skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A New Strategy for High-Voltage Cathodes for K-Ion Batteries: Stoichiometric KVPO4F

Abstract

The exploration of high-energy-density cathode materials is crucial to the practical use of K-ion batteries. Layered K-metal oxides have too high a voltage slope due to their large K+–K+ interaction, resulting in low specific capacity and average voltage. In contrast, the 3D arrangement of K+, with polyanions separating them, reduces the strength of the effective K+-K+ repulsion, which in turn increases specific capacity and voltage. Here, stoichiometric KVPO4F for use as a high-energy-density K-ion cathode is developed. The KVPO4F cathode delivers a reversible capacity of ≈105 mAh g-1 with an average voltage of ≈4.3 V (vs K/K+), resulting in a gravimetric energy density of ≈450 Wh kg-1. During electrochemical cycling, the KxVPO4F cathode goes through various intermediate phases at x = 0.75, 0.625, and 0.5 upon K extraction and reinsertion, as determined by ex situ X-ray diffraction characterization and ab initio calculations. Moreover, our research explains the role of oxygen substitution in KVPO4+xF1-x: the oxygenation of KVPO4F leads to an anion-disordered structure which prevents the formation of K+/vacancy orderings without electrochemical plateaus and hence to a smoother voltage profile.

Authors:
 [1];  [2];  [1];  [2];  [1];  [1];  [2];  [2];  [3]; ORCiD logo [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Sungkyunkwan Univ., Suwon (Korea)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1542315
Alternate Identifier(s):
OSTI ID: 1460888
Grant/Contract Number:  
AC02-05CH11231; AC02‐06CH11357; C02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 26; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; cathodes; fluorophosphate; K‐ion batteries; polyanion

Citation Formats

Kim, Haegyeom, Seo, Dong-Hwa, Bianchini, Matteo, Clément, Raphaële J., Kim, Hyunchul, Kim, Jae Chul, Tian, Yaosen, Shi, Tan, Yoon, Won-Sub, and Ceder, Gerbrand. A New Strategy for High-Voltage Cathodes for K-Ion Batteries: Stoichiometric KVPO4F. United States: N. p., 2018. Web. doi:10.1002/aenm.201801591.
Kim, Haegyeom, Seo, Dong-Hwa, Bianchini, Matteo, Clément, Raphaële J., Kim, Hyunchul, Kim, Jae Chul, Tian, Yaosen, Shi, Tan, Yoon, Won-Sub, & Ceder, Gerbrand. A New Strategy for High-Voltage Cathodes for K-Ion Batteries: Stoichiometric KVPO4F. United States. doi:10.1002/aenm.201801591.
Kim, Haegyeom, Seo, Dong-Hwa, Bianchini, Matteo, Clément, Raphaële J., Kim, Hyunchul, Kim, Jae Chul, Tian, Yaosen, Shi, Tan, Yoon, Won-Sub, and Ceder, Gerbrand. Wed . "A New Strategy for High-Voltage Cathodes for K-Ion Batteries: Stoichiometric KVPO4F". United States. doi:10.1002/aenm.201801591. https://www.osti.gov/servlets/purl/1542315.
@article{osti_1542315,
title = {A New Strategy for High-Voltage Cathodes for K-Ion Batteries: Stoichiometric KVPO4F},
author = {Kim, Haegyeom and Seo, Dong-Hwa and Bianchini, Matteo and Clément, Raphaële J. and Kim, Hyunchul and Kim, Jae Chul and Tian, Yaosen and Shi, Tan and Yoon, Won-Sub and Ceder, Gerbrand},
abstractNote = {The exploration of high-energy-density cathode materials is crucial to the practical use of K-ion batteries. Layered K-metal oxides have too high a voltage slope due to their large K+–K+ interaction, resulting in low specific capacity and average voltage. In contrast, the 3D arrangement of K+, with polyanions separating them, reduces the strength of the effective K+-K+ repulsion, which in turn increases specific capacity and voltage. Here, stoichiometric KVPO4F for use as a high-energy-density K-ion cathode is developed. The KVPO4F cathode delivers a reversible capacity of ≈105 mAh g-1 with an average voltage of ≈4.3 V (vs K/K+), resulting in a gravimetric energy density of ≈450 Wh kg-1. During electrochemical cycling, the KxVPO4F cathode goes through various intermediate phases at x = 0.75, 0.625, and 0.5 upon K extraction and reinsertion, as determined by ex situ X-ray diffraction characterization and ab initio calculations. Moreover, our research explains the role of oxygen substitution in KVPO4+xF1-x: the oxygenation of KVPO4F leads to an anion-disordered structure which prevents the formation of K+/vacancy orderings without electrochemical plateaus and hence to a smoother voltage profile.},
doi = {10.1002/aenm.201801591},
journal = {Advanced Energy Materials},
number = 26,
volume = 8,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

An Initial Review of the Status of Electrode Materials for Potassium-Ion Batteries
journal, May 2017

  • Pramudita, James C.; Sehrawat, Divya; Goonetilleke, Damian
  • Advanced Energy Materials, Vol. 7, Issue 24
  • DOI: 10.1002/aenm.201602911

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Investigation of Potassium Storage in Layered P3-Type K 0.5 MnO 2 Cathode
journal, August 2017

  • Kim, Haegyeom; Seo, Dong-Hwa; Kim, Jae Chul
  • Advanced Materials, Vol. 29, Issue 37
  • DOI: 10.1002/adma.201702480

A combined first principles and experimental study on Na3V2(PO4)2F3 for rechargeable Na batteries
journal, January 2012

  • Shakoor, R. A.; Seo, Dong-Hwa; Kim, Hyungsub
  • Journal of Materials Chemistry, Vol. 22, Issue 38
  • DOI: 10.1039/c2jm33862a

Lithium Batteries and Cathode Materials
journal, October 2004

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
  • DOI: 10.1021/cr020731c

Projector augmented-wave method
journal, December 1994


AVPO 4 F (A = Li, K): A 4 V Cathode Material for High-Power Rechargeable Batteries
journal, January 2016

  • Fedotov, Stanislav S.; Khasanova, Nellie R.; Samarin, Aleksandr Sh.
  • Chemistry of Materials, Vol. 28, Issue 2
  • DOI: 10.1021/acs.chemmater.5b04065

Sodium intercalation chemistry in graphite
journal, January 2015

  • Kim, Haegyeom; Hong, Jihyun; Yoon, Gabin
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/C5EE02051D

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


Synthesis, impedance and electrochemical studies of lithium iron fluorophosphate, LiFePO4F cathode
journal, December 2012


Earth Abundant Fe/Mn-Based Layered Oxide Interconnected Nanowires for Advanced K-Ion Full Batteries
journal, December 2016


Algorithm for generating derivative structures
journal, June 2008


A 3D porous interconnected NaVPO 4 F/C network: preparation and performance for Na-ion batteries
journal, January 2015

  • Xu, Maowen; Cheng, Chuan-Jun; Sun, Qiang-Qiang
  • RSC Adv., Vol. 5, Issue 50
  • DOI: 10.1039/C5RA05161D

Density Functional Theory-Based Bond Pathway Decompositions of Hyperfine Shifts: Equipping Solid-State NMR to Characterize Atomic Environments in Paramagnetic Materials
journal, April 2013

  • Middlemiss, Derek S.; Ilott, Andrew J.; Clément, Raphaële J.
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400201t

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Sodium Storage Behavior in Natural Graphite using Ether-based Electrolyte Systems
journal, November 2014

  • Kim, Haegyeom; Hong, Jihyun; Park, Young-Uk
  • Advanced Functional Materials, Vol. 25, Issue 4
  • DOI: 10.1002/adfm.201402984

First exploration of ultrafine Na7V3(P2O7)4 as a high-potential cathode material for sodium-ion battery
journal, July 2016


K 0.67 Ni 0.17 Co 0.17 Mn 0.66 O 2 : A cathode material for potassium-ion battery
journal, September 2017


Communication—O3-Type Layered Oxide with a Quaternary Transition Metal Composition for Na-Ion Battery Cathodes: NaTi 0.25 Fe 0.25 Co 0.25 Ni 0.25 O 2
journal, January 2017

  • Vassilaras, Plousia; Dacek, Stephen T.; Kim, Haegyeom
  • Journal of The Electrochemical Society, Vol. 164, Issue 14
  • DOI: 10.1149/2.0271714jes

LiVPO4F: A new active material for safe lithium-ion batteries
journal, October 2006


Emerging Non-Aqueous Potassium-Ion Batteries: Challenges and Opportunities
journal, May 2017


Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors
journal, November 2015


Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds
journal, August 2010


Electrode Materials for Rechargeable Sodium-Ion Batteries: Potential Alternatives to Current Lithium-Ion Batteries
journal, May 2012

  • Kim, Sung-Wook; Seo, Dong-Hwa; Ma, Xiaohua
  • Advanced Energy Materials, Vol. 2, Issue 7, p. 710-721
  • DOI: 10.1002/aenm.201200026

K-Ion Batteries Based on a P2-Type K 0.6 CoO 2 Cathode
journal, May 2017

  • Kim, Haegyeom; Kim, Jae Chul; Bo, Shou-Hang
  • Advanced Energy Materials, Vol. 7, Issue 17
  • DOI: 10.1002/aenm.201700098

A comprehensive review of sodium layered oxides: powerful cathodes for Na-ion batteries
journal, January 2015

  • Han, Man Huon; Gonzalo, Elena; Singh, Gurpreet
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE03192J

Non-Aqueous K-Ion Battery Based on Layered K 0.3 MnO 2 and Hard Carbon/Carbon Black
journal, January 2016

  • Vaalma, Christoph; Giffin, Guinevere A.; Buchholz, Daniel
  • Journal of The Electrochemical Society, Vol. 163, Issue 7
  • DOI: 10.1149/2.0921607jes

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Preparation and Characterization of a Stable FeSO 4 F-Based Framework for Alkali Ion Insertion Electrodes
journal, November 2012

  • Recham, Nadir; Rousse, Gwenaëlle; Sougrati, Moulay T.
  • Chemistry of Materials, Vol. 24, Issue 22
  • DOI: 10.1021/cm302428w

Fast adiabatic pulses for solid-state NMR of paramagnetic systems
journal, February 2007


Spin-Transfer Pathways in Paramagnetic Lithium Transition-Metal Phosphates from Combined Broadband Isotropic Solid-State MAS NMR Spectroscopy and DFT Calculations
journal, October 2012

  • Clément, Raphaële J.; Pell, Andrew J.; Middlemiss, Derek S.
  • Journal of the American Chemical Society, Vol. 134, Issue 41
  • DOI: 10.1021/ja306876u

DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids
journal, February 2017


Low-Cost High-Energy Potassium Cathode
journal, January 2017

  • Xue, Leigang; Li, Yutao; Gao, Hongcai
  • Journal of the American Chemical Society, Vol. 139, Issue 6
  • DOI: 10.1021/jacs.6b12598

Investigation of K 3 V 2 (PO 4 ) 3 /C nanocomposites as high-potential cathode materials for potassium-ion batteries
journal, January 2017

  • Han, Jin; Li, Guan-Nan; Liu, Feng
  • Chemical Communications, Vol. 53, Issue 11
  • DOI: 10.1039/C6CC10065A

Conditions for Reversible Na Intercalation in Graphite: Theoretical Studies on the Interplay Among Guest Ions, Solvent, and Graphite Host
journal, September 2016

  • Yoon, Gabin; Kim, Haegyeom; Park, Inchul
  • Advanced Energy Materials, Vol. 7, Issue 2
  • DOI: 10.1002/aenm.201601519

Electrospun NaVPO 4 F/C Nanofibers as Self-Standing Cathode Material for Ultralong Cycle Life Na-Ion Batteries
journal, April 2017


P2- and P3-K x CoO 2 as an electrochemical potassium intercalation host
journal, January 2017

  • Hironaka, Yuya; Kubota, Kei; Komaba, Shinichi
  • Chemical Communications, Vol. 53, Issue 26
  • DOI: 10.1039/C7CC00806F

Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides
journal, July 1997


Recent Progress and Perspective in Electrode Materials for K-Ion Batteries
journal, December 2017

  • Kim, Haegyeom; Kim, Jae Chul; Bianchini, Matteo
  • Advanced Energy Materials, Vol. 8, Issue 9
  • DOI: 10.1002/aenm.201702384

Structural and electrochemical properties of lithium vanadium fluorophosphate, LiVPO4F
journal, August 2005


Recent Progress in Electrode Materials for Sodium-Ion Batteries
journal, July 2016

  • Kim, Hyungsub; Kim, Haegyeom; Ding, Zhang
  • Advanced Energy Materials, Vol. 6, Issue 19
  • DOI: 10.1002/aenm.201600943

Temperature-concentration phase diagram of P 2 -Na x CoO 2 from first-principles calculations
journal, June 2008


Synthesis and Crystallographic Study of Homeotypic LiVPO 4 F and LiVPO 4 O
journal, February 2012

  • Ateba Mba, Jean-Marcel; Masquelier, Christian; Suard, Emmanuelle
  • Chemistry of Materials, Vol. 24, Issue 6
  • DOI: 10.1021/cm3003996

Cracking causing cyclic instability of LiFePO4 cathode material
journal, January 2005


Oxidation under Air of Tavorite LiVPO 4 F: Influence of Vanadyl-Type Defects on Its Electrochemical Properties
journal, November 2016

  • Boivin, Edouard; Chotard, Jean-Noël; Ménétrier, Michel
  • The Journal of Physical Chemistry C, Vol. 120, Issue 46
  • DOI: 10.1021/acs.jpcc.6b07342

Lithium-Ion Battery Supply Chain Considerations: Analysis of Potential Bottlenecks in Critical Metals
journal, October 2017


Theoretical capacity achieved in a LiMn 0.5 Fe 0.4 Mg 0.1 BO 3 cathode by using topological disorder
journal, January 2015

  • Kim, Jae Chul; Seo, Dong-Hwa; Ceder, Gerbrand
  • Energy & Environmental Science, Vol. 8, Issue 6
  • DOI: 10.1039/C5EE00930H

C RYSTAL14 : A program for the ab initio investigation of crystalline solids
journal, March 2014

  • Dovesi, Roberto; Orlando, Roberto; Erba, Alessandro
  • International Journal of Quantum Chemistry, Vol. 114, Issue 19
  • DOI: 10.1002/qua.24658

Tailoring a New 4V-Class Cathode Material for Na-Ion Batteries
journal, January 2016

  • Kim, Jongsoon; Park, Inchul; Kim, Hyungsub
  • Advanced Energy Materials, Vol. 6, Issue 6
  • DOI: 10.1002/aenm.201502147

A profile refinement method for nuclear and magnetic structures
journal, June 1969


Linking Local Environments and Hyperfine Shifts: A Combined Experimental and Theoretical 31 P and 7 Li Solid-State NMR Study of Paramagnetic Fe(III) Phosphates
journal, December 2010

  • Kim, Jongsik; Middlemiss, Derek S.; Chernova, Natasha A.
  • Journal of the American Chemical Society, Vol. 132, Issue 47
  • DOI: 10.1021/ja102678r

Additional Sodium Insertion into Polyanionic Cathodes for Higher-Energy Na-Ion Batteries
journal, May 2017

  • Bianchini, Matteo; Xiao, Penghao; Wang, Yan
  • Advanced Energy Materials, Vol. 7, Issue 18
  • DOI: 10.1002/aenm.201700514

A comparative study on Na2MnPO4F and Li2MnPO4F for rechargeable battery cathodes
journal, January 2012

  • Kim, Sung-Wook; Seo, Dong-Hwa; Kim, Hyungsub
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 10
  • DOI: 10.1039/c2cp40082k

KVPO 4 F and KVOPO 4 toward 4 volt-class potassium-ion batteries
journal, January 2017

  • Chihara, Kuniko; Katogi, Akihiro; Kubota, Kei
  • Chemical Communications, Vol. 53, Issue 37
  • DOI: 10.1039/C6CC10280H

New Form of Li 2 FePO 4 F as Cathode Material for Li-Ion Batteries
journal, November 2012

  • Khasanova, Nellie R.; Drozhzhin, Oleg A.; Storozhilova, Darya A.
  • Chemistry of Materials, Vol. 24, Issue 22
  • DOI: 10.1021/cm302724a

Potassium Ion Batteries with Graphitic Materials
journal, October 2015


    Works referencing / citing this record:

    The first lithium difluorophosphate LiPO 2 F 2 with a neutral polytetrahedral microporous architecture
    journal, January 2019

    • Han, Guopeng; Wang, Ying; Li, Hao
    • Chemical Communications, Vol. 55, Issue 12
    • DOI: 10.1039/c8cc10158b

    The first lithium difluorophosphate LiPO 2 F 2 with a neutral polytetrahedral microporous architecture
    journal, January 2019

    • Han, Guopeng; Wang, Ying; Li, Hao
    • Chemical Communications, Vol. 55, Issue 12
    • DOI: 10.1039/c8cc10158b