WO2020149910A1 - Polycrystalline metal oxides with enriched grain boundaries - Google Patents
Polycrystalline metal oxides with enriched grain boundaries Download PDFInfo
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- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Definitions
- LiNi02 Layered structure lithium nickelate (LiNi02)-based materials have been developed for Lithium-ion battery cathodes because they generally have lower cost, higher capacity and higher rate capability than the historically predominant L1C0O2 cathode material.
- pure LiNi02 materials exhibit poor electrochemical stability and cycling performance.
- non nickel, elemental additives have been formulated into LiNi02 that stabilize the structure improving the cycling performance, but typically at the expense of discharge capacity.
- demands for energy density have increased, research has focused on optimizing and reducing these non-nickel additives to capture the capacity of high Ni materials while at the same time maintaining cycling performance.
- new materials are needed to address the demands for high capacity materials with long cycle life.
- the materials provided herein and methods of forming such materials address this need by maintaining high capacity over a long cycle life.
- particles that include a plurality of crystallites comprising a first composition comprising lithium, nickel, and oxygen; a grain boundary between adjacent crystallites of the plurality of crystallites and comprising a second composition having the layered a-NaFeCk-type structure, a cubic structure, a spinel structure, or a combination thereof; wherein a concentration of aluminum in the grain boundary is greater than a concentration of aluminum in the crystallites, and wherein a concentration of cobalt in the grain boundary is greater than a concentration of cobalt in the crystallites.
- Al enrichment of grain boundaries was non-uniform, incomplete or not achieved, but that when manufacturing processes as provided herein were utilized Al grain boundary enrichment could be achieved, optionally Co and A1 grain boundary enrichment.
- the A1 is substantially uniformly distributed through the plurality of particles.
- the amount of the A1 in the grain boundaries is 0.01 at% to 10 at% of the total transition metal amounts in the remainder of the secondary particle.
- the amount of the Co in the grain boundaries is 0 at% to 10 at% of the total transition metal amounts in the remainder of the secondary particle, optionally 0.1 at% to 10 at% of the total transition metal amounts in the remainder of the secondary particle.
- the amount of the A1 in the grain boundaries is 0.01 at% to 5 at% of the total transition metal amounts in the remainder of the secondary particle
- the amount of the Co in the grain boundaries is 0.01 at% to 10 at% of the total transition metal amounts in the remainder of the secondary particle.
- the amount of aluminum in the grain boundary is equal to or less than the amount of Co in the grain boundary.
- the plurality of crystallites has an a-NaFe02-type layered structure, a cubic structure, a spinel structure, or a combination thereof.
- the first composition, the second composition or both, in any of the forgoing or other aspects are defined by defined by Lii+ x M02+ y , wherein
- M comprises nickel at greater than or equal to 10 atomic percent.
- M comprises an atomic percent of nickel greater than or equal to 75 at%.
- the overall grain boundary comprises cobalt in an amount of about 2 at% to about 99 at%, and aluminum in an amount of about 2 at% to about 99 at%.
- M further comprises an additional metal, wherein the additional metal is present in an amount of about 1 at% to about 90 at%; the additional metal is selected from the group consisting of Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti, Nb, Ta, Cr, Fe, Mo, W, Hf, B, and any combination thereof, whereby the one or more additional elements optionally reside in a Li layer, a M layer, or both.
- the crystallites comprise cobalt, with the cobalt concentration in the range of 1 at% to about 50 at%, optionally, in the range of 1 at% to about 15 at%.
- the crystallites comprise Mn present in an amount of about 1 at% to about 60 at%, and the grain boundary comprises Mn present in an amount of about 1 at% to about 60 at%.
- the grain boundary comprises Ni, Co, and Al.
- the concentration of Ni in the grain boundary is greater than 75 at%.
- Some aspects of a particle include an outer coating on a surface of the particle, the outer coating comprising: an oxide of one or more elements selected from Al, Zr, Y, Co, Ni, Mg, and Li; a fluoride comprising one or more elements selected from Al, Zr, and Li; a carbonate comprising one or more elements selected from Al, Co, Ni, Mn, and Li; or a phosphate or sulfate comprising one or more elements selected from Al and Li.
- an electrochemically active poly crystalline secondary particle comprising: a plurality of crystallites, the plurality of crystallites comprising a first composition defined by Lh+xMCh+y, wherein -0.1 ⁇ x ⁇ 0.3, -0.3 ⁇ y ⁇ 0.3, and wherein M comprises nickel at greater than or equal to 80 atomic percent; and a grain boundary between adjacent crystallites of said plurality of crystallites and comprising a second composition optionally defined by Lh+xMCh+y, wherein -0.1 ⁇ x ⁇ 0.3, -0.3 ⁇ y ⁇ 0.3 and optionally having an a- NaFeCh-type layered structure, a cubic structure, or a combination thereof, wherein a concentration of aluminum in the grain boundary is greater than a concentration of aluminum in the crystallites, and optionally wherein a concentration of cobalt in the grain boundary is greater than a concentration of cobalt in the crystallites, and wherein the aluminum is substantially uniformly distributed through the grain boundary.
- a concentration of cobalt in the crystallites is about 0 to about 17 atomic percent of M in the first composition, and amount of cobalt in the grain boundary is about 0 to about 10 atomic percent of M in the crystallites,.
- M further comprises one or more elements selected from the group consisting of Na, K, Al, Mg, Co, Mn, Ca, Sr, Ba, Zn, Ti, Zr, Y, Cr, Mo, Fe, V, Si, Ga and B, said one or more elements residing in a Li layer, a M layer, or both, of the crystallites.
- M comprises an atomic percent of nickel greater than or equal to 90 percent.
- the electrochemical cells include a cathode active material.
- the cathode active material optionally includes any of the particles as provided above or otherwise herein.
- the electrochemical cell is optionally characterized by an impedance growth at 4.2V less than 100% for greater than 100 cycles at 45 °C, optionally less than 100% for greater than 200 cycles at 45 °C.
- electrochemical cells optionally secondary cells, optionally lithium ion secondary cells that include an anode, an electrolyte, and a cathode, the cathode comprising an electrochemically active cathode active material comprising a plurality of particles, said plurality of particles comprising a plurality of crystallites each comprising a first composition comprising lithium, nickel, and oxygen; a grain boundary between adjacent crystallites of the plurality of crystallites and comprising a second composition having a layered a-NaFeCk-type structure, a cubic structure, a spinel structure, or a combination thereof; wherein the electrochemically active cathode active material has an initial discharge capacity of 180 mAh/g or greater; and wherein the electrochemical cell has an impedance growth at 4.2V less than 50% for greater than 100 cycles at 45 °C.
- Electrochemical cells optionally are characterized by an impedance growth at 50% state of charge of less than 50% for greater than 200 cycles at 45 °C, optionally less than 120% for greater than 200 cycles at 45 °C.
- an electrochemical cell is characterized by an impedance growth at 50% state of charge of less than 50% for greater than 200 cycles at 45 °C.
- each of the crystallites include lithium, nickel, cobalt, and oxygen.
- the crystallites include Al, Mn, Mg, or combinations thereof.
- the first composition, the second composition or both, in any of the forgoing or other aspects are defined by Lh+ x M02+ y , wherein -0.95 ⁇ x ⁇ 0.3,
- M comprises nickel at greater than or equal to 80 atomic percent.
- M in a first composition comprises an atomic percent of nickel greater than or equal to 75 at% relative to total transition metal in the first composition.
- M in a second composition M is optionally less than or equal to 90 at% relative to total transition metal in the second composition.
- the overall grain boundary comprises cobalt in an amount of about 2 at% to about 99 at%, and aluminum in an amount of about 2 at% to about 99 at%.
- M further comprises an additional metal, wherein the additional metal is present in an amount of about 1 at% to about 90 at% relative to total metal in the respective first or second composition; the additional metal is selected from the group consisting of Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti, Nb, Ta, Cr, Fe, Mo, W, Hf, B, and any combination thereof, whereby the one or more additional elements optionally reside in a Li layer, a M layer, or both.
- the crystallites comprise cobalt, with the cobalt concentration in the range of 1 at% to about 50 at%, optionally, in the range of 1 at% to about 15 at%% relative to total transition metal the first composition.
- the crystallites comprise Mn present in an amount of about 1 at% to about 60 at%
- the grain boundary comprises Mn present in an amount of about 1 at% to about 60 at%.
- the grain boundary comprises Ni, Co, and Al.
- the concentration of Ni in the grain boundary is greater than 75 at%.
- FIG. l is a schematic perspective view of of a cross-section of a secondary particle as provided according to some aspects as described herein;
- FIG. 2 illustrates capacity fade for full cells employing secondary particles according to some aspects as provided herein;
- FIG. 3 illustrates impedance growth for full cells employing secondary particles according to some aspects as provided herein;
- FIG. 4 illustrates EDS mapping of secondary particles as provided herein grain boundary enriched with A1 only or A1 in the presence of Co;
- FIG. 5 illustrates a scanning transmission electron micrograph (STEM) image of a small section of a secondary particle according to one aspect as provided herein containing several crystallites from and prepared by enriching the grain boundaries with both 1.9 at% A1 and 4 at% Co, and shows locations at which 3 EDS spot analyses were performed;
- STEM scanning transmission electron micrograph
- FIG. 6 illustrates the EDS spectra of the three spots indicted in FIG. 5;
- FIG. 7 illustrates a STEM image of a small section of a secondary particle according to one aspect as provided herein containing several crystallites from and prepared by enriching the grain boundaries with 1.9 at% A1 in the absence of Co in the process solution, and shows locations at which 2 EDS spot analyses were performed;
- FIG. 8 illustrates the EDS spectra of the three spots indicted in FIG. 7;
- FIG. 9 illustrates EDS mapping of secondary particles as provided herein made by non-aqueous processing for grain boundary enrichment of raw particles during manufacture using A1 alone or A1 in the presence of Co in the process solution;
- FIG. 10 illustrates cycling capacity fade for cells formed with a cathode incorporating active material grain boundary enriched according to an aspect as provided herein prepared with 0 at% A1 in the process solution and with 0.5 at% A1 in the process solution and their dependence on additional Co content;
- FIG. 11 illustrates impedance growth for cells formed with a cathode incorporating active material grain boundary enriched according to an aspect as provided herein prepared with 0 at% A1 in the process solution and with 0.5 at% A1 in the process solution and their dependence on additional Co content;
- FIG. 12 illustrates a synergistic benefit observed from inclusion of A1 in addition to Co enrichment in grain boundaries
- FIG. 13 illustrates cycling capacity fade and impedance growth for cells with cathode materials that were grain boundary enriched according to some aspects as provided herein from 3 at% Co process application with varied A1 levels;
- FIG. 14 illustrates impedance growth at various Al/Co enrichment atomic percent ratios for cathode active materials as provided herein according to some aspects
- FIG. 15 illustrates STEM and results for EDS analyses of 3 spots in a small section of a secondary particle of NCA that was prepared as provided herein, being grain boundary enriched with A1 in the presence of Co;
- FIG. 16 illustrates cycling capacity fade for cells formed with a cathode incorporating control or grain boundary enriched NCA active material according to an aspect as provided herein;
- FIG. 17 illustrates impedance growth for cells formed with a cathode incorporating control or grain boundary enriched NCA active material according to an aspect as provided herein;
- FIG. 18 illustrates cycling capacity fade for cells formed with a cathode incorporating control or grain boundary enriched NCM active material according to an aspect as provided herein;
- FIG. 19 illustrates impedance growth for cells formed with a cathode incorporating control or grain boundary enriched NCM active material according to an aspect as provided herein.
- Ni-based layered materials of the LiMCk type are dense, polycrystalline agglomerates of primary crystals. These are typically made using standard solid-state processes at temperatures in the range of 600 °C to 900 °C starting from a variety of precursor materials.
- Precursor materials are typically transition metal hydroxides (M(OH)2), lithium precursors (e.g., LiOH or LriCCb), or inorganic precursors for other dopants (e.g., hydroxides, carbonates, nitrates).
- M(OH)2 transition metal hydroxides
- LiOH or LriCCb lithium precursors
- inorganic precursors for other dopants e.g., hydroxides, carbonates, nitrates.
- this disclosure provides improved electrochemically active materials such as those suitable for use in a positive electrode (cathode) for a Li-ion secondary cell that, relative to prior materials, reduce the rate of impedance growth and/or capacity fade during charge/discharge cycling of the battery. Also, provided are a variety of methods for achieving high discharge capacity cathode active materials that show reductions in impedance growth and capacity fade as they are cycled relative to the same materials but absent Co and A1 enrichment in the grain boundaries.
- the polycrystalline layered-structure lithiated metal oxides as provided herein exhibit enhanced electrochemical performance and stability.
- the compositions prevent the performance degradation of electrochemically cycled Ni-containing polycrystalline LiMCh-based materials, while maintaining other desirable end-use article properties, e.g, electrochemical capacity of rechargeable lithium-ion cathodes made from such layered metal oxides by reducing the rate of impedance growth during electrochemical cycling.
- Such Co and A1 grain boundary enriched materials may be readily manufactured by calcining a green body formulation including a LiOH and a precursor hydroxide or carbonate to form particles with defined grain boundaries and then enriching the grain boundaries with a combination of Co and A1 such that the resulting particles have grain boundaries where the concentration of Co and A1 in the grain boundary is greater than prior to enrichment and optionally greater than within the primary crystallites, the outer surfaces of which define the edges of the grain boundaries in the secondary particle.
- compositions, systems, and methods of making and using polycrystalline layered-structure lithiated metal oxides having Co and A1 enriched grain boundaries in lithium-ion secondary cells as the means of achieving high initial discharge capacity and low impedance growth during cycling, thereby overcoming prior challenges in high-nickel formulations that may also have high discharge capacity (e.g., >205 mAh/g at C/20).
- the materials as provided include a particle comprising a plurality of crystallites each comprising a first composition.
- the particle formed of a plurality of crystallites may be referred to as a secondary particle.
- the particles as provided herein are uniquely tailored to have grain boundaries between the primary crystallites. Enriching these grain boundaries, subsequent to their formation, with a combination of Co and Al, optionally at particular relative concentrations of Co and Al, results in particles that provide for reduced impedance growth during cycling, improving performance and cycle life of a cell incorporating the particles as a component of a cathode.
- the particles are appreciated to include a grain boundary formed of or including a second composition, wherein a concentration of cobalt and aluminum, for example, in the grain boundary is greater than a concentration of cobalt and aluminum, for example, in the primary crystallite adjacent thereto.
- concentration of Co and A1 in the grain boundary is optionally greater than the average Co and A1 concentration within the adjacent crystallites on average.
- the materials as provided herein are optionally relatively uniform in Co and/or A1 concentration (if either is present at all) within the crystallites. Whether uniform or not, the concentration of Co and A1 in the grain boundary is greater than the concentration of Co and Al, individually or combined as averaged within an adjacent crystallite.
- the provided materials include a further outer coating layer may be disposed on an outer surface of the secondary particle to provide a coated secondary particle.
- the first composition includes poly crystalline layered-structure lithiated metal oxides defined by composition Lh+xMCh+y and optionally a cell or battery formed therefrom, where -0. l ⁇ x ⁇ 0.3 and -0.3 ⁇ y ⁇ 0.3.
- x is -0.1, optionally 0, optionally 0.1, optionally 0.2, or optionally 0.3.
- x is greater than or equal to -0.10, -0.09, -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, -0.01, 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, or 0.30.
- y is -0.3, optionally -0.2, optionally -0.1, optionally 0, optionally 0.1, optionally 0.2, or optionally 0.3.
- y is greater than or equal to -0.30, -0.29, -0.28, -0.27, -0.26, -0.25, -0.24, -0.23, -0.22, -0.21, -0.20, -0.19, -0.18, -0.17, -0.16, -0.15, -0.14, -0.13, -0.12, -0.11, -0.10, -0.09, -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, -0.01, 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23,
- Li need not be exclusively Li, but may be partially substituted with one or more elements selected from the group consisting of Mg, Sr, Na, K, and Ca.
- the one or more elements substituting Li are optionally present at 10 atomic % or less, optionally 5 atomic % or less, optionally 3 atomic % or less, optionally no greater than 2 atomic percent, where percent is relative to total Li in the material.
- M as provided in the first composition includes Ni.
- the amount of Ni in the first composition is optionally from 10 atomic percent to 100 atomic percent (at%) of total M.
- the Ni component of M is greater than or equal to 75 at%.
- the Ni component of M is greater than or equal to 80 at%.
- the Ni component of M is greater than or equal to 85 at%.
- the Ni component of M is greater than or equal to 90 at%.
- the Ni component of M is greater than or equal to 95 at%.
- the Ni component of M is greater than or equal to 75 at%, 76 at%, 77 at%, 78 at%, 79 at%, 80 at%, 81 at%, 82 at%, 83 at%, 84 at%, 85 at%, 86 at%, 87 at%, 88 at%, 89 at%, 90 at%, 91 at%, 92 at%, 93 at%, 94 at%, 95 at%, 96 at%, 97 at%, 98 at%, 99 at%, 99.5 at%, 99.9 at%, or 100 at%.
- M in the first composotion is Ni alone or in combination with one or more additional elements.
- the additional elements are optionally metals.
- an additional element may include or be one or more of Al, Mg, Co, Mn, Ca, Sr, Zn, Ti, Y, Cr, Mo, Fe, V, Si, Ga, or B.
- the additional element may include Mg, Co, Al, or a combination thereof.
- the additional element may be Mg, Al, V, Ti, B, or Mn, or a combination thereof.
- the additional element is selected from the group consisting of Mg, Al, V, Ti, B, or Mn.
- the additional element selected from the group consisting of Mg, Co, and Al.
- the additional element selected from the group consisting of Ca, Co, and Al.
- the additional element is Mn or Mg, or both Mn and Mg.
- the additional element is Mn, Co, Al, or any combination thereof.
- the additional element includes Co and Mn.
- the additional element is Co and Al.
- the additional element is Co.
- An additional element of the first composition may be present in an amount of about 1 to about 90 at%, specifically about 5 to about 80 at%, more specifically about 10 to about 70 at% of M in the first composition.
- the additional element may be present in an amount of about 1 to about 20 at%, specifically about 2 to about 18 at%, more specifically about 4 to about 16 at%, of M in the first composition.
- M is about 75-100 at% Ni, 0-15 at% Co, 0-15 at% Mn, and 0-10 at% additional elements.
- each crystallite may have any suitable shape, which can be the same or different within each particle. Further, the shape of each crystallite can be the same or different in different particles. Because of its crystalline nature, the crystallite may be faceted, the crystallite may have a plurality of flat surfaces, and a shape of the crystallite may approximate a geometric shape. In some aspects, the crystallite may be fused with neighboring crystallites with mismatched crystal planes. The crystallite may optionally be a polyhedron. The crystallite may have a rectilinear shape, and when viewed in cross-section, a portion of or an entirety of the crystallite may be rectilinear. The crystallite may be square, hexagonal, rectangular, triangular, or a combination thereof.
- a secondary particle has a Co and A1 enriched grain boundary, optionally where the atomic percentage of Co and A1 in the grain boundary is higher than the atomic percentage of Co and A1 in the crystallites as averaged throughout.
- the grain boundary 20, 21 is between adjacent crystallites 10, and includes the second composition.
- a second composition may be as described in U.S. Pat. Nos.
- the second composition optionally has the layered a-NaFeCh-type structure, a cubic structure, or a combination thereof.
- a concentration of Co and A1 in the grain boundaries may be greater than a concentration of Co and A1 in the crystallites.
- the second composition as present in part or in whole in the grain boundaries optionally includes lithiated metal oxides defined by composition Lh+xMCh+y, where -0.1 ⁇ x ⁇ 0.3 and -0.3 ⁇ y ⁇ 0.3.
- a second composition and a first composition are identical with the exception of the presence of or increased concentration of Co and A1 in the second composition relative to the first composition.
- x is -0.1, optionally 0, optionally 0.1, optionally 0.2, or optionally 0.3.
- x is greater than or equal to -0.10, -0.09, -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, -0.01, 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, or 0.30.
- y is -0.3, optionally -0.2, optionally -0.1, optionally 0, optionally 0.1, optionally 0.2, or optionally 0.3.
- y is greater than or equal to -0.30, -0.29, -0.28, -0.27, -0.26, -0.25, -0.24, -0.23, -0.22, -0.21, -0.20, -0.19, -0.18, -0.17, -0.16, -0.15, -0.14, -0.13, -0.12, -0.11, -0.10, -0.09, -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, -0.01, 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, or 0.3.
- M as provided in the second composition includes Co and Al.
- the amount of Ni, if present, is optionally from 0.01 atomic percent to 99 atomic percent (at%) of M.
- M in the second composition is free of Ni.
- the amount (i.e. relative concentration) of Ni in the second composition is lower than the amount of Ni in the first composition in relative atomic percent (with respect to the respective composition in which the Ni is present).
- the Ni component of M is less than or equal to 1 at%.
- the Ni component of M is less than or equal to 5 at%.
- the Ni component of M is less than or equal to 10 at%.
- the Ni component of M is less than or equal to 20 at%.
- the Ni component of M is less than or equal to 75 at%.
- the Ni component of M is less than or equal to 80 at%.
- the Ni component of M is less than or equal to 85 at%.
- the Ni component of M is less than or equal to 90 at%.
- the Ni component of M is less than or equal to 95 at%.
- the Ni component of M is less than or equal to 75 at%, 76 at%, 77 at%, 78 at%, 79 at%, 80 at%, 81 at%, 82 at%, 83 at%, 84 at%, 85 at%, 86 at%, 87 at%, 88 at%, 89 at%, 90 at%, 91 at%, 92 at%, 93 at%, 94 at%, 95 at%, 96 at%, 97 at%, 98 at%, 99 at%, or 99.9 at%.
- the nominal or overall formulated composition of the secondary particles for example, characterized by Inductively Coupled Plasma (ICP)
- ICP Inductively Coupled Plasma
- the first composition, or optionally the second composition is defined by the formula LiMO, wherein M is Ni and optionally one or more additional metals that in the second composition must include at least Co and Al.
- the mole fraction of Co and A1 in the first composition, if present, as defines the composition of the crystallites is lower than the mole fraction of the total Co and Al independently or combined in the total particle composition as determined by ICP.
- the mole fraction of Co and Al independently or combined in the first composition can be zero.
- the mole fraction of Co and Al in the second composition independently or combined as defines the grain boundary is higher than the mole fraction of Co and Al independently or combined in the total particle as measured by ICP.
- a second composition located within the grain boundaries includes Co and Al, optionally with the condition that the concentration of Co and Al independently or combined in the grain boundary is greater than the concentration of Co and Al independently or combined in the crystallites, optionally where the concentration of Co in the grain boundary is greater than the concentration of Co in the crystallites, and optionally where the concentration of A1 in the grain boundary is greater than the concentration of A1 in the crystallites.
- liquid solutions that included amounts relative to the total transition metal of the first composition to be enriched of Co of at or between 0 at% and 8 at%, optionally at or between 3 at% and 5 at% Co could be supplemented with 0.01 at% to 10 at% Al, optionally 1.5 at% or less Al, and create materials that showed significantly reduced impedance growth during cycling, where the added Co and Al are incorporated into the grain boundaries of the secondary particle.
- the volume fraction of grain boundaries within a given secondary particle will vary because the primary particle size distribution varies with variations in overall composition and synthetic conditions, and accordingly, the final concentration of Co and Al in the second composition can vary between different secondary particles and within individual secondary particles as well, while still always being greater than the concentrations of Co and Al in the first composition. It is thus most useful that the amount of Co and Al added to the grain boundary be defined relative to the first composition.
- the provided amounts of Co and Al in the process solution are considered average amounts of Co and Al added to the secondary particles and distributed in the grain boundaries of the entire secondary particle and are presented relative to M of the first composition.
- the amount of Co and Al available for enriching the grain boundaries is the amount in the process solution. Therefore, when describing a process solution that is, for example, 1 at% Al and 2 at% Co, this listed at% is relative to the amount of M in the first composition prior to grain boundary enrichment.
- the at% of A1 and Co in the process solution as used herein is always relative to total M in the primary particles to be grain boundary enriched.
- the amount of A1 in the process solution is optionally 0.01 at% to 10 at%, optionally 9 at% or less, optionally 8 at% or less, optionally 7 at% or less, optionally 6 at% or less, optionally 5 at% or less, optionally 4 at% or less, optionally 3 at% or less, optionally 2 at% or less, optionally
- the amount of A1 in the process solution is at or less than an atomic percentage of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5.
- the amount of Co in the process solution is greater than 3 at% and up to 4 at%, and the amount of A1 is less than 1 at%, optionally from 0.1 to 1 at%, optionally 0.1 to less than 1 at%.
- the amount of Co in the process solution is 0.5 at% to 4 at%, and the amount of A1 is 0.01 at% to 10 at%.
- the amount of Co in the process liquid is about 3 at%.
- the amount of A1 is optionally less than 1 at%.
- Amounts of A1 of about 0.3 at% to 0.7 at%, optionally about 0.5 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 3.5 at%.
- the amount of A1 is optionally less than 1 at%.
- Amounts of A1 of about 0.3 to 0.7 at%, optionally about 0.5 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 4 at%.
- the amount of A1 is optionally less than 1.5 at%.
- Amounts of A1 of about 0.7 to 1.3 at%, optionally about 1.0 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 4.5 at%.
- the amount of A1 is optionally less than 1 at%.
- Amounts of A1 of about 0.3 to 0.7, optionally about 0.5 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 3 at%.
- the amount of A1 is optionally less than 1.5 at%.
- Amounts of A1 of about 0.5 to 1.3 at%, optionally about 1.0 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 3 at% to about 4 at%.
- the amount of A1 is optionally less than 1 at%.
- Amounts of A1 of about 0.3 to 0.1.3, optionally about 0.5 at% or about 1.0 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 3 at%.
- the amount of A1 is optionally less than 1.5 at%.
- Amounts of A1 of about 0.5 to 1.3 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co in the process liquid is about 4 at%.
- the amount of A1 is optionally less than 1.0 at%.
- Amounts of A1 of about 0.5 to 0.7 at% are optimal for reducing impedance growth during cycling.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of Co increased from 3 at% to 4 at%, the amount of A1 that produces the most improved results moves from less than 1.3 at% to less than 0.7 at%.
- the A1 is distributed substantially uniformly among the plurality of the secondary particles.
- the amount of A1 relative to the amount of Co in the second composition is equal to or less than 100 at% meaning that the amount of A1 is optionally equal to or less than the amount of Co.
- the amount of A1 relative to Co is less than 90 at%, optionally less than 80 at%, optionally less than 70 at%, optionally less than 60 at%, optionally less than 50 at%, optionally less than 40 at%, optionally less than 30 at%, optionally less than 20 at%, optionally less than 10 at%, optionally less than 9 at%, optionally less than 8 at%, optionally less than 7 at%, optionally less than 6 at%, optionally less than 4 at%, optionally less than 3 at%, optionally less than 2 at%, optionally less than 1 at%. It was found that the amount of Co being greater than the amount of A1 allows for a synergistic relationship that unexpectedly reduces impedance growth relative to Co alone at the same or greater concentrations.
- the A1 present in the second composition or throughout a portion or the whole of the grain boundaries among the plurality of the secondary particles is substantially uniform.
- the result as observed by EDS of the powder by standard techniques is the presence of“hotspots” rich in A1 illustrating uneven or inefficient uptake of A1 into the grain boundaries resulting in separate phases of Al.
- the result is a much more uniform distribution of A1 illustrating the near or total absence of observed hotspots by EDS.
- the number and/or size of hotspots of A1 is reduced by 50% or more, optionally 60% or more, optionally 70% or more, optionally 80% or more, relative to that occurring with A1 grain boundary enrichment in the absence of Co co-enrichment.
- Aluminum uniformity can also be assessed by comparing the EDS at two magnifications.
- Table 2 of Example 1 shows aluminum concentration by EDS for a wide area (around 150 pm X 150 pm) as the first number in the table followed by a second number which is average EDS analyses of much narrower areas (approximately 1 pm X 1 pm) centered on particles with no apparent hotspots. When 4% cobalt is used in the process liquid, these two numbers are close together. However, when cobalt is not used, the non-hotspot narrow areas have much less aluminum compared to the wider area, showing that much more aluminum is centered in hotspots rather than being uniformly distributed among the plurality of secondary particles.
- M in a second composition further includes one or more Ni substituting elements (substitution element).
- the Ni-substituting elements are optionally metals and are not Co or A1 as the presence of these elements results in the observed synergistic reductions in impedance growth.
- a substituting element may include or be one or more of Mg, Mn, Ca, Sr, Zn, Ti, Zr, Hf, Y, Cr, Mo, W, Fe, V, Nb, Ta, Si, Ga, or B.
- a substitution element of the second composition may be present in an amount of about 1 to about 90 at%, specifically about 5 to about 80 at%, more specifically about 10 to about 70 at% of the first composition.
- the additional element may be present in an amount of about 1 to about 20 at%, specifically about 2 to about 18 at%, more specifically about 4 to about 16 at%, of the first composition.
- Li in the second composition need not be exclusively Li, but may be partially substituted with one or more Li -substitution elements selected from the group consisting of Mg, Sr, Na, K, and Ca.
- the one or more Li-substitution elements are optionally present at 10 atomic % or less, optionally 5 atomic % or less, optionally 3 atomic % or less, optionally no greater than 2 atomic percent, where percent is relative to total Li in the as-made material.
- the secondary particles as provided herein may be prepared by synthesizing a green body from at least two components, optionally in powder form. At least two components may include micronized (or non-micronized) lithium hydroxide or its hydrate and a precursor hydroxide(s) comprising nickel, and optionally one or more other elements, and where the precursor hydroxides are optionally obtained by co-precipitation processes. It is appreciated that the final overall composition (although not necessarily distribution) of the elements in the final particle may be adjusted by increasing or decreasing the relative amounts of the precursor materials in the formation of the green body. In some aspects, the lithium hydroxide or its hydrate are micronized.
- the two or more powders forming the green body may be combined and shaken on a paint shaker to thoroughly mix the precursors.
- the green body is then calcined with a controlled air or pure oxygen atmosphere to a maximum temperature. Calcining is optionally preformed following a heating curve.
- the calcined product may then be processed to form a free-flowing powder.
- the precursor hydroxide may be a mixed metal hydroxide.
- the mixed metal hydroxide may include a metal composition of Ni, Co, and Mg.
- the mixed metal hydroxide includes as a metal component 10 - 100 at% Ni, 0 - 15 at% Co, and 0 - 5 at% Mg.
- the mixed metal hydroxide includes Ni from 10-100 at%, Co in the range of 0-30 at%, and Mn in the range of 0.1-80 at%.
- the mixed metal hydroxide includes Ni from 10-100 at%, Co in the range of 0-30 at%, and A1 in the range of 0-10 at%.
- the metals of the mixed metal hydroxide is 92 at% Ni and 8 at% Co.
- the metals of the mixed metal hydroxide is 90 at% Ni, 8 at% Co, and 2 at% Mg.
- the metals of the mixed metal hydroxide is 89 at% Ni, 8 at% Co, 3 at% Mg.
- the metals of the mixed metal hydroxide is 91 at% Ni, 8 at% Co, and 1 at% Mg.
- the metal of the mixed metal hydroxide is 100 at% Ni.
- precursor hydroxide may be made by a precursor supplier, such as Hunan Brunp Recycling Technology Co. Ltd., using standard methods for preparing nickel-hydroxide based materials.
- a secondary particle may be formed by a multi-step process whereby a first material particle is formed and calcined so as to establish the formation of defined grain boundaries optionally with the primary particles having a-NaFeCL structure with few defects.
- the particles are then subject to a liquid process that applies Co and A1 at the desired concentration levels followed by drying and then a second calcination so as to move the Co and A1 precipitated species at the surface selectively into the grain boundaries to thereby form the secondary particle having a concentration of Co and A1 in the grain boundaries that is higher than in the crystallites.
- formation may include: combining a lithium compound, and a hydroxide precursor compound of one or more metals or metalloids (e.g. Ni, Co, and Mg combined as previously generated such as by a co-precipitation reaction) to form a mixture; heat treating the mixture at about 30 to about 200°C to form a dried mixture; heat treating the dried mixture at about 200 to about 500°C for about 0.1 to about 5 hours; then heat treating at 600 °C to less than about 800 °C for about 0.1 to about 10 hours to manufacture the secondary particle.
- a first calcination maximum temperature is relative and specific to the material used in the hydroxide precursor.
- a maximum temperature may be at or less than 850 degrees Celsius, optionally at or less than 720 degrees Celsius, optionally at or less than 715 degrees Celsius, optionally at or less than 710 degrees Celsius, optionally at or less than 705 degrees Celsius, optionally at or less than 700 degrees Celsius.
- the maximum temperature of the first calcination may be about 680 degrees Celsius or less.
- the maximum temperature may be about 660 degrees Celsius or less.
- the maximum temperature may be about 640 degrees Celsius or less.
- the maximum temperature may be less than about 700 degrees Celsius, about 695 degrees Celsius, about 690 degrees Celsius, about 685 degrees Celsius, about 680 degrees Celsius, about 675 degrees Celsius, about 670 degrees Celsius, about 665 degree Celsius, about 660 degrees Celsius, about 655 degrees Celsius, about 650 degrees Celsius, about 645 degrees Celsius, or about 640 degrees Celsius.
- the dwell time at the maximum temperature is optionally less than 10 hours.
- the dwell time at the maximum temperature is less than or equal to 8 hours; optionally less than or equal to 7 hours; optionally less than or equal to 6 hours; optionally less than or equal to 5 hours; optionally less than or equal to 4 hours; optionally less than or equal to 3 hours; optionally less than or equal to 2 hours.
- subsequent processing may include breaking up the calcined material with a mortar and pestle so that the resulting powder passes through a desired sieve, optionally a #35 sieve.
- the powder is optionally then jar milled in a 1 gallon jar with a 2 cm drum YSZ media for optionally 5 minutes or an adequate time such that the material may pass through optionally a #270 sieve.
- the product of the first calcination or milled product may be subsequently processed, optionally in a method so as to result in enriched grain boundaries following a second calcination.
- a process to enrich grain boundaries within a primary particle may be performed by methods or using compositions as illustrated in U.S. Patent Nos. 9,391,317 and 9,209,455 with the exception that the application process uses a liquid solution that includes a level of Co and a level of Al, optionally whereby the level is such to produce a synergistic enrichment of Co and Al in the grain boundaries of the secondary particle.
- the grain-boundary-enriching elements may optionally be applied by suspending the milled product in an aqueous slurry comprising Co, Al, and a lithium compound optionally at a temperature of about 60 degrees Celsius whereby the Co and Al are present in the aqueous solution at the concentrations as described herein.
- the slurry may then be spray dried to form a free-flowing powder which is then subjected to a second calcination optionally with a heating curve following a two ramp/dwell process.
- the first two ramp/dwell temperature profile may be from ambient (about 25 degree Celsius) to 450 degrees Celsius and optionally at a rate of 5 degree Celsius per minute with a 1 hour hold at 450 degrees Celsius.
- the second ramp/dwell may be from 450 degrees Celsius to a maximum temperature at a rate of 2 degree Celsius per minute with a 2 hour hold at the maximum temperature.
- the maximum temperature is less than about 725 degrees Celsius, optionally at or about 700 degrees Celsius. In other aspects, the maximum temperature is about 725 degrees Celsius, optionally 750 degrees Celsius.
- a particle includes a plurality of crystallites with a first composition including poly crystalline layered-structure lithiated metal oxides defined by composition Lh+xMCh+y where -0.1 ⁇ x ⁇ 0.3 and -0.3 ⁇ y ⁇ 0.3.
- x is -0.1, optionally 0, optionally 0.1, optionally 0.2, or optionally 0.3.
- x is greater than or equal to -0.10, -0.09, -0.08, -0.07, -0.06,
- y is -0.3, optionally -0.2, optionally -0.1, optionally 0, optionally 0.1, optionally 0.2, or optionally 0.3.
- y is greater than or equal to -0.30, -0.29, -0.28, -0.27, -0.26, -0.25, -0.24, -0.23, -0.22, -0.21, -0.20, -0.19, -0.18, -0.17, -0.16, -0.15, -0.14, -0.13, -0.12, -0.11, -0.10, -0.09, -0.08, -0.07, -0.06, -0.05, -0.04, -0.03, -0.02, -0.01, 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, or 0.3.
- the crystallites have an amount of Ni of 10 atomic percent to 100 atomic percent (at%) of the M element.
- the Ni component of M is greater than or equal to 75 at%.
- the Ni component of M is greater than or equal to 80 at%.
- the Ni component of M is greater than or equal to 85 at%.
- the Ni component of M is greater than or equal to 90 at%.
- the Ni component of M is greater than or equal to 95 at%.
- the Ni component of M is greater than or equal to 75 at%, 76 at%, 77 at%, 78 at%, 79 at%, 80 at%, 81 at%, 82 at%, 83 at%, 84 at%, 85 at%, 86 at%, 87 at%, 88 at%, 89 at%, 90 at%, 91 at%, 92 at%, 93 at%, 94 at%, 95 at%, 96 at%, 98 at%, 99 at% or 100 at%.
- the M component may include one or more additional elements.
- the additional elements are optionally metals.
- an additional element may include or be one or more of Al, Mg, Co, Mn, Ca, Sr, Zn, Ti, Y, Cr, Mo, Fe, V, Si, Ga, or B.
- the additional element may include Mg, Co, Al, or a combination thereof.
- the additional element may be Mg, Al, V, Ti, B, or Mn, or a combination thereof.
- the additional element consists of Mg, Al, V, Ti, B, or Mn.
- the additional element is Mn or Mg, or both Mn and Mg.
- the additional element of the first composition may be present in an amount of about 1 to about 90 at%, specifically about 5 to about 80 at%, more specifically about 10 to about 70 at% of the first composition.
- the additional element may be present in an amount of about 1 to about 20 at%, specifically about 2 to about 18 at%, more specifically about 4 to about 16 at%, of the first composition.
- M is about 75-100 at% Ni, 0-15 at% Co, 0-15 at% Mn, and 0-10 at% additional elements.
- the resulting secondary particles have grain boundaries whereby the amount of Co and the amount of A1 are greater than in the crystallites.
- the resulting particles optionally demonstrate reductions in impedance growth relative to particles with Co enriched grain boundaries alone, optionally at levels of Co that were thought to be insufficient to significantly improve cycling characteristics of particles without Co enrichment in the grain boundaries.
- the resulting secondary particles are the active material of Li-ion cell cathodes
- the cells cycled between 4.2V and 2.7V at 45 °C optionally exhibit impedance growth in the fully charged (4.2V) state of less than 50% for greater than 50 cycles, optionally greater than 60 cycles, optionally greater than 70 cycles, optionally greater than 80 cycles, optionally greater than 90 cycles, optionally greater than 100 cycles, optionally greater than
- 110 cycles optionally greater than 120 cycles, optionally greater than 130 cycles, optionally greater than 140 cycles, optionally greater than 150 cycles, optionally greater than 200 cycles.
- the cells cycled between 4.2V and 2.7V at 45 °C optionally exhibit impedance growth in the fully charged (4.2V) state of less than 100% for greater than 100 cycles, optionally greater than 110 cycles, optionally greater than 120 cycles, optionally greater than 130 cycles, optionally greater than 140 cycles, optionally greater than 150 cycles, optionally greater than 160 cycles, optionally greater than 170 cycles, optionally greater than 180 cycles, optionally greater than 190 cycles, optionally greater than 200 cycles, optionally greater than 210 cycles, optionally greater than 220 cycles.
- the cells cycled between 4.2V and 2.7V at 45 °C optionally exhibit impedance growth at 50% state of charge (SOC) of less than 50% for greater than 200 cycles, optionally of less than 40% for greater than 200 cycles, optionally of less than 30% for greater than 200 cycles.
- SOC state of charge
- An electrochemical cell as provided herein optionally uses as an electrochemically active material particles as provided herein optionally having an initial discharge capacity of 180 mAh/g of the particles or greater, optionally 185 mAh/g, optionally 190 mAh/g, optionally 195 mAh/g, optionally 200 mAh/g, optionally 210 mAh/g.
- a particle comprising a crystallite 10 comprising a first composition, and grain boundaries 20, 21 comprising a second composition, wherein a concentration of A1 in the grain boundary is greater than a concentration of A1 in the crystallites and a concentration of cobalt in the grain boundary is greater than a concentration of cobalt in the crystallite.
- the particle comprises a plurality of crystallites, and is referred to as a secondary particle.
- an outer layer illustrated at 30 in FIG. 1, such as a passivation layer or a protective layer, may be deposited on an outer surface of the particle.
- the outer layer may fully or partially cover the secondary particle.
- the layer may be amorphous or crystalline.
- the layer may comprise an oxide, a phosphate, a pyrophosphate, a fluorophosphate, a carbonate, a fluoride, an oxyfluoride, or a combination thereof, of an element such as Al, Ti, , B, Li, or Si, or a combination thereof.
- the outer layer comprises a borate, an aluminate, a silicate, a fluoroaluminate, or a combination thereof.
- the outer layer comprises a carbonate.
- the outer layer comprises Zr02, AI2O3, T1O2, AIPO4, AIF3, B2O3, S1O2, L12O, L12CO3, or a combination thereof.
- an outer layer includes or is AIPO4 or L12CO3.
- the layer may be deposited disposed by any process or technique that does not adversely affect the desirable properties of the particle. Representative methods include spray coating and immersion coating, for example.
- Electrodes that include as a component of or the sole electrochemically active material a secondary particle as described herein.
- a secondary particle as provided herein is optionally included as an active component of a cathode.
- a cathode optionally includes a secondary particle disclosed above as an active material, and may further include a conductive agent and/or a binder.
- the conductive agent may comprise any conductive agent that provides suitable properties and may be amorphous, crystalline, or a combination thereof.
- the conductive agent may include a carbon black, such as acetylene black or lamp black, a mesocarbon, graphite, graphene, carbon fiber, carbon nanotubes such as single wall carbon nanotubes or multi wall carbon nanotubes, or a combination thereof.
- the binder may be any binder that provides suitable properties and may include polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and hexafluoropropylene, poly(vinyl acetate), poly(vinyl butyral-co-vinyl alcohol-co vinyl acetate), poly(methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride- co-vinyl acetate, polyvinyl alcohol, poly(l-vinylpyrrolidone-co-vinyl acetate), cellulose acetate, polyvinylpyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene-styrene, tri-block polymer of sulfonated sty
- the cathode may be manufactured by combining the particle as described herein, the conductive agent, and the binder in a suitable ratio, e.g ., about 80 to about 98 weight percent of the particle, about 1 to about 20 weight percent of the conductive agent, and about 1 to about 10 weight percent of the binder, based on a total weight of the particle, the conductive agent, and the binder combined.
- the particle, the conductive agent, and the binder may be suspended in a suitable solvent, such as N-methylpyrrolidinone, and disposed on a suitable substrate, such as aluminum foil, and dried in air. It is noted that the substrate and the solvent are presented for illustrative purposes alone. Other suitable substrates and solvents may be used or combined to form a cathode.
- a cathode as provided herein when cycled with a MCMB 10-28 graphite anode, a polyolefin separator and an electrolyte of 1 M LiPF 6 in 1/1/1 (vol.) EC/DMC/EMC with 1 wt. % VC in a 2025 coin cell optionally demonstrates a significantly reduced impedance growth relative to materials with Co enrichment alone or no grain boundary enrichment.
- One measure of impedance growth may be obtained by high-rate cycling of the cell, with a 1C/1C charge/discharge cycle interspersed in the cycling regime at 20 cycle intervals.
- the 1C charge to 4.2V is followed by a voltage hold during which the cell voltage is maintained at 4.2V until the current decays to C/10 rate, and then the cell is allowed to rest at open circuit for 5 minutes.
- the impedance measurement plotted against cycle number results in a curve with a defined slope. The impedance slope is lower when active particle material has grain boundaries enriched with Co and A1 as described herein relative to particles without such enrichment of grain boundaries or relative to particles having grain boundaries enriched only with Co.
- the impedance growth of cells is at or less than 25% for the first 50 cycles, optionally 50% or less over the first 100 cycles, optionally 63% or less over the first 125 cycles, optionally 75% or less over the first 150 cycles.
- the impedance growth is at or less than 25% over 50 cycles, optionally 50% or less over 100 cycles, optionally 63% or less over 125 cycles, optionally 75% or less the first 150 cycles.
- the battery may be a lithium-ion battery, a lithium-polymer battery, or a lithium battery, for example.
- the battery may include a cathode, an anode, and a separator interposed between the cathode and the anode.
- the separator may be a microporous membrane, and may include a porous film including polypropylene, polyethylene, or a combination thereof, or may be a woven or non-woven material such a glass- fiber mat.
- the anode may include a coating on a current collector.
- the coating may include a suitable carbon, such as graphite, coke, a hard carbon, or a mesocarbon such as a mesocarbon microbead, for example.
- the current collector may be copper foil, for example.
- the battery also includes an electrolyte that may contact the positive electrode (cathode), the negative electrode (anode), and the separator.
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be a linear or cyclic carbonate.
- organic solvents include ethylene carbonate, propylene carbonate, butylene carbonate, trifluoropropylene carbonate, g-butyrolactone, sulfolane, 1,2-dimethoxy ethane, 1,2- diethoxyethane, tetrahydrofuran, 3-methyl-l,3-dioxolane, methyl acetate, ethyl acetate, methylpropionate, ethylpropionate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methylpropyl carbonate, propane sultone, or a combination thereof.
- the electrolyte is a polymer electrolyte.
- Representative lithium salts useful in an electrolyte include but are not limited to LiPFe, LiBF 4 , LiAsFe, LiCIC , UCF3SO3, Li(CF 3 SC>2)2N, LiN(S02C 2 F 5 )2, LiSbFe, LiC(CF 3 S02) 3 , L1C4F9SO 3 , and LiAlCU.
- the lithium salt may be dissolved in the organic solvent. A combination comprising at least one of the foregoing can be used.
- the concentration of the lithium salt can be 0.1 to 2.0M in the electrolyte.
- the electrolyte may be a solid ceramic electrolyte.
- the battery may have any suitable configuration or shape, and may be cylindrical or prismatic.
- Example 1 Poly crystalline 2D a-NaFeCh-type layered structure particles with grain boundary enrichment with A1 and Co.
- Electrochemically active polycrystalline 2D a-NaFeCh-type layered structure particles with or without differing types of grain boundary enrichment and each with high nickel in the cathode material were prepared.
- 03 Mg 0.01 Ni 0.92 Co 0.08 O2 was prepared dry mixing 252.1 g Li(OH)2 (dehydrated, micronized LiOFDFbO from FMC) 961.6 Nio.9iCoo.o8Mgo.oiOH)2 (custom made) in a 1 liter jar. The compounds were mixed by shaking a jar in a paint shaker.
- the mixed compounds were placed in an alumina crucible and sintered. Sintering was performed by heating at a rate of about 5 °C per minute to about 450 °C, and held at about 450 °C for about two hours. The temperature was then raised at about 2 °C per minute to about 700 °C, and held for about six hours. The sample was then allowed to cool naturally to room temperature. The cooled sample was ground for about five minutes to break up any agglomerates to provide Li1.03Mg0.01Ni0.92Co0.08O2. The material was analyzed by XRD demonstrating an a-NaFe02-type structure.
- Samples of Co and A1 grain boundary enriched secondary particles of 100 g each were prepared with the above base material. Li, Co and A1 nitrate salts were dissolved in 100 g of H2O heated to 60 °C. The amounts of A1 and Co added were such to correspond to 1.9 at% and 4 at%, respectively, relative to Ni+Co in the Li1.03Mg0.01Ni0.92Co0.08O2 first composition. The amount of L1NO3 formulated were such that the final Li to transition metal + A1 ratio was 1.01.
- the full cells were cycled through a series of charge and rapid discharge cycles at 45 °C. A low rate discharge capacity and the impedance value were measured every 20 charge/discharge cycles. Some of the materials were further analyzed by EDS as well as cross- section TEM/EDX prior to use in cathode formation.
- Figures 2 and 3 show the capacity fade for full cells cycling at 45 °C and the associated impedance growth.
- Figure 2 shows that the“No Grain-Boundary-Enriching Process” (no slurry, spray dry, or 2 nd calcination) and“No Grain-Boundary -Enriching Elements” (no Co or A1 solutes in aqueous slurry, spray dry, and 2 nd calcination) samples had capacity fade at roughly the same high rate.
- The“No Grain-Boundary-Enriching Elements” material was run through the aqueous slurry and subsequent calcination process but with only water devoid of grain-boundary-enriching elements.
- Figure 3 shows that the 2 materials also had similar rates of impedance increase, demonstrating that the aqueous immersion, spray drying and second calcination process had no significant impact.
- the aluminum-only sample showed a modest improvement over the no-grain- boundary-enriching elements- baseline but the most significant improvement was observed for the cobalt-only grain-boundary enrichment with 10% fade in 300 cycles.
- Table 2 Results for EDS analyses of cathode material powders.
- Quantitative point analyses by STEM/EDS on thin lamellae of the 2 materials confirmed that inclusion of Co in the process formulation with A1 promotes the uptake of A1 into grain boundaries upon subsequent calcination.
- a secondary particle of each material coated on Cu foil as described above was sectioned by focused ion beam (FIB) milling to yield a thin lamella about 100 nm thick.
- FIB focused ion beam
- Figure 5 shows a scanning transmission electron micrograph (STEM) image of a small section containing several crystallites from a particle prepared by the grain-boundary- enrichment process in which both 1.9 at% A1 and 4 at% Co were formulated in the process liquid, and shows locations at which 3 EDS spot analyses were performed, locations 1 and 3 being at the interiors of adjacent crystallites, and location 2 being at the intervening grain boundary.
- Figure 6 shows the EDS spectra collected at the 3 locations marked in Figure 5. Spectrum 2 at the grain boundary shows a clear peak for A1 at about 1.5 keV whereas spectrum 1 and spectrum 3 at the crystallite interiors do not.
- Spectrum 2 at the grain boundary also indicates a higher ratio of Co to Ni than is seen in spectrum 1 and spectrum 3 at the crystallite interiors, as indicated by comparing the 6.9 keV Co peak to the 8.3 keV Ni peak in each spectrum.
- Quantitative results obtained by integrating the Figure 6 spectra are shown in Table 3 illustrating that the spectrum 2 grain boundary location is enriched in both A1 and Co.
- Table 3 Results for 3 EDS point analyses of particles produced using a 1.9 at% Al, 4 at% Co process liquid material.
- STEM-EDS point analyses of the type described above were performed on a total of 11 grain boundary and 10 crystallite interior locations for the 1.9 at% Al, 4 at% Co grain boundary enriched material, and 16 grain boundary and 7 crystallite interior locations for the 1.9 at% Al- only enriched material.
- Table 5 gives the averaged results for those analyses in comparison to the bulk formulated compositions of the materials, and shows that whereas applying the liquid process with Al only and then calcining results in little or no Al enrichment of grain boundaries (measurable quantity of Al detected in 3 of 16 locations), processing with both Al and Co and then calcining results in substantial grain boundary enrichment with both elements.
- Table 5 Averaged EDS point analysis results for grain boundaries (second composition) and crystallite interiors (first composition) of 1.9 at% Al only or 1.9 at% Al, 4 at% Co co-enriched materials.
- Example 2 Grain boundary enrichment with both A1 and Co via a nonaqueous grain boundary enrichment process.
- Electrochemically active polycrystalline 2D a-NaFeCk-type layered structure particles with differing types of grain boundary enrichment and each with high nickel in the cathode material were prepared via a nonaqueous grain boundary enrichment process.
- a material with composition Li1.03Mg0.01Ni0.92Co0.08O2 was prepared by the method of Example 1. 30 g of this material was then dispersed in 40 ml of methanol containing 1.9 at % A1 as dissolved nitrate salt together with or without 4 at% Co nitrate, and with sufficient LiNCh such that the final Li to transition metal + A1 ratio was 1.01.
- FIG. 9 shows A1 EDS maps of the calcined materials, and shows that, as was seen for aqueous-process materials in Example 1, the material formulated only with A1 had more intense and more numerous“hotspots” of A1 than the material formulated with Co together with Al. This result shows that the role of solution-processing with Co in promoting the more uniform uptake of Al by secondary particles is not an artifact of the aqueous process, and that non-aqueous deposition of grain-boundary-enriching elements by solvent evaporation yields the same result as aqueous deposition via acid-base precipitation.
- Example 3 Synergistic benefit obtained by grain boundary enrichment with both A1 and Co.
- Electrochemically active polycrystalline 2D a-NaFeCk-type layered structure particles with differing types of grain boundary enrichment and each with high nickel in the cathode material were prepared from a Li1.03Mg0.01Ni0.92Co0.08O2 base material via the methods of Example 1.
- the A1 and Co process formulations used to make these materials are shown by the matrix in Table 6.
- Table 6 A1 and Co levels in the process solution used to make Example 3 grain boundary enriched materials.
- Li-ion coin cells were built with the materials enriched as in Table 6 and cycled per the methods of Example 1.
- Figure 10 illustrates cycling capacity fade for the cells with 0 at% Al grain-boundary-enriched materials and with 0.5 at% Al grain-boundary-enriched materials and their dependence on formulated Co content.
- the capacities of the various materials decrease with increased Co in the formulations, but their rates of capacity fade do not differ greatly, being in the 4% to 6% range over 200 cycles, and are not substantially impacted by the inclusion or absence of
- Figure 11 shows that increasing the Co level in the formulation reduces impedance growth, with 4.2V impedance growth at 200 cycles decreasing from 250% to 130% as the formulated Co level is increased from 3 at% to 4 at%, and that further inclusion of 0.5 at% Al in the solution process formulation substantially reduces impedance growth at all levels of Co in the formulation, with impedance growth at 200 cycles dropping from
- Figure 12 further shows that a synergistic benefit is observed from inclusion of Al in the solution process formulation, with impedance being reduced by a greater amount than can be obtained by only further increasing the Co concentration.
- Figure 13 shows cycling capacity fade (left) and impedance growth (right) for cells with cathode materials grain boundary enriched from 3 at% Co solution process formulation with varied A1 levels.
- the figure shows that increasing the formulated A1 level decreases the cathode material’s capacity without significantly impacting capacity fade (all cells faded in the 6%-8% range over 200 cycles), but that increasing the formulated A1 level from 0 at% to 1 at% reduces 4.2V impedance growth at 200 cycles from 200% to 120%, while even higher A1 levels cause impedance growth to increase slightly.
- the impedance increases plotted in Figure 13 are summarized in Figure 14, which shows that for 3 at% Co in the process solution together with Al, minimum impedance growth is obtained when the process solution’s formulated atomic% ratio of Al/Co is about 0.3-0.4.
- Example 4 Al and Co grain boundary enrichment of an NCA material.
- NCA materials of similar overall composition were made, one having Co and Al grain boundary enrichment and one not.
- a base material was made by blending hydroxide precursors together and firing in an oxygen atmosphere until a final lithiated oxide was formed and sintered.
- Material 1 NCA base material having first composition LiNi0.93Co0.04Al0.03O2, grain boundary-enriched with additional 4 at% Co, 0.6 at% Al relative to total M in the first composition.
- a precursor transition metal hydroxide was used for this process. It contained at transition metal 4 at% Co and 3 at% Al and the balance Ni.
- a micronized Li OH powder was made by placing 51 g of LiOH into a plastic jar with 500 g of Y-stabilized zirconia 1 ⁇ 4” spheres and shaking on a paint shaker for 45 minutes. This micronized powder was then transferred to another plastic jar containing 190.15 g of the transition metal hydroxide precursor and the two powders were blended by shaking the jar on a paint shaker for a further 10 minutes.
- the roughly 240 g of blended powder was split between two crucibles and fired in an oxygen atmosphere by first ramping to 450 °C at 5 °C/min and soaking at temperature for 2 hours, and then ramping to 680 °C at 2 °C/min and soaking for 6 hours.
- the furnace was allowed to cool to 130 °C and the powder was removed and placed into ajar mill.
- the jar mill contained 1 ⁇ 2” drum media and was used to mill the powder for 2 minutes.
- the powder was then sieved through a 270 mesh sieve.
- the material was analyzed by XRD demonstrating an a-NaFeCk-type structure.
- the powder was then coated with Co and A1 by making a solution of 80 g water, 9.5 g cobalt nitrate (4 at% Co relative to total M in LiMCfe base composition), 1.9 g aluminum nitrate (0.6 at% A1 relative to total M in LiMCk base composition), 2.7 g lithium nitrate and heating to 60 °C. To this was added 80 g of the previously prepared powder. The slurry was allowed to stir for 25 minutes after which it was spray dried to remove the water from the slurry and prepare a dry powder.
- Figure 15 shows STEM micrographs of a thinly sectioned secondary particle of the thus-prepared material that was coated on Cu foil as described in Example 1.
- Figure 15 also provides the Al/Ni and Co/Ni atomic ratio results for 3 EDS point analyses of an interior grain boundary (GB) and bulk areas of the adjacent primary particles, showing that the grain boundary is enriched with both Co and Al.
- Material 2 comparative NCA base material having homogeneous first composition
- LiNi0.89Co0.08Al0.03O2 [00122] A precursor transition metal hydroxide was used for this process. It contained 8 at% Co and 3 at% A1 and the balance Ni.
- a micronized LiOH powder was made by placing 25.5 g of LiOH into a plastic jar with 500 g of Y-stabilized zirconia 1 ⁇ 4” spheres and shaking on a paint shaker for 45 minutes. This micronized powder was then transferred to another plastic jar containing 95.1 g of the transition metal hydroxide and the two blended by shaking on a paint shaker for a further 10 minutes.
- the roughly 120 g of powder was placed in one crucible and fired in an oxygen atmosphere by first ramping to 450 °C at 5 °C/min and soaking at temperature for 2 hours, and then ramping to 680 °C at 2 °C/min and soaking for 6 hours.
- the furnace was then allowed to cool to 130 °C and the powder was removed and placed into ajar mill.
- the jar mill contained 1 ⁇ 2” drum media and was used to mill the powder for 2 minutes.
- the powder was then sieved through a 270 mesh sieve.
- the material was analyzed by XRD demonstrating an a-NaFeCk-type structure.
- the above cathode materials 1 and 2 were assembled in coin cells as described in Example 1.
- the cells were 1C/1C cycled at 45 °C, with 10 second discharge DCR being measured at 100% state of charge (SOC) for every cycle and at 50% SOC every 20 th cycle.
- SOC state of charge
- the capacity fade and impedance growth results for 2 cells Li-ion coin cells made with each material are presented in Figure 16 and Figure 17, respectively.
- the grain boundary-enriched material #1 contained Co enriched between bulk crystallites in the grain boundaries while material #2 contained an equivalent overall amount of Co uniformly distributed throughout the secondary particle.
- Material #1 had only slightly higher overall A1 content than material #2, but the excess A1 ( ⁇ 16 % more A1 than material #2) was all concentrated in the grain boundaries.
- FIG 16 shows that the grain boundary-enriched material #1, in addition to having slightly higher capacity ( ⁇ 1%) than the homogeneous material #2, had only 8% capacity fade in 200 cycles as compared to >30% fade for material #2.
- Figure 17 shows that cells with grain boundary-enriched material #1 had 100% impedance growth at full SOC (4.2V) and 30% impedance growth at 50% SOC after 200 cycles, while cells with material #2 had >800% impedance growth at full SOC and >200% impedance growth at 50% SOC after 200 cycles.
- Example 5 A1 and Co grain boundary enrichment of an NCM material.
- NCM base material having first composition LiNio.8Coo.1Mno.1O2 (NCM 811) was prepared from co-precipitated precursor transition metal hydroxide containing 10 at% Co and 10 at% Mn and the balance Ni.
- a micronized LiOH powder was made by placing 87.7 g of LiOH into a plastic jar with 500 g of Y-stabilized zirconia 1 ⁇ 4” spheres and shaking on a paint shaker for 45 minutes. This micronized powder was then transferred to another plastic jar containing 335.7 g of the precursor transition metal hydroxide and the two blended by shaking on a paint shaker for a further 10 minutes.
- the roughly 440 g of powder was split between three crucibles and fired in an oxygen atmosphere by first ramping to 450 °C at 5 °C/min and soaking at temperature for 2 hours, and then ramping to 770 °C at 2 °C/min and soaking for 10 hours at 770 °C.
- the furnace was then allowed to cool to 130 °C and the powder was removed and placed into ajar mill.
- the jar mill contained 3 ⁇ 4” drum media and was used to mill the powder for 2 minutes.
- the powder was then sieved through a 270 mesh sieve.
- the powder was then divided into base (no further treatment) or grain-boundary- enriched with Co and A1 by making a solution of 200 g water, 11.9 g cobalt nitrate (2 at% Co relative to base composition), 3.1 g aluminum nitrate (0.4 at% Al), 3.4 g lithium nitrate and heating to 60 °C. To this was added 200 g of the previously prepared lithiated precursor powder. The slurry was allowed to stir for 10 minutes after which it was spray dried to remove the water from the slurry and prepare a dry powder.
- This powder was then fired in an air atmosphere by first ramping to 450 °C at 5 °C/min and soaking at temperature for 1 hour, and then ramping to 770 °C at 2 °C/min and soaking for 0.25 hour. The furnace was then allowed to cool to 130 °C and the powder was removed from the furnace and sieved through a 270 mesh sieve.
- the overall composition of the synthesized cathode powder was LiNio.o79Coo.nMno.o9Alo.oo 6 02
- the grain boundary enriched material had much lower impedance growth than the similar composition, homogeneous base material (Figure 19), having 45% impedance growth at 100% SOC and 38% impedance growth at 50% SOC after 200 cycles, as compared to 225% impedance growth at 100% SOC and 70% impedance growth at 50% SOC after 200 cycles for the base material.
- Patents, publications, and applications mentioned in the specification are indicative of the levels of those skilled in the art to which the disclosure pertains. These patents, publications, and applications are incorporated herein by reference to the same extent as if each individual patent, publication, or application was specifically and individually incorporated herein by reference.
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EP19910735.0A EP3912209A4 (en) | 2019-01-17 | 2019-10-23 | Polycrystalline metal oxides with enriched grain boundaries |
JP2021541559A JP2022522999A (en) | 2019-01-17 | 2019-10-23 | Polycrystalline metal oxide with concentrated grain boundaries |
KR1020217025781A KR20210105440A (en) | 2019-01-17 | 2019-10-23 | Polycrystalline metal oxide with enhanced grain boundaries |
PCT/US2020/013038 WO2020150084A1 (en) | 2019-01-17 | 2020-01-10 | Stable cathode materials |
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