TY - JOUR
T1 - Improved Electrochemical Behavior and Thermal Stability of Li and Mn-Rich Cathode Materials Modified by Lithium Sulfate Surface Treatment
AU - Sclar, Hadar
AU - Maiti, Sandipan
AU - Sharma, Rosy
AU - Erickson, Evan M.
AU - Grinblat, Judith
AU - Raman, Ravikumar
AU - Talianker, Michael
AU - Noked, Malachi
AU - Kondrakov, Aleksandr
AU - Markovsky, Boris
AU - Aurbach, Doron
N1 - Publisher Copyright:
© 2022 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2022/3/1
Y1 - 2022/3/1
N2 - High-energy cathode materials that are Li-and Mn-rich lithiated oxides—for instance, 0.35Li2MnO3. 0.65LiNi0.35Mn0.45Co0.20O2 (HE-NCM)—are promising for advanced lithium-ion bat-teries. However, HE-NCM cathodes suffer from severe degradation during cycling, causing gradual capacity loss, voltage fading, and low-rate capability performance. In this work, we applied an effective approach to creating a nano-sized surface layer of Li2SO4 on the above material, providing mitigation of the interfacial side reactions while retaining the structural integrity of the cathodes upon extended cycling. The Li2SO4 coating was formed on the surface of the material by mixing it with nanocrystalline Li2SO4 and annealing at 600◦C. We established enhanced electrochemical behavior with ~20% higher discharge capacity, improved charge-transfer kinetics, and higher rate capability of HE-NCM cathodes due to the presence of the Li2SO4 coating. Online electrochemical mass spectrometry studies revealed lower CO2 and H2 evolution in the treated samples, implying that the Li2SO4 layer partially suppresses the electrolyte degradation during the initial cycle. In addition, a ~28% improvement in the thermal stability of the Li2SO4-treated samples in reactions with battery solution was also shown by DSC studies. The post-cycling analysis allowed us to conclude that the Li2SO4 phase remained on the surface and retained its structure after 100 cycles.
AB - High-energy cathode materials that are Li-and Mn-rich lithiated oxides—for instance, 0.35Li2MnO3. 0.65LiNi0.35Mn0.45Co0.20O2 (HE-NCM)—are promising for advanced lithium-ion bat-teries. However, HE-NCM cathodes suffer from severe degradation during cycling, causing gradual capacity loss, voltage fading, and low-rate capability performance. In this work, we applied an effective approach to creating a nano-sized surface layer of Li2SO4 on the above material, providing mitigation of the interfacial side reactions while retaining the structural integrity of the cathodes upon extended cycling. The Li2SO4 coating was formed on the surface of the material by mixing it with nanocrystalline Li2SO4 and annealing at 600◦C. We established enhanced electrochemical behavior with ~20% higher discharge capacity, improved charge-transfer kinetics, and higher rate capability of HE-NCM cathodes due to the presence of the Li2SO4 coating. Online electrochemical mass spectrometry studies revealed lower CO2 and H2 evolution in the treated samples, implying that the Li2SO4 layer partially suppresses the electrolyte degradation during the initial cycle. In addition, a ~28% improvement in the thermal stability of the Li2SO4-treated samples in reactions with battery solution was also shown by DSC studies. The post-cycling analysis allowed us to conclude that the Li2SO4 phase remained on the surface and retained its structure after 100 cycles.
KW - Li-and Mn-rich cathode materials
KW - Li-ion batteries
KW - LiSO surface treatment
KW - cycling performance in Li cells
KW - thermal behavior
UR - http://www.scopus.com/inward/record.url?scp=85127373054&partnerID=8YFLogxK
U2 - 10.3390/inorganics10030039
DO - 10.3390/inorganics10030039
M3 - Article
AN - SCOPUS:85127373054
SN - 2304-6740
VL - 10
JO - Inorganics
JF - Inorganics
IS - 3
M1 - 39
ER -
