Exploring the performance of carbonate and ether-based electrolytes for anode-free lithium metal batteries operating under various conditions

Hagos, Teklay Mezgebe; Bezabh, Hailemariam Kassa; Redda, Haylay Ghidey; Moges, Endalkachew Asefa; Huang, Wei‐Hsiang; Huang, Chen‐Jui; Su, Wei‐Nien; Dai, Hongjie; Hwang, Bing‐Joe

doi:10.1016/j.jpowsour.2021.230388

Cited by 7 publications

(4 citation statements)

References 30 publications

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“…To better distinguish the phase transition temperatures of different electrolytes, differential scanning calorimetry (DSC) was carried in Figure S2. As reported by previous literatures, 20,22 the melting point of [PP 13 ][FSI] IL and HFE is 4 °C and −94 °C, respectively. The LIL (Figure S2a) shows a high melting point (T m ) of −3 °C and a crystallization temperature (T c ) of −46 °C, 20 but HIL (Figure S2b) and LHCE (Figure S2c) only exhibit a glass transition temperature (T g ) below −80 °C, indicating HIL and LHCE can keep liquid state at ultralow temperature.…”

Section: ■ Introductionsupporting

confidence: 73%

Establish an Advanced Electrolyte/Graphite Interphase by an Ionic Liquid-Based Localized Highly Concentrated Electrolyte for Low-Temperature and Rapid-Charging Li-Ion Batteries

Wang

Zhang

Han

et al. 2022

ACS Sustainable Chem. Eng.

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Ionic liquid electrolytes (ILEs) possess nonflammability, low volatility, good thermal stability, and high electrochemical stability, but poor compatibility with graphite (Gr) because of the irreversible cointercalation of the organic cations into the Gr interlayers, which severely limits their application in Gr anodes. Herein, a facile strategy is reported to solve the compatibility between ILEs and Gr by using a kind of ionic liquid-based localized highly concentrated electrolyte (LHCE) to establish a thin and robust solid electrolyte interphase (SEI) to inhibit the cointercalation of cations into the Gr anode. Simultaneously, the anion-derived inorganic SEI layer possesses lower interphase impedance than the solvent-derived organic SEI layer formed by a commercial carbonate electrolyte, hence the Gr/ Li cells manifest a fast-charging capability with superior rate capability, good cycling stability, and impressive low-temperature charge/discharge performance at −30 °C. This work offers a new design strategy for advanced electrolytes for next-generation LIBs with high safety, fast-charging ability, and low-temperature applications.

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Section: ■ Introductionsupporting

confidence: 73%

Establish an Advanced Electrolyte/Graphite Interphase by an Ionic Liquid-Based Localized Highly Concentrated Electrolyte for Low-Temperature and Rapid-Charging Li-Ion Batteries

Wang

Zhang

Han

et al. 2022

ACS Sustainable Chem. Eng.

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“…To enable the low-temperature performance, carboxylate solvents are regarded as great candidates owing to their lower freezing point, lower viscosity, and higher dielectric constant than carbonate solvents (Table S1, Supporting Information). [18,19] Among them, ethyl acetate (EA) has attracted a lot of attention because of its low cost and extremely low freezing point of −84 °C than other conventional solvents. For example, EA-based electrolyte was reported to enable an ultra-lowtemperature LIBs at −70 °C.…”

Section: Introductionmentioning

confidence: 99%

“…, Supporting Information), the Li metal foils soaked in 1m-DE and 3m-DE become powder and the electrolytes get reddish-brown (FigureS5b, Supporting Small 2023,19, 2300571 …”

mentioning

confidence: 99%

High‐Energy‐Density Lithium Metal Batteries with Impressive Li⁺ Transport Dynamic and Wide‐Temperature Performance from −60 to 60 °C

Han

Wang

Huang

et al. 2023

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temperature range between −20 and 55 °C. [3][4][5] Especially LIBs hardly work when the temperature is below −30 °C because of commercial carbonate electrolytes, which often include LiPF 6 salt, cyclic ethylene carbonate (EC), and linear carbonate solvents (such as dimethyl carbonate (DMC), diethyl carbonate (DEC)). The commercial carbonate electrolytes usually exhibit high freezing points and high viscosity at low temperature, resulting in sluggish Li + transport and charge transfer kinetics at low temperature. [6][7][8] This severely limits their application in electric vehicles, defense applications, and space exploration. The requirements for developing high-energydensity and wide-temperature energy storage devices become very urgent. [9,10] To improve energy density, lithium (Li) metal batteries (LMBs) containing Li metal anode and nickel (Ni)-rich LiNi x Co y Mn z O 2 (x ≥ 0.9) cathode have attracted extensive attention due to low electrochemical potential of Li metal (−3.04 V compared to standard hydrogen electrode) and high specific capacity (3860 mA h g −1 of Li metal, >200 mA h g −1 of LiNi 0.9 Co 0.05 Mn 0.05 O 2 ). [11][12][13] However, LiPF 6 salt is easily decomposed to produce HF and carbonate solvents are continuously oxidized/reduced at electrode/electrolyte interface, which will cause serious corrosion to Ni-rich cathode and Li metal anode. [14] As a result, during the cycling process, Li dendrites High-energy-density Li metal batteries (LMBs) with Nickel (Ni)-rich cathode and Li-metal anode have attracted extensive attention in recent years. However, commercial carbonate electrolytes bring severe challenges including poor cycling stability, severe Li dendrite growth and cathode cracks, and narrow operating temperature window, especially hardly work at below −40 °C. In this work, a 2.4 m lithium difluoro(oxalato)borate (LiDFOB) in ethyl acetate (EA) solvent with 20 wt% fluorocarbonate (FEC) (named 2.4m-DEF) is designed to solve Li + transport dynamic at low temperature and improve interfacial stability between electrolyte with Li anode or Ni-rich cathode. Beneficial lower freezing point, lower viscosity, and higher dielectric constant of EA solvent, the electrolyte exhibits excellent Li + transport dynamic. Relying on the unique Li + solvation structure, more DFOB − anions and FEC solvents are decomposed to establish a stable solid electrolyte interface at electrolyte/ electrode. Therefore, LiNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM90)/Li LMB with 2.4m-DEF enables excellent rate capability (184 mA h g −1 at 30 C) and stable cycling performance with ≈93.7% of capacity retention after 200 cycles at 20 C and room temperature. Moreover, the NCM90/Li LMB with 2.4m-DEF exhibits surprising ultra-low-temperature performance, showing 173 mA h g −1 at −40 °C and 152 mA h g −1 at −60 °C, respectively.

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“…), 1 M LiPF 6 in EA/FEC/TTE/EMC (2:1:5:2 by vol. ), dual additives (KPF 6 and TMSP), and a dual-salt of 2 M LiFSI+1 M LiTFSI in DME/DOL (1:1, v/v); (2) surface engineering/functional layer coating like poly(ethylene oxide) (PEO@Cu), multilayer graphene (MLG@Cu), a binder-free ultrathin spin-coated graphene oxide (GO@Cu), backside of gold sputter perforated polyimide film (PI@Au), and bismuth graphite blend @ Cu substrate regulating lithium deposition; (3) using formation protocols including a dual-salt LiDFOB/LiBF 4 electrolyte with thermal formation treatment; and (4) extra Li source formation using DEC solvent decomposition and a preloaded sacrificial agent Li 2 O on the cathode surface . In addition, Manthiram et al demonstrated a novel anode-free Cu||Li 2 S cell cycled with an ether-based electrolyte.…”

Section: Introductionmentioning

confidence: 99%

A Powerful Protocol Based on Anode-Free Cells Combined with Various Analytical Techniques

et al. 2021

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Conspectus Lithium (Li) metal is the ultimate negative electrode due to its high theoretical specific capacity and low negative electrochemical potential. However, the handling of lithium metal imposes safety concerns in transportation and production due to its reactive nature. Recently, anode-free lithium metal batteries (AFLMBs) have drawn much attention because of several of their advantages, including higher energy density, lower cost, and fewer safety concerns during cell production compared to LMBs. Pushing the reversible Coulombic efficiency (CE) of AFLMBs up to 99.98% is key to achieving their 80% capacity retention over more than 1000 cycles. However, interfacial irreversible phenomena such as electrolyte decomposition reactions on both electrodes, dead Li formation, and Li dendrite formation result in poor capacity retention and short circuits in LMBs and AFLMBs. Therefore, it is of great importance and scientific interest to explore those interfacial irreversible phenomena to improve the cell’s cycle life. Although significant contributions toward mitigating electrolyte decomposition, dead lithium, and dendritic lithium formation have been reported at the lithium anode, real irreversible phenomena are usually hidden or difficult to discover due to excess lithium employed in LMBs and simultaneous events taking place in both electrodes or at the interfaces. An integrated protocol is suggested to include Li||Cu, cathode||Li, and cathode||Cu configurations to provide overall quantification and determination of various sources of irreversible Coulombic efficiency (irr-CE) in AFLMBs and LMBs. Combining Li||Cu, cathode||Li, and cathode||Cu configurations is essential for separating the root sources of the capacity loss and irr-CE in LMBs and AFLMBs. Remarkably, integrating an anode-free cell with various analytical techniques can serve as a powerful protocol to decouple and quantify those interfacial irreversible phenomena according to our recent reports. In this Account, we focus on the protocol based on an anode-free cell combined with various analytical methods to investigate interfacial irreversible phenomena. Complementary advanced tools such as transmission X-ray microscopy (visualizing Li plating/stripping mechanism), nuclear magnetic resonance spectroscopy (quantifying dead lithium), and gas chromatography–mass spectroscopy (decoupling interfacial reactions) were employed to extract the intrinsic reasons and sources of individual irreversible reactions in LMBs and AFLMBs. Quantitative evaluation of nucleation and growth of Li metal deposition are addressed, along with solid electrolyte interphase (SEI) fracture, visualization of lithium dendrite growth, decoupling of oxidative and reductive electrolyte decomposition mechanisms, and irreversible efficiency (i.e., dead Li and SEI formation) to reveal the intrinsic causes of individual irr-CE in AFLMBs. Meanwhile, an anode-free protocol can also be utilized as a powerful and multifunctional tool to develop electrolyte formulations or artificial layers fo...

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Exploring the performance of carbonate and ether-based electrolytes for anode-free lithium metal batteries operating under various conditions

Cited by 7 publications

References 30 publications

Establish an Advanced Electrolyte/Graphite Interphase by an Ionic Liquid-Based Localized Highly Concentrated Electrolyte for Low-Temperature and Rapid-Charging Li-Ion Batteries

Establish an Advanced Electrolyte/Graphite Interphase by an Ionic Liquid-Based Localized Highly Concentrated Electrolyte for Low-Temperature and Rapid-Charging Li-Ion Batteries

High‐Energy‐Density Lithium Metal Batteries with Impressive Li⁺ Transport Dynamic and Wide‐Temperature Performance from −60 to 60 °C

A Powerful Protocol Based on Anode-Free Cells Combined with Various Analytical Techniques

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Exploring the performance of carbonate and ether-based electrolytes for anode-free lithium metal batteries operating under various conditions

Cited by 7 publications

References 30 publications

Establish an Advanced Electrolyte/Graphite Interphase by an Ionic Liquid-Based Localized Highly Concentrated Electrolyte for Low-Temperature and Rapid-Charging Li-Ion Batteries

Establish an Advanced Electrolyte/Graphite Interphase by an Ionic Liquid-Based Localized Highly Concentrated Electrolyte for Low-Temperature and Rapid-Charging Li-Ion Batteries

High‐Energy‐Density Lithium Metal Batteries with Impressive Li+ Transport Dynamic and Wide‐Temperature Performance from −60 to 60 °C

A Powerful Protocol Based on Anode-Free Cells Combined with Various Analytical Techniques

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High‐Energy‐Density Lithium Metal Batteries with Impressive Li⁺ Transport Dynamic and Wide‐Temperature Performance from −60 to 60 °C