Rational solvent molecule tuning for high-performance lithium metal battery electrolytes

Rudnicki, Paul E.; Zhang, Zewen; Huang, Zhuojun; Çelik, Hasan; Oyakhire, Solomon T.; Chen, Yuelang; Kong, Xian; Kim, Sang Cheol; Xiao, Xin; Wang, Hansen; Zheng, Yu; Kamat, Gaurav A.; Kim, Mun Sek; Bent, Stacey F.; Qin, Jian; Cui, Yi; Bao, Zhenan

doi:10.1038/s41560-021-00962-y

Cited by 392 publications

(366 citation statements)

References 62 publications

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“…Moreover, it should be noted that the unique monofluorination strategy dramatically increases the dipole moment of the end group from 0.08 Debye (-CH3) to 0.48 Debye (-CH2F), which is also much higher than previously reported difluorine substitution of -CHF2 and -CF3 groups (Figure S11). 23,24 In summary, the mono-fluorinated FDEE enhances the oxidation stability and retains the high salt solubility of ether solvents. The high local polarity of -CH2F enables peculiar Li + …F-CH2-interaction for reduced anion coordination and high ionic conductivity.…”

Section: Unique Properties Of Fdee and Reduced LI + -Anion Coordinationmentioning

confidence: 99%

“…30 The stark difference for FDEE is likely due to the special Li + …F-CH2-interaction between FDEE and Li + , as suggested by the induced chemical shifts of 7 Li-NMR and 19 F-NMR (Figure 1f and Figure S6-8). 23,24,31 Such interaction apparently increases the solvating ability of FDEE (Figure S9) to reduce the anion coordination for more facial ionic conduction. 29,32 As indicated in Figure 1g, the ionic conductivity of FDEE-LHCE (~3.25 mS cm -1 ) is about twice of that in DEE-LHCE (~1.71 mS cm -1 ).…”

Section: Unique Properties Of Fdee and Reduced LI + -Anion Coordinationmentioning

confidence: 99%

“…[19][20][21][22] Several ether molecules with difluoro or trifluoro functional groups have demonstrated enhanced high voltage stabilities for LMBs (under 4.3~4.4 V). 23,24 Nevertheless, salt dissolution ability of the solvent would be compromised due to the existence of multi-fluorinated moieties at the vicinity of Li +coordination sites (e.g., oxygen atoms).…”

Section: Introductionmentioning

confidence: 99%

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Monofluoro-ether electrolyte design with reduced Li+-anion coordination enables fast-charging ultrahigh-voltage lithium metal batteries

Ruan

Tan

Chen

et al. 2022

Preprint

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Ether-based electrolytes are particularly useful for lithium metal batteries (LMBs) and have shown improved anodic stability with the high concentration design. Nevertheless, the vaunted anion-reinforced solvation in concentrated electrolytes has non-negligible adverse effect on ion conduction and battery rate performance. Here, we propose a new solvent design strategy of ether monofluorination to tune the Li+-anion interaction for fast-charging LMBs. With the highly polar monofluoro functional groups, the ether-based electrolyte not only exhibits excellent high oxidation stability due to the strong electron-withdrawing effect of F, but also has a greatly increased ionic conductivity because of reduced anion coordination. The unique solvation structure also enables the formation of robust and highly conductive interphases at both the Li anode and NMC811 surfaces. High Li CEs (~99.4%) and stable long-term cycling with low overpotential under ultrahigh current densities (10 mA cm-2) could be achieved for Li anode. Li||NMC811 cells exhibit outstanding cycling performance under ultrahigh cut-off voltages of 4.6 V and 4.7 V, or at high current densities (5.1 mA cm-2). This work provides critical insights into the ion-solvent interactions in the solvation complex and their profound influence on the battery electrochemical performances.

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Section: Unique Properties Of Fdee and Reduced LI + -Anion Coordinationmentioning

confidence: 99%

Section: Unique Properties Of Fdee and Reduced LI + -Anion Coordinationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Monofluoro-ether electrolyte design with reduced Li+-anion coordination enables fast-charging ultrahigh-voltage lithium metal batteries

Ruan

Tan

Chen

et al. 2022

Preprint

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“…The assembled Li||Cu cell with the electrolyte achieved the outstanding CE of 99.7% at 1.0 mA cm −2 and 3.0 mAh cm −2 . Moreover, Cui et al focused on the control of various properties of solvents through the modification of functional groups, 42 and investigated the discrepancy in the electrolyte properties of different fluorinated DEOE molecules (Figure 4D). MD and diffusion‐ordered spectroscopy (DOSY) showed that the Li + ‐anion cluster (LAC) percentage and other parameters change regularly with the alteration of the substituted functional group (Figure 4E), proving that the strong binding solvent ability could reduce the aggregation of Li + ‐FSI and obtain higher conductivity.…”

Section: Anion Regulationmentioning

confidence: 99%

“…High‐concentration electrolyte (HCE) and others could greatly reduce the number of solvent‐separated ion pair (SSIP) structures and free solvent molecules, which is mainly composed of contact ion pair (CIP) and aggregates (AGGs) 29,39–41 . CIP and AGGs are the complexes of oppositely charged Li + and anions associated due to coulomb interaction, in which AGGs have more than two Li + using the same anion as the center to count the coordinating Li + number 42 . As reported, 43,44 due to the interfacial electric double layer (EDL) generated by the dissolution of Li on the electrode surface, only the anions in the solvated structure can participate in the construction of sustainable SEI together with other electrolyte components.…”

Section: Introductionmentioning

confidence: 99%

Structural regulation chemistry of lithium ion solvation for lithium batteries

Wang

et al. 2022

EcoMat

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The performance of Li batteries is influenced by the Li+ solvation structure, which can be precisely adjusted by the components of the electrolytes. In this review, we overview the strategies for optimizing electrolyte solvation structures from three different perspectives, including anion regulation, binding energy regulation, and additive regulation. These strategies can optimize the composition of the electrode‐electrolyte interface, enhance the anti‐oxidative stability of electrolytes as well as regulate the behaviors of anions, solvents, and Li+ during the cycling process. Moreover, we also provide our insights into these aspects as well as present perspectives on high‐performance Li batteries.

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In Situ Cross‐Linked Plastic Crystal Electrolytes for Wide‐Temperature and High‐Energy‐Density Lithium Metal Batteries

Wang

Geng

Zhao

et al. 2022

Adv Funct Materials

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The development of high-energy-density lithium metal batteries has been significantly hampered mainly due to the poor electrolyte-electrode compatibility, narrow operating temperature range, and stringent safety concerns of conventional electrolytes. Here, an in situ cross-linked plastic crystal-based electrolyte (CPCE) with an optimized composition design is proposed. Based on the interaction of succinonitrile (SN) and ethoxylated trimethylolpropane triacrylate (ETPTA) with polar carbonyl groups, CPCE delivers well-tuned energy levels and a concentrated coordination structure, leading to an improved electrochemical window and stable electrodeelectrolyte interface. In addition, the crystallization of SN molecules is also inhibited, ensuring suitable ion migration in bulky CPCE over a wide temperature range. Moreover, both the nonleakage of cross-linked ETPTA and the nonflammability of the plastic crystal electrolyte (PCE) further reinforce the safety of CPCE. As a result, the well-designed CPCE achieves high ion conductivity with a wide electrochemical window (≈5.4 V vs Li + /Li) and a broad operating temperature range (−20 to 100 °C). It also delivers dendrite-free lithium plating with high Coulombic efficiency of up to ≈99.1%. The Cu|CPCE|LiNi 0.8 Co 0.1 Mn 0.1 O 2 anode-free pouch cell exhibits high energy density (≈1520 Wh L −1 ) and high safety during abuse tests. This study paves a new pathway to realize the practical application of high-energy-density lithium metal battery energy storage systems.

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Rational solvent molecule tuning for high-performance lithium metal battery electrolytes

Cited by 392 publications

References 62 publications

Monofluoro-ether electrolyte design with reduced Li+-anion coordination enables fast-charging ultrahigh-voltage lithium metal batteries

Monofluoro-ether electrolyte design with reduced Li+-anion coordination enables fast-charging ultrahigh-voltage lithium metal batteries

Structural regulation chemistry of lithium ion solvation for lithium batteries

In Situ Cross‐Linked Plastic Crystal Electrolytes for Wide‐Temperature and High‐Energy‐Density Lithium Metal Batteries

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