Understanding the electrochemical features of ZnFe2O4, anode for LIBs, by deepening its physico-chemical properties

Spada, Daniele; Ambrosetti, Marco; Mozzati, Maria Cristina; Albini, Benedetta; Galinetto, P.; Cini, Alberto; Fittipaldi, Maria; Bini, Marcella

doi:10.1016/j.materresbull.2022.112132

Cited by 9 publications

(5 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Cyclic voltammograms of the carbon-coated samples are shown in Figure 5. The electrochemical reactions for GeFe2O4 are the same accepted worldwide for the spinels applied in the battery field, i.e., conversion and alloying combined mechanism [35,36]: The electrochemical reactions for GeFe 2 O 4 are the same accepted worldwide for the spinels applied in the battery i.e., conversion and alloying combined mechanism [35,36]:…”

Section: Electrochemical Characterizationmentioning

confidence: 99%

Pure and (Sn or Mg) Doped GeFe2O4 as Anodes for Sodium-Ion Batteries

Ambrosetti,

Quinzeni,

Girella

et al. 2024

Batteries

Self Cite

View full text Add to dashboard Cite

GeFe2O4 (GFO) is a germanium mineral whose spinel crystal structure determines its interesting functional properties. Recently, it was proposed for application as an anode for Sodium and Lithium-Ion Batteries (SIBs and LIBs) thanks to its combined conversion and alloying electrochemical mechanism. However, its entire potential is limited by the poor electronic conductivity and volumetric expansion during cycling. In the present paper, pure and Sn or Mg doped GFO samples obtained from mechano-chemical solid-state synthesis and properly carbon coated were structurally and electrochemically characterized and proposed, for the first time, as anodes for SIBs. The spinel cubic structure of pure GFO is maintained in doped samples. The expected redox processes, involving Fe and Ge ions, are evidenced in the electrochemical tests. The Sn doping demonstrated a beneficial effect on the long-term cycling (providing 150 mAh/g at 0.2 C after 120 cycles) and on the capacity values (346 mAh/g at 0.2 C with respect to 300 mAh/g of the pure one), while the Mg substitution was less effective.

show abstract

Section: Electrochemical Characterizationmentioning

confidence: 99%

Pure and (Sn or Mg) Doped GeFe2O4 as Anodes for Sodium-Ion Batteries

Ambrosetti,

Quinzeni,

Girella

et al. 2024

Batteries

Self Cite

View full text Add to dashboard Cite

show abstract

“…[90] Migration of the Zn 2+ cations from 8a to 16d sites during the initial stage of lithiation has already been reported for spinel ZnFe 2 O 4 . [88,89,91,92] At low Li-uptake, Li + ions show a preference for the vacant octahedral over vacant tetrahedral sites; [89] at higher Li-uptake, further insertion of Li + ions causes Zn 2+ cations to migrate to vacant octahedral (16c) sites to reduce electrostatic repulsion from Li + ions inserted into octahedral sites, [91,92] with the resulting structure allowing for easy Li-ion transport within channels no longer blocked by Zn 2+ cations. [89] From HEO-3 onward, zinc shows the neighborhood of strongly distorted/disordered oxide species, with just the first coordination shell visible; therefore, the modification is not reversible.…”

Section: Electrode At Different Socmentioning

confidence: 99%

Charge Storage Mechanism in Electrospun Spinel‐Structured High‐Entropy (Mn_0.2Fe_0.2Co_0.2Ni_0.2Zn_0.2)₃O₄ Oxide Nanofibers as Anode Material for Li‐Ion Batteries

Triolo

Maisuradze

et al. 2023

Small

View full text Add to dashboard Cite

High‐entropy oxides (HEOs) have emerged as promising anode materials for next‐generation lithium‐ion batteries (LIBs). Among them, spinel HEOs with vacant lattice sites allowing for lithium insertion and diffusion seem particularly attractive. In this work, electrospun oxygen‐deficient (Mn,Fe,Co,Ni,Zn) HEO nanofibers are produced under environmentally friendly calcination conditions and evaluated as anode active material in LIBs. A thorough investigation of the material properties and Li+ storage mechanism is carried out by several analytical techniques, including ex situ synchrotron X‐ray absorption spectroscopy. The lithiation process is elucidated in terms of lithium insertion, cation migration, and metal‐forming conversion reaction. The process is not fully reversible and the reduction of cations to the metallic form is not complete. In particular, iron, cobalt, and nickel, initially present mainly as Fe3+, Co3+/Co2+, and Ni2+, undergo reduction to Fe0, Co0, and Ni0 to different extent (Fe < Co < Ni). Manganese undergoes partial reduction to Mn3+/Mn2+ and, upon re‐oxidation, does not revert to the pristine oxidation state (+4). Zn2+ cations do not electrochemically participate in the conversion reaction, but migrating from tetrahedral to octahedral positions, they facilitate Li‐ion transport within lattice channels opened by their migration. Partially reversible crystal phase transitions are observed.

show abstract

“…A sharp cathodic peak at a voltage of about 0.5-0.6 V is observed at the first discharge cycle (Figure 5a). This peak corresponds to the lithiation of ZFO with formation of Li x ZnFe 2 O 4 (Equation ( 1)) and the reversible reduction of Zn 2+ to Zn 0 and Fe 3+ to Fe 0 during further lithiation of Li x ZnFe 2 O 4 with the formation of Li 2 O, followed by the formation of the LiZn alloy (Equations ( 2) and ( 3)) and the solid electrolyte interphase (SEI) layer on the electrode surface due to the electrolyte decomposition [5,13]. For the first charge cycle (delithiation), a broad anodic peak at E ≈ 1.85 V is observed, corresponding to the disappearance of the LiZn alloy and the destruction of Li 2 O with the oxidation of Zn 0 and Fe 0 to ZnO and Fe 2 O 3 , respectively (Equations ( 4) and ( 5)).…”

Section: Electrochemical Performancementioning

confidence: 99%

Synthesis of ZnFe2O4 Nanospheres with Tunable Morphology for Lithium Storage

Volkov,

Kamenskii,

Tolstopjatova

et al. 2023

Nanomaterials

View full text Add to dashboard Cite

ZnFe2O4 (ZFO) nanospheres with complex structures have been synthesized by a one-step simple solvothermal method using two different types of precursors—metal chlorides and nitrates —and were fully characterized by XRD, SEM, XPS, and EDS. The ZFO nanospheres synthesized from chloride salts (ZFO_C) were loose with a size range of 100–200 nm, while the ZFO nanospheres synthesized from nitrate salts (ZFO_N) were dense with a size range of 300–500 nm but consisted of smaller nanoplates. The different morphologies may be caused by the different hydrolysis rates and different stabilizing effects of chloride and nitrate ions interacting with the facets of forming nanoparticles. Electrochemical tests of nitrate-based ZFO nanospheres as anode materials for lithium-ion batteries demonstrated their higher cyclic stability. The ZFO_C and ZFO_N samples have initial specific discharge/charge capacities of 1354/1020 and 1357/954 mAh∙g−1, respectively, with coulombic efficiencies of 75% and 71%. By the 100th cycle, ZFO_N has a capacity of 276 mAh∙g−1, and for ZFO_C, only 210 mAh∙g−1 remains after 100 cycles.

show abstract

Understanding the electrochemical features of ZnFe2O4, anode for LIBs, by deepening its physico-chemical properties

Cited by 9 publications

References 40 publications

Pure and (Sn or Mg) Doped GeFe2O4 as Anodes for Sodium-Ion Batteries

Pure and (Sn or Mg) Doped GeFe2O4 as Anodes for Sodium-Ion Batteries

Charge Storage Mechanism in Electrospun Spinel‐Structured High‐Entropy (Mn_0.2Fe_0.2Co_0.2Ni_0.2Zn_0.2)₃O₄ Oxide Nanofibers as Anode Material for Li‐Ion Batteries

Synthesis of ZnFe2O4 Nanospheres with Tunable Morphology for Lithium Storage

Contact Info

Product

Resources

About

Understanding the electrochemical features of ZnFe2O4, anode for LIBs, by deepening its physico-chemical properties

Cited by 9 publications

References 40 publications

Pure and (Sn or Mg) Doped GeFe2O4 as Anodes for Sodium-Ion Batteries

Pure and (Sn or Mg) Doped GeFe2O4 as Anodes for Sodium-Ion Batteries

Charge Storage Mechanism in Electrospun Spinel‐Structured High‐Entropy (Mn0.2Fe0.2Co0.2Ni0.2Zn0.2)3O4 Oxide Nanofibers as Anode Material for Li‐Ion Batteries

Synthesis of ZnFe2O4 Nanospheres with Tunable Morphology for Lithium Storage

Contact Info

Product

Resources

About

Charge Storage Mechanism in Electrospun Spinel‐Structured High‐Entropy (Mn_0.2Fe_0.2Co_0.2Ni_0.2Zn_0.2)₃O₄ Oxide Nanofibers as Anode Material for Li‐Ion Batteries