CN-122000331-A - Polycrystalline metal oxide with enriched grain boundaries

Abstract

Electrochemically active secondary particles are provided that provide excellent capacity and improved cycle life. The particles are characterized by selectively enriched grain boundaries, wherein the grain boundaries are enriched in Al. Al enrichment reduces the impedance increase during cycling, thereby improving capacity and cycle life. Methods of forming the electrochemically active material are also provided, as are electrodes and electrochemical cells using the secondary particles.

Inventors

• A pron
• D. OVER
• S. Sri Ramulu
• K. Shaxin
• J. RUMPEL

Assignees

• 坎麦克斯动力有限责任公司

Dates

Publication Date

20260508

Application Date

20191023

Priority Date

20190117

Claims (20)

1. 1.A particle, comprising: a plurality of crystallites comprising a first composition comprising lithium, nickel, and oxygen; between adjacent ones of said plurality of crystallites and comprising a layer -A grain boundary of a second composition of NaFeO 2 -type structure, cubic structure, spinel structure, or a combination thereof; wherein the concentration of aluminum in the grain boundaries is greater than the concentration of aluminum in the crystallites, and optionally wherein the concentration of cobalt in the grain boundaries is greater than the concentration of cobalt in the crystallites.
2. 2. The particle of claim 1, wherein the aluminum is substantially uniformly distributed in the plurality of particles.
3. 3. The particle of claim 1, wherein the amount of aluminum in the grain boundaries is 0.01 at% to 10 at% relative to the total transition metals in the first composition.
4. 4. The particle of claim 1, wherein the concentration of aluminum in the second composition is equal to or less than the concentration of Co in the second composition.
5. 5. The particle of any one of claims 1-4, wherein the plurality of crystallites have an alpha-NaFeO 2 layered structure, a cubic structure, a spinel structure, or a combination thereof.
6. 6. The particle of any one of claims 1-4, wherein the crystallites comprise a first composition defined by Li 1+x MO 2+y , wherein -0.1≤x≤0.3, -0.3.Ltoreq.y≤0.3 and Wherein M comprises greater than or equal to 10 atomic percent nickel.
7. 7. The particle of claim 6, wherein M comprises greater than or equal to 75 at atomic percent of nickel.
8. 8. The particle of any one of claims 1-4, wherein the grain boundaries comprise cobalt in an amount of about 2at% to about 99 at% relative to the total transition metals in the second composition and aluminum in an amount of about 0.5 at% to about 99 at% relative to the total transition metals in the second composition.
9. 9. The particle of claim 6 wherein M further comprises an additional metal, wherein the additional metal is present in an amount of about 1 at% to about 90 at%; The additional metal is selected from Mg, sr, co, al, ca, cu, zn, mn, V, ba, zr, ti, cr, fe, mo, B and any combination thereof.
10. 10. The particles of claim 6, wherein the crystallites comprise cobalt in a concentration in the range of 0 at% to about 50 at% relative to the total transition metals in the first composition, optionally 1 at% to about 50 at% relative to the total transition metals in the first composition.
11. 11. The particle of claim 6, wherein the crystallites comprise cobalt in a concentration in the range of 1 at% to about 10 at% relative to the total transition metal in the first composition.
12. 12. The particle of any one of claims 1-4, wherein The crystallites comprise Mn present in an amount of about 1 at% to about 60 at%, and The grain boundaries comprise Mn present in an amount of about 1 at% to about 60 at%, where at% is relative to the crystallites or the total transition metal in the grain boundaries, respectively.
13. 13. The particle of any one of claims 1-4, wherein the grain boundaries comprise Ni, co, and Al.
14. 14. The particle of any one of claims 1-4, wherein the Ni concentration in the grain boundaries is less than 90 at% relative to the total transition metal in the grain boundaries.
15. 15. The particle of any one of claims 1-4, further comprising an overcoat on the surface of the particle, the overcoat comprising: oxides of one or more elements selected from Al, zr, Y, co, ni, mg and Li; A fluoride containing one or more elements selected from Al, zr, and Li; a carbonate comprising one or more elements selected from Al, co, ni, mn and Li; a sulfate comprising one or more elements selected from Al, co, ni, mn and Li, or Phosphate containing one or more elements selected from Al and Li.
16. 16. An electrochemically active polycrystalline secondary particle comprising: A plurality of crystallites comprising a first composition defined by Li 1+x MO 2+y , wherein -0.1≤x≤0.3, -0.3.Ltoreq.y≤0.3 and Wherein M comprises greater than or equal to 80 atomic percent nickel, and And comprising a grain boundary of the second composition optionally having an alpha-NaFeO 2 -type layered structure, a cubic structure, a spinel structure, or a combination thereof, between adjacent ones of the plurality of crystallites, wherein the concentration of aluminum in the grain boundary is greater than the concentration of aluminum in the crystallites, and wherein the concentration of cobalt in the grain boundary is greater than the concentration of cobalt in the crystallites, and wherein the aluminum is substantially uniformly distributed in the grain boundary.
17. 17. The particle of claim 16, wherein the concentration of cobalt in the grain boundaries is greater than the concentration of aluminum in the grain boundaries.
18. 18. The particle of claim 16, wherein the concentration of cobalt in the crystallites is from about 0 to about 17 atomic%, and The cobalt concentration in the grain boundaries is about 0.5 to about 32 atomic percent, each based on the total atomic transition metal composition of the particle.
19. 19. The particle of claim 16, wherein M further comprises one or more elements selected from Al, mg, co, mn, ca, sr, ba, zn, ti, zr, Y, cr, mo, fe, V, si, ga and B, the one or more elements being located in the Li layer, M layer, or both of the crystallites.
20. 20. The particle of claim 16, wherein M comprises greater than or equal to 90 atomic percent of nickel.

Description

Polycrystalline metal oxide with enriched grain boundaries The application is a divisional application of patent application No. 201980094065.8, the application date of the original application is 2019, 10 month and 23 days, and the application is named as 'polycrystalline metal oxide with enriched grain boundaries'. Cross reference to related applications The present application depends on and claims priority from U.S. patent application Ser. No. 16/250,615 filed on 1 month 17 of 2019, U.S. patent application Ser. No. 16/250,762 filed on 1 month 17 of 2019, and U.S. patent application Ser. No. 16/250,622 filed on 1 month 17 of 2019, each of which is incorporated herein by reference in its entirety. FIELD Polycrystalline metal oxide particles, methods of making the same, and electrochemical cells or batteries (batteries) containing the same are disclosed. Background Layered lithium nickel oxide (LiNiO 2) based materials have been developed for lithium ion battery cathodes because they generally have lower cost, higher capacity and higher rate capability than the LiCoO 2 cathode materials that have been dominant in the past. But pure LiNiO 2 materials exhibit poor electrochemical stability and cycling performance. To address this, non-nickel elemental additives have been formulated into LiNiO 2 that stabilize the structure to improve cycling performance, but generally at the expense of discharge capacity. As the demand for energy density increases, research has focused on optimizing and reducing these non-nickel additives to harvest the capacity of high Ni materials while maintaining cycle performance. Accordingly, new materials are needed that address the need for high capacity materials with long cycle life. The materials and methods of forming these materials provided herein address this need by maintaining high capacity over long cycle life. SUMMARY The following summary is provided to facilitate an understanding of some of the innovative features unique to the present disclosure and is not intended to be a full description. A full appreciation of the various aspects of the disclosure can be gained by taking the entire specification, claims, drawings, and abstract as a whole. Secondary particles are provided that are found to have greatly reduced impedance growth when used as cathode electrochemically active materials in lithium ion secondary batteries (Li-ion secondary cell). It was found that by selectively enriching the grain boundaries between crystallites in the secondary particles with a combination of Co and Al, improved impedance properties can be achieved and these improved impedance properties are achieved in many electrochemically active materials of different compositions. Thus provided are particles comprising a plurality of crystallites comprising a first composition comprising lithium, nickel and oxygen, between adjacent crystallites of the plurality of crystallites and comprising a layer having a layer shapeA grain boundary of the second composition of NaFeO 2 -type structure, cubic structure, spinel structure, or a combination thereof, wherein the concentration of aluminum in the grain boundary is greater than the concentration of aluminum in the crystallites, and wherein the concentration of cobalt in the grain boundary is greater than the concentration of cobalt in the crystallites. In some aspects, it was found that Al enrichment of grain boundaries was not uniform, complete, or achieved, but that Al grain boundary enrichment, optionally Co and Al grain boundary enrichment, could be achieved when using the manufacturing methods provided herein. Thus, in some aspects, al is substantially uniformly distributed among the plurality of particles. In some aspects, the amount of Al in the grain boundaries is 0.01 at% to 10 at% of the total transition metal amount in the remainder of the secondary particles. Optionally, the amount of Co in the grain boundaries is 0 at% to 10 at% of the total transition metal amount in the remainder of the secondary particles, optionally 0.1 at% to 10 at% of the total transition metal amount in the remainder of the secondary particles. Optionally, the amount of Al in the grain boundaries is 0.01 at% to 5 at% of the total transition metal amount in the remainder of the secondary particles and the amount of Co in the grain boundaries is 0.01 at% to 10 at% of the total transition metal amount in the remainder of the secondary particles. Optionally, the amount of aluminum in the grain boundaries is equal to or less than the amount of Co in the grain boundaries. In some aspects, the plurality of crystallites has an alpha-NaFeO 2 layered structure, a cubic structure, a spinel structure, or a combination thereof. Optionally, the first composition, the second composition, or both of any of the above aspects or other aspects are defined by Li 1+xMO2+y, wherein -0.1≤x≤0.3, -0.3.Ltoreq.y≤0.3 and Wherein M comprises greater than or equal to 10 atomic percent nickel. Optio