Lithium intercalation mechanisms and critical role of multi-doping in LiFexMn2−x−yTiyO4 as high-capacity cathode material for lithium-ion batteries

Callegari, Daniele; Coduri, Mauro; Fracchia, Martina; Ghigna, Paolo; Braglia, Luca; Tamburini, Umberto Anselmi; Quartarone, Eliana

doi:10.1039/d2tc00573e

Cited by 11 publications

(9 citation statements)

References 35 publications

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“…There is no peak observed in the CV curve for Fe because Fe is redox inactive and acts as an electrochemical stabilizer . Also, there is no peak observed for Al because Al is a redox inactive dopant in this material, and therefore, it is not influencing the CV behavior.…”

Section: Resultsmentioning

confidence: 94%

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Shivamurthy

Thripuranthaka

Shelke

et al. 2022

ACS Appl. Energy Mater.

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Disorder-structured spinel oxides are opening frontiers for high-capacity/high-voltage cathodes to meet the challenges of independence on cobalt-containing cathodes toward cheap and sustainable energy storage sources in Li-ion batteries (LIBs). In the present work, a series of Co-free materials: LiMn 2-x-y-z Ni x Fe y Al z O 4 (x = 0.8−0.5, y = 0.1−0.25, and z = 0.1−0.25) with spinel/rock salt disordered structures are reported. The refinement studies confirmed that the materials synthesized are of mixed phase, and the I 311 /I 400 peaks ratio confirms that the synthesized materials are stable enough for electrochemical applications. This article addresses the influence of the secondary phase on the electrochemical activity and the reduction of the Mn 3+ ratio to alleviate the Mn dissolution issue for bettered stability. The optimized LiMnNi 0.7 Fe 0.1 Al 0.2 O 4 is appraised as a cathode material in the voltage range between 3.5 and 5 V (vs. Li + /Li) with an initial discharge capacity of 148.7 mA h g −1 at a rate of 1 C. This material showed very good cycling stability with a capacity retention of 79.5% after 1000 cycles. The cyclic voltammetry studies showed that the material can be a potential candidate for 5 V applications.

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Section: Resultsmentioning

confidence: 94%

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Shivamurthy

Thripuranthaka

Shelke

et al. 2022

ACS Appl. Energy Mater.

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“…These observed redox peaks are dominating the overall redox behavior of the materials, which influences the high voltage operational capabilities of the cathode active materials. In CV, Fe and Al have not shown any redox activity because these two are redox-inactive but act as an electrochemical stabilizer to improve stability. , …”

Section: Resultsmentioning

confidence: 99%

“…20 From the literature, there are some theoretical studies that suggest that the majority of Mn ions will be at the surface in a trivalent state. 45,46 These trivalent Mn ions will disproportionate into tetravalent and divalent Mn ions, and the tetravalent Mn ions will be retained in a solid state, whereas the divalent Mn ions will be dissolved into an Energy & Fuels 110) and is more susceptible to Mn dissolution, which leads to capacity loss and reduced cycle life. 55 Our materials also showed the same behavior and correlate with the experimental studies, and the material with a more exposed (111) plane surface has shown superior performance.…”

Section: Impact Of Plane Orientation On the Electrochemical Performancementioning

confidence: 99%

Influence of the Crystal Plane Orientation in Enhancing the Electrochemical Performance of a Trication-Substituted Cathode for Li-Ion Batteries

Shivamurthy,

Thripuranthaka,

Shelke

et al. 2024

Energy Fuels

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High-voltage spinel cathodes with low nickel are promising candidates for Li-ion batteries owing to their high energy and power density, thermal stability, and eco-friendliness. However, the high operating voltage (∼4.7 V) leads to the decomposition of electrolytes, structural disorder, and deterioration of the cathode−electrolyte interphase (CEI) as well as hinders practical capability. We have synthesized trication-substituted spinel cathode materials with exposed (111) crystal planes and truncated octahedral shapes. These materials have demonstrated high specific discharge capacity and high rate capability up to 1000 cycles with a voltage window of 3.5−5 V. The crystal plane orientation of these materials has been investigated using X-ray diffraction of electrodes and electron microscopic studies and correlated with the electrochemical performance of the surface plane of exposed cathode materials. Among the three synthesized materials, the LMNFA2 cathode has shown a specific discharge capacity of 109.29 mAh g −1 at 1 C after 1000 cycles with a capacity retention of 76.3%, which is nearly equal to the previously reported dual-phase material with the same metal compositions.

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“…All three samples experienced severe capacity reduction owing to the well-known phenomenon of J-T distortion in spinel LMOs [51]. In terms of cycle performance, LMO-W was the most stable, with a capacity retention of 82% after the 100th cycle, whereas LMO-E and LMO-G experienced more noticeable capacity loss, with capacity retentions of 79% and 70%, respectively, at the 100th cycle [51,64]. Small particles can improve the electrochemical performance by enhancing the Li + ion diffusion kinetics [41]; however, their high surface areas lead to a more unstable cycle life and capacity degradation after a limited number of cycles.…”

Section: Electrochemical Characterizationmentioning

confidence: 98%

Unraveling the Mechanism and Practical Implications of the Sol-Gel Synthesis of Spinel LiMn2O4 as a Cathode Material for Li-Ion Batteries: Critical Effects of Cation Distribution at the Matrix Level

et al. 2023

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Spinel LiMn2O4 (LMO) is a state-of-the-art cathode material for Li-ion batteries. However, the operating voltage and battery life of spinel LMO needs to be improved for application in various modern technologies. Modifying the composition of the spinel LMO material alters its electronic structure, thereby increasing its operating voltage. Additionally, modifying the microstructure of the spinel LMO by controlling the size and distribution of the particles can improve its electrochemical properties. In this study, we elucidate the sol-gel synthesis mechanisms of two common types of sol-gels (modified and unmodified metal complexes)—chelate gel and organic polymeric gel—and investigate their structural and morphological properties and electrochemical performances. This study highlights that uniform distribution of cations during sol-gel formation is important for the growth of LMO crystals. Furthermore, a homogeneous multicomponent sol-gel, necessary to ensure that no conflicting morphologies and structures would degrade the electrochemical performances, can be obtained when the sol-gel has a polymer-like structure and uniformly bound ions; this can be achieved by using additional multifunctional reagents, namely cross-linkers.

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Lithium intercalation mechanisms and critical role of multi-doping in LiFe_xMn_2−x−yTi_yO₄ as high-capacity cathode material for lithium-ion batteries

Abstract: The ever-growing demand for Li-ion batteries requires high-capacity electrode materials that should also be environmentally benign, Co-free, secure and durable, to achieve an optimal compromise between sustainability and functional performances....

Cited by 11 publications

References 35 publications

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Formation of the Secondary Phase Domain by Multi-Cation Substitution for the Superior Electrochemical Performance of Spinel Cathodes for High-Voltage Li-Ion Batteries

Influence of the Crystal Plane Orientation in Enhancing the Electrochemical Performance of a Trication-Substituted Cathode for Li-Ion Batteries

Unraveling the Mechanism and Practical Implications of the Sol-Gel Synthesis of Spinel LiMn2O4 as a Cathode Material for Li-Ion Batteries: Critical Effects of Cation Distribution at the Matrix Level

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