LOW-COBALT AND COBALT-FREE, HIGH-ENERGY CATHODE MATERIALS FOR LITHIUM BATTERIES
20230108718 · 2023-04-06
Inventors
Cpc classification
C01P2004/61
CHEMISTRY; METALLURGY
H01M4/583
ELECTRICITY
C01P2002/76
CHEMISTRY; METALLURGY
Y02P70/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M4/525
ELECTRICITY
H01M4/505
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M2004/021
ELECTRICITY
C01P2002/88
CHEMISTRY; METALLURGY
H01M4/485
ELECTRICITY
C01G53/50
CHEMISTRY; METALLURGY
C01P2004/62
CHEMISTRY; METALLURGY
C01P2002/72
CHEMISTRY; METALLURGY
H01M10/0525
ELECTRICITY
International classification
H01M4/525
ELECTRICITY
H01M10/0525
ELECTRICITY
Abstract
Described herein are low or no-cobalt materials useful as electrode active materials in a cathode for lithium or lithium-ion batteries. For example, compositions of matter are described herein, such as electrode active materials that can be incorporated into an electrode, such as a cathode. The disclosed electrode active materials exhibit high specific energy and voltage, and can also exhibit high rate capability and/or long operational lifetime.
Claims
1. An electrode active material comprising: Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d, wherein: a is from 0.9 to 1.1, b is from 0 to 0.05, c is from 0 to 0.67, d is from 1.9 to 2.1, and M is Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these, the electrode active material exhibiting a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.19 V to 4.30 V vs. Li.sup.+/Li.
2. The electrode active material of claim 1, wherein M is a combination of Mn and Al; a combination of Mn, Mg, and Al; a combination of Mn and Mg; a combination of Al and Mg; a combination of Ti, Mg, and Al; at least Al; at least Fe; at least Zn; a combination of Fe and Zn.
3-4. (canceled)
5. The electrode active material of claim 1, wherein b is 0 or wherein b is less than 0.01.
6. The electrode active material of claim 1, wherein a is from 0.9 to 1.
7. The electrode active material of claim 1, wherein a is from 1 to 1.1.
8. The electrode active material of claim 1, wherein b is from 0 to 0.01 and wherein c is from 0 to 0.01.
9. (canceled)
10. The electrode active material of claim 1, wherein d is from 1.95 to 2.05.
11. The electrode active material of claim 1, exhibiting or characterized by a tapped density of from 2.0 g.Math.cm.sup.−3 to 3.5 g.Math.cm.sup.−3.
12. The electrode active material of claim 1, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
13. The electrode active material of claim 1, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a 1C discharge rate of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1 at 25° C.
14-16. (canceled)
17. The electrode active material of claim 1, wherein the minimum is at a voltage of from 4.20 V to 4.30 V vs. Li.sup.+/Li.
18-19. (canceled)
20. The electrode active material of claim 1, wherein the minimum has a magnitude of from −3000 mAh.Math.g.sup.−1V.sup.−1 to −300 mAh.Math.g.sup.−1V.sup.−1.
21-28. (canceled)
29. The electrode active material of claim 1, exhibiting or characterized by a specific energy after 500 charge-discharge cycles of more than 80% of an original specific energy of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
30. The electrode active material of claim 1, exhibiting or characterized by a specific energy after 1000 charge-discharge cycles of more than 80% of an original specific energy of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
31-32. (canceled)
33. The electrode active material of claim 1, wherein only a portion comprises or is characterized by a rhombohedral crystal structure or a rhombohedral R
34. (canceled)
35. The electrode active material of claim 1, having or characterized by a surface region and a bulk region, wherein the surface region corresponds to a first portion of the active material or particles thereof within 20% of a cross-sectional dimension from a surface of the active material or particles thereof, and wherein the bulk region corresponds to a second portion of the active material or particles thereof deeper than the surface region.
36. The electrode active material of claim 35, wherein the bulk region is free or substantially free of or does not exhibit a spinel, P4.sub.332 or Fd
37-39. (canceled)
40. The electrode active material of claim 1, comprising particles of Li.sub.aN.sub.1-b-cCo.sub.bM.sub.cO.sub.d having cross-sectional dimensions of from 500 nm to 30 μm.
41-49. (canceled)
50. An electrode active material comprising: Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d, wherein: a is from 0.9 to 1.1, b is from 0 to 0.05, c is from 0 to 0.67, d is from 1.9 to 2.1, and M is Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these, the electrode active material exhibiting or characterized by a specific energy for a single discharge between 4.4 V and 3 V vs. Li.sup.+/Li at a C/10 discharge rate of from 850 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
51-54. (canceled)
55. The electrode active material of claim 50, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a 1C discharge rate at 25° C. of from 80% to 100% of a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a C/10 discharge rate at 25° C.
56. The electrode active material of claim 50, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a 1C discharge rate at 25° C. of from 85% to 100% of a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a C/10 discharge rate at 25° C.
57-67. (canceled)
68. The electrode active material of claim 50, exhibiting a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.15 V to 4.30 V vs. Li.sup.+/Li.
69-101. (canceled)
102. An electrode comprising the electrode active material of claim 1.
103. (canceled)
104. An electrochemical cell, comprising: a cathode comprising the electrode of claim 102; an anode; and an electrolyte between the cathode and the anode.
105. The electrochemical cell of claim 104, wherein the anode comprises graphite, carbon, silicon, lithium titanate (Li.sub.4Ti.sub.5O.sub.12), tin, antimony, zinc, phosphorous, lithium, or a combination thereof or wherein the electrolyte is a liquid electrolyte, a semi-solid electrolyte, or a solid electrolyte.
106-116. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0050] This disclosure provides a novel class of low-cobalt or cobalt-free lithium transition-metal layered oxides, useful as positive electrode (cathode) active materials for rechargeable lithium-based batteries. The described active materials include those excluding cobalt, currently universally present in layered oxide cathodes in commercial lithium-ion batteries. Instead, the described class of cathodes uses raw materials of higher earth abundance and lower cost, more secure supply chains, and less adverse impacts on the environment.
[0051] The described active materials can be easily tuned in chemical compositions to provide high specific energy, high voltage, high rate capability, and/or long operational lifetime over a wide temperature range (from subzero to elevated temperatures), as well as desirable safety features under abuse (e.g., short circuit, overcharge, rupture). These active materials are readily compatible with existing components in commercial lithium-ion batteries, such as graphite/silicon anodes, polymeric separators, and nonaqueous aprotic carbonate-based electrolytes.
[0052] Cathodes of the described active materials have been evaluated and validated in pouch-format full battery cells. The active materials can be synthesized via established industrial manufacturing processes, i.e., metal co-precipitation, lithiation calcination, and optionally subsequent surface treatments. A series of metals and/or non-metals are incorporated to enable desirable specific energy and rate capability, operational lifetime, and safety in the absence of cobalt or in very low concentrations of cobalt. The described cathodes demonstrate promise for future low-cobalt or cobalt-free, high-energy-density lithium-based batteries, including both lithium-ion and lithium-metal chemistries in either liquid, semi-solid, or all-solid-state electrolyte systems.
[0053] With rapid expansion of global electric mobility, there is a growing consensus to reduce cobalt usage in lithium-based battery cathode materials. Though cobalt-free commercial cathodes exist (e.g., lithium iron phosphate and lithium manganese oxide), they offer much lower energy contents and cannot meet the stringent requirements of next-generation automotive batteries for passenger electric vehicles. Emerging cobalt-free cathode technologies such as 5 V spinel oxides, layered lithium-excess oxides, sulfur, and metal fluorides all necessitate a fundamental change of current lithium battery chemistry, which likely will take a decade or more development time.
[0054] Lithium transition-metal layered oxides have been and are expected to continue to be the cathode material of choice for portable electronics and passenger electric cars at least through the next decade. However, these materials, despite varying formulations, universally contain cobalt in significant amounts. Cobalt is deemed essential for performance and stability, but is a scarce metal with a vulnerable supply chain and has a high cost as a result. Plus, owing to high toxicity and questionable mining practices in Central Africa, cobalt causes unfavorable impacts on the environment. Different from all commercial layered oxide cathodes, this disclosure relates to a new class of cathode materials of high energy content with low or zero cobalt usage.
[0055] The use of cobalt in commercial lithium-ion battery cathodes involves a series of challenges. To begin with, cobalt is scarce and can only be found in a few places on earth. Nearly two thirds of global cobalt mining comes from the Democratic Republic of Congo (DRC), a Central African country with unstable political regimes. In addition, cobalt mining in DRC sometimes skimps on environmental protections and exploits child labor. Even without disruptions of the global cobalt supply chain, demand for cobalt can outstrip production in the coming decade, with a projected ten-fold production increase of electric cars in 2025 compared to 2018. In comparison, nickel, manganese, aluminum, iron, zinc, and many other metals and non-metals, are far more earth-abundant and available. These metals and non-metals are also much less geographically concentrated than cobalt.
[0056] The active materials described herein reduce the dependence on cobalt of commercial layered oxide cathodes for lithium-based batteries, thus leading to more secure supply chains, lower cost, and less adverse environmental impacts. In addition, through a tuning in chemical composition and synthesis, the described cathode materials can offer high specific energy, high voltage, high rate capability, and/or long operational lifetime over a wide temperature range, as well as desirable safety features under abuse conditions, in comparison to commercial layered oxide cathode materials.
[0057] Since cobalt suppresses nickel and lithium anti-site defects (i.e., cation disorder) in layered oxides, cobalt elimination can adversely affect specific capacity, voltage, rate capability, and operational lifetime of the cathode material. Advantageously, the active materials described herein mitigate these issues by incorporating a series of alternative metals and/or non-metals, besides nickel, which compensate for the lack of cobalt. Advantageously, these alternative metals and non-metals can be incorporated easily through co-precipitation, lithiation calcination, and/or subsequent surface treatments. Advantageously, the synthesis comprising co-precipitation, lithiation calcination, and/or subsequent surface treatments is useful, or in some cases critical, to mitigate the issues of specific capacity, voltage, rate capability, and operational lifetime of the cathode material without cobalt.
[0058] Besides portable electronics and electric vehicles, the described cathode active materials can be useful in unmanned aerial systems, robots, military batteries, and large-scale energy storage systems. The flexibility in compositional designs can enable cathode materials with either very high specific energy and rate capability or very long operational lifetime, geared towards a variety of market needs.
Electrode Active Materials
[0059] The electrode active materials described herein include those exhibiting high specific energy measured on a cathode level, such as from about 600 Wh.Math.kg.sup.−1 to about 1000 Wh.Math.kg.sup.−1. Example specific energies may be from 625 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 650 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 675 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 700 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 725 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 750 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 775 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 800 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 825 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 850 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 875 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 900 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 925 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 950 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, or from 975 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1. The specific energy can correspond to a discharge from about 5 V to about 3 V vs. Li.sup.+/Li, for example. It will be appreciated that some electrode active materials can discharge to lower voltages, such as about 2 V vs. Li.sup.+/Li, which can allow some electrode active materials to exhibit specific energies significantly higher than if they are only discharged to about 3 V vs. Li.sup.+/Li or greater. Additionally, some electrode active materials can be charged to voltages higher than about 5 V vs. Li.sup.+/Li, providing some additional energy. For comparison purposes, discharging from a voltage higher than about 5 V vs. Li.sup.+/Li or to a voltage lower than about 3 V vs Li.sup.+/Li may not provide the same information as a discharge from about 5 V to about 3 V vs Li.sup.+/Li. The specific energy can correspond to a discharge at a particular temperature, such as room temperature, 25° C. It will be appreciated that some electrode active materials may exhibit different specific energies and rate capabilities at different temperatures. The specific energy can correspond to a discharge at a particular discharge rate, such as 1C or C/10. It will be appreciated that some electrode active materials may exhibit different specific energies when discharged at different rates. The specific energy can correspond to a discharge of an electrode of a particular composition and thickness, such as those comprising an electrode active material content of at least 90% by weight and an electrode active material areal capacity loading of at least 2.0 mAh.Math.cm.sup.2. It will be appreciated that some electrode active materials may exhibit different specific energies in electrodes of different compositions or thicknesses. The specific energy can correspond to a discharge of an electrode in a particular battery cell configuration, such as a coin-format half battery cell paired with lithium metal as the counter electrode infused with a commercial non-aqueous electrolyte. It will be appreciated that some electrode active materials may exhibit different specific energies in different battery cell configurations.
[0060] The electrode active materials described herein include those exhibiting a high voltage measured on a cathode level, such as from 4.15 V to 4.30 V vs. Li.sup.+/Li, at a minimum of from −300 mAh.Math.g.sup.−1V.sup.−1 to −3000 mAh.Math.g.sup.−1V.sup.−1, in a dQ.Math.dV.sup.−1 curve during discharge. Example high voltages may be from 4.16 V to 4.30 V vs. Li.sup.+/Li, from 4.17 V to 4.30 V vs. Li.sup.+/Li, from 4.18 V to 4.30 V vs. Li.sup.+/Li, from 4.19 V to 4.30 V vs. Li.sup.+/Li, from 4.20 V to 4.30 V vs. Li.sup.+/Li, from 4.21 V to 4.30 V vs. Li.sup.+/Li, or from 4.22 V to 4.30 V vs. Li.sup.+/Li. In some examples, the minimum in a dQ.Math.dV.sup.−1 curve during discharge may be −400 mAh.Math.g.sup.−1V.sup.−1 or lower, may be −500 mAh.Math.g.sup.−1V.sup.−1 or lower, −600 mAh.Math.g.sup.−1V.sup.−1 or lower, −700 mAh.Math.g.sup.−1V.sup.−1 or lower, −800 mAh.Math.g.sup.−1V.sup.−1 or lower, −900 mAh.Math.g.sup.−1V.sup.−1 or lower, −1000 mAh.Math.g.sup.−1V.sup.−1 or lower, −1200 mAh.Math.g.sup.−1V.sup.−1 or lower, −1400 mAh.Math.g.sup.−1V.sup.−1 or lower, −1600 mAh.Math.g.sup.−1V.sup.−1 or lower, −1800 mAh.Math.g.sup.−1V.sup.−1 or lower, or −2000 mAh.Math.g.sup.−1V.sup.−1 or lower. It will be appreciated that a dQ.Math.dV.sup.−1 curve may exhibit maximums during charge at voltages significantly higher than those of minimums during discharge. A maximum may refer to a highest magnitude, such as in a particular range, and may refer to a positive peak or zenith, representing a local maximum value, which may, in some cases, be an absolute maximum value. For comparison purposes, voltages of maximums during charge in a dQ.Math.dV.sup.−1 curve may not provide the same information as those of minimums during discharge in said dQ.Math.dV.sup.−1 curve. The voltage can correspond to a method for calculation of the dQ.Math.dV.sup.−1 curves, such as a voltage sampling step of 0.02 V. It will be appreciated that some calculation methods may exhibit different voltages and/or minimums of different values expressed by mAh.Math.g.sup.−1V.sup.−1 in dQ.Math.dV.sup.−1 curves during discharge. The voltage can correspond to a discharge at a particular temperature, such as room temperature, 25° C. It will be appreciated that some electrode active materials may exhibit different voltages at different temperatures. The voltage can correspond to a discharge at a particular discharge rate, such as C/10. It will be appreciated that some electrode active materials may exhibit different voltages when discharged at different rates. The voltage can correspond to a discharge of an electrode of a particular composition and thickness, such as those comprising an electrode active material content of at least 90% by weight and an electrode active material areal capacity loading of at least 2.0 mAh.Math.cm.sup.−2. It will be appreciated that some electrode active materials may exhibit different voltages in electrodes of different compositions or thicknesses. The voltage can correspond to a discharge of an electrode in a particular battery cell configuration, such as a coin-format half battery cell paired with lithium metal as the counter electrode infused with a commercial non-aqueous electrolyte. It will be appreciated that some electrode active materials may exhibit different voltages in different battery cell configurations
[0061] A wide variety of compositions for the electrode active materials are contemplated herein. In general, the electrode active materials comprise or are characterized by a chemical formula of Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d. Here, M represents one or more metals and/or non-metals, such as Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these.
[0062] The subscript a in the chemical formula Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d represents the relative amount of Li (lithium) in the electrode active materials. In general, the amount of Li can vary from Li-rich to Li-deficient. For example, a may be from about 0.9 to about 1.1 in general, or from 0.9 to 1.0 or from 1.0 to 1.1. In some cases, a may be or may be about 0.9, 0.905, 0.91, 0.915, 0.92, 0.925, 0.93, 0.935, 0.94, 0.945, 0.95, 0.955, 0.96, 0.965, 0.97, 0.975, 0.98, 0.985, 0.99, 0.995, 1, 1.005, 1.01, 1.015, 1.02, 1.025, 1.03, 1.035, 1.04, 1.045, 1.05, 1.055, 1.06, 1.065, 1.07, 1.075, 1.08, 1.085, 1.09, 1.095, or 1.1.
[0063] The subscript b in the chemical formula Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d represents the relative amount of Co (cobalt) in the electrode active materials. In general, the amount of Co is very low—such as where b is from 0 to 0.1 or from 0 to 0.05. In some cases, b may be or may be about 0, 0.005, 0.010, 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100.
[0064] The subscript c in the chemical formula Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d represents the relative amount of metal(s) and/or non-metal(s) M in the electrode active materials. In general, c can vary from about 0 to about 0.67. In some cases, c may be from about 0 to about 0.5. Since M can correspond to one or multiple metals and/or non-metals, it will be appreciated that the stoichiometric coefficient for the individual metals and/or non-metals may total to c. Example values for c may be or may be about 0, 0.005, 0.010, 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.105, 0.110, 0.115, 0.120, 0.125, 0.130, 0.135, 0.140, 0.145, 0.150, 0.155, 0.160, 0.165, 0.170, 0.175, 0.180, 0.185, 0.190, 0.195, 0.200, 0.205, 0.210, 0.215, 0.220, 0.225, 0.230, 0.235, 0.240, 0.245, 0.250, 0.255, 0.260, 0.265, 0.270, 0.275, 0.280, 0.285, 0.290, 0.295, 0.300, 0.305, 0.310, 0.315, 0.320, 0.325, 0.330, 0.335, 0.340, 0.345, 0.350, 0.355, 0.360, 0.365, 0.370, 0.375, 0.380, 0.385, 0.390, 0.395, 0.400, 0.405, 0.410, 0.415, 0.420, 0.425, 0.430, 0.435, 0.440, 0.445, 0.450, 0.455, 0.460, 0.465, 0.470, 0.475, 0.480, 0.485, 0.490, 0.495, 0.500, 0.505, 0.510, 0.515, 0.520, 0.525, 0.530, 0.535, 0.540, 0.545, 0.550, 0.555, 0.560, 0.565, 0.570, 0.575, 0.580, 0.585, 0.590, 0.595, 0.600, 0.605, 0.610, 0.615, 0.620, 0.625, 0.630, 0.635, 0.640, 0.645, 0.650, 0.655, 0.660, 0.665, 0.666, 0.667, or 0.670.
[0065] The subscript d in the chemical formula Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d represents the relative amount of O (oxygen) in the electrode active materials. In general, the amount of O can vary from O-rich to O-deficient. For example, d may be from about 1.9 to about 2.1 in general, or from 1.95 to 2.05, from 1.9 to 2.0, from 1.95 to 2.05, from 2.0 to 2.05, or from 2.05 to 2.1. In some cases, d may be or may be about 1.9, 1.905, 1.91, 1.915, 1.92, 1.925, 1.93, 1.935, 1.94, 1.945, 1.95, 1.955, 1.96, 1.965, 1.97, 1.975, 1.98, 1.985, 1.99, 1.995, 2, 2.005, 2.01, 2.015, 2.02, 2.025, 2.03, 2.035, 2.04, 2.045, 2.05, 2.055, 2.06, 2.065, 2.07, 2.075, 2.08, 2.085, 2.09, 2.095, 2.1.
[0066] The subscript 1-b-c in the chemical formula Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d represents the relative amount of Ni (nickel) in the electrode active materials. In general, the amount of Ni can vary from relatively low to relatively high, though the relative amount of Ni may be dependent upon the amounts of Co and metals and/or non-metals M in the electrode active materials. For example, 1-b-c may be from about 1 to about 0.5 or from 1 to 0.33. In some cases, 1-b-c may be or may be about 0.330, 0.333, 0.334, 0.335, 0.340, 0.345, 0.350, 0.355, 0.360, 0.365, 0.370, 0.375, 0.380, 0.385, 0.390, 0.395, 0.400, 0.405, 0.410, 0.415, 0.420, 0.425, 0.430, 0.435, 0.440, 0.445, 0.450, 0.455, 0.460, 0.465, 0.470, 0.475, 0.480, 0.485, 0.490, 0.495, 0.500, 0.505, 0.510, 0.515, 0.520, 0.525, 0.530, 0.535, 0.540, 0.545, 0.550, 0.555, 0.560, 0.565, 0.570, 0.575, 0.580, 0.585, 0.590, 0.595, 0.600, 0.605, 0.610, 0.615, 0.620, 0.625, 0.630, 0.635, 0.640, 0.645, 0.650, 0.655, 0.660, 0.665, 0.670, 0.675, 0.680, 0.685, 0.690, 0.695, 0.700, 0.705, 0.710, 0.715, 0.720, 0.725, 0.730, 0.735, 0.740, 0.745, 0.750, 0.755, 0.760, 0.765, 0.770, 0.775, 0.780, 0.785, 0.790, 0.795, 0.800, 0.805, 0.810, 0.815, 0.820, 0.825, 0.830, 0.835, 0.840, 0.845, 0.850, 0.855, 0.860, 0.865, 0.870, 0.875, 0.880, 0.885, 0.890, 0.895, 0.900, 0.905, 0.910, 0.915, 0.920, 0.925, 0.930, 0.935, 0.940, 0.945, 0.950, 0.955, 0.960, 0.965, 0.970, 0.975, 0.980, 0.985, 0.990, 0.995, or 1.000.
[0067] The electrode active materials may be in or prepared in a powder form, such as comprising individual secondary particles having cross-sectional dimensions (e.g., diameters) of from about 500 nm to about 30 μm. For example, the cross-sectional dimensions may be from 500 nm to 1.0 μm, from 1.0 μm to 2.5 μm, from 2.5 m to 5.0 μm, from 5.0 μm to 7.5 μm, from 7.5 μm to 10 μm, from 10 μm to 15 μm, from 15 μm to 20 μm, or from 20 μm to 30 μm. The electrode active material may exhibit a tapped density of from about 2.0 g.Math.cm.sup.−3 to about 3.5 g.Math.cm.sup.−3, such as from 2.0 g.Math.cm.sup.−3 to 2.1 g.Math.cm.sup.−3, from 2.1 g.Math.cm.sup.−3 to 2.2 g.Math.cm.sup.−3, from 2.2 g.Math.cm.sup.−3 to 2.3 g.Math.cm.sup.−3, from 2.3 g.Math.cm.sup.−3 to 2.4 g.Math.cm.sup.−3, from 2.4 g.Math.cm.sup.−3 to 2.5 g.Math.cm.sup.−3, from 2.5 g.Math.cm.sup.−3 to 2.6 g.Math.cm.sup.−3, from 2.6 g.Math.cm.sup.−3 to 2.7 g.Math.cm.sup.−3, from 2.7 g.Math.cm.sup.−3 to 2.8 g.Math.cm.sup.−3, from 2.8 g.Math.cm.sup.−3 to 2.9 g.Math.cm.sup.−3, from 2.9 g.Math.cm.sup.−3 to 3.0 g.Math.cm.sup.−3, from 3.0 g.Math.cm.sup.−3 to 3.1 g.Math.cm.sup.−3, from 3.1 g.Math.cm.sup.−3 to 3.2 g.Math.cm.sup.−3, from 3.2 g.Math.cm.sup.−3 to 3.3 g.Math.cm.sup.−3, from 3.3 g.Math.cm.sup.−3 to 3.4 g.Math.cm.sup.−3, or from 3.4 g.Math.cm.sup.−3 to 3.5 g.Math.cm.sup.−3.
[0068] The electrode active materials may exhibit good operational lifetime, such as where a specific energy degradation after 500 cycles is less than or about 20%, less than or about 15%, or less than or about 10%. In some cases, the specific energy degradation after 1000 cycles may be less than or about 20%, less than or about 15%, or less than or about 10%. In some cases, the specific energy degradation after 100 cycles may be less than or about 10%, less than or about 5%, or less than or about 2.5%.
Cathodes
[0069] The electrode active materials described herein can be cathode active materials and useful as cathodes (positive electrodes).
[0070] Depending on the cathode configuration, the cathode active material 110 may have any suitable dimensions or mass. The electrode active material of cathode active material 110 may optionally be mixed with binders or conductive additives, as known in the art.
Electrochemical Cells
[0071] The electrode active materials, cathode active materials, and cathodes described herein can be useful in electrochemical cells and batteries.
[0072] The cathode current collector 205 may comprise aluminum, for example. The cathode active material 210 may correspond to any of the electrode active materials described herein. The cathode active 210 material may be mixed with a binder, a conductive additive, a liquid or a solid electrolyte, etc.
[0073] The anode current collector 215 may comprise copper. In some cases, the anode current collector 215 may not be used. Example materials for the anode active material 220 may include, but is not limited to, graphite, carbon, silicon, lithium titanate (Li.sub.4Ti.sub.5O.sub.12), tin, antimony, zinc, phosphorous, lithium, or a combination thereof. The anode active material 220 may be mixed with a binder, a conductive additive, a liquid or a solid electrolyte, etc.
[0074] The separator 225 may be any suitable non-reactive material. Example separators may be polymeric membranes like polypropylene, poly(methyl methacrylate), or polyacrylonitrile, or may be solid or ceramic electrolytes. The separator 225 may include (e.g., have pores filled with) an electrolyte or may function as an electrolyte itself, which may be used to conduct ions back and forth between the cathode active material 210 and the anode active material 220. Example electrolytes may be or include an organic solvent, such as ethylene carbonate, dimethyl carbonate, or diethyl carbonate, or solid or ceramic electrolytes. Electrolytes may include dissolved lithium salts, such as LiPF.sub.6, LiBF.sub.4, or LiClO.sub.4, and other additives.
Methods
[0075] The Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d materials may be synthesized through metal co-precipitation and lithiation calcination. First, dissolvable salts of nickel, cobalt, and M, including but not limited to, nitrates, chlorides, acetates, sulfates, oxalates, and a combination thereof, are mixed to make an aqueous solution with appropriate metal molar ratios. The concentration of the mixed-metal ion aqueous solution may be from 0.1 mol.Math.L.sup.−1 to 3.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution is pumped into a tank reactor at a controlled rate under a non-oxidizing gaseous atmosphere. An aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and a combination thereof, at 0.2 mol.Math.L.sup.−1 to 10 mol.Math.L.sup.−1 is separately pumped into the tank reactor to maintain a pH of 8.0 to 12.5. A chelating agent, for example an aqueous solution of ammonium hydroxide, is also pumped into the tank reactor to maintain an appropriate concentration of the chelating agent inside the tank reactor. The co-precipitation reaction takes place at a controlled temperature of 30° C. to 80° C.
[0076] Subsequently, a precursor P is obtained through washing, filtering, and drying of the material from the tank reactor and mixed with a lithium salt and an additive material X at appropriate molar ratios. The lithium salt comprises a lithium carbonate, a lithium hydroxide, a lithium acetate, a lithium oxide, a lithium oxalate, and a combination thereof. The additive material X comprises salts of M, including but not limited to, oxides, carbonates, nitrates, acetates, oxalates, hydroxides, fluorides, isopropoxides, and a combination thereof. The mixed precursor P, lithium salt, and additive material X is calcined at 600° C. to 1000° C. under a flowing gaseous atmosphere of an oxygen content from 21% (air) to 100% (pure oxygen) to obtain the lithiated oxide L.
[0077] In some examples, the lithiated oxide L is the final product, Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d. Optionally, the lithiated oxide L is further subject to a surface treatment. During the surface treatment, the lithiated oxide L is mixed with a liquid comprising deionized water, boric acid, phosphoric acid, ethanol, isopropanol, and a combination thereof.
[0078] After drying, the lithiated oxide L is mixed with a lithium salt and an additive material Y at appropriate molar ratios. The lithium salt comprises a lithium carbonate, a lithium hydroxide, a lithium acetate, a lithium oxide, a lithium oxalate, and a combination thereof. The additive material Y comprises salts of M, including but not limited to, oxides, carbonates, nitrates, acetates, oxalates, hydroxides, fluorides, isopropoxides, and a combination thereof.
[0079] The mixed lithiated oxide L, lithium salt, and additive material Y is subsequently calcined at elevated temperature, optionally under a flowing gaseous atmosphere of an oxygen content from 21% (air) to 100% (pure oxygen), to obtain the final product, Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d.
[0080] The synthesis of Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d may be similar to the established production methods, but also provides a series of advantages: (i) a precise control of metal co-precipitation of nickel and other metals and/or non-metals at appropriate molar ratios that enables homogenous mixing at the atomic scale, (ii) a precise control of metal co-precipitation and lithiation calcination that enables fine tuning of the morphology and microstructure of the material secondary and primary particles, and (iii) an optional surface treatment that reduces residual lithium species and enhances surface stability of the material. It will be appreciated that the properties of lithium transition-metal layered oxides are extremely sensitive to their synthesis conditions. The synthesis described is useful for enabling the high specific energy, high voltage, high rate capability, long operational lifetime, and desirable safety of Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d.
[0081] The invention may be further understood by the following non-limiting examples.
Example 1
[0082] Low-cobalt cathode active materials comprising LiNi.sub.0.9Co.sub.0.05Mn.sub.0.05O.sub.2, LiNi.sub.0.9Co.sub.0.05Al.sub.0.05O.sub.2, and LiNi.sub.0.9Co.sub.0.04Mn.sub.0.04Al.sub.0.01Mg.sub.0.01O.sub.2 were prepared according to the methods described herein. Dissolvable salts of nickel, cobalt, manganese, aluminum, and magnesium were used to make aqueous solutions of varying molar ratios at 2.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution was pumped into a tank reactor at a controlled rate under nitrogen atmosphere. An aqueous solution of potassium hydroxide at 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 1.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 11.5±0.5. The co-precipitation reaction took place at 50±5° C. Subsequently, precursors comprising Ni.sub.0.9Co.sub.0.05Mn.sub.0.05(OH).sub.2, Ni.sub.0.9Co.sub.0.05Al.sub.0.05(OH).sub.2, and Ni.sub.0.9Co.sub.0.04Mn.sub.0.04Al.sub.0.01Mg.sub.0.01(OH).sub.2 were obtained through washing, filtering, and drying and mixed with lithium hydroxide at a molar ratio of 1:1.03±0.02. The mixed precursor and lithium hydroxide was calcinated at 750±20° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate to obtain LiNi.sub.0.9Co.sub.0.05Mn.sub.0.05O.sub.2, LiNi.sub.0.9Co.sub.0.05Al.sub.0.05O.sub.2, and LiNi.sub.0.9Co.sub.0.04Mn.sub.0.04Al.sub.0.01Mg.sub.0.01O.sub.2. It will be appreciated that the lithium and oxygen contents in these chemical compositions are based on stoichiometry, but the lithium and oxygen contents may deviate from their stoichiometric values.
[0083]
[0084]
[0085] The cathode active materials exhibited a tapped density of about 2.5 g.Math.cm.sup.−3 to 2.6 g.Math.cm.sup.−3. The cathode active material was formed into a composite cathode electrode by depositing a slurry of the cathode active material in N-Methyl-2-Pyrrolidone onto an aluminum foil current collector and allowing the solvent to evaporate. The areal capacity loading of the cathode active material is about 2.0 mAh.Math.cm.sup.−2. The cathode was assembled into an electrochemical cell with either a lithium metal anode or a graphite anode, a separator comprising a blend of polypropylene and polyethylene soaked with a nonaqueous carbonate-based electrolyte comprising 1.0 molar LiPF.sub.6 in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (3:7 by weight) with an additive of vinylene carbonate (2% by weight). Voltage profiles were obtained for charging and discharging the electrochemical cell.
[0086]
[0087]
Example 2
[0088] Cobalt-free cathode active materials comprising LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2 and LiNi.sub.0.9Mn.sub.0.05Mg.sub.0.05O.sub.2 were prepared according to the methods described herein. Dissolvable salts of nickel, manganese, aluminum, and magnesium are used to make aqueous solutions of varying molar ratios at 2.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution was pumped into a tank reactor at a controlled rate under nitrogen atmosphere. An aqueous solution of potassium hydroxide at 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 1.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 11.5±0.5. The co-precipitation reaction took place at 50±5° C. Subsequently, precursors comprising Ni.sub.0.9Mn.sub.0.05Al.sub.0.05(OH).sub.2 and Ni.sub.0.9Mn.sub.0.05Mg.sub.0.05(OH).sub.2 were obtained through washing, filtering, and drying and mixed with lithium hydroxide at a molar ratio of 1:1.03±0.02. The mixed precursor and lithium hydroxide was calcinated at 750±20° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate to obtain LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2 and LiNi.sub.0.9Mn.sub.0.05Mg.sub.0.05O.sub.2. It will be appreciated that the lithium and oxygen contents in these chemical compositions are based on stoichiometry, but the lithium and oxygen contents may deviate from their stoichiometric values.
[0089]
[0090] The cathode active materials exhibited a tapped density of about 2.5 g.Math.cm.sup.−3 to 2.6 g.Math.cm.sup.−3. The cathode active material was formed into a composite cathode electrode by depositing a slurry of the cathode active material in N-Methyl-2-Pyrrolidone onto an aluminum foil current collector and allowing the solvent to evaporate. The areal capacity loading of the cathode active material was around 2.0 mAh.Math.cm.sup.−2. The cathode was assembled into an electrochemical cell with either a lithium metal anode or a graphite anode, a separator comprising a blend of polypropylene and polyethylene soaked with a nonaqueous carbonate-based electrolyte comprising 1.0 molar LiPF.sub.6 in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (3:7 by weight) with an additive of vinylene carbonate (2% by weight). Voltage profiles were obtained for charging and discharging the electrochemical cell.
[0091]
[0092]
Example 3
[0093] The compositions described above in Example 1 and Example 2 were formed into coin half battery cells with lithium metal as the counter electrode for further evaluation.
[0094]
[0095] To calculate the dQ.Math.dV.sup.−1 plots, lithium metal coin cells were cycled at C/10 rate within 2.8 V and 4.4 V vs. Li.sup.+/Li. The cycling data used for calculating the dQ/dV curves are separated by 0.02 V steps. The dQ/dV value at each voltage is calculated by the formula in Eq. 1. The charge, Q.sub.2, in Eq. 1 is the total charge at the voltage of interest, V.sub.2, with the proceeding data point at voltage V.sub.1 and total charge for that charge or discharge cycle at Q.sub.1. Since data used for dQ/dV calculation is acquired every 0.02 V, ΔV is always 0.02 V, with the unit mAh.Math.g.sup.−1V.sup.−1. The voltage step of 0.02 V between acquired data points prevents noise from impacting the magnitude of the mAh.Math.g.sup.−1V.sup.−1, which can increase to very large values when AV is set to small values.
Then data points (x, y) can be plotted with
[0096]
[0097]
[0098]
[0099]
[0100]
[0101] Long-term cycling of LiNi.sub.0.90Co.sub.0.05Mn.sub.0.05O.sub.2, LiNi.sub.0.90Co.sub.0.05Al.sub.0.05O.sub.2, LiNi.sub.0.90Co.sub.0.04Mn.sub.0.04Al.sub.0.01Mg.sub.0.01O.sub.2, and LiNi.sub.0.90Mn.sub.0.05Al.sub.0.05O.sub.2 in pouch full battery cells paired with graphite anodes is shown in
[0102]
Example 4
[0103] Cobalt-free cathode active materials comprising LiNiO.sub.2 and LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2 were prepared according to the methods described herein. Dissolvable salts of nickel, manganese, and aluminum were used to make aqueous solutions of varying molar ratios at 2.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution was pumped into a tank reactor at a controlled rate under nitrogen atmosphere. An aqueous solution of potassium hydroxide at 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 1.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 11.5±0.5. The co-precipitation reaction took place at 50±5° C. Subsequently, precursors comprising Ni(OH).sub.2 and Ni.sub.0.9Mn.sub.0.05Al.sub.0.05(OH).sub.2 were obtained through washing, filtering, and drying and mixed with lithium hydroxide at a molar ratio of 1:1.03±0.02. The mixed precursor and lithium hydroxide was calcinated at 720±50° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate to obtain LiNiO.sub.2 and LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2. It will be appreciated that the lithium and oxygen contents in these chemical compositions are based on stoichiometry, but the lithium and oxygen contents may deviate from their stoichiometric values.
[0104]
[0105] The cathode active material exhibited a tapped density of about 2.5 g.Math.cm.sup.−3 to 2.7 g.Math.cm.sup.−3. The cathode active material was formed into a composite cathode electrode by depositing a slurry of the cathode active material in N-Methyl-2-Pyrrolidone onto an aluminum foil current collector and allowing the solvent to evaporate. The areal capacity loading of the cathode active material was 2.4 mAh.Math.cm.sup.−2 to 2.6 mAh.Math.cm.sup.−2. The cathode was assembled into an electrochemical cell with a lithium metal anode, a separator comprising a blend of polypropylene and polyethylene soaked with a nonaqueous carbonate-based electrolyte comprising 1.0 molar LiPF.sub.6 in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (3:7 by weight) with an additive of vinylene carbonate (2% by weight). Galvanostatic voltage profiles were obtained for charging and discharging the electrochemical cell.
[0106]
Example 5
[0107] Cobalt-free cathode active materials comprising LiNiO.sub.2, LiNi.sub.0.98Ta.sub.0.02O.sub.2, LiNi.sub.0.98Zr.sub.0.02O.sub.2, and LiNi.sub.0.98Mg.sub.0.02O.sub.2 were prepared according to the methods described herein. First, cathode active material precursor comprising Ni(OH).sub.2 was prepared using dissolvable salts of nickel in aqueous solutions at 2.0 mol.Math.L.sup.−1. The aqueous solution was pumped into a tank reactor at a controlled rate. An aqueous solution of potassium hydroxide at 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 1.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 11.75±0.25. The co-precipitation reaction took place at 50±5° C. Subsequently, precursor comprising Ni(OH).sub.2 was obtained through washing, filtering, and drying. To obtain LiNiO.sub.2, the precursor comprising Ni(OH).sub.2 was mixed with lithium hydroxide at a molar ratio of 1:1.02±0.03. The mixed precursor and lithium hydroxide was calcinated at 690±20° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate. To obtain LiNi.sub.0.98Ta.sub.0.02O.sub.2, LiNi.sub.0.98Zr.sub.0.02O.sub.2, or LiNi.sub.0.98Mg.sub.0.02O.sub.2, precursor comprising Ni(OH).sub.2 was mixed with either tantalum oxide, zirconium oxide, or magnesium oxide, and additionally lithium hydroxide at a molar ratio of 0.98:0.02:1.02±0.03. The mixed precursor, either tantalum oxide, zirconium oxide, or magnesium oxide, and lithium hydroxide was calcinated at 720±30° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate. It will be appreciated that the lithium and oxygen contents in these chemical compositions are based on stoichiometry, but the lithium and oxygen contents may deviate from their stoichiometric values.
[0108] The cathode active material exhibited a tapped density of about 2.5 g.Math.cm.sup.−3 to 2.7 g.Math.cm.sup.−3. The cathode active material was formed into a composite cathode electrode by depositing a slurry of the cathode active material in N-Methyl-2-Pyrrolidone onto an aluminum foil current collector and allowing the solvent to evaporate. The areal capacity loading of the cathode active material was around 2.0 mAh.Math.cm.sup.−2. The cathode was assembled into an electrochemical cell with a lithium metal anode, a separator comprising a blend of polypropylene and polyethylene soaked with a nonaqueous carbonate-based electrolyte comprising 1.0 molar LiPF.sub.6 in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (3:7 by weight) with an additive of vinylene carbonate (2% by weight). Galvanostatic voltage profiles were obtained for charging and discharging the electrochemical cell.
[0109]
[0110] To calculate the dQ.Math.dV.sup.−1 plots, lithium metal coin cells were cycled at C/10 rate within 2.8 and 4.4 V vs. Li.sup.+/Li. The cycling data used for calculating the dQ/dV curves are separated by 0.02 V steps. The dQ/dV value at each voltage is calculated by the formula in Eq. 1, described above. The charge, Q.sub.2, in Eq. 1 is the total charge at the voltage of interest, V.sub.2, with the proceeding data point at voltage V.sub.1 and total charge for that charge or discharge cycle at Q.sub.1. Since data used for dQ/dV calculation is acquired every 0.02 V, ΔV is always 0.02 V, with the unit mAh.Math.g.sup.−1V.sup.−1. The voltage step of 0.02 V between acquired data points prevents noise from impacting the magnitude of the mAh.Math.g.sup.−1V.sup.−1, which can increase to very large values when AV is set to small values. The data points (x, y) can be plotted with
Comparative Example 1
[0111] A cobalt-free cathode active material comprising LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2 was prepared according to the methods described herein. Dissolvable salts of nickel, manganese, and aluminum were used to make aqueous solutions of varying molar ratios at 2.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution was pumped into a tank reactor at a controlled rate under nitrogen atmosphere. An aqueous solution of potassium hydroxide at 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 1.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 11.5±0.5. The co-precipitation reaction took place at 50±5° C. Subsequently, precursor comprising Ni.sub.0.9Mn.sub.0.05Al.sub.0.05(OH).sub.2 was obtained through washing, filtering, and drying and mixed with lithium hydroxide at a molar ratio of 1:1.03±0.07. The mixed precursor and lithium hydroxide was calcinated at 750±20° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate to obtain LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2. It will be appreciated that the lithium and oxygen contents in these chemical compositions are based on stoichiometry, but the lithium and oxygen contents may deviate from their stoichiometric values.
[0112] The cathode active material exhibited a tapped density of about 2.5 g.Math.cm.sup.−3. The cathode active material was formed into a composite cathode electrode by depositing a slurry of the cathode active material in N-Methyl-2-Pyrrolidone onto an aluminum foil current collector and allowing the solvent to evaporate. The areal capacity loading of the cathode active material was around 2.0 mAh.Math.cm.sup.−2. The cathode was assembled into an electrochemical cell with a lithium metal anode, a separator comprising a blend of polypropylene and polyethylene soaked with a nonaqueous carbonate-based electrolyte comprising 1.0 molar LiPF.sub.6 in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (3:7 by weight) with an additive of vinylene carbonate (2% by weight). Galvanostatic voltage profiles were obtained for charging and discharging the electrochemical cell.
[0113]
[0114] In
Comparative Example 2
[0115] A low-cobalt cathode active material precursor comprising Ni.sub.0.9Co.sub.0.05Mn.sub.0.05(OH).sub.2 or Ni.sub.0.9Co.sub.0.05Mn.sub.0.05CO.sub.3 was prepared according to the methods described herein. Dissolvable salts of nickel, cobalt, and manganese were used to make aqueous solutions of varying molar ratios at 0.5 mol.Math.L.sup.−1 to 2.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution was pumped into a tank reactor at a controlled rate under nitrogen atmosphere. An aqueous solution of potassium hydroxide or sodium carbonate at 1.0 mol.Math.L.sup.−1 to 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 0.5 mol.Math.L.sup.−1 to 2.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 8.0 to 12.5. The co-precipitation reaction took place at 50±10° C. and the total reactor time varied from 4 h to 48 h. Subsequently, precursor comprising LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05(OH).sub.2 or Ni.sub.0.9Co.sub.0.5Mn.sub.0.05CO.sub.3 was obtained through washing, filtering, and drying of the material from the tank reactor. The precursor would then be used to make the LiNi.sub.0.9Co.sub.0.05Mn.sub.0.05O.sub.2 cathode material.
[0116]
Comparative Example 3
[0117] Cobalt-free cathode active materials comprising LiNi.sub.0.95Mn.sub.0.05O.sub.2 and LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2 were prepared according to the methods described herein. First, cathode active material precursor comprising Ni.sub.0.95Mn.sub.0.05(OH).sub.2 was prepared using dissolvable salts of nickel and manganese in aqueous solutions of varying molar ratios at 2.0 mol.Math.L.sup.−1. The mixed-metal ion aqueous solution was pumped into a tank reactor at a controlled rate under nitrogen atmosphere. An aqueous solution of potassium hydroxide at 6.0 mol.Math.L.sup.−1 and ammonium hydroxide at 1.0 mol.Math.L.sup.−1 was separately pumped into the tank reactor to maintain a pH of 11.65±0.25. The co-precipitation reaction took place at 50±5° C. Subsequently, precursor comprising Ni.sub.0.95Mn.sub.0.05(OH).sub.2 was obtained through washing, filtering, and drying. To obtain LiNi.sub.0.95Mn.sub.0.05O.sub.2, the precursor comprising Ni.sub.0.95Mn.sub.0.05(OH).sub.2 was mixed with lithium hydroxide at a molar ratio of 1:1.02±0.03. The mixed precursor and lithium hydroxide was calcinated at 700±20° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate. To obtain LiNi.sub.0.9Mn.sub.0.05Al.sub.0.05O.sub.2, precursor comprising Ni.sub.0.95Mn.sub.0.05(OH).sub.2 was first dry-mixed with aluminum isopropoxide at a molar ratio of 0.95:0.05 via ball milling at 120 rpm for 24 h, then the precursor mixed with aluminum isopropoxide was further mixed with lithium hydroxide at a molar ratio of 1:1.02±0.03. The mixed precursor, aluminum isopropoxide, and lithium hydroxide was calcinated at 750±20° C. for 17.5±7.5 h under an oxygen atmosphere of a 2.75±2.25 liter per minute flow rate. It will be appreciated that the lithium and oxygen contents in these chemical compositions are based on stoichiometry, but the lithium and oxygen contents may deviate from their stoichiometric values.
[0118] The cathode active material exhibited a tapped density of about 2.5 g.Math.cm.sup.−3. The cathode active material was formed into a composite cathode electrode by depositing a slurry of the cathode active material in N-Methyl-2-Pyrrolidone onto an aluminum foil current collector and allowing the solvent to evaporate. The areal capacity loading of the cathode active material was around 2.0 mAh.Math.cm.sup.−2. The cathode was assembled into an electrochemical cell with a lithium metal anode, a separator comprising a blend of polypropylene and polyethylene soaked with a nonaqueous carbonate-based electrolyte comprising 1.0 molar LiPF.sub.6 in a solvent mixture of ethylene carbonate and ethyl methyl carbonate (3:7 by weight) with an additive of vinylene carbonate (2% by weight). Galvanostatic voltage profiles were obtained for charging and discharging the electrochemical cell.
[0119]
REFERENCES
[0120] Kim, J., Lee, H., Cha, H., Yoon, M., Park, M. & Cho, J. Prospect and Reality of Ni-Rich Cathode for Commercialization. Advanced Energy Materials, 8, 1702028 (2018). [0121] Bianchini, M., Roca-Ayats, M., Hartmann, P., Brezesinski, T. & Janek, J. There and Back Again—The Journey of LiNiO.sub.2 as A Cathode Active Material. Angewandte Chemie-International Edition, 58, 2-27 (2019). [0122] Neigel, T., Schipper, F., Erickson, E. M., Susai, F. A., Markovsky, B. & Aurbach, D. Structural and Electrochemical Aspects of LiNi.sub.0.8Co.sub.0.1Mn.sub.0.1O.sub.2 Cathode Materials Doped by Various Cations. ACS Energy Letters, 4, 508-516 (2019). [0123] Li, H., Cormier, M., Zhang, N., Inglis, J., Li, J. & Dahn, J. R. Is Cobalt Needed in Ni-Rich Positive Electrode Materials for Lithium Ion Batteries? Journal of the Electrochemical Society, 166, A429-A439 (2019). [0124] Ryu, H. H., Park, K. J., Yoon, D. R., Aishova, A., Yoon, C. S. & Sun, Y. K., Li[Ni.sub.0.9Co.sub.0.09W.sub.0.01]O.sub.2: A New Type of Layered Oxide Cathode with High Cycling Stability. Advanced Energy Materials, 9, 1902698 (2019). [0125] Aishova et al., 2019, “Cobalt-Free High-Capacity Ni-Rich Layered Li[Ni.sub.0.9Mn.sub.0.1]O.sub.2 Cathode,” Advanced Energy Materials, 1903179. [0126] Zhang et al., 2019, “Cobalt-Free Nickel-Rich Positive Electrode Materials with a Core-Shell Structure,” Chem. Mater, 31, 10150-10160. [0127] Mu et al., 2019, “Dopant Distribution in Co-Free High-Energy Layered Cathode Materials,” Chem. Mater., 31, 9769-9776. [0128] U.S. Pat. Nos. 5,264,201, 6,677,082, 6,680,143, 6,964,828, 7,078,128, 7,585,43, 7,648,693, 7,985,503, 8,241,791, 8,377,412, 8,426,066, 8,685,565, 8,784,770, 9,412,996. [0129] U.S. Patent Application Publication Nos. US 2001/0010807, US 2003/0027048, US 2006/0105239, US 2006/0147798, US 2009/0207246, US 2009/0224212, US 2011/0260099, US 2012/0301786, US 2015/0050522, US 2015/0132651, US 2015/0188136, US 2016/0372748, US 2017/0054147, US 2017/0338471, US 2017/0358796, US 2018/0019464, US 2019/0140276, US 2019/0221843. [0130] PCT International Application Publication No. WO/2018/200631. [0131] Chinese Patent or Publication Nos. CN101139108A, CN102437323B, CN103456946B, CN103715409A, CN103943844A, CN104319391A, CN106257718B, CN108199027A, CN109686970A, CN109904447A, CN109962223A, CN109970106A. [0132] Korean Patent or Publication Nos. KR2016023496A, KR1702572B1, KR102021151B1.
ILLUSTRATIVE ASPECTS
[0133] As used below, any reference to a series of aspects (e.g., “Aspects 1-4”) or non-enumerated group of aspects (e.g., “any previous or subsequent aspect”) is to be understood as a reference to each of those aspects disjunctively (e.g., “Aspects 1-4” is to be understood as “Aspects 1, 2, 3, or 4”).
[0134] Aspect 1 is an electrode active material comprising: Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d, wherein: a is from 0.9 to 1.1, b is from 0 to 0.05, c is from 0 to 0.67, d is from 1.9 to 2.1, and M is Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these.
[0135] Aspect 2 is an electrode active material comprising: Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d, wherein: a is from 0.9 to 1.1, b is from 0 to 0.1, c is from 0 to 0.67, d is from 1.9 to 2.1, and M is Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, Tm, or any combination of these; and wherein the electrode active material exhibits or is characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, and exhibits or is characterized by a specific energy for a 1C discharge rate between 5 V and 3 V vs. Li.sup.+/Li that is from 80% to 100% of a specific energy for a C/10 discharge rate between 5 V and 3 V vs. Li.sup.+/Li at 25° C.
[0136] Aspect 3 is an electrode active material comprising: Li.sub.aNi.sub.1-b-cCo.sub.bM.sub.cO.sub.d, wherein a is from 0.9 to 1.1, b is from 0 to 0.05, c is from 0 to 0.67, d is from 1.9 to 2.1, and M is at least one element selected from the group consisting of Mn, Al, Mg, Fe, Cr, B, Ti, Zr, Ga, Zn, V, Cu, Yb, Li, Na, K, F, Ba, Ca, Lu, Y, Nb, Mo, Ru, Rh, Ta, Pr, W, Ir, In, Tl, Sn, Sr, S, P, Cl, Ge, Sb, Er, Te, La, Ce, Nd, Dy, Eu, Sc, Se, Si, Tc, Pd, Pm, Sm, Gd, Tb, Ho, and Tm; and wherein the electrode active material exhibits a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.15 V to 4.30 V vs. Li.sup.+/Li.
[0137] Aspect 4 is the electrode active material of any previous or subsequent aspect, wherein M is a combination of Mn and Al; a combination of Mn, Mg, and Al; a combination of Mn and Mg; a combination of Al and Mg; or a combination of Ti, Mg, and Al.
[0138] Aspect 5 is the electrode active material of any previous or subsequent aspect, wherein M comprises Fe or Zn or both Fe and Zn.
[0139] Aspect 6 is the electrode active material of any previous or subsequent aspect, wherein the active material is free or substantially free of Co.
[0140] Aspect 7 is the electrode active material of any previous or subsequent aspect, wherein b is 0 or wherein b is less than 0.01.
[0141] Aspect 8 is the electrode active material of any previous or subsequent aspect, wherein a is from 0.9 to 1.
[0142] Aspect 9 is the electrode active material of any previous or subsequent aspect, wherein a is from 1 to 1.1.
[0143] Aspect 10 is the electrode active material of any previous or subsequent aspect, wherein b is from 0 to 0.01 and wherein c is from 0 to 0.01.
[0144] Aspect 11 is the electrode active material of any previous or subsequent aspect, wherein c is from 0.1 to 0.5, from 0.1 to 0.2, or from 0.2 to 0.4.
[0145] Aspect 12 is the electrode active material of any previous or subsequent aspect, wherein d is from 1.95 to 2.05.
[0146] Aspect 13 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a tapped density of from 2.0 g.Math.cm.sup.−3 to 3.5 g.Math.cm.sup.−3.
[0147] Aspect 14 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a tapped density of from 2.3 g.Math.cm.sup.−3 to 3.0 g.Math.cm.sup.−3.
[0148] Aspect 15 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a tapped density of from 2.5 g.Math.cm.sup.−3 to 2.8 g.Math.cm.sup.−3.
[0149] Aspect 16 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0150] Aspect 17 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1 at 25° C.
[0151] Aspect 18 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li of from 700 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, from 800 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1, or 900 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0152] Aspect 19 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle, for a current rate of C/10, which has a minimum of −300 mAh.Math.g.sup.−1 V.sup.−1 or lower during discharge at a voltage of from 4.15 V to 4.30 V vs. Li.sup.+/Li.
[0153] Aspect 20 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.15 V to 4.30 V vs. Li.sup.+/Li.
[0154] Aspect 21 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.16 V to 4.30 V vs. Li.sup.+/Li.
[0155] Aspect 22 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.17 V to 4.30 V vs. Li.sup.+/Li.
[0156] Aspect 23 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.18 V to 4.30 V vs. Li.sup.+/Li.
[0157] Aspect 24 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.19 V to 4.30 V vs. Li.sup.+/Li.
[0158] Aspect 25 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.20 V to 4.30 V vs. Li.sup.+/Li.
[0159] Aspect 26 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.21 V to 4.30 V vs. Li.sup.+/Li.
[0160] Aspect 27 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge at a voltage of from 4.22 V to 4.30 V vs. Li.sup.+/Li.
[0161] Aspect 28 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −300 mAh.Math.g.sup.−1V.sup.−1 or lower, such as from −300 mAh.Math.g.sup.−1V.sup.−1 to −3000 mAh.Math.g.sup.−1V.sup.−1.
[0162] Aspect 29 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −400 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0163] Aspect 30 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −500 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0164] Aspect 31 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −600 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0165] Aspect 32 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −800 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0166] Aspect 33 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −1000 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0167] Aspect 34 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −1500 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0168] Aspect 35 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −2000 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0169] Aspect 36 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a dQ.Math.dV.sup.−1 curve at the second charge-discharge formation cycle for a current rate of C/10 having a minimum during discharge with a magnitude of −2500 mAh.Math.g.sup.−1V.sup.−1 or lower.
[0170] Aspect 37 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a 1C discharge rate of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0171] Aspect 38 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a single discharge between 5 V and 3 V vs. Li.sup.+/Li at a C/10 discharge rate of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0172] Aspect 39 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy after 500 charge-discharge cycles of more than 80% of an original specific energy of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0173] Aspect 40 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy after 1000 charge-discharge cycles of more than 85% of an original specific energy of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0174] Aspect 41 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy after 500 charge-discharge cycles of more than 90% of an original specific energy of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0175] Aspect 42 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy after 100 charge-discharge cycles of more than 95% of an original specific energy of from 600 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1.
[0176] Aspect 43 is the electrode active material of any previous or subsequent aspect, wherein only a portion comprises or is characterized by a rhombohedral crystal structure or a rhombohedral R
[0177] Aspect 44 is the electrode active material of any previous or subsequent aspect, wherein 99 volume percent or less of the electrode active material comprises or is characterized by a rhombohedral crystal structure or a rhombohedral R
[0178] Aspect 45 is the electrode active material of any previous or subsequent aspect, having or characterized by a surface region and a bulk region, wherein the surface region corresponds to a first portion of the active material or particles thereof within 20% of a cross-sectional dimension from a surface of the active material or particles thereof, and wherein the bulk region corresponds to a second portion of the active material or particles thereof deeper than the surface region.
[0179] Aspect 46 is the electrode active material of any previous or subsequent aspect, wherein the bulk region is free or substantially free of or does not exhibit a spinel, P4.sub.332 or Fd
[0180] Aspect 47 is the electrode active material of any previous or subsequent aspect, wherein at least a portion of the surface region comprises or is characterized by a spinel, P4.sub.332 or Fd
[0181] Aspect 48 is the electrode active material of any previous or subsequent aspect, wherein the bulk region is free or substantially free of or does not exhibit LiFePO.sub.4 (Pmnb/Pnma) or another polyanionic structure.
[0182] Aspect 49 is the electrode active material of any previous or subsequent aspect, wherein at least a portion of the surface region comprises or is characterized by LiFePO.sub.4 (Pmnb/Pnma) or another polyanionic structure.
[0183] Aspect 50 is the electrode active material of any previous or subsequent aspect, comprising particles of Li.sub.aN.sub.1-b-cCo.sub.bM.sub.cO.sub.d having cross-sectional dimensions of from 500 nm to 30 μm.
[0184] Aspect 51 is the electrode active material of any previous or subsequent aspect, comprising a plurality of secondary particles.
[0185] Aspect 52 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles have cross-sectional dimensions of from 500 nm to 30 μm.
[0186] Aspect 53 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles have cross-sectional dimensions of from 500 nm to 2.5 μm.
[0187] Aspect 54 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles have cross-sectional dimensions of from 2.5 μm to 7.5 μm.
[0188] Aspect 55 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles have cross-sectional dimensions of from 7.5 μm to 15 μm.
[0189] Aspect 56 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles have cross-sectional dimensions of from 15 μm to 30 μm.
[0190] Aspect 57 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles are substantially monodisperse.
[0191] Aspect 58 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles are polydisperse and comprise a first portion having a first cross-sectional dimension distribution and a second portion having a second cross-sectional dimension distribution that is at least a factor of 10 larger than the first cross-sectional dimension distribution.
[0192] Aspect 59 is the electrode active material of any previous or subsequent aspect, wherein the plurality of secondary particles are substantially spherical in shape.
[0193] Aspect 60 is the electrode active material of any previous or subsequent aspect, wherein at least some of the secondary particles each comprise a plurality of primary particles.
[0194] Aspect 61 is the electrode active material of any previous or subsequent aspect, wherein the plurality of primary particles have cross-sectional dimensions of from 10 nm to m.
[0195] Aspect 62 is the electrode active material of any previous or subsequent aspect, wherein the plurality of primary particles have cross-sectional dimensions of from 10 nm to 100 nm.
[0196] Aspect 63 is the electrode active material of any previous or subsequent aspect, wherein the plurality of primary particles have cross-sectional dimensions of from 100 nm to 1000 nm.
[0197] Aspect 64 is the electrode active material of any previous or subsequent aspect, wherein the plurality of primary particles have cross-sectional dimensions of from 1 μm to 10 μm.
[0198] Aspect 65 is the electrode active material of any previous or subsequent aspect, wherein the plurality of primary particles are substantially monodisperse.
[0199] Aspect 66 is the electrode active material of any previous or subsequent aspect, wherein at least some of the secondary particles each independently consist of one primary particle.
[0200] Aspect 67 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a 1C discharge rate between 5 V and 3 V vs. Li.sup.+/Li of from 80% to 100% of a specific energy for a C/10 discharge rate between 5 V and 3 V vs. Li.sup.+/Li at 25° C.
[0201] Aspect 68 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a 1C discharge rate between 5 V and 3 V vs. Li.sup.+/Li of from 85% to 100% of the specific energy for a C/10 discharge rate between 5 V and 3 V vs. Li.sup.+/Li at 25° C.
[0202] Aspect 69 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a 1C discharge rate between 5 V and 3 V vs. Li.sup.+/Li of from 90% to 100% of the specific energy for a C/10 discharge rate between 5 V and 3 V vs. Li.sup.+/Li at 25° C.
[0203] Aspect 70 is the electrode active material of any previous or subsequent aspect, exhibiting or characterized by a specific energy for a 1C discharge rate between 5 V and 3 V vs. Li.sup.+/Li of from 750 Wh.Math.kg.sup.−1 to 1000 Wh.Math.kg.sup.−1 at 25° C.
[0204] Aspect 71 is an electrode comprising the electrode active material of any previous aspect.
[0205] Aspect 72 is the electrode of any previous aspect, further comprising a current collector.
[0206] Aspect 73 is an electrochemical cell, comprising: a cathode comprising the electrode of any previous aspect; an anode; and an electrolyte between the cathode and the anode.
[0207] Aspect 74 is the electrochemical cell of any previous or subsequent aspect, wherein the anode comprises graphite, carbon, silicon, lithium titanate (Li.sub.4Ti.sub.5O.sub.12), tin, antimony, zinc, phosphorous, lithium, or a combination thereof.
[0208] Aspect 75 is the electrochemical cell of any previous or subsequent aspect, wherein the cathode or the anode or both independently comprise one or more of an active material, a current collector, a solid electrolyte, a binder, or a conductive additive.
[0209] Aspect 76 is the electrochemical cell of any previous or subsequent aspect, wherein the electrolyte is a liquid electrolyte.
[0210] Aspect 77 is the electrochemical cell of any previous or subsequent aspect, wherein the electrolyte is a semi-solid electrolyte.
[0211] Aspect 78 is the electrochemical cell of any previous or subsequent aspect, wherein the electrolyte is a solid electrolyte.
[0212] Aspect 79 is the electrochemical cell of any previous or subsequent aspect, wherein the electrolyte is a non-aqueous electrolyte.
STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS
[0213] All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference.
[0214] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art.
[0215] When a group of substituents is disclosed herein, it is understood that all individual members of those groups and all subgroups and classes that can be formed using the substituents are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. As used herein, “and/or” means that one, all, or any combination of items in a list separated by “and/or” are included in the list; for example “1, 2 and/or 3” is equivalent to “‘1’ or ‘2’ or ‘3’ or ‘1 and 2’ or ‘1 and 3’ or ‘2 and 3’ or ‘1, 2 and 3’”.
[0216] Every formulation or combination of components described or exemplified can be used to practice the invention, unless otherwise stated. Specific names of materials are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same material differently. It will be appreciated that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials, and synthetic methods are intended to be included in this invention. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.
[0217] As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term “comprising”, particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the recited components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
[0218] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.