Revealing electrolyte oxidation <i>via</i> carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by <i>in situ</i> Fourier transform infrared spectroscopy

Zhang, Yirui; Katayama, Yu; Tatara, Ryoichi; Giordano, Livia; Yu, Yang; Fraggedakis, Dimitrios; Sun, Jame; Maglia, Filippo; Jung, Roland; Bazant, Martin Z.

doi:10.1039/c9ee02543j

Cited by 267 publications

(340 citation statements)

References 119 publications

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“…The CEI film is resulted from the decomposition of the carbonate solvent (Figure 9A2) and harmful for the cycling performance. [ 4a ] SR was supposed to happen between the LiPF 6 and moisture, as the F 1s spectra of all electrode materials split into two peaks, which is related to LiF/Li x PO y F z (≈685 eV) and C‐F (≈687 eV), respectively (Figure 9B1). [ 59 ] The reduced peak area of LiF and Li x PO y F z for the 3% LCO electrode demonstrates that the formation of the CEI in this sample is efficiently mitigated due to the construction of LCO on the surface (Figure 9B2), which is related to the conductive impedance of Li + passing through the CEI.…”

Section: Resultsmentioning

confidence: 99%

“…[ 3 ] Meanwhile, the highly reactive Ni 4+ produced at high voltage would induce parasitic side reactions (SR) at the interface of electrode/electrolyte, generating cathode electrolyte interphase (CEI) derived from the electrolyte decomposition, TM migration and dissolution. [ 4 ] The SR, coupled with the irreversible oxygen loss, further induces the capacity loss and voltage fading. [ 5 ] In this case, the biggest challenge is to improve the structure stability and stabilize the reversible oxygen‐related reactions, which are crucial to establish high energy density LIBs with superior cycling stability.…”

Section: Introductionmentioning

confidence: 99%

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Pseudo‐Bonding and Electric‐Field Harmony for Li‐Rich Mn‐Based Oxide Cathode

Chen

Zou

Deng

et al. 2020

Adv Funct Materials

174

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The practical application of Li-rich Mn-based oxide cathode is predominately retarded by the capacity decline and voltage fading, associated with the structure distortion and anionic redox reactions. Here, a linkagefunctionalized modification approach to tackle these challenges via a synchronous lithium oxidation strategy is reported. The doping of Ce in the bulk phase activates the pseudo-bonding effect, effectively stabilizing the lattice oxygen evolution and suppressing the structure distortion. Interestingly, it also induces the formation of spinel phase Li 4 Mn 5 O 12 in the subsurface, which in turn constructs the phase boundaries, thereby arousing the interior self-built-in electric field to prevent the outward migration of bulk oxygen anions and boost the charge transfer. Moreover, the formed coating layer Li 2 CeO 3 with oxygen vacancies accelerates Li + diffusion and mitigates electrolyte cauterization. The corresponding cathode exhibits superior longcycle stability after 300 cycles with only a 0.013% capacity drop and 1.76 mV voltage decay per cycle. This work sheds new light on the development of Li-rich Mn-based oxide cathodes toward high energy density applications.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Pseudo‐Bonding and Electric‐Field Harmony for Li‐Rich Mn‐Based Oxide Cathode

Chen

Zou

Deng

et al. 2020

Adv Funct Materials

174

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“…During charging, the voltage of the cathode electrodes is increased until a defined upper cut-off value leading to delithiated stage, i.e., extraction of Li ions from the layered structure [73,76,77].…”

Section: Micro Cracking Of Secondary Particle Structurementioning

confidence: 99%

Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries

et al. 2020

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Driven by the increasing plea for greener transportation and efficient integration of renewable energy sources, Ni-rich metal layered oxides, namely NMC, Li [Ni1−x−yCoyMnz] O2 (x + y ≤ 0.4), and NCA, Li [Ni1−x−yCoxAly] O2, cathode materials have garnered huge attention for the development of Next-Generation lithium-ion batteries (LIBs). The impetus behind such huge celebrity includes their higher capacity and cost effectiveness when compared to the-state-of-the-art LiCoO2 (LCO) and other low Ni content NMC versions. However, despite all the beneficial attributes, the large-scale deployment of Ni-rich NMC based LIBs poses a technical challenge due to less stability of the cathode/electrolyte interphase (CEI) and diverse degradation processes that are associated with electrolyte decomposition, transition metal cation dissolution, cation–mixing, oxygen release reaction etc. Here, the potential degradation routes, recent efforts and enabling strategies for mitigating the core challenges of Ni-rich NMC cathode materials are presented and assessed. In the end, the review shed light on the perspectives for the future research directions of Ni-rich cathode materials.

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“…Previous characterizations of the CEI suggest that its composition is nearly identical to that of the solid electrolyte interphase (SEI) on the anode side of the battery. For example, Fourier transform infrared (FTIR) spectroscopy (Aurbach et al, 1991;Kanamura et al, 1996;Aurbach, 1998;Hong et al, 2012;Zhang et al, 2020), mass spectrometry (MS) (Liu et al, 2016), and X-ray spectroscopies (Eriksson et al, 2002;Edström et al, 2004;Lu et al, 2009;Carroll et al, 2013;Malmgren et al, 2013;Yamamoto et al, 2014;Jarry et al, 2015;Fang et al, 2018;Källquist et al, 2019;Li et al, 2019) show that the CEI contains commonly observed electrolyte decomposition products such as PEO-type polymers, organic and inorganic carbonates, inorganic oxides, and fluorinated compounds. The similarity in composition between the CEI and the anodic SEI has led to the speculation that the CEI is formed from anode-cathode crosstalk (Cuisinier et al, 2013;Lu et al, 2013;Malmgren et al, 2013;Fang et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

Reversible Deposition and Stripping of the Cathode Electrolyte Interphase on Li2RuO3

et al. 2020

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Performance decline in Li-excess cathodes is generally attributed to structural degradation at the electrode-electrolyte interphase, including transition metal migration into the lithium layer and oxygen evolution into the electrolyte. Reactions between these new surface structures and/or reactive oxygen species in the electrolyte can lead to the formation of a cathode electrolyte interphase (CEI) on the surface of the electrode, though the link between CEI composition and the performance of Li-excess materials is not well understood. To bridge this gap in understanding, we use solid-state nuclear magnetic resonance (SSNMR) spectroscopy, dynamic nuclear polarization (DNP) NMR, and electrochemical impedance spectroscopy (EIS) to assess the chemical composition and impedance of the CEI on Li 2 RuO 3 as a function of state of charge and cycle number. We show that the CEI that forms on Li 2 RuO 3 when cycled in carbonate-containing electrolytes is similar to the solid electrolyte interphase (SEI) that has been observed on anode materials, containing components such as PEO, Li acetate, carbonates, and LiF. The CEI composition deposited on the cathode surface on charge is chemically distinct from that observed upon discharge, supporting the notion of crosstalk between the SEI and the CEI, with Li +-coordinating species leaving the CEI during delithiation. Migration of the outer CEI combined with the accumulation of poor ionic conducting components on the static inner CEI may contribute to the loss of performance over time in Li-excess cathode materials.

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Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy

Abstract: Carbonate oxidation via dehydrogenation on LiNi0.8Co0.1Mn0.1O2 at voltages as low as 3.8 VLi was revealed by in situ FT-IR measurements.

Cited by 267 publications

References 119 publications

Pseudo‐Bonding and Electric‐Field Harmony for Li‐Rich Mn‐Based Oxide Cathode

Pseudo‐Bonding and Electric‐Field Harmony for Li‐Rich Mn‐Based Oxide Cathode

Degradation and Aging Routes of Ni-Rich Cathode Based Li-Ion Batteries

Reversible Deposition and Stripping of the Cathode Electrolyte Interphase on Li2RuO3

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