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Zheng, Guorui

Publications and source records attributed to Zheng, Guorui.

Stabilizing LiCoO 2 at 4.6 V by regulating anti-oxidative solvents

For LiCoO 2 (LCO) operating at high voltages (>4.5 V vs. Li/Li + ), the intensive side reactions between LCO and traditional ethylene carbonate (EC)-based electrolytes with LiPF 6 salts can produce plenty of corrosive species (such as HF and HPO 2 F 2 ), causing severe surface degradation. Herein, anti-oxidative fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC) were selected as co-solvents to reduce the generation of corrosive species. Besides, PF 6 − anions enrich the Helmholtz plane of the LCO/electrolyte interface and promote the formation of a robust cathode/electrolyte interphase (CEI) featuring LiF/Li x PO y F z /Li 3 PO 4 inorganics and P-containing organics under the synergy of fluorinated solvents, which significantly inhibits the catalysis of highly oxidative Co 4+ /O n− (0 < n < 2). Benefiting from the reduced corrosive species and reinforced CEI, the layered structure of the LCO surface is well preserved during long-term cycling, with a highly reversible O3/H1-3 phase transition. Consequently, a LCO||graphite pouch cell exhibits a remarkable capacity retention of 85.7% after 500 cycles in 3.0–4.55 V. Furthermore, this work provides a new insight into developing advanced functional electrolytes for high-voltage lithium-ion batteries.

Co/O loss↗

In situ probing the origin of interfacial instability of Na metal anode

The unstable and fragile solid electrolyte interphase (SEI) has restricted the application of Na metal anodes. Despite numerous research efforts being put into understanding its chemical composition and physical properties, direct observation of its formation remains a challenge due to the lack of temporal and spatial resolution. Here, through combined in situ probing techniques, we exhibit two pivotal stages associated with SEI instability during the often -neglected formation process. It is revealed that Na metal that is not uniformly passivated at the initial (passivating) stage will trigger unrestricted electrolyte decomposition and homogeneous components distribution during the subsequent (growing) stage. SEI with homogenously distributed components is found to have higher solubility than that with a layered structure evolved from a compact passivation layer. Furthermore, through demonstrating an SEI dissolution model that is closely related to its formation process and compositional distribution, this work sheds light on an uncharted territory of Na metal batteries.

25 ENERGY STORAGE↗

Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy

Abstract Structural and interfacial instability of the LiCoO 2 cathode under a voltage exceeding 4.5 V (vs Li/Li + ) severely hinders its practical applications for high‐energy‐density lithium batteries. Herein, a modified electrolyte with nitriles (suberonitrile or 1,3,6‐hexanetricarbonitrile) and fluoroethylene carbonate (FEC) coadditives is demonstrated to form an ultrathin and uniform interface layer on LiCoO 2 cathode under a synergetic effect. As such, LiCoO 2 /Li cells display excellent cyclability at a cutoff voltage of 4.6 V with a capacity retention over 72% after 300 cycles and 60% after 200 cycles at 30 and 55 °C, respectively, even achieving operation at a high current rate (10 C) upon 500 cycles as compared to the controls with fast‐falling capacity to zero. Furthermore, an adsorption‐coordination mechanism between nitriles and cobalt and synergetic effect of coadditives are explored by the alliance of spectroscopic analysis and theoretical calculations. The contributed lone‐pairs on the N 2p orbital of nitriles in coordination lowers the real oxidation state of Co 3+/4+ so that it decreases its catalysis on electrolytes, and the synergy from nitrile‐derived species regulates FEC to form an LiF‐containing electron‐insulated interface layer. This work shares a new insight to nitriles with the synergy of coadditives and paves a way to refine (ultra)high‐voltage LiCoO 2 cathode for high‐energy‐density energy storages.

Yang, Xuerui↗