High entropy oxides (FeNiCrMnX)3O4 (X=Zn, Mg) as anode materials for lithium ion batteries

Xiao, Bin; Wu, Gang; Wang, Tongde; Wei, Zhengang; Shen, Baolong; Qi, Jiqiu; Wei, Fuxiang; Meng, Qingkun; Ren, Yaojian; Xue, Xiaolan; Zheng, Junchao; Mao, Jing; Dai, Kun

doi:10.1016/j.ceramint.2021.08.303

Cited by 51 publications

(31 citation statements)

References 31 publications

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“…At a rate of C/5, we observed excellent stability for 100 reversible cycles (Figure 5F), showcasing the strong potential of the senary HEO as a practical anode choice for LIB applications. The overall electrochemical performance of our senary HEO is comparable to the best reported values from HEOs synthesized by other methods in the literature (Table S1, Supporting Information), [7,25,44,[46][47][48][49][50][51] which confirms the desired material quality by our approach.…”

Section: Introductionsupporting

confidence: 82%

Rapid Synthesis of High‐Entropy Oxide Microparticles

Dong

Hong

Gao

et al. 2022

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High‐entropy nanoparticles have received notable attention due to their tunable properties and broad material space. However, these nanoparticles are not suitable for certain applications (e.g., battery electrodes), where their microparticle (submicron to micron) counterparts are more preferred. Conventional methods used for synthesizing high‐entropy nanoparticles often involve various ultrafast shock processes. To increase the size thereby achieving high‐entropy microparticles, longer reaction time (e.g., heating duration) is usually used, which may also lead to undesired particle overgrowth or even densified microstructures. In this work, an approach based on Joule heating for synthesizing high‐entropy oxide (HEO) microparticles with uniform elemental distribution is reported. In particular, two key synthesis conditions are identified to achieve high‐quality HEO microparticles: 1) the precursors need to be loosely packed to avoid densification; 2) the heating time needs to be accurately controlled to tens of seconds instead of using milliseconds (thermal shock) that leads to nanoparticles or longer heating duration that forms bulk structures. The utility of the synthesized HEO microparticles for a range of applications, including high‐performance Li‐ion battery anode and water oxidation catalyst. This study opens up a new door toward synthesizing high‐entropy microparticles with high quality and broad material space.

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Section: Introductionsupporting

confidence: 82%

Rapid Synthesis of High‐Entropy Oxide Microparticles

Dong

Hong

Gao

et al. 2022

Small

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“…In the following positive scan, the anodic current before 1.2 V was steady and a broad oxidation peak was found at ≈1.5 V, indicating that a re‐conversion (i.e., Li + release) reaction took place. [ 33,44 ] In the second cycle, the cathodic peaks of all electrodes moved toward lower overpotential, reflecting that the lithiation processes became facilitated. It is noted that both the reduction and oxidation curves basically overlapped from the second cycle onward.…”

Section: Resultsmentioning

confidence: 99%

“…[ 48–53 ] Our 4 M Cu also outperforms many recently reported HEOs in terms of high‐rate performance, such as (Co 0.2 Cu 0.2 Mg 0.2 Ni 0.2 Zn 0.2 )O (≈280 mAh g −1 @1000 mA g −1 ), (Ni 0.2 Co 0.2 Mn 0.2 Fe 0.2 Ti 0.2 )O (401 mAh g −1 @1000 mA g –1 ), (Mg 0.2 Ti 0.2 Zn 0.2 Cu 0.2 Fe 0.2 ) 3 O 4 (272 mAh g −1 @2000 mA g −1 ), (FeNiCrMnZn) 3 O 4 (≈300 mAh g −1 @2000 mA g −1 ), (FeCoNiCrMn) 3 O 4 (≈180 mAh g −1 @2000 mA g −1 ), (FeCoNiCrMnZnLi) 3 O 4 (≈173 mAh g −1 @2000 mA g −1 ), and (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O (≈300 mAh g −1 @1800 mA g −1 ). [ 23,28,32,33,54,55 ] The fast charging–discharging characteristics of the proposed 4 M Cu HESO electrode is promising.…”

Section: Resultsmentioning

confidence: 99%

“…Actually, the chemical composition plays a critical role in determining the electrochemical performance of HEO electrodes. [31][32][33] Various constituent elements can give rise to different redox potentials, charge-discharge capacities, and reversibility. Moreover, the solid-solution single-phase formation ability of the compositional elements is also of great concern.…”

Section: Introductionmentioning

confidence: 99%

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Effects of Elemental Modulation on Phase Purity and Electrochemical Properties of Co‐free High‐Entropy Spinel Oxide Anodes for Lithium‐Ion Batteries

Patra

Nguyen

Tsai

et al. 2022

Adv Funct Materials

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High entropy oxide (HEO) is a new class of lithium-ion battery anode with high specific capacity and excellent cyclability. The beauty of HEO lies in the unique tailorable properties with respect to tunable chemical composition, which enables the use of infinite element combinations to develop new electrode materials. This study synthesizes a series of Co-free spinel-type HEOs via a facile hydrothermal method. Based on quaternary medium-entropy (CrNiMnFe) 3 O 4 , the fifth elements of V, Mg, and Cu are added, and their ability to form single-phase HEOs is investigated. It is demonstrated that the chemical composition of HEOs is critical to the phase purity and corresponding charge-discharge performance. The oxygen vacancy concentration seems to be decisive for the rate capability and reversibility of the HEO electrodes. An inactive spectator element is not necessary for achieving high cyclability, given that the phase purity of the HEO is wisely controlled. The single-phase (CrNiMnFeCu) 3 O 4 shows a great high-rate capacity of 480 mAh g −1 at 2000 mA g −1 and almost no capacity decay after 400 cycles. Its phase transition behavior during the lithiation/delithiation process is characterized with operando X-ray diffraction. A (CrNiMnFeCu) 3 O 4 ||LiNi 0.8 Co 0.1 Mn 0.1 O 2 cell is constructed with 590 Wh kg −1 (based on electrode materials) gravimetric energy density.

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“…[ 21 , 34 ] In the subsequent positive scan, a broad anodic peak centered at ≈1.5 V was observed, reflecting a reconversion (i.e., Li + release) reaction of the electrode. [ 35 , 36 ] It is noted that the cathodic charge is larger than the anodic charge in the first cycle, which is ascribed to the SEI formation and irreversible trapping of Li + within the electrode. From the second cycle onward, the CV curves almost overlap, indicating great electrochemical lithiation/delithiation reversibility of the HEO electrode.…”

Section: Resultsmentioning

confidence: 99%

Charge–Discharge Mechanism of High‐Entropy Co‐Free Spinel Oxide Toward Li⁺ Storage Examined Using Operando Quick‐Scanning X‐Ray Absorption Spectroscopy

et al. 2022

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Transition metal high-entropy oxides (HEOs) are an attractive class of anode materials for high-performance lithium-ion batteries (LIBs). However, owing to the multiple electroactive centers of HEOs, the Li + storage mechanism is complex and debated in the literature. In this work, operando quick-scanning X-ray absorption spectroscopy (XAS) is used to study the lithiation/delithiation mechanism of the Cobalt-free spinel (CrMnFeNiCu) 3 O 4 HEO. A monochromator oscillation frequency of 2 Hz is used and 240 spectra are integrated to achieve a 2 min time resolution. High-photon-flux synchrotron radiation is employed to increase the XAS sensitivity. The results indicate that the Cu 2+ and Ni 2+ cations are reduced to their metallic states during lithiation but their oxidation reactions are less favorable compared to the other elements upon delithiation. The Mn 2+/3+ and Fe 2+/3+ cations undergo two-step conversion reactions to form metallic phases, with MnO and FeO as the intermediate species, respectively. During delithiation, the oxidation of Mn occurs prior to that of Fe. The Cr 3+ cations are reduced to CrO and then Cr 0 during lithiation. A relatively large overpotential is required to activate the Cr reoxidation reaction. The Cr 3+ cations are found after delithiation. These results can guide the material design of HEOs for improving LIB performance.

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High entropy oxides (FeNiCrMnX)3O4 (X=Zn, Mg) as anode materials for lithium ion batteries

Cited by 51 publications

References 31 publications

Rapid Synthesis of High‐Entropy Oxide Microparticles

Rapid Synthesis of High‐Entropy Oxide Microparticles

Effects of Elemental Modulation on Phase Purity and Electrochemical Properties of Co‐free High‐Entropy Spinel Oxide Anodes for Lithium‐Ion Batteries

Charge–Discharge Mechanism of High‐Entropy Co‐Free Spinel Oxide Toward Li⁺ Storage Examined Using Operando Quick‐Scanning X‐Ray Absorption Spectroscopy

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High entropy oxides (FeNiCrMnX)3O4 (X=Zn, Mg) as anode materials for lithium ion batteries

Cited by 51 publications

References 31 publications

Rapid Synthesis of High‐Entropy Oxide Microparticles

Rapid Synthesis of High‐Entropy Oxide Microparticles

Effects of Elemental Modulation on Phase Purity and Electrochemical Properties of Co‐free High‐Entropy Spinel Oxide Anodes for Lithium‐Ion Batteries

Charge–Discharge Mechanism of High‐Entropy Co‐Free Spinel Oxide Toward Li+ Storage Examined Using Operando Quick‐Scanning X‐Ray Absorption Spectroscopy

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Charge–Discharge Mechanism of High‐Entropy Co‐Free Spinel Oxide Toward Li⁺ Storage Examined Using Operando Quick‐Scanning X‐Ray Absorption Spectroscopy