Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte

Xue, Weimin; Huang, Mingjun; Li, Yutao; Zhu, Yun; Gao, Rui; Xiao, Xianghui; Zhang, Wenxu; Li, Sipei; Xu, Guiyin; Yu, Yang; Li, Peng; Lopez, Jeffrey; Yu, Daiwei; Dong, Yanhao; Fan, Weiwei; Shi, Zhe; Xiong, Rui; Sun, Chengjun; Hwang, Inhui; Lee, Ivan; Johnson, Jeremiah A.; Li, Ju

doi:10.1038/s41560-021-00792-y

Cited by 454 publications

(329 citation statements)

References 54 publications

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“…26 ). LiFSI has a highly reactive fluorine bound to the S of sulfone (a leaving group) 78,79 , while LiTFSI displays a trifluoromethyl substituent with less-reactive fluorine despite possessing the same sulfonylimide backbone. LiFSI is reported to render an SEI that is mostly Li 2 O (ref.…”

Section: Discussionmentioning

confidence: 99%

“…Similarly, FEC, a widely used solvent in all-fluorine electrolytes, releases HF at moderate temperatures (>40 °C), particularly in the presence of Lewis acids 92 , which may pose challenges to its practical use as a base solvent. Fortunately, these challenges have started to be overcome by emerging molecularly designed solvent chemistries (for example, fluoroethers 93 , sulfonyl fluorides 78,79 and sulfones 94,95 ) engineered to suppress corrosion and provide stability at cathode potentials, thus enabling the use of imide-based salts such as LiFSI and LiTFSI at high voltages. As such, these systems have proven to be excellent sandboxes, providing insights into how to gain control over the electrochemical reactions that occur at the Li/electrolyte interface, with a large design space still to be explored for Li.…”

Section: Discussionmentioning

confidence: 99%

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Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes

et al. 2021

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes

et al. 2021

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“…These results have shown a pathway that emphasizes molecular design to develop novel electrolytes and overcome the challenges facing next-generation battery chemistries such as lithium metal. 27 , 28 However, little is known about the influence of building block connectivity. Within both works mentioned above, the same fluoroether design strategy was employed, where the fluorinated moieties are sandwiched by ether moieties ( Figure 1 ).…”

Section: Introductionmentioning

confidence: 99%

Effect of Building Block Connectivity and Ion Solvation on Electrochemical Stability and Ionic Conductivity in Novel Fluoroether Electrolytes

Mirmira

Amanchukwu

2021

ACS Cent. Sci.

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Novel electrolytes are required for the commercialization of batteries with high energy densities such as lithium metal batteries. Recently, fluoroether solvents have become promising electrolyte candidates because they yield appreciable ionic conductivities, high oxidative stability, and enable high Coulombic efficiencies for lithium metal cycling. However, reported fluoroether electrolytes have similar molecular structures, and the influence of ion solvation in modifying electrolyte properties has not been elucidated. In this work, we synthesize a group of fluoroether compounds with reversed building block connectivity where ether moieties are sandwiched by fluorinated end groups. These compounds can support ionic conductivities as high as 1.3 mS/cm (30 °C, 1 M salt concentration). Remarkably, we report that the oxidative stability of these electrolytes increases with decreasing fluorine content, a phenomenon not observed in other fluoroethers. Using Raman and other spectroscopic techniques, we show that lithium ion solvation is controlled by fluoroether molecular structure, and the oxidative stability correlates with the “free solvent” fraction. Finally, we show that these electrolytes can be cycled repeatedly with lithium metal and other battery chemistries. Understanding the impact of building block connectivity and ionic solvation structure on electrochemical phenomena will facilitate the development of novel electrolytes for next-generation batteries.

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“…High voltage operations (e.g., 4.4 or 4.5 V in full cells paired with a graphite anode) could compensate for the capacity loss; however, substantial metallic lithium formation on the graphite anode catalyzed by the deposited manganese species and the formation of thicker resistant rock‐salt phase on the cathode will ultimately lead to a rapid capacity fade. [ 11,28,29 ] Additionally, although surface modifications on high‐Ni cathode are proved to be beneficial on preventing continuous surface degradations, the mechanical deterioration caused by the anisotropic lattice distortion remains unsolved. Therefore, a rationally designed composition of ultrahigh‐Ni cathodes to achieve the sweet spot among cost, capacity, cycle life, and safety is critically needed, but it still requires more endeavors.…”

Section: Introductionmentioning

confidence: 99%

A Cobalt‐ and Manganese‐Free High‐Nickel Layered Oxide Cathode for Long‐Life, Safer Lithium‐Ion Batteries

Cui

Xie

Manthiram

2021

Advanced Energy Materials

110

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High‐nickel LiNi1−x−yMnxCoyO2 and LiNi1−x−yCoxAlyO2 cathodes are receiving growing attention due to the burgeoning demands on high‐energy‐density lithium‐ion batteries. The presence of both cobalt and manganese in them, however, triggers multiple issues, including high cost, high toxicity, rapid surface deterioration, and severe transition‐metal dissolution. Herein, a Co‐ and Mn‐free ultrahigh‐nickel LiNi0.93Al0.05Ti0.01Mg0.01O2 (NATM) cathode that exhibits 82% capacity retention over 800 deep cycles in full cells, outperforming two representative high‐Ni cathodes LiNi0.94Co0.06O2 (NC, 52%) and LiNi0.90Mn0.05Co0.05O2 (NMC, 60%) is presented. It is demonstrated that a titanium‐enriched surface along with aluminum and magnesium as the stabilizing ions in NATM not only ameliorates unwanted side reactions with the electrolyte and structural disintegrity, but also mitigates transition‐metal dissolution and active lithium loss on the graphite anode. As a result, the graphite anode paired with NATM displays an ultrathin (≈8 nm), monolayer anode‐electrolyte interphase architecture after extensive cycling. Furthermore, NATM displays considerably enhanced thermal stability with an elevated exothermic temperature (213 °C for NATM vs 180 and 190 °C for NC and NMC, respectively) and remarkably reduced heat release. This work sheds light on rational compositional design to adopt ultrahigh‐Ni cathodes in lithium‐based batteries with low cost, long service life, and improved thermal stability.

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Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte

Cited by 454 publications

References 54 publications

Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes

Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes

Effect of Building Block Connectivity and Ion Solvation on Electrochemical Stability and Ionic Conductivity in Novel Fluoroether Electrolytes

A Cobalt‐ and Manganese‐Free High‐Nickel Layered Oxide Cathode for Long‐Life, Safer Lithium‐Ion Batteries

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