Decoupling the origins of irreversible coulombic efficiency in anode-free lithium metal batteries

Huang, Chen‐Jui; Thirumalraj, Balamurugan; Tao, Hsien-Chu; Shitaw, Kassie Nigus; Sutiono, Hogiartha; Hagos, Tesfaye Teka; Beyene, Tamene Tadesse; Kuo, Li-Ming; Wang, Chun‐Chieh; Wu, She‐Huang; Su, Wei‐Nien; Hwang, Bing‐Joe

doi:10.1038/s41467-021-21683-6

Cited by 156 publications

(135 citation statements)

References 46 publications

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“…1c ). Figure 1d displays the cross-sectional SEM image of the cycled Zn electrodes in ZS electrolyte, where the Zn electrode is depleted with 12 μm in thickness of Zn foil left, indicating the formation of the large amounts of electronically-disconnected (i.e., “dead”) Zn and by-products 35 , 36 . In contrast, the cycled Zn electrode in La 3+ -ZS electrolyte shows a dense Zn-deposition layer with ~74 μm Zn foil left (Fig.…”

Section: Resultsmentioning

confidence: 99%

Lanthanum nitrate as aqueous electrolyte additive for favourable zinc metal electrodeposition

et al. 2022

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Aqueous zinc batteries are appealing devices for cost-effective and environmentally sustainable energy storage. However, the zinc metal deposition at the anode strongly influences the battery cycle life and performance. To circumvent this issue, here we propose the use of lanthanum nitrate (La(NO3)3) as supporting salt for aqueous zinc sulfate (ZnSO4) electrolyte solutions. Via physicochemical and electrochemical characterizations, we demonstrate that this peculiar electrolyte formulation weakens the electric double layer repulsive force, thus, favouring dense metallic zinc deposits and regulating the charge distribution at the zinc metal|electrolyte interface. When tested in Zn||VS2 full coin cell configuration (with cathode mass loading of 16 mg cm−2), the electrolyte solution containing the lanthanum ions enables almost 1000 cycles at 1 A g−1 (after 5 activation cycles at 0.05 A g−1) with a stable discharge capacity of about 90 mAh g−1 and an average cell discharge voltage of ∼0.54 V.

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Section: Resultsmentioning

confidence: 99%

Lanthanum nitrate as aqueous electrolyte additive for favourable zinc metal electrodeposition

et al. 2022

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“…The CE in the half cell configuration, with bare Cu, AO and BTO working electrodes allows the quantification of Li loss upon stripping. This can have two sources, namely “dead” Li (Li metal electrically isolated from the current collector) and SEI species that are formed due to electrolyte reduction 38 . On comparing the BTO scaffold (high dielectric) with the AO scaffold (low dielectric), it is seen that the BTO-based scaffold maintains a much higher CE over several additional cycles as shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

High dielectric barium titanate porous scaffold for efficient Li metal cycling in anode-free cells

et al. 2021

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Li metal batteries are being intensively investigated as a means to achieve higher energy density when compared with standard Li-ion batteries. However, the formation of dendritic and mossy Li metal microstructures at the negative electrode during stripping/plating cycles causes electrolyte decomposition and the formation of electronically disconnected Li metal particles. Here we investigate the use of a Cu current collector coated with a high dielectric BaTiO3 porous scaffold to suppress the electrical field gradients that cause morphological inhomogeneities during Li metal stripping/plating. Applying operando solid-state nuclear magnetic resonance measurements, we demonstrate that the high dielectric BaTiO3 porous scaffold promotes dense Li deposition, improves the average plating/stripping efficiency and extends the cycling life of the cell compared to both bare Cu and to a low dielectric scaffold material (i.e., Al2O3). We report electrochemical tests in full anode-free coin cells using a LiNi0.8Co0.1Mn0.1O2-based positive electrode and a LiPF6-based electrolyte to demonstrate the cycling efficiency of the BaTiO3-coated Cu electrode.

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“…To assess the feasibility of adding the nitrate to enable the dilute ether electrolyte under high voltages, LMBs, with a LiCoO2 cathode and 1 M LiTFSI in DME, were cycled at a high charge cutoff voltage of 4.3 V. A low cathode areal loading of 0.3 mAh cm -2 and excess Li were used to ensure only a small amount of Li metal was cycled, the impact of electrolyte stability on the Li anode is deliberately minimized. 34 As shown in Figure 1B, in only the 7 th cycle, the cell with the nitrate-free dilute ether electrolyte failed to reach the cutoff voltage (<4.2 V), demonstrating that the conventional dilute ether electrolyte has extremely poor high-voltage compatibility. In stark contrast, the NO3 --containing ether electrolyte (i.e., 1 M LiTFSI/DME with 50 mM LiNO3) could achieve 93% capacity retention with a limited polarization increase (Figure S2) after 1000 cycles.…”

Section: Resultsmentioning

confidence: 97%

High-voltage dilute ether electrolytes enabled by regulating interfacial structure

Wang

Zhang

et al. 2022

Preprint

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Poor oxidation stability of ether solvents at the cathode restricts the use of dilute ether electrolytes with conventional concentrations around 1 M in high-voltage lithium metal batteries. Here we develop an anion-adsorption approach to altering the ether solvent environment within the electrical double layer (EDL) at the cathode, by adding a small amount of nitrate, so that the oxidation tolerance of nitrate-containing dilute ether electrolytes is enhanced up to 4.4 V (versus Li/Li+), leading to complete compatibility with high-voltage cathodes and exhibiting superior cycling stability. Constant-potential molecular dynamics simulations reveal that ether molecules are mostly excluded from the cathode because of nitrate occupation in the inner layer of the EDL, thus suppressing ether oxidative decomposition. This work highlights that regulating the interfacial structure by adding surface adsorbates, rather than passivating cathode-electrolyte interphase or changing ion solvation, can help to enhance the oxidation stability of ether solvents. It also provides design criteria for adsorption-type additives to achieve high-voltage dilute ether electrolytes.

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Decoupling the origins of irreversible coulombic efficiency in anode-free lithium metal batteries

Cited by 156 publications

References 46 publications

Lanthanum nitrate as aqueous electrolyte additive for favourable zinc metal electrodeposition

Lanthanum nitrate as aqueous electrolyte additive for favourable zinc metal electrodeposition

High dielectric barium titanate porous scaffold for efficient Li metal cycling in anode-free cells

High-voltage dilute ether electrolytes enabled by regulating interfacial structure

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