ARL 25-22.pdf

Invention Disclosure

ARL 25-22P

TITLE OF INVENTION:

Substituted Lithium Nickel Manganese Oxides with Improved Performance as Lithium-ion Battery Cathodes

EXECUTIVE SUMMARY OVERVIEW:

(The purpose of this overview is to provide a brief summarized overview of the invention as described in this invention disclosure document and a direct explanation on what is new about the invention and information about potential military and commercial uses)

LiNi0.5Mn1.5O4 (LNMO) is a lithium battery cathode material that has gained attention due to its safety properties and high energy density owing to its relatively high voltage of 4.7 V vs Li [1-4] compared to 3.9 V for NMC (LiNixMnyCozO2) [5] and 3.5 V for LiFePO4 [6]. A higher operating voltage will reduce the number of cells needed in a battery pack, leading to a higher pack volumetric energy density. LNMO has a spinel structure, which allows for fast lithium-ion movement owing to its network of empty edge-shared MO6 octahedra bridged by face-shared LiO4 tetrahedra, which connects three-dimensionally and forms a 3-D lithium-ion conduction path [7]. LNMO also exhibits a relatively low cost per watt-hour owing to the abundance of nickel and manganese compared to cobalt and the higher energy density compared to LiFePO4 and NMC 532 in a graphite full cell [8]. This is particularly attractive since about 50% of the cost of a battery results from the cost of the cathode material and about 30-40% of electric vehicle cost is from the battery [9]. These characteristics and being cobalt-free make it suitable for use in electric vehicles, power tools and portable electronics.

However, the high voltage of operation is challenging for conventional electrolytes which reduces their cycling stability particularly at elevated temperature [10]. Its performance can be improved by changes such as novel synthesis methods, cation or anion substitution, novel electrolytes, coatings and controlled cycling conditions [3].

Herein, we show that cation and anion substitutions which increase the lithium content of LNMO improve the discharge and charge rate capability, as well as the cycle life. Furthermore, the optimized substitution reduces the amount of Ni needed by up to 40wt. % compared to unsubstituted LNMO. This will substantially decrease the cost compared to unsubstituted LNMO.

Li-stuffed spinel-structured composition via substitutional methods that maintain electroneutrality based on the AB2O4 spinel framework and in which Lithium is sited on both tetrahedral and octahedral sites and allows for isovalent substitution of Mn4+ by Ti4+ are described. These substitution methods can be used alone or in combination as described by the general formula Li1+a+b+c+dNi0.5-2a-b-1.5c-d/2QaMdMn1.5+c/2-1.5d-eTieO4-b-

4dXb+4d wherein Q comprises any of Fe(III), Cr(III), Co(III), Mn(III), Ni(III), Ga and / or Al, wherein X comprises any of F, Cl, Br, and/or I, and M comprises any of Mg, Ca, Sr, Ni(II) and/or Zn, 0 ≤ a ≤ 0.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.2, 0 ≤ e ≤ 1.5, (a + b + c + d ) > 0, and (2a-b-1.5c-2-d/2 ≤ 0.5). The substitutions lead to compositions with greatly improved discharge and charge rate capability and greatly improved cycle life.

Furthermore, the cost of the material will decrease significantly owing to the reduced amount of nickel compared to unsubstituted LNMO. The described compositions exhibit improved discharge and charge rate capability and cycle life compared to previously described substitutions methods [4, 11-12] that do not lead to a Li-stuffed spinel.

REFERENCES

1. Y. Gao, K. Myrtle, M. Zhang, J.N. Reimers, J.R. Dahn, 1996 Phys. Rev. B 54, 16670

2. K. Amine, H. Tukamoto, H. Yasuda, Y. Fujita, J. Power Sources, 1997, 68, 604.

3. D. Liu, W. Zhu, J. Trottier, C. Gagnon, F. Barray, A. Guerfi, A. Mauger, H. Groult, C.M. Julien, J.B. Goodenough, K. Zaghib, RSC Adv., 2014, 4, 154.

4. A. Manthiram, J. Phys. Chem. Lett., 2011, 2, 176.

5. Lu Z., MacNeil D. D. and Dahn J. R. 2001, Electrochem. Solid-State Lett. 4 A200.

6. Padhi A. K., Nanjundaswamy K. S. and Goodenough J. B. 1997 J. Electrochem.

Soc. 144 1188.

7. Allen, J.L.; Crear, B.A.; Choudhury, R.;Wang, M.J.; Tran, D.T.; Ma, L.; Piccoli, P.M.; Sakamoto, J.; Wolfenstine, J. Fast Li-Ion Conduction in Spinel-Structured Solids. Molecules 2021, 26, 2625. https://doi.org/10.3390/molecules26092625

8. M. Wentker, M. Greenwood, and J. Leker, Energies 2019, 12(3), 504;

https://doi.org/10.3390/en12030504

9. J.-J Marie, S. Gifford, Faraday Insights, Issue 18, September, 2023, The Faraday Institute.

10. L. Hu, Z Xue, K. Amine, Z. Zhang, 2014 J. Electrochem. Soc. 161 A1777.

11. Z. Cui, F. Zou, H. Celio, A. Manthiram, Paving Pathways Toward Long-Life Graphite/LiNi0.5Mn1.5O4 Full Cells: Electrochemical and Interphasial Points of View.

Adv. Funct. Mater. 2022, 32, 2203779. https://doi.org/10.1002/adfm.202203779

12. S. Patoux, L. Sannier, H. Lignier, Y. Reynier, C. Bourbon, S. Jouanneau, F. Le Cas, S. Martinet, Electrochimica Acta 53 (2008) 4137-4145.

https://doi.org/10.3390/molecules26092625 https://doi.org/10.3390/en12030504 https://doi.org/10.1002/adfm.202203779

1. What is this Invention?

(e.g., a short 3-sentence “summarized” description as a more “detailed” description will be required further into this invention disclosure)

A positive electrode material composition for use in Li-ion batteries which is based on a Li-stuffed spinel composition based on modification of cobalt-free LiNi0.5Mn1.5O4. The improved composition exhibits higher discharge and charge capability as well as improved cycle life. Furthermore, the cost compared to LiNi0.5Mn1.5O4 is significantly lower owing to the reduction of Nickel (Ni) by up to 40 wt.%.

2. What is the basic premise of the design? The design is based on a composition of matter with improved performance as a Li-ion battery positive electrode.

3. What is new about this Invention? A novel composition of matter with improved discharge/charge rate and cycle life performance as a Li-ion battery positive electrode is described.

4. Has this Invention been verified?

(e.g., does it exist, is it factual, is there a test module) Yes, the invention has been verified through x-ray diffraction, cell build and electrochemical testing.

5. Identify Potential Military Uses of the Invention:

(if CTI exists, please mark accordingly) The material will reduce the time needed to charge Li-ion batteries and enable high power discharge. The life of the battery will be improved. The cost will be lower than existing cathode materials on a $ / kWh basis and since about 50% of the cost of the battery is coming from the positive electrode, the overall cost of the battery will be significantly lower. Typical applications include drones, hybrid electric vehicles, soldier power.

6. Identify Potential Commercial Uses of the Invention: The lower cost of the material compared to any existing cathodes will be attractive to EV manufacturers to produce lower cost batteries and move closer to cost parity with internal combustion engine powered vehicles. The high power capability and low cost will be attractive for EVTOL and power tool use.

PUBLICATION OF THE INVENTION:

If a description of the invention has been published (publicly disclosed, verbally or in writing), list the type of publication and the dates. Please also provide a detailed explanation of the circumstances surrounding this external disclosure (e.g., what are the provisions of a funding agreement, etc.). Also, identify any further planned reports or publications. If none, so state.

Not applicable.

LIST ANY KNOWN RELATED PATENTS, PUBLICATIONS or PATENT

APPLICATIONS:

Also identify any previous reports, drawings, publications, or correspondence describing or showing the invention. List any known closely related patents, patent applications, reports, publications, devices, or methods. If none, so state.

US 12,272,821 by first inventor. See references in attachment.

IS AN EMBODIMENT OF THE INVENTION AVAILABLE FOR INSPECTION?

Yes

NATURE AND EXTENT OF PAST USE, PRESENT USE, AND FUTURE USE

AS WELL AS APPLICATIONS AND ADVANTAGES OF THIS INVENTION:

Past: Rechargeable Li-ion batteries were invented using LiCoO2 as positive electrode.

Present: Premium rechargeable Li-ion batteries have moved towards using LiNixMnyCozO2 where cobalt is minimized to give higher energy batteries of lower cost and less concern about mining practice of cobalt in the Republic of Congo.

For lower cost and where high energy density is not required LiFePO4 has become a commonly used Li-ion positive electrode material.

Future: The composition described in this invention will enable higher energy density cells than LiFePO4 at a lower cost per kWH. At the cell level, the energy density will be comparable to LiNixMnyCozO2 where x=5, y=2, z=2. The pack level cost will be reduced owing to the higher voltage of the invention of 4.7V relative to 4.1V for LiNixMnyCozO2 and 3.5 V for LiFePO4 which will require fewer cells to achieve a desired pack level voltage.

DETAILED DESCRIPTION OF THE INVENTION:

Provide the following information concerning the disclosed invention and in the indicated sequence (or reference other submitted papers that contain the requested information – please do not cut and paste): SEE ATTACHMENT

A. Specifically describe the invention and its operation. You may use and attach copies of sketches, prints, photographs, paper, and illustrations, all of which should be signed, witnessed and dated. Alternatively, this form should be signed, witnessed and dated if the invention description is incorporated into this form. Use numbers and descriptive names in descriptions and drawings. For inventions that are methods list the steps involved in the method.

For inventions that are apparatus describe all the elements.

See attachment

B. State the advantages of the invention over presently known devices, systems or processes. Also discuss/provide a background of the prior art.

See attachment

C. Discuss the problems which the invention is designed to solve, referring to any prior invention of a similar nature with which you may be familiar (e.g limitations or disadvantages).

See attachment

D. List all known and other possible uses for the invention.

E. List the features of the invention that are believed to be novel – how does this invention differ from present technology.

Novel composition of matter which is of lower cost, higher rate capability and improved cycle life for use in a Li-on battery.

F. Please provide an abstract of your invention. This should be limited to no more than 250 words and will be used to facilitate discussion with the Invention Evaluation Committee.

Li-stuffed spinel-structured compositions based on the spinel structure and in which Lithium is sited on both tetrahedral and octahedral sites are described. These substitution methods are described by the general formula Li1+a+b+c+dNi0.5-2a-b-1.5c-d/2QaMdMn1.5+c/2-1.5d-eTieO4-b-4dXb+4d wherein Q comprises any of Fe(III), Cr(III), Co(III), Mn(III), Ni(III), Ga and / or Al, wherein X comprises any of F, Cl, Br, and/or I, and M comprises any of Mg, Ca, Sr, Ni(II) and/or Zn, 0 ≤ a ≤ 0.1, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.2, 0 ≤ e ≤ 1.5, (a + b + c + d ) > 0, and (2a-b-1.5c-2-d/2 ≤ 0.5). The substitutions lead to compositions with greatly improved rate capability and cycle life. Furthermore, the cost of the material will decrease significantly compared to the state-of-the-art owing to the reduced amount of nickel compared to unsubstituted LNMO. LNMO itself exhibits a relatively low cost per watt-hour owing to the abundance of nickel and manganese compared to cobalt and the higher energy density compared to LiFePO4 and NMC 532 in a graphite full cell. This is particularly desirable since about 50% of the cost of a battery results from the cost of the cathode material and about 30-40% of electric vehicle cost is from the battery. The described compositions use up to 40% less Nickel than LNMO, further lowering the cost.

These characteristics described make the invention suitable for use in electric vehicles, drones, power tools and portable electronics.