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

Title: The impact of alkali‐ion intercalation on redox chemistry and mechanical deformations: Case study on intercalation of Li, Na, and K ions into FePO 4 cathode

Journal Article · · Electrochemical Science Advances
 [1];  [2]; ORCiD logo [1]
  1. The School of Chemical Engineering Oklahoma State University Stillwater Oklahoma USA
  2. Department of Mechanical Engineering Rowan University Glassboro New Jersey USA

Abstract Batteries made of charge carriers from Earth‐crust abundant materials (e.g., Na, K, and Mg) have received extensive attention as an alternative to Li‐ion batteries for grid storage. However, a lack of understanding of the behavior of these larger ions in the electrode materials hinders the development of electrode structures suitable for these large ions. In this study, we investigate the impact of alkali ions (Li, Na, and K) on the redox chemistry and mechanical deformations of iron phosphate composite cathodes by using electrochemical techniques and in situ digital image correlation. Na‐ion and Li‐ion intercalation demonstrate a nearly linear correlation between electrochemical strains and the state of charge and discharge. The strain development shows nonlinear dependance on the state of charge and discharge for K ions. Strain rate calculations show that K ion intercalation results in a progressive increase in the strain rate for all cycles. Li and Na intercalation induce nearly constant strain rates with the exception of the first discharge cycle of Na intercalation. When the same amount of ions are inserted into the electrode, the electrode shows the lowest strain generation upon Li intercalation compared to larger alkali ions. Na and K ions induce similar volumetric changes in the electrode when the state of charge and discharge is around 30%. Although the electrode experiences larger absolute strain generation at the end of the discharge cycles upon Na intercalation, strain rates were found to be greater for K ions. Potential‐dependent behaviors also demonstrate more sluggish redox reactions during K intercalation, compared to Li and Na. Our quantitative analysis suggests that the strain rate, rather than the absolute value of strain, is the critical factor in amorphization of the crystalline electrode.

Research Organization:
Oklahoma State Univ., Stillwater, OK (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0021251
OSTI ID:
1813615
Alternate ID(s):
OSTI ID: 1813617; OSTI ID: 1830681
Journal Information:
Electrochemical Science Advances, Journal Name: Electrochemical Science Advances Vol. 2 Journal Issue: 4; ISSN 2698-5977
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (24)

Comparison of electrochemical performances of olivine NaFePO 4 in sodium-ion batteries and olivine LiFePO 4 in lithium-ion batteries journal January 2013
Investigation of sodium insertion–extraction in olivine Na x FePO 4 (0 ≤ x ≤ 1) using first-principles calculations journal January 2016
Amorphous iron phosphate: potential host for various charge carrier ions journal October 2014
Electrochemical strain evolution in iron phosphate composite cathodes during lithium and sodium ion intercalation journal September 2020
Advanced Cathode Materials for Sodium-Ion Batteries: What Determines Our Choices? journal April 2017
Rate dependence of the reaction mechanism in olivine NaFePO 4 Na-ion cathode material journal May 2018
In-situ preparation and electrochemical characterization of submicron sized NaFePO4 cathode material for sodium-ion batteries journal April 2017
Origin of non-SEI related coulombic efficiency loss in carbons tested against Na and Li journal January 2014
Phosphate Framework Electrode Materials for Sodium Ion Batteries journal January 2017
Dual-doping to suppress cracking in spinel LiMn 2 O 4 : a joint theoretical and experimental study journal January 2016
Particle shapes and surface structures of olivine NaFePO 4 in comparison to LiFePO 4 journal January 2014
Feeling the strain: enhancing ionic transport in olivine phosphate cathodes for Li- and Na-ion batteries through strain effects journal January 2016
Towards K-Ion and Na-Ion Batteries as “Beyond Li-Ion” journal February 2018
In Situ Observation of LiNiO[sub 2] Single-Particle Fracture during Li-Ion Extraction and Insertion journal January 1999
Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO 4 journal February 2017
Comparison between Na-Ion and Li-Ion Cells: Understanding the Critical Role of the Cathodes Stability and the Anodes Pretreatment on the Cells Behavior journal January 2016
Revealing the Mechanism of Sodium Diffusion in Na x FePO 4 Using an Improved Force Field journal March 2018
Structural absorption by barbule microstructures of super black bird of paradise feathers journal January 2018
Strain Evolution in Lithium Manganese Oxide Electrodes journal February 2018
In Situ Atomic-Scale Imaging of Phase Boundary Migration in FePO 4 Microparticles During Electrochemical Lithiation journal July 2013
Sodiation vs. Lithiation of FePO 4 : A comparative kinetic study journal October 2016
Atomic visualization of a non-equilibrium sodiation pathway in copper sulfide journal March 2018
Cracking causing cyclic instability of LiFePO4 cathode material journal January 2005
Surface investigation of chemically delithiatied FePO4 as a cathode material for sodium ion batteries journal June 2018

Similar Records

In Situ Probing Potassium-Ion Intercalation-Induced Amorphization in Crystalline Iron Phosphate Cathode Materials
Journal Article · Wed Sep 01 00:00:00 EDT 2021 · Nano Letters · OSTI ID:1813615

Na-Ion Intercalation and Charge Storage Mechanism in Two-Dimensional Vanadium Carbide
Journal Article · Fri Jul 14 00:00:00 EDT 2017 · Advanced Energy Materials · OSTI ID:1813615

Probing the Formation of Cathode-Electrolyte Interphase on Lithium Iron Phosphate Cathodes via Operando Mechanical Measurements
Journal Article · Sat Sep 02 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces · OSTI ID:1813615

Related Subjects