Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives

Lapping, J. G.; Borkiewicz, O. J.; Wiaderek, K. M.; Allen, Jan L.; Jow, T. Richard; Cabana, Jordi

doi:10.1021/acsami.0c04110

Title: Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO₄ Derivatives

Abstract

In an effort to improve the cycle life and rate capability of olivine LiCoPO₄, Cr, Fe, and Si were added to produce nominal Li_1.025Co_0.84Fe_0.10Cr_0.05Si_0.01(PO₄)_1.025. This cathode material has an energy density comparable to LiCoPO₄, with markedly improved electrochemical performance. Here, we apply operando X-ray diffraction to gain an understanding of the crystallographic delithiation mechanism of this new substituted electrode material, compared to both LiCo_0.75Fe_0.25PO₄ and LiCo_0.75Fe_0.25PO₄. Throughout charging, the extent of solid-solution domains was significantly increased in Li_1.025Co_0.84Fe_0.10Cr_0.05Si_0.01(PO₄)_1.025 and LiCo_0.75Fe_0.25PO₄ compared to LiCoPO₄. These domains reduce the mechanical strain during electrode function, providing a clear explanation for the high durability with Co substitution. Li_1.025Co_0.84Fe_0.10Cr_0.05Si_0.01(PO₄)_1.025 operated at notably higher average potential than LiCo_0.75Fe_0.25PO₄, which would increase the energy density of the cell. Ex situ measurements reveal the persistence of structural irreversibilities in the substituted phase after the first cycle, identifying avenues for further improvement in durability. Overall, this finding sheds light on the strategies for judicious cation substitution in LiCoPO₄ electrodes to maximize the cycle life while preserving high energy density, especially compared to LiFePO₄.

Authors:

Lapping, J. G. ^[1]; Borkiewicz, O. J. ^[2]; Wiaderek, K. M. ^[2]; Allen, Jan L. ^[3]; Jow, T. Richard ^[3];

^[1]

Univ. of Illinois, Chicago, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
Army Research Lab., Adelphi, MD (United States)

Publication Date:: 2020-04-09

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: US Army Research Laboratory (USARL); USDOE Office of Science (SC)

OSTI Identifier:: 1660418

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 12; Journal Issue: 18; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; Lithium-ion battery; crystallography; electrochemistry; lithium cobalt phosphate; operando x-ray diffraction

Citation Formats


                    Lapping, J. G., Borkiewicz, O. J., Wiaderek, K. M., Allen, Jan L., Jow, T. Richard, and Cabana, Jordi. Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives.  United States: N. p., 2020. 
Web.  doi:10.1021/acsami.0c04110.

Copy to clipboard


                    Lapping, J. G., Borkiewicz, O. J., Wiaderek, K. M., Allen, Jan L., Jow, T. Richard, & Cabana, Jordi. Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives.  United States.  https://doi.org/10.1021/acsami.0c04110

Copy to clipboard


                    Lapping, J. G., Borkiewicz, O. J., Wiaderek, K. M., Allen, Jan L., Jow, T. Richard, and Cabana, Jordi. Thu .  
"Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives".  United States.  https://doi.org/10.1021/acsami.0c04110.  https://www.osti.gov/servlets/purl/1660418.

Copy to clipboard


                    
@article{osti_1660418,

  title        = {Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives},

  author       = {Lapping, J. G. and Borkiewicz, O. J. and Wiaderek, K. M. and Allen, Jan L. and Jow, T. Richard and Cabana, Jordi},

  abstractNote = {In an effort to improve the cycle life and rate capability of olivine LiCoPO4, Cr, Fe, and Si were added to produce nominal Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025. This cathode material has an energy density comparable to LiCoPO4, with markedly improved electrochemical performance. Here, we apply operando X-ray diffraction to gain an understanding of the crystallographic delithiation mechanism of this new substituted electrode material, compared to both LiCo0.75Fe0.25PO4 and LiCo0.75Fe0.25PO4. Throughout charging, the extent of solid-solution domains was significantly increased in Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 and LiCo0.75Fe0.25PO4 compared to LiCoPO4. These domains reduce the mechanical strain during electrode function, providing a clear explanation for the high durability with Co substitution. Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 operated at notably higher average potential than LiCo0.75Fe0.25PO4, which would increase the energy density of the cell. Ex situ measurements reveal the persistence of structural irreversibilities in the substituted phase after the first cycle, identifying avenues for further improvement in durability. Overall, this finding sheds light on the strategies for judicious cation substitution in LiCoPO4 electrodes to maximize the cycle life while preserving high energy density, especially compared to LiFePO4.},

  doi          = {10.1021/acsami.0c04110},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 18,

  volume       = 12,

  place        = {United States},

  year         = {2020},

  month        = {4}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acsami.0c04110

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

Padhi, A. K.
Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
DOI: 10.1149/1.1837571

Olivine LiFePO ₄ : the remaining challenges for future energy storage
journal, January 2015

Wang, Jiajun; Sun, Xueliang
Energy & Environmental Science, Vol. 8, Issue 4
DOI: 10.1039/C4EE04016C

Olivine LiCoPO[sub 4] as 4.8 V Electrode Material for Lithium Batteries
journal, January 1999

Amine, K.
Electrochemical and Solid-State Letters, Vol. 3, Issue 4
DOI: 10.1149/1.1390994

Improved cycle life of Fe-substituted LiCoPO4
journal, October 2011

Allen, J. L.; Jow, T. R.; Wolfenstine, J.
Journal of Power Sources, Vol. 196, Issue 20
DOI: 10.1016/j.jpowsour.2011.06.057

Direct Observation of Antisite Defects in LiCoPO ₄ Cathode Materials by Annular Dark- and Bright-Field Electron Microscopy
journal, October 2013

Truong, Quang Duc; Devaraju, Murukanahally Kempaiah; Tomai, Takaaki
ACS Applied Materials & Interfaces, Vol. 5, Issue 20
DOI: 10.1021/am403018n

Vanadium Substitution of LiFePO ₄ Cathode Materials To Enhance the Capacity of LiFePO ₄ -Based Lithium-Ion Batteries
journal, November 2012

Chiang, Ching-Yu; Su, Hui-Chia; Wu, Pin-Jiun
The Journal of Physical Chemistry C, Vol. 116, Issue 46
DOI: 10.1021/jp307047w

Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties
journal, April 2009

Meethong, Nonglak; Kao, Yu-Hua; Speakman, Scott A.
Advanced Functional Materials, Vol. 19, Issue 7, p. 1060-1070
DOI: 10.1002/adfm.200801617

Why Substitution Enhances the Reactivity of LiFePO ₄
journal, December 2012

Omenya, Fredrick; Chernova, Natasha A.; Zhang, Ruibo
Chemistry of Materials, Vol. 25, Issue 1
DOI: 10.1021/cm303259j

Changes in Electronic Structure upon Li Deintercalation from LiCoPO ₄ Derivatives
journal, February 2018

Lapping, Jacob G.; Delp, Samuel A.; Allen, Joshua L.
Chemistry of Materials, Vol. 30, Issue 6
DOI: 10.1021/acs.chemmater.7b04739

Crystal and magnetic structures of electrochemically delithiated Li1−xCoPO4 phases
journal, January 2009

Ehrenberg, Helmut; Bramnik, Natalia N.; Senyshyn, Anatoliy
Solid State Sciences, Vol. 11, Issue 1
DOI: 10.1016/j.solidstatesciences.2008.04.017

Electrochemical Delithiation/Relithiation of LiCoPO ₄ : A Two-Step Reaction Mechanism Investigated by in Situ X-ray Diffraction, in Situ X-ray Absorption Spectroscopy, and ex Situ ⁷ Li/ ³¹ P NMR Spectroscopy
journal, July 2014

Kaus, Maximilian; Issac, Ibrahim; Heinzmann, Ralf
The Journal of Physical Chemistry C, Vol. 118, Issue 31
DOI: 10.1021/jp503306v

Identifying the Structure of the Intermediate, Li _2/3 CoPO ₄ , Formed during Electrochemical Cycling of LiCoPO ₄
journal, October 2014

Strobridge, Fiona C.; Clément, Raphaële J.; Leskes, Michal
Chemistry of Materials, Vol. 26, Issue 21
DOI: 10.1021/cm502680w

X-ray Absorption Spectroscopic Study on the Electronic Structure of Li ₁ _- _x CoPO ₄ Electrodes as 4.8 V Positive Electrodes for Rechargeable Lithium Ion Batteries
journal, June 2005

Nakayama, Masanobu; Goto, Satoshi; Uchimoto, Yoshiharu
The Journal of Physical Chemistry B, Vol. 109, Issue 22
DOI: 10.1021/jp050569s

Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO ₄
journal, February 2007

Bramnik, Natalia N.; Nikolowski, Kristian; Baehtz, Carsten
Chemistry of Materials, Vol. 19, Issue 4
DOI: 10.1021/cm062246u

Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe _x Co _{1– x} PO ₄
journal, May 2016

Strobridge, Fiona C.; Liu, Hao; Leskes, Michal
Chemistry of Materials, Vol. 28, Issue 11
DOI: 10.1021/acs.chemmater.6b00319

The AMPIX electrochemical cell: a versatile apparatus for in situ X-ray scattering and spectroscopic measurements
journal, November 2012

Borkiewicz, Olaf J.; Shyam, Badri; Wiaderek, Kamila M.
Journal of Applied Crystallography, Vol. 45, Issue 6
DOI: 10.1107/S0021889812042720

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013

Toby, Brian H.; Von Dreele, Robert B.
Journal of Applied Crystallography, Vol. 46, Issue 2
DOI: 10.1107/S0021889813003531

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Shannon, R. D.
Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
DOI: 10.1107/S0567739476001551

Similar Records in DOE PAGES and OSTI.GOV collections:

Changes in Electronic Structure upon Li Deintercalation from LiCoPO₄ Derivatives

Journal Article Lapping, Jacob G. ; Delp, Samuel A. ; Allen, Joshua L. ; ... - Chemistry of Materials

On the path toward the design of Li-ion batteries with increased energy densities, efforts are focused on the development of positive electrodes that can maximize the voltage of the full cell. However, the development of novel materials that operate at high voltage, while also showing high efficiency and meeting strict safety standards, is an ongoing challenge. LiCoPO₄ is being explored as a possible candidate, as the Co^2+/3+ redox couple operates at 4.8 V versus Li⁺/Li⁰. The presence of phosphate groups is typically expected to stabilize the compound against oxygen loss, yet the changes in Co-O bonding upon Li extraction havemore »« less
Cited by 1
https://doi.org/10.1021/acs.chemmater.7b04739

Full Text Available
Improving the cycle stability of LiCoPO{sub 4} nanocomposites as 4.8 V cathode: Stepwise or synchronous surface coating and Mn substitution

Journal Article Örnek, Ahmet ; Can, Mustafa ; Yeşildağ, Ali - Materials Characterization

Nanostructured LiCo{sub 1−x}Mn{sub x}PO{sub 4}/C (x = 0 and 0.05) materials were successfully produced as superior quality cathodes by combined sol-gel and carbothermal reduction methods. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma (ICP), cyclic voltammetry (CV) and galvanostatic measurements were applied to determine the phase purity, morphology and electrochemical qualifications. HR-TEM analysis reveals that the thickness of the surface carbon layer of 5 to 10 nm range with the uniform distribution. LiCo{sub 0·95}Mn{sub 0·05}PO{sub 4}/C particles were betweenmore »« less
https://doi.org/10.1016/J.MATCHAR.2016.04.009
Influence of isovalent ion substitution on the electrochemical performance of LiCoPO{sub 4}

Journal Article Kishore, M.V.V.M. Satya ; Varadaraju, U V - Materials Research Bulletin

LiCo{sub 1-x}M {sub x}PO{sub 4} (M = Mg{sup 2+}, Mn{sup 2+} and Ni{sup 2+}; 0 {<=} x {<=} 0.2) compounds have been synthesized by solid-state reaction method and studied as cathode materials for secondary lithium batteries. LiCoPO{sub 4} exhibits a discharge plateau at {approx}4.7 V with an initial discharge capacity of 125 mAh/g and on cycling capacity falls. Substitution of Co{sup 2+} with Mg{sup 2+}/Mn{sup 2+}/Ni{sup 2+} in LiCoPO{sub 4} has an influence on the initial discharge capacity and on cycling behaviour. The capacity retention of LiCoPO{sub 4} is improved by manganese substitution. Among the manganese substituted phases, LiCo{sub 0.95}Mn{submore »« less
https://doi.org/10.1016/j.materresbull.2005.05.011
Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe _x Co _{1– x} PO ₄

Journal Article Strobridge, Fiona C. ; Liu, Hao ; Leskes, Michal ; ... - Chemistry of Materials

The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention because of the good capacity retention at high rates for LiFePO₄. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFemore »« less
Cited by 9
https://doi.org/10.1021/acs.chemmater.6b00319
Influence of gradual cobalt substitution on lithium nickel phosphate nano-scale composites for high voltage applications

Journal Article Örnek, Ahmet ; Bulut, Emrah ; Can, Mustafa - Materials Characterization

The carbon-free LiNiPO{sub 4} and cobalt doped LiNi{sub 1−x}Co{sub x}PO{sub 4}/C (x = 0.0–1.0) were synthesized and investigated for high voltage applications (> 4 V) for Li-ion batteries. Nano-scale composites were prepared by handy sol–gel approach using citric acid under slightly reductive gas atmosphere (Ar-H{sub 2}, 85:15%). Structural and morphological characteristics of the powders were revealed by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM) and inductively coupled plasma (ICP). Except for a small impurity phase (Ni{sub 3}P), phase pure samples crystallized in the olivine-lattice structure with a linear relationship between lattice parametersmore »« less
https://doi.org/10.1016/J.MATCHAR.2015.05.029

Similar Records

Title: Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives

Abstract

Citation Formats

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries journal, April 1997

Olivine LiFePO 4 : the remaining challenges for future energy storage journal, January 2015

Olivine LiCoPO[sub 4] as 4.8 V Electrode Material for Lithium Batteries journal, January 1999

Improved cycle life of Fe-substituted LiCoPO4 journal, October 2011

Direct Observation of Antisite Defects in LiCoPO 4 Cathode Materials by Annular Dark- and Bright-Field Electron Microscopy journal, October 2013

Vanadium Substitution of LiFePO 4 Cathode Materials To Enhance the Capacity of LiFePO 4 -Based Lithium-Ion Batteries journal, November 2012

Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties journal, April 2009

Why Substitution Enhances the Reactivity of LiFePO 4 journal, December 2012

Changes in Electronic Structure upon Li Deintercalation from LiCoPO 4 Derivatives journal, February 2018

Crystal and magnetic structures of electrochemically delithiated Li1−xCoPO4 phases journal, January 2009

Electrochemical Delithiation/Relithiation of LiCoPO 4 : A Two-Step Reaction Mechanism Investigated by in Situ X-ray Diffraction, in Situ X-ray Absorption Spectroscopy, and ex Situ 7 Li/ 31 P NMR Spectroscopy journal, July 2014

Identifying the Structure of the Intermediate, Li 2/3 CoPO 4 , Formed during Electrochemical Cycling of LiCoPO 4 journal, October 2014

X-ray Absorption Spectroscopic Study on the Electronic Structure of Li 1 - x CoPO 4 Electrodes as 4.8 V Positive Electrodes for Rechargeable Lithium Ion Batteries journal, June 2005

Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO 4 journal, February 2007

Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe x Co 1– x PO 4 journal, May 2016

The AMPIX electrochemical cell: a versatile apparatus for in situ X-ray scattering and spectroscopic measurements journal, November 2012

GSAS-II : the genesis of a modern open-source all purpose crystallography software package journal, March 2013

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal, September 1976

Title: Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO₄ Derivatives

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

Olivine LiFePO ₄ : the remaining challenges for future energy storage
journal, January 2015

Olivine LiCoPO[sub 4] as 4.8 V Electrode Material for Lithium Batteries
journal, January 1999

Improved cycle life of Fe-substituted LiCoPO4
journal, October 2011

Direct Observation of Antisite Defects in LiCoPO ₄ Cathode Materials by Annular Dark- and Bright-Field Electron Microscopy
journal, October 2013

Vanadium Substitution of LiFePO ₄ Cathode Materials To Enhance the Capacity of LiFePO ₄ -Based Lithium-Ion Batteries
journal, November 2012

Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties
journal, April 2009

Why Substitution Enhances the Reactivity of LiFePO ₄
journal, December 2012

Changes in Electronic Structure upon Li Deintercalation from LiCoPO ₄ Derivatives
journal, February 2018

Crystal and magnetic structures of electrochemically delithiated Li1−xCoPO4 phases
journal, January 2009

Electrochemical Delithiation/Relithiation of LiCoPO ₄ : A Two-Step Reaction Mechanism Investigated by in Situ X-ray Diffraction, in Situ X-ray Absorption Spectroscopy, and ex Situ ⁷ Li/ ³¹ P NMR Spectroscopy
journal, July 2014

Identifying the Structure of the Intermediate, Li _2/3 CoPO ₄ , Formed during Electrochemical Cycling of LiCoPO ₄
journal, October 2014

X-ray Absorption Spectroscopic Study on the Electronic Structure of Li ₁ _- _x CoPO ₄ Electrodes as 4.8 V Positive Electrodes for Rechargeable Lithium Ion Batteries
journal, June 2005

Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO ₄
journal, February 2007

Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe _x Co _{1– x} PO ₄
journal, May 2016

The AMPIX electrochemical cell: a versatile apparatus for in situ X-ray scattering and spectroscopic measurements
journal, November 2012

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976