Designing Advanced In Situ Electrode/Electrolyte Interphases for Wide Temperature Operation of 4.5 V Li||LiCoO 2 Batteries
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99 GENERAL AND MISCELLANEOUS↗
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A Fast‐Charging and High‐Temperature All‐Organic Rechargeable Potassium Battery
Abstract Developing fast‐charging, high‐temperature, and sustainable batteries is critical for the large‐scale deployment of energy storage devices in electric vehicles, grid‐scale electrical energy storage, and high temperature regions. Here, a transition metal‐free all‐organic rechargeable potassium battery (RPB) based on abundant and sustainable organic electrode materials (OEMs) and potassium resources for fast‐charging and high‐temperature applications is demonstrated. N‐doped graphene and a 2.8 m potassium hexafluorophosphate (KPF 6 ) in diethylene glycol dimethyl ether (DEGDME) electrolyte are employed to mitigate the dissolution of OEMs, enhance the electrode conductivity, accommodate large volume change, and form stable solid electrolyte interphase in the all‐organic RPB. At room temperature, the RPB delivers a high specific capacity of 188.1 mAh g −1 at 50 mA g −1 and superior cycle life of 6000 and 50000 cycles at 1 and 5 A g −1 , respectively, demonstrating an ultra‐stable and fast‐charging all‐organic battery. The impressive performance at room temperature is extended to high temperatures, where the high‐mass‐loading (6.5 mg cm −2 ) all‐organic RPB exhibits high‐rate capability up to 2 A g −1 and a long lifetime of 500 cycles at 70–100 °C, demonstrating a superb fast‐charging and high‐temperature battery. The cell configuration demonstrated in this work shows great promise for practical applications of sustainable batteries at extreme conditions.
25 ENERGY STORAGE↗
Spatial Effect on the Performance of Carboxylate Anode Materials in Na-Ion Batteries
Developing low-voltage carboxylate anode materials is critical for achieving low-cost, high-performance, and sustainable Na-ion batteries (NIBs). However, the structure design rationale and structure-performance correlation for organic carboxylates in NIBs remains elusive. Herein, the spatial effect on the performance of carboxylate anode materials is studied by introducing heteroatoms in the conjugation structure and manipulating the positions of carboxylate groups in the aromatic rings. Planar and twisted organic carboxylates are designed and synthesized to gain insight into the impact of geometric structures to the electrochemical performance of carboxylate anodes in NIBs. Among the carboxylates, disodium 2,2’-bipyridine-5,5’-dicarboxylate (2255-Na) with a planar structure outperforms the others in terms of highest specific capacity (210 mAh g -1 ), longest cycle life (2000 cycles), and best rate capability (up to 5 A g -1 ). Further, the cyclic stability and redox mechanism of 2255-Na in NIBs are exploited by various characterization techniques. Moreover, high-temperature (up to 100 °C) and all-organic batteries based on a 2255-Na anode, a polyaniline (PANI) cathode, and an ether-based electrolyte are achieved and exhibited exceptional electrochemical performance. Therefore, this work demonstrates that designing organic carboxylates with extended planar conjugation structures is an effective strategy to achieve high-performance and sustainable NIBs.
25 ENERGY STORAGE↗
A novel battery scheme: Coupling nanostructured phosphorus anodes with lithium sulfide cathodes
Lithium-ion batteries are approaching their theoretical limit and can no longer keep up with the increasing demands of human society. Lithium-sulfur batteries, with a high theoretical specific energy, are promising candidates for next generation energy storage. However, the use of Li metal in Li-S batteries compromises both safety and performance, enabling dendrite formation and causing fast capacity degradation. Previous studies have probed alternative battery systems to replace the metallic Li in Li-S system, such as a Si/Li2S couple, with limited success in performance. Recently, there is a focus on red P as a favorable anode material to host Li. In this work, we establish a novel battery scheme by utilizing a P/C nanocomposite anode and pairing it with a Li 2 S coated carbon nanofiber cathode. We find that red P anode can be compatible in ether-based electrolyte systems and can be successfully coupled to a Li 2 S cathode. Our proof of concept full-cell displays remarkable specific capacity, rate and cycling performances. We expect our work will provide a useful alternative system and valuable insight in the quest for next generation energy storage devices.
25 ENERGY STORAGE↗
Simply Fabricatable Reference Electrode for Studying Li Metal Interfaces Operando
Reference electrodes are essential for studying Li metal interfaces, yet their integration into coin cells remains challenging due to geometric constraints and assembly complexity. Here, we present a simple three-electrode coin cell design in which a thin Cu film is evaporated directly onto a trilayer PP/PE/PP separator, forming a conductive and flexible in situ current collector. The microporous Cu preserves separator porosity and pressure uniformity, avoiding artifacts introduced by wire- or mesh-type references. It is easily activated by Li plating and provides stable potentials for over 10 days in ether-based electrolytes without affecting Coulombic efficiency (>99%) or Li deposition morphology. Operando measurements using this design reveal electrode-specific impedance evolution and voltage responses otherwise obscured in two-electrode setups, uncovering a correlation between the SEI resistance and electrolyte ionic conductivity. This microporous Cu reference electrode offers a robust and accessible platform for characterizing reactive interfaces under realistic cycling conditions.
Sacci, Robert [ORNL] (ORCID:0000000200735221)↗
Elucidating Sodium-Sulfur Battery Chemistry using Operando Transmission X-ray Microscopy and X-ray Absorption Spectroscopy
Room-temperature sodium-sulfur (Na-S) batteries offer a beneficial and cost-effective solution for powering modern electric grids and devices. However, Na-S batteries suffer from performance decay during battery cycling due to the sluggish kinetics and polysulfide shuttling. Revealing the conversion mechanism of the Na-S chemistry is critical to designing high-capacity and stable Na-S batteries. In this study, we employed operando X-ray microscopy and operando X-ray absorption spectroscopy to elucidate the sulfur conversion in a carbon host using an ether-based electrolyte. We reveal the structural and chemical evolution of the sulfur cathode during cycling, which results in volume expansion and the dissolution of active material, ultimately affecting the battery performance. Our work provides fundamental insight into the sulfur reaction scheme, addressing the lingering challenges before establishing inexpensive Na-S batteries for broad applications, including portable electronics and large-scale energy storage.
Jagadeesan, Sathya Narayanan [SLAC National Accele↗
A Green, Fire–Retarding Ether Solvent for Sustainable High–Voltage Li–Ion Batteries at Standard Salt Concentration
Lithium-ion batteries (LIBs) are increasingly encouraged to enhance their environmental friendliness and safety while maintaining optimal energy density and cost-effectiveness. Although various electrolytes using greener and safer glyme solvents have been reported, the low charge voltage (usually lower than 4.0 V vs Li/Li + ) restricts the energy density of LIBs. Herein, tetraglyme, a less-toxic, non-volatile, and non-flammable ether solvent, is exploited to build safer and greener LIBs. It is demonstrated that ether electrolytes, at a standard salt concentration (1 m), can be reversibly cycled to 4.5 V vs Li/Li + . Anchored with Boron-rich cathode-electrolyte interphase (CEI) and mitigated current collector corrosion, the LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode delivers competitive cyclability versus commercial carbonate electrolytes when charged to 4.5 V. Synchrotron spectroscopic and imaging analyses show that the tetraglyme electrolyte can sufficiently suppress the overcharge behavior associated with the high-voltage electrolyte decomposition, which is advantageous over previously reported glyme electrolytes. The new electrolyte also enables minimal transition metal dissolution and deposition. NMC811||hard carbon full cell delivers excellent cycling stability at C/3 with a high average Coulombic efficiency of 99.77%. In conclusion, this work reports an oxidation-resilient tetraglyme electrolyte with record-high 4.5 V stability and enlightens further applications of glyme solvents for sustainable LIBs by designing Boron-rich interphases.
36 MATERIALS SCIENCE↗
Structure–Activity Relationships in Ether-Functionalized Solid-State Metal–Organic Framework Electrolytes
The structure–property relationships of metal–organic framework (MOF)-based solid-state electrolytes are not well understood. Herein, a systematic investigation of 12 Zr(IV)-based UiO-66 MOFs with varying ether-chain functional groups was carried out to elucidate the critical microscopic interactions that facilitate improved solid-state electrolyte performance. Enhanced sampling molecular dynamics (MD) simulations were employed and revealed a three-tier ion hopping mechanism: linker–linker hopping, linker-counterion hopping, and counterion-counterion hopping. Detailed structural analysis of the MD trajectories revealed that the chemistry and morphology of the linker groups affect the relative stability and population distribution of the electrolyte components, such that crown-ether-based linker groups enhance the probability of extended, low-barrier ion percolation pathways. As a result, we were able to tune the ionic conductivities by rationally manipulating the counterion distributions, linker binding strengths, and the configurational entropy (multivariability of the linkers). The resulting performance of these MOF-based solid-state electrolytes was significantly enhanced, with a methoxy-functionalized framework (UiO-66-L1 100 ) achieving high ionic conductivities of 2.32 × 10 –4 S/cm and 2.07 × 10 –3 S/cm at 30 °C and 90 °C, respectively, an order of magnitude greater than other all-solid-state MOF electrolyte systems. The electrolyte stability was evaluated with LiIn|LPSCl|MOF:LiTFSI|LPSCl|LiIn symmetric cells, showing excellent Li plating/stripping processes for over 2 months.
36 MATERIALS SCIENCE↗
Enabling Silicon Anodes with Novel Isosorbide-Based Electrolytes
Silicon is seen as one of the most promising anode candidates for next-generation lithium-ion batteries, due to its high theoretical capacity and energy density. However, many technical barriers remain to its implementation, due to its high chemical/electrochemical reactivities with standard electrolytes and incomplete passivation from large volume changes. Herein, we report an isosorbide dimethyl ether (IDE) based electrolyte, which exhibits greatly improved stability, as evidenced by long cycle life and calendar life. An analysis of the cycled silicon surface shows minimal decomposition of organic species from IDE solvent, confirming that the electrolyte maintains a limited chemical reactivity with nucleophilic lithiated silicon (Li x Si). Here, this research opens up new avenues for designing new electrolytes which could ultimately enable the practical application of silicon anodes.
25 ENERGY STORAGE↗
Electrode-omics reveals epochs in silicon anode evolution underpinning electrochemomechanical resilience
Here, we advance electrode-omics to identify evolutionary bursts by which ethereal locally superconcentrated electrolytes (LSCEs) mitigate silicon anode degradation through its epochs of electrochemical and chemical reactions. Anode composites form initially at high potential from ethereal solvent and anion [bis(fluorosulfonyl)imide (FSI − )] redox. A first evolutionary burst at lower potential enriches composites with lithium alkoxides (LiO–R) and lithium oxide (Li 2 O) and depletes sulfur oxides (SO x ) species. As the cells are cycled, a second evolutionary burst takes place, where previously extinct SO x species reemerge concurrently with a loss of LiO–R and Li 2 O. This identifies reactions rooted in “SuFEx” chemistry, where oxoanionic LiO–R and Li 2 O species, electrochemically generated in the solid-electrolyte interphase, chemically react with FSI − in the electrolyte to form emergent species. This sequence of evolutionary bursts produces a mechanically resilient composite that reduces silicon anode cracking over hundreds of cycles, leading to overpotential increase of only ~0.01 volts after 200 cycles.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ultrahigh coulombic efficiency electrolyte enables Li||SPAN batteries with superior cycling performance
Raising the coulombic efficiency of lithium metal anode cycling is the deciding step in realizing long-life rechargeable lithium batteries. Here, we designed a highly concentrated salt/ether electrolyte diluted in a fluorinated ether: 1.8 M LiFSI in DEE/BTFE (diethyl ether/bis(2,2,2-trifluoroethyl)ether), which realized an average coulombic efficiency of 99.37% at 0.5 mA cm -2 and 1 mAh cm -2 for more than 900 cycles. This electrolyte also maintained a record coulombic efficiency of 98.7% at 10 mA cm -2 , indicative of its ability to provide fast-charging with high cathode loadings. Morphological studies reveal dense, dendrite free Li depositions after prolonged cycling, while surface analyses confirmed the formation of a robust LiF-rich SEI layer on the cycled Li surface. Moreover, we discovered that this ether-based electrolyte is highly compatible with the low-cost, high-capacity SPAN (Sulfurized polyacrylonitrile) cathode, where the constructed Li||SPAN cell exhibited reversible cathode capacity of 579 mAh g -1 and no capacity decay after 1200 cycles. A cell where a high areal loading SPAN electrode (>3.5 mAh cm -2 ) is paired with only onefold excess Li was constructed and cycled at 1.75 mA cm -2 , maintaining a coulombic efficiency of 99.30% for the lithium metal. Computational simulations revealed that at saturation, the Li-FSI complex forms contact ion pairs, with a first solvation shell comprising DEE molecules, and a second solvation shell with a mix of DEE/BTFE. This study provides a path to enable high energy density Li||SPAN batteries with stable cycling.
36 MATERIALS SCIENCE↗
Pushing Lithium–Sulfur Batteries towards Practical Working Conditions through a Cathode–Electrolyte Synergy
Abstract The commercialization of lithium–sulfur (Li−S) batteries is still hindered by the unsatisfactory cell performance under practical working conditions, which is mainly caused by the sluggish cathode redox kinetics, severe polysulfide shuttling, and poor Li stripping/plating reversibility. Herein, we report an effective strategy by combining Se‐doped S hosted in an ordered macroporous framework with a highly fluorinated ether (HFE)‐based electrolyte to simultaneously address the aforementioned issues in both cathode and anode. A reversible and stable high areal capacity of >5.4 mAh cm −2 with high Coulombic efficiency >99.2 % can be achieved under high areal Se/S loading (5.8 mg cm −2 ), while the underlying mechanism was further revealed through synchrotron X‐ray probes and Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS). The practical application potential was further evaluated at low (0 °C) and high (55 °C) temperatures under high areal Se/S loading (>5.0 mg cm −2 ) and thin Li metal (40 μm).
Zhao, Chen↗
Pushing Lithium–Sulfur Batteries towards Practical Working Conditions through a Cathode–Electrolyte Synergy
The commercialization of lithium-sulfur (Li-S) batteries is still hindered by the unsatisfactory cell performance under practical working conditions, which is mainly caused by the sluggish cathode redox kinetics, severe polysulfide shuttling, and poor Li striping/platting reversibility. We reported an effective strategy by combining Se-doped S hosted in an ordered macroporous framework with highly fluorinated ether (HFE)-based electrolyte to simultaneously address the aforementioned issues in both cathode and anode. A reversible and stable high areal capacity of > 5.4 mAh cm -2 with high coulombic efficiency > 99.2% can be achieved under high areal Se/S loading (5.8 mg cm -2 ), while the underlying mechanism was further revealed through synchrotron X-ray probes and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The practical application potential was further evaluated at low (0 °C) and high (55 °C) temperatures under high areal Se/S loading (> 5.0 mg cm -2 ) and thin Li metal (40 µm).
25 ENERGY STORAGE↗
Lithium-Ion Battery Testing Capable of Simulating “Ultralow” Lunar Temperatures
The first-ever lithium-ion battery cycler capable of testing the coin and pouch cells under ultralow (≤40 °C) temperatures down to -175 °C to simulate extreme climates found in the lunar and space missions, high-altitude air vehicles, polar regions of Earth, and military expeditionary missions is enthusiastically reported. The extremely cold temperatures are achieved through a tailored extreme low-temperature system (ELTS) with liquid nitrogen flow and the ability to reach temperatures between -175 and 25 °C, using 1 kΩ and 1 MΩ resistors at varying currents of 1–4 mA and 1–4 μA, respectively, is validated. Employing the ELTS, Li 4 Ti 5 O 12 (LTO)||Li cells with 1 m lithium bis(fluorosulfonyl)imide in cyclopentyl methyl ether as an electrolyte developed in this research group are charged and discharged at room temperature (cycling rate C/5), -20 (C/10), -40 (C/40), and -60 °C (C/50), which exhibited discharge capacities of 159.04, 119.12, 101.79, and 33.06 mAh g -1 , respectively. Moreover, the LTO||Li cell produced a reversible capacity of 7.12 mAh g -1 tested at -100 °C for the first time.
25 ENERGY STORAGE↗
Ex situ poly-DOL coatings for lithium metal protection
Schematic illustration of the poly-DOL coating layer developed through an ex situ method to improve lithium metal cycling performance in ether and carbonate electrolytes.
Zhao, Yifan↗
Selective Plasticization of Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene– PEO– Polystyrene Triblock Copolymer Electrolytes
The plasticization of a polymer electrolyte usually promotes its ionic conductivity but decreases its storage modulus due to the increased polymer chain flexibility. Herein, we show that such a tradeoff between the ionic conductivity and the mechanical robustness of the polymer electrolyte can be alleviated by selective plasticization of the ion-conductive block, such as poly(ethylene oxide) (PEO) in a polystyrene (PS)– PEO–PS block copolymer (SEO) electrolyte using an ether type plasticizer, tetraethylene glycol dimethyl ether (TEGDME). In this work, at maximum plasticizer loading, the room temperature ionic conductivity increases by up to 3 orders, whereas the storage modulus, G' reduces to half, is still on the order of 10 2 MPa. At above the melting temperature of the PEO block, the dynamic storage modulus, G' of the plasticized membrane surpasses its dry PS-PEO-PS counterpart. Such a phenomenon results from that, a) TEGDME co-crystallizes with PEO to promote its crystallinity and hence the storage modulus, b) TEGDME swells the amorphous PEO phase to enhance the polymer chain segmental mobility and hence ionic conductivity, and c) the PS phase remains intact from TEGDME to keep the SEO elastic.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Solvents and catalyst preparations for lithium-oxygen batteries
An electrochemical device includes a lithium anode having a red poly(benzonitrile) coating covering at least a portion of the anode; a separator and an air cathode comprising reduced graphene oxide over gas diffusion layer; and an electrolyte comprising an ether solvent, benzonitrile, and a lithium salt.
Wang, Hsien-Hau↗