EP4358830A1 - Nouvelle stratégie de dopage pour matériaux d'électrode d'oxyde en couches utilisés dans des batteries au lithium-ion - Google Patents

Nouvelle stratégie de dopage pour matériaux d'électrode d'oxyde en couches utilisés dans des batteries au lithium-ion

Info

Publication number
EP4358830A1
EP4358830A1 EP22829440.1A EP22829440A EP4358830A1 EP 4358830 A1 EP4358830 A1 EP 4358830A1 EP 22829440 A EP22829440 A EP 22829440A EP 4358830 A1 EP4358830 A1 EP 4358830A1
Authority
EP
European Patent Office
Prior art keywords
salt
composition
hydroxide precursor
ranges
solution
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
EP22829440.1A
Other languages
German (de)
English (en)
Inventor
Huolin XIN
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.)
University of California
Original Assignee
University of California
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 US17/358,460 external-priority patent/US20220336802A1/en
Priority claimed from US17/508,540 external-priority patent/US11728482B2/en
Application filed by University of California filed Critical University of California
Publication of EP4358830A1 publication Critical patent/EP4358830A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • 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
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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
    • C01P2002/89—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by mass-spectroscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

  • the invention relates to a composition for a new positive electrode material more particularly to a composition used in a lithium ion battery that has high energy density, long life cycle and reduced reliance on the toxic cobalt.
  • the cathode materials can have high capacity and high energy density.
  • LiNi033Mn033Co033O2 has been commercialized and widely deployed in battery packs in electric vehicles.
  • materials with higher Ni content such as LiNi05Mn03Co02O2, LiNi06Mn02Co02O2, and LiNi08Mn01Co01O2 have been developed and are on the verge of market penetration.
  • all five of these materials have Co, which is undesired.
  • Cobalt has been widely considered essential for the whole class of layered oxide materials.
  • LiNi096Ti00 2 Mg00 2 O 2 (ref: Chemistry of Materials 31 (23), 9769-9776).
  • LiNi0 2 material one of the problems with LiNi0 2 material is that it at high charge voltages between 4.2- 4.4 voltage (at >75% of delithiation), it has an undesired H2 to H3 two-phase transition, i.e., the oxygen lattice in the material will transform from a cubic close packed structure to a hexagonal close packed structure.
  • a recent electron microscopy study showed that the stacking fault formed in the H3 phase accelerates the oxygen release.
  • LiNi096Ti00 2 Mg00 2 O 2 co-doping with 2% of Ti and 2% Mg is not sufficient to fully eliminate the two-phase transition.
  • LiNi096Ti00 2 Mg00 2 O 2 co-doping with 2% of Ti and 2% Mg is not sufficient to fully eliminate the two-phase transition.
  • Lii+ X Mi- c q lithium-rich materials
  • this class of materials is known to have a short life cycle.
  • This class of materials after surface passivation can have much improved capacity retention.
  • one of the unsolved problems of this material is that it has a rapid voltage fading problem. Basically, even though the capacity retention is good, the energy retention of these materials is still poor.
  • Low-cost elements such as Titanium (Ti), Molybdenum (Mo), Zinc (Zn) and more expensive elements such as Niobium (Nb), Yttrium (Y), Zirconium (Zr), Scandium (Sc), Vanadium (V), and Chromium (Cr) can stabilize the surface rock salt layer for N ⁇ -, Mn-, and Co- containing layered oxides. These elements can improve oxygen retention on the surface of lithium-containing layered oxides.
  • Yttrium (Y), Boron (B), Magnesium (Mg), Titanium (Ti), Tungsten (W), Antimony (Sb), Tantalum (Ta), and Aluminum (Al) can also improve the thermal stability of LiNiC and in principle have oxygen retaining effects in LiNi0 2 .
  • these elements tend to intermix with lithium, reducing battery capacity when doped above the 2% doping threshold. Therefore, it is difficult to use a single dopant to acquire the desired oxygen retention effect.
  • a second consideration is based on reducing strain and impeding the development of defects in the layered material, particularly when they are charged to high voltages. During that charging process, lithium is extracted from the cathode material, and undesired strain and defects are developed due to volume change and phase transformation.
  • Embodiments of the invention are given in the dependent claims. Embodiments of the present invention can be freely combined with each other if they are not mutually exclusive.
  • the present invention features a composition that may be used in a cathode for a battery, such as a lithium ion battery.
  • the composition is according to the formula: Li a Ni b Dl Xl D2 Xz ... Dn X i 0 2 .
  • “a” ranges from 1 to 1.04.
  • “b” ranges from 0.33 to 0.95.
  • n is greater than or equal to 5.
  • Dn are impurity doping elements that are not nickel (Ni).
  • D1 , D2. Dn may be different impurity doping elements selected from the following elements:
  • Mn Ti, Mg, Mo, Nb, Al, Zr, Cr, V, Y, Sc, B, W, Sb, Co, Fe, and Ta.
  • the composition may be according to one of the following formulas: i) LiaNibMn c TidMg e M0fNbgOh, or ii) LiaNibMncAljZrkCnVmOh.
  • a ranges from about 1 to 1 .03
  • b ranges from about 0.33 to 0.95
  • c ranges from about 0.01 to 0.666
  • m each ranges from about 0.001 to 0.025
  • h ranges from about 1 .9 to 2.1 .
  • Non-limiting examples of the composition include LiNi09Mn003Ti002Mg002Mo002Nb001O2, LiNi08Mn013Ti002Mg002Mo002Nb001 O2, LiNi07Mn023Ti002Mg002Mo002Nb001O2, LiNi06Mn033Ti002Mg002Mo002Nb001 O2, LiNi05Mn043Ti002Mg002Mo002Nb001O2, and LiNi08Mn013AI002Zr002Cr002V001O2.
  • the composition used in a lithium-excess cathode for a lithium ion battery is represented by a formula: Li 1+a) Mn b Ni c Dl Xi D2 X2 ... Dn Xn 0 2 .
  • a ranges from 0.01 to 0.33.
  • b ranges from 0.45 to 0.65.
  • c ranges from 0.09 to 0.15.
  • n is greater than or equal to 5.
  • Dn are impurity doping elements that are not Mn or Ni.
  • Dn may be different impurity doping elements selected from the following elements: Ti, Mg, Mo, Nb, Al, Zr, Cr, V, Y, Sc, B, W, Sb, Co, Fe, and Ta.
  • the composition may be according to the following formula: LiaMnbNicCodTieMofNbgTahSbiOj.
  • the ratios of elements ranges as follows: a from about 1 .10 to 1 .2; b from about 0.45 to 0.65; c from about 0.09 to 0.15; d from about 0.05 to 0.15; e, f, g, h, and i from about 0.001 to 0.02; and j from about 1 .9 to 2.2.
  • the cobalt content is low and is used for structural stability of the material.
  • a non-limiting example of the composition is
  • One of the unique and inventive technical features of the present invention is the new doping strategy called high-entropy doping, which is the use of more than 4 impurity elements as dopants.
  • the technical feature of the present invention advantageously provides for improved oxygen retention and stability to allow for a longer life cycle.
  • the improved structural stability and life cycle of the compositions described herein may be attributed to the following aspects: (1) mitigated surface oxygen loss due to the pinning effects of the hierarchically and randomly distributed dopants; (2) reduced lattice expansion/contraction and defects generation through strain accommodation by different chemical environments; and (3) suppressed cation mixing through solute-drag effects of the multi-component dopants in TM layers.
  • the intrinsically enhanced stability through high-entropy doping ensures the stability of the cathode composition in terms of life cycle and stability. None of the presently known prior references or work has the unique inventive technical feature of the present invention.
  • Another unique and inventive feature of the present invention is that it provides novel compositions of high entropy metal alloys (an alloy that has more than four metal elements) with improved mechanical properties.
  • high entropy metal alloys an alloy that has more than four metal elements
  • local ordering or compositional heterogeneity at the nanoscale
  • the novel compositions of the present invention may allow for high entropy doping in layered oxides that could block unwanted structural transformation during charging, like what occurs in the two-phase transition in LiNiCh.
  • FIG. 1 A shows charge/discharging profiles of high-entropy doped LiNi0 2 material (red) vs the TiMg-doped material (green); It shows the charging curve is smooth indicating there is no obvious two phase transition.
  • FIG. 1 B shows the cycling performance of the high-entropy doped LiNi0 2 material (blue) vs the TiMg-doped material (magenta). The cycling performance of the high entropy-doped LiNi0 2 is excellent.
  • FIG. 1C shows the rate performance of the high entropy-doped LiNi0 2 is much better than the TiMg-binary doped material.
  • FIGs. 2A-2B show the high-entropy doped Li-rich material has high capacity retention at high charge rate (290 mAh/g at 0.2 C and 205 mAh/g at 2C) and there is very little voltage fade as the material undergoes electrochemical cycling.
  • FIG. 3 shows that the LiNi Mn Ti Mg Mo Nb O cathode particles contain all of the dopants uniformly.
  • FIGs. 4A-4B show that the LiNi08Mn013Ti002Mg002Mo002Nb001O2 synthesized has a layered oxide structure (space group R-3m), the same as L1NO 2 and L1C0O 2 .
  • FIG. 5 shows initial charge/discharge profile and coulombic efficiency of NMC-811 and HE-LNMO
  • FIGs. 6A-6B show that the LiNi Mn Ti Mg Mo Nb O (HE-LNMO) has much better capacity retention when charged to high voltages, 4.4V and 4.5V, respectively, compared to the commercial LiNi Mn Co O (NMC-811) material.
  • FIG. 6C shows that the LiNi08Mn013Ti002Mg002Mo002Nb001O2 (HE-LNMO) has a much better life cycle than that of the commercial LiNi08Mn01Co01O2 (NMC-811) material.
  • the life cycle reaches more than 1000 cycles with a capacity retention of 85% at 1000 cycles.
  • FIG. 7 shows that the LiNi08Mn013Ti002Mg002Mo002Nb001O2 (HE-LNMO) has extremely good stability in graphite full cells. With a cut-off voltage of 4.3V and 4.2V vs. graphite, the capacity retention is 98.9% and 99.5% after 100 cycles respectively.
  • FIGs. 8A-8B show that the LiNi08Mn013Ti002Mg002Mo002Nb001O2 (HE-LNMO) has extremely good thermal stability.
  • the HE-LNMO material is about 100°C more stable than the LiNi Mn Co O (NMC-811) material.
  • the thermal stability of the HE- LNMO material is comparable to LiNi Mn Co O (NMC-532). This measurement supports that the high- entropy “cocktail” effect can improve the structural stability of high-Ni content material at highly charged states.
  • FIGs. 9A-9C show that the LiNi08Mn013Ti002Mg002Mo002Nb001O2 (HE-LNMO) also has a zero- strain property, i.e., the material has nearly zero volume change as it is charged to 4.3 V vs Li/Li + .
  • the a and b lattice parameters are extracted from the XRD data shown in FIG. 9C.
  • the volume expansion is then calculated by calculating the volume of the material unit cell as shown in FIG. 9B.
  • the HE-LNMO material has nearly no volume change up to 4.3 V vs Li/Li + .
  • FIGs. 10A-10B show the charge/discharge curve and cycle stability of (H E-N i90) and NMC-811 (2.5V-4.4V, C/3). Compared with NMC-811 , HE-Ni90 shows better capacity retention at a higher Ni-level.
  • FIG. 10C shows the CV curve of HE-Ni90 and NMC-811 in a half-cell (2.6V-4.5V).
  • FIGs. 11 A-11 B show the ex-situ XRD and lattice change of LiNi Mn Ti Mg Mo Nb O (HE-Ni90) during delithiation.
  • FIG. 11A shows the ex-situ XRD of HE-Ni90 at different charge cut-off voltages.
  • FIG. 11 B shows lattice parameter (a and c) and volume changes during the charge process based on the ex-situ XRD pattern.
  • FIGs. 12A-12B show the cycling stability of LiNi Mn Ti Mg Mo Nb O (HE-Ni60) and LiNioeMno O (NM-64) (2.5V-4.4V, C/3). Compared with NM-64, HE-Ni60 shows better capacity retention.
  • FIGs. 12C-12D show the cycling stability of LiNi Mn Ti Mg Mo Nb O (HE-Ni70) and LiNio Mno O (NM-73) (2.5V-4.4V, C/3). Compared with NM-73, HE-Ni70 shows better capacity retention.
  • FIG. 12A-12B show the cycling stability of LiNi Mn Ti Mg Mo Nb O (HE-Ni70) and LiNio Mno O (NM-73) (2.5V-4.4V, C/3). Compared with NM-73, HE-Ni70 shows better capacity retention.
  • FIG. 13A shows the thermal stability of LiNi Mn Ti Mg Mo Nb O (HE-Ni60) vs LiNi Mn Co O (NMC-622). Compared with commercial NMC-622, HE-N O shows 33 degrees Celsius higher thermal stability.
  • FIG. 13B shows the thermal stability of LiNi05Mn043Ti002Mg002Mo002Nb001O2 (HE-Ni50) vs LiNi05Mn03Co0 2 O 2 (NMC-532). Compared with commercial NMC-532, HE-Ni50 shows 36 degrees Celsius higher thermal stability.
  • FIG. 14 shows EDS elemental maps of LiNi08Mn013AI002Zr002Cr002V001O2 (ACZV-LNMO). The result shows the similar element distribution to the HE-LNMO, in which Ni, Mn and Al are uniformly distributed while V, Cr and Zr are enriched on the surface.
  • FIGs. 15A-15D show the electrochemical performance of AZCV-LNMO.
  • FIG. 15A shows the charge/discharge profile of AZCV-LNMO
  • FIGs. 15B and 15C show the dQ/dV profile of AZCV-LNMO and NMC-811
  • FIG. 15D shows the cycling performance in half-cell.
  • FIGs. 16A-16B show the structure evolution of AZCV-LNMO.
  • FIG. 16A shows the ex-situ XRD of AZCV-LNMO (Cut-off at 4.4V, with 0.1 V step).
  • FIG. 16B shows the axis strain along the a- and c-axis.
  • FIG. 17 shows the cycling stability of HE-N50 compared with NMC-532 (top), HE-N60 compared with NMC-622 (middle), and HE-N70 compared with NMC-701515 (bottom).
  • FIG. 18 shows the normalized DSC results of HE-N50/NMC-532 and HE-N60/NMC-622. All the cathodes were delithiated to 4.5V vs. Li anode.
  • FIGs. 19A-19D show the structure evolution of HE-N50 and NMC-532.
  • FIG. 19A shows the ex- situ XRD of HE-N50 (Cut-off at 4.4V, with 0.1V step) and
  • FIG. 19B shows the ex-situ XRD of NMC-532 at the same condition.
  • FIG. 19C shows the axis strain along the a- and c-axis.
  • FIG. 19D shows the volume expansion of HE-N50 and NMC-532.
  • FIGs. 20A-20D show the structure evolution of HE-N60 and NMC-622.
  • FIG. 20A shows the ex- situ XRD of HE-N60 (Cut-off at 4.4V, with 0.1 V step) and
  • FIG. 20B shows the ex-situ XRD of NMC-622 at the same condition.
  • FIG. 20C shows the axis strain along the a- and c-axis.
  • FIG. 20D shows the volume expansion of HE-N60 and NMC-622.
  • FIGs. 21A-21D show the structure evolution of HE-N70 and NMC-701515.
  • FIG. 21A shows the ex-situ XRD of HE-N70 (Cut-off at 4.4V, with 0.1V step) and
  • FIG. 21 B shows the ex-situ XRD of NMC- 751515 at the same condition.
  • FIG. 21 C shows the axis strain along the a- and c-axis.
  • FIG. 21 D shows the volume expansion of HE-N70 and NMC-701515.
  • high-entropy doping strategy or “cocktail doping strategy” may refer to a method that allows a minimum of four impurity elements to be introduced into the host materials.
  • host materials may refer to any layered cathode materials used in lithium-ion batteries, including, but not limited to, lithium nickelate and Li-manganese-rich nickel-manganese-cobalt oxide.
  • life cycle refers to the number of complete charge/discharge cycles that the battery is able to support before its capacity falls below 80% of the battery’s original capacity.
  • the term “capacity retention” may refer to a measure of the ability of a battery to retain stored energy during an extended open-circuit rest period. In some embodiments, the capacity retention is the remaining capacity after a period of storage of a fully charged battery or battery pack.
  • thermally stable may refer to the ability to withstand decomposition at high temperatures in fully charged states.
  • discharge capacity may referto a measure ofthe rate at which a battery is discharged relative to its maximum capacity and is a key feature that can reflect the health of a battery. It is often expressed as a C-rate in order to normalize against battery capacity, which is often very different between batteries.
  • a C-rate is a measure ofthe rate at which a battery is discharged relative to its maximum capacity.
  • a 1C rate means that the discharge current will discharge the entire battery in 1 hour.
  • a low C- rate may be below about 0.5C.
  • a high C-rate may be greater than or equal to about 1 C.
  • capacity fading or “capacity loss” may refer to a phenomenon observed in rechargeable battery usage where the amount of charge a battery can deliver at the rated voltage decreases with use.
  • the term “voltage fading” may refer to the decrease in average discharge voltage as the material undergoes electrochemical cycling.
  • the present invention features a composition for a positive electrode material that can be used in a lithium ion battery that allows for high energy density, long life cycle and zero reliance on the toxic cobalt.
  • the present invention features a composition that may be used in a cathode for a battery.
  • the battery is a lithium ion battery.
  • the composition is according to the formula: Li a Ni b Dl Xl D2 X2 ... Dn X i 0 2 .
  • “a” ranges from 1 to 1 .04.
  • “b” ranges from 0.33 to 0.95.
  • n is greater than or equal to 5.
  • D1 , D2. Dn are impurity doping elements that are not nickel (Ni).
  • D1 , D2. Dn may be different impurity doping elements selected from the following elements: Mn, Ti, Mg, Mo, Nb, Al, Zr, Cr, V, Y, Sc, B, W, Sb, Co, Fe, and Ta.
  • the doping elements, D1 , D2. Dn are not limited in any way to said aforementioned examples of elements. Other doping elements known to those skilled in the art may be used. Equivalents or substitutes are within the scope of the present invention.
  • x ⁇ , x 2 . and x n are selected from the range such that the sum of the x t s is less than 1 .
  • one of ordinary skill in the art would not select x 1 : x 2 . and x n to be simultaneously the maximum value in the range because that would result in a sum greater than or equal to 1 , i.e.
  • the composition may be according to one of the following formulas: i) LiaNibMncTidMg e MOfNbgOh, or ii) LiaNibMncAljZrkCnVmOh.
  • a ranges from about 1 to 1 .03
  • b ranges from about 0.33 to 0.95
  • c ranges from about 0.01 to 0.666
  • m each ranges from about 0.001 to 0.025
  • h ranges from about 1 .9 to 2.1 .
  • Non-limiting examples of the composition include LiNi09Mn003Ti002Mg002Mo002Nb001O2, LiNi08Mn013Ti002Mg002Mo002Nb001O2, LiNi07Mn023Ti002Mg002Mo002Nb001O2, LiNi06Mn033Ti002Mg002Mo002Nb001O2, LiNi05Mn043Ti002Mg002Mo002Nb001O2, and LiNi08Mn013AI002Zr002Cr002V001O2.
  • the present invention features a composition used in a cathode for a lithium ion battery represented by the formula LiaNibMn c TidMg e MOfNbgOh.
  • the composition with the formula LiaNi b MncTi d MgeMO f NbgO h comprises ratios of elements in a range of: a from about 1 to 1 .03; b from about 0.33 to 0.95; c from about 0.01 to 0.666; d from about 0.001 to 0.025; e from about 0.001 to 0.025; f from about 0.001 to 0.025; g from about 0.001 to 0.025; and h from about 1 .9 to 2.1 .
  • the range of b may be between about 0.33 to 0.5, 0.4 to 0.55, 0.45 to 0.6, 0.5 to 0.65, 0.55 to 0.7, 0.6 to 0.75, 0.65 to 0.8, 0.7 to 0.85, 0.75 to 0.9, or 0.8 to 0.95.
  • the respective proportions of the elements in the compositions may vary by plus or minus 10%.
  • the formula of the composition may be any one of the following: LiNi09Mn003Ti002Mg002Mo002Nb001O2 (HE-Ni90), LiNi08Mn013Ti002Mg002Mo002Nb001O2, LiNi07Mn023Ti002Mg002Mo002Nb001O2 (HE-Ni70), LiNi06Mn033Ti002Mg002Mo002Nb001O2 (HE-Ni-60), or LiN i05Mn0 43 Ti00 2 Mg00 2 Mo00 2 N bo0 1 0 2 (H E-N ⁇ 50) .
  • the cathode material for a Lithium (Li) ion battery with a composition LiaNi b MncTi d MgeMO f NbgO h has a longer life cycle compared to other compositions with the same Ni content, i.e., with the same b value, such as, but not limited to, LiNi08Mn0i6Ti002Mg002O2, LiNi08Mn01Co01O2, LiNio7Mno3O, LiNio6Mno 4 O, or LiNio5Mno5O 2 .
  • the composition may go through 1000 charge/discharge cycles before its capacity falls below 80% of its original capacity. In some embodiments, the composition has a capacity retention of about 98% after 100 charge/discharge cycles. In other embodiments, the composition has a capacity retention of about 85% after 1000 charge/discharge cycles.
  • the cathode material for a Lithium (Li) ion battery with a composition LiaNi b MncTi d MgeMO f NbgO h eliminates the toxic, expensive, and single sourced cobalt from the composition.
  • the composition reduces Ni content, which lowers the cost of the cathode electrode material.
  • there is less change in Ni-metal bond length in the composition which indicates less strain of the material in the charged state.
  • the cathode material for a Lithium (Li) ion battery with a composition LiaNi b Mn c Ti d Mg e M0 f NbgO h is more thermally stable than other compositions with the same Ni content, i.e., with the same b value, such as, but not limited to, LiNi08Mn0i6Ti002Mg002O2, LiNi08Mn01Co01O2, LiNio6Mno4O, and LiNio5Mno5O2.
  • the composition is thermally stable up to about 286°C. In another embodiment, the composition is thermally stable up to about 288°C.
  • the composition is thermally stable up to about 300°C. In other embodiments, the composition is 100°C more stable compared to a composition with the formula LiNi08Mn0 1 Co0 1 O 2 (NMC-811). In another embodiment, the composition is 33°C more stable than a composition with a formula LiNi06Mn0 2 Co0 2 O 2 . In yet another embodiment, the composition is 36°C more stable than a composition with a formula LiNi05Mn03Co02O2.
  • the cathode material for a Lithium (Li) ion battery with a composition LiaNi b Mn c Ti d Mg e M0 f NbgO h has a higher capacity than other compositions with the same Ni content, i.e., with the same b value, such as, but not limited to, LiNi08Mn0i6Ti002Mg002.
  • the discharge capacity of the composition reaches about 210 mhA/g. In other embodiments, at a high C- rate, the discharge capacity of the composition reaches about 160 mhA/g.
  • the discharge capacity of the composition ranges from about 200 to 210 mhA/g (2.5 - 4.4V vs Li/Li + ).
  • a low C-rate may be below about 0.5C.
  • a high C-rate may be greater than or equal to about 1C.
  • the present invention features a composition used in a lithium- excess cathode for a lithium ion battery.
  • the composition is represented by a formula: Li 1+a ⁇ Mn b Ni c Dl Xi D2 X2 ... Dn Xn 0 2 .
  • a ranges from 0.01 to 0.33.
  • b ranges from 0.45 to 0.65.
  • c ranges from 0.09 to 0.15.
  • n is greater than or equal to 5.
  • D1 , D2. Dn are impurity doping elements that are not Mn or Ni.
  • D1 , D2. Dn may be different impurity doping elements selected from the following elements: Ti, Mg, Mo, Nb, Al, Zr, Cr, V, Y, Sc, B, W,
  • the doping elements, D1 , D2. Dn, are not limited in any way to said aforementioned examples of elements. Other doping elements known to those skilled in the art may be used. Equivalents or substitutes are within the scope of the present invention.
  • a, b, and c are selected from their respective ranges such that 1 - - ft - c is greater than zero. In other words, one of ordinary skill in the art would not select a, b, and c from their respective ranges such that 1 -a-b-c is less than or equal to zero. Thus, as a non-limiting example, one of ordinary skill in the art would not select a, b, and c to be simultaneously the maximum value in their respective ranges because that would result in 1 -a-b-c to be less than zero, i.e. a is not 0.33, b is not 0.65, and c is not 0.15 simultaneously.
  • x ⁇ , x 2 . and x n are selected from the range such that the sum of the x t s is less than 1 .
  • one of ordinary skill in the art would not select x 1 : x 2 . and x n to be simultaneously the maximum value in the range because that would result in a sum greater than or equal to 1 , i.e.
  • the composition used in a cathode for a lithium ion battery is represented by a formula: LiaMnbNicCodTieMofNbgTahSbiOj.
  • the composition with the formula: LiaMn b NicCO d TieMO f NbgTa h SbiOj comprises ratios of elements in the range of: a from about 1.10 to 1.2; b from about 0.45 to 0.65; c from about 0.09 to 0.15; d from about 0.05 to 0.15; e from about 0.001 to 0.02; f from about 0.001 to 0.02; g from about 0.001 to 0.02; h from about 0.001 to 0.02; i from about 0.001 to 0.02; and j from about 1 .9 to 2.2.
  • the respective proportions of the elements in the compositions may vary by plus or minus 10%.
  • the composition may comprise
  • the composition having the formula LiaMnbNicCodTieMofNbgTahSbiOj has a longer life cycle than the undoped Li-Mn-rich layered oxide. In one embodiment, the composition has a capacity retention of about 95% after 30 charge/discharge cycles. In some embodiments, the composition having the formula LiaMn b NicCo d TieMo f NbgTa h SbiOj does not experience voltage fading.
  • the discharge capacity of the composition reaches 282 mhA/g. In other embodiments, at a high C-rate, the discharge capacity of the composition reaches 180 to 210 mhA/g.
  • a low C-rate may be below about 0.5C.
  • a high C-rate may be greater than or equal to about 1C.
  • the present invention features a cathode for a lithium ion battery.
  • the cathode may comprise any of the compositions described herein.
  • the present invention features a lithium ion battery comprising an anode, a cathode, and an electrolyte separator.
  • the cathode may comprise any of the compositions described herein.
  • the anode may comprise lithium.
  • the electrolyte separator is non-aqueous.
  • the present invention features an electrochemical cell comprising an anode, a cathode, and an electrolyte interposed between the cathode and the anode.
  • the cathode may comprise any of the compositions described herein.
  • the anode may comprise lithium.
  • the electrolyte is non-aqueous.
  • the present invention also features a method of doping layered cathode materials in lithium ion batteries by using a “high entropy” doping strategy to introduce more than four impurity elements to the host materials.
  • the present invention features a method for synthesizing a cathode material for a lithium ion battery.
  • the method comprises preparing a hydroxide precursor powder, mixing the hydroxide precursor powder with a lithium salt to prepare the cathode material precursor, and calcining the cathode material precursor to form the cathode material.
  • the cathode material precursor can be calcined at a temperature in the range of about 650°C - 780°C. As a non-limiting example, the cathode material precursor is calcined at a temperature of about 730°C. In some embodiments, the cathode material precursor can be calcined for a period of time ranging from about 8-14 hours. As a non-limiting example, the cathode material precursor is calcined for about 12 hours.
  • the step of preparing the hydroxide precursor powder may comprise preparing a hydroxide precursor solution by dissolving, in a solvent, nickel salt, and five or more salts selected from the following: Mn salt, Ti salt, Mg salt, Mo salt, Nb salt, Al salt, Zr salt, Cr salt, V salt, Y salt, Sc salt, B salt, W salt, Sb salt, Co salt, Fe salt, and Ta salt; preparing a base solution comprising at least one base dissolved in a solvent; mixing the hydroxide precursor solution with the base solution to produce the hydroxide precursor powder; isolating the hydroxide precursor powder from the solution; and drying the hydroxide precursor powder.
  • the metal salts are not limited to the aforementioned examples, and may be any suitable metal salt.
  • the step of preparing the hydroxide precursor powder may comprise preparing a hydroxide precursor solution by dissolving, in a solvent, nickel salt, manganese salt, and five or more salts selected from the following: Ti salt, Mg salt, Mo salt, Nb salt, Al salt, Zr salt, Cr salt, V salt, Y salt, Sc salt, B salt, W salt, Sb salt, Co salt, Fe salt, and Ta salt; preparing a base solution comprising at least one base dissolved in a solvent; mixing the hydroxide precursor solution with the base solution to produce the hydroxide precursor powder; isolating the hydroxide precursor powder from the solution; and drying the hydroxide precursor powder.
  • the metal salts are not limited to the aforementioned examples, and may be any suitable metal salt.
  • the hydroxide precursor powder is prepared by a method comprising: dissolving nickel salt, manganese salt, aluminum salt, zirconium salt, chromium salt, and vanadium salt in a solvent to make a hydroxide precursor solution; preparing a base solution comprising at least one base dissolved in a solvent; mixing the hydroxide precursor solution with the base solution to produce the hydroxide precursor powder; isolating the hydroxide precursor powder from the solution; and drying the hydroxide precursor powder.
  • the hydroxide precursor powder is prepared by a method comprising: dissolving nickel salt, manganese salt, magnesium salt, titanium salt, niobium salt, and molybdenum salt in a solvent to make a hydroxide precursor solution; preparing a base solution comprising at least one base dissolved in a solvent; mixing the hydroxide precursor solution with the base solution to produce the hydroxide precursor powder; isolating the hydroxide precursor powder from the solution; and drying the hydroxide precursor powder.
  • the hydroxide precursor powder is prepared by a method comprising: dissolving nickel salt, manganese salt, cobalt salt, titanium salt, niobium salt, molybdenum salt, tantalum salt, and antimony salt in a solvent to make a hydroxide precursor solution; preparing a base solution comprising at least one base dissolved in a solvent; mixing the hydroxide precursor solution with the base solution to produce the hydroxide precursor powder; isolating the hydroxide precursor powder from the solution; and drying the hydroxide precursor powder.
  • Non-limiting examples of metal salts that may be used to prepare the composition include: NiS0 -6H 0, MnS0 -4H 0, MgS0 -7H 0, a Ti0S0 solution, Nb(HC 0 4 ) 5 , and (NH )eMo 0 24 , and LiOH.
  • the metal salts are not limited to the aforementioned examples, and may be any suitable metal salt.
  • the solvent may be water.
  • the base may be NaOH.
  • HE-Ni50, HE-N O and HE-Ni70 are synthesized using a coprecipitation method in a solution of water.
  • Nio Mno Tioo Mgoo NbooiMooo (OH is synthesized. First, NiS0 -6H 2 0 (99.8%, Fisher), MnS0 -4H 2 0 (99%, Fisher), MgS0 -7H 2 0 (98% ACROS), Ti0S0 solution (Sigma-Aldrich), Nb(HC 0 (Alfa-Aesar), and (NH )bMq q (99.98%, Sigma-Aldrich) are dissolved in pure water with a total transition metal (TM) concentration of 1 M. The TM solution is mixed uniformly using magnetic stirring for 12h and stored in an Ar-filled bottle.
  • TM transition metal
  • EXAMPLE 1 The following is a non-limiting example of the present invention. It is to be understood that said example is not intended to limit the present invention in any way. Equivalents or substitutes are within the scope of the present invention.
  • HE-LNMO is synthesized using a typical co-precipitation method in a solution of water.
  • a hydroxide precursor with a stoichiometric ratio of Nio Mnoi Tioo Mgoo NbooiMooo (OH) is synthesized.
  • NiS0 -6H 2 0 99.8%, Fisher
  • MnS0 -4H 2 0 99%, Fisher
  • MgS0 -7H 2 0 98% ACROS
  • Ti0S0 solution Sigma-Aldrich
  • Nb(HC 0 4 )s Alfa-Aesar
  • (NH )bMq q 99.98%, Sigma-Aldrich
  • the TM solution is mixed uniformly using magnetic stirring for 12h and stored in an Ar-filled bottle.
  • a base solution with 2M NaOH and 1.67M NH 4 OH is mixed and prepared before the reaction.
  • a portion (30mL) of the base solution is used as a starting solution.
  • the pH of the starting solution is adjusted to 11 .0 via diluted sulfuric acid, and the reaction is started by injecting both TM solution and base solution simultaneously with the flow around 4mL/min.
  • the laurel-green precipitate is collected via vacuum filtration and washed with pure water to remove the residual ions, and then dried in a vacuum oven at 110°C.
  • the dried TM hydroxide precursor powder is mixed thoroughly with LiOH powder with 5% excess Li as compensation at high temperature.
  • the HE-LNMO precursor is calcined in a tube furnace at 730°C for 12h under an oxygen flow of 0.5L/min.
  • the cathode slurry is prepared by uniformly mixing the active material, super P carbon, and 5% polyvinylidene fluoride (PVDF) in N-methyl-1 ,2-pyrrolidone (NMP) at a mass ratio of 8:1 :1 .
  • PVDF polyvinylidene fluoride
  • NMP N-methyl-1 ,2-pyrrolidone
  • the well-mixed slurry is coated on Al foil and dried in a vacuum oven overnight at 105°C.
  • the electrode is cut into disks with a diameter of 12mm, and the mass loading of active material is 2 - 3mg/cm 2 .
  • the counter electrode is replaced by commercial graphite coated on copper foil.
  • the electrochemical performance is conducted on a NEWARE BTS-4000 battery test system at room temperature (25°C).
  • the test voltage is 2.5V - 4.4V, and the current rate is 0.1 C to 2C.
  • GITT is tested using a typical step profile at 0.1 C with a 20 min pulse current and 5 min rest.
  • CV and EIS tests are conducted on a PINE workstation, CV is tested from 2.5V-4.5V at 0.1 mV/s scanning speed.
  • the (S)TEM experiments were performed on a transmission electron microscope with a field emission source operated at 200 KeV.
  • the atomic-resolution ADF imaging was performed in high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) mode.
  • Energy-dispersive X- ray spectroscopy (EDS) analysis was performed with Super-X EDS detectors integrated into the TEM.
  • the in-situ delithiation experiments were conducted with a Nanofactory STM-TEM holder.
  • the soft X-ray absorption including TEY and FY mode is performed at beamline 10-1 at Stanford Synchrotron Radiation Lightsource (SSRL), and the energy shift is calibrated by the transition metal foil.
  • the in-situ heating and charging/discharging XRD are performed on beamline 11-ID-C at the Advanced Photon Source (APS).
  • the beamline is optimized for high-energy x-ray diffraction at 105.7keV.
  • the charged electrode including a current collector (cut off at 4.3V) is fixed on a heating holder. The beam passes through the electrode and the diffraction pattern is recorded on the detector. All the XRD data are calibrated and analyzed by GSAS-II software.
  • TXM imaging is conducted at beamline 18-ID FXI at NSLS II, which offers advanced capabilities for studying the morphology and oxidation states of dynamic systems in 2-D and 3-D with 30 nm resolution.
  • the HE-LNMO cathode with a nominal composition of LiNi08Mn013Nb001Mo002Ti002Mg002O2 is prepared by a co-precipitation method.
  • the structure and chemistry of the as-prepared HE-LNMO were comprehensively investigated by multimodal characterization including transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques.
  • FIG. 4A shows a representative atomic-resolution high-angle annular dark-field (HAADF-STEM) image of a HE-LNMO primary particle along the [100] zone axis.
  • HAADF-STEM high-angle annular dark-field
  • Electrochemical tests were performed to evaluate the performance of the HE-LNMO cathode.
  • commercial NMC-811 cathode was also tested by using identical parameters.
  • the charge/discharge profiles (2.5 V to 4.4 V vs. Li/Li + , FIG. 5) showed that HE-LNMO delivers an initial discharge capacity of 205.5 mAh/g which is comparable to that of the commercial NMC-811 (208.2 mAh/g); in the meantime, the first-cycle Coulombic efficiency (CE) of HE-LNMO reached 90%, significantly improved compared with the 82% of NMC-811.
  • HE-LNMO achieved a specific energy of 789 Wh/kg at 0.1C.
  • NMC-811 showed a characteristic charge plateau at 4.25 V caused by the H2- H3 phase transformation, which is generally considered as the fingerprint of irreversible structural damage and oxygen release in high-Ni NMC cathodes.
  • the detrimental H2-H3 phase transformation in HE-LNMO was significantly suppressed as indicated by the flattened plateau at the same voltage.
  • FIGs. 6A-6B show the long-term cycling performances of HE-LNMO in both half-cells and full-cells.
  • HE-LNMO showed remarkable capacity retention at different cut-off voltages, for example, 98.5% capacity retention after 100 cycles at 2.5-4.4V, and 98% capacity retention after 50 cycles at 2.8-4.5V.
  • NMC-811 only showed 87.1 % retention after 100 cycles at 2.5-4.4V, and 85.8% retention after 50 cycles at 2.8-4.5V.
  • HE-LNMO also showed excellent cycling performance at different cut-off voltages (FIG. 7), e.g., 99.5% retention at 2.5-4.2V and 98.9% at 2.5-4.3V after 100 cycles, comparable with the state-of-the-art high-Ni cathode.
  • FIG. 8A shows the DSC profiles of a series of Ni-rich cathodes with different Ni contents.
  • EXAMPLE 2 The following is a non-limiting example of the present invention. It is to be understood that said example is not intended to limit the present invention in any way. Equivalents or substitutes are within the scope of the present invention.
  • FIG. 14 shows that Mn, Al, V, Cr, and Zr, are uniformly doped into the LiNi0 2 .
  • FIGs. 15A-15D show the second charge/discharge curve and dQ/dV curve of ACZV-LNMO compared with that of NMC-811.
  • the Ni content was changed to determine if the doping strategy is still effective.
  • Co-free cathode with designed formula LiNi05Mn04Ti003Mg003Nb002Mo002O2, LiNi06Mn03Ti003Mg003Nb002Mo002O2 and LiNi07Mn02Ti003Mg003Nb002Mo002O2 were synthesized (denoted as HE-N50, HE-N60 and HE-N70, respectively).
  • HE-N50, HE-N60 and HE-N70 can be used interchangeably with HE-Ni50, HE-N16O and HE-Ni70, respectively.
  • HE-N50 and HE-N60 were also evaluated by DSC shown in FIG. 18. When charged at 4.5V (CC+CV), both HE-N50 and HE-N60 show higher peak temperatures than NMC-532 and NMC-622. For HE-N50, the peak temperature of exothermic peak is around 300°C at 4.5V, significantly higher than the value in most NMC cathodes.
  • High-entropy materials are an emerging class of novel materials composed of a large number of components. Through the combination of multiple principal elements, the configurational entropy can be maximized and robust properties can be achieved. Stimulated by the emerging concept of entropy stabilization in metallic alloys, the strategy was rapidly extended to oxide systems for energy storage. However, due to the fact that high-Ni content provides the only route for high-energy-density layered oxide cathodes, the conventional near-equimolar strategy becomes not feasible.
  • compositionally complex doping is capable to stabilize high-Ni layered oxides through accommodating the volumetric and structural changes of the host 03 lattice during repeated Li + intercalation/deintercalation, without sacrificing their capacities.
  • the significantly enhanced structural stability and life cycle can be attributed to the following aspects: (1) mitigated surface oxygen loss due to the pinning effects of the hierarchically and randomly distributed dopants; (2) reduced lattice expansion/contraction and defects generation through strain accommodation by different chemical environments; (3) suppressed cation mixing through solute-drag effects of the multi-component dopants in TM layers.
  • the intrinsically enhanced stability through high-entropy doping ensures the superior stability of HE-LNMO cathode in both the long-term cycling conditions and thermal abuse conditions.
  • the large volume change which ubiquitously exists in high-Ni cathode materials may cause both structural degradations and mechanical failures of the cathodes.
  • the large lattice contraction along the c axis unavoidably results in the detrimental 01 stacking faults/phase and thereby the deactivation of high-Ni cathode due to the high energy barrier for Li + to intercalate back into the lattice.
  • local strain concentration originating from heterogeneous volume change could directly cause mechanical failure of the cathodes via the formation of multiscale cracks (including both intergranular cracking and intragranular cracking).
  • a zero-strain high-Ni cathode for LIBs is prepared through a novel high-entropy doping strategy.
  • a high-entropy doping strategy is proposed to fabricate a zero-strain high-Ni and Cofree layered cathode with superior structural/mechanical stability and long life cycle.
  • the lattice strain of the high-Ni cathode during operation is pushed down to an unprecedented 0.3%, far below the critical value of zero-strain (1%).
  • the significantly reduced lattice strain leads to an ultra-stable lattice structure that can effectively resist chemomechanical cracking as well as lattice defects during long-term cycling.
  • the oxygen loss and detrimental phase transformation are considerably mitigated and leads to superior structural stability in both harsh long-cycle chemomechanical conditions and thermal abuse conditions.
  • descriptions of the inventions described herein using the phrase “comprising” includes embodiments that could be described as “consisting essentially of or “consisting of, and as such the written description requirement for claiming one or more embodiments ofthe present invention using the phrase “consisting essentially of or “consisting of is met.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une nouvelle manière de doper des matériaux de cathode en couches dans des batteries au lithium-ion. À l'aide d'une stratégie de dopage "à entropie élevée" ou "cocktail'', plus de quatre éléments d'impureté peuvent être introduits dans les matériaux hôtes. La présente invention applique cette stratégie de dopage à entropie élevée à un matériau d'oxyde en couches à haute teneur en nickel et à un matériau riche en lithium-manganèse. Cette nouvelle stratégie de dopage à entropie élevée permet aux matériaux d'oxyde en couches utilisés dans l'électrode positive d'une batterie au lithium-ion d'avoir une densité d'énergie élevée, un cycle de longue durée de vie et une dépendance réduite au cobalt onéreux et toxique, tous ceux-ci étant des attributs souhaités pour améliorer la performance des batteries au lithium-ion et réduire leur coût.
EP22829440.1A 2021-06-25 2022-06-24 Nouvelle stratégie de dopage pour matériaux d'électrode d'oxyde en couches utilisés dans des batteries au lithium-ion Pending EP4358830A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US17/358,460 US20220336802A1 (en) 2020-06-25 2021-06-25 New doping strategy for layered oxide electrode materials used in lithium-ion batteries
US17/508,540 US11728482B2 (en) 2020-06-25 2021-10-22 Doping strategy for layered oxide electrode materials used in lithium-ion batteries
PCT/US2022/035007 WO2022272139A1 (fr) 2021-06-25 2022-06-24 Nouvelle stratégie de dopage pour matériaux d'électrode d'oxyde en couches utilisés dans des batteries au lithium-ion

Publications (1)

Publication Number Publication Date
EP4358830A1 true EP4358830A1 (fr) 2024-05-01

Family

ID=84544705

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22829440.1A Pending EP4358830A1 (fr) 2021-06-25 2022-06-24 Nouvelle stratégie de dopage pour matériaux d'électrode d'oxyde en couches utilisés dans des batteries au lithium-ion

Country Status (2)

Country Link
EP (1) EP4358830A1 (fr)
WO (1) WO2022272139A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117154086A (zh) * 2023-07-28 2023-12-01 南京大学 一种Fe/Mg掺杂调控的层状富锂正极材料、制备方法以及锂离子电池
CN117832477A (zh) * 2024-03-05 2024-04-05 宁德时代新能源科技股份有限公司 正极活性材料、二次电池和用电装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10606353B2 (en) * 2012-09-14 2020-03-31 Interaxon Inc. Systems and methods for collecting, analyzing, and sharing bio-signal and non-bio-signal data
CA2950906A1 (fr) * 2014-05-30 2015-12-03 Cerora, Inc. Evaluation multimodale de sante a l'aide d'examens de saccades neuro-ophtalmologiques
WO2020047253A1 (fr) * 2018-08-31 2020-03-05 Blackthorn Therapeutics, Inc. Biomarqueurs multimodaux prédictifs de la gravité d'un symptôme transdiagnostique
EP4048140A4 (fr) * 2019-10-25 2024-02-28 Ellipsis Health Inc Modèles de traitement de langage acoustique et naturel pour la sélection par commande vocale et la surveillance de conditions de santé comportementale

Also Published As

Publication number Publication date
WO2022272139A1 (fr) 2022-12-29
WO2022272139A9 (fr) 2023-03-09

Similar Documents

Publication Publication Date Title
US20220411284A1 (en) Cathode active material, method for manufacturing same, and lithium secondary battery comprising cathode containing same
US9653725B2 (en) Lithium rechargeable battery
US20190123347A1 (en) Ni based cathode material for rechargeable lithium-ion batteries
US11492266B2 (en) Processes for preparing positive electrode active substance for non-aqueous electrolyte secondary batteries
Knight et al. Effect of nickel oxidation state on the structural and electrochemical characteristics of lithium-rich layered oxide cathodes
JP2015213075A (ja) 高い比容量および優れたサイクルを有する積層リチウムリッチ錯体金属酸化物
EP3632851A1 (fr) Matériau actif de cathode composite, cathode et batterie au lithium chacune comprenant le matériau actif de cathode composite et procédé de préparation du matériau actif de cathode composite
EP2067198A2 (fr) Cathodes d'oxyfluorure et d'oxyde de spinelle à substituants cationiques pour batteries au lithium
JP2013543219A (ja) リチウムイオン電池正極材料上の金属ハロゲン化物コーティングおよびそれに対応する電池
EP4358830A1 (fr) Nouvelle stratégie de dopage pour matériaux d'électrode d'oxyde en couches utilisés dans des batteries au lithium-ion
US20230170478A1 (en) Cathode active material for lithium secondary battery, production method thereof, and lithium secondary battery comprising same
US11728482B2 (en) Doping strategy for layered oxide electrode materials used in lithium-ion batteries
US20220336802A1 (en) New doping strategy for layered oxide electrode materials used in lithium-ion batteries
JP2023523668A (ja) 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP2024500898A (ja) リチウム二次電池用正極活物質、その製造方法およびこれを含むリチウム二次電池
EP3347936A1 (fr) Matériau oxyde métallique de lithium, son utilisation dans une électrode positive d'une pile rechargeable, et procédé de préparation d'un tel matériau oxyde métallique de lithium
JP7258373B6 (ja) 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP7258372B2 (ja) 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
US20220020982A1 (en) Cathode active material and lithium secondary battery comprising same
KR102523095B1 (ko) 양극활물질, 이의 제조방법, 및 상기 양극활물질을 포함하는 리튬이차전지
JP2022523183A (ja) 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
JP2022521083A (ja) 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
WO2023039517A2 (fr) Cathodes de sel gemme riches en li à haute énergie ayant une migration de cations inhibée
Seo et al. The Synthesis and Electrochemical Properties of Lithium Manganese Oxide (Li 2 MnO 3)
JP7402566B2 (ja) 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240125

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR