EP3912211A1 - Matériaux de cathode stables - Google Patents

Matériaux de cathode stables

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Publication number
EP3912211A1
EP3912211A1 EP20741079.6A EP20741079A EP3912211A1 EP 3912211 A1 EP3912211 A1 EP 3912211A1 EP 20741079 A EP20741079 A EP 20741079A EP 3912211 A1 EP3912211 A1 EP 3912211A1
Authority
EP
European Patent Office
Prior art keywords
particle
lithium
crystallites
composition
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20741079.6A
Other languages
German (de)
English (en)
Other versions
EP3912211A4 (fr
Inventor
Jane REMPEL
David Ofer
Jennifer Nelson
Adrian Pullen
Kenan Sahin
Suresh Sriramulu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CAMX Power LLC
Original Assignee
CAMX Power LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/250,622 external-priority patent/US10950857B2/en
Priority claimed from US16/250,615 external-priority patent/US10501335B1/en
Priority claimed from PCT/US2019/057630 external-priority patent/WO2020149910A1/fr
Priority claimed from US16/728,379 external-priority patent/US11424449B2/en
Application filed by CAMX Power LLC filed Critical CAMX Power LLC
Priority claimed from PCT/US2020/013038 external-priority patent/WO2020150084A1/fr
Publication of EP3912211A1 publication Critical patent/EP3912211A1/fr
Publication of EP3912211A4 publication Critical patent/EP3912211A4/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This disclosure is directed to electrochemically active materials for use in a cathode of a secondary battery.
  • LiMCh materials based on lithium nickel oxide (LiNi02) in a layered structure are desirable as lithium battery cathode materials because they generally provide lower cost, higher capacity, and higher rate capability than lithium cobalt oxide (L1C0O2).
  • pure LiNi02 materials exhibit poor electrochemical stability and cycling performance. It has been found that by substituting varying amounts of other metals for some or much of the bulk material Ni in LiNiCh, some of the capacity and cost benefits of LiNiCh can be obtained with improved electrochemical cycling stability.
  • electrochemically active particles that include grain boundaries with a higher electrochemical affinity for lithium that exhibit improved cycling ability with comparable capacity relative to base materials without stabilized grain boundaries.
  • electrochemical affinity for Li By increasing the electrochemical affinity for Li by selectively increasing the oxidation potential of the grain boundary region of the particles, the inventors found they could increase capacity retention and reduce impedance growth during cycling without significantly reducing capacity relative to that of the active material without grain boundary stabilization.
  • electrochemically active particles that may be used as an active material in a cathode of an electrochemical cell (or other such device), that include: a plurality of crystallites comprising a first composition comprising lithium, nickel, and oxygen; and a grain boundary between adjacent crystallites of the plurality of crystallites and comprising a second composition comprising lithium, nickel, and oxygen; wherein the grain boundary has a higher electrochemical affinity for lithium than the crystallites.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein lithium is present in the grain boundary at a higher concentration than lithium inside the crystallites when the particle is at a state of charge greater than or equal to 10 percent.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein lithium is present in the grain boundary at a higher concentration than lithium in the crystallites when an electrode incorporating the particles is charged to a potential greater than or equal to 4.1 V versus lithium, or wherein lithium is present in the grain boundary at a higher concentration than lithium in the crystallites at a charge capacity of 40 mAh/g or greater.
  • Electrochemical cells that incorporate one or more of the electrochemically active particles as provided herein. Electrochemical cells are also provided that include in the cathode one or more of the electrochemically active particles as provided herein.
  • FIG. 1 illustrates that as the amount of Ni substitution in LiMCk by other metals increases, the amount of Li extracted from LiMCk upon charging to a given potential decreases;
  • FIG. 2 illustrates that LiMCk materials with lower Ni content than LiMCk are delithiated to a lesser extent than LiMCk when the materials are charged to the same potential;
  • FIG. 3 shows the locations of EDS line scans in a thin lamella prepared from a particle of grain boundary-modified LiMCk material of Example 4;
  • FIG. 4 shows results of EDS line scans in a thin lamella prepared from a particle of grain boundary-modified LiMCk material of Example 4 with A and C representative of the LSI scan line of FIG. 3, and B and D representative of the LS2 scan line of FIG. 3;
  • FIG. 5 shows XRD results for the charged and fresh cathode electrodes of the grain boundary -modified LiMCk material of Example 3 and its uniform-composition LiMCk base;
  • FIG. 6 shows high resolution XRD results for the charged electrodes of the grain boundary-modified LiMCk material of Example 3 and its uniform-composition LiMCk base with peak position offset and scaled to the (104) peak;
  • FIG. 7 illustrates discharge capacity as a function of cycle number for grain boundary-modified LiMCk material of Example 1 and its uniform-composition LiMCk precursor during cycling at 45 °C in full coin cells;
  • FIG. 8 illustrates a comparison of the impedance increase during cycle life measurement at 45 °C of materials as illustrated in FIG. 7 in full coin cells;
  • FIG. 9 illustrates discharge capacity as a function of cycle number for grain boundary-modified LiMCh material of Example 2 and its uniform-composition LiMCh precursor during cycling at 45 °C in full coin cells;
  • FIG. 10 illustrates a comparison of the impedance increase during cycle life measurement at 45 °C of materials as illustrated in FIG. 9 in full coin cells.
  • FIG. 11 illustrates discharge capacity as a function of cycle number for grain boundary -modified LiMCh material of Examples 3-5 and its uniform-composition LiMCh precursor during cycling at 45 °C in full coin cells;
  • FIG. 12 illustrates a comparison of the impedance increase during cycle life measurement at 45 °C of materials as illustrated in FIG. 11 in full coin cells;
  • FIG. 13 illustrates the increased fracture toughness of particles with low Ni in the grain boundaries relative to the adjacent crystallites
  • FIG. 14 illustrates the reduction in the rate of impedance of materials as provided herein according to some aspects wherein the open symbols are bulk materials and the closed boxes are selectively reduced in Ni at the grain boundaries.
  • the inventors of this disclosure found that electrochemically extracting high levels of lithium from polycrystalline LiMCh-based materials having 2D a-NaFeCh-type layered structure induces the 2D layers of transition metal atoms within the crystallite grain boundaries to reorganize into a NiO-type rock salt structure with associated reduction in transition metal oxidation state and loss of oxygen, and introduction of defects like oxygen vacancies and intermixing of nickel between nickel and lithium layers in the ceramic.
  • This restructuring is initiated at grain boundaries and propagates deeper into the crystallites with repeated cycling. Sometimes, that restructuring is associated with mechanical damage including the appearance of cracks between adjacent crystallites. This loss of material stability at high levels of lithium extraction results in decreasing capacity and increasing impedance of the cathode materials as they are cycled.
  • This disclosure is based on the discovery that the performance of LiNiCk-based materials can be improved by designing the materials to retain more lithium in the grain boundary region at the end of charge by raising the oxidation potential of this region; thus, preventing or slowing down grain boundary reconstruction, reducing the likely formation of NiO and LriO, and as is illustrated in this disclosure, reducing the rate of impedance growth for these materials.
  • polycrystalline LiMCk-based materials including 2D a-NaFeCk-type layered structure that selectively retain more Li in the grain boundaries than in their crystallites’ interior structure when the materials are charged and/or have increased stability in particular regions of the particles so as to reduce the rate of impedance growth during charge/discharge cycling of the battery and optionally improve cycle life. Even in the charged state, these materials retain Li in the grain boundary where it is needed to stabilize the delithiated crystallite material against structural reconstruction propagating from the grain boundaries, while still releasing Li from the bulk crystallite structure to provide for high cycling capacity.
  • Retention of higher Li levels in the grain boundaries of charged materials relative to the bulk crystallites can be accomplished by selectively raising the local oxidation potential of the grain boundary region, thereby preventing grain boundaries from being delithiated to as great an extent as the LiMCk bulk crystallites when the materials are charged to a given electrochemical potential.
  • the nature of the role that raising the local oxidation potential in the composition of L1MO2 grain boundaries plays in promoting Li retention in those grain boundaries can be understood by referring to Figure 1, which shows C/20 1 st charge curves in Li metal anode half cells for cathode materials having varying proportions of Ni as M in L1MO2.
  • the metals replacing a portion of the Ni in the bulk (not selective localization) of the LNO materials of Figure 1 and Table 1 include Co and Mn that are representative of metals that effectively lessen the tendency for oxidation of L1MO2 relative to Ni when the L1MO2 materials are charged, and A1 which is representative of metals that are not oxidized at all when L1MO2 materials are charged.
  • the relative amounts of such metal substituents impact these bulk materials’ extent of oxidation and retention of Li. Therefore, although both NCM 811 and NCA have Ni composing 80% of M in L1MO2, NCA retains more Li when it is charged to 4.3 V vs. Li because whereas both Co and Mn in NCM 811 can be oxidized, A1 in NCA cannot be oxidized.
  • the differing impacts of raising the local oxidation potential in the L1MO2 structure can generally be understood by considering simplified concepts such as the metals’ oxidation potentials and/or their electron count in the context of crystal field theory.
  • the mean oxidation state of M in the structure is +3.
  • the M atoms are in a relatively strong octahedral field, which will therefore be stabilized by metals with d 6 (tf 5 crystal field configuration) and d 3 (tf 5 crystal field configuration) electron counts.
  • oxidation of Ni atoms to the more stable tf 5 configuration requires simultaneous transfer of two electrons and charge-compensating Li + ions, whereas oxidation of Ni atoms in LiNiCL proceeds by a more facile single electron/single ion process.
  • A1 in L1MO2 is already in the 3+ oxidation state and does not have an accessible 4+ oxidation state at realistic battery cathode material potentials.
  • the preceding discussion of oxidation and Li retention in the bulk L1MO2 cathode materials illustrates how raising the oxidation potential in the grain boundaries of L1MO2 materials can provide for greater retention of Li in the grain boundaries than in the bulk crystallites when those materials are charged.
  • the refrained Figure 1 data that are plotted in Figure 2 illustrate how much Li will be retained in the grain boundaries relative to the amount of Li retained in the LNO bulk crystallites when the material is oxidized (charged) to a given potential.
  • the figure shows that the grain boundaries will retain more Li than the bulk crystallites at any potential or state of charge up to 4.3 V vs. Li.
  • these data can be normalized to the Li content of one of the other materials; for example, to show that materials with NCM(811) bulk crystallites and NCM(523) grain boundaries would also retain more Li in their grain boundaries than in the bulk crystallites when they were charged. Note that the 4.3 V vs. Li is illustrative, and similarly higher amount of Li can be retained in the grain boundaries than in the bulk even when the materials are charged to potentials higher or lower than 4.3 V vs. Li.
  • SoC state of charge
  • full charge is achieved at a potential of 4.1 V or greater, optionally 4.2 V or greater, optionally 4.3 V or greater, optionally 4.4 V or greater vs. Li.
  • electrochemical affinity for lithium is defined as the tendency to retain lithium when oxidized to a certain potential or voltage. Therefore, a material with a higher electrochemical affinity will retain more lithium when charged to a certain potential than a material with a lower electrochemical affinity for lithium.
  • the potential can be a range of relevant potentials.
  • a material with a higher electrochemical affinity for lithium implies that the material (or a portion of the material) will have a higher lithium content compared to a material with a lower electrochemical affinity when both materials are at the same potential.
  • particles that include a plurality of crystallites comprising a first composition comprising lithium, nickel, and oxygen and having a layered a-NaFeCk-type structure, 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, a monoclinic structure, or a combination thereof, wherein the second composition has either a higher electrochemical affinity for lithium relative to the first composition and/or compared to a material with a lower electrochemical affinity when both materials are at the same potential; and/or wherein nickel is present in the second composition at a lower concentration than nickel in the first composition.
  • particles that include a plurality of crystallites comprising a first composition including layered-layered compositions with an overall formula of zLiMCk»( 1 -zjLbM’Ck where z is in the range of 0.7 ⁇ z ⁇ 1.0, optionally 0.8 ⁇ z ⁇ 0.95 moles per mole of the composition.
  • the layered-layered materials also include 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, a monoclinic structure, or a combination thereof.
  • M can include Ni, Co, Mn, or a combination thereof, and M’ can include one or more of Mn, Ti, or Cr. It is noted that the oxidation potentials and electrochemical affinity of the grain boundary regions of the layered-layered materials may be as described for other materials as provided herein.
  • M optionally includes Ni alone or with one or more of Co, Mn, V, or Fe.
  • the Ni component of M is optionally at or greater than 0.3 to 0.95 moles per mole of M.
  • Co if present in M is optionally present at 0 to 0.33 moles per mole of M.
  • Mn if present in M, is optionally present at equal to or greater than 0.05 to 0.8 moles per mole of M.
  • M includes Ni at greater than 0.3 to 0.95 moles per mole of M, Co at 0 to 0.33 moles per mole of M, and Mn at 0.05 to 0.5 moles per mole of M.
  • M’ includes Mn alone or in addition to one or more of Ti, Zr, Ru, Re, and Pt.
  • compositions having a layered a-NaFeCk-type structure hexagonal metal oxide layers are separated by planes of the alkali metal (e.g. Li).
  • the metal oxide layers form metal centered oxygen octahedra that are separated by alkali metal ions. These metal oxide layers are laterally offset to provide a three-layer structure.
  • the coordinates of the atoms and the cell parameters can vary according to the composition.
  • Compositions having this structure type may have cell parameters in which a is about 2.75 to about 2.95 angstroms (A), and c is about 13.9 to about 14.6 A.
  • materials as provided herein 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 where the grain boundaries include a second composition.
  • the particles are appreciated to include a grain boundary formed of or including a second composition, wherein the second composition differs from the first composition in that the electrochemical affinity for Li in the second composition is increased relative to a first composition defining the crystallites of the secondary particle and/or the second composition has a lower concentration of Ni relative to the first composition.
  • the particles as provided herein are capable of maintaining a greater amount of Li in the grain boundary than in the crystallites at any particular state of charge greater than zero.
  • the particles as provided herein are capable of maintaining a greater amount of Li in the grain boundary than in the crystallites when the particle is at a given potential, or over a range of potentials.
  • the provided materials have a lower concentration of Ni in the grain boundary region relative to the adjacent crystallites.
  • the provided materials include a further outer coating layer that may be disposed on an outer surface of the secondary particle to provide a coated secondary particle.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein the grain boundary has a higher electrochemical affinity for lithium than the crystallites.
  • Higher electrochemical affinity for Li in the grain boundary promotes an increased concentration of Li in the grain boundary relative to the crystallites at any particular state of charge.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein nickel is present in the grain boundary at a lower concentration than nickel concentration inside the crystallites.
  • the molar lithium content per mole of a second composition defining the grain boundary relative to the molar Li content per mole of a first composition defining the crystallites is found to be higher at a state of charge of 10% or greater, optionally 20% or greater, optionally 30% or greater, optionally 40% or greater, optionally 50% or greater, optionally 60% or greater, optionally 70% or greater, optionally 80% or greater, optionally 90% or greater, optionally 95% or greater, optionally 96% or greater, optionally 97% or greater, optionally 98% or greater, optionally 99% or greater, optionally 100%.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein the grain boundary has a higher electrochemical affinity for lithium than the crystallites at a state of charge of 10% or greater.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein the grain boundary has a higher electrochemical affinity for lithium than the crystallites at a state of charge of 80% or greater.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein the grain boundary has a higher electrochemical affinity for lithium than the crystallites at a state of charge of 100%.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein lithium is present in the grain boundary at a higher concentration than lithium inside the crystallites when the particle is at a state of charge greater than or equal to 10 percent.
  • the molar lithium concentration per mole of a second composition defining the grain boundary relative to the molar concentration of Li per mole of the first composition defining the crystallites is found to be higher at a state of charge of 10% or greater, optionally 20% or greater, optionally 30% or greater, optionally 40% or greater, optionally 50% or greater, optionally 60% or greater, optionally 70% or greater, optionally 80% or greater, optionally 90% or greater, optionally 95% or greater, optionally 96% or greater, optionally 97% or greater, optionally 98% or greater, optionally 99% or greater, optionally 100%.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein lithium is present in the grain boundary at a higher concentration than lithium inside the crystallites when the particle is at a state of charge greater than or equal to 20 percent.
  • electrochemically active 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 comprising lithium, nickel, and oxygen; wherein lithium is present in the grain boundary at a higher concentration than lithium inside the crystallites when the particle is at a state of charge greater than or equal to 80 percent.
  • electrochemically active particles that may be used in a cathode of an electrochemical cell that may 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 comprising lithium, nickel, and oxygen; wherein lithium is present in the grain boundary at a higher concentration than lithium in the crystallites when an electrode incorporating the particle is charged to a potential greater than or equal to 4.00 V versus lithium.
  • the Ni mole fraction within the second region of less than or equal to 0.95 results in the improved electrochemical performance of the materials. It was found that by reducing Ni levels in the grain boundary region(s) of the particles that enhanced stability to the overall particle could be obtained.
  • the ratio of mole fraction of Ni in the second composition relative to the mole fraction of Ni in the first composition is in the range of 0.95 to 0.5.
  • the ratio of the mole fraction of Ni in the second composition to the mole fraction of Ni in the first composition is 0.95 or less, optionally 0.90, optionally 0.85, optionally 0.80, optionally 0.75, optionally 0.7, optionally 0.65, optionally 0.6, optionally 0.55, or less.
  • the lithium is present in the grain boundary (second composition) at a higher concentration than lithium in the crystallites (first composition) when an electrode incorporating the particle is charged to a potential greater than or equal to 4.1 V versus lithium.
  • the lithium is present in the grain boundary at a higher concentration than lithium in the crystallites when an electrode incorporating the particle is charged to a potential greater than or equal to 4.2 V versus lithium.
  • the lithium is present in the grain boundary at a higher concentration than lithium in the crystallites when an electrode incorporating the particle is charged to a potential greater than or equal to 4.25 V versus lithium.
  • the lithium is present in the grain boundary at a higher concentration than lithium in the crystallites when an electrode incorporating the particle is charged to a potential greater than or equal to 4.3 V versus lithium.
  • the increase in the amount of Li retained in the second composition of the grain boundary relative to the bulk is optionally 0.02 moles Li per mole of the second composition or greater at the potential as provided in the preceding paragraphs.
  • the moles of Li per mole of the second composition is greater than the moles of Li per mole of the first composition by 0.01, optionally by 0.02, optionally by 0.05, optionally by 0.1, optionally 0.15, optionally 0.2, optionally 0.25 , optionally 0.3.
  • the elemental composition of the first composition and the second composition are identical with the exception of differing relative amounts of each of the individual metal constituents with the proviso that the amount of Ni in the second composition is lower than the amount of Ni in the first composition.
  • a second composition includes one or more additional metals not present in the first composition wherein the one or more additional metals may substitute for the Ni in the crystal lattice of the second region to thereby promote increased order to these regions and improved cycle life and reduced internal resistance.
  • electrochemically active particles that may be used in a cathode of an electrochemical cell that may 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 comprising lithium, nickel, and oxygen; lithium is present in the grain boundary at a higher concentration than lithium in the crystallites at a charge capacity of the particles of 40 mAh/g or greater.
  • the concentration of Li in the grain boundaries is increased relative to the crystallites when the particle is charged to a capacity of optionally 50 mAh/g or greater, optionally 60 mAh/g or greater, optionally 70 mAh/g or greater, optionally 80 mAh/g or greater, optionally 90 mAh/g or greater, optionally 100 mAh/g or greater, optionally 110 mAh/g or greater, optionally 120 mAh/g or greater, optionally 130 mAh/g or greater, optionally 140 mAh/g or greater, optionally 150 mAh/g or greater, optionally 160 mAh/g or greater, optionally 170 mAh/g or greater, optionally 180 mAh/g or greater, optionally 190 mAh/g or greater, optionally 200 mAh/g or greater, optionally 220 mAh/g or greater.
  • the moles of Li per mole of the second composition is greater than the moles of Li per mole of the first composition by 0.01, optionally by 0.02, optionally by 0.05, optionally 0.1, optionally 0.15, optionally 0.2, optionally 0.25, optionally 0.3.
  • the increase in the amount of Li retained in the second composition of the grain boundary relative to the amount of Li retained in the first composition of the crystallite is 0.01 moles Li per mole of the second composition or greater, optionally 0.15 moles Li per mole of the second composition or greater, optionally 0.2 moles Li per mole of the second composition or greater, optionally 0.25 moles Li per mole of the second composition or greater, optionally 0.3 moles Li per mole of the second composition or greater.
  • the amount of Li retained in the second composition is greater, optionally by the foregoing amount, than the amount of Li retained in the first composition at a charge capacity of the particle of 50 mAh/g or greater, optionally 60 mAh/g or greater, optionally 70 mAh/g or greater, optionally 80 mAh/g or greater, optionally 90 mAh/g or greater, optionally 100 mAh/g or greater, optionally 110 mAh/g or greater, optionally 120 mAh/g or greater, optionally 130 mAh/g or greater, optionally 140 mAh/g or greater, optionally 150 mAh/g or greater, optionally 160 mAh/g or greater, optionally 170 mAh/g or greater, optionally 180 mAh/g or greater, optionally 190 mAh/g or greater, optionally 200 mAh/g or greater, optionally 220 mAh/g or greater.
  • a particle with that includes a second composition present in the grain boundary regions, optionally exclusively in the grain boundary region wherein the second composition has a lower concentration of Ni relative to the concentration of Ni in the first composition of the crystallites leads to increased physical stability of the particle and increased fracture toughness or fracture resistance.
  • One method of measuring stability of a particle is through measurement of fracture toughness.
  • Fracture toughness measurements may be made by placing a known quantity of particles as provided herein in a die and applying a suitable amount of pressure, optionally at 900 MPa, and then measuring the increase in the amount of fines generated in the material by the application of the pressure. This serves as a direct measurement of physical particle stability that the inventors found corresponds directly with reduced rates of impedance growth during cycling.
  • the amount of fines increases by less than 50 number percent in the provided particles following application of 890 MPa or 900 MPa of pressure. Measurement of fines in a sample following application of pressure may be made by particle size analyses by recognized techniques.
  • Fines as defined herein are particles (or particle fragments) that have a size as measured by particle size analyses of 3.5 pm or lower.
  • the absolute number of particles is known and the percent pass is the number of fines related to the total particle number as determined in the analyses.
  • particle surface area correlates with improved performance such as cycle life or reduction in impedance growth.
  • increased surface area may be measured by techniques such as Brunauer-Emmett-Teller (BET) surface area measurements.
  • BET Brunauer-Emmett-Teller
  • samples of particle material may be crushed in a 2 cm diameter die in a hydraulic press to the desired pressure.
  • a total mass of 2.5 g of powder may be placed in the die and crushed to form a pellet.
  • the pellet may then be placed in 20 mL of water and subjected to ultrasonic dispersion for 30 minutes.
  • a small portion of the dispersed slurry may be added to a Malvern Mastersizer 3000 laser-light particle size instrument equipped with a liquid cell.
  • the ultrasonic function may be used during the measurement and an average of five measurements used to calculate the final result.
  • the distribution may be calculated using properties for NiO taken from the instrument library.
  • the percent fines generated by application of pressure in a die decreases with decreasing relative Ni concentration in the grain boundary relative to the crystallites.
  • the percent fines generated in by the application of pressure in the die are equal to or less than a percentage of 50, 40, 35, 30, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, or 2 percent.
  • the concentration of nickel in the second composition is lower than the concentration of nickel in the first composition, and the fracture resistance is such that when the material is pressed to a pressure of 900 MPa, less than 15% fines are generated.
  • the number of fines is generated is less than 15 percent, optionally less than 14 percent, optionally less than 13%, optionally less than 12%, optionally less than
  • the material is an NCA material with 90 atomic percent Ni or above the number of fines generated is less than 7%, optionally less than
  • the material is an NCM material with 80 atomic percent Ni or above the number of fines generated is less than 6 percent, optionally less than 5 percent, optionally less than 4 percent, optionally less than 3 percent, optionally less than 2 percent.
  • the first composition that defines the crystallites of the secondary particle includes polycrystalline layered-structure lithiated metal oxides defined by composition defined by Formula I:
  • 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.
  • Li need not be exclusively Li, but may be partially substituted with one or more elements selected from the group consisting of Mg, Sr,
  • 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
  • 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
  • the Ni component of M is greater than or equal to 95 at%.
  • the Ni component of M is greater than or equal to 95 at%.
  • Ni component of M is greater than or equal to 75 at%, 76 at%, 77 at%, 78 at%, 79 at%, 80 at%,
  • M in the first composition 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 Mg, Sr, Co, Al, Ga, Ca, Cu, Zn, Mn, V,
  • 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 is 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,
  • 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% of total M, 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 or within 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 crystallite is optionally a single crystal and a particle is optionally an agglomerate of single crystals.
  • the particles include a grain boundary that separates two adjacent crystallites.
  • a grain boundary includes a second composition.
  • the grain boundary includes a second composition having the a-NaFeCh-type structure with the generic Formula II:
  • M’ is defined as M in the first composition but with a relatively lower mole Ni per mole of LiMCh.
  • the Ni sites in the crystal structure are substituted with one or more substitution elements that increases the electrochemical affinity for lithium of the structure relative to the unsubstituted material such that the amount of the substitution elements are at a greater mole per mole concentration in the second composition than in the first composition, and optionally at a state of charge of 80% or greater or at a charge capacity of 150 mAh/g or greater, -0.6 ⁇ x ⁇ -0.2.
  • x is -0.6, optionally -0.65, optionally -0.7, optionally
  • y is -0.3, optionally
  • 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,
  • Ni in the second composition can be in the range of 0 to 0.99 moles per mole of M’ in the second composition.
  • 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 moles per mole of M’.
  • the Ni component of M’ is less than or equal to 0.5 moles per mole of M’.
  • the Ni component of M’ is less than or equal to
  • the Ni component of M’ is less than or equal to 0.10 moles per mole of M’.
  • the Ni component of M’ is less than or equal to 0.20 moles per mole of M’.
  • the Ni component of M’ is less than or equal to 0.75 moles per mole of M’.
  • the Ni component of M’ is less than or equal to 0.80 moles per mole of M ⁇
  • the Ni component of M’ is less than or equal to 0.85 moles per mole of M ⁇
  • the Ni component of M’ is less than or equal to 0.90 moles per mole of M’.
  • the Ni component of M’ is less than or equal to 0.95 moles per mole of M’.
  • the nominal or overall formulated composition of the secondary particles for example, characterized by Inductively Coupled
  • Plasma (ICP) optionally the first composition, or optionally the second composition, is defined by the nominal formula LiMC , wherein M is Ni and optionally one or more substitution elements that in the second composition must include at least one element substituting for Ni in the crystal structure that imparts greater electrochemical affinity for Li to the second composition relative to the first composition.
  • the mole fraction of the substitution element in the first composition if present, as defines the composition of the crystallites is lower than the mole fraction of the total substitution element(s) independently or combined in the total particle composition as determined by ICP.
  • the mole fraction of the substitution element independently or combined in the first composition can be zero.
  • the mole fraction of the substitution element in the second composition independently or combined as defines the grain boundary is higher than the mole fraction of the substitution element(s) independently or combined in the total particle as measured by ICP.
  • substitution elements that can potentially be included in M’ in Formula II and promote the retention of Li in the grain boundaries of charged high-Ni LiMCh cathode materials include a variety of elements that can substitute for Ni in the LiM’Ch structure.
  • Such doping elements can promote Li retention (i.e. greater electrochemical affinity for Li) by being more resistant to oxidation (having higher oxidation potential) than the Ni atoms they are substituting for, by stabilizing the structure to oxidation, or by inductively raising the oxidation potential of nearby Ni atoms.
  • trivalent (3+) ions of doping elements that can directly substitute for Ni 3+ are less easily oxidized than the Ni ions when the material is charged, they will promote Li retention; substitution of Ni(III) by Al(III) is an example. If tetravalent (4+) ions substitute for Ni 3+ , they are charge-compensated by Ni ions in the 2+ state and their inductive effects raise the potential for oxidation of those Ni ions to the 4+ state; substitution of Ni(III) by Mn(IV) is an example. Alternatively, if difficult to oxidize 2+ ions substitute for Ni, they are charge-compensated by Ni ions in the 4+ state; substitution of Ni(III) by Mg (II) is an example.
  • doping ions In order to substitute for Ni in the LiM’Ch structure, doping ions must be of size comparable to that of the Ni ions, and in order to facilitate retention of Li, they must raise the local oxidation potential.
  • the relative impact of a given ion’s impact on the oxidation potential can often be estimated from its ionization energy relative to that of Ni 3+ . Therefore, ions of size comparable to Ni 3+ and having comparable or higher ionization energy can potentially serve to stabilize oxidized cathodes’ grain boundaries by increasing their retention of Li.
  • the following table provides the ionization energies and hexacoordinate (octahedral environment) ionic radii for examples of ions that might stabilize the grain boundaries of charged high-Ni L1MO2 cathode materials by increasing the grain boundaries’ retention of Li.
  • M’ further includes one or more substitution elements that may be selected from a group that oxidize less than nickel when electrochemically charged to 4.3V or higher relative to Li metal anode.
  • M’ can comprise Ni and a combination of Co and Mn, which oxidizes less than nickel when charged to 4.3 V.
  • M’ may include Ni and one more elements selected from the group comprising Mn, Cr, Fe, Ti, V, Co, Cu, Zn, Zr, Nb, Sb, W, Sc, Al, Mo, Y, etc., which oxidize less than Ni when charged to 4.3 V relative to lithium metal.
  • M’ excludes the combination of Ni with Co alone, Al alone, or a combination of Co and Al, and Co, Al, or both may be present with doping of one or more additional substitution elements as provided herein.
  • M’ may include an element selected from the group of elements that will not oxidize when charged to 4.3 V relative to lithium such as Y, Sc, Ga, In, Tl, Si, Ge, Sn, Pb, etc.
  • 4.3V is chosen as a representative example only.
  • the voltage can also be lower (e.g. 4.0, 4.1, 4.2, etc. vs. Li) or higher (4.35, 4.4, 4.5 V, 4.6V, 4.7V vs. Li). Specific voltage of interest would depend on the operating potential of the battery when the cathode is paired with the anode.
  • the second composition of the grain boundaries has greater electrochemical affinity for Li such that when an electrode incorporating the particle is charged to a potential greater than or equal to 4.1 V versus lithium, optionally greater than or equal to 4.2 V versus lithium, optionally greater than or equal to 4.3 V versus lithium, the grain boundary retains greater than 0.15 moles of lithium per mole of the second composition at said potential.
  • the second composition of the grain boundaries has greater electrochemical affinity for Li such that when an electrode incorporating the particle is charged to a capacity of 100 mAh/g or greater, optionally 200 mAh/g or greater, the grain boundary retains greater than 0.15 moles of lithium per mole of the second composition at said potential.
  • the second composition comprises lithium in an amount of about 0.1 to about 1.3 moles, specifically about 0.15 to about 1.2 moles, more specifically about 0.3 to about 1.1 moles, per mole of the second composition; nickel in an amount of about 0.1 to about 0.999 mole, specifically about 0.2 to about 0.90 mole, more specifically about 0.3 to about 0.85 mole, per mole of the second composition; manganese in an amount of about 0.02 to about 0.99 mole, specifically about 0.04 to about 0.90 mole, more specifically about 0.06 to about 0.80 mole, per mole of the second composition; and oxygen in an amount of about 1.7 to about 2.3 moles, specifically about 1.8 to about 2.2 moles, more specifically about 1.9 to about 2.1 moles per mole of the second composition.
  • the second composition may further comprise an additional metal, and the additional metal of the second composition may be present in an amount of about 0.01 to about 0.9 mole, specifically about 0.05 to about 0.8 mole, more specifically about 0.1 to about 0.7 mole, per mole of the second composition.
  • the additional metal of the second composition may be present in an amount of about 0.01 to about 0.2 mole, specifically about 0.02 to about 0.18 mole, more specifically about 0.04 to about 0.16 mole, per mole of the second composition.
  • the additional metal of the second composition may include Mg, Sr, Ca, Cu, Zn,
  • the additional metal of the second composition includes Mg, Al, V, Ti, B, Zr, or Mn, or a combination thereof.
  • the additional metal of the second composition includes of Mg, Al, V, Ti, B, Zr, or
  • the additional metal of the second composition is Mn or Mg is specifically mentioned.
  • the additional metal of the first composition and the additional metal of the second composition are each Mg.
  • the first composition further comprises Mn, and the Mn is present in the first composition in an amount of about 0.01 to about 0.6 mole, specifically about 0.02 to about 0.5 mole, per mole of the first composition, and the second composition comprises Mn, and the Mn is present in the second composition in an amount of about 0.01 to about 0.6 mole, specifically about 0.02 to about 0.5 mole, per mole of the second composition.
  • the grain boundary is between adjacent crystallites, is on a surface of the crystallite, and comprises or consists of the second composition.
  • the second composition has the layered a-NaFeCh-type structure, a cubic structure, a monoclinic structure, or a combination thereof.
  • the grain boundary includes at least one substitution element such that the electrochemical affinity for Li of the second composition is greater than that of the first composition as found in the bulk crystallites.
  • An embodiment in which the grain boundaries include or consist of a layered a-NaFeCh-type structure is specifically mentioned.
  • the shape of the grain boundary is defined by the shape of the crystallite adjacent to the grain boundary.
  • the shape of the grain boundary may approximate a geometric shape.
  • the grain boundary may have a rectilinear shape, and when viewed in cross-section the grain boundary may be rectilinear.
  • the grain boundary may be square, hexagonal, rectangular, triangular, or a combination thereof.
  • a direction of a surface of the grain boundary corresponds to a direction of a surface of the adjacent crystallite(s).
  • the surface of the grain boundary and the surface of the crystallite may have any of a variety of orientations relative to an outer surface of the secondary particle.
  • the direction of the surface of the crystallite and the direction of the surface of the grain boundary may be parallel to or be different from the direction of a nearest outer surface of the secondary particle.
  • a direction of a tangent of the nearest outer surface of the particle is different than the direction of the surface of the grain boundary and the direction of the surface of the adjacent particle.
  • the grain boundaries may intersect to form an angle therebetween.
  • disposed on adjacent faces of a crystallite is a first grain boundary and second grain boundary.
  • the first grain boundary and the second grain boundary intersect at an angle E.
  • the angle E may be defined by the shape of the crystallite on which the first grain boundary and the second grain boundary are disposed.
  • a shape of a crystallite is influenced by a crystal structure of the crystallite. While not wanting to be bound by theory, it is understood that because the crystal structure of the first composition governs the shape of the crystallite, the angle between the first and second grain boundaries is influenced by the crystal structure of the first composition.
  • the first and second grain boundaries may intersect at any angle, specifically an angle of about 10 to about 170 degrees, specifically about 20 to about 160 degrees, more specifically about 30 to about 150 degrees, so long as the angle is consistent with the crystal structure of the first composition.
  • a length and a width of the grain boundary may each independently be about 10 to about 1000 nm, specifically about 60 to about 900 nm, more specifically about 70 to about 800 nm.
  • the length and width of the grain boundaries are perpendicular to each other and are parallel to the surface of the adjacent crystallite(s).
  • a thickness of the grain boundary may be about 0.5 to about 30 nm, specifically about 1 to about 20 nm, more specifically about 1 to about 10 nm.
  • the thickness of the grain boundary is substantially perpendicular to the length and the width of the grain boundary and may be perpendicular to the surface of the adjacent crystallite.
  • the composition of the grain boundary may be substantially uniform or may vary along the thickness.
  • An average grain boundary length and an average grain boundary width of the plurality of grain boundaries may each independently be about 10 to about 1000 nm, specifically about 60 to about 900 nm, more specifically about 70 to about 800 nm. Also, an average grain boundary thickness of the plurality of grain boundaries may be about 0.1 to about 30 nm, specifically about 1 to about 20 nm, more specifically about 1 to about 10 nm.
  • a particle as provided herein includes an outer coating such as a passivation layer or a protective layer that may be deposited on an outer surface of the secondary particle to provide a coated secondary particle.
  • the coating may fully or partially cover the secondary particle.
  • the outer coating layer may be amorphous or crystalline.
  • the outer coating layer may comprise an oxide, a sulfate, a phosphate, a pyrophosphate, a fluorophosphate, a carbonate, a fluoride, an oxyfluoride, or a combination thereof, of a metal such as Zr, Al, Ti, Al, B, or Si, or a combination thereof.
  • the outer coating layer includes a borate, an aluminate, a silicate, a fluoroaluminate, or a combination thereof.
  • the outer coating layer comprises a carbonate.
  • the layer comprises Zr02, AI2O3, T1O2, AIPO4, AIF3, B2O 3 , S1O2, L12O, L12CO 3 , or a combination thereof.
  • a layer comprising AIPO4 or L12CO 3 is specifically mentioned.
  • an outer coating layer includes oxide of one or more elements selected from Al, Zr, Y, Co, Ni, Mg, and Li.
  • an outer coating layer includes a fluoride comprising one or more elements selected from Al, Zr, and Li.
  • an outer coating layer includes a carbonate comprising one or more elements selected from Al, Co, Ni, Mn, and Li.
  • an outer coating includes a sulfate comprising one or more elements selected from Al, Co, Ni, Mn, and Li.
  • an outer coating includes a phosphate comprising one or more elements selected from A1 and Li.
  • the layer may be deposited by any process or technique that does not adversely affect the desirable properties of the secondary particle. Representative methods include spray coating and immersion coating, for example.
  • a secondary particle may be formed by a multi-step process whereby a first composition particle is formed and calcined so as to establish the formation of defined grain boundaries optionally with the crystallites having a-NaFeCh structure with few defects.
  • the resulting secondary particles are then subjected to a liquid process that applies one or more substitution elements at the desired concentration levels followed by drying and then a second calcination so as to move the substitution element precipitated species at the surface selectively into the grain boundaries to thereby form the secondary particle with a stabilized grain boundary that has a higher electrochemical affinity for Li than the bulk 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 950 °C for about 0.1 to about 20 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 by a method so as to result in stabilized grain boundaries following a second calcination.
  • a process to stabilize grain boundaries and create a greater grain boundary electrochemical affinity for Li than the crystallites within a primary particle may be performed by suspending the product of the first calcination in an aqueous slurry comprising one or more substitution elements and a lithium compound optionally at a temperature of about 60 degrees Celsius whereby the substitution element(s) is present in the aqueous solution at the concentrations as desired so as to result in stabilization.
  • the slurry may then be spray dried to form a free-flowing powder that is then subjected to a second calcination optionally with a heating curve following a two-step ramp/dwell process.
  • a substitution element(s) may be dispersed in a non-aqueous solvent along with suspended polycrystalline material.
  • the non-aqueous solvent can be removed by evaporation with the substitution elements precipitated out on the surface of the poly crystalline material that is then subjected to a second calcination optionally with a heating curve following a two-step ramp/dwell process.
  • the first of the two ramp/dwell temperature profiles may be from ambient (about 25 degrees Celsius) to 450 degrees Celsius and optionally at a rate of 5 degrees Celsius per minute with a
  • the second ramp/dwell step may be from 450 degrees Celsius to a maximum temperature at a rate of 2 degree Celsius per minute with a
  • the maximum temperature is less than or equal to about 850 degrees Celsius.
  • cathodes for a lithium-ion battery comprising the secondary particle.
  • the cathode comprises the secondary particle disclosed above as an active material, and may further include a conductive agent and a binder.
  • the conductive agent may include any conductive agent that provides suitable properties and may be amorphous, crystalline, or a combination thereof.
  • the conductive agent may comprise a carbon black, such as acetylene black or lamp black, a mesocarbon, graphite, carbon fiber, carbon nanotubes such as single wall carbon nanotubes or multi-wall carbon nanotubes, or a combination thereof.
  • the binder may include any binder that provides suitable properties and may comprise 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 styrene
  • the cathode may be manufactured by combining the secondary particle, the conductive agent, and the binder in a suitable ratio, e.g., about 80 to about 98 weight percent of the secondary particle, about 2 to about 20 weight percent of the conductive agent, and about 2 to about 10 weight percent of the binder, based on a total weight of the secondary particle, the conductive agent, and the binder.
  • the secondary particle, the conductive agent, and the binder may be suspended in a suitable solvent, such as N-methylpyrrolidone, and disposed on a suitable substrate, such as aluminum foil, and dried in air.
  • 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 graphitized mesocarbon such as a mesocarbon microbead, for example.
  • the anode may also include lithium metal or a material capable of alloying (e.g. Si, Ge, etc.) or conversion reactions (e.g. metal oxides or sulfides) with lithium.
  • the anode maybe be titanium containing materials such as lithium titanate spinel (LuTisOii), or titanium niobium oxide or titanium niobium tungsten oxide or titanium oxide.
  • the current collector may be copper foil or nickel foil or titanium foil or aluminum 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, methyl butyrate, 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, L1BF4, LiAsFe, LiCIC , UCF3SO3, Li(CF 3 S02)2N, LiN(S02C 2 F 5 )2, LiSbFe, LiC(CF 3 SC>2) 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 2.0 M in the electrolyte.
  • the electrolyte may be a solid ceramic electrolyte.
  • Example 1 Preparation and testing of Li1.n1Mgn.n1Nin.9nC0n nsYn.n2O2
  • a polycrystalline base material with overall composition Li1.01Mg0.01Ni0.92Co0.08O2 was synthesized by standard solid-state synthesis techniques. 2.7 grams (g) yttrium nitrate hexahydrate (Y(N03)3 ⁇ ⁇ EEO) (99.9% Alfa Aesar, Ward Hill, MA) was dissolved into 30 milliliters (ml) of 40 °C methanol in a glass beaker. Once dissolved, 35 grams (g) of polycrystalline base material (Li1.01Mg0.01Ni0.92Co0.08O2) was added to the solution. The solution was stirred for 3 minutes to ensure the base was distributed in the methanol solution. The methanol was removed from the solution by evaporation on a rotary evaporator at 40 degrees Celsius (°C) and 20 mmHg.
  • Y(N03)3 ⁇ ⁇ EEO 99.9% Alfa Aesar, Ward Hill, MA
  • the dry powder was placed in an alumina crucible and calcined. Calcination was performed by heating at a rate of 5 °C per minute to about 130 °C and then holding at about 130 °C for about six hours. The temperature was then raised at about 5° C per minute to about
  • the material as synthesized above was cast into cathode electrodes.
  • the material was first mixed with PVdF, conductive carbon, and NMP solvent to prepare an electrode slurry.
  • the electrode slurry was coated on to aluminum foil using a doctor blade approach.
  • the coated foil was dried at 130 °C to drive off the NMP leaving behind a coated electrode.
  • the electrode was then pressed, punched, and assembled into coin cells with Li metal anode (half cells) or with graphite anode (full cells), and tested.
  • Table 3 shows the half-cell results for the Example 1 and Comparative example 1 electrodes tested between 4.3 Volts (V) - 3.0 V, showing that treatment with yttrium does not significantly change the discharge capacity as measured in half cells.
  • Figure 7 and Figure 8 show the full cell results of accelerated cycle life measurements carried out at 45 °C. Material with yttrium exhibits more stable cycling and much reduced impedance increase compared to the base material. Presence of yttrium in the grain boundary region enhances lithium retention at the end of charge, and thereby reduces the damage to the material resulting in improved cycle life at 45 °C. Capacity retention and rate of impedance growth during accelerated cycle life testing at 45 °C are shown in Figure 7 and Figure 8, respectively.
  • Table 3 Electrochemical capacity (mAh/g) of powders prepared in Example 1
  • Example 2 Preparation and testing of Li1.01Mg0.01Ni0.87Co0.11Fe0.02O2 [00103] 0.61 g iron acetate (Fe(C2H302)2) (Alfa Aesar, Ward Hill, MA) and 3.08 g cobalt nitrate hexahydrate (Co(N03)2 ⁇ 6H2O) were dissolved into 30 ml of 40 °C methanol in a glass beaker. Once dissolved, 35 g of Base (Li1.01Ni0.92Co0.08Mg0.01O2) was added to the solution. The solution was stirred for 3 minutes to ensure the base was distributed in the methanol solution. The methanol was removed from the solution by evaporation on a rotary evaporator at 40 °C and 20 mmHg.
  • the dry powder was placed in an alumina crucible and calcined. Calcination was performed by heating at a rate of 5 °C per minute to about 130 °C, and held at about 130 °C for about six hours. The temperature was then raised at about 5 °C per minute to about 450 °C, and held for about 1 hour. The temperature was then raised at about 2 °C per minute to 700 °C and held at about 700 °C for two hours. The sample was then allowed to cool naturally to room temperature.
  • Li1.01Mg0.01Ni0.87Co0.11Fe0.02O2 cathode material was electrochemically tested along with the untreated base material control with Li1.01Ni0.92Co0.08Mg0.01O2 composition in full coin cells opposite a graphite anode, 1M L1PF6 in 1 : 1 : 1 EC:DMC:EMC with 1% VC (EDEV1) electrolyte, and a polymer separator.
  • Full coin cells were cycled between 2.7 and 4.2 V at 45 °C using accelerated charge and discharge rates.
  • Figure 9 and Figure 10 show the rate of capacity fade and impedance increase, respectively, during the accelerated cycle life testing.
  • Example 3 Preparation of Lii.oiMgo.oiNio.8975Coo.o897Mno.oi28C>2.
  • a coating with 1/1/1 Ni/Co/Mn composition was formulated for grain boundary enrichment.
  • a L1MO2 material with this composition is expected to have 37% of the lithium retained when it is charged to 4.3V vs. Li.
  • the base material used was Li1.01Mg0.01Ni0.92Co0.08O2.
  • a solution of 200 ml water was made with manganese nitrate tetrahydrate (6.78 g), nickel nitrate heptahydrate (8.34 g), cobalt nitrate hexahydrate (7.86 g) and lithium nitrate (2.85 g) and was heated to 60 °C.
  • Table 4 Summary of physico-chemical characterization of materials prepared with grain boundary region having the composition LiNiCoMnCh.
  • Example 4 Preparation of Lii.oiMgo.oiNio.8975Coo.o769Alo.oi28Mno.oi28C>2.
  • a polycrystalline base cathode material with overall composition Li1.01Mg0.01Ni0.92Co0.08O2 (base material) was synthesized by standard solid-state synthesis techniques. The grain boundaries of base material were then fortified with elements which, in combination with nickel, still form a layered 2D a-NaFe02 structure, but which exhibit a significantly reduced degree of oxidation at 4.3 V. Incorporation of these elements, specifically A1 and Mn demonstrated promotion of Li retention.
  • the overall composition of this A1 and Mn-grain-boundary-enriched material (referred to as NAM111 enriched) was Lii.oiMgo.oiNio.8975Coo.o769Alo.oi28Mno.oi2802. The material was synthesized according to the following procedure.
  • a solution of 100 ml water was made with manganese nitrate tetrahydrate (3.38 g), nickel nitrate heptahydrate (3.92 g), aluminum nitrate nonahydrate (5.05 g) and lithium nitrate (1.42 g) and was heated to 60 °C. To this was added 100 g of the base material and the dispersion was stirred for 20 minutes. The dispersion was then spray dried to generate a free- flowing powder. This powder was then calcined at 700 °C for two hours (NAM111 enriched) under a flow of CCh-free air.
  • NAM111 enriched The polycrystalline cathode material, NAM111 enriched, was then analyzed to confirm that the grain boundaries were indeed enriched in A1 and Mn.
  • a 100 nm thick section of the polycrystalline particle of NAM111 enriched was prepared using focused ion beam milling. EDS line scans were performed across two different grain boundaries at the indicated locations in Figure 3.
  • Figure 4 A and B shows the atomic ratios of aluminum, manganese and cobalt relative to nickel across these grain boundaries. As can be seen, there is clear enrichment of aluminum and manganese at these grain boundaries, but not cobalt. That is, the concentration of manganese at the grain boundaries is higher than the concentration of manganese in the crystallites. Also, the concentration of aluminum in the grain boundaries is higher than the concentration of aluminum in the crystallites.
  • Figure 4 C and D illustrate the atomic percent of nickel relative to the total atomic content of nickel, aluminum, manganese and cobalt across these grain boundaries. As can be seen, the concentration of nickel at the grain boundaries is lower than the concentration of nickel in the crystallites.
  • Example 5 Preparation of Lii.oiMgo.oiNio.9038Coo.o769Mno.oi92C>2.
  • Li1.01Mg0.01Ni0.92Co0.08O2 (base material) of Example 3 and 4 was used for the synthesis of the
  • Ni and Mn grain boundary enriched material (referred to as NMl 1 Enriched), with an overall final composition of Lii.oiMgo.oiNio.9038Coo.o769Mno.oi9202.
  • the material was synthesized according to the following procedure.
  • a solution of 100 ml water was made with manganese nitrate tetrahydrate (5.90 g), nickel nitrate heptahydrate (5.09 g), and lithium nitrate (1.42 g) and was heated to 60 °C. To this was added 100 g of the base material and the dispersion was stirred for 10 minutes. The dispersion was then spray dried to generate a free-flowing powder. This powder was then calcined at 700 °C for two hours under a flow of CCte-free air.
  • Example 6 Electrochemical testing of NMC111, NAM111, and NM11 Grain Boundary Enriched Materials.
  • Cathode electrodes with NCM111 enriched - sample 1 described in Example 3, Base Material and NAM111 Enriched material described in Example 4, and NM11 Enriched Material of Example 5 were prepared and electrochemically tested.
  • Cathode active materials were first mixed with PVdF binder, conductive carbon, and NMP solvent to prepare an electrode slurry.
  • the electrode slurry was coated onto aluminum foil using a draw down table. The coated foil was dried at 130 °C to drive off the NMP leaving behind a coated electrode. The electrode was then pressed, punched, and assembled into coin cells with Li metal anode (half cells) or with graphite anode (full cells), and tested.
  • Example 7 XRD Analysis of the charged grain boundary-enriched materials.
  • Figure 5 shows x-ray diffraction data for the homogeneous Li1.01Mg0.01Ni0.92Co0.08O2 base material and NCM111 grain boundary enriched material of Example 3 with the overall composition of Li 1.0 iMgo.oiNio.8975Coo.o897Mno.oi2802 (Sample 1).
  • Cathode electrodes coated on A1 current collectors were X-rayed either fresh or charged to 4.3V vs. Li. Electrodes were charged in coin cells opposite a Li metal counter electrode. Charged electrodes were harvested, washed, and dried prior to x-ray diffraction.
  • X-ray diffraction spectra were collected using a continuous scan between 12 and 120 degrees in 2- theta at 0.75 degrees/min using an automated Shimadzu XRD-6000 diffractometer with a Cu X-ray tube.
  • the two cathode materials have essentially identical diffractograms, and many of the peaks for both materials shift to significantly higher 20 values when they are charged.
  • the low 2Q shoulder for the charged grain boundary-modified Lii.oiMgo.oiNio.8975Coo.o897Mno.oi2802 cathode in Figure 6 is an indication that it retains more Li in its grain boundaries than in its bulk crystallites when it is charged.
  • Example 8 Preparation of Li1.01Mg0.01Ni0.90Co0.08Nd0.02O2.
  • a polycrystalline grain boundary enriched material with overall composition of Li1.01Mg0.01Ni0.90Co0.08Nd0.02O2 was synthesized as follows: 2.7 grams (g) neodymium nitrate hexahydrate (Nd(N03)3 ⁇ 6H2O) (99.9% Sigma Aldrich Milwaukee, WI) was dissolved into 30 milliliters (ml) of 40 °C methanol in a glass beaker. Once dissolved, 30 grams (g) of polycrystalline base material (Li1.01Mg0.01Ni0.92Co0.08O2) was added to the solution. The solution was stirred for 3 minutes to ensure the base was distributed in the methanol solution. The methanol was removed from the solution by evaporation on a rotary evaporator at 40 degrees Celsius (°C) and 20 mmHg.
  • the dry powder was placed in an alumina crucible and calcined. Calcination was performed by heating at a rate of 5 °C per minute to about 130 °C and then holding at about 130 °C for about six hours. The temperature was then raised at about 5° C per minute to about 450 °C and then holding for about 1 hour. The temperature was then raised at about 2 °C per minute to 700 °C and held at about 700 °C for two hours. The sample was then allowed to cool naturally to room temperature.
  • Example 9 Preparation of Li1.01Mg0.01Ni0.90Co0.08Ga0.02O2.
  • a polycrystalline grain boundary enriched material with overall composition of Li1. 01 Mg 0.01 Ni 0.90 Co 0.08 Ga 0.02 O2 was synthesized as follows:. 1.55 grams (g) gallium nitrate hydrate (Ga(N03)3 ⁇ H2O) (99.999% Sigma Aldrich Milwaukee, WI) was dissolved into 30 milliliters (ml) of 40 °C ethanol in a glass beaker. Once dissolved, 30 grams (g) of polycrystalline base material (Li1. 01 Mg 0.01 Ni 0.92 Co 0.08 O2) was added to the solution. The solution was stirred for 3 minutes to ensure the base was distributed in the methanol solution. The methanol was removed from the solution by evaporation on a rotary evaporator at 40 degrees Celsius (°C) and 20 mmHg.
  • the dry powder was placed in an alumina crucible and calcined. Calcination was performed by heating at a rate of 5 °C per minute to about 130 °C and then holding at about 130 °C for about six hours. The temperature was then raised at about 5° C per minute to about 450 °C and held there for about 1 hour. The temperature was then raised at about 2 °C per minute to 700 °C and held at about 700 °C for two hours. The sample was then allowed to cool naturally to room temperature.
  • Example 10 Preparation of Li1.01Mg0.01Ni0.90Co0.08B0.02O2.
  • a polycrystalline grain boundary enriched material with overall composition of Li1. 01 Mg 0.01 Ni 0.90 Co 0.08 B 0.02 O2 was synthesized as follows:. 0.21 grams (g) boron trioxide (B2O 3 ) (99% Sigma Aldrich Milwaukee, WI) was dissolved into 40 milliliters (ml) of 40 °C methanol in a glass beaker. Once dissolved, 30 grams (g) of polycrystalline base material (Li1. 01 Mg 0.01 Ni 0.92 Co 0.08 O2) was added to the solution. The solution was stirred for 3 minutes to ensure the base was distributed in the methanol solution. The methanol was removed from the solution by evaporation on a rotary evaporator at 40 degrees Celsius (°C) and 20 mmHg.
  • B2O 3 boron trioxide
  • the dry powder was placed in an alumina crucible and calcined. Calcination was performed by heating at a rate of 5 °C per minute to about 130 °C and then holding at about 130 °C for about six hours. The temperature was then raised at about 5° C per minute to about 450 °C and then held there for about 1 hour. The temperature was then raised at about 2 °C per minute to 700 °C and held at about 700 °C for two hours. The sample was then allowed to cool naturally to room temperature.
  • Example 11 Preparation of Li1.01Mg0.01Ni0.90Co0.08Fe0.02O2.
  • a grain boundary enriched material with overall composition of Li1.01Mg0.01Ni0.90Co0.08Fe0.02O2 was synthesized as follows:. 1.23 grams (g) iron acetate anhydrous (Fe(OOCFb)2) (99.9% Alfa Aesar, Ward Hill, MA) was dissolved into 30 milliliters (ml) of 40 °C methanol in a glass beaker. Once dissolved, 35 grams (g) of poly crystalline base material (Li1.01Mg0.01Ni0.92Co0.08O2) was added to the solution. The solution was stirred for 3 minutes to ensure the base was distributed in the methanol solution. The methanol was removed from the solution by evaporation on a rotary evaporator at 40 degrees Celsius (°C) and 20 mmHg.
  • the dry powder was placed in an alumina crucible and calcined. Calcination was performed by heating at a rate of 5 °C per minute to about 130 °C and then holding at about 130 °C for about six hours. The temperature was then raised at about 5° C per minute to about 450 °C and then holding for about 1 hour. The temperature was then raised at about 2 °C per minute to 700 °C and held at about 700 °C for two hours. The sample was then allowed to cool naturally to room temperature.
  • Example 12 Electrochemical testing of cathode materials of Examples 1 and 8 to 11.
  • Cathode active materials of Example 1, 8, 9, 10, and 11 were formulated into cathode electrodes. Materials were first mixed with PVdF, conductive carbon, and NMP solvent to prepare an electrode slurry. Electrode slurries were then coated on to aluminum foil using a doctor blade approach. The coated foils were dried at 130 °C to drive off the NMP leaving behind coated electrodes. Electrodes were then pressed, punched, and assembled into coin cells with Li metal counter electrodes, polymer separator, and carbonate electrolyte. Half cells were then tested for capacity and rate capability (charged to 4.3V and discharged to 3.0V). Electrochemical performance data for the enriched materials and the un-enriched poly crystalline base material are shown in Table 5.
  • Table 5 Electrochemical performance of materials described in Examples 1, 8, 9, 10, and 11. Capacity normalized by the weight of active 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.
  • NCA material having a first composition of various amounts ofNi, Co, and A1 (atomic ratio 86: 12:2, 89:8:3, or 93 :4:3, respectively) were prepared from co-precipitated precursor transition metal hydroxide containing the appropriate amounts of Ni, Co and Al.
  • 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 NCM or NCA transition metal hydroxide precursors and the two were 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 sieved powder was then divided into base (no further treatment) or grain- boundary-enriched with Co and Al by making a solution of 200 g water, 11.9 g cobalt nitrate (2 at% Co relative to the total metal content of the base composition), 3.1 g aluminum nitrate (0.4 at% A1 relative to the total metal content of the base composition), 3.4 g lithium nitrate and heating to 60 °C. To this was added 200 g of the previously prepared lithiated precursor powder (base materials). 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 resulting base or grain boundary enriched particles were crushed in a 2 cm diameter die in a hydraulic press to the desired pressure. A total mass of 2.5 g of powder was placed in the die and crushed to form a pellet. The pellet was then placed in 20 mL of water and subjected to ultrasonic dispersion for 30 minutes. Once dispersed, a small portion of the dispersed slurry was tested on a Malvern Mastersizer 3000 laser-light particle size instrument equipped with a liquid cell. To ensure full dispersion of fines, the ultrasonic function was used during the measurement and an average of 5 measurements were used to calculate the final result. The particle distribution was calculated using properties for NiO taken from the instrument library. The results of this process using the exemplary NCM811 material with or without Ni poor grain boundary regions are illustrated in FIG. 13.
  • 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. [00140] The foregoing description is illustrative of particular aspects of the invention, but is not meant to be a limitation upon the practice thereof.

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Abstract

L'invention concerne des particules électrochimiquement actives appropriées pour être utilisées comme matériau actif dans une cathode d'une cellule électrochimique au lithium-ion qui comprennent : une pluralité de cristallites comprenant une première composition contenant du lithium, du nickel et de l'oxygène ; et une limite de grain entre des cristallites adjacents de la pluralité de cristallites et comprenant une seconde composition contenant du lithium, du nickel et de l'oxygène ; la limite de grain ayant une affinité électrochimique plus élevée pour le lithium que les cristallites. L'affinité électrochimique plus élevée pour le Li conduit à une rétention de Li accrue dans les limites de grain pendant la charge par rapport aux cristallites en vrac et stabilise la structure des limites de grain et des cristallites pour une stabilité de cyclage améliorée sans perte sensible de capacité.
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US16/728,379 US11424449B2 (en) 2019-01-25 2019-12-27 Stable cathode materials
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