Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Enabling high areal capacity for Co-free high voltage spinel materials in next-generation Li-ion batteries

Journal Article · · Journal of Power Sources
The rapidly growing technological demand for lithium-ion batteries has prompted the development of novel cathode materials with high energy density, low cost, and improved safety. High voltage spinel, LiNi0.5Mn1.5O4 (LNMO), is one of the most promising candidates yet to be commercialized. The two primary obstacles for this material are the inferior electronic conductivity and fast capacity degradation in full cells due to the high operating voltage. By systematically addressing these limitations, we successfully develop a thick LNMO electrode with areal capacity loadings up to 3 mAh·cm–2. The optimized thick electrode is paired with a commercial graphite anode at both the coin cell and pouch cell level, achieving a full cell capacity retention as high as 72% and 78%, respectively, after 300 cycles. We attribute this superior cycling stability to careful optimizations of cell components and testing conditions, with a specific focus improving electronic conductivity and high voltage compatibility. These results suggest precise control of materials quality, electrode architecture and electrolyte optimization can soon support the development of a cobalt-free battery system based on a thick LNMO cathode (>4 mAh·cm2), which will eventually meet the needs of next-generation Li-ion batteries with reduced cost, improved safety, and assured sustainability.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of California San Diego, La Jolla, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
Grant/Contract Number:
AC02-05CH11231; EE0008442
OSTI ID:
1826540
Alternate ID(s):
OSTI ID: 1640280
OSTI ID: 1969443
Journal Information:
Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 473; ISSN 0378-7753
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Higher, Stronger, Better…︁ A Review of 5 Volt Cathode Materials for Advanced Lithium-Ion Batteries journal June 2012
Thick Electrode Batteries: Principles, Opportunities, and Challenges journal July 2019
Additives for Cycle Life Improvement of High‐Voltage LNMO‐Based Li‐Ion Cells journal October 2019
A High-Voltage and High-Capacity Li 1+ x Ni 0.5 Mn 1.5 O 4 Cathode Material: From Synthesis to Full Lithium-Ion Cells journal June 2016
Graphite//LiNi 0.5 Mn 1.5 O 4 Cells Based on Environmentally Friendly Made-in-Water Electrodes journal December 2016
Identification of LiNi0.5Mn1.5O4 spinel in layered manganese enriched electrode materials journal March 2011
Fluorinated electrolytes for 5-V Li-ion chemistry: Dramatic enhancement of LiNi0.5Mn1.5O4/graphite cell performance by a lithium reservoir journal July 2014
Comparative study of different crystallographic structure of LiNi0.5Mn1.5O4−δ cathodes with wide operation voltage (2.0–5.0V) journal September 2007
Understanding the capacity fading mechanism in LiNi0.5Mn1.5O4/graphite Li-ion batteries journal February 2013
Effects of cell positive cans and separators on the performance of high-voltage Li-ion batteries journal September 2012
Failure mechanisms of LiNi0.5Mn1.5O4 electrode at elevated temperature journal October 2012
Characterization tests for plug-in hybrid electric vehicle application of graphite/LiNi0.4Mn1.6O4 cells with two different separators and electrolytes journal November 2014
Evidence of loss of active lithium in titanium-doped LiNi0.5Mn1.5O4/graphite cells journal January 2015
Polyacrylonitrile-polyvinylidene fluoride as high-performance composite binder for layered Li-rich oxides journal August 2017
Simultaneously fabricating homogeneous nanostructured ionic and electronic pathways for layered lithium-rich oxides journal October 2018
A carbonate-free, sulfone-based electrolyte for high-voltage Li-ion batteries journal May 2018
Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries journal October 2017
Gas Evolution in LiNi 0.5 Mn 1.5 O 4 /Graphite Cells Studied In Operando by a Combination of Differential Electrochemical Mass Spectrometry, Neutron Imaging, and Pressure Measurements journal February 2016
Surface and Interface Issues in Spinel LiNi 0.5 Mn 1.5 O 4 : Insights into a Potential Cathode Material for High Energy Density Lithium Ion Batteries journal May 2016
Cobalt-Free Nickel-Rich Positive Electrode Materials with a Core–Shell Structure journal November 2019
Electrochemical Cross-Talk Leading to Gas Evolution and Capacity Fade in LiNi 0.5 Mn 1.5 O 4 /Graphite Full-Cells journal December 2016
Understanding the Capacity Loss in LiNi 0.5 Mn 1.5 O 4 –Li 4 Ti 5 O 12 Lithium-Ion Cells at Ambient and Elevated Temperatures journal May 2018
Synergistic Effect of Partially Fluorinated Ether and Fluoroethylene Carbonate for High-Voltage Lithium-Ion Batteries with Rapid Chargeability and Dischargeability journal December 2017
Overcoming the Challenges of 5 V Spinel LiNi 0.5 Mn 1.5 O 4 Cathodes with Solid Polymer Electrolytes journal October 2019
Nanoscale Phase Separation, Cation Ordering, and Surface Chemistry in Pristine Li 1.2 Ni 0.2 Mn 0.6 O 2 for Li-Ion Batteries journal May 2013
Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox journal December 2017
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials journal April 2018
A multifunctional phosphite-containing electrolyte for 5 V-class LiNi 0.5 Mn 1.5 O 4 cathodes with superior electrochemical performance journal January 2014
Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries journal January 2016
Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density journal January 2018
Design principles for high transition metal capacity in disordered rocksalt Li-ion cathodes journal January 2018
LixNi0.25Mn0.75Oy (0.5 ≤x≤ 2, 2 ≤y≤ 2.75) compounds for high-energy lithium-ion batteries journal January 2009
GSAS-II : the genesis of a modern open-source all purpose crystallography software package journal March 2013
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries journal January 2014
How lithium dendrites form in liquid batteries journal October 2019
Cobalt in lithium-ion batteries journal February 2020
Tris(pentafluorophenyl)silane as an Electrolyte Additive for 5 V LiNi 0.5 Mn 1.5 O 4 Positive Electrode journal January 2016
Lithium Bis(2,2,2-trifluoroethyl)phosphate Li[O 2 P(OCH 2 CF 3 ) 2 ]: A High Voltage Additive for LNMO/Graphite Cells journal January 2018
Principal Factors of Carbon Conductive Agents that Contribute to the Gas Formation in High-Voltage Cathode Systems journal January 2015
Lithium Oxalate as Capacity and Cycle-Life Enhancer in LNMO/Graphite and LNMO/SiG Full Cells journal January 2018
Is Cobalt Needed in Ni-Rich Positive Electrode Materials for Lithium Ion Batteries? journal January 2019
A Bottom-Up Approach to Lithium-Ion Battery Cost Modeling with a Focus on Cathode Active Materials journal February 2019

Cited By (1)

On the electrochemical properties of the Fe–Ti doped LNMO material LiNi 0.5 Mn 1.37 Fe 0.1 Ti 0.03 O 3.95 text January 2022