As the use of cordless and portable devices, such as laptop computers, becomes more and more common, the need keeps increasing for compact, lightweight batteries with high energy density to use as power sources for those devices. In particular, lithium batteries are commonly cited as examples of batteries that could be dominant for portable devices.
In lithium-ion batteries, the cathode is typically the most expensive active component. Additionally, the cathode generally comprises the highest mass fraction of the battery and can play a critical role in determining the energy density of the battery by setting the positive electrode potential. Moreover, the cathode often limits the charge/discharge rate of the battery system.
There are currently three major classes of cathodes that are typically used in lithium-based batteries. Olivines, such as LiFePO4, have been used, as have stabilized LiMn2O4 spinels. In addition, stabilized Li(Ni, Co, or Al)O2 layered oxides have been investigated. One example of a stabilized layered oxide currently available uses LiCoO2, with a maximum voltage of 4 V, as the positive electrode active material. However, LiCoO2 can be costly because cobalt is an expensive material. Nickel and aluminum are sometimes used as a substitute for costly cobalt.
The crystal structure of LiNiO2 can change during charging/discharging cycles, which can lead to deterioration of the cathode. Thus, the use of this material for a cathode can have significant drawbacks.
The use of olivines, stabilized LiMn2O4 spinels, and stabilized Li(Ni, Co, or Al)O2 layered oxides as a cathode in a lithium-ion battery have each been investigated thoroughly. Each of these compounds has been relatively optimized, and only incremental improvements are anticipated.
Thus, there exists a need in the art for an improved material for a cathode in a lithium-ion battery, capable of high energy density.
The present invention provides novel and advantageous materials for use as a cathode in a lithium-ion battery. The materials of the subject invention can provide improved energy density and charge/discharge properties over existing materials.
In one embodiment of the present invention, a compound can be of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal.
In another embodiment, a lithium-ion battery can include a cathode, and the cathode can comprise a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal.
In yet another embodiment, a material for a cathode of a battery can include a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal.
In yet another embodiment, a method for producing a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4 is provided, wherein M is a transition metal.
Advantageously, the compounds, materials, batteries, and methods of the present invention can provide increased energy density to meet the increasing demands for power for portable devices.
The present invention provides novel and advantageous compounds and materials for use as a cathode in a lithium-ion battery. The materials of the subject invention can provide improved energy density and charge/discharge properties over existing materials.
In one embodiment of the present invention, a compound can be of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal. The transition metal can be any transition metal, including, but not limited to, titanium, manganese, iron, cobalt, nickel, zinc, zirconium, molybdenum, silver, cadmium, hafnium, tantalum, tungsten, platinum, gold, palladium, chromium, or copper.
In a particular embodiment, the transition metal, M, can be chromium, copper, or cobalt.
In the compound of the general form, Li2MxNi0.5-x-yMn1.5+yO4 (where M is a transition metal), x can have a value in the range of 0.02 to 0.08, inclusive; and y can have a value in the range of 0.05 to 0.25, inclusive. However, the values of x and y can depend on which transition metal, M, is present.
For example, x can have a value in any of the following ranges, each of which is inclusive of the endpoints: 0.02 to 0.03; 0.02 to 0.04; 0.02 to 0.05; 0.02 to 0.06; 0.02 to 0.07; 0.02 to 0.08; 0.03 to 0.04; 0.03 to 0.05; 0.03 to 0.06; 0.03 to 0.07; 0.03 to 0.08; 0.04 to 0.05; 0.04 to 0.06; 0.04 to 0.07; 0.04 to 0.08; 0.05 to 0.06; 0.05 to 0.07; 0.05 to 0.08; 0.06 to 0.07; 0.06 to 0.08; or 0.07 to 0.08.
Also, y can have a value in any of the following ranges, each of which is inclusive of the endpoints: 0.05 to 0.06; 0.05 to 0.07; 0.05 to 0.08; 0.05 to 0.09; 0.05 to 0.10; 0.05 to 0.11; 0.05 to 0.12; 0.05 to 0.13; 0.05 to 0.14; 0.05 to 0.15; 0.05 to 0.16; 0.05 to 0.17; 0.05 to 0.18; 0.05 to 0.19; 0.05 to 0.20; 0.05 to 0.21; 0.05 to 0.22; 0.05 to 0.23; 0.05 to 0.24; 0.05 to 0.25; 0.06 to 0.07; 0.06 to 0.08; 0.06 to 0.09; 0.06 to 0.10; 0.06 to 0.11; 0.06 to 0.12; 0.06 to 0.13; 0.06 to 0.14; 0.06 to 0.15; 0.06 to 0.16; 0.06 to 0.17; 0.06 to 0.18; 0.06 to 0.19; 0.06 to 0.20; 0.06 to 0.21; 0.06 to 0.22; 0.06 to 0.23; 0.06 to 0.24; 0.06 to 0.25; 0.07 to 0.08; 0.07 to 0.09; 0.07 to 0.10; 0.07 to 0.11; 0.07 to 0.12; 0.07 to 0.13; 0.07 to 0.14; 0.07 to 0.15; 0.07 to 0.16; 0.07 to 0.17; 0.07 to 0.18; 0.07 to 0.19; 0.07 to 0.20; 0.07 to 0.21; 0.07 to 0.22; 0.07 to 0.23; 0.07 to 0.24; 0.07 to 0.25; 0.08 to 0.09; 0.08 to 0.10; 0.08 to 0.11; 0.08 to 0.12; 0.08 to 0.13; 0.08 to 0.14; 0.08 to 0.15; 0.08 to 0.16; 0.08 to 0.17; 0.08 to 0.18; 0.08 to 0.19; 0.08 to 0.20; 0.08 to 0.21; 0.08 to 0.22; 0.08 to 0.23; 0.08 to 0.24; 0.08 to 0.25; 0.09 to 0.10; 0.09 to 0.11; 0.09 to 0.12; 0.09 to 0.13; 0.09 to 0.14; 0.09 to 0.15; 0.09 to 0.16; 0.09 to 0.17; 0.09 to 0.18; 0.09 to 0.19; 0.09 to 0.20; 0.09 to 0.21; 0.09 to 0.22; 0.09 to 0.23; 0.09 to 0.24; 0.09 to 0.25; 0.10 to 0.11; 0.10 to 0.12; 0.10 to 0.13; 0.10 to 0.14; 0.10 to 0.15; 0.10 to 0.16; 0.10 to 0.17; 0.10 to 0.18; 0.10 to 0.19; 0.10 to 0.20; 0.10 to 0.21; 0.10 to 0.22; 0.10 to 0.23; 0.10 to 0.24; 0.10 to 0.25; 0.11 to 0.12; 0.11 to 0.13; 0.11 to 0.14; 0.11 to 0.15; 0.11 to 0.16; 0.11 to 0.17; 0.11 to 0.18; 0.11 to 0.19; 0.11 to 0.20; 0.11 to 0.21; 0.11 to 0.22; 0.11 to 0.23; 0.11 to 0.24; 0.11 to 0.25; 0.12 to 0.13; 0.12 to 0.14; 0.12 to 0.15; 0.12 to 0.16; 0.12 to 0.17; 0.12 to 0.18; 0.12 to 0.19; 0.12 to 0.20; 0.12 to 0.21; 0.12 to 0.22; 0.12 to 0.23; 0.12 to 0.24; 0.12 to 0.25; 0.13 to 0.14; 0.13 to 0.15; 0.13 to 0.16; 0.13 to 0.17; 0.13 to 0.18; 0.13 to 0.19; 0.13 to 0.20; 0.13 to 0.21; 0.13 to 0.22; 0.13 to 0.23; 0.13 to 0.24; 0.13 to 0.25; 0.14 to 0.15; 0.14 to 0.16; 0.14 to 0.17; 0.14 to 0.18; 0.14 to 0.19; 0.14 to 0.20; 0.14 to 0.21; 0.14 to 0.22; 0.14 to 0.23; 0.14 to 0.24; 0.14 to 0.25; 0.15 to 0.16; 0.15 to 0.17; 0.15 to 0.18; 0.15 to 0.19; 0.15 to 0.20; 0.15 to 0.21; 0.15 to 0.22; 0.15 to 0.23; 0.15 to 0.24; 0.15 to 0.25; 0.16 to 0.17; 0.16 to 0.18; 0.16 to 0.19; 0.16 to 0.20; 0.16 to 0.21; 0.16 to 0.22; 0.16 to 0.23; 0.16 to 0.24; 0.16 to 0.25; 0.17 to 0.18; 0.17 to 0.19; 0.17 to 0.20; 0.17 to 0.21; 0.17 to 0.22; 0.17 to 0.23; 0.17 to 0.24; 0.17 to 0.25; 0.18 to 0.19; 0.18 to 0.20; 0.18 to 0.21; 0.18 to 0.22; 0.18 to 0.23; 0.18 to 0.24; 0.18 to 0.25; 0.19 to 0.20; 0.19 to 0.21; 0.19 to 0.22; 0.19 to 0.23; 0.19 to 0.24; 0.19 to 0.25; 0.20 to 0.21; 0.20 to 0.22; 0.20 to 0.23; 0.20 to 0.24; 0.20 to 0.25; 0.21 to 0.22; 0.21 to 0.23; 0.21 to 0.24; 0.21 to 0.25; 0.22 to 0.23; 0.22 to 0.24; 0.22 to 0.25; 0.23 to 0.24; 0.23 to 0.25; or 0.24 to 0.25.
The compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal, can be used as a material for a cathode for a battery. The battery can be, for example, a lithium-ion battery. Thus, in another embodiment of the present invention, a lithium-ion battery can include a cathode, and the cathode can comprise a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal. In a particular embodiment, x can have a value in the range of 0.02 to 0.08, inclusive; and y can have a value in the range of 0.05 to 0.25, inclusive. Though, as previously discussed, the values of x and y can be dependent on the transition metal, M. Thus, x and y can have values in any of the ranges listed above.
In specific embodiments, the transition metal can be chromium, copper, or cobalt.
The compounds and materials of the present invention can provide increased energy density over existing materials used as cathodes for batteries. Additionally, the compounds and materials of the present invention can provide good energy density at low cost.
Because the manganese oxidation state is mainly Mn4+, the compounds and materials of the present invention can be very stable such that effectively no manganese dissolution occurs. In addition, the use of a nickel reduction-oxidation (redox) couple can increase the lithium intercalation potential of the material to about 4.7 V.
Referring to
Batteries of the subject invention can also be used for many other common applications, including but not limited to cellular phones, laptop computers, and portable digital music players.
Additionally, compounds and materials of the present invention surprisingly exhibit improved charge/discharge cycle properties. Referring to
A compound of the general form Li2MxNi0.5-x-yMn1.5+yO4 (where M is a transition metal) can be prepared by, for example, sol-gel methods. In an embodiment, a mixture of Li(CH3COO).2H2O, Ni(CH3COO)2.4H2O, and Mn(CH3COO)2.4H2O can be prepared in distilled water, and a an M acetate (where M is a transition metal) can be added to the solution. The solution can then be added to an aqueous solution of an acid. The acid can be, for example, citric acid.
The pH of the mixed solution can optionally be adjusted by adding a basic solution. The basic solution can be, for example, an ammonium hydroxide solution. The mixed solution can then be heated to obtain a gel. The mixed solution can be heated at a temperature of from about 50° C. to about 300° C. for a period of time of from about 30 minutes to about 72 hours. In a particular embodiment, the mixed solution can be heated at a temperature of about 75° C. for a period of time of about from 8 hours to about 16 hours to obtain a transparent gel.
The gel can be decomposed at a temperature of from about 200° C. to about 600° C. for a period of time of from about 1 hour to about 72 hours, and then calcined at a temperature of about 500° C. to about 1000° C. for a period of time of about 1 hour to about 72 hours. In an embodiment, the gel can be decomposed in air. In a particular embodiment, the gel can be decomposed at a temperature of about 400° C. for about 10 hours in air and then calcined at a temperature of about 800° C. for about 10 hours to give the compound of the general form Li2MxNi0.5-x-yMn1.5+yO4 (where M is a transition metal). Referring to
Referring to
The compounds, materials, batteries, and methods of the present invention can provide show minimized distortion. Referring to
Advantageously, the compounds, materials, batteries, and methods of the present invention can provide increased energy and power density over existing materials, at low cost, as well as displaying improved charge/discharge properties.
Table 1 shows first principles calculations for lithium diffusion activation barriers for lithium ion batteries at room temperature. The calculations are for simulated supercell LiM1/2Mn3/2O4 (where M is a transition metal, such as Co, Cr, Cu, Fe, or Ni), which is comprised of an 8 formula unit. The calculations are based on the density functional theory (DFT) applied within the general gradient approximation (GGA) using PAW pseudopotentials. First principle methods rely on the basic laws of physics such as quantum mechanics and statistical mechanics, and therefore do not require any experimental input beyond the nature of the constituent elements (and in some cases the structure).
Referring to Table 1, copper and cobalt doping can provide a low lithium diffusion activation barrier at room temperature. That is, charge/discharge rates can be faster if copper or cobalt is used as the transition metal in the spinel framework of an electrode material of the present invention.
The invention includes, but is not limited to, the following embodiments:
A compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal.
The compound according to embodiment 1, wherein M is chromium.
The compound according to embodiment 1, wherein M is copper.
The compound according to embodiment 1, wherein M is cobalt.
The compound according to any of embodiments 1-4, wherein a lithium intercalation potential of the compound is about 4.7 V.
The compound according to any of embodiments 1-5, wherein the energy density of the compound is about 1000 W-hr/kg.
A material for a cathode of a battery, wherein the material comprises a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal.
The material according to embodiment 7, wherein M is chromium.
The material according to embodiment 7, wherein M is copper.
The material according to embodiment 7, wherein M is cobalt.
The material according to any of embodiments 7-10, wherein a lithium intercalation potential of the battery is about 4.7 V.
The material according to any of embodiments 7-11, wherein the energy density of the material is about 1000 W-hr/kg.
The material according to any of embodiments 7-12, wherein the battery is a lithium-ion battery.
A lithium-ion battery comprising a cathode, wherein the cathode comprises a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal.
The lithium-ion battery according to embodiment 14, wherein M is chromium.
The lithium-ion battery according to embodiment 14, wherein M is copper.
The lithium-ion battery according to embodiment 14, wherein M is cobalt.
The lithium-ion battery according to any of embodiments 14-17, wherein a lithium intercalation potential of the compound is about 4.7 V.
The lithium-ion battery according to any of embodiments 14-18, wherein the energy density of the compound is about 1000 W-hr/kg.
A method of preparing a compound of the general form Li2MxNi0.5-x-yMn1.5+yO4, wherein M is a transition metal, the method comprising:
preparing a first solution by mixing Li(CH3COO).2H2O, Ni(CH3COO)2.4H2O, and Mn(CH3COO)2.4H2O in water;
adding an M acetate to the first solution, wherein M is the transition metal;
adding the first solution to an aqueous solution of an acid to form a mixed solution;
heating the mixed solution to obtain a gel;
decomposing the gel; and
calcining the gel.
The method according to embodiment 20, wherein the acid is citric acid.
The method according to any of embodiments 20-21, further comprising adding a basic solution to the mixed solution before heating the mixed solution.
The method according to embodiment 22, wherein the basic solution is an ammonium hydroxide solution.
The method according to any of embodiments 20-23, wherein the mixed solution is heated at a temperature of about 75° C. for a period of time of from about 8 hours to about 16 hours.
The method according to any of embodiments 20-24, wherein the gel is decomposed in air.
The method according to any of embodiments 20-25, wherein the gel is decomposed in air at a temperature of about 400° C. for a period of time of about 10 hours.
The method according to any of embodiments 20-26, wherein the gel is calcined at a temperature of about 800° C. for a period of time of about 10 hours.
The method according to any of embodiments 20-27, wherein a lithium intercalation potential of the compound is about 4.7 V.
The method according to any of embodiments 20-28, wherein the energy density of the compound is about 1000 W-hr/kg.
The method according to any of embodiments 20-29, wherein M is chromium.
The method according to any of embodiments 20-29, wherein M is Copper.
The method according to any of embodiments 20-29, wherein M is cobalt.
The following examples illustrate procedures for practicing the invention. These examples should not be construed as limiting. All percentages are by weight and all solvent mixture proportions are by volume unless otherwise noted. It will be apparent to those skilled in the art that the examples involve use of materials and reagents that are commercially available from known sources, e.g., chemical supply houses, so no details are given respecting them.
Sol solutions were prepared from stoichiometric mixtures of Li(CH3COO).2H2O, Ni(CH3COO)).4H2O, and Mn(CH3COO)2.4H2O in distilled water. The solution was then added dropwise to a continuously stirred aqueous solution of citric acid. The pH of the mixed solution was adjusted by adding ammonium hydroxide solution. The solution was then heated at a temperature of about 75° C. overnight. A transparent gel was obtained. The resulting gel precursors were decomposed at a temperature of about 400° C. for about 10 hours in air and then calcined at a temperature of about 800° C. for about 10 hours.
Sol solutions were prepared from stoichiometric mixtures of Li(CH3COO).2H2O, Ni(CH3COO)2.4H2O, and Mn(CH3COO)2.4H2O in distilled water. Chromium acetate was added to the distilled water according to the stoichiometry. The solution was then added dropwise to a continuously stirred aqueous solution of citric acid. The pH of the mixed solution was adjusted by adding ammonium hydroxide solution. The solution was then heated at a temperature of about 75° C. overnight. A transparent gel was obtained. The resulting gel precursors were decomposed at a temperature of about 400° C. for about 10 hours in air and then calcined at a temperature of about 800° C. for about 10 hours to produce a compound of the form Li2CrxNi0.5-x-yMn1.5+yO4.
Sol solutions were prepared from stoichiometric mixtures of Li(CH3COO).2H2O, Ni(CH3COO)2.4H2O, and Mn(CH3COO)2.4H2O in distilled water. Copper acetate was added to the distilled water according to the stoichiometry. The solution was then added dropwise to a continuously stirred aqueous solution of citric acid. The pH of the mixed solution was adjusted by adding ammonium hydroxide solution. The solution was then heated at a temperature of about 75° C. overnight. A transparent gel was obtained. The resulting gel precursors were decomposed at a temperature of about 400° C. for about 10 hours in air and then calcined at a temperature of about 800° C. for about 10 hours to produce a compound of the form Li2CuxNi0.5-x-yMn1.5+yO4.
Sol solutions were prepared from stoichiometric mixtures of Li(CH3COO).2H2O, Ni(CH3COO)2.4H2O, and Mn(CH3COO)2.4H2O in distilled water. Cobalt acetate was added to the distilled water according to the stoichiometry. The solution was then added dropwise to a continuously stirred aqueous solution of citric acid. The pH of the mixed solution was adjusted by adding ammonium hydroxide solution. The solution was then heated at a temperature of about 75° C. overnight. A transparent gel was obtained. The resulting gel precursors were decomposed at a temperature of about 400° C. for about 10 hours in air and then calcined at a temperature of about 800° C. for about 10 hours to produce a compound of the form Li2CoxNi0.5-x-yMn1.5+yO4.
All patents, patent applications, provisional applications, and publications referred to or cited herein, supra or infra, are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.
It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.
This application claims the benefit of U.S. provisional application Ser. No. 61/162,766, filed Mar. 24, 2009, which is incorporated herein by reference in its entirety.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US10/28483 | 3/24/2010 | WO | 00 | 7/7/2011 |
Number | Date | Country | |
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61162766 | Mar 2009 | US |