Identifying and Addressing Critical Challenges of High-Voltage Layered Ternary Oxide Cathode Materials

Zhang, Shu; Ma, Jun; Hu, Zhenglin; Cui, Guanglei; Chen, Liquan

doi:10.1021/acs.chemmater.9b01557

Cited by 179 publications

(113 citation statements)

References 267 publications

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“…[ 52 ] Enhancing the upper cut‐off voltage over 4.3 V will accelerate the decomposition of the liquid electrolyte, the generation of gases, and the dissolution of active metal cations. [ 53 ] The gas evolution with NRLO electrodes is composition‐ and voltage‐dependent. When the charging voltage was below 4.3 V, no evident CO 2 or O 2 were detected with various NMC compositions, as shown in Figure a.…”

Section: Factors Influencing Nrlo Stabilitymentioning

confidence: 99%

Probing and Resolving the Heterogeneous Degradation of Nickel‐Rich Layered Oxide Cathodes across Multi‐Length Scales

et al. 2020

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though new energy storage devices such as lithium-sulfur batteries [2] and lithium-air batteries [3] have shown great promise due to large theoretical capacity, lithium ion batteries (LIBs) are still dominating in portable electronic devices, prevailing in electric vehicles, and gradually entering grid-energy storage markets. [4] The unsatisfactory energy density of cathodes is widely recognized as the critical bottleneck for higher-performance LIBs. [5] Among various cathodes, Ni-rich layered lithium transition-metal oxides possessing a larger reversible capacity (>180 mAh g −1) than LiCoO 2 (140 mAh g −1), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (160 mAh g −1), LiMn 2 O 4 (120 mAh g −1), and LiFePO 4 (160 mAh g −1), are regarded as one of the most promising cathodes for the next-generation LIBs. [6] In 2016, American electric vehicle company Tesla launched Model 3 with LiNi 0.85 Co 0.10 Al 0.05 O 2 as the cathode for its electric vehicle battery, a testament to the huge potential of Ni-rich layered oxides (NRLOs) (Scheme 1). NRLO cathodes generally consist of two main categories-LiNi 1−x−y Co x Mn y O 2 (NMC) and LiNi 1−x−y Co x Al y O 2 (NCA). The evolution from LiCoO 2 /LiNiO 2 / LiMnO 2 to LiNi 1−x−y Co x Mn y O 2 has been introduced in previous reviews. [7] Briefly, synthesizing LiCoO 2 with the low-defect density was relatively accessible due to the large difference in ionic radius between Li + and Co 3+ , but the irreversible structural change takes place when more than half a fraction of Li + is extracted from its lattice, restricting the capacity. Stoichiometric LiNiO 2 is difficult to prepare due to the instability of trivalent Ni at high temperatures, and the cation mixing between Li and Ni weakens the cycling stability of LiNiO 2. [8] Synthesis of the layered LiMnO 2 phase is not straightforward either, and the capacity fades rapidly because the structural transformation from layered to spinel phase is inevitable upon cycling. [9] LiNi 1−x−y Co x Mn y O 2 combines the strengths of nickel (high capacity), cobalt (good rate capability), and manganese (benign stability). [7] The redox couples of Ni 2+ /Ni 3+ /Ni 4+ and Co 3+ /Co 4+ contribute to the majority of the capacity. The existence of cobalt suppresses the cation mixing during the synthesis of stoichiometric compounds, while manganese helps stabilize the Ni-rich layered oxides (NRLO) are widely considered among the most promising cathode materials for high energy-density lithium ion batteries. However, the high proportion of Ni content accelerates the cycling degradation that restricts their large-scale applications. The origins of degradation are indeed heterogeneous and thus there are tremendous efforts devoted to understanding the underlying mechanisms at multi-length scales spanning atom/lattice, particle, porous electrode, solid-electrolyte interface, and cell levels and mitigating the degradation of the NRLO. This review combines various advanced in situ/ex situ analysis techniques developed for resolving NRLO degradation at multi-length scales and aims...

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Section: Factors Influencing Nrlo Stabilitymentioning

confidence: 99%

Probing and Resolving the Heterogeneous Degradation of Nickel‐Rich Layered Oxide Cathodes across Multi‐Length Scales

et al. 2020

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“…As the "blood" of the battery, the electrolyte is an indispensable solvent for the transport and dissolution of Li + ions. [27] The most widely used electrolyte formula of LIBs is the mixture of conducting salts (LiPF 6 , LiBF 4 ) and organic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) etc. [28,29] .…”

Section: General Background For Libsmentioning

confidence: 99%

“…[28] The electrolyte will be oxidized if the potential of cathode (μ C ) is lower than the HOMO; similarly, the electrolyte will be reduced if the potential of anode (μ A ) is higher than the LUMO. [27] A complex passive protective layer will be formed on the surface of the electrode when the potential exceeds the stability limit of the electrolyte, which is called electrode-electrolyte interface (EEI) layer and can also be called CEI layer when it formed on the cathode surface. A uniform and thin CEI layer is able to protect the active site on the cathode surface from being consumed and the further corrosion of electrolyte by-products, and prevent the transition metal from dissolving.…”

Section: Regulation On Cathode-electrolyte Interphase By Additivesmentioning

confidence: 99%

“…[31] The chemical composition, structure and stability of the CEI layer are the keys to determine the performance of LIBs. Discouragingly, the spontaneously-formed CEI membrane consisting of Li 2 CO 3 , LiF, RÀ O-Li, RÀ OÀ CO 2 -Li and other electrolyte decomposition products is usually friable, uneven and thick, which inevitably increases of total impedance of LIBs, resulting in shorter cycle life and lower safety [32,27] . Therefore, it is not easy to form a qualified cathode passivation layer of LIBs which not only enable the fast Li + migration between the electrode and electrolyte, but also ensure the electronic insulation.…”

Section: Regulation On Cathode-electrolyte Interphase By Additivesmentioning

confidence: 99%

“…Common film-forming additives such as fluoroethylene carbonate (FEC), [34] vinyl ethylene carbonate (VEC), [35] vinylene carbonate (VC) [36] and so on can be applied both in the cathode and anode. [27] In addition, the electrolyte additives commonly used in cathode materials include sulfur-containing compounds (DTD, PES, ES) [36,37] , phosphorous-containing compounds (TTSPi, 5F-TPrP) [36,38] , nitrogen-containing compounds (SN), [39] silicon-containing compounds (TMSP) [40,41] and boroncontaining compounds (TMSB, TMOBX, LiBOB) [42,43,44,45] as well as other compounds containing various functional groups. [27] The function of electrolyte additives with various characteristic elements are often different.…”

Section: Roles Of Electrolyte Additives For Libs Cathodementioning

confidence: 99%

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Regulation of Cathode‐Electrolyte Interphase via Electrolyte Additives in Lithium Ion Batteries

Wang

et al. 2020

Chemistry An Asian Journal

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As the power supply of the prosperous new energy products, advanced lithium ion batteries (LIBs) are widely applied to portable energy equipment and large‐scale energy storage systems. To broaden the applicable range, considerable endeavours have been devoted towards improving the energy and power density of LIBs. However, the side reaction caused by the close contact between the electrode (particularly the cathode) and the electrolyte leads to capacity decay and structural degradation, which is a tricky problem to be solved. In order to overcome this obstacle, the researchers focused their attention on electrolyte additives. By adding additives to the electrolyte, the construction of a stable cathode‐electrolyte interphase (CEI) between the cathode and the electrolyte has been proven to competently elevate the overall electrochemical performance of LIBs. However, how to choose electrolyte additives that match different cathode systems ideally to achieve stable CEI layer construction and high‐performance LIBs is still in the stage of repeated experiments and exploration. This article specifically introduces the working mechanism of diverse electrolyte additives for forming a stable CEI layer and summarizes the latest research progress in the application of electrolyte additives for LIBs with diverse cathode materials. Finally, we tentatively set forth recommendations on the screening and customization of ideal additives required for the construction of robust CEI layer in LIBs. We believe this minireview will have a certain reference value for the design and construction of stable CEI layer to realize desirable performance of LIBs.

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Juggling Formation of HF and LiF to Reduce Crossover Effects in Carbonate Electrolyte with Fluorinated Cosolvents for High‐Voltage Lithium Metal Batteries

Zhang

Zeng

Ma³

et al. 2022

Adv Funct Materials

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Fluorinated solvents emerge as a promising strategy to improve performance of lithium metal batteries (LMBs). However, most of them are prone to produce corrosive HF and deteriorate electrode interface, inducing cathode-to-anode detrimental crossover of transition metal-ions. Here, fluorinated aromatic hydrocarbons in dimethyl carbonate (DMC)-based diluted highly concentrated electrolyte (DHCE) are employed to juggle formation of HF and LiF, enabling stable cycling of high-voltage LiNi 0.7 Co 0.1 Mn 0.2 O 2 (NCM712) and LiCoO 2 (LCO). The nature of aromatics in this carbonate-based DHCE makes them difficult to undergo β-hydrogen assisted defluorination, evidencing by the high energy barrier and high bond energy of β-sites hydrogen. The advanced DHCE restrains HF formation but strengthens LiF formation, which not only suppresses impedance growth, transition-metal dissolution, and stress crack on the cathode, but achieves highly reversible Li stripping/plating with an outstanding average Coulombic efficiency up to 99.3%. The Li||NCM712 cell and Li||LCO cell both exhibits superior cycling stability at high operation voltage. Even under stringent conditions, the 4.4 V Li||NCM712 full battery retains >95% of the initial capacity over 100 cycles, advancing practical high-voltage LMBs. This study designs an efficient electrolyte that generates robust electrode/electrolyte interphases and restrains by-products formation spontaneously, thus shedding new light on electrolyte toward applicable LMBs.

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Identifying and Addressing Critical Challenges of High-Voltage Layered Ternary Oxide Cathode Materials

Cited by 179 publications

References 267 publications

Probing and Resolving the Heterogeneous Degradation of Nickel‐Rich Layered Oxide Cathodes across Multi‐Length Scales

Probing and Resolving the Heterogeneous Degradation of Nickel‐Rich Layered Oxide Cathodes across Multi‐Length Scales

Regulation of Cathode‐Electrolyte Interphase via Electrolyte Additives in Lithium Ion Batteries

Juggling Formation of HF and LiF to Reduce Crossover Effects in Carbonate Electrolyte with Fluorinated Cosolvents for High‐Voltage Lithium Metal Batteries

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