Tuning and understanding the solvent ratios of localized saturated electrolytes for lithium-metal batteries

Yi, Michael S.; Su, Laisuo; Manthiram, Arumugam

doi:10.1039/d3ta01061a

Cited by 6 publications

(3 citation statements)

References 46 publications

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“…However, the continual cycling in LHCE leads to a development of more ionically conductive interphases, which greatly reduces the impedance growth and stabilizes the long-term performance as seen here. 40,41 Additional discussion on this topic will be presented in the subsequent sections. Figure 2i also demonstrates enhanced rate capability of the LHCE-SG full cell compared to that of the LFEC-SG full cell across all tested rates.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Impact of Electrolyte on Direct-Contact Prelithiation of Silicon-Graphite Anodes in Lithium-Ion Cells with High-Nickel Cathodes

Yi,

Cui,

Manthiram

2024

ACS Appl. Mater. Interfaces

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Silicon-based anodes offer high specific capacities to enhance the energy density of lithium-ion batteries, but are severely hindered by the immense volume expansion and subsequent breakage of the solid-electrolyte-interphase (SEI) during cycling. Herein, we utilize an effective strategy, known as direct-contact prelithiation, to mitigate the challenges associated with expansion and surface instability in SiO x /graphite (SG) anodes. It involves introducing lithium into the anode via physical contact with lithium metal and electrolyte before cycling. Prelithiation of SG anodes with an advanced localized high-concentration electrolyte is shown to develop a mechanically robust artificial SEI that tolerates better the electrode volume expansion. The modified SG anode paired with the high-Ni cathode LiNi 0.90 Mn 0.05 Co 0.05 O 2 delivers a high initial capacity of 191 mA h g −1 with 80% capacity retention over 150 cycles, compared to 46% retention with a conventional electrolyte. The bolstered SEI layer with reduced surface reactivity is due to the reduced electrolyte consumption and regulated SEI formation during cycling. Furthermore, the advanced electrolyte and fortified SG anode help reduce cathode degradation, transition-metal dissolution, and loss of active lithium. This study highlights viable prelithiation strategies to stabilize Si-based anodes for high-energy-density batteries through electrolyte design.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Impact of Electrolyte on Direct-Contact Prelithiation of Silicon-Graphite Anodes in Lithium-Ion Cells with High-Nickel Cathodes

Yi,

Cui,

Manthiram

2024

ACS Appl. Mater. Interfaces

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“…Here we selected an Al foil as the counter electrode that is commonly used in the literature . However, the high-voltage stability of an electrolyte in a practical LMB may not be the same as that measured in a Li | Al cell because they have different counter electrodes. , Therefore, the LSV data measured with a Li | Al cell can only be used to compare the relative high-voltage stability of different electrolytes.…”

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confidence: 99%

“…27 However, the high-voltage stability of an electrolyte in a practical LMB may not be the same as that measured in a Li | Al cell because they have different counter electrodes. 14,28 Figure 3c further compares the cycling performances of Cu | LiNiO 2 (LNO).anode-free cells with the three electrolytes. The charge cutoff voltage was set to 4.4 V. The cell with the LHCE3 has the best capacity retention after 100 cycles.…”

mentioning

confidence: 99%

Impact of High-Nickel Cathodes and Test Conditions on the Coulombic Efficiency of Lithium Metal in Advanced Electrolytes

Su,

Cui,

Manthiram

2023

ACS Materials Lett.

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Uncontrollable Li plating morphology and inferior Coulombic efficiency (CE) are major challenges that limit the practical viability of lithium−metal batteries (LMBs). With the design of advanced electrolytes, promising CEs (∼99.5%) have been shown in Cu | Li cells. However, the impact of cathode materials and their operating conditions in the cells on the CE has not been systematically evaluated. Here, we compare the CE of Li metal in Cu | Li cells and Cu | LiNi 1−x−y Mn x Co y O 2 cells with different Ni contents. We also evaluate the CE with different cutoff charge voltages (4.4 and 4.6 V). The cathode as well as increasing Ni content or cutoff voltage all negatively impact the Li CE in advanced electrolytes. The chemical crossover from the cathode to the anode alters the composition of the solid-electrolyte interphase (SEI) on the surface of Li metal. The crossed over sulfur and nitrogen species and the formation of less inorganic components like LiF in the Li SEI could lead to inferior Li CE. This study highlights the importance of considering the compatibility of advanced electrolytes both with Li metal and cathodes for LMBs.

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Deconstructing the High Voltage Degradation Mechanisms in Na_2/3Ni_1/3Mn_2/3O₂ with Single Crystals and Advanced Electrolyte

Darga,

Manthiram

2024

Adv Funct Materials

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Sodium layered oxide cathodes can uniquely benefit from the existing lithium‐ion battery industry as sodium‐ion batteries gain traction as a potential low‐cost, drop‐in replacement. However, achieving relevant energy density with a suitable cycle life remains a challenge for sodium layered oxides. At high operating potentials, several competing degradation mechanisms prevent P2‐type Na2/3Ni1/3Mn2/3O2 (≈550 Wh kg−1) from achieving meaningful cycle life—with bulk structural instability and surface reactivity being the primary retractors. Herein, the issue of particle cracking is addressed through detailed synthesis methods of “single‐crystal” materials. By comparison to a polycrystalline baseline, the single‐crystal materials quantify the capacity loss due to isolation of active material caused by intergranular particle cracking. The single crystal materials are then employed in cells with an advanced, “localized saturated electrolyte” (LSE) to demonstrate the magnitude of capacity loss due to electrolyte decomposition at the cathode surface. Mitigation of the surface reactivity through the LSE electrolyte effectively demonstrates the elevated importance of surface reactivity at high voltages despite the onset of egregious particle cracking. This work aims to guide future research into understanding molten‐salt assisted syntheses and advance the debate on surface versus bulk degradation.

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Tuning and understanding the solvent ratios of localized saturated electrolytes for lithium-metal batteries

Abstract: LiPF6-based localized saturated electrolytes (LSEs) have shown to greatly stabilize lithium-metal batteries with high-Ni cathodes to attain high energy densities for commerical feasbility. A mixture of fluoroethylene carbonate (FEC) and...

Cited by 6 publications

References 46 publications

Impact of Electrolyte on Direct-Contact Prelithiation of Silicon-Graphite Anodes in Lithium-Ion Cells with High-Nickel Cathodes

Impact of Electrolyte on Direct-Contact Prelithiation of Silicon-Graphite Anodes in Lithium-Ion Cells with High-Nickel Cathodes

Impact of High-Nickel Cathodes and Test Conditions on the Coulombic Efficiency of Lithium Metal in Advanced Electrolytes

Deconstructing the High Voltage Degradation Mechanisms in Na_2/3Ni_1/3Mn_2/3O₂ with Single Crystals and Advanced Electrolyte

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Tuning and understanding the solvent ratios of localized saturated electrolytes for lithium-metal batteries

Abstract: LiPF6-based localized saturated electrolytes (LSEs) have shown to greatly stabilize lithium-metal batteries with high-Ni cathodes to attain high energy densities for commerical feasbility. A mixture of fluoroethylene carbonate (FEC) and...

Cited by 6 publications

References 46 publications

Impact of Electrolyte on Direct-Contact Prelithiation of Silicon-Graphite Anodes in Lithium-Ion Cells with High-Nickel Cathodes

Impact of Electrolyte on Direct-Contact Prelithiation of Silicon-Graphite Anodes in Lithium-Ion Cells with High-Nickel Cathodes

Impact of High-Nickel Cathodes and Test Conditions on the Coulombic Efficiency of Lithium Metal in Advanced Electrolytes

Deconstructing the High Voltage Degradation Mechanisms in Na2/3Ni1/3Mn2/3O2 with Single Crystals and Advanced Electrolyte

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Deconstructing the High Voltage Degradation Mechanisms in Na_2/3Ni_1/3Mn_2/3O₂ with Single Crystals and Advanced Electrolyte