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Title: Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

Journal Article · · Chemical Reviews
ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [5];  [6];  [5];  [2]
  1. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
  2. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States, Department of Materials Science and Engineering, University of California Berkeley, California 94720, United States
  3. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  4. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
  5. Energy and Environmental Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  6. Chemical Sciences and Engineering, Argonne National Laboratory, Lemont, Illinois 60439, United States

We report that the rapidly expanding field of nonaqueous multivalent intercalation batteries offers a promising way to overcome safety, cost, and energy density limitations of state-of-the-art Li-ion battery technology. We present a critical and rigorous analysis of the increasing volume of multivalent battery research, focusing on a wide range of intercalation cathode materials and the mechanisms of multivalent ion insertion and migration within those frameworks. The present analysis covers a wide variety of material chemistries, including chalcogenides, oxides, and polyanions, highlighting merits and challenges of each class of materials as multivalent cathodes. The review underscores the overlap of experiments and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex experimental results. In conclusion, on the basis of our critical review of the literature, we provide suggestions for future multivalent cathode studies, including a strong emphasis on the unambiguous characterization of the intercalation mechanisms.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
3F-31144; AC02-05CH11231
OSTI ID:
1343461
Alternate ID(s):
OSTI ID: 1476467
Journal Information:
Chemical Reviews, Journal Name: Chemical Reviews Vol. 117 Journal Issue: 5; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 820 works
Citation information provided by
Web of Science

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Prussian Blue MgLi Hybrid Batteries journal April 2016
Ionic Conductivity and Magnesium Vacancy Mobility in Magnesium Oxide journal November 1980
Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries journal January 2014
Confession of a Magnesium Battery journal August 2015
Mg Desolvation and Intercalation Mechanism at the Mo 6 S 8 Chevrel Phase Surface journal August 2015
Performance Enhancement and Mechanistic Studies of Magnesium–Sulfur Cells with an Advanced Cathode Structure journal July 2016
Vanadium oxide–propylene carbonate composite as a host for the intercalation of polyvalent cations journal November 2005
On the Utility of Spinel Oxide Hosts for Magnesium-Ion Batteries journal October 2015
Nanostructured Layered Cathode for Rechargeable Mg-Ion Batteries journal July 2015
Characterization of magnesium-intercalated V2O5/carbon composites journal July 2003
Investigation of the intercalation of polyvalent cations (Mg2+, Zn2+) into λ-MnO2 for rechargeable aqueous battery journal January 2014
Performance Improvement of Magnesium Sulfur Batteries with Modified Non-Nucleophilic Electrolytes journal October 2014
Materials Design Rules for Multivalent Ion Mobility in Intercalation Structures journal August 2015
Theoretical Study of the Structural Evolution of a Na 2 FeMn(CN) 6 Cathode upon Na Intercalation journal May 2015
Electrochemical Behaviour of V 2 O 5 Xerogel and V 2 O 5 Xerogel/C Composite in an Aqueous LiNO 3 and Mg(NO 3 ) 2 Solutions journal May 2010
A review on the problems of the solid state ions diffusion in cathodes for rechargeable Mg batteries journal December 2007
Design principles for solid-state lithium superionic conductors journal August 2015
Synthesis, crystal structure and electrochemical properties of LiFePO4F cathode material for Li-ion batteries journal November 2014
A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions journal June 2002
Alpha manganese dioxide for lithium batteries: A structural and electrochemical study journal February 1992
Structure and compatibility of a magnesium electrolyte with a sulphur cathode journal August 2011
Electrochemical Energy Storage for Green Grid journal May 2011
Electrochemical Intercalation of Mg 2+ in Magnesium Manganese Silicate and Its Application as High-Energy Rechargeable Magnesium Battery Cathode journal June 2009
Reversible Calcium Ion Batteries Using a Dehydrated Prussian Blue Analogue Cathode journal July 2016
Li2MnSiO4 cathodes modified by phosphorous substitution and the structural consequences journal June 2014
A High Power Rechargeable Nonaqueous Multivalent Zn/V 2 O 5 Battery journal August 2016
Influence of relative humidity on the structure and electrochemical performance of sustainable LiFeSO 4 F electrodes for Li-ion batteries journal January 2015
Todorokite-type MnO2 as a zinc-ion intercalating material journal December 2013
Electrochemical Insertion/Extraction of Calcium Ions Using Crystalline Vanadium Oxide journal January 2004
Electrochemically-induced reversible transition from the tunneled to layered polymorphs of manganese dioxide journal August 2014
Concentration dependent electrochemical properties and structural analysis of a simple magnesium electrolyte: magnesium bis(trifluoromethane sulfonyl)imide in diglyme journal January 2016
Kinetic and Thermodynamic Studies of Mg[sup 2+] and Li[sup +] Ion Insertion into the Mo[sub 6]S[sub 8] Chevrel Phase journal January 2004
Factors affecting Li mobility in spinel LiMn2O4—A first-principles study by GGA and GGA+U methods journal August 2010
Comparing electrochemical performance of transition metal silicate cathodes and chevrel phase Mo6S8 in the analogous rechargeable Mg-ion battery system journal July 2016
Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond journal October 2014
Electrochemical and chemical insertion/deinsertion of magnesium in spinel-type MgMn 2 O 4 and lambda-MnO 2 for both aqueous and non-aqueous magnesium-ion batteries journal January 2015
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries journal January 2012
The Intercalation Phase Diagram of Mg in V 2 O 5 from First-Principles journal May 2015
Electrolyte roadblocks to a magnesium rechargeable battery journal January 2012
Direct Observation of an Anomalous Spinel-to-Layered Phase Transition Mediated by Crystal Water Intercalation journal October 2015
Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V 2 O 5 · n H 2 O Xerogel Material journal April 2016
The Electrochemical Behavior of Alkali and Alkaline Earth Metals in Nonaqueous Battery Systems—The Solid Electrolyte Interphase Model journal January 1979

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