Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries
Not Available
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Anion modification for stable solid electrolyte interphase in anode-free lithium metal batteries
The durability of anode-free Li metal batteries is largely limited by the undesired Li plating/stripping irreversibility on the current collector due to the infinite volume change, uncontrollable Li dendrite growth, and continuous parasitic reactions between Li metal and the electrolyte. To address these challenges, the formation of a stable and robust solid electrolyte interphase (SEI) with high ionic conductivity and strong mechanical strength is critical. Here, we developed an advanced electrolyte by introducing LiNO 3 into the localized high concentration electrolyte (LHCE) with lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2-dimethoxyethane (DME) solvent, and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TFTE) diluent to in situ construct a LiF and Li x N y O z co-enriched passivation layer on the Cu current collector. The synergetic effect of high mechanical strength of LiF and high ionic conductivity of Li x N y O z endows the Li metal anode with a high Coulombic efficiency (CE) of 99.35%. In conclusion, in anode-free Li metal pouch cell using LiFePO 4 (LFP) as a cathode holds an exceptionally improved capacity retention under the charging/discharging rate of 1/3 C, demonstrating great promise for developing dendrite-free and safe Li metal batteries.
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Balancing solvation: stabilizing lithium metal batteries via optimized cosolvents for ionic-liquid electrolytes
In this study, we examined three cosolvents with distinct solvation capabilities for ionic-liquid electrolytes based on 1-methyl-1-propyl pyrrolidinium bis(fluorosulfonyl)imide (Py13FSI). We demonstrate that 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG) notably enhances the cycle life of Py13FSI-based electrolytes, outperforming 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropylether (TTE) and diglyme (DG). Electrochemical and surface analyses showed that this improvement could be attributed to the formation of a favorable cathode interphase, promoting efficient Li+ transport with reduced overpotential. Spectroscopic techniques (FTIR, Raman, and NMR spectroscopy) and molecular dynamics simulations revealed that cosolvents with varying solvation abilities can influence the solvation structures in Py13FSI-based electrolytes. The mild solvating strength and lithium stability of FDG are key contributors to its effectiveness. Conversely, DG, a strong solvating solvent, destabilized the Py13FSI-DG electrolyte at the lithium metal anode, while TTE, a non-solvating solvent, failed to enhance lithium transport or form a stable cathode interphase. Our findings highlight that balanced solvation exerted by the cosolvents is critical for forming a stable electrolyte–cathode interface, potentially through FSI decomposition. This study offers valuable insights into the development of durable ionic-liquid electrolytes, emphasizing the importance of selecting cosolvents with optimal solvation properties.
Li, Xinlin [Argonne National Laboratory (ANL), Arg↗
Rational solvent molecule tuning for high-performance lithium metal battery electrolytes
Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. In this study, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amount of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar –CHF 2 is identified as the optimal group rather than fully fluorinated –CF 3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO 4 industrial pouch cells under realistic testing conditions. The correlation of Li + –solvent coordination, solvation environments and battery performance is investigated to understand structure–property relationships.
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Scalable, Ultrathin, and High-Temperature-Resistant Solid Polymer Electrolytes for Energy-Dense Lithium Metal Batteries
We report all-solid-state batteries (ASSBs) demonstrate great promise, offering high energy density, good thermal stability, and safe operation compared with traditional Li-ion batteries. Among various solid-state electrolytes (SSEs), solid polymer electrolytes (SPEs) offer an attractive choice due to their thinness, low density, and good manufacturability. However, ultrathin SPEs that work with practical current densities or at high temperatures remain challenging, limiting applicable conditions of SPE-based batteries. Here, the authors report a novel scalable, ultrathin, and high-temperature-resistant SPE for ASSBs. This design includes an electrospun polyacrylonitrile (PAN) matrix and polyethylene oxide (PEO)/Li salt ionic conductor, which offers a stable LiF and Li 3 N containing SSE/Li interface. The unique interface—as well as the good mechanical strength—inhibits lithium dendrites and prevents short circuiting. As a result, symmetrical Li-Li cells deliver more than 300 h cyclability at 0.5 mA cm -2 . ASSBs fabricated with only 5 µm-thickness PAN-PEO/lithium bis(trifluoromethanesulfonyl)imide reach 300 cycles at 0.3 C rate at 60 °C. The excellent thermal stability of PAN also results in safer SPEs at high temperatures. The design extends battery operation up to temperatures of 120 and 150 °C, where it achieves 500 cycles at C/2 rate and 100 cycles at 2C rate, respectively.
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A Bilayer Electrolyte Design to Enable High-Areal-Capacity Composite Cathodes in Polymer Electrolytes Based Solid-State Lithium Metal Batteries
High-areal-capacity cathodes are needed for energy-dense solid-state batteries. Here, we demonstrate a bilayer polymer electrolyte design for cycling 3–6 mAh/cm 2 NMC811 composite cathodes. In this work, the bilayer electrolyte comprises a cross-linked poly(ethylene oxide) (PEO)-based electrolyte layer and a linear-PEO-based electrolyte layer. The former provides dendritic resistance, and the latter provides a seamless interface with the cathode during cycling. Using a single layer of either membrane led to severe shorting or extremely low Coulombic efficiency (CE) in the first cycle. The general concept of a rigid dendrites-inhibiting electrolyte facing Li anode and a softer, cathode-integrated electrolyte that ensures contact with the cathodes during cycling may present a pattern for enabling high-energy-density cathodes.
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Visualizing electrode assembly movement and lithiation heterogeneity in lithium-metal batteries using operando energy dispersive X-ray diffraction
There is renewed interest in Li-metal anodes in order to increase the energy density of battery cells. Here, we demonstrate an operando X-ray crystallography method to visualize lithiation gradients and electrode assembly movement during electrochemical cycling of a Li-metal cell containing a Ni-Mn-Co layered oxide cathode (NMC811). During charge, deposition of Li + ions from the cathode increases the Li foil thickness; during discharge, the thickness decreases as Li + ions are stripped off the foil. Additionally, the resulting periodic movement is observed through tracking of Bragg peaks from the ordered phases of the cathode and separator. In addition to this 3.6 μm/mAh displacement, continuous mossy Li build-up on the anode causes an irreversible drift of the assembly, which is similar to 11.3 μm/cycle. Furthermore, our data indicate significant lithiation gradients in the NMC811 cathode during the oxide relithiation, which is not observed during the delithiation.
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Tailored Solvation and Interface Structures by Tetrahydrofuran-Derived Electrolyte Facilitates Ultralow Temperature Lithium Metal Battery Operations
Ineffectiveness of Li-ion batteries (LIBs) in cold climates hinders electronics to work in various conditions including frigid environments, despite high demands. Given that intrinsic properties of LIB materials cause this problem, optimized cell chemistries ultimately are required for low-temperature usage. In this study, Li-metal batteries (LMBs) composed of a Li-metal anode (LMA) stabilized by a localized high-concentration electrolyte (LHCE) are found to significantly enhance low-temperature performance. The LHCE allows the LMA to have compact and regular deposition and excellent plating/stripping efficiency at sub-zero temperatures. The LHCE produces an inorganic-rich solid-electrolyte interphase with larger amounts of Li 2 O/LiF interfaces, dominance of ion aggregates in Li + solvation, and enhanced Li + transport, which can greatly improve the LMA stability. LMB full cells based on LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes with the tailored electrolyte show high retentions of 75 and 64 % at -20 and -40 °C, respectively. Furthermore, the LMB configuration retains its charge-discharge capability even at -60 °C.
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In situ formation of polymer-inorganic solid-electrolyte interphase for stable polymeric solid-state lithium-metal batteries
Composite polymer electrolytes (CPEs) for solid-state Li-metal batteries (SSLBs) still suffer from gradually increased interface resistance and unconstrained Li-dendrite growth. Herein, we addressed the challenges by designing a LiF-rich inorganic solid-electrolyte interphase (SEI) through introducing a fluoride-salt-concentrated interlayer on CPE film. The rigid but flexible CPE helps accommodate the volume change of electrodes, while the polymeric highly concentrated electrolyte (PHCE) surface-layer regulates Li-ion flux due to the formation of a stable LiF-rich SEI via anion reduction. The designed CPE-PHCE presents enhanced ionic conductivity and high oxidation stability of >5.0 V (versus Li/Li + ). Furthermore, it dramatically reduces the interfacial resistance and achieves a high critical current density of 4.5 mA cm –2 . The SSLBs, fabricated with thin CPE-PHCE membranes (<100 μm) and Co-free LiNiO 2 cathodes, exhibit exceptional electrochemical performance and long cycling stability. Lastly, this approach of SEI design can also be applied to other types of batteries.
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Long‐Life Lithium‐Metal Batteries with an Ultra‐High‐Nickel Cathode and Electrolytes with Bi‐Anion Activity
Abstract Anion chemistry in electrolytes can greatly dictate the nature and quality of passivation layers on both cathode and anode surfaces. This will be more significant when it comes to highly reactive Li‐metal anode and aggressive high‐nickel cathodes. Herein, a competitive bi‐anion activity is found in electrolytes with the co‐existence of two anions, which leads to a controlled Li‐salt decomposition kinetics and entirely favorable interphasial chemistry on both Li‐metal anode and ultrahigh‐nickel cathode. The proposed bi‐anion localized high‐concentration electrolytes are demonstrated to exhibit superior electrochemical compatibility toward Li metal and long‐term cycling stabilities under both 4.4 and 4.6 V in Li‐metal batteries with ultrahigh‐nickel cathode. This study sheds fresh light on dendrite‐free Li‐metal anodes and provides guidance to achieve high‐energy‐density batteries.
Chemistry↗
A Fluoride-Rich Solid-Like Electrolyte Stabilizing Lithium Metal Batteries
To address the problems associated with Li metal anodes, a fluoride-rich solid-like electrolyte (SLE) that combines the benefits of solid-state and liquid electrolytes is presented. Its unique triflate-group-enhanced frame channels facilitate the formation of a functional inorganic-rich solid electrolyte interphase (SEI), which not only improves the reversibility and interfacial charge transfer of Li anodes but also ensures uniform and compact Li deposition. Furthermore, these triflate groups contribute to the decoupling of Li + and provide hopping sites for rapid Li + transport, enabling a high room-temperature ionic conductivity of 1.1 mS cm -1 and a low activation energy of 0.17 eV, making it comparable to conventional liquid electrolytes. Consequently, Li symmetric cells using such SLE achieve extremely stable plating/stripping cycling over 3500 h at 0.5 mA cm -2 and support a high critical current up to 2 mA cm -2 . Here, the assembled Li||LiFePO 4 solid-like batteries exhibit exceptional cyclability for over 1 year and a half, even outperforming liquid cells. Additionally, high-voltage cylindrical cells and high-capacity pouch cells are demonstrated, corroborating much simpler processibility in battery assembly compared to all-solid-state batteries.
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A Solution-Processable High-Modulus Crystalline Artificial Solid Electrolyte Interphase for Practical Lithium Metal Batteries
The solid electrolyte interphase (SEI) has been identified as a key challenge for Li metal anodes. The brittle and inhomogeneous native SEI generated by parasitic reactions between Li and liquid electrolytes can devastate battery performance; therefore, artificial SEIs (ASEIs) have been proposed as an effective strategy to replace native SEIs. Herein, as a collaboration between academia and industrial R&D teams, a multifunctional (crystalline, high modulus, and robust, Li + ion conductive, electrolyte-blocking, and solution processable) ASEI material, LiAl-FBD (where “FBD” refers to 2,2,3,3-tetra-fluoro-1,4-butanediol), for improving Li metal battery performance is designed and synthesized. The LiAl-FBD crystal structure consists of Al 3+ ions bridged by FBD 2– ligands to form anion clusters while Li + ions are loosely bound at the periphery, enabling an Li + ion conductivity of 9.4 × 10 –6 S cm –1 . Further, the fluorinated, short ligands endow LiAl-FBD with electrolyte phobicity and high modulus. The ASEI is found to prevent side reactions and extend the cycle life of Li metal electrodes. Specifically, pairing LiAl-FBD coated 50 μm thick Li with industrial 3.5 mAh cm –2 NMC811 cathode and 2.8 μL mAh –1 lean elec-trolyte, the Li metal full cells show superior cycle life compared to bare ones, achieving 250 cycles at 1 mA cm –2 .
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An Inorganic‐Rich Solid Electrolyte Interphase for Advanced Lithium‐Metal Batteries in Carbonate Electrolytes
Abstract In carbonate electrolytes, the organic–inorganic solid electrolyte interphase (SEI) formed on the Li‐metal anode surface is strongly bonded to Li and experiences the same volume change as Li, thus it undergoes continuous cracking/reformation during plating/stripping cycles. Here, an inorganic‐rich SEI is designed on a Li‐metal surface to reduce its bonding energy with Li metal by dissolving 4 m concentrated LiNO 3 in dimethyl sulfoxide (DMSO) as an additive for a fluoroethylene‐carbonate (FEC)‐based electrolyte. Due to the aggregate structure of NO 3 − ions and their participation in the primary Li + solvation sheath, abundant Li 2 O, Li 3 N, and LiN x O y grains are formed in the resulting SEI, in addition to the uniform LiF distribution from the reduction of PF 6 − ions. The weak bonding of the SEI (high interface energy) to Li can effectively promote Li diffusion along the SEI/Li interface and prevent Li dendrite penetration into the SEI. As a result, our designed carbonate electrolyte enables a Li anode to achieve a high Li plating/stripping Coulombic efficiency of 99.55 % (1 mA cm −2 , 1.0 mAh cm −2 ) and the electrolyte also enables a Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) full cell (2.5 mAh cm −2 ) to retain 75 % of its initial capacity after 200 cycles with an outstanding CE of 99.83 %.
Liu, Sufu↗
Low melting alkali-based molten salt electrolytes for solvent-free lithium-metal batteries
Not provided.
Materials Science↗
Stabilizing ultrahigh-nickel layered oxide cathodes for high-voltage lithium metal batteries
Not Available
Zhang, Xianhui↗
Achieving stable all-solid-state lithium-metal batteries by tuning the cathode-electrolyte interface and ionic/electronic transport within the cathode
All-solid-state batteries with sulfide electrolytes and high-nickel layered oxide cathodes attract much interest due to their high specific energy. However, their cycling performance is primarily influenced by the interface between the sulfide electrolyte and the high-Ni layered oxide particles, which requires the use of composite cathodes with high ionic and electronic conductivities to achieve a kinetically stable interface inside the cathode. Here, we apply Ti 2 O 3 particles to the high-Ni cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811), where Ti 2 O 3 not only acts as an electronic conductor to provide a fast diffusion path for electrons in the composite cathode, but also absorbs the lattice oxygen released from NCM811 cathode during cycling, stabilizing the Li 6 PS 5 Cl/NCM811 interface and suppressing electrolyte oxidation. The as-modified cathode exhibits an initial specific capacity of 192 mAh g -1 and retains 166 mAh g -1 after 140 cycles at 0.1C rate with a good capacity retention of 86.5%. Furthermore, the composite cathode displays high rate capability even at 1C rate. By contrast, the unmodified Li 6 PS 5 Cl/NCM811 cathode shows poor cycling performance with only 130 mAh g -1 remaining after 130 cycles. This work provides a new direction for the design of cathodes for all-solid-state batteries that can deliver high specific energy with long cycle life.
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