# Patent

## Title
Lithium-ion secondary battery

## Abstract

A lithium-ion battery includes a cathode that includes an active cathode material. The active cathode material includes a cathode mixture that includes a lithium cobaltate and a manganate spinel a manganate spinel represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 or Li(1+x1)Mn2Oz1. The lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.9:0.1 to about 0.6:0.4. A lithium-ion battery pack employs a cathode that includes an active cathode material as described above. A method of forming a lithium-ion battery includes the steps of forming an active cathode material as described above; forming a cathode electrode with the active cathode material; and forming an anode electrode in electrical contact with the cathode via an electrolyte.

## Background
RELATED APPLICATIONS
This application is a continuation of International Application No. PCT/US2007/014591, which designated the United States and was filed on Jun. 22, 2007, published in English, which is a continuation of U.S. patent application Ser. No. 11/485,068, filed Jul. 12, 2006, which is a continuation-in-part of U.S. patent application Ser. No. 11/474,056, filed on Jun. 23, 2006 now abandoned, and to U.S. patent application Ser. No. 11/474,056, filed on Jun. 23, 2006. U.S. patent application Ser. No. 11/474,056 is a continuation-in-part of Int'l. App. No. PCT/US2005/047383, which designated the U.S. and was filed on Dec. 23, 2005 published in English, which claims the benefit of U.S. Provisional Application No. 60/639,275 filed on Dec. 28, 2004, U.S. Provisional Application No. 60/680,271 filed on May 12, 2005; and U.S. Provisional Application No. 60/699,285 filed on Jul. 14, 2005. The entire teachings of the above-mentioned applications are incorporated herein by reference.
INCORPORATION BY REFERENCE
U.S. patent application, filed on Jun. 22, 2007 under 60/936,825, which is entitled “Low Pressure Current Interrupt Device For Batteries”; U.S. patent application, filed on Jun. 22, 2007 under 11/821,585, which is entitled “Integrated Current-Interrupt Device For Lithium-Ion Cells”; U.S. Provisional Application No. 60/717,898, filed on Sep. 16, 2005; International Application No. PCT/US2005/047383, filed on Dec. 23, 2005; U.S. patent application Ser. No. 11/474,081, filed on Jun. 23, 2006; U.S. patent application Ser. No. 11/474,056, filed on Jun. 23, 2006; U.S. Provisional Application No. 60/816,977, filed on Jun. 28, 2006; U.S. patent application Ser. No. 11/485,068, filed on Jul. 12, 2006; U.S. patent application Ser. No. 11/486,970, filed on Jul. 14, 2006; and U.S. Provisional Application No. 60/852,753, filed on Oct. 19, 2006 are all incorporated herein by reference in their entirety.


BACKGROUND OF THE INVENTION
Rechargeable batteries, such as lithium-ion rechargeable batteries, are widely used as electrical power for battery-powered portable electronic devices, such as cellular telephones, portable computers, camcorders, digital cameras, PDAs and the like. A typical lithium-ion battery pack for such portable electronic devices employs multiple cells that are configured in parallel and in series. For example, a lithium-ion battery pack may include several blocks connected in series where each block includes one or more cells connected in parallel. Each block typically has an electronic control that monitors voltage levels of the block. In an ideal configuration, each of the cells included in the battery pack is identical. However, when cells are aged and cycled, cells tend to deviate from the initial ideal conditions, resulting in an unbalanced cell pack (e.g., unidentical capacity, impedance, discharge and charge rate). This unbalance among the cells may cause over-charge or over-discharge during normal operation of the rechargeable batteries, and in turn can impose safety concerns, such as explosion (i.e., rapid gas release and possibility for fire).
Traditionally, the conventional lithium-ion rechargeable batteries have employed LiCoO2-type materials as the active component of lithium-ion battery cathodes. For such a lithium-ion cell employing LiCoO2-type active cathode materials to be fully charged, the charge voltage is usually 4.20V. With lower charging voltage, the capacity is lower, which corresponds to lower utilization of active LiCoO2 materials. On the other hand, with higher charging voltage, the cell is less safe. In general, it is a challenge for LiCoO2-based lithium-ion cells to have a high capacity, for example higher than about 3 Ah due to a high safety concern. In order to minimize the safety concern, lowering the charge voltage is one option. However, this will lower the cell capacity, and in turn lower cell energy density. To obtain high capacity, increasing the number of cells in one battery pack may be another option rather than increasing the charge voltage. However, the increase in the number of cells can result in increased probability of unbalance among the cells, which can cause over-charge or over-discharge during normal operation, as discussed above.
The largest mainstream cell that is typically used in the industry currently is a so-called “18650” cell. This cell has an outer diameter of about 18 mm and a length of 65 mm. Typically, the 18650 cell utilizes LiCoO2 and has a capacity between 1800 mAh and 2400 mAh but cells as high as 2600 mAh are currently being used. It is generally believed that it is not safe to use LiCoO2 in a larger cell than the 18650 cell because of a safety concern associated with LiCoO2. Other cells larger than the 18650 cells exist in the art, for example, “26650” cells having an outer diameter of about 26 mm and a length of 65 mm. The 26650 cells typically do not contain LiCoO2 and have worse performance characteristics in terms of Wh/kg and Wh/L than the 18650 cells employing LiCoO2.
Therefore, there is a need to develop new active cathode materials for lithium-ion batteries that minimize or overcome the above-mentioned problems. In particular, there is a need to develop new active cathode materials that can enable manufacturing large batteries, for example, larger than the conventional LiCoO2-based batteries (e.g., 18650 cells) in volume and/or Ah/cell.
SUMMARY OF THE INVENTION
The present invention is generally directed to (1) an active cathode material that includes a mixture of at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel and an olivine compound, (2) a lithium-ion battery having such an active cathode material, (3) a method of forming such a lithium-ion battery, (4) a battery pack comprising one or more cells, each of the cells including such an active cathode material, and (5) a system that includes such a battery pack or lithium-ion battery and a portable electronic device.
In one embodiment, the present invention is directed to an active cathode material that includes a mixture of electrode materials. The mixture includes: at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel and an olivine compound. The manganate spinel is represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where:
x1 and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3;
y1 and y2 are each independently greater than 0.0 and equal to or less than 0.3;
z1 is equal to or greater than 3.9 and equal to or less than 4.1; and
A′ is at least one member of the group consisting of magnesium, aluminum, cobalt, nickel and chromium.
The olivine compound is represented by an empirical formula of Li(1−x2)A′′x2MPO4 where:
x2 is equal to or greater than 0.05 and equal to or less than 0.2, or

    
    
        x2 is equal to or greater than 0.0 and equal to or less than 0.1; and
    
    


M is at least one member of the group consisting of iron, manganese, cobalt and magnesium; and
A′′ is at least one member of the group consisting of sodium, magnesium, calcium, potassium, nickel and niobium.
In another embodiment, the present invention is directed to an active cathode material that includes a mixture including: a lithium nickelate selected from the group consisting of LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel represented by an empirical formula of Li(1+x7)Mn2-y7Oz7 where x7 and y7 are each independently equal to or greater than 0.0 and equal to or less than 1.0; and z7 is equal to or greater than 3.9 and equal to or less than 4.2.
The present invention is also directed to a lithium-ion battery having a cathode that includes an active cathode material. The active cathode material includes a mixture of electrode materials. The mixture includes: at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel and an olivine compound. The manganate spinel is represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where:
x1 and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3;
y1 and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3;
z1 is equal to or greater than 3.9 and equal to or less than 4.1; and
A′ is at least one member of the group consisting of magnesium, aluminum, cobalt, nickel and chromium.
The olivine compound is represented by an empirical formula of Li(1−x2)A′′x2MPO4 where:
x2 is equal to or greater than 0.05 and equal to or less than 0.2, or
x2 is equal to or greater than 0.0 and equal to or less than 0.1; and
M is at least one member of the group consisting of iron, manganese, cobalt and magnesium; and
A′′ is at least one member of the group consisting of sodium, magnesium, calcium, potassium, nickel and niobium.
In one embodiment, the mixture includes: at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel and an olivine compound. The manganate spinel and olivine compound are as described above. In another embodiment, the mixture includes: a lithium nickelate selected from the group consisting of a lithium cobaltate, LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel as described above. The battery has a capacity greater than about 3.0 Ah/cell.
In yet another embodiment, the present invention is directed to a lithium-ion battery having a cathode that includes an active cathode material, the active cathode material comprising a cathode mixture that includes a lithium cobaltate and a manganate spinel represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where y1 and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3, and the other variables are as described above. The lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.95:0.05 to about 0.55:0.45.
Also included in the present invention is a battery pack that includes one or more cells, preferably a plurality of cells. The cell(s) of the battery pack are as described above for the lithium-ion batteries of the invention. In one embodiment, the mixture includes: at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel and an olivine compound. The manganate spinel and olivine compound are as described above for the lithium-ion batteries of the invention. In another embodiment, the mixture includes a lithium nickelate selected from the group consisting of a lithium cobaltate, LiCoO2-coated LiNi0.8Co0.15Al0.5O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel as described above. Preferably the battery pack includes a plurality of cells and at least one cell of the cells has a capacity greater than about 3.0 Ah/cell. In yet another embodiment, the mixture includes a lithium cobaltate and a manganate spinel represented by an empirical formula of Li(1+x1)Mn1-y1A′y2)2-x2Oz1, wherein the variables are as described above, and the lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.95:0.05 to about 0.55:0.45.
A method of forming a lithium-ion battery having a cathode that includes an active cathode material as described above is also included in the present invention. The method includes forming an active cathode material as described above. The method further includes the steps of forming a cathode electrode with the active cathode material; and forming an anode electrode in electrical contact with the cathode electrode via an electrolyte, thereby forming a lithium-ion battery
A system that includes a portable electronic device and a battery pack as described above is also included in the present invention.
The lithium-ion batteries of the invention, which employ a novel blend of two or more different types of active cathode materials in the positive electrode, have safer chemistry characteristics than conventional lithium-ion batteries that solely employ LiCoO2 as the active material of the lithium-ion battery cathodes. In particular, an active cathode material of the invention enables manufacturing of large batteries, e.g., larger than the 18650 cells, for use in these mobile devices partly due to its safety and high capacity in terms of energy density and power density. The present invention also allows for economical manufacturing of larger cells compared to what is common in today's industry (e.g., the 18650 cells), in part due to lower cathode costs and in part due to lower electronics costs. These higher capacity type cells allow lower cost without sacrificing overall safety. These higher capacity type cells can in turn minimize the number of electronic components needed for charge control, which allows lowering of electronic component costs overall for a battery pack utilizing multiple cells connected in series or parallel.
The present invention can be used in mobile electronic devices such as portable computers, cell phones and portable power tools. The present invention can also be used in batteries for hybrid electric vehicles.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a cylindrical-shaped lithium-ion battery typical of that used commercially today and specifically representative of an 18650 type lithium-ion battery.
FIG. 2 is a schematic representation of an example of an oblong-shaped can for a lithium-ion battery of the invention.
FIG. 3 is a schematic circuitry showing how cells in the invention are preferably connected when arranged together in a battery pack.
FIG. 4 is a photographic top, see-through view of a battery pack of the invention.
FIGS. 5(a)-5(d) are schematic drawings comparing different spatial utilizations of different battery form factors including the battery of this invention (FIG. 5(a)) and comparison examples typical of commercial batteries used today including two 18650 cells in parallel (FIG. 5(b)), a prismatic cell containing a wound jelly roll electrode structure (FIG. 5(c)) and a prismatic cell containing a stacked electrode structure (FIG. 5(d)).
FIG. 6 is a graph showing typical charge curves of a battery of the invention and a control battery at room temperature.
FIG. 7 is a graph showing relative capacity retention during charge-discharge cycling at room temperature of a battery of the invention and two control batteries: cycling conditions: constant charge constant voltage (CCCV) charging using 0.7 C constant charge followed by constant voltage charge at 4.2 V and then 1 C discharge to 2.75 V.
FIG. 8 is a graph showing relative capacity retention during charge-discharge cycling at 60° C. of a battery of the invention and a control battery under the conditions described in FIG. 7.
FIG. 9 is a graph showing the rate capability for an average and standard deviation of eight batteries of the invention and two control commercial 18650 batteries where the batteries are charged under the charge conditions described in FIG. 7 and discharged to 2.75 V at the rates indicated in the figure.
FIG. 10 is a graph showing the total heat of reaction of cathode mixtures of the invention, which includes a lithium cobaltate and a manganate spinel, and of the lithium cobaltate and the manganate spinel, in DSC tests.
FIG. 11 is a graph showing the maximum heat flow during reaction of cathode mixtures of the invention, which includes a lithium cobaltate and a manganate spinel, in DSC tests.
FIG. 12 is a graph showing time spent by a lithium-ion battery of the invention, which includes a cathode mixture that includes a lithium cobaltate and a manganate spinel, prior to rapid cell reaction (e.g., fire or explosion) during abuse testing.
FIG. 13 is a graph showing cyclability of a lithium-ion battery of the invention, which includes 70 wt % of LiCoO2 and 30 wt % of Li1+x1Mn2O4 as an active cathode material, and showing cyclability of two commercially available 18650 batteries with 100 wt % of LiCoO2 as an active cathode material.



DETAILED DESCRIPTION OF THE INVENTION
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
In one embodiment, the present invention relates to an active cathode material mixture that can be employed in an electrode of a lithium-ion battery that allows lithium to be reversibly intercalated and extracted. The active cathode material comprises a mixture that includes: at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel and an olivine compound.
A lithium nickelate that can be used in the invention includes at least one modifier of either the Li atom or Ni atom, or both. As used herein, a “modifier” means a substituent atom that occupies a site of the Li atom or Ni atom, or both, in a crystal structure of LiNiO2. In one embodiment, the lithium nickelate includes only a modifier of Li atom (“Li modifier”). In another embodiment, the lithium nickelate includes only a modifier of Ni atom (“Ni modifier”). In yet another embodiment, the lithium nickelate includes both of the Li and Ni modifiers. Examples of the Li modifier include barium (Ba), magnesium (Mg), calcium (Ca) and strontium (Sr). Examples of the Ni modifier include those modifiers for Li and in addition aluminum (Al), manganese (Mn) and boron (B). Other examples of the Ni modifier include cobalt (Co) and titanium (Ti). Preferably, the lithium nickelate is coated with LiCoO2. The coating can be a gradient coating or a spot-wise coating.
One particular type of a lithium nickelate that can be used in the invention is represented by an empirical formula of Lix3Ni1-z3M′z3O2 where 0.05<x3<1.2 and 0<z3<0.5, and M′ is one or more elements selected from a group consisting of Co, Mn, Al, B, Ti, Mg, Ca and Sr. Preferably, M′ is one or more elements selected from a group consisting of Mn, Al, B, Ti, Mg, Ca and Sr.
Another particular type of a lithium nickelate that can be used in the invention is represented by an empirical formula of Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x4 is equal to or greater than about 0.1 and equal to or less than about 1.3; x5 is equal to or greater than 0.0 and equal to or less than about 0.2; y4 is equal to or greater than 0.0 and equal to or less than about 0.2; z4 is equal to or greater than 0.0 and equal to or less than about 0.2; a is greater than about 1.5 and less than about 2.1; A* is at least one member of the group consisting of barium (Ba), magnesium (Mg) and calcium (Ca); and Q is at least one member of the group consisting of aluminum (Al), manganese (Mn) and boron (B). Preferably, y4 is greater than zero. In one preferred embodiment, x5 is equal to zero, and z4 is greater than 0.0 and equal to or less than about 0.2. In another embodiment, z4 is equal to zero, and x5 is greater than 0.0 and equal to or less than about 0.2. In yet another embodiment, x5 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In yet another embodiment, x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. Various examples of lithium nickelates where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2 can be found in U.S. Pat. Nos. 6,855,461 and 6,921,609 (the entire teachings of which are incorporated herein by reference).
A specific example of the lithium nickelate is LiNi0.8Co0.15Al0.05O2. A preferred specific example is LiCoO2-coated LiNi0.8Co0.15Al0.05O2. The spot-wise coated cathode has LiCoO2 not fully coated on top of a nickelate core particle, so that the higher reactivity nickelate is deactivated and hence safer. The composition of LiNi0.8Co0.15Al0.05O2 coated with LiCoO2 can naturally deviate slightly in composition from the 0.8:0.15:0.05 weight ratio between Ni:Co:Al. Deviation may be approximately 10-15% for the Ni, 5-10% for Co and 2-4% for Al.
Another specific example of the lithium nickelate is Li0.97Mg0.03Ni0.9Co0.1O2. A preferred specific example is LiCoO2-coated Li0.97Mg0.03Ni0.9Co0.1O2. The spot-wise coated cathode has LiCoO2 not fully coated on top of a nickelate core particle, so that the higher reactivity nickelate is deactivated and hence safer. The composition of Li0.97Mg0.03Ni0.9Co0.1O2 coated with LiCoO2 can naturally deviate slightly in composition from the 0.03:0.9:0.1 weight ratio between Mg:Ni:Co. Deviation may be approximately 2-4% for Mg, 10-15% for Ni and 5-10% for Co.
Another preferred nickelate that can be used in the present invention is Li(Ni1/3Co1/3Mn1/3)O2, which is also called “333-type nickelate.” This 333-type nickelate can be optionally coated with LiCoO2 as described above.
Suitable examples of lithium cobaltates that can be used in the invention include LiCoO2 that is modified by at least one of modifiers of Li and Co atoms. Examples of the Li modifiers are as described above for Li for LiNiO2. Examples of the Co modifiers include the modifiers for Li and aluminum (Al), manganese (Mn) and boron (B). Other examples include nickel (Ni) and titanium (Ti). Particularly, lithium cobaltates represented by an empirical formula of Lix6M′(1-y6)Co(1-z6)M′′z6O2, where x6 is greater than 0.05 and less than 1.2; y6 is equal to or greater than 0 and less than 0.1, z6 is equal to or greater than 0 and less than 0.5; M′ is at least one member of magnesium (Mg) and sodium (Na) and M′′ is at least one member of the group consisting of manganese (Mn), aluminum (Al), boron (B), titanium (Ti), magnesium (Mg), calcium (Ca) and strontium (Sr), can be used in the invention.
Another example of lithium cobaltates that can be used in the invention includes LiCoO2.
It is particularly preferred that the compounds have a spherical-like morphology as this improves packing and production characteristics.
Preferably, a crystal structure of each of the lithium cobaltate and lithium nickelate is independently a R-3m type space group (rhombohedral, including distorted rhombohedral). Alternatively, a crystal structure of the lithium nickelate can be in a monoclinic space group (e.g., P2/m or C2/m). In a R-3m type space group, the lithium ion occupies the “3a” site (x=0, y=0 and z=0) and the transition metal ion (i.e., Ni in a lithium nickelate and Co in a lithium cobaltate) occupies the “3b” site (x=0, y=0, z=0.5). Oxygen is located in the “6a” site (x=0, y=0, z=z0, where z0 varies depending upon the nature of the metal ions, including modifier(s) thereof).
Olivine compounds that can be used in the invention are generally represented by a general formula Li1−x2A′′x2MPO4, where x2 is equal to or greater than 0.05, or x2 is equal to or greater than 0.0 and equal to or greater than 0.1; M is one or more elements selected from a group consisting of Fe, Mn, Co, or Mg; and A′′ is selected from a group consisting of Na, Mg, Ca, K, Ni, Nb. Preferably, M is Fe or Mn. More preferably, LiFePO4 or LiMnPO4, or both are used in the invention. In a preferred embodiment, the olivine compounds are coated with a material having high electrical conductivity, such as carbon. In a more preferred embodiment, carbon-coated LiFePO4 or carbon-coated LiMnPO4 is used in the invention. Various examples of olivine compounds where M is Fe or Mn can be found in U.S. Pat. No. 5,910,382 (the entire teachings of which are incorporated herein by reference).
The olivine compounds have typically a small change in crystal structure upon charging/discharging, which makes the olivine compounds superior in terms of cycle characteristic. Also, safety is generally high even when a battery is exposed to a high temperature environment. Another advantage of the olivine compounds (e.g., LiFePO4 and LiMnPO4) is their relatively low cost.
Manganate spinel compounds have a manganese base, such as LiMn2O4. While the manganate spinel compounds typically have low specific capacity (e.g., in a range of about 100 to 115 mAh/g), they have high power delivery when formulated into electrodes and are typically safe in terms of chemical reactivity at higher temperatures. Another advantage of the manganate spinel compounds is their relatively low cost.
One type of manganate spinel compounds that can be used in the invention is represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where A′ is one or more of Mg, Al, Co, Ni and Cr; x1 and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3; y1 and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3; z1 is equal to or greater than 3.9 and equal to or less than 4.1. Preferably, A′ includes a M3+ ion, such as Al3+, Co3+, Ni3+ and Cr3+, more preferably Al3+. The manganate spinel compounds of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 can have enhanced cyclability and power compared to those of LiMn2O4.
In some embodiments where the cathode mixtures of the invention include a manganate spinel, the manganate spinel for the invention includes a compound represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1, where y1 and y2 are each independently greater than 0.0 and equal to or less than 0.3, and the other values are the same as described above.
In other embodiments where the cathode mixtures of the invention include a manganate spinel, the manganate spinel for the invention includes a compound represented by an empirical formula of Li(1+x1)Mn2Oz1, where x1 and z1 are each independently the same as described above.
Alternatively, the manganate spinel for the invention includes a compound represented by an empirical formula of Li1+x7Mn2-y7Oy7 where x7 and y7 are each independently equal to or greater than 0.0 and equal to or less than 1.0; and z7 is equal to or greater than 3.9 and equal to or less than 4.2.
Specific examples of the manganate spinel that can be used in the invention include LiMn1.9Al0.1O4, Li1+x1Mn2O4, Li1+x7Mn2-y7O4, and their variations with Al and Mg modifiers. Various other examples of manganate spinel compounds of the type Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 can be found in U.S. Pat. Nos. 4,366,215; 5,196,270; and 5,316,877 (the entire teachings of which are incorporated herein by reference).
The active cathode materials of the invention can be prepared by mixing two or more active cathode components described above (i.e., a lithium cobaltate, a lithium nickelate, a manganate spinel and an olivine compound), preferably in a powdered form. Generally, the olivine compounds, such as LiFePO4, manganate spinel compounds, such as Li(1+x1)(Mn1-y1A′y2)2-x2Oz1, and lithium nickelates, such as Li(Ni1/3Co1/3Mn1/3)O2, have high safety. Generally, lithium cobaltates, such as LiCoO2 and lithium nickelates, such as Li(Ni1/3Co1/3Mn1/3)O2 and Lix4Ni1-y4-z4Coy4Qz4Oa-type compounds have a high-energy density. General properties of some cathode components for the cathode materials of the invention are summarized in Table 1.







TABLE 1







Typical Attributes of Active Cathode Materials of the Invention















1st Cycle



Density
C/20 Capacity
1 C Capacity
Efficiency


Cathode Material
(g/cc)
(mAh/g)
(mAh/g)
(%)





lithium cobaltate
5.05
150
145
96


lithium nickelate
4.80
210
180
92


olivine (M = Fe)
3.30
155
140
95


manganate spinel
4.20
120
115
94









Characteristics of the cathode materials of the invention relate to capacity, cyclability, and safety. For example, the cathode materials of the invention can exhibit different capacities depending on the charge/discharge rate and other external conditions, such as electrolyte choice and electrode formulation. “Capacity” is defined herein as the number of Li ions that can reversibly be removed from the crystal structures of lithium-based materials, such as those of the invention. “Reversibility,” as defined herein, means that the structure substantially maintains its integrity and that Li can be intercalated back to restore the initial crystal structure. In theory, this is the definition of capacity at an infinitely small rate. “Safety,” as defined herein, means structural stability or structural integrity; if a material decomposes during cycling or is easily decomposed or causes gassing at elevated temperatures, the material is considered unsafe, particularly if the decomposition or gassing leads to initiation of thermal runaway behavior inside the cell or produces high internal pressure. Polarization behavior adds yet another dimension to capacity and the effects of polarization behavior to performance of a lithium-ion battery are determined by the interaction between the lithium-ion cell and the control electronics of the battery pack or application device using the lithium-ion cell.
Formulation of an electrode suitable for high energy and power, and sufficient safety, can be achieved by a specific ratio of components (i.e., a lithium cobaltate, a lithium nickelate, a manganate spinel and an olivine compound) of the active cathode materials of the invention.
In one embodiment, an active cathode material of the invention includes a lithium nickelate that includes at least one modifier of either the Li atom or Ni atom, or both. Preferably, the lithium nickelate is represented by an empirical formula of Lix3Ni(1-z3)M′z3O2 described above. Alternatively, the lithium nickelate is represented by an empirical formula of Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa described above. In a specific example, the lithium nickelate is represented by an empirical formula of Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. Specific examples of the lithium nickelate are as described above.
In a second embodiment, an active cathode material of the invention includes a lithium cobaltate represented by an empirical formula of Lix6Co(1-z6)M′′z6O2 described above. Specific examples of the lithium cobaltate are as described above.
In a third embodiment, an active cathode material of the invention includes an olivine compound represented by an empirical formula of Li(1−x2)A′′x2MPO4 described above. Specific examples of the olivine compound are as described above. In a preferred embodiment, M is iron or magnesium. In a preferred embodiment, the olivine compound is coated with carbon.
In a fourth embodiment, an active cathode material of the invention includes a lithium cobaltate, such as LiCoO2, and a manganate spinel. The lithium cobaltate and manganate spinel, including specific examples thereof, are as described above. Preferably, the lithium cobaltate, and manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.8:0.2 to about 0.4:0.6. In one example of the fourth embodiment, the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1. In another example of the fourth embodiment, the manganate spinel is represented by Li1+x7Mn2-y7Oz7, preferably Li1+x7Mn2Ox7 (e.g., Li1+x7Mn2O4). In yet another example of the fourth embodiment, the manganate spinel is represented by Li1+x1Mn2Oz1.
In a fifth embodiment, an active cathode material of the invention includes a lithium nickelate and a manganate spinel represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 described above. The lithium nickelate and manganate spinel, including specific examples thereof, are as described above. Preferably, the lithium nickelate and manganate spinel are in a weight ratio of lithium nickelate:manganate spinel between about 0.9:0.1 to about 0.3:0.7. In one example of the fifth embodiment, the lithium nickelate is Li(Ni1/3Co1/3Mn1/3)O2, LiNi0.8Co0.15Al0.05O2 or Li0.97Mg0.03Ni0.9Co0.1O2. Preferably, the lithium nickelate is LiCo0.2-coated, LiNi0.8Co0.15Al0.05O2 or Li0.97Mg0.03Ni0.9Co0.1O2. When LiCoO2-coated, LiNi0.8Co0.15Al0.05O2 or Li0.97Mg0.03Ni0.9Co0.1O2 is used, the lithium nickelate and manganate spinel are preferably in a weight ratio of lithium nickelate-to-manganate spinel between about 0.9:0.1 to about 0.3:0.7. When Li(Ni1/3Co1/3Mn1/3)O2 is used, the lithium nickelate and manganate spinel are preferably in a weight ratio of lithium nickelate:manganate spinel between about 0.7:0.3 to about 0.3:0.7.
In a sixth embodiment, an active cathode material of the invention includes at least one lithium nickelate selected from the group consisting of Li(Ni1/3Co1/3Mn1/3)O2 and LiCoO2-coated LiNi0.8Co0.15Al0.05O2; and a manganate spinel represented by Li1+x7Mn2-y7Oz7, preferably Li1+x1Mn2O4, such as LiMn2O4. Preferably, the lithium nickelate and manganate spinel are in a weight ratio of lithium nickelate:manganate spinel between about 0.9:0.1 to about 0.3:0.7. When Li(Ni1/3Co1/3Mn1/3)O2 is used, the lithium nickelate and manganate spinel are in a weight ratio of lithium nickelate:manganate spinel between about 0.9:0.1 to about 0.5:0.5.
In a seventh embodiment, the active cathode material of the invention includes a lithium cobaltate, such as LiCoO2, a manganate spinel and a lithium nickelate. The lithium cobaltate, manganate spinel and lithium nickelate, including specific examples thereof, are as described above. Preferably, the lithium cobaltate, manganate spinel and lithium nickelate are in a weight ratio of lithium cobaltate:manganate spinel:lithium nickelate between about 0.05 and about 0.8: between about 0.05 and about 0.7 (e.g., between about 0.05 and about 0.3, or between about 0.3 and about 0.7): between about 0.05 and about 0.9 (e.g., between about 0.4 and about 0.9, or between about 0.05 and about 0.8). In one example, the lithium nickelate is represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa. In a second example, the lithium nickelate is represented by Lix3Ni(1-z3)M′z3O2, more preferably LiNi0.8Co0.15Al0.05O2 that is gradient- or spot-wise coated with LiCoO2. In a third example, the lithium nickelate is Li(Ni1/3Co1/3Mn1/3)O2. In a fourth example, the lithium nickelate includes at least one modifier of both the Li and Ni atoms, such as Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2, and the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz0. Preferably, when Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa and Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 are used, the lithium cobaltate, manganate spinel and lithium nickelate are in a weight ratio of lithium cobaltate:manganate spinel:lithium nickelate between about 0.05 and about 0.30: between about 0.05 and about 0.30: between about 0.4 and about 0.9. In a fifth example, the lithium nickelate is Li(Ni1/3Co1/3Mn1/3)O2 or optionally LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and the manganate spinel is represented by Li(1+x1)Mn1-y1A′y2)2-x2Oz1. In this fifth example, when Li(Ni1/3Co1/3Mn1/3)O2 is used, Li(Ni1/3Co1/3Mn1/3)O2, Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 and lithium cobaltate are in a weight ratio of Li(Ni1/3Co1/3Mn1/3)O2: Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 lithium cobaltate between about 0.05 and about −0.8; between about 0.3 and about −0.7: between about 0.05 and −about 0.8.
In an eighth embodiment, an active cathode material of the invention includes two or more lithium nickelates and a manganate spinel. The lithium nickelates and manganate spinel, including specific examples thereof, are as described above. Preferably, lithium nickelates and manganate spinel are in a weight ratio of lithium nickelates:manganate spinel between about 0.05 and about 0.8: between about 0.05 and about 0.9. Preferably, the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1. In one example, the lithium nickelates include a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa. In another example, the lithium nickelates includes a lithium nickelate represented by Lix3Ni(1-z3)M′z3O2. Alternatively, the lithium nickelates includes a lithium nickelate including at least one modifier of both the Li and Ni atoms, such as Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In a specific example, the lithium nickelates include Li(Ni1/3Co1/3Mn1/3)O2 and a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa. In another specific example, the lithium nickelates include Li(Ni1/3Co1/3Mn1/3)O2; and a lithium nickelate that includes at least one modifier of both the Li and Ni atoms, such as Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In yet another specific example, the lithium nickelates include Li(Ni1/3Co1/3Mn1/3)O2 and a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa, and the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1. In this specific example, the lithium nickelates and manganate spinel are in a weight ratio of Li(Ni1/3Co1/3Mn1/3)O2:Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa:Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 between about 0.05 and about 0.8: between about 0.05 and about 0.7: between about 0.05 and about 0.9.
In a ninth embodiment, an active cathode material of the invention includes a lithium cobaltate, such as LiCoO2, and an olivine compound represented by Li(1−x2)A′′x2MPO4 described above, preferably coated with carbon. The lithium cobaltate and olivine compound, including specific examples thereof, are as described above. Preferably, the lithium cobaltate and olivine compound are in a weight ratio of lithium cobaltate:olivine compound between about 0.9:0.1 to about 0.3:0.7. In one example, the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese, such as LiFePO4 and LiMnPO4. In this example, preferably, the lithium cobaltate and olivine compound are in a weight ratio of lithium cobaltate:olivine compound between about 0.8:0.2 to about 0.4:0.6.
In a tenth embodiment, an active cathode material of the invention includes a lithium nickelate, and an olivine compound represented by Li(1−x2)A′′x2MPO4 described above, preferably coated with carbon. The lithium nickelate and olivine compound, including specific examples thereof, are as described above. Preferably, the lithium nickelate and olivine compound are in a weight ratio of lithium nickelate:olivine compound between about 0.9:0.1 to about 0.3:0.7. In one example, the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese, such as LiFePO4 and LiMnPO4. In a second example, the lithium nickelates include a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa. In a third example, the lithium nickelates includes a lithium nickelate represented by Lix3Ni(1-z3)M′z3O2. Alternatively, the lithium nickelates includes a lithium nickelate including at least one modifier of both the Li and Ni atoms, such as Lix4A*x2Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In a specific example, the lithium nickelate is Li(Ni1/3Co1/3Mn1/3)O2 and the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese. Preferably, in the second example, the lithium nickelate and olivine compound are in a weight ratio of lithium nickelate:olivine compound between about 0.9:0.1 to about 0.5:0.5. In a second specific example, the lithium nickelate is represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa, preferably Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2, and the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese. In a third specific example, the lithium nickelate is LiNiO8Co0.15Al0.5O2, preferably LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese. Preferably, in the third specific example, the lithium nickelate and olivine compound are in a weight ratio of lithium nickelate:olivine compound between about 0.9:0.1 to about 0.3:0.7.
In an eleventh embodiment, an active cathode material of the invention includes two or more lithium nickelates, and an olivine compound, preferably an olivine compound represented by Li(1−x2)A′x2MPO4 where M is iron or manganese. The lithium nickelates and olivine compound, including specific examples thereof, are as described above. Preferably, the olivine compound is coated with carbon. In this embodiment, the lithium nickelates and olivine compound are in a weight ratio of lithium nickelates:olivine compound between about 0.05 and about 0.9: between about 0.05 and 0.9. In one example, the lithium nickelates include a lithium nickelate represented by Lix4A′x5Ni(1-y4-z4)Coy4Qz4Oa. In another example, the lithium nickelates includes a lithium nickelate represented by Lix3Ni(1-z3)M′z3O2. Alternatively, the lithium nickelates includes a lithium nickelate including at least one modifier of both the Li and Ni atoms, such as Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In a specific example, the lithium nickelate is represented by an empirical formula of Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In one specific example, the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese, such as LiFePO4 and LiMnPO4, and the lithium nickelates include Li(Ni1/3Co1/3Mn1/3)O2 and a lithium nickelate including at least one modifier of both the Li and Ni atoms, such as Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In this example, the lithium nickelates and olivine compound are preferably in a weight ratio of Li(Ni1/3Co1/3Mn1/3)O2 lithium nickelate:olivine compound between about 0.05 and about 0.8: between about 0.05 and about 0.7: between about 0.05 and about 0.9.
In a twelfth embodiment, an active cathode material of the invention includes a lithium nickelate, a lithium cobaltate, such as LiCoO2, and an olivine compound represented by Li(1−x2)A′′x2MPO4 described above. The lithium nickelate, lithium cobaltate and olivine compound, including specific examples thereof, are as described above. In this embodiment, the lithium nickelate, lithium cobaltate and olivine compound are preferably in a weight ratio of lithium cobaltate:olivine compound: lithium nickelate between about 0.05 and about 0.8: between about 0.05 and about 0.7: between about 0.05 and about 0.9. In one example, the lithium nickelates include a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa. In another example, the lithium nickelates includes a lithium nickelate represented by Lix3Ni(1-z3)M′z3O2. Alternatively, the lithium nickelates includes a lithium nickelate including at least one modifier of both the Li and Ni atoms, such as Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In one specific example, the lithium nickelate is represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa, preferably Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2, and the olivine compound is represented by Li(x2)A′′x2MPO4 where M is iron or manganese. In this specific example, the lithium nickelate, lithium cobaltate and olivine compound are preferably in a weight ratio of lithium cobaltate:olivine compound: lithium nickelate between about 0.05 and about 0.30: between about 0.05 and about 0.30: between about 0.4 and about 0.9. In a second specific example, the lithium nickelate is Li(Ni1/3Co1/3Mn1/3)O2, and the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese. In the second specific example, preferably the lithium nickelate, lithium cobaltate and olivine compound are in a weight ratio of lithium nickelate:olivine:lithium cobaltate between about 0.05-0.8: about 0.3-0.7: about 0.05-0.8. In a third specific example, the lithium nickelate is LiNi0.08Co0.15Al0.05O2, preferably LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and the olivine compound is represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese.
In a thirteenth embodiment, an active cathode material of the invention includes a manganate spinel, an olivine compound, preferably an olivine compound represented by Li(1−x2)A′′x2MPO4 where M is iron or manganese, and a lithium nickelate. The manganate spinel, olivine compound and lithium nickelate, including specific examples thereof, are as described above. In this embodiment, manganate spinel, olivine compound and lithium nickelate are preferably in a weight ratio of manganate spinel:olivine:lithium nickelate between about 0.05-0.9: about 0.05-0.9: about 0.05-0.9. In one example, the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1. In another example, the manganate spinel is represented by Li1+x7Mn2-y7Oz7. In yet another example, the manganate spinel is represented by Li1+x1Mn2O4, such as LiMn2O4. In one specific example, the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 and the lithium nickelate includes at least one modifier of both the Li and Ni atoms, such as a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. In a second specific example, the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 and the lithium nickelate is represented by Lix3Ni(1-x3)M′z3O2, preferably LiNi0.8Co0.15Al0.05O2, more preferably LiCoO2-coated LiNi0.8Co0.15Al0.05O2. In a third specific example, the manganate spinel is represented by Li(1+x1)(Mn1-y1A′y1)2-x1Oz1 and the lithium nickelate is Li(Ni1/3Co1/3Mn1/3)O2. In a fourth specific example, the managanate is represented by Li1+x7Mn2-y7O4 or Li1+x1Mn2O4, or is a variation thereof modified with Al and Mg, and the lithium nickelate is selected from the group consisting of Li(Ni1/3Co1/3Mn1/3)O2, and LiCoO2-coated LiNi0.8Co0.15Al0.05O2.
In a fourteenth embodiment, an active cathode material of the invention includes two or more lithium nickelates as described above. In one example, the active cathode material includes Li(Ni1/3Co1/3Mn1/3)O2. In a specific example, the active cathode material includes Li(Ni1/3Co1/3Mn1/3)O2 and a lithium nickelate including at least one modifier of both the Li and Ni atoms, such as a lithium nickelate represented by Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa where x5, y4 and z4 are each independently greater than 0.0 and equal to or less than about 0.2. Preferably, in this example, the lithium nickelates are in a weight ratio of Li(Ni1/3Co1/3Mn1/3)O2: Lix4A*x5Ni(1-y4-z4)Coy4Qz4Oa between about 0.7:0.3 to about 0.3:0.7. In another specific example, the active cathode material includes Li(Ni1/3Co1/3Mn1/3)O2 and LiNi0.8Co0.15Al0.05O2, more preferably LiCoO2-coated LiNi0.8Co0.15Al0.05O2. Preferably, in this example, the lithium nickelates are in a weight ratio of Li(Ni1/3Co1/3Mn1/3)O2:LiNi0.8Co0.15Al0.05O2 between about 0.8:0.2 to about 0.2:0.8.
In a fifteenth embodiment, an active cathode material of the invention includes a lithium cobaltate and a manganate spinel, as described above. In a preferred embodiment, the manganate spinel is represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz0, wherein the variables are as described above. Examples of the lithium cobaltate, including preferred values, are as described above. In this embodiment, the lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.95:0.05 to about 0.55:0.45, preferably between about 0.9:0.1 to about 0.6:0.4, more preferably between about 0.8:0.2 to about 0.6:0.4, even more preferably between about 0.75:0.25 to about 0.65:0.45, such as about 0.7:0.3.
In the fifteenth embodiment, preferably, the lithium cobaltate is represented by an empirical formula of Lix6M′(1-y6)Co(1-z6)M′′z6O2 where: x6 is greater than 0.05 and less than 1.2; y6 is greater than or equal to 0 and less than 0.1; z6 is equal to or greater than 0 and less than 0.5; M′ is at least one of magnesium (Mg) and sodium (Na) and M′′ is at least one member of the group consisting of manganese, aluminum, boron, titanium, magnesium, calcium and strontium. In one specific embodiment, the lithium cobaltate is LiCoO2 doped with Mg and/or coated with a refractive oxide or phosphate, such as ZrO2 or Al2(PO4)3. In another specific embodiment, the lithium cobaltate is LiCoO2 with no modifiers.
In the fifteenth embodiment, preferably, the manganate spinel does not have the A′ modifier, i.e., y2 is equal to zero in the formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1. In a specific embodiment, the manganate spinel includes a compound represented by an empirical formula of Li(1+x1)Mn2Oz1 where the variables are as described above. In another specific embodiment, the manganate spinel includes a compound represented by an empirical formula of Li1+x7Mn2-y7Oz7 where the variables are as described above, preferably Li1+x7Mn2-y7O4. Alternatively, the manganate spinel includes a compound represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1, where y1 and y2 are each independently greater than 0.0 and equal to or less than 0.3, and other values are the same as described above.
In a even more preferred embodiment where the active cathode material includes a lithium cobaltate and a manganate spinel, the lithium cobaltate is LiCoO2 with no modifiers and the manganate spinel does not have the A′ modifier.
It is noted that the suitable cathode materials described herein are characterized by empirical formulas that exist upon manufacture of lithium-ion batteries in which they are incorporated. It is understood that their specific compositions thereafter are subject to variation pursuant to their electrochemical reactions that occur during use (e.g., charging and discharging).
Another aspect of the present invention is directed to a lithium-ion battery that employs the active cathode materials of the invention described above. Preferably, the battery has a greater than about 2.2 Ah/cell capacity. More preferably, the battery has a greater than about 3.0 Ah/cell capacity, such as equal to or greater than about 3.3 Ah/cell; equal to or greater than about 3.5 Ah/cell; equal to or greater than about 3.8 Ah/cell; equal to or greater than about 4.0 Ah/cell; equal to or greater than about 4.2 Ah/cell; between about 3.0 Ah/cell and about 6 Ah/cell; between about 3.3 Ah/cell and about 6 Ah/cell; between about 3.3 Ah/cell and about 5 Ah/cell; between about 3.5 Ah/cell and about 5 Ah/cell; between about 3.8 Ah/cell and about 5 Ah/cell; and between about 4.0 Ah/cell and about 5 Ah/cell.
In one embodiment, the batteries of the invention include an active cathode material including a mixture that includes: at least one of a lithium cobaltate and a lithium nickelate; and at least one of a manganate spinel represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz0 described above and an olivine compound represented by an empirical formula of Li(1−x2)A′′x2MPO4 described above. In another embodiment, the batteries of the invention include an active cathode material including a mixture that includes: at least one of a lithium cobaltate and a lithium nickelate selected from the group consisting of LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel having an empirical formula of Li(1+x7)Mn2-y7O7 described above. In yet another embodiment, the batteries of the invention include an active cathode material including a mixture that includes: a lithium nickelate selected from the group consisting of LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel having an empirical formula of Li(1+x7)Mn2-y7Oz7 described above. The batteries each independently have a capacity as described above, preferably greater than about 3.0 Ah/cell.
In a preferred embodiment, cell building for the batteries of the invention utilize a larger format in terms of Ah/cell than is currently used in the industry such as in the case for 18650 cells.
FIG. 1 shows a cylindrical shape lithium-ion battery (10), which includes a positive electrode (1), coated onto an aluminum foil, a negative electrode (2), coated onto a copper foil, a separator positioned between the positive and negative electrodes (3), a can containing the wound components (4), an electrically insulated (5a) (from can) top that is crimped onto the can (5b) (top may contain a current-interrupt-device CID, and a vent (5c)), nickel lead that is electrically connecting the anode with the top, and an aluminum lead that is electrically connecting the cathode with the can (6). A PTC switch (7) can be located inside or outside the can. Insulators are also located at the top (8) and the bottom (9) of the can that keep foils from touching each other and insulates foil ends from can.
The negative active material (anode) can include any material allowing lithium to be inserted in or removed from the material. Examples of such materials include carbonaceous materials, for example, non-graphitic carbon, artificial carbon, artificial graphite, natural graphite, pyrolytic carbons, cokes such as pitch coke, needle coke, petroleum coke, graphite, vitreous carbons, or a heat treated organic polymer compound obtained by carbonizing phenol resins, furan resins, or similar, carbon fibers, and activated carbon. Further, metallic lithium, lithium alloys, and an alloy or compound thereof are usable as the negative active materials. In particular, the metal element or semiconductor element allowed to form an alloy or compound with lithium may be a group IV metal element or semiconductor element, such as but not limited to, silicon or tin. In particular amorphous tin, that is doped with a transition metal, such as cobalt or iron/nickel, is a metal that has high promise for anode material in these type batteries. Oxides allowing lithium to be inserted in or removed from the oxide at a relatively low potential, such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide, and nitrides can be similarly usable as the negative active materials.
The positive electrode of the batteries or cells of the invention include the active cathode materials of the invention described above. In particular, the batteries of the invention employ the active cathode materials including two or more advantages of: high specific capacity of the lithium nickelates (e.g., Li(Ni1/3Co1/3Mn1/3)O2 or LiNi0.8Co0.15Al0.05O2) or lithium cobaltates (e.g., LiCoO2); relatively high safety of the olivine compounds (e.g., LiFePO4) or manganate spinels (e.g., Li1+x1Mn2O4 or LiMn2O4). When the active cathode materials of the invention are used in a positive electrode structure for use in the lithium batteries of the invention, the resulting batteries are sufficiently safe and have high capacity in terms of Wh/kg and/or Wh/L. The cells of the invention typically have a form factor that is larger (e.g., 183665 form factor), both in terms of absolute volume and Ah/cell, compared to currently available 18650 cells. The increased cell size and capacity are made possible at least partly by the relatively higher safety of the mixed cathode. The cells of the invention for lithium batteries can have safer properties than corresponding cells utilizing solely LiCoO2 as the cathode material, although the cells have similar or higher capacities.
Since each one of the cathode components in the mixture has unique chemistry, it is particularly important to have an electrolyte that has additives suitable for SEI formation of each chemical. For instance, a suitable electrolyte for batteries having cathodes containing manganate spinel and lithium cobaltate and anodes containing graphite may contain one or more additives of LiBOB (lithium bis(oxalato)borate), BP (biphenyl), PS (propylene sulfite), and VC (vinyl carbonate), which are suitable for these types of compounds.
Examples of the non-aqueous electrolytes include a non-aqueous electrolytic solution prepared by dissolving an electrolyte salt in a non-aqueous solvent, a solid electrolyte (inorganic electrolyte or polymer electrolyte containing an electrolyte salt), and a solid or gel-like electrolyte prepared by mixing or dissolving an electrolyte in a polymer compound or the like.
The non-aqueous electrolytic solution is prepared by dissolving a salt in an organic solvent. The organic solvent can include any suitable type that has been generally used for batteries of this type. Examples of such organic solvents include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole, acetate, butyrate, propionate and the like. It is preferred to use cyclic carbonates such as propylene carbonate, or chain carbonates such as dimethyl carbonate and diethyl carbonate. These organic solvents can be used singly or in a combination of two types or more.
Additives or stabilizers may also be present in the electrolyte, such as VC (vinyl carbonate), VEC (vinyl ethylene carbonate), EA (ethylene acetate), TPP (triphenylphosphate), phosphazenes, LiBOB (lithium bis(oxalato)borate), LiBETI, LiTFSI, BP (biphenyl), PS (propylene sulfite), ES (ethylene sulfite), AMC (allylmethylcarbonate), and APV (divinyladipate). These additives are used as anode and cathode stabilizers or flame retardants, which may make a battery have higher performance in terms of formation, cycle efficiency, safety and life. Since each one of the cathode components in the mixture has unique chemistries it is particularly important to have an electrolyte that has additives suitable for SEI formation of each chemical. For instance a suitable electrolyte for a Li-ion battery having a spinel and cobaltate mixed cathode and a graphite anode may contain additives of LiBOB, PS and VC stabilizers, which respectively are suitable for the individual compounds' SEI formations. The additives can be added into the electrolytes in any suitable amount known in the art, for example, between about 4 wt % and about 6 wt % of BP (e.g., about 5.5. wt %), about 1 wt % of VC, and/or about 0.5 wt % of PS.
The solid electrolyte can include an inorganic electrolyte, a polymer electrolyte and the like insofar as the material has lithium-ion conductivity. The inorganic electrolyte can include, for example, lithium nitride, lithium iodide and the like. The polymer electrolyte is composed of an electrolyte salt and a polymer compound in which the electrolyte salt is dissolved. Examples of the polymer compounds used for the polymer electrolyte include ether-based polymers such as polyethylene oxide and cross-linked polyethylene oxide, polymethacrylate ester-based polymers, acrylate-based polymers and the like. These polymers may be used singly, or in the form of a mixture or a copolymer of two kinds or more.
A matrix of the gel electrolyte may be any polymer insofar as the polymer is gelated by absorbing the above-described non-aqueous electrolytic solution. Examples of the polymers used for the gel electrolyte include fluorocarbon polymers such as polyvinylidene fluoride (PVDF), polyvinylidene-co-hexafluoropropylene (PVDF-HFP) and the like.
Examples of the polymers used for the gel electrolyte also include polyacrylonitrile and a copolymer of polyacrylonitrile. Examples of monomers (vinyl based monomers) used for copolymerization include vinyl acetate, methyl methacrylate, butyl methacylate, methyl acrylate, butyl acrylate, itaconic acid, hydrogenated methyl acrylate, hydrogenated ethyl acrylate, acrlyamide, vinyl chloride, vinylidene fluoride, and vinylidene chloride. Examples of the polymers used for the gel electrolyte further include acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene-1-styrene copolymer resin, acrylonitrile-chlorinated polyethylene-propylenediene-styrene copolymer resin, acrylonitrile-vinyl chloride copolymer resin, acrylonitrile-methacylate resin, and acrylonitrile-acrylate copolymer resin.
Examples of the polymers used for the gel electrolyte include ether based polymers such as polyethylene oxide, copolymer of polyethylene oxide, and cross-linked polyethylene oxide. Examples of monomers used for copolymerization include polypropylene oxide, methyl methacrylate, butyl methacylate, methyl acrylate, butyl acrylate.
In particular, from the viewpoint of oxidation-reduction stability, a fluorocarbon polymer is preferably used for the matrix of the gel electrolyte.
The electrolyte salt used in the electrolyte may be any electrolyte salt suitable for batteries of this type. Examples of the electrolyte salts include LiClO4, LiAsF6, LiPF6, LiBF4, LiB(C6H5)4, LiB(C2O4)2, CH3SO3Li, CF3SO3Li, LiCl, LiBr and the like.
Referring back to FIG. 1, in one embodiment of the invention, the separator 3 separates the positive electrode 1 from the negative electrode 2. The separator 3 can include any film-like material having been generally used for forming separators of non-aqueous electrolyte secondary batteries of this type, for example, a microporous polymer film made from polypropylene, polyethylene, or a layered combination of the two. In addition, if a solid electrolyte or gel electrolyte is used as the electrolyte of the battery 10, the separator 3 does not necessarily need to be provided. A microporous separator made of glass fiber or cellulose material can in certain cases also be used. Separator thickness is typically between 9 and 25 μm.
In one embodiment, the positive electrode is made by coating a material that includes the active cathode material(s) of the invention onto a metal foil, such as Al or Cu foil. Preferably, the coating has a density of between about 3 g/cm3 and about 4.5 g/cm3, more preferably between about 3.5 g/cm3 and about 4.0 g/cm3, such as about 3.6 g/cm3. The thickness of the coating is in a range of between about 15 μm and about 80 μm, preferably between about 20 μm and about 80 μm, more preferably between about 50 μm and about 80 μm (e.g., about 70 μm). Generally, the coating material includes about 93-96 wt % of the active cathode material, carbon black and graphite in an amount of about 1-3 wt %, and about 2-5 wt % of one or more additives known in the art, such as PVDF. In one particular embodiment, the positive electrode is produced by mixing the cathode material at about 94 wt % together with about 3 wt % of a conductive agent (e.g. acetylene black), and about 3 wt % of a binder (e.g., PVDF). The mix is dispersed in a solvent (e.g., N-methyl-2-pyrrolidone (NMP)), in order to prepare a slurry. This slurry is then applied to both surfaces of an aluminum current collector foil, which typically has a thickness of about 20 um, and dried at about 100-150° C. The dried electrode is then calendared by a roll press, to obtain a compressed positive electrode.
The negative electrode is typically prepared by mixing about 93 wt % of graphite as a negative active material, about 3 wt % of conductive carbon (e.g. acetylene black), and about 4 wt % of a binder (e.g. PVDF). The negative electrode is then prepared from this mix in a process similar to that described above for positive electrode except that a copper current collector foil, typically of 10-15 μm thickness, is used.
The negative and positive electrodes and a separator formed of a polymer film (e.g., polyethylene) with micro pores, of thickness about 25 um, are laminated and spirally wound to produce a spiral type electrode element. Preferably this roll has an oblong shape.
One or more positive lead current carrying tabs are attached to the positive current collector and then welded to the battery top. A vent is also available, for example, at the top of the battery. A negative lead, made of nickel metal, connects the negative current collector to the bottom of the battery can.
An electrolyte containing for instance PC, EC, DMC, DEC solvents with 1M LiPF6 and suitable additives at 0.5-3 wt. % each, such as VC, LiBOB, PF, LiTFSI, BP, is vacuum filled in the battery can 4 having the spirally wound “jelly roll”, and the battery is then sealed via an insulating seal gasket 8. A safety valve 5c, current interrupt device, and a PTC device may also be present at the battery top to enhance safety. A cylindrical non-aqueous electrolyte lithium-ion secondary battery having an outer diameter of 18 mm and a height of 65 mm as shown in FIG. 1 is typical of lithium-ion cells used in the industry.
For a cell having an oblong shape as shown in FIG. 2, a similar method as described above for a cylindrical cell of the invention can be used except that the electrodes are prepared and wound to form a cell having an oblong shape, for example, with a thickness of about 17 mm or about 18 mm, a width of about 44 mm or about 36 mm, a height of about 64 mm or about 65 mm. In some specific embodiments, the cell (or battery) has a thickness of about 17 mm, a width of about 44 mm and a height of about 64 mm; a thickness of about 18 mm, a width of about 36 mm and a height of about 65 mm; or a thickness of about 18 mm, a width of about 27 mm and a height of about 65 mm.
The cells or batteries of the invention can be cylindrical or prismatic (stacked or wound), preferably prismatic, and more preferably of a prismatic shape that is oblong. Although the present invention can use all types of prismatic cans, an oblong can is preferred partly due to the two features described below.
As shown in FIGS. 5(a)-5(d), the available internal volume of an oblong shape, such as the 183665 form factor, is larger than the volume of two 18650 cells, when comparing stacks of the same external volume. In particular, FIGS. 5(a)-(b) show a comparison of an oblong cross section (FIG. 5(a)) to a cylindrical cross section for two 18650 cells (FIG. 5(b)). The additional useable space is 12%. When assembled into a battery pack, the oblong cell fully utilizes more of the space that is occupied by the battery pack. This enables novel design changes to the internal cell components that can increase key performance features without sacrificing cell capacity relative to that found in the industry today. Design features such as mixing in components of higher safety, but relatively lower capacity, while still realizing high capacity on the pack level is therefore available. In addition, again due to the larger available volume, one can elect to use thinner electrodes which have relatively higher cycle life. The thinner electrodes also have higher rate capability. Furthermore, a prismatic cell casing (e.g., an oblong-shaped cell casing) has larger flexibility. For instance, an oblong shape can flex more at the waist point compared to a cylindrically shaped can, which allows less flexibility as stack pressure is increasing upon charging. The increased flexibility decreases mechanical fatigue on the electrodes, which in turn causes higher cycle life. Also, separator pore clogging is improved by the relatively lower stack pressure.
A particularly desired feature, allowing relatively higher safety, is available for the oblong shaped can compared to the prismatic can whose cross-section is illustrated in FIG. 5(c). The oblong shape provides a snug fit to the jelly roll, which minimizes the amount of electrolyte necessary for the battery. The relatively lower amount of electrolyte results in less available reactive material during a misuse scenario and hence higher safety. In addition, cost is lower due to a lower amount of electrolyte. In the case of a prismatic can with a stacked electrode structure, whose cross-section is illustrated in FIG. 5(d), full volume utilization is possible without unnecessary electrolyte, but this type of can design is more difficult and hence more costly from a manufacturing point-of-view.
With the prismatic cells (or batteries) of the invention, particularly with the oblong-shaped cells (or batteries) of the invention, relatively long cycle life can be achieved partly due to the cell's ability to expand and contract during lithium transfers between the anode and cathode of the cell.
In another aspect, the present invention is directed to a battery pack including one or more cells as described above for the lithium-ion batteries of the invention.
In a preferred embodiment, the battery pack includes a plurality of cells and each of the cells includes an active cathode material described above. Cells of a battery packs of the invention are connected with each other in series or parallel, or in series and in parallel (e.g., packs having 2 cells in parallel and 3 cells in series, a so-called 2p3s configuration). Preferably, at least one cell of the cells included in the battery pack has a capacity greater than about 3.0 Ah/cell, more preferably greater than about 4.0 Ah/cell. In a specific embodiment, each cell of the battery pack of the invention includes an active cathode material including a mixture that includes: at least one of a lithium cobaltate and a lithium nickelate, as described above; and at least one of a manganate spinel represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 described above and an olivine compound represented by an empirical formula of Li(1+x2)A′′x2MPO4 described above. In another specific embodiment, each cell of the battery pack includes a cathode mixture that includes: at least one of a lithium cobaltate and a lithium nickelate selected from the group consisting of LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel having an empirical formula of Li(1+x7)Mn2-y7Oz7 as described above. In this specific embodiment, at least one cell of the battery pack has a capacity greater than about 3.0 Ah/cell. In yet another specific embodiment, each cell of the battery pack includes a cathode mixture that includes: a lithium nickelate selected from the group consisting of LiCoO2-coated LiNi0.8Co0.15Al0.05O2, and Li(Ni1/3Co1/3Mn1/3)O2; and a manganate spinel having an empirical formula of Li(1+x7)Mn2-y7Oz7 as described above. In yet another specific embodiment, each cell of the battery pack includes a cathode mixture that includes a lithium cobaltate as described above and a manganate spinel a manganate spinel represented by an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 described above. The lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.95:0.05 to about 0.55:0.45.
In a more preferred embodiment, the battery pack includes a plurality of cells, and the cells of a battery pack of the invention are connected only in series and no cells are connected in parallel. Such a configuration is demonstrated schematically in FIG. 3 and FIG. 4. The non-parallel feature of the pack allows less expensive individual control and monitoring of each cell in the pack, without having to incorporate extra circuitry for detection of individual cell parameters for cells connected in parallel, which is costly and cumbersome due to incorporation of extra algorithms in software and probe terminals.
FIG. 3 shows one embodiment of the invention showing three cells of the invention connected in series. These cells, due to their safer performance characteristics, can be made larger compared to cells employing LiCoO2 as the choice of cathode active material. This allows connecting cells into packs, having fewer cells connected in parallel.
FIG. 4 shows a top, see-through view of battery pack 30 of the invention where three cells 32 of the invention are connected in series with each other.
In one specific embodiment, the battery packs of the invention have a 2p3s configuration where cells are assembled in packs having 2 cells in parallel and 3 cells in series, as can be seen in the conventional 18650 type cells typically used for laptop markets currently. In other embodiments, the battery packs of the invention have 3s or 4s configurations, taking advantage of the larger cell capacity enabled by the invention to simplify, and therefore lower cost and improve safety, the resulting battery pack.
Preferably, the cells included in the battery pack have oblong-shaped can 20 as shown generally in FIG. 2. The preference for this shape is illustrated in FIG. 5 and includes full volume utilization, no unnecessary electrolyte inside the cell can, and relative ease of manufacturing. The capacity of the cells in the battery pack is typically equal to or greater than about 3.3 Ah. The internal impedance of the cells is preferably less than about 50 milliohms, more preferably less than 30 milliohms.
A new battery design of the invention described above can use a larger cell sizes and can potentially replace two parallel 18650 cells (2p block). An advantage of using this configuration is that control electronics can monitor only one cell in the block instead of two, which is the case for a 2p block of 18650 cells. This type of monitoring can allow detection of defects, such as shorts, in the cells, errors that may not be detected for a block having one defect and one non-defect cell. In addition, cost advantages can be realized by using relatively less battery components such as PTC and CID devices and electronic wiring, which connects cells in parallel and to control circuitry, per battery pack.
In order to raise capacity in 18650 cells, companies such as Sony, Sanyo, MBI (Panasonic), LG, and Samsung have been gradually increasing the packing level of active material (graphite and cobaltate) in the cell since their implementation in the early 90's. The higher degree of packing has in part been accomplished by increasing electrode dimensions in terms of electrode width, increased densification of electrodes, increased thickness of the electrodes, less tolerance on the overcapacity of the anode capacity/cathode capacity ratio, and a tighter fit of the jelly roll in the battery steel can. However, one drawback of these approaches has been less safety as seen by an increased level of safety incidents in the field lately. Another drawback is a decreased cycle life. Also, a typical 18650 cell can is made by steel. As capacity of this type cell has increased, so has the density and thickness of electrodes, along with the degree of packing of the jelly roll in the can. The graphite and metal oxide particulates in the anode and cathode electrodes of the 18650 cell continuously change their dimensions as lithium is intercalated and de-intercalated upon charging and discharging. Many metal oxide materials increase their size, due to increase in lattice parameters, when lithium is removed from the structure. LiCoO2 and LiNiO2 are two examples of cathode materials that increase their c-axis when lithium is gradually removed from the structure. Similarly, when lithium is inserted into graphite the c-axis lattice parameter is increased. This means that upon charging, a battery containing LiCoO2— and graphite-based electrodes, both the anode and the cathode electrodes increase their thickness. This generally leads to an increased stack pressure in the cell, as the steel can limit expansion. Two typical types of degradation in the cylindrical, conventional LiCoO2-based lithium cells are believed to be: (1) increased stack pressure imposed by the sturdy cylindrical steel can causes electrodes to clog the separator pores, and (2) mechanical fatigue of relatively thick electrodes causes the electrodes to degrade earlier due to poor connectivity leading to decreased electronic conductivity.
On the other hand, the invention described herein realizes that combinations of electrode materials for the cathode having two or more active material components, one having high capacity, the other having a relatively higher safety, can allow for lithium-ion batteries of high safety while at the same time achieving high capacity in battery packs employing those cells, in particular oblong-shaped cells. In addition, not only are the cells safe enough and of high enough capacity for commercialization objectives, but they also exhibit significantly high cycle life. For example, oblong-shaped cells having an external dimension of about 64 mm in height, about 36 mm in width and about 18 mm in thickness (see Example 4) showed higher voltage, better cycle life and better rate capability than commercially available 18650 cells from LG and SANYO (see Example 6). Lager cells having superior cycle life, high safety, and high capacity can also be made by utilizing the present invention. Even for powercells, it is believed that the present invention can replace power cells of 18650-type or 26 mm diameter in the art. Also HEV-type batteries can benefit from the present invention.
In yet another aspect, the present invention also includes a system that includes a portable electronic device and a cell or battery (e.g., lithium-ion battery), and battery pack as described above. Examples of the portable electronic devices include portable computers, power tools, toys, portable phones, camcorders, PDAs and hybrid-electric vehicles. In one embodiment, the system includes a battery pack of the invention. Features of the battery pack are as described above.
The invention is illustrated by the following examples which are not intended to be limiting in any way.
EXEMPLIFICATION
Example 1-3 and a Comparative Example
Using known active cathode material performance properties that include discharge capacity, average discharge voltage, first discharge vs. first charge efficiency, and material density, performance features can be compared for batteries resulting from mixtures of cathode materials. For a lithium-ion battery as described above, a cathode is used that consists of a mixture of active cathode materials that includes lithium cobaltate (x %), manganate spinel (y %), and lithium nickelate (z %). The manganate spinel and lithium nickelate cathode materials are of the preferred type mentioned in the descriptive text above. Performance features for these cathode materials are representative of individual cathode materials in their representative class and for capacity, average discharge voltage, first cycle efficiency, and density are: lithium cobaltate—145 mAh/g, 3.70 V, 96.0%, 4.9 g/cm3; manganate spinel—115 mAh/g, 3.80 V, 94.0%, 4.1 g/cm3; lithium nickelate—180 mAh/g, 3.50 V, 92.0%, 4.6 g/cm3. For the case when x=40, y=60, and z=0, the resulting active cathode material of this example has the properties of 127 mAh/g, 3.75 V, 94.8%, and 4.4 g/cm3.
Designing a fixed capacity 5 Ah lithium-ion cell and allowing the weight of the battery to vary in order that the capacity requirement is achieved, allows calculation of key battery performance and cost features for comparison under different cathode scenarios. Additional key parameters that must be fixed in the battery design include cell cross-sectional area (4.4×6.4 cm), cell thickness (1.85 cm), cathode coating area (2079 cm2), cathode electrode area (2×1099 cm2), anode coating area (2181 cm2), anode electrode area (2×1127 cm2), separator area (2416 cm2), Al case thickness (500 μm) and density (3.70 g/cm3), coated cathode formulation (94% active material, 3% conductive carbon, 3% binder), cathode conductive carbon material density (1.50 g/cm3), cathode binder material density (1.80 g/cm3), cathode porosity (20%), cathode Al foil thickness (15 μm) and density (2.70 g/cm3), coated anode formulation (93% active material, 2% conductive carbon, 5% binder), anode active material capacity (330 mAh/g) and density (2.20 g/cm3), anode first discharge vs. first charge efficiency (93%), anode conductive carbon material density (1.50 g/cm3), anode binder material density (1.80 g/cm3), anode porosity (30%), Cu anode foil thickness (12 μm) and density (8.90 g/cm3), anode/cathode capacity ratio (1.1), separator thickness (25 μm) and porosity (45%), electrolyte density (1.20 g/cm3), cell insulator and tab weight (1.00 g), coating solvent identity (NMP) and fraction (60% by volume), and associated material cost parameters.
The lithium-ion battery resulting from use of the cathode material described in this example has properties as shown in Table 2.











TABLE 2






Energy

Cell Material




Density
Cost
Cost for Pack
Advantage


Cathode Material
(Wh/L)
($/Wh)
of 3 Cells ($)
vs. LiCoO2







Example 1
407
0.176
13.76
Energy


(x = 40, y = 60, z = 0)



Density,






Cost,






Safety


Example 2
406
0.162
12.64
Energy


(x = 15, y = 15,



Density,


z = 70)



Cost,






Safety


Example 3
404
0.166
12.85
Energy


(x = 20, y = 60,



Density,


z = 20)



Cost,






Safety


Comparative
401
0.208
15.97


Example 1


(x = 100)









Example 4
An Oblong Cell with High Capacity Having an Active Cathode Material Including LiCoO2/LiMn2O4 
94 wt. % mixed cathode with a weight ratio of 70:30 for LiCoO2:LiMn2O4, 3 wt. % of carbon black and 3 wt. % of PVDF were mixed in NMP under stirring. The electrode slurry was coated onto a 15 micrometer thick Al current collector. The Al current collector had a dimension of width of 56 mm and length of 1568 mm. The slurry was coated on both sides of the Al current collector. The coating length was 1510 and 1430 mm for side 1 and side 2. The process media NMP was removed by heating the coated electrode at 150° C. for a few minutes. The electrode was pressed to control the coated density. The 2-side coating was identical in every aspect. The thickness of the total electrode was 140 micrometers. The composite cathode density was 3.6 g/cc. Two Al tabs with about a width of 3 mm, length of 55 mm and thickness of 0.2 mm were welded onto the uncoated Al current collector.
93 wt. % of graphite, 2 wt. % of carbon black and 5 wt. % of PVDF binder were mixed in NMP under stirring. The electrode slurry was coated onto a 12 micrometer thick Cu current collector. The Cu current collector had a dimension of width of 57.5 mm and length of 1575 mm. The slurry was coated on both sides of the Cu current collector. The coating length was 1495 and 1465 mm for side 1 and side 2 respectively. The process media NMP was removed by heating the coated electrode at 150° C. for a few minutes. The electrode was pressed to control the coated density. The 2-side coating was identical in every aspect. The thickness of the total electrode was 130 micrometers. The composite anode density was 1.8 g/cc. Two Ni tabs with about a width of 3 mm, length of 55 mm and thickness of 0.2 mm was welded onto the uncoated Cu current collector.
The cathode and anode were separated by a microporous separator, with a thickness of 25 micrometers, width of 60 mm and length of 310 cm. They were wounded into a jelly-roll. The jelly-roll was pressed into a prismatic format.
The pressed jelly-roll was inserted into a prismatic Al case, with Al thickness of 0.4 mm. The case had an external dimension of about 64 mm in height, 36 mm in width and 18 mm in thickness. The positive tab was welded on to the top Al cap, and the negative tab was welded onto a connection passing through the Al case. An Al cap was welded onto the Al case. Approximately 10 g 1M LiPF6 EC/PC/EMC/DMC electrolyte solution was added into the cell under vacuum. After formation, the cell was completely sealed.
This cell had a capacity of 4.4 Ah at C/5 discharge rate. The nominal voltage was 3.7 V. The total cell weight was approximately 89 g. The cell energy density was approximately 183 Wh/kg and 440 Wh/liter.
Example 5A
Prophetic Example
A Cell with an Active Cathode Material Including LiCoO2/LiMn1.9Al0.1O4 
In this example, a prismatic cell with an active cathode material including LiCoO2/LiMn1.9Al0.1O4 is designed. This cell can be made by a similar procedure as described above in Example 4. For this example, the cathode mix includes 94 wt. % of mixed cathode with a weight ratio of 70:30 for LiCoO2:LiMn1.9Al0.1O4, 3 wt. % of carbon black and 3 wt. % of PVDF. The electrode slurry is coated onto a 15 micrometer thick Al current collector. The Al current collector has a dimension of width of 56 mm and length of 1913 mm. The slurry is coated on both sides of the Al current collector. The coating length is 1913 and 1799 mm for side 1 and side 2. The process media NMP is removed by heating the coated electrode at 150° C. for a few minutes. The electrode is pressed to control the porosity of 25% volume. The 2-side coating is identical in every aspect. The thickness of the single coating layer is 50 micrometers. The composite cathode density is 3.36 g/cc. An Al tab with a width of 5 mm, length of 64 mm and thickness of 0.1 mm is welded onto the uncoated Al current collector.
93 wt. % of graphite, 2 wt. % of carbon black and 5 wt. % of PVDF binder is mixed in NMP under stirring. The electrode slurry is coated onto a 12 micrometer thick Cu current collector. The Cu current collector has a dimension of width of 58 mm and length of 1940 mm. The slurry is coated on both sides of the Cu current collector. The coating length is 1903 and 1857 mm for side 1 and side 2 respectively, leaving 10 mm Cu uncoated. The process media NMP is removed by heat the coated electrode at 150° C. for a few minutes. The electrode is pressed to control the porosity of 37% volume. The 2-side coating is identical in every aspect. And the thickness of the single coating layer is 53 micrometers. The calculated composite anode density is 1.35 g/cc. A Ni tab with a width of 5 mm, length of 64 mm and thickness of 0.5 mm can be welded onto the uncoated Cu current collector.
The cathode and anode are separated by a microporous separator, with a thickness of 25 micrometers, width of 60 mm and length of 4026 mm. They are then wounded into a jelly-roll. The jelly-roll is pressed into a prismatic format.
The pressed jelly-roll is inserted into a rectangular Al case, with Al thickness of 0.5 mm. The case has an external dimension of 64 mm in height, 44 mm in width and 17 mm in thickness. The positive tab is welded on to the top Al cap, and the negative tab is welded onto the Al case. An Al cap is welded onto the Al case. Approximately 12.3 g 1M LiPF6 EC/EMC/DMC electrolyte solution is added into the cell under vacuum. After formation, the cell is completely sealed.
This cell has a calculated capacity of 4.5 Ah at C/5 discharge rate. The calculated nominal voltage is 3.7V. The total calculated cell weight is approximately 96 g. The calculated cell energy density is approximately 174 Wh/kg and 350 Wh/L.
Example 5B
Prophetic Example
A Cell with an Active Cathode Material Including LiCoO2/LiMn1.9Al0.14/LiNi0.8Al0.05Co0.15O2 
In this example, a prismatic cell with an active cathode material including LiCoO2/LiMn1.9Al0.1O4/LiNi0.8Al0.5Co0.15O2 is designed. This cell can be made by a similar procedure as described above in Example 4.
94 wt. % of mixed cathode with a weight ratio of 10:50:40 for LiCoO2: LiMn1.9Al0.1O4:LiNi0.8Al0.05Co0.15O2, 3 wt. % of carbon black and 3 wt. % of PVDF are mixed in NMP under stirring. The electrode slurry is coated onto a 15 micrometer thick Al current collector. The Al current collector has a dimension of width of 56 mm and length of 1913 mm. The slurry is coated on both sides of the Al current collector. The coating length is 1913 and 1799 mm for side 1 and side 2. The process media NMP is removed by heat the coated electrode at 150° C. for a few minutes. The electrode is pressed to control the porosity of 25% volume. The 2-side coating is identical in every aspect. And the thickness of the single coating layer is 56 micrometers. The calculated composite cathode density is 3.2 g/cc. An Al tab with a width of 5 mm, length of 64 mm and thickness of 0.1 mm is welded onto the uncoated Al current collector.
93 wt. % of graphite, 2 wt. % of carbon black and 5 wt. % of PVDF binder are mixed in NMP under stirring. The electrode slurry is coated onto a 12 micrometer thick Cu current collector. The Cu current collector has a dimension of width of 58 mm and length of 1940 mm. The slurry is coated on both sides of the Cu current collector. The coating length is 1903 and 1857 mm for side 1 and side 2 respectively, leaving 10 mm Cu uncoated. The process media NMP is removed by heat the coated electrode at 150° C. for a few minutes. The electrode is pressed to control the porosity of 37% volume. The 2-side coating is identical in every aspect. The thickness of the single coating layer is 60 micrometers. The calculated composite anode density is 1.35 g/cc. A Ni tab with a width of 5 mm, length of 64 mm and thickness of 0.5 mm is welded onto the uncoated Cu current collector.
The cathode and anode are separated by a microporous separator, with a thickness of 25 micrometers, width of 60 mm and length of 4026 mm. They are wounded into a jelly-roll. The jelly-roll is then pressed into a prismatic format.
The pressed jelly-roll is inserted into a rectangular Al case, with Al thickness of 0.5 mm. The case has an external dimension of 64 mm in height, 44 mm in width and 17 mm in thickness. The positive tab is welded on to the top Al cap, and the negative tab is welded onto the Al case. An Al cap is welded onto the Al case. Approximately 12.3 g 1M LiPF6 EC/EMC/DMC electrolyte solution is added into the cell under vacuum. After formation, the cell is completely sealed.
This cell has a calculated capacity of 5 Ah at C/5 discharge rate. The calculated nominal voltage is 3.67V. The total calculated cell weight is approximately 101 g. The calculated cell energy density is approximately 181 Wh/kg and 362 Wh/L.
Example 6
Cell Tests
The cell of Example 4 was cycled (i.e. charged and discharged) as follows:
The cell was charged with a constant current of 0.7 C to a voltage of 4.2 V and then was charged using a constant voltage of 4.2 V. The constant voltage charging was ended when the current reached 44 mA. After resting at the open circuit state for 30 minutes, it was discharged with a constant current of C/5. The discharge ended when the cell voltage reached 2.75 V. These procedures were repeated for 3 times.
Then the cell was charged with a constant current of 0.7 C to a voltage of 4.2 V and then subsequently was charged using a constant voltage of 4.2 V. The constant voltage charging was ended when the current reached 44 mA. After resting at the open circuit state for 30 minutes, it was discharged with a constant current of 1 C. The discharge ended when the cell voltage reached 2.75 V. These procedures repeated continuously to obtain cycle life data.
For rate capability testing, eight cells were charged as described about and discharge was performed to 2.75 V using different current rates ranging in value from C/5 to 2 C.
As a comparison example, an LG 18650 of LG in Seoul, Korea (“LG”) and a SANYO 18650 cell were tested with the procedures described above. Cells were typically tested at 23° C. (room temperature) and 60° C. Results of the cell tests were shown in FIGS. 6-9. As can be seen in FIGS. 6-9, a cell of the present invention showed higher voltage (FIG. 6), better cycle life at room temperature (FIG. 7), better cycle life at 60° C., (FIG. 8) and better rate capability (FIG. 9).
Example 7
Safety Tests for Lithium-ion Batteries Including a Mixture of Lithium Cobaltate and Manganate Spinel
The safety of a lithium-ion battery, consisting of a single or multiple cells, is generally dependent on the chemistry internal to the lithium-ion cell(s). In all cases, a lithium-ion cell will contain materials with some given amount of energy, that energy being capable of release through certain abuse scenarios that may cause fire or explosion from the cell. Typically, lithium-ion cells are designed for acceptable safety performance through one or more of the followings: (1) careful selection of materials, (2) proper engineering design of internal cell chemicals and components, (3) incorporation of safety devices into the cell, and (4) control electronics (i.e. pack electronics, software control) that maintain safe operation of cell(s). In addition, preferably, manufacturing environment is carefully controlled to avoid defects and foreign particulates that may cause internal shorts, which can initiate rapid heating and thermal runaway.
Preferably, the lithium-ion cells (batteries) of the invention are designed to withstand abuse scenarios that might be encountered during their use. One reference for the abuse scenarios is the UL safety testing protocols for lithium-ion cells, UL 1642. General categories of abuse include mechanical abuse, electronic abuse and temperature abuse.
DSC Tests
DSC tests were run on cathode mixtures that included LiCoO2 and Li1.1Mn1.96 Mg0.03O4. DSC tests were also run on the individual cathode materials. For the DSC testing, the cathodes were prepared by mixing LiCoO2, Li1.1Mn1.96Mg0.03O4 (in the designed ratios), carbon black and polyvinylidene fluoride (93:3.5:3.5, w:w:w) in n-methyl-2-pyrrolidone. The slurry was then cast on aluminum foil and dried at 110° C. for overnight. And the coated electrode was then calendared to the controlled thickness with a target loading density of 3.3 to 3.7 g/cc depending on the ratio of LiCoO2 to the manganate spinel to ensure the same porosity for all the electrodes. Disks were then punched out of the foil. Lithium foil was used as an anode. The electrolyte was 1M LiPF6 in a mixture of EC, PC and DEC. The coin cells made were tested at C/5 for two cycles between 3.0 V and 4.3 V, then fully charged to 4.3V before DSC study. The cells were then opened in an Ar-filled glove box. The electrode materials were recovered from the aluminum foil and sealed into a gold plated stainless steel pan. The measurements were carried out using a temperature scan rate of 5° C./min.
FIG. 10 shows the total heat of reaction for different cathode material samples (diamonds in FIG. 10) where the amount of the manganate spinel material was varied from 0 to 100%. This data was a measure of the chemical safety of a Li-ion cell, with lower total heat indicating increased safety. Also plotted in FIG. 10 is a theoretical prediction for the total heat based on a simple combination of the pure materials (open circles in FIG. 10). As shown in FIG. 10, the actual measured values showed unexpected enhanced improvement over the predicted value in the safety of the cells.
Rate of Heat Release Tests
Another measure of safety is generally the rate at which the available energy can be released. For two cathode samples with similar amounts of energy, the sample that releases heat at a slower rate would be expected to be safer. FIG. 11 shows data for a range of cathode samples with varying the amount of Li1.1Mn1.96 Mg0.03O4. Based on this data, there appears to be an optimum range for safety based on maximum rate of reaction. The data shown in FIG. 11 suggested that a mixture of approximately 20-50% of Li1.1Mn1.96 Mg0.03O4 and 80-50% of LiCoO2 was optimal.
FIG. 12 shows data for different cathode materials used in full-sized Li-ion cells. The cathode materials included an undoped manganate spinel (Li1+x1Mn2O4) and LiCoO2. The amount of an undoped manganate spinel (Li1+x1Mn2O4) was varied from 0-50%. Based on a temperature environment test of subjecting the cell to 150° C., a test that typically would result in fire/explosion of Li-ion cells, the time at 150° C. before fire/explosion was measured. The data of FIG. 12 indicates an advantage associated with the cathode sample containing from 20-50% of the manganate spinel. In these cases, the cells were able to withstand the high temperature treatment for longer time, indicating increased chemical stability.
Cell Temperature During Discharge
Under high loading conditions, the temperature of Li-ion cells will generally increase significantly. The maximum temperature is typically related to the cell chemistry, and engineering of the cells. As shown in Table 3, the maximum temperatures measured at the surface of cells of the invention, which included 70% LiCoO2 and 30% of Li1+x1Mn2O4 as the cathode materials of the cells, under different discharge rate were lower than the comparable cells with cathode of pure LiCoO2 from SANYO, Japan.







TABLE 3







Maximum Temperature (° C.) at Discharge Rates from C/5


(1⁄5 of a cycle) to 2C (2 cycles)













C/5
C/3
C/2
1C
2C


















Invention
25.0
27.6
28.7
36.3
49.7



Comparable cell
25.6
26.2
29.2
37.7
52.5










Example 8
Cycle Life for Lithium-Ion Batteries Including a Mixture of Lithium Cobaltate and Manganate Spinel
One of the important performance parameters of Li-ion cells is the capacity and the retention of the capacity (cycle life) in the service life of the cells. The cycle life was typically measured by the number of cycles when the cell capacity is 80% of the initial capacity. FIG. 13 shows that the cells of the invention with cathode of 70% LiCoO2 and 30% of Li1+x1Mn2O4 have much longer cycle life than those comparable, commercially available cells with cathode of pure LiCoO2 from LG, Korea (“LG”) and from SANYO, Japan (“Sanyo”).
EQUIVALENTS
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

## Claims

1. A lithium-ion battery having a cathode that includes an active cathode material, the active cathode material comprising a cathode mixture that includes:
a) a lithium cobaltate; and
b) a manganate spinel represented by
i) an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where
x1 and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3,
y1 and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3,
z1 is equal to or greater than 3.9 and equal to or less than 4.1, and
A′ is at least one member of the group consisting of magnesium, aluminum, nickel and chromium, or

ii) an empirical formula of Li(1+x1)Mn2Oz1 where:
x1 is equal to or greater than 0.01 and equal to or less than 0.3; and
z1 is equal to or greater than 3.9 and equal to or less than 4.1,


wherein the lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.9:0.1 to about 0.6:0.4.

2. The lithium-ion battery of claim 1, wherein the lithium cobaltate and manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.8:0.2 to about 0.6:0.4.

3. The lithium-ion battery of claim 1, wherein the cathode material includes a lithium cobaltate that is a modified lithium cobaltate with at least one modifier selected from the group consisting of a lithium modifier and a cobalt modifier and wherein the lithium modifier is at least one member selected from the group consisting of magnesium (Mg) and sodium (Na), and wherein the cobalt modifier is at least one member of the group consisting of manganese (Mn), aluminum (Al), boron (B), titanium (Ti), magnesium (Mg), calcium (C) and strontrium (Sr).

4. The lithium-ion battery of claim 1, wherein the lithium cobaltate is LiCoO2.

5. The lithium-ion bttery of claim 4, wherein the lithium cobaltate is LiCoO2 coated with ZrO2.

6. The lithium-ion battery of claim 1, wherein the manganate spinel is Li(1+x1)(Mn1-y1A′y2)2-x2Oz1, wherein y2 is greater than 0.0 and equal to or less than 0.3.

7. The lithium-ion battery of claim 6, wherein the manganate spinel is Li1.1Mn1.96Mg0.03O4.

8. The lithiumion battery of claim 1, wherein the manganate spinel is Li(1+x1)Mn2Oz1.

9. The lithium-ion battery of claim 1, wherein the lithium-ion battery has a capacity greater than about 3.0 Ah/cell.

10. The lithium-ion battery of claim 9, wherein the lithium-ion battery has a capacity greater than about 4.0 Ah/cell.

11. A lithium-ion battery having a cathode that includes an active cathode material, the active cathode material comprising a cathode mixture that includes:
a) LiCoO2; and
b) Li(1+x1)Mn2Oz1 where:
x1 is equal to or greater than 0.01 and equal to or less than 0.3; and
z1 is equal to or greater than 3.9 and equal to or less than 4.1,


wherein LiCoO2 and Li(1+x1)Mn2Oz1 are in a weight ratio of lithium cobaltate: manganate spinel between about 0.9:0.1 to about 0.6:0.4.

12. The lithium-ion battery of claim 11, wherein the LiCoO2 is coated with ZrO2.

13. The lithium-ion battery of claim 11, wherein the weight ratio of lithium cobaltate: manganate spinel is between about 0.8:0.2 to about 0.6:0.4.

14. The lithium-ion battery of claim 11, wherein the battery has a prismatic cross-sectional shape.

15. The lithium-ion battery of claim 11, wherein the battery has an oblong cross-sectional shape.

16. The lithium-ion battery of claim 11, wherein the lithium-ion battery has a capacity greater than about 3.0 Ah/cell.

17. A method of forming a lithium-ion battery, comprising:
a) forming an active cathode material including a cathode mixture that includes a lithium cobaltate and a manganate spinel in a weight ratio of lithium cobaltate:manganate spinel between about 0.9:0.1 to about 0.6:0.4, wherein the manganate spinel is represented by
i) an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where
x1 and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3,
y1 and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3,
z1 is equal to or greater than 3.9 and equal to or less than 4.1, and
A′ is at least one member of the group consisting of magnesium, aluminum, nickel and chromium, or

ii) an empirical formula of Li(1+x1)Mn2Oz1 where:
x1 is equal to or greater than 0.01 and equal to or less than 0.3, and
z1 is equal to or greater than 3.9 and equal to or less than 4.1;


b) forming a cathode electrode with the active cathode material; and
c) forming an anode electrode in electrical contact with the cathode via an electrolyte, thereby forming a lithium-ion battery.

18. The method of claim 17, wherein the lithium-ion battery is formed to have a capacity greater than about 3.0 Ah/cell.

19. The method of claim 18, wherein the lithium-ion battery is formed to have a capacity greater than about 4.0 Ah/cell.

20. A battery pack comprising a plurality of cells, wherein each of the cells includes an active cathode material including a cathode mixture that includes:
a) a lithium cobaltate; and
b) a manganate spinel represented by
i) an empirical formula of Li(1+x1)(Mn1-y1A′y2)2-x2Oz1 where
x1 and x2 are each independently equal to or greater than 0.01 and equal to or less than 0.3,
y1 and y2 are each independently equal to or greater than 0.0 and equal to or less than 0.3,
z1 is equal to or greater than 3.9 and equal to or less than 4.1, and
A′ is at least one member of the group consisting of magnesium, aluminum, nickel and chromium, or

(ii) an empirical formula of Li(1+x1)Mn2Oz1 where:
x1 is equal to or greater than 0.01 and equal to or less than 0.3, and
z1 is equal to or greater than 3.9 and equal to or less than 4.1,


wherein the lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate:manganate spinel between about 0.9:0.1 to about 0.6:0.4.

21. The battery pack of claim 20, wherein the capacity of the cells is equal to or greater than about 3.3 Ah/cell.

22. The battery pack of claim 20, wherein the internal impedance of the cells is less than about 50 milliohms.

23. The battery pack of claim 20, wherein the cells are in series and no cells are connected in parallel.

24. The battery pack of claim 20, wherein at least one cell a prismatic cross-sectional shape.

25. The battery pack of claim 24, wherein the prismatic cross-sectional shape is an oblong shape.

26. The battery pack of claim 20, wherein the lithium cobaltate is LiCoO2 and the manganate spinal is Li(1+x1)Mn2Oz1.

27. The battery pack of claim 26, wherein the lithium cobaltate and the manganate spinel are in a weight ratio of lithium cobaltate: manganate spinel between about 0.8:0.2 to about 0.6:0.4.