LITHIUM-ION BATTERY MATERIALS WITH IMPROVED PROPERTIES
20170271676 · 2017-09-21
Inventors
- Bin Li (San Diego, CA)
- Steven Kaye (San Diego, CA, US)
- Doron Greenberg (Agoura Hills, CA, US)
- Conor Riley (San Diego, CA, US)
- Jingning Shan (San Diego, CA, US)
- Jen-Hsien Yang (San Diego, CA, US)
Cpc classification
H01M4/5825
ELECTRICITY
H01M4/136
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M4/485
ELECTRICITY
H01M4/505
ELECTRICITY
H01M2004/021
ELECTRICITY
H01M4/525
ELECTRICITY
H01M4/58
ELECTRICITY
International classification
H01M4/136
ELECTRICITY
Abstract
A cobalt-containing phosphate material can comprise lithium (Li) (or, alternatively or additionally other alkali metal(s)), cobalt (Co), phosphate (PO.sub.4), and at least two additional metals other than Li and Co (e.g., as dopants and/or metal oxides), and can have a molar ratio of Co to a total amount of Co and the additional metals (e.g., as dopants and/or metal oxides) of at least 0.2, at least 0.3, at least 0.5, at least 0.7, or at least about 0.75. The cobalt-containing phosphate material can have a molar ratio of Co to a total amount of Co and the additional metals (e.g., as dopants and/or metal oxides) ranging from 0.2 to 0.98, from 0.3 to 0.98, from 0.3 to 0.94, from 0.5 to 0.98, from 0.5 to 0.94, or alternatively from 0.5 to 0.9, from 0.7 to 0.9, or from 0.75 to 0.85.
Claims
1.-19. (canceled)
20. An electrode material comprising: an active material comprising lithium (Li), cobalt (Co), phosphate (PO.sub.4), and at least two additional metals other than Li and Co, and having a molar ratio of Co to a total amount of Co and the additional metals of at least 0.2, the electrode material having its specific capacity at a voltage of 4.5 V which is at least 10% of its specific capacity at a voltage of 2.0 V, as measured upon discharge at a current of 7.5 mA/g from 4.95 V to 2.0 V versus a Li/Li+ counterelectrode; wherein at least one of the additional metals is a transition metal other than Co; wherein the transition metal is selected from the group consisting of iron (Fe), titanium (Ti), vanadium (V), niobium (Nb), zirconium (Zr), hafnium (Hf), molybdenum (Mo), tantalum (Ta), tungsten (W), manganese (Mn), copper (Cu), chromium (Cr), nickel (Ni), zinc (Zn), and silver (Ag); and a coating over the active material, the coating comprising a material selected from the group consisting of an electrochemically inert material and a metal oxide.
21. The electrode material of claim 20, wherein the transition metal is Fe.
22. The electrode material of claim 20, wherein the additional metals include two different transition metals selected from the group consisting of Fe, Ti, V, Nb, Zr, Hf, Mo, Ta, W, Mn, Cu, Cr, Ni, Zn, and Ag.
23. The electrode material of claim 22, wherein a first one of the two different transition metals is Fe.
24. The electrode material of claim 23, wherein a second one of the two different transition metals is selected from the group consisting of Ti, V, Nb, Zr, Hf, Mo, Ta, and W.
25. The electrode material of claim 24, wherein the second one of the two different transition metals is selected from the group consisting of Ti, V, and Nb.
26. The electrode material of claim 20, wherein at least one of the additional metals is a rare earth element.
27. The electrode material of claim 26, wherein the rare earth element is selected from the group consisting of yttrium (Y), scandium (Sc), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), and terbium (Tb).
28. The electrode material of claim 27, wherein the rare earth element is selected from the group consisting of Y, La, and Ce.
29.-31. (canceled)
32. The electrode material of claim 20, wherein the electrode material includes an olivine phase including Li, Co, PO.sub.4, and at least one of the additional metals and wherein the olivine phase includes a first one of the additional metals, and the electrode material includes a secondary phase including a second one of the additional metals.
33. (canceled)
34. The electrode material of claim 32, wherein the secondary phase includes a phosphate of the second one of the additional metals.
35. The electrode material of claim 32, wherein the secondary phase includes a hydroxide of the second one of the additional metals.
36. The electrode material of claim 32, wherein the secondary phase includes a carbonate of the second one of the additional metals.
37. The electrode material of claim 32, wherein the secondary phase includes a nitrate of the second one of the additional metals.
38.-182. (canceled)
183. The electrode material of claim 20 comprising particles of the active material and a coating over at least a portion of an outer surface of the particles of the active material.
184. The electrode material of claim 20, wherein the coating material is an electrochemically inert material.
185. The electrode material of claim 20, wherein the coating material is a metal oxide.
186. The electrode material of claim 20, wherein the coating material is an electrochemically inert metal oxide.
187. The electrode material of claim 185, wherein the metal oxide is selected from the group consisting of SiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3 and TiO.sub.2.
188. The electrode material of claim 185, wherein the metal oxide is SiO.sub.2.
189. The electrode material of claim 185, wherein the metal oxide is ZrO.sub.2.
190. The electrode material of claim 185, wherein the metal oxide is Al.sub.2O.sub.3.
191.-192. (canceled)
Description
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
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DETAILED DESCRIPTION
[0092] Definitions: The following definitions apply to some of the aspects described with respect to some embodiments of the invention. These definitions may likewise be expanded upon herein.
[0093] As used herein, the singular terms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object can include multiple objects unless the context clearly dictates otherwise. The use of the term “a” or “an” when used in conjunction with the term “comprising” in the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
[0094] The term “about” references all terms in the range unless otherwise stated. For example, about 1, 2, or 3 can refer to about 1, about 2, or about 3, and can also refer to from about 1-3, from about 1-2, and from about 2-3.
[0095] As used herein, the terms “substantially” and “substantial” refer to a considerable degree or extent. When used in conjunction with an event or circumstance, the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation, such as accounting for typical tolerance levels or variability of the embodiments described herein.
[0096] As used herein, the term “sub-micron range” refers to a general range of dimensions less than about 1 μm or less than about 1,000 nm, such as less than about 999 nm, less than about 900 nm, less than about 800 nm, less than about 700 nm, less than about 600 nm, less than about 500 nm, less than about 400 nm, less than about 300 nm, or less than about 200 nm, and down to about 1 nm or less. In some instances, the term can refer to a particular sub-range within the general range, such as from about 1 nm to about 10 nm, from about 1 nm to about 100 nm, from about 100 nm to about 200 nm, from about 200 nm to about 300 nm, from about 300 nm to about 400 nm, from about 400 nm to about 500 nm, from about 500 nm to about 600 nm, from about 400 nm to about 600 nm, from about 600 nm to about 700 nm, from about 700 nm to about 800 nm, from about 800 nm to about 900 nm, or from about 900 nm to about 999 nm.
[0097] As used herein, the term “main group element” refers to a chemical element in any of Group IA (or Group 1), Group IIA (or Group 2), Group IIIA (or Group 13), Group IVA (or Group 14), Group VA (or Group 15), Group VIA (or Group 16), Group VIIA (or Group 17), and Group VIIIA (or Group 18). A main group element is also sometimes referred to as a s-block element or a p-block element.
[0098] As used herein, the term “alkali metals” refers to any chemical element in Group 1, such as lithium, sodium, potassium, rubidium, cesium, or francium.
[0099] As used herein, the term “alkali earth metals” refers to any chemical element in Group 2, such as beryllium, magnesium, calcium, strontium, barium, or radium.
[0100] As used herein, the term “transition metal” refers to a chemical element in any of Group IVB (or Group 4), Group VB (or Group 5), Group VIB (or Group 6), Group VIIB (or Group 7), Group VIIIB (or Groups 8, 9, and 10), Group IB (or Group 11), and Group IIB (or Group 12). A transition metal is also sometimes referred to as a d-block element.
[0101] As used herein, the term “rare earth element” refers to any of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu.
[0102] As used herein, the terms “battery properties” or “electrochemical properties” refers to one or more properties such as specific capacity, high-voltage specific capacity, volumetric capacity, specific energy, volumetric energy density, potential, capacity retention, rate capability, cycling capability, irreversible capacity, coulombic efficiency, thermal stability, energy efficiency, and cycling voltage, among other properties known in the art. To the extent certain battery properties can vary with temperature, such properties are specified at room temperature (or 25° C.), unless the context clearly dictates otherwise.
[0103] As used herein, the term “specific capacity” refers to the amount (e.g., total or maximum amount) of electrons or lithium ions a material is able to hold (or discharge) per unit mass and can be expressed in units of mAh/g. In certain aspects and embodiments, specific capacity can be measured in a constant current discharge analysis which includes discharge at a defined rate over a defined voltage range against a defined counterelectrode. For example, specific capacity can be measured upon discharge at a rate of about 0.05 C (e.g., about 7.5 mA/g) from 4.95 V to 2.0 V versus a Li/Li+ counterelectrode. For example, high-voltage discharge capacity can be measured upon discharge at a rate of about 0.05 C (e.g., about 7.5 mA/g) from 4.95V to 4.5 V versus a Li/Li+ counterelectrode. Other discharge rates also can be used, such as a rate of about 0.1 C (e.g., about 15 mA/g), or about 0.5 C (e.g., about 75 mA/g), or about 1.0 C (e.g., about 150 mA/g).
[0104] As used herein, the term “specific energy” refers to the amount (e.g., total or maximum amount) of electrical energy stored per unit weight. Specific energy can be expressed in units of Wh/kg. In certain aspects and embodiments, specific energy can be measured in a constant current discharge analysis which includes discharge at a defined rate over a defined voltage range against a defined counterelectrode. For example, specific energy can be measured upon discharge at a rate of about 0.05 C (e.g., about 7.5 mA/g) from V to 2.0 V versus a Li/Li+ counterelectrode. Other discharge rates also can be used, such as a rate of about 0.1 C (e.g., about 15 mA/g), or about 0.5 C (e.g., about 75 mA/g), or about 1.0 C (e.g., about 150 mA/g).
[0105] As used herein, a rate “(C)” refers to the discharge current as a fraction or multiple relative to a “1 C” current value under which a battery (in a substantially fully charged state) would substantially fully discharge in one hour.
[0106] As used herein, the term “rate capability” refers to the amount of electrical charge a material can transport as a function of current. Rate capability can be expressed in units of mAh/g at 1 C, but may be expressed at other currents or rates. In certain aspects and embodiments, rate capability can be evaluated by determining specific capacity (e.g., as measured in a constant current discharge analysis) at a defined relatively higher rate (e.g., 1 C, 2 C, 5 C, 10 C, or 20 C), and comparing (e.g., as a percentage basis) to specific capacity determined at a defined relatively lower rate (e.g., 0.05 C, 0.1 C, or 0.5 C).
[0107] As used herein, the terms “cycle” or “cycling” refer to complementary discharging and charging processes.
[0108] As used herein, the term “capacity retention” refers to an extent of retention of a (maximum) specific capacity over multiple defined number of cycles. In certain aspects and embodiments, capacity retention can be evaluated by determining (maximum) specific capacity (e.g., as measured in a constant current discharge analysis) of an “nth” cycle relative (e.g., on a percentage basis) to a determined specific capacity of an initial cycle or another reference cycle (e.g., 1st cycle, 2nd cycle, 3rd cycle, 4th cycle, 5th cycle, 6th cycle, 7th cycle, gth cycle, 9th cycle, or 10th cycle).
[0109] As used herein, the term “structural properties” refers to any physical property of an embodiment of the present invention, including, but not limited to, crystal structure or crystallographic properties, thermal properties, melting point, and so forth. In some instances, the term is directed to changes in crystal structure and/or crystallographic properties.
[0110] As used herein, the term “composite” refers to a combination of two or more materials differing in form or composition. In some instances, the constituents substantially retain their identities, meaning, they do not dissolve or merge completely into one another although they act in concert. Normally, the components can be identified through experimental means.
[0111] As used herein, the term “blend” refers to a mixture of multiple components. In some instances, the components are mixed in such a way that the combination or constituent parts are substantially indistinguishable from one another, and, in other instances, the components substantially retain their identities or remain distinguishable. A “blend” can be used to describe a uniform or nonuniform mixture of two or more components or materials.
[0112] As used herein, the term “dopant” refers to an element or a molecule introduced into a material as a relatively minor component thereof on molar basis. A dopant may alter the structural or electrochemical properties of the material. In an embodiment of the present invention, the elements or molecules of the dopant may take the place of elements that were in the crystal lattice of the material or may alter the structural properties of the crystal lattice of the material.
[0113] As used herein, the terms “alloy” or “alloying” refer to a homogeneous mixture, intermetallic compound, or solid solution of two or more metals and/or nonmetals. In some instances, atoms of one element can replace or occupy interstitial positions between atoms of another element.
[0114] As used herein, the term “calcination” refers to a thermal treatment process applied to materials in order to bring about a chemical, physical, or structural change in the material, but may also refer to thermal decomposition, phase transition, or removal of a volatile fraction in a material. The calcination process normally takes place at temperatures below the melting point of the product materials.
[0115] As used herein, the term “Co capacity” refers to an extent (e.g., on a percentage basis) of a (maximum or total) specific capacity arising from oxidation or reduction of cobalt atoms in a material. For example, Co capacity can be measured by determining (maximum) specific capacity (e.g., as measured in a constant current discharge analysis) upon discharge from 4.5 V to 4.3 V relative (e.g., on a percentage basis) to a determined specific capacity upon discharge from 4.95 V to 2.0 V.
[0116] As used herein, the terms “anode” and “cathode” refer to the electrodes at which oxidation and reduction occur, respectively, during battery discharge. During charging of the battery, the sites of oxidation and reduction are typically reversed.
[0117] Also, as used herein, the words “preferred,” “preferably,” and “more preferably” refer to embodiments of the invention that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.
Cobalt-Rich Phosphate Material
[0118] Embodiments of the present invention improve the battery properties of cobalt-based phosphate materials by forming a cobalt-rich phosphate material that incorporates Li, Co, PO.sub.4 and additional components. The additional components may be coated on, mixed in, dispersed through the bulk of, or reacted with the base LiCoPO.sub.4 material. The combination of additional components and base LiCoPO.sub.4 may form a composite, blend, alloy, or the additional components may act as dopants.
[0119] Embodiments of the present invention improve the battery properties of electrodes comprising cobalt-based phosphate materials. In one preferred approach, electrode materials are prepared by forming a composite material comprising a first component, which is a cobalt-based phosphate material, and a second component, which is a metal phosphate, metal fluoride, metal oxide, metal hydroxide, metal carbonate, metal nitrate or mixture thereof. The second component can be coated on, or dispersed through the bulk of, or otherwise combined with the first component. The presence of the second component improves the performance of batteries fabricated from the materials, and electrochemical activity can be observed from the second component depending on the particular composition. Also disclosed is a method for preparing the materials as well as electrodes fabricated from the materials and Li-ion cells which include such electrodes.
[0120] A cobalt-rich phosphate material is provided which includes at least one phase (e.g., an olivine-type phase) or component having the formula:
Li.sub.1-x-wCo.sub.1-y(N.sub.w).sup.p(M.sub.y).sup.q(PO.sub.4).sub.1-a (I)
wherein:
[0121] a) each M is independently one or more of a Group IIA (or Group 2), Group IIIA (or Group 3), Group IIIB (or Group 13), transition metal, or rare earth element;
[0122] b) q is an integer or non-integer that can independently vary from q=1 to q=8;
[0123] c) y can independently vary from 0<y≦0.9;
[0124] d) each N is independently one or more of a Group IA (or Group 1), Group IIA (or Group 2), Group IIIA (or Group 3), Group IIIB (or Group 13), transition metal, or rare earth element;
[0125] e) p is an integer or non-integer that can independently vary from p=O to p=2;
[0126] f) w can independently vary from 0≦w≦0.3;
[0127] g) x can independently vary from −0.3≦x≦0.3; and
[0128] h) a can independently vary from −0.5≦a≦0.5 or −0.3≦a≦0.3.
[0129] In formula (I), M is one or more, as defined by q, Group IIA, IIIA, IIIB, transition metal elements, or rare earth elements. M is preferably Fe, Ti, V, Ta, W, Cr, Cu, Zn, Zr, Y, La, Ag, Al, Nb, Hf, Mo, Mn, Ni, or Mg, and more preferably Fe, Mn, V, Cr, Ni, Ti, Cu, Nb, Zr, Hf, Mo, Ta, W, or Zn, and more preferably Fe, V, Ti, or Nb. Preferably, q, the number of additional, unique M dopants, is 2, 3, or 4. In some embodiments, q is from 1 to 8, and, in some embodiments, q is from 1 to 6, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 7, from 2 to 6, from 2 to 5, from 2 to 4, or from 2 to 3. More preferably, q is 2 or 3, or q is 1 or 2. The doping content or amount of each M in the composition is defined by y, and can independently vary from about 0<y≦0.9. Preferably, y is about 0.01≦y≦0.7 or about 0.05≦y≦0.7. More preferably, y is about 0.01≦y≦0.5, about 0.05≦y≦0.5, about 0.1≦y≦0.5, 0.01≦y≦0.3, about 0.05≦y≦0.3, about 0.1≦y≦0.3, 0.01≦y≦0.2, about 0.05≦y≦0.2, or about 0.1≦y≦0.2. The number of additional unique N dopants is 0 to 2, as defined by p. Preferably, p is 0 or 1. The doping content or amount of each N in the composition is defined by w, and can independently vary from about 0≦w≦0.3. Preferably, w is about 0≦w≦0.2, about 0≦w≦0.1, about 0.01≦w≦0.2, about 0.05≦w≦0.2, about 0.01≦w≦0.1, about 0.05≦w≦0.1. The value of x can vary from about −0.3≦x≦0.3, and is preferably about −0.3≦x≦0.1, and more preferably about −0.3≦x≦0, about −0.2≦x≦0, about −0.1≦x≦0, about −0.3≦x≦0, about −0.2≦x<0, or about −0.1≦x<0. In some embodiments, the value of x may also specifically be about 0.3, 0.28, 0.25, 0.23, 0.2, 0.18, 0.15, 0.12, 0.1, 0.8, 0.5, 0.3, 0.2, 0.15, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0, −0.01, −0.02, −0.03, −0.05, −0.08, −0.1, −0.12, −0.15, −0.18, −0.2, −0.22, −0.25, −0.28, or −0.3. The value of a can vary from about −0.3≦a≦0.3, and is preferably about −0.3≦a≦0.1, about −0.2≦a≦0.1, about −0.1≦a≦0.1, about −0.2≦a<0, or about 0<a≦0.1, and, in some embodiments, a is about 0. More generally, a can take on any value to satisfy valence and charge balance requirements with respect to positively charged elements in formula (I). In some embodiments, formula (I) contains the condition that 0.2≦1-y<1.0 or 0.2≦1-y≦0.98. In some embodiments, 1-y is preferably about 0.3≦1-y≦0.9 or about 0.3<1-y≦0.98, and more preferably about 0.35≦1-y≦0.75, about 0.35≦1-y≦0.98, about 0.5≦1-y≦0.98, or about 0.7≦1-y≦0.98. In some embodiments, y is such that an overall composition of the cobalt-rich phosphate material has a molar ratio of Co, relative to a combined molar amount of Co and the additional M's, that is at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.75, and up to about 0.98 or more. In some embodiments, the cobalt-rich phosphate material also includes a secondary phase including at least one M, and y is such that an overall composition of the cobalt-rich phosphate material has a molar ratio of Co, relative to a combined molar amount of Co and the additional M's within the olivine phase and the secondary phase, that is at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.75, and up to about 0.98 or more.
[0130] Cobalt-rich phosphate materials of formula (I) show improved battery properties when used as positive electrode active materials. In some embodiments, the improved battery properties are discharge capacity, specific capacity, specific energy, rate capability, cycling capability, cycling voltage, and improved discharge rate characteristics. Without limitation, for example, and with reference to
[0131] In some embodiments of the present invention, when charged, discharged, or cycled at a rate of 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C) between 2.0 V and 4.95 V versus Li/Li+, specific capacity is about 90 mAh/g or greater, or preferably about 100 mAh/g or greater. Preferably, specific capacity is about 130 mAh/g or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C), or about 140 mAh/g or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). More preferably, specific capacity is about 150 mAh/g or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). The stated values or ranges of specific capacity can be based on a weight of an active material alone, but also can be based on, or adjusted to account for, a combined weight of the active material and another one or more components, such as a set of conductive additives as further explained below.
[0132] In some embodiments of the present invention, when charged, discharged, or cycled at a rate of 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C) between 4.5 V and 4.95 V versus Li/Li+, specific capacity is about 50 mAh/g or greater, or preferably about 60 mAh/g or greater. Preferably, specific capacity is about 90 mAh/g or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C), or about 100 mAh/g or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). More preferably, specific capacity is about 110 mAh/g or greater, about 120 mAh/g or greater, or about 130 mAh/g or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). The stated values or ranges of specific capacity can be based on a weight of an active material alone, but also can be based on, or adjusted to account for, a combined weight of the active material and another one or more components, such as a set of conductive additives as further explained below.
[0133] In some embodiments of the present invention, when charged, discharged, or cycled at a rate of 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C) between 2.0 V and 4.95 V versus Li/Li+, specific capacity at a voltage of 4.5 V is at least 10% of specific capacity at a voltage of 2.0 V. Preferably, specific capacity at a voltage of 4.5 V is at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, or at least 80% of specific capacity at a voltage of 2.0 V.
[0134] In some embodiments of the present invention, when charged, discharged, or cycled at a rate of 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C) between 2.0 V and 4.95 V versus Li/Li+, specific energy is about 400 Wh/kg or greater. Preferably, specific energy is about 500 Wh/kg or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C), or about 550 Wh/kg or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). More preferably, specific energy is about 600 Wh/kg or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C), or about 650 Wh/kg or greater at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). The stated values or ranges of specific energy can be based on a weight of an active material alone, but also can be based on, or adjusted to account for, a combined weight of the active material and another one or more components, such as a set of conductive additives as further explained below.
[0135] In some embodiments of the present invention, rate capability at 1 C is about 100 mAh/g or greater. Preferably, rate capability at 1 C is about 130 mAh/g or greater, or about 140 mAh/g or greater. More preferably, rate capability at 1 C is about 150 mAh/g or greater. In some embodiments, rate capability is such that, at 1 C, at 5 C, or even at 10 C, at least about 60%, at least about 70%, at least about 80%, at least about 85%, or at least about 90%, and up to about 95%, up to about 98%, or more of a low-rate discharge capacity (e.g., at C/20) is retained. The stated values or ranges of rate capability can be based on a weight of an active material alone, but also can be based on, or adjusted to account for, a combined weight of the active material and another one or more components, such as a set of conductive additives as further explained below.
[0136] In some embodiments, cycling capability or capacity retention is such that, after 100 cycles, after 200 cycles, after 300 cycles, after 400 cycles, after 500 cycles, after 600 cycles, after 1,000 cycles, or even after 5,000 cycles, at least about 50%, at least about 60%, at least about 70%, at least about 75%, or at least about 80%, and up to about 85%, up to about 90%, or more of an initial or maximum discharge capacity is retained.
[0137] In some embodiments, when charged, discharged, or cycled at a rate of 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C) between 2.0 V and 4.95 V versus Li/Li+, the cobalt-rich phosphate material has at least 10% of its (maximum) specific capacity at a voltage of at least 4.5 V, at least 30% of its (maximum) specific capacity at the voltage of at least 4.5 V, at least 50% of its (maximum) specific capacity at the voltage of at least 4.5 V, at least 10% of its (maximum) specific capacity at the voltage of at least 4.6 V, at least 30% of its (maximum) specific capacity at the voltage of at least 4.6 V, at least 50% of its (maximum) specific capacity at the voltage of at least 4.6 V, at least 10% of its (maximum) specific capacity at the voltage of at least 4.7 V, at least 30% of its (maximum) specific capacity at the voltage of at least 4.7 V, at least 10% of its (maximum) specific capacity at the voltage of at least 4.8 V, or at least 30% of its (maximum) specific capacity at the voltage of at least 4.8 V.
[0138] Embodiments of the present invention, can be seen in
[0139] In one embodiment, one M is Fe, and another M is Ti. In this embodiment, the molar ratio of Fe, relative to a combined molar amount of Co, Fe, and Ti, can vary from about 0.01-0.5, and the molar ratio of Ti, relative to the combined molar amount of Co, Fe, and Ti, can vary from about 0.05-0.3. The molar ratio of Co, relative to the combined molar amount of Co, Fe, and Ti, varies between about 0.2 and 0.98 as a function of Fe and Ti, with the total of Fe, Ti, and Co equal to 1.0. (
[0140] Titanium doping (or the molar ratio of titanium) in some embodiments of the present invention can vary from about 0.01 to 0.3. Preferably, Ti doping is about 0.05 to 0.25. More preferably, Ti doping is about 0.05 to 0.20. In some embodiments, Ti doping can be about 0.01-0.3, 0.02-0.3, 0.05-0.3, 0.1-0.3, 0.15-0.3, 0.2-0.3, 0.25-0.3, 0.05-0.25, 0.05- 0.20, 0.05-0.15, 0.05-0.1, 0.01-0.15, 0.01-0.1, 0.01-0.08, or 0.01-0.05. In some embodiments, Ti doping can be about 0.01, 0.02, 0.03, 0.05, 0.08, 0.10, 0.12, 0.15, 0.18, 0.20, 0.25, or 0.30. (
[0141] Battery properties for Ti doped embodiments of the present invention are at least or greater than about 500 Wh/kg, and/or 120 mAh/g and/or 140 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C), when charged, discharged, or cycled between 2.0 V and 4.95 V versus Li/Li+. In some embodiments, battery properties can vary from about 500 to 800 Wh/kg, 120-160 mAh/g, or 140-170 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). Preferably, battery properties for Ti doped materials can be about 550-750 Wh/kg, 140-160 mAh/g, or 150-170 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). In some embodiments, specific energy is at least or greater than about 500 Wh/kg. In some embodiments, specific energy is at least or greater than about 550 Wh/kg. In some embodiments, specific energy is at least or greater than about 600 Wh/kg. In some embodiments, specific energy is at least or greater than about 650 Wh/kg. In some embodiments, specific energy is at least or greater than about 675 Wh/kg. In some embodiments, specific energy is at least or greater than about 700 Wh/kg. In some embodiments, specific energy is at least or greater than about 725 Wh/kg. In some embodiments, specific capacity is at least or greater than about 120 mAh/g. In some embodiments, specific capacity is at least or greater than about 130 mAh/g. In some embodiments, specific capacity is at least or greater than about 140 mAh/g. In some embodiments, specific capacity is at least or greater than about 150 mAh/g. In some embodiments, specific capacity is at least or greater than about 160 mAh/g. In some embodiments, specific capacity is about 170 mAh/g or greater than about 170 mAh/g. In some embodiments, rate capability is at least or greater than about 120 mAh/g at 1 C. In some embodiments, rate capability is at least or greater than about 130 mAh/g at 1 C. In some embodiments, rate capability is at least or greater than about 140 mAh/g at 1 C. In some embodiments, rate capability is at least or greater than about 150 mAh/g at 1 C. In some embodiments, rate capability is at least or greater than about 160 mAh/g at 1 C. In some embodiments, rate capability is about, or greater than about, 170 mAh/g at 1 C. In some embodiments, battery properties for Ti doped materials can be about 500, 525, 550, 575, 600, 625, 650, 675, or 700 Wh/kg, about 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, or 167 mAh/g at 1 C (or another rate higher or lower than 1 C, such as 0.05 C). (
[0142] In one embodiment, one M is Fe, and another M is V. In this embodiment, the molar ratio of Fe, relative to a combined molar amount of Co, Fe, and V, can vary from about 0.01-0.5, and the molar ratio of V, relative to the combined molar amount of Co, Fe, and V, can vary from about 0.01-0.3. The molar ratio of Co, relative to the combined molar amount of Co, Fe, and V, varies between about 0.2 and 0.98 as a function of Fe and V, with the total of Fe, V, and Co equal to 1.0. Preferably, when Fe is about 0.10±0.05, V is about 0.05±0.05; when Fe is about 0.20±0.05, V is about 0.05±0.05; and when Fe is about 0.30±0.05, V is about 0.05±0.05 or 0.10±0.05. (
[0143] Vanadium doping (or the molar ratio of vanadium) in some embodiments of the present invention can vary from about 0.01 to 0.3. Preferably, V doping is about 0.03 to 0.25. More preferably, V doping is about 0.05 to 0.20. In some embodiments, V doping can be about 0.01-0.3, 0.02-0.3, 0.05-0.3, 0.1-0.3, 0.15-0.3, 0.2-0.3, 0.25-0.3, 0.05-0.25, 0.05-0.20, 0.05-0.15, 0.05-0.1, 0.01-0.15, 0.01-0.1, 0.01-0.08, or 0.01-0.05. In some embodiments, V doping can be about 0.01, 0.02, 0.03, 0.05, 0.08, 0.10, 0.12, 0.15, 0.18, 0.20, 0.25. (
[0144] Battery properties for V doped embodiments of the present invention are at least or greater than about 400 Wh/kg and/or 100 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). In some embodiments, battery properties can vary from about 400 to 700 Wh/kg, or 100-150 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). In some embodiments, specific energy is at least or greater than about 400 Wh/kg. In some embodiments, specific energy is at least or greater than about 450 Wh/kg. In some embodiments, specific energy is at least or greater than about 500 Wh/kg. In some embodiments, specific energy is at least or greater than about 550 Wh/kg. In some embodiments, specific energy is at least or greater than about 575 Wh/kg. In some embodiments, specific energy is at least or greater than about 600 Wh/kg. In some embodiments, specific energy is at least or greater than about 625 Wh/kg. In some embodiments, specific capacity is at least or greater than about 100 mAh/g. In some embodiments, specific capacity is at least or greater than about 110 mAh/g. In some embodiments, specific capacity is at least or greater than about 120 mAh/g. In some embodiments, specific capacity is at least or greater than about 130 mAh/g. In some embodiments, specific capacity is at least or greater than about 140 mAh/g. In some embodiments, specific capacity is at least or greater than about 150 mAh/g. In some embodiments, battery properties for V doped materials can be about 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, or 700 Wh/kg, or about 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, or 167 mAh/g at 1 C (or another rate higher or lower than 1 C, such as 0.05 C). (
[0145] In one embodiment, one M is Fe, and another M is Nb. In this embodiment, the molar ratio of Fe, relative to a combined molar amount of Co, Fe, and Nb, can vary from about 0.01-0.5, and the molar ratio of Nb, relative to the combined molar amount of Co, Fe, and Nb, can vary from about 0.01-0.3. The molar ratio of Co, relative to the combined molar amount of Co, Fe, and Nb, varies between about 0.2 and 0.98 as a function of Fe and Nb, with the total of Fe, Nb, and Co equal to 1.0. (
[0146] Niobium doping (or the molar ratio of Niobium) in some embodiments of the present invention can vary from about 0.01 to 0.30. Preferably, Nb doping is about 0.01 to 0.20. More preferably, Nb doping is about 0.01 to 0.15. In some embodiments, Nb doping can be about 0.01-0.3, 0.02-0.3, 0.05-0.3, 0.1-0.3, 0.15-0.3, 0.2-0.3, 0.25-0.3, 0.01-0.25, 0.01- 0.20, 0.01-0.15, 0.01-0.1, 0.01-0.08, 0.01-0.05, 0.02-0.15, 0.05-0.15, 0.02-0.10, 0.03-0.08, or 0.03-0.12. In some embodiments, Nb doping can be about 0.01, 0.02, 0.03, 0.05, 0.08, 0.10, 0.12, 0.15, 0.18, 0.20, 0.25 or 0.30. (
[0147] Battery properties for Nb doped embodiments of the present invention are at least or greater than about 400 Wh/kg and/or 100 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). In some embodiments, battery properties for Nb doped materials can vary from about 400 to 700 Wh/kg, or 120-170 mAh/g at 0.05 C (or another rate higher or lower than 0.05 C, such as 1 C). In some embodiments, specific energy is at least or greater than about 400 Wh/kg. In some embodiments, specific energy is at least or greater than about 450 Wh/kg. In some embodiments, specific energy is at least or greater than about 500 Wh/kg. In some embodiments, specific energy is at least or greater than about 550 Wh/kg. In some embodiments, specific energy is at least or greater than about 575 Wh/kg. In some embodiments, specific energy is at least or greater than about 600 Wh/kg. In some embodiments, specific energy is at least or greater than about 625 Wh/kg. In some embodiments, specific capacity is at least or greater than about 100 mAh/g. in some embodiments, specific capacity is at least or greater than about 110 mAh/g. in some embodiments, specific capacity is at least or greater than about 120 mAh/g. in some embodiments, specific capacity is at least or greater than about 130 mAh/g. in some embodiments, specific capacity is at least or greater than about 140 mAh/g. in some embodiments, specific capacity is at least or greater than about 150 mAh/g. In some embodiments, battery properties for Nb doped materials can be about 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, or 700 Wh/kg, or about 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, or 167 mAh/g at 1 C (or another rate higher or lower than 1 C, such as C). (
[0148] In one embodiment, one M is Fe, and another M is Y. In this embodiment, the molar ratio of Fe, relative to a combined molar amount of Co, Fe, and Y, can vary from about 0.01-0.5, and the molar ratio of Y, relative to the combined molar amount of Co, Fe, and Y, can vary from about 0.02-0.2. The molar ratio of Co, relative to the combined molar amount of Co, Fe, and Y, varies between 0.3 and 0.97 as a function of Fe and Y, with the total of Fe, Y, and Co equal to 1.0. (
[0149] In one embodiment, one M is Fe, and another M is Zr. In this embodiment, the molar ratio of Fe, relative to a combined molar amount of Co, Fe, and Zr, can vary from about 0.01-0.5, and the molar ratio of Zr, relative to the combined molar amount of Co, Fe, and Zr, can vary from about 0.02-0.2. The molar ratio of Co, relative to the combined molar amount of Co, Fe, and Zr, varies between 0.3 and 0.97 as a function of Fe and Zr, with the total of Fe, Zr, and Co equal to 1.0. (
[0150] In one embodiment, one M is Fe, and another M is Ce. In this embodiment, the molar ratio of Fe can vary from about 0.01-0.5, and the molar ratio of Ce can vary from about 0.02-0.2. The molar ratio of Co varies between 0.3 and 0.97 as a function of Fe and Ce, with the total of Fe, Ce, and Co equal to 1.0.
[0151] In one embodiment, one M is Fe, and another M is Hf. In this embodiment, the molar ratio of Fe can vary from about 0.01-0.5, and the molar ratio of Hf can vary from about 0.02-0.2. The molar ratio of Co varies between 0.3 and 0.97 as a function of Fe and Hf, with the total of Fe, Hf, and Co equal to 1.0.
[0152] In one embodiment, one M is Fe, and another M is Mo. In this embodiment, the molar ratio of Fe can vary from about 0.01-0.5, and the molar ratio of Mo can vary from about 0.02-0.2. The molar ratio of Co varies between 0.3 and 0.97 as a function of Fe and Mo, with the total of Fe, Mo, and Co equal to 1.0.
[0153] In one embodiment, one M is Fe, and another M is Ta. In this embodiment, the molar ratio of Fe can vary from about 0.01-0.5, and the molar ratio of Ta can vary from about 0.02-0.2. The molar ratio of Co varies between 0.3 and 0.97 as a function of Fe and Ta, with the total of Fe, Ta, and Co equal to 1.0.
[0154] In one embodiment, one M is Fe, and another M is W. In this embodiment, the molar ratio of Fe can vary from about 0.01-0.5, and the molar ratio of W can vary from about 0.02-0.2. The molar ratio of Co varies between 0.3 and 0.97 as a function of Fe and W, with the total of Fe, W, and Co equal to 1.0.
[0155]
[0156] Materials of formula (I) are useful as positive electrode active materials in nonaqueous electrolyte secondary batteries. In another aspect, an embodiment of the present invention provides a battery which comprises an electrolyte; a negative electrode having an insertion active material; and a positive electrode comprising a compound of formula (I), characterized by an ability to release lithium ions for insertion into the negative electrode active material.
[0157] In one aspect of the present invention, a cobalt-rich phosphate material is provided, which includes at least one olivine-type phase or component having the formula:
Li.sub.1-xCo.sub.1-y-zM.sub.yM′.sub.z(PO.sub.4).sub.1-a (II)
or
Li.sub.1-xCo.sub.1-yM.sub.y(PO.sub.4).sub.1-a (III)
wherein:
[0158] a) each M/M′ is independently one or more of Fe, Mn, V, Cr, Ni, Ti, Cu, Ce, Hf, Mo, Ta, W, Nb, Zr, and Zn;
[0159] b) −0.3≦x≦0.3;
[0160] c) 0.01≦y≦0.5 or 0.05≦y≦0.5;
[0161] d) 0.01≦z≦0.5 or 0.05≦z≦0.5;
[0162] e) −0.5≦a≦0.5 or −0.3≦a≦0.3;
[0163] f) with the condition that 0.15≦1-y-z, 0.18≦1-y-z, or 0.2≦1-y-z (or 0.15 ≦1-y, 0.18≦1-y, or 0.2≦1-y).
[0164] In formulas (II) and (III), M and M′ are preferably different from Co and different from one another. In some embodiments, at least one of M and M′ is a metal having an oxidation state in the range of +2 to +5 in a discharged state of the cobalt-rich phosphate material, such as +2, +3, +4, or +5. For example, M is Fe having an oxidation state of +2, and M′ is Ti or another metal having an oxidation state of +4. In some embodiments, M is Fe, and M′ is Ti, V, Nb, Zr, Hf, Mo, Ta, or W. For example, M is Fe, and M′ is Ti, V, or Nb. Preferably, y is about 0.01≦y≦0.5, about 0.05≦y≦0.5, about 0.1≦y≦0.5, 0.01≦y≦0.3, about 0.05≦y≦0.3, about 0.1≦y≦0.3, 0.01≦y≦0.2, about 0.05≦y≦0.2, or about 0.1≦y≦0.2. Preferably, z is about 0.01≦z≦0.5, about 0.05≦z≦0.5, about 0.1≦z≦0.5, 0.01≦z≦0.3, about 0.05≦z≦0.3, about 0.1≦z≦0.3, 0.01≦z≦0.2, about 0.05≦z≦0.2, or about 0.1≦z≦0.2. The value of x can vary from about −0.3≦x≦0.3, and is preferably about −0.3≦x≦0.1, and more preferably about −0.3≦x≦0, about −0.2≦x≦0, about −0.1≦x≦0, about −0.3≦x<0, about −0.2≦x<0, or about −0.1≦x<0. In some embodiments, the value of x may also specifically be about 0.3, 0.28, 0.25, 0.23, 0.2, 0.18, 0.15, 0.12, 0.1, 0.8, 0.5, 0.3, 0.2, 0.15, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0, −0.01, −0.02, −0.03, −0.05, −0.08, −0.1, −0.12, −0.15, −0.18, −0.2, −0.22, −0.25, −0.28, or −0.3. The value of a can vary from about −0.3≦a≦0.3, and is preferably about −0.3≦a≦0.1, about −0.2≦a≦0.1, about −0.1≦a≦0.1, about −0.2≦a<0, or about 0<a≦0.1, and, in some embodiments, a is about 0. More generally, a can take on any value to satisfy valence and charge balance requirements with respect to positively charged elements in formulas (II) and (III). In some embodiments, formulas (II) and (III) contain the condition that 0.2≦1-y-z<1.0 (or 0.2≦1-y<1.0) or 0.2≦1-y-z≦0.98 (or 0.2≦1-y≦0.98). In some embodiments, 1-y-z is preferably about 0.3≦1-y-z≦0.9 or about 0.3≦1-y-z≦0.98, and more preferably about 0.35≦1-y-z≦0.75, about 0.35≦1-y-z≦0.98, about 0.5≦1-y-z≦0.98, or about 0.7≦1-y-z≦0.98, and 1-y is preferably about 0.3≦1-y≦0.9 or about 0.3≦1-y≦0.98, and more preferably about 0.35≦1-y≦0.75, about 0.35≦1-y≦0.98, about 0.5≦1-y≦0.98, or about 0.7≦1-y≦0.98. In some embodiments for formula (II), y and z are such that an overall composition of the cobalt-rich phosphate material has a molar ratio of Co, relative to a combined molar amount of Co, M, and M′, that is at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.75, and up to about 0.98 or more. In some embodiments for formula (II), the cobalt-rich phosphate material also includes a secondary phase including M′, and y and z are such that an overall composition of the cobalt-rich phosphate material has a molar ratio of Co, relative to a combined molar amount of Co, M, and M′ within the olivine phase and the secondary phase, that is at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.75, and up to about 0.98 or more. In some embodiments for formula (III), the cobalt-rich phosphate material also includes a secondary phase including M′, and y is such that an overall composition of the cobalt-rich phosphate material has a molar ratio of Co, relative to a combined molar amount of Co, M, and M′ within the olivine phase and the secondary phase, that is at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.75, and up to about 0.98 or more.
[0165] Cobalt-rich phosphate materials of formulas (II) and (III) show improved battery properties when used as positive electrode active materials. In some embodiments, the improved battery properties are similar to those set forth above for formula (I), and those battery properties are also applicable for formulas (II) and (III).
[0166] Formulas (I), (II) and (III) describe embodiments of the cobalt-rich phosphate material wherein the material is in its “discharged” state (e.g., substantially fully lithiated state). As the battery is charged from its discharged state into a charged state, an amount lithium is removed from the active material as described in Formulas (I), (II), or (III). The resulting structure, containing less lithium than in the as-prepared state as well as one or more transition metals in a higher oxidation state than in the as-prepared state, is characterized by lower values of x. The active materials of embodiments of this invention include such materials in their nascent state (i.e., as manufactured prior to inclusion in an electrode) and materials formed during operation of the battery (i.e., by insertion or removal of Li or other alkaline metal).
[0167] In one aspect of the present invention, a cobalt-rich phosphate material is provided which comprises multiple phases as a result of doping with or incorporation of additional materials. In one embodiment, the additional phases provide improved electrical conductivity and/or lithium ion diffusivity.
[0168] In one aspect of the present invention, an electrode material is provided which comprises two components or two phases: a first component which is a cobalt-rich phosphate material and a second component which is a metal oxide, a metal phosphate, metal hydroxide, metal carbonate, metal nitrate or mixture thereof. In one embodiment, the second component is coated on the first component. In another embodiment, the second component is dispersed through the bulk of the first component. In another embodiment, the second component is reacted with the first component. In one embodiment, the electrode material improves battery performance.
[0169] In one aspect of the present invention, an electrode material is provided which comprises two components or two phases, wherein the composition of the first component comprises a cobalt-rich phosphate material of formula (I), and the composition of the second component comprises oxides, phosphates, hydroxides, carbonates, or nitrates of alkali, alkali earth, and transition metals, such as Ti, V, Na, Ta, W, Cr, Cu, Zn, Zr, Y, La, Ag, or Mg. In one embodiment, M is two or more of Fe, Mn, V, Cr, Ni, Ti, Cu, or Zn. In another embodiment, the second component is one or more compounds that react with the first component to form a solid solution in which the metal of the second component occupies the partial Li or Co/M sites. In another embodiment, the second component is one or more compounds that react with the phosphate in the first component to form other phases like Nasicon or pyrophosphate. In another embodiment, the second component is one or more compounds that are coated on or dispersed through the bulk of the first component. In some embodiments, the second component includes at least one M, and may also include at least one N. For example, the second component can include an oxide, a phosphate, a hydroxide, a carbonate, or a nitrate of at least one M.
[0170] In one aspect of the present invention, an electrode material is provided which comprises two components or two phases, wherein the composition of the first component comprises a cobalt-rich phosphate material with formula (II) or (III), and the composition of the second component comprises oxides, hydroxides, carbonates, or nitrates of alkali, alkali earth, and transition metals, such as Ti, V, Na, Ta, W, Cr, Cu, Zn, Zr, Y, La, Ag, or Mg. In one embodiment, M/M′ are one or more of Fe, Mn, V, Cr, Ni, Ti, Cu, or Zn. In another embodiment, the second component is one or more compounds that react with the first component to form a solid solution in which the metal of the second component occupies the partial Li or Co/M/M′ sites. In another embodiment, the second component is one or more compounds that react with the phosphate in the first component to form other phases like Nasicon or pyrophosphate. In another embodiment, the second component is one or more compounds that are coated on or dispersed through the bulk of the first component. In some embodiments, the second component includes M′. For example, the second component can include an oxide, a phosphate, a hydroxide, a carbonate, or a nitrate of M′.
[0171] In one aspect of the present invention, an electrode material is provided which has been coated with a layer of oxide material. In one embodiment, the oxide layer can improve the capacity retention and cycle life in comparison to uncoated electrode material with a limited loss of capacity. In some embodiments, oxide candidates and modification conditions are selected to coat a layer of oxide or dope oxides into available high voltage electrode materials on the basis of Cobalt containing phosphates. Examples of oxides that can be used to coat the electrode material include, for example, SiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3 and TiO.sub.2. In general, the process of coating the electrode material includes mixing the oxide precursor with uncoated electrode material, and then annealing the mixture to form an oxide layer on the electrode material. In some embodiments, the mixing step can include, for example, sonication (sometimes called aging), stirring, magnetic stirring, ball milling, or other methods that involve high shear (mixing). In some embodiments, ball milling provided the coated electrode materials with the best cycle life. In some embodiments, the layer of oxide on the electrode material can minimize the reaction between the electrolyte and electrode materials. In some embodiments, the oxide precursor's addition process, such as high speed mixing or ball milling, to the electrode material changes the crystallinity of the electrode material, so the electrode materials are post-treated (e.g., annealed) to increase crystallinity of the electrode materials.
[0172] In some embodiments, the oxide coated electrode material is produced by a two- step process. After the uncoated electrode material is prepared, oxide precursors (Tetraethyl orthosilicate (TEOS) for SiO.sub.2, Zirconium(IV) propoxide solution 70% for ZrO.sub.2, Aluminum isopropoxide for Al.sub.2O.sub.3, Titanium(IV) isopropoxide for TiO.sub.2) are added to the uncoated electrode material along with iso-propanol in a glove box. The percentage of oxides corresponding to the initial precursor loadings can be calculated based on 100% transfer from the precursors to the oxides. The uncoated electrode material and oxide precursor are mixed as described herein, dried under vacuum at 70-100° C. for approximately 2 hours, and then transferred to N.sub.2 filled glove box. The milled and dried precursors are then heated at approximately at 5° C./min for 12 h under N.sub.2 flow, and then cooled to room temperature at approximately 5° C./min. In some embodiments, the second heating step (annealing) is performed in the range of 350-800° C. In some embodiments, the coated electrode materials are annealed in the range of 400-500° C. Annealing is performed under 800° C. avoid a loss in Co capacity, and therefore, the electrode material capacity.
[0173] In some embodiments, the coated electrode material includes particles having a core and coating surrounding at least portion of the core. The core comprises an active material comprising lithium (Li), cobalt (Co), phosphate (PO.sub.4), and at least two additional metals other than Li and Co, and the coating surrounding the core is made as described herein. In some embodiments, the particles contain multiple cores surrounded by the coating. In some embodiments, the coating is an oxide coating.
[0174] The core and coating may have different structures (e.g., different degrees of crystallinity) and different morphologies. The structure and morphologies of the particles vary in function of the thickness of the coating around the core. Coulombic efficiency and capacity retention are also affected by the thickness of the coating in the electrode material. In some embodiments, the weight percentage of oxide coating on the electrode material is about 0.25-1 wt %. Higher weight percentage of oxide coating material (e.g. 2.5-5 wt %) can reduce capacity and coulombic efficiency. In some embodiments, the coated electrode material is crystalline, or at least essentially crystalline. In some embodiments, the coated electrode material may not be fully crystalline, and may appear amorphous. Such coatings may be amorphous or may have some degrees of crystal structure.
[0175] Additional improvements in battery properties can be attained by optimizing the composition of a cobalt-rich phosphate material of formula (I), (II), or (III). Specifically, further improvements in properties such as specific energy, rate capability, and capacity retention can be attained by optimizing or otherwise adjusting for an amount of lithium, an amount and type of a set of conductive additives, or both.
[0176] In one aspect, a cobalt-rich phosphate material is provided with an excess amount of lithium to yield a lithium-rich electrode material that provides improved battery properties, including high specific energy, excellent rate capability, and excellent capacity retention. Without wishing to be bound by a particular theory, excess lithium can mitigate against, or decrease the occurrence of, cation antisite defects by reducing aliovalent M (or M′) ions on Li sites, so as to improve Li+ diffusivity as well as electronic conductivity. A cation antisite defect refers to a type of defect in which Li and M (or M′) ions exchange positions. Aliovalent antisite cations on Li sites, such as M2+ cations on Li sites, can lead to trapping of migrating Li+ vacancies and blocking of Li+ diffusion pathways, thereby reducing electrochemical capacity. In some instances, excess lithium also can compensate for potential loss of lithium during synthesis at high temperatures.
[0177] For example, in the case of Lil-xCol-y-zMyM′z(PO.sub.4)1-a of formula (II) or Lil-x Col-yMy(PO.sub.4)1-a of formula (III), excess lithium can be attained by adjusting the value of x to be x<0 (or 1-x>1), such as about −0.3≦x<0, about −0.3≦x≦−0.2, about −0.2≦x≦−0.1, about −0.2≦x<0, or about −0.1≦x<0. In some embodiments, the value of x may also specifically be about −0.01, −0.02, −0.03, −0.05, −0.08, −0.1, −0.12, −0.15, −0.18, −0.2, −0.22, −0.25, −0.28, or −0.3. In some embodiments, x is such that an overall composition of the cobalt-rich phosphate material has a molar ratio of Li, relative to a combined molar amount of Co, M, and M′, that is greater than about 1 and up to about 1.1, up to about 1.2, up to about 1.3, or more.
[0178] In another aspect, a cobalt-rich phosphate material is provided as a combination of a lithium-rich electrode material along with a set of conductive additives, which can correspond to a single conductive additive, a pair of different conductive additives, or a combination of three or more different conductive additives. Without wishing to be bound by a particular theory, the inclusion of a conductive additive can improve battery properties through one or more of the following mechanisms: (1) the conductive additive can enhance electrical conductivity; (2) the conductive additive can improve electrical coupling between particles of an active material and a current collector as well as inter-particle coupling; and (3) the presence of the conductive additive can control electrode porosity for optimized electrolyte access to the active material and improved Li+ transport. In some instances, synergistic effects of excess lithium along with an optimized amount and type of conductive additive can yield further improved battery properties, including further improvements in specific energy, rate capability, and capacity retention.
[0179] Suitable conductive additives include those in a particulate form, and having a surface area greater than about 1 m.sup.2/g and up to about 3,000 m.sup.2/g or more, such as from about 10 m.sup.2/g to about 100 m.sup.2/g, from about 100 m.sup.2/g to about 500 m.sup.2/g, from about 500 m.sup.2/g to about 1,000 m.sup.2/g, from about 1,000 m.sup.2/g to about 2,000 m.sup.2/g, or from about 2,000 m.sup.2/g to about 3,000 m.sup.2/g. An average particle size or an average grain size can be about 1 μm or greater, or can be in the sub-micron range, such as from about 1 nm to about 100 nm or from about 1 nm to about 10 nm. In some embodiments, a conductive additive is electrically conductive, and can have an electrical conductivity of at least about 10-2 S/cm, such as at least about 10-1 S/cm, at least about 1 S/cm, at least about 10 S/cm, or at least about 100 S/cm, and up to about 10,000 S/cm or more. Examples of suitable conductive additives include carbon-based additives, such as carbon black, acetylene black, graphite, and fullerenic carbon nanotubes. Specific examples of carbon-based additives include Super P Li (about 60 m.sup.2/g available from Timcal), KJ600 (about 1,400 m.sup.2/g available from Akzo Nobel), KJ300 (about 800 m.sup.2/g available from Akzo Nobel), SFG6 (available from Timcal), and Timrex HSAG300 (available from Timcal).
[0180] An amount of a particular conductive additive can be expressed in terms of a weight percent of the additive relative to a combined weight of an active material and a set of conductive additives (or wt %). For example, an amount of a conductive additive can be in the range of about 0.1 wt % to about 20 wt %, such as from about 0.1 wt % to about 18 wt %, from about 0.1 wt % to about 15 wt %, from about 0.5 wt. % to about 10 wt %, from about 0.5 wt % to about 8 wt %, from about 0.5 wt % to about 5 wt %, or from about 0.5 wt % to about 3 wt %, and, in the case of a combination of multiple conductive additives, a total amount of the additives can be in the range of about 0.1 wt % to about 20 wt %, such as from about 0.1 wt % to about 18 wt %, from about 0.1 wt % to about 15 wt %, from about 0.5 wt. % to about 10 wt %, from about 0.5 wt % to about 8 wt %, from about 0.5 wt % to about 5 wt %, or from about 0.5 wt % to about 3 wt %.
[0181] Resulting battery properties can depend upon the identity of a particular conductive additive used, an amount of the conductive additive used, and, in the case of a combination of multiple conductive additives, a relative amount of each additive within the combination. Accordingly, the resulting battery properties can be fine-tuned or optimized by proper selection of a set of conductive additives and adjusting amounts of those additives. For some embodiments, a relatively small amount of a conductive additive can be desirable, such as in the range of about 0.5 wt % to about 5 wt % or from about 0.5 wt % to about 3 wt %. In the case of a carbon-based additive, synergistic effects between excess lithium and reduced carbon content can yield further improved battery properties, including further improvements in specific energy, rate capability, and capacity retention. Improvements at reduced carbon content are further magnified when battery properties are expressed at a whole cell level, such as when specific capacity and specific energy are expressed in terms of a combined weight of an active material and a carbon-based additive.
[0182] In one aspect of the present invention, a method of making a cobalt-rich phosphate material with one or more improved battery properties is provided. Methods of making cobalt-rich phosphate materials as embodiments of the present invention include high energy milling processes, such as ball or attritor milling, grinding, sol-gel, hydrothermal, solvothermal, or synthesis from a melt, all with or without subsequent heat treatment. The products are then calcinated under high temperatures. These methods produce compositions wherein the dopants may form a solid solution with the LiCoPO.sub.4, other novel phases, similar to Nasicon or pyrophosphate, or the dopants are dispersed within the LiCoPO.sub.4 base material.
[0183] In one aspect of the present invention, a nonaqueous electrolyte secondary battery is provided, comprising: a positive electrode containing a positive electrode active material containing a cobalt-rich phosphate material; a negative electrode; and a nonaqueous electrolyte, wherein the cobalt-rich phosphate material comprises formula (I). A set of conductive additives also can be included along with the cobalt-rich phosphate material.
[0184] In one aspect of the present invention, a nonaqueous electrolyte secondary battery is provided, comprising: a positive electrode containing a positive electrode active material containing a cobalt-rich phosphate material; a negative electrode; and a nonaqueous electrolyte, wherein the cobalt-rich phosphate material comprises formula (II) or (III). A set of conductive additives also can be included along with the cobalt-rich phosphate material.
[0185] In one aspect of the present invention, a nonaqueous electrolyte secondary battery is provided, comprising: a positive electrode containing a positive electrode active material which comprises two components or two phases; a negative electrode; and a nonaqueous electrolyte, wherein the two component positive electrode active material comprises the formula (I), and the composition of the second component comprises oxides, phosphates, hydroxides, carbonates, or nitrates of alkali, alkali earth, and transition metals, such as Ti, V, Na, Ta, W, Cr, Cu, Zn, Zr, Y, La, Ag, Mg. In one embodiment, M is two or more of Fe, Mn, V, Cr, Ni, Ti, Cu, Zn. In another embodiment, the second component is one or more compounds that react with the first component to form a solid solution in which the metal of the second component occupies the partial Li or Co/M sites. In another embodiment, the second component is one or more compounds that react with the phosphate in the first component to form other phases like Nasicon or pyrophosphate. In another embodiment, the second component is one or more compounds that are coated on or dispersed through the bulk of the first component. A set of conductive additives also can be included along with the positive electrode active material.
[0186] In one aspect of the present invention, a nonaqueous electrolyte secondary battery is provided, comprising: a positive electrode containing a positive electrode active material which comprises two components or two phases; a negative electrode; and a nonaqueous electrolyte, wherein the two component positive electrode active material comprises the formula (II) or (III), and the composition of the second component comprises oxides, hydroxides, carbonates, or nitrates of alkali, alkali earth, and transition metals, such as Ti, V, Na, Ta, W, Cr, Cu, Zn, Zr, Y, La, Ag, Mg. In one embodiment, M/M′ are one or more of Fe, Mn, V, Cr, Ni, Ti, Cu, Zn. In another embodiment, the second component is one or more compounds that react with the first component to form a solid solution in which the metal of the second component occupies the partial Li or Co/M/M′ sites. In another embodiment, the second component is one or more compounds that react with the phosphate in the first component to form other phases like Nasicon or pyrophosphate. In another embodiment, the second component is one or more compounds that are coated on or dispersed through the bulk of the first component. A set of conductive additives also can be included along with the positive electrode active material.
[0187] Transition metals and rare earth elements useful herein, in addition to Fe and Co, include the elements of Groups 3-11 of the Periodic Table, including those selected from the group consisting of Ti (Titanium), V (Vanadium), Mn (Manganese), Cu (Copper), Zn (Zinc), Y (Yttrium), Zr (Zirconium), Nb (Niobium), Mo (Molybdenum), Ag (Silver), La (Lanthanum), Hf (Hafnium), Ta (Tantalum), W (Tungsten), and mixtures thereof. Preferred are those selected from the group consisting of Ti, V, Mn, Ni, Cu, Zn, Y, Zr, Nb, Ag, La, and mixtures thereof. Particularly useful transition metals include Co, Fe, Nb, Mn, V, Ti and mixtures thereof. A preferred embodiment comprises a mixture of Co, Fe, and Mn. Another preferred embodiment comprises a mixture of Co, Fe, and Ti. Another preferred embodiment comprises a mixture of Co, Fe, and V.
[0188] Another preferred embodiment comprises a mixture of Co, Fe, and Nb. Although a variety of oxidation states for such transition metals is available, in some embodiments it is most preferable that the transition metals have a +2 oxidation state.
[0189] Alkali metals useful herein include the elements of Group 1. Preferred are Na and K. Particularly preferred is Na.
[0190] Alkali earth metals useful herein include the elements of Group 2. Preferred are Be, Mg, and Ca. Particularly preferred are Mg and Ca.
[0191] Rare earth metals useful herein include Yttrium (Y), Scandium (Sc), Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Samarium (Sm), Europium (Eu), Gadolinium (Gd), or Terbium (Tb). Preferred are Y and La. Embodiments incorporating rare earth metals include, but are not limited to: LiFe.sub.0.2Co.sub.0.65Y.sub.0.15PO.sub.4, LiFe.sub.0.2Co.sub.0.75Y.sub.0.05PO.sub.4, LiFe.sub.0.2Co.sub.0.70Y.sub.0.10PO.sub.4, LiFe.sub.0.5Co.sub.0..sub.45Y.sub.0.05PO.sub.4, LiFe.sub.0.5Co.sub.0.40Y.sub.0.10PO.sub.4, and LiFe.sub.0.5Co.sub.0.35Y.sub.0.15PO.sub.4.
[0192] M may further comprises one or more Group 13 or 14 elements. Preferably, such elements do not include C (carbon), N (nitrogen), and P (phosphorus). Preferred Group 13 or 14 elements include Al (Aluminum), Ga (Gallium), In (Indium), Tl (Thallium), Si (Silicon), and Ge (Germanium). Particularly preferred is Al.
[0193] Non-limiting examples of cobalt-rich phosphate materials include the following: [0194] LiCo.sub.0.4Fe.sub.0.5Nb.sub.0.1PO.sub.4 [0195] LiCo.sub.0.35Fe.sub.0.5Ti.sub.0.15PO.sub.4 [0196] LiCo.sub.0.35Fe.sub.0.5V.sub.0.15PO.sub.4 [0197] LiCo.sub.0.35Fe.sub.0.5V.sub.0.15PO.sub.4 [0198] LiCo.sub.0.8Fe.sub.0.1Ti.sub.0.1PO.sub.4 [0199] LiCo.sub.0.75Fe.sub.0.1Ti.sub.0.15PO.sub.4 [0200] Li.sub.1.3Co.sub.0.35Fe.sub.0.5V.sub.0.3(PO.sub.4).sub.1.3 [0201] Li.sub.1.3Co.sub.0.55Fe.sub.0.3V.sub.0.3(PO.sub.4).sub.1.3 [0202] LiFe.sub.0.2Co.sub.0.75Ce.sub.0.05PO.sub.4 [0203] LiFe.sub.0.2Co.sub.0.7Ce.sub.0.1PO.sub.4 [0204] LiFe.sub.0.2Co.sub.0.65Ce.sub.0.15PO.sub.4 [0205] LiFe.sub.0.2Co.sub.0.75Hf.sub.0.05PO.sub.4 [0206] LiFe.sub.0.2Co.sub.0.7Hf.sub.0.1PO.sub.4 [0207] LiFe.sub.0.2Co.sub.0.65Hf.sub.0.15PO.sub.4 [0208] LiFe.sub.0.2Co.sub.0.75Mo.sub.0.05PO.sub.4 [0209] LiFe.sub.0.2Co.sub.0.7Mo.sub.0.1PO.sub.4 [0210] LiFe.sub.0.2Co.sub.0.65Mo.sub.0.1PO.sub.4 [0211] LiFe.sub.0.2Co.sub.0.75Ta.sub.0.05PO.sub.4 [0212] LiFe.sub.0.2Co.sub.0.7Ta.sub.0.1PO.sub.4 [0213] LiFe.sub.0.2Co.sub.0.65Ta.sub.0.15PO.sub.4 [0214] LiFe.sub.0.2Co.sub.0.75W.sub.0.05PO.sub.4 [0215] LiFe.sub.0.2Co.sub.0.7W.sub.0.1PO.sub.4 [0216] LiFe.sub.0.2Co.sub.0.65W.sub.0.15PO.sub.4 [0217] LiFe.sub.0.2Co.sub.0.75Ti.sub.0.05PO.sub.4 [0218] LiFe.sub.0.2Co.sub.0.7Ti.sub.0.1PO.sub.4 [0219] LiFe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0220] LiFe.sub.0.2Co.sub.0.75V.sub.0.05PO.sub.4 [0221] LiFe.sub.0.2Co.sub.0.7V.sub.0.1PO.sub.4 [0222] LiFe.sub.0.2Co.sub.0.65V.sub.0.15PO.sub.4 [0223] LiFe.sub.0.2Co.sub.0.65Y.sub.0.15PO.sub.4 [0224] LiFe.sub.0.2Co.sub.0.75Y.sub.0.05PO.sub.4 [0225] LiFe.sub.0.2Co.sub.0.70Y.sub.0.10PO.sub.4 [0226] LiFe.sub.0.5Co.sub.0.45Y.sub.0.05PO.sub.4 [0227] LiFe.sub.0.5Co.sub.0.40Y.sub.0.10PO.sub.4 [0228] LiFe.sub.0.5Co.sub.0.35Y.sub.0.15PO.sub.4 [0229] LiFe.sub.0.2Co.sub.0.65Zr.sub.0.15PO.sub.4 [0230] LiFe.sub.0.2Co.sub.0.75Zr.sub.0.05PO.sub.4 [0231] LiFe.sub.0.2Co.sub.0.70Zr.sub.0.10PO.sub.4 [0232] LiFe.sub.0.5Co.sub.0.45Zr.sub.0.05PO.sub.4 [0233] LiFe.sub.0.5Co.sub.0.40Zr.sub.0.10PO.sub.4 [0234] LiFe.sub.0.5Co.sub.0.35Zr.sub.0.15PO.sub.4 [0235] LiFe.sub.0.1Co.sub.0.5Ti.sub.0.1PO.sub.4 [0236] LiFe.sub.0.2Co.sub.0.7Nb.sub.0.1PO.sub.4 [0237] LiFe.sub.0.2Co.sub.0.65Ti.sub.0.15(PO.sub.4).sub.1.03 [0238] Li.sub.1.23Fe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0239] Li.sub.1.13Fe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0240] Li.sub.1.03Fe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0241] LiFe.sub.0.45Co.sub.0.25Mn.sub.0.3PO.sub.4 [0242] LiFe.sub.0.4Co.sub.0.05Mn.sub.0.55PO.sub.4 [0243] LiFe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0244] LiFe.sub.0.1Co.sub.0.75Ti.sub.0.15PO.sub.4 [0245] LiCo.sub.0.55Mn.sub.0.3Ti.sub.0.15PO.sub.4 [0246] LiCo.sub.0.45Mn.sub.0.3Ti.sub.0.25PO.sub.4 [0247] LiFe.sub.0.2Co.sub.0.65Ti.sub.0.15(PO.sub.4).sub.0.94 [0248] LiFe.sub.0.2Co.sub.0.7Ti.sub.0.1PO.sub.4 [0249] Li .sub.1.1Fe.sub.0.5Co.sub.0.35V.sub.0.3(PO.sub.4).sub.1.3 [0250] Li .sub.1.1Fe.sub.0.3Co.sub.0.55V.sub.0.3(PO.sub.4).sub.1.3 [0251] Li.sub.1.2Fe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0252] Li.sub.1.2Fe.sub.0.2Co.sub.0.7Ti.sub.0.1PO.sub.4 [0253] Li.sub.1.2Fe.sub.0.1Co.sub.0.75Ti.sub.0.15PO.sub.4 [0254] Li.sub.1.1Fe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0255] Li.sub.1.1Fe.sub.0.2Co.sub.0.7Ti.sub.0.1PO.sub.4 [0256] Li.sub.1.1Fe.sub.0.1Co.sub.0.75Ti.sub.0.15PO.sub.4 [0257] Li.sub.1.1Fe.sub.0.1Co.sub.0.5Ti.sub.0.1PO.sub.4 [0258] LiFe.sub.1.1Fe.sub.0.1Co.sub.0.55Ti.sub.0.05PO.sub.4 [0259] LiFe.sub.0.1Co.sub.0.55Nb.sub.0.05PO.sub.4 [0260] Li.sub.1.05Fe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0261] Li.sub.1.05Fe.sub.0.2Co.sub.0.7Ti.sub.0.1PO.sub.4 [0262] Li.sub.1.05Fe.sub.0.1Co.sub.0.75Ti.sub.0.15PO.sub.4 [0263] Li.sub.1.05Fe.sub.0.1Co.sub.0.5Ti.sub.0.1PO.sub.4 [0264] Li.sub.1.05Fe.sub.0.1Co.sub.0.55Ti.sub.0.05PO.sub.4 [0265] LiFe.sub.0.1Co.sub.0.65Ti.sub.0.25PO.sub.4 [0266] LiCo.sub.0.75sMn.sub.0.1Ti.sub.0.15PO.sub.4 [0267] LiCo.sub.0.65Mn.sub.0.3Ti.sub.0.05PO.sub.4 [0268] LiCo.sub.0.55Mn.sub.0.2Ti.sub.0.25PO.sub.4 [0269] LiCo.sub.0.7Mn.sub.0.5Ti.sub.0.1PO.sub.4 [0270] LiCo.sub.0.7Mn.sub.0.1Ti.sub.0.5PO.sub.4 [0271] LiCo.sub.0.6Mn.sub.0.3Ti.sub.0.1PO.sub.4 [0272] LiFe.sub.0.2Co.sub.0.75Ti.sub.0.05PO.sub.4 [0273] LiFe.sub.0.2Co.sub.0.65Ti.sub.0.15PO.sub.4 [0274] LiFe.sub.0.2Co.sub.0.7Ti.sub.0.1PO.sub.4 [0275] LiFe.sub.0.4Co.sub.0.55V.sub.0.05PO.sub.4 [0276] LiFe.sub.0.4Co.sub.0.45V.sub.0.15PO.sub.4 [0277] LiFe.sub.0.2Co.sub.0.75Ta.sub.0.05PO.sub.4 [0278] Li.sub.1.04.Fe.sub.0.3Co.sub.0.65V.sub.0.0.4(PO.sub.4).sub.1.04 [0279] Li.sub.1.1Fe.sub.0.15Co.sub.0.55V.sub.0.3(PO.sub.4).sub.1.1 [0280] Li .sub.1.2Fe.sub.0.1Co.sub.0.9V.sub.0.2(PO.sub.4).sub.1.2 [0281] Li.sub.1.2Fe.sub.0.5Co.sub.0.35V.sub.0.5(PO.sub.4).sub.1.2 [0282] Li.sub.1.2Fe.sub.0.3Co.sub.0.55V.sub.0.5(PO.sub.4).sub.1.2 [0283] Li .sub.1.1Fe.sub.0.05Co.sub.0.95V.sub.0.1(PO.sub.4).sub.1.1 [0284] Li.sub.1.05Co.sub.0.5Fe.sub.0.1V.sub.0.1PO.sub.4 [0285] Li.sub.1.1Co.sub.0.5Fe.sub.0.1V.sub.0.1PO.sub.4 [0286] Li.sub.1.05Co.sub.0.55Fe.sub.0.1V.sub.0.05PO.sub.4 [0287] Li.sub.1.1Co.sub.0.55Fe.sub.0.1V.sub.0.05PO.sub.4 [0288] LiFe.sub.0.1Co.sub.0.55Ti.sub.0.05PO.sub.4 [0289] LiFe.sub.0.1Co.sub.0.7Ti.sub.0.2PO.sub.4 [0290] LiCo.sub.0.75Fe.sub.0.2V.sub.0.05PO.sub.4 [0291] LiCo.sub.0.7Fe.sub.0.2Cu.sub.0.1PO.sub.4 [0292] LiFe.sub.0.4Co.sub.0.45Ti.sub.0.15PO.sub.4 [0293] LiFe.sub.0.3Co.sub.0.45Ti.sub.0.25PO.sub.4 [0294] LiFe.sub.0.3Co.sub.0.5Ti.sub.0.2PO.sub.4 [0295] LiFe.sub.0.2Co.sub.0.6Ti.sub.0.2PO.sub.4 [0296] LiCo.sub.0.75Fe.sub.0.2Nb.sub.0.05PO.sub.4 [0297] LiCo.sub.0.45Fe.sub.0.5Nb.sub.0.05PO.sub.4 [0298] LiCo.sub.0.4Fe.sub.0.5Nb.sub.0.1PO.sub.4 [0299] LiCo.sub.0.65Fe.sub.0.2Ti.sub.0.15PO.sub.4 [0300] LiCo.sub.0.35Fe.sub.0.5V.sub.0.15PO.sub.4 [0301] LiCo.sub.0.35Fe.sub.0.5Ti.sub.0.15PO.sub.4 [0302] LiCo.sub.0.7Fe.sub.0.2Ti.sub.0.1PO.sub.4 [0303] LiCo.sub.0.4Fe.sub.0.5Ti.sub.0.1PO.sub.4 [0304] LiFe.sub.0.33Co.sub.0.33Mn.sub.0.33PO.sub.4 [0305] LiFe.sub.0.2Co.sub.0.5PO.sub.4 [0306] LiFe.sub.0.5C0.sub.0.5PO.sub.4 [0307] LiFe.sub.0.2Co.sub.0.65Y.sub.0.15PO.sub.4 [0308] LiFe.sub.0.2Co.sub.0.75Y.sub.0.05PO.sub.4 [0309] LiFe.sub.0.2Co.sub.0.70Y.sub.0.10PO.sub.4 [0310] LiFe.sub.0.5Co.sub.0.45 Y.sub.0.05PO.sub.4 [0311] LiFe.sub.0.5Co.sub.0.40Y.sub.0.10PO.sub.4 [0312] LiFe.sub.0.5Co.sub.0.35Y.sub.0.15PO.sub.4 [0313] LiFe.sub.0.2Co.sub.0.65Zr.sub.0.15PO.sub.4 [0314] LiFe.sub.0.2Co.sub.0.75Zr.sub.0.05PO.sub.4 [0315] LiFe.sub.0.2Co.sub.0.70Zr.sub.0.10PO.sub.4 [0316] LiFe.sub.0.2Co.sub.0.45Zr.sub.0.05PO.sub.4 [0317] LiFe.sub.0.5Co.sub.0.40Zr.sub.0.10PO.sub.4 [0318] LiFe.sub.0.5Co.sub.0.35Zr.sub.0.15PO.sub.4 [0319] LiFe.sub.0.2Co.sub.0.75Ce.sub.0.05PO.sub.4 [0320] LiFe.sub.0.2Co.sub.0.7Ce.sub.0.1PO.sub.4 [0321] LiFe.sub.0.2Co.sub.0.65Ceo.1s PO.sub.4 [0322] LiFe.sub.0.2Co.sub.0.75Hf.sub.0.05PO.sub.4 [0323] LiFe.sub.0.2Co.sub.0.7Hf.sub.0.1PO.sub.4 [0324] LiFe.sub.0.2Co.sub.0.65Hf.sub.0.15PO.sub.4 [0325] LiFe.sub.0.2Co.sub.0.75Mo.sub.0.05PO.sub.4 [0326] LiFe.sub.0.2Co.sub.0.7Mo.sub.0.1PO.sub.4 [0327] LiFe.sub.0.2Co.sub.0.65Mo.sub.0.1PO.sub.4 [0328] LiFe.sub.0.2Co.sub.0.75Ta.sub.0.05PO.sub.4 [0329] LiFe.sub.0.2Co.sub.0.7Ta.sub.0.1PO.sub.4 [0330] LiFe.sub.0.2Co.sub.0.65Ta.sub.0.15PO.sub.4 [0331] LiFe.sub.0.2Co.sub.0.75W.sub.0.05PO.sub.4 [0332] LiFe.sub.0.2Co.sub.0.7W.sub.0.1PO.sub.4 [0333] LiFe.sub.0.2Co.sub.0.65W.sub.0.15PO.sub.4 [0334] Li Coo.4Fe.sub.0.5Nb.sub.0.1PO.sub.4
Method of Synthesis
[0335] The synthesis of the cobalt-rich phosphate materials can be carried out using a variety of techniques, including solid-state chemistry techniques such as solid-state synthesis, mechanochemical activation, carbothermal reduction, or microwave processing, and solution chemistry techniques such as hydrothermal processing, sol-gel processing, precipitation methods, emulsion-drying methods, and spray pyrolysis. (See Jugovic et al., J. Power Sources 190:538-544 (2009), which is hereby incorporated by reference in its entirety).
[0336] One preferable method for the synthesis of the cobalt-rich phosphate materials is to use high energy milling processes to produce a fine powder, such as using ball or attritor milling, or by grinding. (Pranger et al., J. Phys. Chem. Solids 67:1338-1342 (2006); Kim et al. J. Phys. Chem. Solids 69:2371-2377 (2008), which are hereby incorporated by reference in their entirety). One desirable technique is ball milling, which can involve forming an alloy or a substantially homogeneous blend from a mixture of precursor materials in a ball milling device. In some embodiments, stoichiometric amounts of the precursor materials are used, based on a desired composition of the resulting cobalt-rich phosphate material. The precursor materials along with a set of conductive additives can be provided as powders, and, during ball milling, particles of the powders can undergo repeated collisions with grinding ball bearings, causing deformation, welding, and fracture of the particles that can result in micro-structural and chemical composition changes. Ball milling can be carried out in an inert gas atmosphere, such as one including helium, neon, argon, krypton, xenon, or a mixture thereof, or in a reactive gas atmosphere, such as one including a reactive component that contributes to micro-structural and chemical composition changes. As a result of ball milling, the precursor materials are mixed such that a resulting particulate material is an alloy, a blend, or a combination of an alloy and a blend. Depending upon ball milling conditions used, the resulting particulate material can include particles of an active material having a relatively small particle or crystallite size, such as having an average particle size or an average grain size in the range of about 1 nm to about 10 μm, such as in the sub-micron range. In some instances, smaller particle sizes can yield superior battery properties relative to larger particle sizes, as a result of surface area effects. A conductive additive can be coated on, dispersed with, or otherwise combined or reacted with the particles of the active material. In some instances, a conductive additive can be added to the active material subsequent to synthesis of the active material, instead of, or in conjunction with, during synthesis of the active material. Addition of the conductive additive subsequent to synthesis can be carried out by a high energy milling process, such as ball or attritor milling.
[0337] Milling conditions to obtain embodiments of the present invention may be varied depending upon the particular machine used. The ball milling time to produce embodiments of the present invention can vary from about 0 hours to 10 hours. In some embodiments, the ball milling time to produce cobalt-rich phosphate materials is from about 1-10 hours, 2-9 hours, 3-8 hours, 4-6 hours, 1-8 hours, 1-6 hours, 1-5 hours, 1-3 hours, 2-10 hours, 3-10 hours, 5-10 hours, 7-10 hours, 8-10 hours, 3-6 hours, 4-8 hours, or 3-7 hours. In some embodiments, the ball milling time is about 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.
[0338] Compounds added to a LiCoPO.sub.4 base material to produce embodiments of the present invention may be added in any form, such as, but not exclusively, oxides, nitrides, hydroxides, hydrides, or salts. For example, compounds may be added as oxides, such as Nb.sub.2O.sub.5, TiO.sub.2, V.sub.2O.sub.5, MoO.sub.2, WO.sub.3, V.sub.2O.sub.3, Ta.sub.2O.sub.5, HfO.sub.2, or CeO.sub.2.
[0339] Referring to formula (I), precursor materials can include a source of Li, a source of Co, a source of each N, a source of each M, and a source of PO.sub.4. Referring to formulas (II) and (III), precursor materials can include a source of Li, a source of Co, a source of M, a source of M′, and a source of PO.sub.4. Sources of Li, Co, N, M, and M′ include metal- containing salts or other metal-containing compounds, such as fluorides, chlorides, bromides, iodides, nitrates, nitrites, nitrides, sulfates, sulfites, bisulfites, carbonates, bicarbonates, borates, phosphates, silicates, antimonates, arsenates, germanates, oxides, hydroxides, hydrides, acetates, oxalates, and so forth. Metal-containing salts can be used in a hydrated or dehydrated form. Examples of lithium sources include lithium dihydrogen phosphate (LiH.sub.2PO.sub.4), lithium carbonate (Li.sub.2CO.sub.3), lithium hydroxide (LiOH), or mixtures thereof. Examples of cobalt sources include cobalt carbonate (CoCO.sub.3), cobalt hydroxide (Co(OH).sub.2), or mixtures thereof. Examples of titanium sources include oxides, such as TiO.sub.2, Ti.sub.2O.sub.3, TiO, and mixtures thereof. Examples of iron sources include oxalates, such as FeC.sub.2O.sub.4.2H.sub.2O. Examples of phosphate sources include LiH.sub.2PO.sub.4, ammonium dihydrogenphosphate (NH.sub.4H.sub.2PO.sub.4), or mixtures thereof.
[0340] In some embodiments, a source of one element also can serve as a source of at least one other element. For example, LiH.sub.2PO.sub.4 can serve as a source of both lithium and phosphate, and can be used in place of separate sources of lithium and phosphate, such as LiOH and NH.sub.4H.sub.2PO.sub.4, thereby reducing material cost. If excess lithium is desired, Li.sub.2CO.sub.3 can be used as a secondary source of lithium. In some embodiments, the use of LiH.sub.2PO.sub.4 as a source of lithium and phosphate and CoCO.sub.3 as a source of cobalt can provide a number of advantages, including improvements in specific capacity and specific energy (
[0341] After compounds are milled, ground and/or otherwise mixed, they are then calcinated under high temperatures. High temperature methods that can be used to form compounds of embodiments of the present invention include those found in Padhi et al., J. Electrochem. Soc. 144:1609-1613 (1997) and Yun et al., J. Power Sources 1361-1368 (2006), which are hereby incorporated by reference in their entirety. Calcination produces compositions wherein the dopants may form a solid solution with the LiCoPO.sub.4, other novel phases, similar to Nasicon or pyrophosphate, or the dopants are dispersed within the LiCoPO.sub.4 base material.
[0342] Calcination temperatures to produce embodiments of the present invention are greater than about 300° C. In some embodiments, calcination temperatures are from about 400° C. to 800° C. In some embodiments, calcination temperatures are greater than about 450° C. In some embodiments, calcination temperatures are greater than about 500° C. In some embodiments, calcination temperatures are greater than about 550° C. In some embodiments, calcination temperatures are greater than about 600° C. In some embodiments, calcination temperatures are greater than about 650° C. In some embodiments, calcination temperatures are greater than about 700° C. In some embodiments, calcination temperatures are greater than about 750° C. In some embodiments, calcination temperatures can be about 400-800° C., 450-750° C., 500-700° C., 550-650° C., 400-750° C., 400-700° C., 400-600° C., 400-550° C., 400-500° C., 400-450° C., 450-800° C., 500-800° C., 550-800° C., 600-800° C., 650-800° C., 700-800° C., 500-650° C., 500-600° C., 450-500° C., 500-550° C., 550-600° C., 600-650° C., 650-700° C., or 700-750° C. In some embodiments, calcination temperatures may be about 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., or 800° C.
[0343] Calcination times to produce embodiments of the present invention can vary from about 30 minutes to 30 hours. In some embodiments, calcination times are greater than 10 hours. In some embodiments, calcination times are greater than 12 hours. In some embodiments, calcination times are greater than 15 hours. In some embodiments, calcination times are greater than 10 hours. In some embodiments, calcination times are greater than 18 hours. In some embodiments, calcination times are greater than 20 hours. In some embodiments, calcination times are greater than 24 hours. In some embodiments, calcination times are greater than 28 hours. In some embodiments, calcination times can be about 12-28 hours, 15-24 hours, 18-20 hours, 10-28 hours, 15-28 hours, 15-20 hours, 18-24 hours, 12-30 hours, 12-24 hours, 12-20 hours, 12-18 hours, 15-30 hours, 20-30 hours, 24-30 hours, 10-15 hours, 10-18 hours, or 18-24 hours. In some embodiments, calcination times may be about 10, 12, 15, 18, 20, 24, 28, or 30 hours.
[0344] Depending upon the particular set of additives used and conditions during the synthesis, the resulting electrode material can include the set of additives as a coating, as a set of dispersed components within a blend, as a set of alloying components or a set of dopants, or as a combination thereof. Irrespective of the ultimate form the final material takes, the electrode material can be represented by the formulas (I), (II), or (III).
Conditioning of Cobalt-Rich Phosphate Materials
[0345] The cobalt-rich phosphate materials described herein can be conditioned prior to sale or use in a commercial application. For example, an electrode, such as a cathode, comprising an electrode material, an electrochemical cell, or a battery can be conditioned by cycling prior to commercial sale or use in commerce. A method of conditioning a battery can, for example, comprise conditioning a battery for commercial sale. Such method can comprise, for example, providing a battery, and cycling such battery through at least 1, at least 2, at least 3, at least 4, or at least 5 cycles, each cycle comprising charging the battery and discharging the battery at a rate of 0.05 C (e.g., a current of 7.5 mA/g) between 4.95 V and 2.0 V versus a reference counterelectrode, such as a graphite anode. Charging and discharging can be carried out at a higher or lower rate, such as at a rate of 0.1 C (e.g., a current of 15 mA/g), at a rate of 0.5 C (e.g., a current of 75 mA/g), or at a rate of 1 C (e.g., a current of 150 mA/g).
Uses of Cobalt-Rich Phosphate Materials
[0346] The cobalt-rich phosphate materials described herein can be used for a variety of battery applications—essentially for any application where it would be advantageous to use a low cost, low-toxicity material that has superior electrochemical performance, high specific capacity, and improved cycling. For example, the materials can be substituted in place of conventional Li-ion battery materials for consumer applications.
[0347]
[0348] The operation of the battery 100 is based upon reversible intercalation and de-intercalation of Li ions into and from materials of the anode 102 and the cathode 106. Other implementations of the battery 100 are contemplated, such as those based on conversion chemistry. Referring to
EXAMPLES
[0349] The following examples describe specific aspects of some embodiments of the invention to illustrate and provide a description for those of ordinary skill in the art. The examples should not be construed as limiting the invention, as the examples merely provide specific methodology useful in understanding and practicing some embodiments of the invention.
Example 1
[0350] Stoichiometric ratios of LiOH, Co(OH).sub.2, FeC.sub.2O.sub.4.2H.sub.2O, NH.sub.4H.sub.2PO.sub.4, TiO.sub.2, and carbon-based additive (Super P Li) were added into reaction vessels along with 288 g of 5 mm diameter chrome steel ball bearings. The total mass of materials was 7.7 g. The wells were sealed, removed from glove box, then milled at 38 g for 4 h in a planetary ball mill. The milled precursors were heated to 700° C. at 5° C./min for 18 h under N.sub.2 flow, and finally cooled to room temperature at 4° C./min. A preferred stoichiometric ratio was LiOH:FeC.sub.2O.sub.4.2H.sub.2O:Co(OH).sub.2:NH.sub.4H.sub.2PO.sub.4:TiO.sub.2=1:0.1:0.8:0.1 with 18 wt % carbon. The batteries were assembled in a high purity argon filled glove box (M-Braun, O.sub.2 and humidity contents <0.1 ppm). Samples of powder were formulated into slurries with poly(vinylidene fluoride) (Sigma-Aldrich) and Super P Li (TIMCAL, 85:7.5:7.5) in 1-methyl-2-pyrrolidinone (Sigma-Aldrich, anhydrous, 99.5%), and were deposited and dried on aluminum current collectors prior to battery assembly. Cells were made using lithium as an anode, glass fiber filters (Millipore) as separators, and electrolyte including 1M LiPF.sub.6 in a EC:EMC=1:2 solution. Cells were cycled at room temperature from 2.0 V to 4.95 V, unless otherwise specified. Cell testing protocol was: [0351] Cycle 1: charging C/20, discharging C/10 [0352] Cycle 2-5: charging C/10, discharging C/10 [0353] Cycle 6: charging: 2 C, OCV (0.5 h), 1 C, OCV (0.5 h), 0.5 C, OCV (0.5 h), 0.1 C, OCV (0.5 h), 0.05 C, OCV (0.5 h); discharging 2 C, OCV (0.5 h), 1 C, OCV (0.5 h), 0.5 C, OCV (0.5 h), 0.1 C, OCV (0.5 h), 0.05 C, OCV (0.5 h)
Example 2
[0354] Stoichiometric ratios of LiOH, Co(OH).sub.2, FeC.sub.2O.sub.4.2H.sub.2O, NH.sub.4H.sub.2PO.sub.4, TiO.sub.2, and carbon-based additive (Super P Li) were added into a reaction tank along with 1842 g of 5 mm diameter chrome steel ball bearings. The total mass of materials was 42.2 g. The tank was sealed, removed from glove box, attached to an attritor mill and milled at 600 rpm for 6 h. The milled precursors were heated to 700° C. at 5° C./min for 18 h under N.sub.2 flow, and finally cooled to room temperature at 4° C./min. A preferred stoichiometric ratio was LiOH:FeC.sub.2O.sub.4.2H.sub.2O:Co(OH).sub.2:NH.sub.4H.sub.2PO.sub.4:TiO.sub.2=1:0.1:0.8:0.1 with 18 wt % carbon. The same cell making sample and testing procedures were applied as in Example 1.
Example 3
[0355]
Example 4
[0356]
Example 5
[0357]
Example 6
[0358]
Example 7
[0359]
Example 8
[0360]
[0361]
Example 9
[0362] Figures Sa and Sb illustrate ternary maps comparing (maximum) specific capacity (Figure Sa, mAh/g) and (maximum) specific energy (Figure Sb, Wh/kg) on 1st cycle as a function of cobalt, iron and vanadium (V.sub.2O.sub.5) in the cobalt-rich materials in an embodiment of the present invention. The cobalt-rich materials were formed using similar conditions as set forth in Examples 1 and 2. Fe amounts were varied from 0.0-0.5. Co amounts were varied from 0.35-0.95. V amounts were varied from 0.05-0.25.
Example 10
[0363]
Example 11
[0364]
Example 12
[0365]
[0366]
Example 13
[0367]
Example 14
[0368]
Example 15
[0369]
Example 16
[0370]
Example 17
[0371]
Example 18
[0372] Stoichiometric ratios of LiOH, Co(OH).sub.2, FeC.sub.2O.sub.4.2H.sub.2O, NH.sub.4H.sub.2PO.sub.4, TiO.sub.2, and carbon-based additive (Super P Li or KJ600) were added into a reaction tank along with 1842 g of 5 mm diameter chrome steel ball bearings. The total mass of materials was 42.2 g for at least one set of measurements. The tank was sealed, removed from glove box, attached to an attritor mill and milled at 600 rpm for 6 h. The milled precursors were heated to 700° C. at 5° C./min for 18 h under N.sub.2 flow, and finally cooled to room temperature at 4° C./min. The stoichiometric ratios were varied to include different amounts of Li and carbon, and included LiOH:FeC.sub.2O.sub.4.2H.sub.2O:Co(OH).sub.2:NH.sub.4H.sub.2PO.sub.4:TiO.sub.2=1.05:0.1:0.8:1:0.1 with 5 wt % carbon-based additive. The batteries were assembled in a high purity argon filled glove box (M-Braun, O.sub.2 and humidity contents <0.1 ppm). Samples of powder were formulated into slurries with poly(vinylidene fluoride) (Sigma-Aldrich) and Super P Li (TIMCAL, 85:7.5:7.5) in 1-methyl-2-pyrrolidinone (Sigma-Aldrich, anhydrous, 99.5%), and were deposited and dried on aluminum current collectors prior to battery assembly. Cells were made using lithium or graphite as an anode, glass fiber filters (Millipore) or Cellguard 2400 as separators, and electrolyte including 1 M LiPF.sub.6 in a EC:EMC=1:2 solution or with 2 wt % TTSP additives. Cells were cycled at room temperature from 2.0 V to 4.95 V with different rates: C/20 (based on theoretical capacity of 150 mAh/g or with 1 C corresponding to 150 mA/g) for both charge and discharge on 1st cycle from 3rd cycle both charging and discharging rates are 1 C. The 2nd cycle was rate testing and the testing protocol was: charging at 1 C, OCV (0.5 h), then 0.5 C, OCV (0.5 h), then 0.1 C, OCV (0.5 h), then 0.05 C, OCV (0.5 h) and discharging at 1 C, OCV (0.5 h), then 0.5 C, OCV (0.5 h), then 0.1 C, OCV (0.5 h), then 0.05 C, OCV (0.5h).
[0373]
[0374]
[0375]
[0376]
[0377]
Example 19
[0378]
Example 20
[0379] Synthesis of a cobalt-rich phosphate material was carried out using an alternative set of precursors (LiOH, CoCO.sub.3, FeC.sub.2O.sub.4.2H.sub.2O, LiH.sub.2PO.sub.4, and TiO.sub.2), and resulting battery properties were compared to those using a previous, first set of precursors (LiOH, Co(OH).sub.2, FeC.sub.2O.sub.4.2H.sub.2O, NH.sub.4H.sub.2PO.sub.4, and TiO.sub.2) as set forth in Examples 1, 2, and 18. Stoichiometric ratios of LiOH, CoCO.sub.3, FeC.sub.2O.sub.4.2H.sub.2O, LiH.sub.2PO.sub.4, TiO.sub.2, and carbon-based additive (Super P Li or KJ600) were added into a reaction tank along with 1842 g of 5 mm diameter chrome steel ball bearings. The total mass of materials was 42.2 g for at least one set of measurements. The tank was sealed, removed from glove box, attached to an attritor mill and milled at 600 rpm for 6 h. The milled precursors were heated to 700° C. at 5° C./min for 18 h under N.sub.2 flow, and finally cooled to room temperature at 5° C./min. The stoichiometric ratios included LiOH:FeC.sub.2O.sub.4.2H.sub.2O:CoCO.sub.3:LiH.sub.2PO.sub.4:TiO.sub.2=0.05:0.1:0.8:1.0:0.1 with 5 wt % carbon-based additive. The batteries were assembled in a high purity argon filled glove box (M-Braun, O.sub.2 and humidity contents <0.1 ppm). Samples of powder were formulated into slurries with poly(vinylidene fluoride) (Sigma-Aldrich) and Super P Li (TIMCAL, 85:7.5:7.5) in 1-methyl-2-pyrrolidinone (Sigma-Aldrich, anhydrous, 99.5%), and were deposited and dried on aluminum current collectors prior to battery assembly. Cells were made using graphite as an anode, glass fiber filters (Millipore) as separators, and electrolyte including IM LiPF.sub.6 in a EC:EMC=1:2 solution. Cells were cycled at room temperature from 2.0 V to 4.95 V with different rates: C/20 (based on theoretical capacity of 150 mAh/g or with 1 C corresponding to 150 mA/g) for both charge and discharge on 1st cycle, and 1 C for later cycling.
[0380]
Example 21
[0381] Synthesis of an oxide coated cobalt-rich phosphate material was carried out, and resulting battery properties were compared to the same uncoated electrode materials. Stoichiometric ratios of LiOH, CoCO.sub.3, FeC.sub.2O.sub.4.2H.sub.2O, etc., were added into a reaction tank along with 1842 g of 5 mm diameter chrome steel ball bearings. The total mass of materials was 42.2 g for at least one set of measurements. The tank was sealed, removed from glove box, attached to an attritor mill and milled at 600 rpm for 3 h. The milled precursors were heated to 700° C. at 5° C./min for 18 h under N.sub.2 flow (19 L/min), and finally cooled to room temperature at 5° C./min. Oxide precursors (Tetraethyl orthosilicate (TEOS) for SiO.sub.2, Zirconium(N) propoxide solution 70% for ZrO.sub.2, Aluminum isopropoxide for Al.sub.2O.sub.3, Titanium(N) isopropoxide for TiO.sub.2) were added to the above prepared electrode materials along with 5 mL iso-propanol in a glove box. The percentage of oxides corresponding to the initial precursor loadings were calculated based on 100% transfer from the precursors to the oxides. For example, for coating 0.15%, 0.25%, 0.5%, 1%, 2% and 5 wt % SiO.sub.2 onto 600 mg electrode materials, approximately 0.9, 1.5, 3.1, 6.1, 12.2 and 31.6 mg oxides, respectively, were used. The tank was sealed, removed from glove box, attached to an attritor mill and milled at 600 rpm for 3 h. After milling, the mixtures were first dried under vacuum at 70-100° C. for 2 hours, and then transferred to N.sub.2 filled glove box. The milled and dried precursors were heated to 500° C. at 5° C./min for 12 h under N.sub.2 flow, and finally cooled to room temperature at 5° C./min. In some tests, a broad annealing temperature ranging from 350 to 800° C. were used and coated phosphate battery materials annealed in the range of 400-500° C. were found to show improved cycle life and capacity retention when compared to the control (i.e., uncoated battery materials).
[0382] The batteries were assembled in a high purity argon filled glove box (M-Braun, O.sub.2 and humidity contents <0.1 ppm). Samples of powder were formulated into slurries with poly(vinylidene fluoride) (Sigma-Aldrich) and Super P Li (TIMCAL, 85:7.5:7.5) in 1-methyl-2-pyrrolidinone (Sigma-Aldrich, anhydrous, 99.5%), and were deposited and dried on aluminum current collectors prior to battery assembly. Cells were made using lithium as an anode, glass fiber filters (Millipore) as separators, and electrolyte including 1M LiPF.sub.6 in a EC:EMC=1:2 solution. Cells were cycled at room temperature from 2.0 V to 4.95 V with different rates: C/20 (based on theoretical capacity of 150 mAh/g or with 1 C corresponding to 150 mA/g) for both charge and discharge on 1st cycle, and 1 C for later cycling
[0383]
[0384] As shown in
[0385] The entire disclosures of all references cited in this application are incorporated by reference.
[0386] While the invention has been described with reference to the specific embodiments thereof, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention as defined by the appended claims. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, method, or process to the objective, spirit and scope of the invention. All such modifications are intended to be within the scope of the claims appended hereto. In particular, while the methods disclosed herein have been described with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or re-ordered to form an equivalent method without departing from the teachings of the invention. Accordingly, unless specifically indicated herein, the order and grouping of the operations are not limitations of the invention.