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CN-122025618-A - LTO coated LRMO cathode and synthesis

CN122025618ACN 122025618 ACN122025618 ACN 122025618ACN-122025618-A

Abstract

A method of forming a high energy density composite cathode material is disclosed. The method includes providing a lithium-rich manganese layered oxide (LRMO), coating the LRMO with a TiO 2 precursor, and ball milling the TiO 2 -coated LRMO with LiH to form a Li x TiO 2 -coated LRMO composite, wherein x is less than or equal to 1 and greater than zero.

Inventors

  • ZHANG WENKUI
  • HUANG HUI
  • XIA YANG
  • ZHANG LIYUAN
  • WANG YISHUN
  • LIANG CHU
  • YANG XIAOGUANG
  • Robert J. Kudra
  • Hiodor James Miller

Assignees

  • 福特全球技术公司

Dates

Publication Date
20260512
Application Date
20181012
Priority Date
20171016

Claims (14)

  1. 1. A method of forming a composite cathode material, the method comprising: providing a lithium-rich manganese layered oxide; Coating the manganese layered oxide with a TiO 2 precursor, and The TiO 2 -coated manganese layered oxide is ball milled with LiH to form a Li x TiO 2 -coated manganese layered oxide composite, where x is less than or equal to 1 and greater than zero.
  2. 2. The method of claim 1, wherein coating the manganese layered oxide with the TiO 2 precursor comprises reacting the manganese layered oxide with a titanium salt, deionized water, and an alcohol.
  3. 3. The method of claim 2, wherein the reacting is performed in a hydrothermal reactor.
  4. 4. The method of claim 2, wherein the reaction is performed at a temperature of 100 ℃ to 300 ℃ for 1 hour to 12 hours.
  5. 5. The method of claim 2, wherein the coating comprises calcining after reacting the manganese layered oxide to form the TiO 2 -coated manganese layered oxide.
  6. 6. The method of claim 5, wherein the calcining is performed at 300 ℃ to 500 ℃ for 30 minutes to 8 hours.
  7. 7. The method of claim 6, wherein the calcining is performed at a heating rate of 1 ℃ per minute to 10 ℃ per minute.
  8. 8. The method of claim 1, wherein the TiO 2 is 0.1 wt% to 9 wt% of the TiO 2 coated manganese layered oxide.
  9. 9. The method of claim 1, wherein the manganese layered oxide is xLi 2 MnO 3 •(1-x)LiMO 2 , wherein M is Mn, ni, co, fe, cr, ti, al, mg, V, a rare earth metal, or a combination thereof, and x is less than or equal to 1 and greater than or equal to zero.
  10. 10. The method of claim 1, wherein the ball milling is performed at a rate of 200 rpm to 750 rpm for 6 hours to 24 hours.
  11. 11. The method of claim 1, wherein the providing comprises co-precipitating the manganese layered oxide.
  12. 12. A cathode composite, the cathode composite comprising: A lithium-rich manganese layered oxide having the formula xLi 2 MnO 3 •(1-x)LiMO 2 , wherein M is Mn, ni, co, fe, cr, ti, al, mg, V, a rare earth metal, or a combination thereof, and x is less than or equal to 1 and greater than or equal to zero, and A ball-milled Li x TiO 2 coating on the surface of the manganese layered oxide, Wherein the Li x TiO 2 coating is formed by ball milling the manganese layered oxide coated with TiO 2 precursor with LiH.
  13. 13. The cathode composite of claim 12, wherein the ratio of LiH to TiO 2 for ball milling is from 1:1 to 1.10:1.
  14. 14. The cathode composite of claim 12, wherein the manganese layered oxide has the formula Li [ Li (1-x-y-z) Ni x Co y Mn z ]O 2 , and x, y, and z are each independently less than or equal to 1 and greater than zero, or are absent.

Description

LTO coated LRMO cathode and synthesis The application is a divisional application of an application patent application with the application date of 2018, 10-month and 12-date, the application number of 201811188662.0 and the name of 'LRMO cathode coated with LTO and synthesis'. Technical Field The present disclosure relates to a lithium ion battery cathode material and a method of producing the lithium ion cathode material. Background Lithium ion batteries present rechargeable electrochemical energy storage technology. Due to the electrochemical potential and theoretical capacity provided by lithium ion batteries, this technology has shown promise in large energy storage systems (such as those related to the electrification of power transmission systems in automotive applications) and in providing a fixed energy storage solution to enable efficient use of renewable energy sources. The energy density of conventional lithium ion batteries may not be able to meet the demands in new generation applications. Coating the surface of the cathode material with electrochemically inert oxides has been considered an effective method of improving the electrochemical performance of lithium ion batteries, however, in some cases, the cycling stability has not been improved. The lithium-rich manganese layered oxide or LRMO shows high specific capacity (i.e., >280 mAh g -1) and high operating voltage. While LRMO cathode materials may potentially meet the high energy requirements of mobile electronic devices and electric vehicles, LRMO exhibits poor cycling performance, poor rate capability, and voltage decay. Disclosure of Invention According to one embodiment, a method of forming a high energy density composite cathode material is disclosed. The method includes providing a lithium-rich manganese layered oxide (LRMO), coating the LRMO with a TiO 2 precursor, and ball milling the TiO 2 -coated LRMO with LiH to form a Li xTiO2 -coated LRMO composite, wherein x is less than or equal to 1 and greater than zero. According to one or more embodiments, coating the LRMO with the TiO 2 precursor may include reacting the LRMO with a titanium salt, deionized water, and an alcohol. Alternatively, the reaction may be performed in a hydrothermal reactor. The reaction may be conducted at a temperature of about 100 ℃ to about 300 ℃ for about 1 to about 12 hours. In one or more embodiments, the coating can include calcination to form TiO 2 to coat the LRMO after the LRMO reaction. In addition, calcination may be performed at about 300 ℃ to about 500 ℃ for about 30 minutes to about 8 hours. Calcination may be performed at a heating rate of about 1 ℃ per minute to about 10 ℃ per minute. In one or more embodiments, the TiO 2 can be about 0.1 wt% to about 9 wt% of the LRMO coated TiO 2. In some embodiments, LRMO may be xLi 2MnO3•(1-x)LiMO2, where M may be Mn, ni, co, fe, cr, ti, al, mg, V, a rare earth metal, or a combination thereof, and x may be less than or equal to 1 and greater than zero. In one or more embodiments, ball milling may be performed at a rate of about 200 rpm to about 750 rpm for about 6 hours to about 24 hours. In some embodiments, providing may include co-precipitating LRMO. According to one embodiment, a method of forming a high energy density composite cathode material is disclosed. The method includes reacting lithium-rich manganese layered oxide (LRMO) with a TiO 2 precursor in a hydrothermal reactor, calcining the LRMO of the coating precursor, and ball milling the LRMO of the coating precursor with LiH to form a Li xTiO2 coated LRMO composite, where x is less than or equal to 1 and greater than zero. According to one or more embodiments, the LRMO may be xLi 2MnO3•(1-x)LiMO2, where M may be Mn, ni, co, fe, cr, ti, al, mg, V, a rare earth metal, or a combination thereof, and x may be less than or equal to 1 and greater than zero. In some embodiments, the TiO 2 precursor may be about 0.1 wt% to about 9 wt% of the LRMO of the coating precursor. In one or more embodiments, calcination may be performed at a heating rate of about 1 ℃ per minute to about 10 ℃ per minute. In some embodiments, ball milling may be performed at a rate of about 200 rpm to about 750 rpm for about 6 hours to about 24 hours. In one or more embodiments, the ratio of LiH to TiO 2 for ball milling may be about 1:1 to about 1.10:1. According to one embodiment, a high energy density cathode composite is disclosed. The high energy density cathode composite includes a lithium-rich manganese layered oxide (LRMO) having the formula xLi 2MnO3•(1-x)LiMO2, wherein M is Mn, ni, co, fe, cr, ti, al, mg, V, a rare earth metal, or a combination thereof, and x is less than or equal to 1 and greater than or equal to zero. The high energy density cathode composite also includes a ball-milled Li xTiO2 coating on the surface of the LRMO. According to one or more embodiments, the Li xTiO2 coating may be a ball-milled LiH and TiO 2 precursor composite coating on LRMO. In some