground and sieved to produce doped and undoped cathode active materials, the titanium doped active material being LiNi 0.643 Mn 0.347 Ti 0.01 The O2-containing, cobalt-doped active material is LiNi 0.643 Mn 0.347 Co 0.01 FIG. 3 shows the normalized tap density of the cathode active materials prepared with no dopant, 1 mol% Ti, or 1 mol% Co dopant by pre-baking the precursor mixture. As can be seen from FIG. 3, the tap density of the doped cathode active materials with 1 mol% Ti or 1 mol% Co was higher than the cathode active material without dopant. The cathode active materials prepared without pre-baking the precursor mixture showed similar results to those shown in FIG. 3. Example 3

[0049] Doped and undoped cathode active materials formed with and without the prebaked precursor mixture were prepared using a process similar to that described in Example 2, where 1 mol% Al2O3, 1 mol% Ca(OH)2, 1 mol% Mg (e.g., Mg(OH)2), 1 mol% TiO2 or 1 mol% Co2O3 dopant materials were used to dope the cathode active materials. The doped or undoped cathode active materials were mixed with carbon black and PVDF (poly-(vinylidene fluoride)) in N-methyl-2-pyrrolidone to form a slurry. The mass ratio of cathode active material:carbon black:PVDF was 90:5:5. The slurry was cast onto aluminum foil, vacuum dried, and then roll pressed to form a 14 mm cathode electrode disk. The loading of the cathode active material was about 13 mg / cm 2 and the density of the cathode electrode was approximately 3 g / cc. A half-cell coin cell was fabricated using a 14 mm cathode electrode disk and a lithium metal disk as the anode electrode. The coin cell was assembled in an argon-filled glove box by placing the 14 mm disk on top of the large coin cell can, followed by stacking the separator, lithium metal disk, spacer, spring, and then the small coin cell can together in that order. 80 μL of 1 M LiPF6 in a 1:4 mass fluoroethylene carbonate / dimethyl carbonate (FEC / DMC) electrolyte solution was added between the large and small coin cell cans. Finally, the large and small coin cell cans were crimped with a coin cell crimper to form a seal.

[0050] The coin cells were tested using an Arbin cycler and placed in a temperature controlled chamber at 25°C to ensure that the test environment was maintained at a constant temperature during testing. After the coin cells were allowed to sit for 3 hours, they were then charged and discharged at a constant rate of C / 20 for one cycle. After charging, a CV hold process was applied until the current reached C / 50, after which the coin cells were charged and discharged at a constant rate of C / 3 for 30 cycles. Then, a CV hold process was applied at the end of each charge until the current reached C / 20. Finally, the coin cells were charged and discharged at a constant rate of C / 20 for one cycle, followed by a CV hold until the current reached C / 50 after charging.

[0051] 4 and 5 show normalized energy and charge retention results for coin cells described herein having cathodes prepared with 1 mol% Al, 1 mol% Ca, 1 mol% Mg, 1 mol% Ti, and 1 mol% Co dopants without pre-baking the precursor mixture. As can be seen in FIG. 4 and FIG. 5, the energy and capacity retention of the coin cells containing the dopant materials were improved, respectively, compared to the cells without the dopant. The coin cells having cathodes prepared without pre-baking the precursor mixture showed similar results to those shown in FIG. 4 and FIG. 5.

[0052] FIG. 6 shows the first cycle efficiency of coin cells described herein prepared without pre-baking the precursor mixture and having cathodes containing cathode active materials with no Ca dopant, 0.125 mol% Ca, 0.25 mol% Ca, 0.5 mol% Ca, 1 mol% Ca or 3 mol% Ca dopant. In addition to the Ca dopant, each of the cathode active materials also contained 1 mol% Ta and 0.4 mol% Ti as dopants. As can be seen from FIG. 6, the first cycle efficiency of the coin cells is improved by including 0.125 mol% Ca, 0.25 mol% Ca, and 0.5 mol% Ca dopant compared to without the Ca dopant. Example 4

[0053] Full cells (i.e., pouch cells) containing cathode electrodes containing undoped or doped cathode active materials prepared without pre-baking the precursor mixture were prepared and tested. The cathode electrodes for the full cells had a mass ratio of cathode active material:carbon black:PVDF of 96:2:2 and a loading of cathode active material of approximately 18 mg / cm. 2 The cathode electrodes were prepared similarly to those prepared for the half-cells discussed in Example 3, except that the density of the cathode electrodes was about 3 g / cc. The cathode electrodes were formed on a 54×54 mm disk. Graphite was used as the anode. A full cell was prepared by sandwiching the anode electrode with two cathode electrodes and wrapping each electrode with a separator to form an electrode stack. The stack was then sealed in a pouch bag filled with 1.5 g of electrolyte. The electrolyte was formed by dissolving 0.9 M LiPF6 and 0.3 M LiFSI in an electrolyte solution of 25:5:70 ethylene carbonate / ethyl methyl carbonate / dimethyl carbonate (EC / EMC / DMC) by mass. The pouch bag was sealed with a hot seal machine. The full cell was then washed with isopropane wipes. The full cell was assembled in a dry room with a dew point of −25° C.

[0054] All cells were tested using an Arbin cycler and placed in a temperature controlled chamber at 40°C to ensure that the test environment was maintained at a constant temperature during testing. All cells were formed by going through a formation process before testing. All cells were first charged to 3.0V at a constant rate of C / 50, and a CV hold process was applied to all cells for 8 hours. All cells were then charged to 4.055V at a constant rate of C / 5, and a CV hold process was applied to all cells until the current reached C / 20, after which all cells were left for 12 hours. All cells were formed after charging and discharging at a rate of C / 20.

[0055] After the formation process, all cells were first tested by charging and discharging at a constant rate of C / 2 for one cycle, and a CV hold process was applied to all cells until the current reached C / 50 after charging. Then, the cells were charged and discharged at a constant rate of C / 2 for 200 cycles, and a CV hold process was applied to all cells until the current reached C / 20 at the end of each charging process.

[0056] FIG. 7 shows that the percentage energy loss results for full cells described herein having cathodes containing no dopant, 1 mol% Zr dopant, 1 mol% Zr and 1 mol% Ti dopant, 1 mol% Zr, 1 mol% Ti and 1 mol% Al dopant, or 1 mol% Zr, 1 mol% Ti, 1 mol% Al and 1 mol% Mg dopant are 19.5%, 12%, 6.5%, and 4.8%. As seen in FIG. 7, the energy loss of full cells containing different types and amounts of dopant materials was reduced compared to the energy loss of full cells containing no dopant. Furthermore, the energy loss of full cells was reduced to less than 20% with a single dopant after 200 cycles, the energy loss of full cells was reduced to less than 15% with two dopants after 200 cycles, and the energy loss of full cells was reduced to less than 10% with three or four different dopants after 200 cycles.

[0057] Although specific embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications may be made in the systems and methods described herein without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure.

[0058] A feature, material, characteristic, or group described in connection with a particular aspect, embodiment, or example should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless inconsistent therewith. All of the features disclosed herein (including any accompanying claims, abstract, and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive. Protection is not limited to the details of any of the foregoing embodiments. Protection extends to any novel one or any novel combination of features disclosed herein (including any accompanying claims, abstract, and drawings), or any novel one or any novel combination of steps of any method or process so disclosed.

[0059] Furthermore, certain features described in the present disclosure in the context of separate implementations may be implemented in combination in a single implementation. Conversely, various features described in the context of a single implementation may also be implemented in multiple implementations separately or in any suitable subcombination. Furthermore, although features may be described above as acting in a particular combination, one or more features from a claimed combination may, in some cases, be deleted from the combination, and the combination may be claimed as a subcombination or a variation of the subcombination.

[0060] Moreover, although operations may be shown in the figures or described herein in a particular order, such operations need not be performed in the particular order shown, or in sequential order, or all operations need not be performed to achieve desired results. Other operations not shown or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between any of the described operations. Furthermore, operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the figures. Depending on the embodiment, certain of the above-described steps may be omitted and other steps may be added. Furthermore, the features and attributes of certain embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Also, it should be understood that the separation of various system components in the above-described implementations should not be understood as requiring such separation in all implementations, and the described components and systems may generally be integrated into a single product or packaged into multiple products. For example, any of the components for the energy storage system described herein may be provided separately or may be integrated (e.g., packaged together or attached together) to form the energy storage system.

[0061] For the purpose of this disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages can be achieved according to any particular embodiment. Thus, for example, a person skilled in the art will recognize that the present disclosure can be embodied or implemented to achieve one advantage or group of advantages as taught herein, without necessarily achieving other advantages as taught or suggested herein.

[0062] Conditional language such as "can," "could," "might," or "may," unless otherwise specified or understood otherwise within the context in which it is used, is generally intended to convey that certain embodiments include certain features, elements, and / or steps, but other embodiments do not. Thus, such conditional language does not generally imply that the features, elements, and / or steps are in any way required by one or more embodiments, or that one or more embodiments necessarily include logic for determining whether those features, elements, and / or steps should be included in or performed in any particular embodiment, with or without user input or prompting.

[0063] Conjunctions such as the phrase "at least one of X, Y, and Z," unless otherwise noted, are understood with the context in which they are generally used to convey that an item, term, etc. can be either X, Y, or Z. Thus, such conjunctive language is generally not intended to imply that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0064] As used herein, language of degree, such as "approximately," "about," "generally," and "substantially," denotes a value, amount, or characteristic that approaches a stated value, amount, or characteristic that still performs a desired function or achieves a desired result.

[0065] The scope of the present disclosure is not intended to be limited by the specific disclosure of embodiments in this section or elsewhere herein, but may be defined by the claims, as presented in this section or elsewhere herein, or as presented in the future. The language of the claims should be interpreted broadly based on the language used in the claims, and not limited to the examples described herein or during the prosecution of this application, which examples should be interpreted as non-exclusive.

[0066] Although specific embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and modifications may be made in the systems and methods described herein without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure. Thus, the scope of the present invention is defined solely by reference to the appended claims.

Claims

1. Chemical formula (I) or chemical formula (II) (I)Li １＋ａ Ni x Mn 1-xM ｂ O ｃ (II)LiNi x Mn 1-+M ｂ O ｃ a doped cathode active material comprising a compound having any one of the compositions: During the ceremony, M is a dopant element; a is a value between 0 and 0.3; b is a value between 0.001 and 0.3; c is a value of 2 or 4, and The doped cathode active material, wherein x is a value between 0.4 and 0.

8.

2. The compound has the formula LiNi ｘ Mn １－ｘ M ｂ O ２ 10. The doped cathode active material of claim 1 having a composition of:

3. 3. The doped cathode active material of claim 1, wherein the dopant element is a metal selected from the group consisting of Al, Ca, B, Mg, Ti, Ta, Zr, Mo, W, Y, Co, Na, and combinations thereof.

4. 3. The doped cathode active material of claim 1, wherein the dopant element is a metal selected from the group consisting of Al, Ca, Mg, Ti, Ta, Co, W, Zr, and combinations thereof.

5. 3. The doped cathode active material of claim 1, wherein the doped cathode active material has a tap density of at least 1 g / cc.

6. 3. The doped cathode active material of claim 1, wherein a is a value between 0 and 0.

15.

7. 3. The doped cathode active material of claim 1, wherein b is a value between 0.001 and 0.

08.

8. 3. An electrode film comprising the doped cathode active material of claim 1 or 2.

9. A cathode electrode comprising the electrode film of claim 8 disposed on a current collector.

10. The cathode electrode according to claim 9 . separator, anode electrode, electrolytes, and An energy storage device including a housing, wherein the electrolyte, the cathode electrode, the separator, and the anode electrode are disposed within the housing.

11. The energy storage device of claim 10 , wherein the energy storage device is a battery.

12. 12. The energy storage device of claim 11, wherein the battery is configured to have at least 80% discharge capacity retention after 30 cycles at a C / 3 rate.

13. 11. The energy storage device of claim 10, wherein the operating voltage of the energy storage device is 4.35V.

14. 3. A process for forming the doped cathode active material of claim 1 or 2, comprising: mixing a transition metal precursor, a dopant material, and a lithium source to form an active material mixture; and heating the active material mixture to form the doped cathode active material.

15. The process of claim 14 , wherein the dopant material comprises a plurality of particles.

16. The plurality of particles have a D of 1 μm to 5 μm ５０ 16. The process of claim 15, including a particle size distribution.

17. 15. The process of claim 14, wherein the dopant material is selected from the group consisting of a metal, a metal oxide, a metal hydroxide, a metal carbonate, a metal bicarbonate, and combinations thereof.

18. 15. The process of claim 14, wherein the dopant material comprises a metallic element selected from the group consisting of Al, Ca, B, Mg, Ti, Ta, Zr, Mo, W, Y, Co, Na, and combinations thereof.

19. 20. The process of claim 18, wherein the metallic element is selected from the group consisting of Al, Ca, Mg, Ti, Ta, Co, Zr, Na, W, Zr, and combinations thereof.

20. The dopant material is Al ２ O ３ , Ta ２ O ５ , TiO ２ , Co ２ O ３ , W.O. ｘ , Ta, Ca(OH) ２ , NaHCO ３ 15. The process of claim 14, wherein the hydroxyl group is selected from the group consisting of:

21. The process of claim 14 , wherein the transition metal precursor is a spherical transition metal precursor.

22. 15. The process of claim 14, wherein the transition metal precursor is selected from the group consisting of a transition metal oxide, a transition metal hydroxide, a transition metal carbonate, and combinations thereof.

23. 23. The process of claim 22, wherein the transition metal precursor comprises a transition metal element selected from the group consisting of Ni, Mn, Ti, Co, and combinations thereof.

24. The transition metal precursor is Ni ｘ Mn １－ｘ (OH) ２ , Ni ｘ Mn １－ｘ CO ３ and combinations thereof, wherein x is from 0.5 to 0.

7.

25. The lithium source is LiOH.H ２ O, Li ２ CO ３ 15. The process of claim 14, wherein the hydroxyl group is selected from the group consisting of:

26. 15. The process of claim 14, wherein the molar ratio of lithium source to dopant material is from 1:0.0005 to 1:0.

1.

27. 15. The process of claim 14, wherein the molar ratio of the transition metal precursor to the dopant material is from 1:0.001 to 1:0.

1.

28. 15. The process of claim 14, wherein the transition metal precursor and the dopant material are premixed to form a precursor mixture, and the precursor mixture is mixed with the lithium source to form the active material mixture.

29. 15. The process of claim 14, wherein the lithium source is a lithium salt.

30. The lithium salt is LiOH.H ２ O, Li ２ CO ３ 30. The process of claim 29, wherein the hydroxyl group is selected from the group consisting of:

31. 30. The process of claim 28, wherein the precursor mixture is preheated.

32. 32. The process of claim 31, wherein preheating is at a temperature of 400 to 600°C.

33. 32. The process of claim 31 , wherein the precursor mixture is preheated for a period of between 3 and 7 hours.

34. 32. The process of claim 31 , wherein the preheating is performed in an atmosphere containing oxygen.

35. 35. The process of claim 34, wherein preheating is performed in air.

36. The process of claim 14, wherein the active material mixture is heated at a temperature of 700 to 1000°C.

37. The process of claim 14, wherein the active material mixture is heated for a period of 3 to 15 hours.

38. 15. The process of claim 14, wherein the heating is carried out in an atmosphere containing oxygen.

39. 39. The process of claim 38, wherein the heating is performed in air.

40. 15. The process of claim 14, wherein the heating is performed under a gas flow.

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