Dictating the interfacial stability of nickel-rich LiNi0.90Co0.05Mn0.05O2 via a diazacyclo electrolyte additive – 2-Fluoropyrazine

Zhang, Xiaozhen; Liu, Gaopan; Zhou, Ke; Cheng, Yong; Jiao, Tianpeng; Huang, Lin; Zou, Yue; Wang, Mingsheng; Yang, Yong; Zheng, Jianming

doi:10.1016/j.jcis.2022.03.089

Cited by 12 publications

(8 citation statements)

References 32 publications

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“…There is a thick and uneven surface film covering the electrode surface of SiO x /C cycled in the baseline electrolyte, which can be attributed to the accumulation of the excessive electrolyte decomposition byproducts, resulting in the SEI film being too thick to distinguish the SiO x /C active material clearly (Figures b,e, and S9b,e). In comparison, the SEI film formed on the SiO x /C electrode surface with the APS-added electrolyte is more uniform and flat (Figures c,f, and S9c,f), implying the limited decomposition of the electrolyte. It is reasonable to speculate that the APS-derived SEI film could better adapt to the considerable volume change of the SiO x /C electrode during the repeated lithiation/delithiation process.…”

Section: Resultsmentioning

confidence: 96%

“…There is a thick and uneven surface film covering the electrode surface of SiO x /C cycled in the baseline electrolyte, which can be attributed to the accumulation of the excessive electrolyte decomposition byproducts, resulting in the SEI film being too thick to distinguish the SiO x /C active material clearly (Figures 4b,e, and S9b,e). 55 In comparison, the SEI film formed on the SiO S9h). However, the expansion of the electrode cycled with the APS-containing electrolyte is 157%, which is apparently lower than the baseline group (Figures 4i and S9i).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Strengthening the Interfacial Stability of the Silicon-Based Electrode via an Electrolyte Additive─Allyl Phenyl Sulfone

Liu

Gao

Meng

et al. 2022

ACS Appl. Mater. Interfaces

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Silicon-based anodes have received widespread attention because of their high theoretical capacity, which, however, still faces challenges for practical applications due to the large volume changes during repeated charge/discharge processes, despite being developed for many years. Herein, we explore an electrolyte additive, allyl phenyl sulfone (APS), to enhance the interfacial stability and long-term durability of the SiO x /C electrode. It is revealed that additive APS contributes to forming a dense and robust solid electrolyte interphase film with high mechanical strength and favorable lithium-ion diffusion kinetics, which effectively suppresses the parasitic side reactions at the electrode-electrolyte interface. Meanwhile, the strong interaction between APS and trace water/acid in the electrolyte is further beneficial for enhancing the interfacial stability. By incorporating 0.5 wt% APS, the cycling stability of the silicon-based electrode is significantly improved, reserving a capacity of 777 mAh g–1 after 200 cycles at 0.5C and 30 °C (79.3% capacity retention), which well exceeds that of the baseline electrolyte (57.8% capacity retention). More importantly, additive APS effectively promotes the cycling performance of the corresponding SiO x /C||NCM90 (LiNi0.9Co0.05Mn0.05O2) full battery. This work provides valuable understanding in developing new electrolyte additives to enable the commercial application of high-energy density lithium-ion batteries using silicon-based anodes.

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Section: Resultsmentioning

confidence: 96%

“…There is a thick and uneven surface film covering the electrode surface of SiO x /C cycled in the baseline electrolyte, which can be attributed to the accumulation of the excessive electrolyte decomposition byproducts, resulting in the SEI film being too thick to distinguish the SiO x /C active material clearly (Figures 4b,e, and S9b,e). 55 In comparison, the SEI film formed on the SiO S9h). However, the expansion of the electrode cycled with the APS-containing electrolyte is 157%, which is apparently lower than the baseline group (Figures 4i and S9i).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Strengthening the Interfacial Stability of the Silicon-Based Electrode via an Electrolyte Additive─Allyl Phenyl Sulfone

Liu

Gao

Meng

et al. 2022

ACS Appl. Mater. Interfaces

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“…To further examine the advantages of the synthesized W-doped cathode in terms of the electrochemical performance, a comparison was performed to the previously published data of rich-Ni NCM cathode. [51][52][53][54][55][56][57][58] The W 6+ doping could considerably enhance the electrochemical performance in both capacity retention and rate performance. To make clear such an advantage, a radar map is shown in Figure 11, where the capacity retention, rate capacity, and initial specific capacity are used as evaluation indicators.…”

Section: R T N a F Cmentioning

confidence: 99%

Atomic Horizons Interpretation on Enhancing Electrochemical Performance of Ni‐Rich NCM Cathode via W Doping: Dual Improvements in Electronic and Ionic Conductivities from DFT Calculations and Experimental Confirmation

Gao

Huang

Dong

et al. 2022

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270 mAh g −1 , are candidates for the next generation of lithium-ion batteries (LIBs). [7,8] NCM cathodes with high nickel content have attracted increasing attention because of their higher capacities when more nickel cations provide a more electron transfer from Ni 2+ /Ni 3+ and Ni 3+ /Ni 4+ redox pairs. [9,10] Meanwhile, since the relative content of expensive cobalt will be reduced, the production cost will also be decreased. Therefore, it is a trend to increase the proportion of nickel in the ternary system of LiNi 1−x−y Co x Mn y O 2 . [11] However, when the nickel content exceeds 80%, [12,13] the battery suffers from serious capacity degradation during the cycle.The main role of elemental doping is to reduce the mixing of Li and Ni cations and stabilize the crystal structure. It is a feasible approach to slow the capacity decay. Presently, it has been found that W 6+ is a good choice as a doping element. W 6+ has a higher valence and stronger bond energy compared to other ions (such as Al 3+ , Mg 2+ , Ba 2+ , and Zn 2+ ), resulting in a dual functional enhancement of the electronic and cationic conductivities. In 2018, Kim [14] proposed that, after the doping with 1 mol% W into Ni-rich LiNi 0.9 Co 0.05 Mn 0.05 O 2 cathode, the salt rock phase with surface segregation could protect the cathode material from harmful reactions and improve the cycle stability. In 2019, Park [15] reported that 1 mol% W doping in LiNi 0.9 Co 0.05 Mn 0.05 O 2 cathode significantly improved the capacity retention from 60% to 89% after 500 cycles at a 4.3 V cutoff voltage. It was believed that the reason for the cathode performance improvement of the W-doped LiNi 0.9 Co 0.05 Mn 0.05 O 2 in the abovementioned reports was mainly due to the internal stress reduction to stabilize the bulk structure so that the formation of harmful microcracks was inhibited. Shang et al. [16] suggested that adding W stabilized the structure and slowed the diffusion of the rock salt phase from the surface to the interior. However, researchers have conflicting opinions on the effects of the formed rock salt structure after doping. For instance, concerning the abovementioned conflicting opinions, that is, Kim thinks the existence of rock salt phase is good, whereas Shang thinks it is bad. Furthermore, reports on the formation of the rock salt phase by non-W cation doping are controversial. Jianming Zheng et al. [17] believeThe rapid capacity degradation and poor rate capability hinder the application of Rich-Ni layered LiNi x Co y Mn z O 2 (NCM) as cathode materials for highenergy lithium-ion batteries. In this study, density functional theory (DFT) calculations, combined with conventional electrochemical measurements, reveal from the atomic view that the dual improvements in electronic and ionic conductivities are the main facts for the property enhancement. The bandgap of the cathode material is reduced to 1.1623 eV due to the increased number of electrons near the Fermi level after W intercalation. Such improved electronic conductivity subsequently lea...

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“…During the recent decades, lithium-ion batteries (LIBs) have played an indispensable role in energy storage for portable electronics and electric vehicles with large capacities, high energy density, and output voltages. − In lithium-ion batteries, four important components are involved, cathode, anode, electrolyte, and separator, in which the cathode currently limits the energy density and dominates the battery cost. The current popularly applied commercial cathode materials for lithium-ion batteries include lithium nickel cobalt manganese oxides (NCM) , and olivine-type lithium iron phosphate (LFP). − However, how to improve theoretical capacity, rate performance, structural instability, electronic conductivity, and Li + transfers is always challenging for researchers to develop high-performance, low-cost, and high-safety cathode materials. , Extensive efforts have been made to circumvent these drawbacks, such as carbon coating, conductive agent hybridizing, element doping, and particle size reduction. , Nevertheless, these modifying strategies from an inorganic perspective always meet some new problems. For example, common ionic/electronic conductive additives are usually electrochemically inactive, which decrease the energy density of batteries.…”

Section: Introductionmentioning

confidence: 99%

“…7−9 However, how to improve theoretical capacity, rate performance, structural instability, electronic conductivity, and Li + transfers is always challenging for researchers to develop high-performance, low-cost, and highsafety cathode materials. 10,11 Extensive efforts have been made to circumvent these drawbacks, such as carbon coating, conductive agent hybridizing, element doping, and particle size reduction. 12,13 Nevertheless, these modifying strategies from an inorganic perspective always meet some new problems.…”

Section: Introductionmentioning

confidence: 99%

Synergy and Symbiosis Analysis of Capacity-Contributing Polypyrrole and Carbon-Coated Lithium Iron Phosphate Nanostructures for High-Performance Cathode Materials

Zhen

Wang

et al. 2023

ACS Appl. Nano Mater.

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To address the existing problems of commercial inorganic cathodes, including relatively low capacity, poor rate performance, structural instability, and low conductivity, it is critical to introduce a conductive matrix accompanied with electrochemical activity. Conductive polymers have great potential as electrodes with good conductivity, high redox activity, and potential. In this study, carbon-coated lithium iron phosphate (C-LiFePO4) nanoparticles were effectively dispersed in a polypyrrole (PPy) matrix by in situ pulverization. PPy, as an active nanostructure, significantly improves conductivity and accelerates Li+ diffusion. To further explore the synergy and symbiosis mechanism of PPy and C-LiFePO4 (hereinafter called C-LFP in the composite), the nanoparticle dispersion, carburization dependence, and heat treatment preference were investigated. Therefore, a reasonable amount of PPy (25 wt %) hybridization, a moderately wrapped carbon buffer layer (5.3 wt %), and a suitable heat treatment (100 °C) were employed to prepare the (C-LFP)0.75(PPy)0.25 nanocomposite. With a smaller particle size, uniformly dispersed morphology, and good synergy effect between PPy and C-LiFePO4, (C-LFP)0.75(PPy)0.25 delivers a high discharge capacity (209.1 mAh g–1 at 0.1C), a superior rate capability (86.1 mAh g–1 at 10C), and an outstanding capacity retention (83.5% of the initial values after 500 cycles at 0.5C).

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Dictating the interfacial stability of nickel-rich LiNi0.90Co0.05Mn0.05O2 via a diazacyclo electrolyte additive – 2-Fluoropyrazine

Cited by 12 publications

References 32 publications

Strengthening the Interfacial Stability of the Silicon-Based Electrode via an Electrolyte Additive─Allyl Phenyl Sulfone

Strengthening the Interfacial Stability of the Silicon-Based Electrode via an Electrolyte Additive─Allyl Phenyl Sulfone

Atomic Horizons Interpretation on Enhancing Electrochemical Performance of Ni‐Rich NCM Cathode via W Doping: Dual Improvements in Electronic and Ionic Conductivities from DFT Calculations and Experimental Confirmation

Synergy and Symbiosis Analysis of Capacity-Contributing Polypyrrole and Carbon-Coated Lithium Iron Phosphate Nanostructures for High-Performance Cathode Materials

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