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

Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries

Journal Article · · Nature Nanotechnology

Rechargeable Li-metal batteries using high-voltage cathodes can deliver the highest possible energy densities among all electrochemistries. However, the notorious reactivity of metallic lithium as well as the catalytic nature of high-voltage cathode materials largely prevents their practical application. Here, we report a non-flammable fluorinated electrolyte that supports the most aggressive and high-voltage cathodes in a Li-metal battery. Our battery shows high cycling stability, as evidenced by the efficiencies for Li-metal plating/stripping (99.2%) for a 5 V cathode LiCoPO4 (-99.81%) and a Ni-rich LiNi0.8Mn0.1,Co0.3,O2 cathode (-99.93%). At a loading of 2.0 mAh cm-2, our full cells retain -93% of their original capacities after 1,000 cycles. Surface analyses and quantum chemistry calculations show that stabilization of these aggressive chemistries at extreme potentials is due to the formation of a several-nanometre-thick fluorinated interphase.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE) - Office of Vehicle Technology - Battery Materials Research (BMR) Program
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1484290
Journal Information:
Nature Nanotechnology, Vol. 13, Issue 8; ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

References (66)

Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries January 2018
Challenges for Rechargeable Li Batteries February 2010
Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions January 2015
Study of the Cathode–Electrolyte Interface of LiMn[sub 1.5]Ni[sub 0.5]O[sub 4] Synthesized by a Sol–Gel Method for Li-Ion Batteries January 2010
The absolute electrode potential: an explanatory note (Recommendations 1986) January 1986
Oxidative Stability and Initial Decomposition Reactions of Carbonate, Sulfone, and Alkyl Phosphate-Based Electrolytes April 2013
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions May 2009
Electronic Structure Modeling of Electrochemical Reactions at Electrode/Electrolyte Interfaces in Lithium Ion Batteries December 2012
From ultrasoft pseudopotentials to the projector augmented-wave method January 1999
First-principles prediction of redox potentials in transition-metal compounds with LDA + U December 2004
Electrolyte solution for the improved cycling performance of LiCoPO4/C composite cathodes March 2013
Fluorinated electrolytes for 5 V lithium-ion battery chemistry January 2013
Molecular Modeling of Electrolytes January 2014
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals July 2007
Electrical Energy Storage for the Grid: A Battery of Choices November 2011
An experimental determination of absolute half‐cell emf’s and single ion free energies of solvation May 1977
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries October 2004
Suppression of dendritic lithium formation by using concentrated electrolyte solutions April 2008
Electrolytes and Interphases in Li-Ion Batteries and Beyond October 2014
G n theory : G June 2011
The Impact of Electrolyte Additives and Upper Cut-off Voltage on the Formation of a Rocksalt Surface Layer in LiNi 0.8 Mn 0.1 Co 0.1 O 2 Electrodes January 2017
Hole polaron formation and migration in olivine phosphate materials March 2012
Crystal Surface and State of Charge Dependencies of Electrolyte Decomposition on LiMn 2 O 4 Cathode January 2014
Lithium metal anodes for rechargeable batteries January 2014
Stability of Solid Electrolyte Interphase Components on Lithium Metal and Reactive Anode Material Surfaces March 2016
Comparison of G3 and G4 Theories for Radical Addition and Abstraction Reactions April 2009
Special Synergy between Electrolyte Additives and Positive Electrode Surface Coating to Enhance the Performance of Li[Ni 0.6 Mn 0.2 Co 0.2 ]O 2 /Graphite Cells January 2016
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries March 2015
Nanostructured high-energy cathode materials for advanced lithium batteries October 2012
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] February 1997
Why does the B3LYP hybrid functional fail for metals? July 2007
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set July 1996
A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions June 2002
Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries August 2017
First-principles study of surface properties of Li Fe P O 4 : Surface energy, structure, Wulff shape, and surface redox potential October 2007
Effects of Carbonate Solvents and Lithium Salts on Morphology and Coulombic Efficiency of Lithium Electrode January 2013
Ab Initio Characterization of the Electrochemical Stability and Solvation Properties of Condensed-Phase Ethylene Carbonate and Dimethyl Carbonate Mixtures January 2015
Reviving the lithium metal anode for high-energy batteries March 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set October 1996
Challenges in the development of advanced Li-ion batteries: a review January 2011
Fire-extinguishing organic electrolytes for safe batteries November 2017
Hydrofluoroether electrolytes for lithium-ion batteries: Reduced gas decomposition and nonflammable October 2011
Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries February 2016
Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents January 2009
Spherical nanoporous LiCoPO4/C composites as high performance cathode materials for rechargeable lithium-ion batteries January 2011
Building better batteries February 2008
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 May 2016
First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces November 2016
Interfacial Study on Solid Electrolyte Interphase at Li Metal Anode: Implication for Li Dendrite Growth January 2016
Synergetic Effects of Inorganic Components in Solid Electrolyte Interphase on High Cycle Efficiency of Lithium Ion Batteries February 2016
Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries January 2017
Improved cycle life of Fe-substituted LiCoPO4 October 2011
Very Stable Lithium Metal Stripping–Plating at a High Rate and High Areal Capacity in Fluoroethylene Carbonate-Based Organic Electrolyte Solution May 2017
Importance of Reduction and Oxidation Stability of High Voltage Electrolytes and Additives August 2016
Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives December 2016
Promise and reality of post-lithium-ion batteries with high energy densities March 2016
A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles December 2015
Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO 4 February 2007
Nonflammable Electrolytes for Li-Ion Batteries Based on a Fluorinated Phosphate January 2002
Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries January 2018
Fluorinated electrolyte for 4.5 V Li(Ni0.4Mn0.4Co0.2)O2/graphite Li-ion cells March 2016
Effect of oxygen partial pressure on the discharge capacity of LiCoPO4 June 2005
Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries January 2015
A Review of Solid Electrolyte Interphases on Lithium Metal Anode November 2015
Stable lithium electrodeposition in liquid and nanoporous solid electrolytes August 2014
Towards high throughput screening of electrochemical stability of battery electrolytes August 2015