US-12620585-B2 - Nickel and cobalt-free cathode for lithium-ion batteries and method of manufacture

Abstract

A nickel-free and cobalt-free cathode material for a lithium (Li) battery is provided. The cathode material includes, Li a Al 1-x-y-z Fe x Mn y Zn 2 O 2-δ , wherein a, x, y, z, and δ are in the following ranges: 0.95≤a≤1.2; 0≤x≤0.3; 0≤y≤0.3; 0≤z≤0.3; 0.5≤x+y+z≤0.99; 0≤δ≤0.1. In various embodiments, the present invention provides an improved Co-free/Ni-free Li-ion battery (LIB) cathode that exhibits good thermal stability and is capable of realizing a high cell voltage and specific capacity comparable to, or exceeding, currently known Li(NiCoMn)O 2 cathodes. The novel cathode chemistry in accordance with the embodiments of the present invention eliminates any potential cobalt supply issues and lowers the overall cost of the battery.

Inventors

• Akihiro Kushima
• Yoshiya Fujiwara
• Yoshiyuki Morita
• Akihisa Tanaka
• Kazuki Chiba

Assignees

• UNIVERSITY OF CENTRAL FLORIDA RESEARCH FOUNDATION, INC.
• HONDA MOTOR CO., LTD.

Dates

Publication Date

20260505

Application Date

20221028

Claims (6)

1. 1 . A cathode material for use in a lithium (Li)-ion battery, the cathode material comprising: Li a Al 1-x-y-z Fe x Mn y Zn z O 2-δ , wherein a, x, y, z, and δ are in a range of 0.95≤a≤1.2; 0≤x≤0.3; 0≤y≤0.3; 0≤z≤0.3; 0.5≤x+y+z≤0.99; 0≤δ≤0.1, wherein the cathode material comprises Zn and at least one of Mn or Fe, and wherein the cathode material does not comprise Ni or Co.
2. 2 . The cathode material of claim 1 , wherein the cathode material has a layered rock-salt structure characterized by an X-ray diffraction (XRD) pattern obtained using Cu-Kα radiation (λ=0.15418 nm) comprising at least one characteristic peak corresponding to (104), (110), (113), (101), (102) or (003) lattice spacings and wherein the observed (003) peak is located between 2θ=17.5° to 20.5°.
3. 3 . The cathode material of claim 1 , wherein the cathode material is synthesized using a method selected from co-precipitation, citrate process, hydrothermal, ion exchange and solid-state reactions.
4. 4 . A lithium (Li)-ion battery (LIB) comprising: a cathode composed of a cathode material comprising Li a Al 1-x-y-z Fe x Mn y Zn z O 2-δ , wherein a, x, y, z, and δ are in a range of 0.95≤a≤1.2; 0≤x≤0.3; 0≤y≤0.3; 0≤z≤0.3; 0.5≤x+y+z ≤0.99; 0≤δ≤0.1, wherein the cathode material comprises Zn and at least one of Mn or Fe, and wherein the cathode material does not comprise Ni or Co; an anode; and an electrolyte positioned between the anode and the cathode.
5. 5 . The LIB of claim 4 , wherein the cathode material has a layered rock-salt structure characterized by an X-ray diffraction (XRD) pattern obtained using Cu-Kα radiation (λ=0.15418 nm) comprising at least one characteristic peak corresponding to (104), (110), (113), (101), (102) or (003) lattice spacings and wherein the observed (003) peak is located between 2θ=17.5° to 20.5°.
6. 6 . The LIB of claim 4 , wherein the cathode material is synthesized using a method selected from co-precipitation, citrate process, hydrothermal, ion exchange and solid-state reactions.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63/275,208, filed Nov. 3, 2021, and entitled “Nickel and Cobalt-Free Cathode for Lithium-Ion Batteries and Method of Manufacture,” which is herein incorporated by reference in entirety. BACKGROUND OF THE INVENTION In a typical solid-state lithium-ion battery (LIB), the anode and the cathode are separated by an electrolyte. During the charging and discharging of the battery the lithium ions travel within the electrolyte positioned between the anode and cathode. Lithium cobalt oxide (LiCoO2) is commonly used as the cathode for Li-ion batteries (LIB). However, less than 10% of the supply of cobalt comes as a primary product, with the remainder of the cobalt supply being produced as a by-product of nickel and copper. Moreover, the source of most of the global cobalt is concentrated in certain regions of the world and there are increasing concerns regarding child labor and unsafe working conditions in the extraction of cobalt in these regions. Therefore, it is becoming increasingly difficult to meet the increasing demands for Li-ion batteries, particularly for electric vehicle (EV) applications, where the cost of the battery is a significant portion of the overall cost of the vehicle. Additionally, the current Li-ion battery technology does not fully satisfy the current application requirements and further development, beyond the current LIB technology, is essential. Recently, because of the supply and cost issues related to obtaining cobalt, NCM (nickel, cobalt, manganese) and NCA (nickel, cobalt, aluminum) cathodes, having reduced cobalt content, are being used for EV applications. Additionally, other cathodes, including LiMn2O4 (lithium manganese oxide) with spinel structure and olivine-type LiFePO4 (lithium iron phosphate) have been commercially used. Among these materials, LiCoO2 and NCM have superior cyclability and charge/discharge efficiency and have been used in a wide range of applications. However, they are less competitive in applications that require mid-capacity to high-capacity batteries, such as EVs, due to their high cost resulting from the use of Ni and Co, which are in limited supply. Alternatively, LiMn2O4 and LiFePO4 cathodes are low cost, with an abundant supply of Mn/Fe that is environmentally friendly, but they experience low capacities (140-160 mAh/g). Accordingly, what is needed in the art is a Li-ion battery that does not contain nickel and/or cobalt, while at the same time achieves a high energy density to avoid supply issues and that remains cost competitive. However, it is difficult to eliminate cobalt from the cathode of the LIB because doing so causes instability in the crystalline structure of the cathode, resulting in safety issues. However, in view of the art considered as a whole at the time the present invention was made, it was not obvious to those of ordinary skill in the field of this invention how the shortcomings of the prior art could be overcome. While certain aspects of conventional technologies have been discussed to facilitate disclosure of the invention, Applicant in no way disclaims these technical aspects, and it is contemplated that the claimed invention may encompass one or more of the conventional technical aspects discussed herein. The present invention may address one or more of the problems and deficiencies of the prior art discussed above. However, it is contemplated that the invention may prove useful in addressing other problems and deficiencies in a number of technical areas. Therefore, the claimed invention should not necessarily be construed as limited to addressing any of the particular problems or deficiencies discussed herein. In this specification, where a document, act or item of knowledge is referred to or discussed, this reference or discussion is not an admission that the document, act or item of knowledge or any combination thereof was at the priority date, publicly available, known to the public, part of common general knowledge, or otherwise constitutes prior art under the applicable statutory provisions or is known to be relevant to an attempt to solve any problem with which this specification is concerned. SUMMARY OF THE INVENTION In various embodiments, the present invention provides an improved Co-free/Ni-free Li-ion battery (LIB) cathode that exhibits good thermal stability and is capable of realizing a high cell voltage and specific capacity comparable to, or exceeding, currently known Li(NiCoMn)O2 cathodes. The novel cathode chemistry in accordance with the embodiments of the present invention eliminates the cobalt supply issues and lowers the cost of the battery. Based on density functional theory (DFT) calculations, the role of Ni, Co, and Mn in an NCM (nickel, cobalt, manganese) cathode have been identified, wherein Mn stabilizes oxygen and Co/Ni compensates for Li+ removal. Through calculations of various elemental