Healable and conductive sulfur iodide for solid-state Li-S batteries.

Solid-state Li-S batteries (SSLSBs) are made of low-cost and abundant materials free of supply chain concerns. Owing to their high theoretical energy densities, they are highly desirable for electric vehicles1-3. However, the development of SSLSBs has been historically plagued by the insulating nature of sulfur4,5 and the poor interfacial contacts induced by its large volume change during cycling6,7, impeding charge transfer among different solid components. Here we report an S9.3I molecular crystal with I2 inserted in the crystalline sulfur structure, which shows a semiconductor-level electrical conductivity (approximately 5.9 × 10-7 S cm-1) at 25 °C; an 11-order-of-magnitude increase over sulfur itself. Iodine introduces new states into the band gap of sulfur and promotes the formation of reactive polysulfides during electrochemical cycling. Further, the material features a low melting point of around 65 °C, which enables repairing of damaged interfaces due to cycling by periodical remelting of the cathode material. As a result, an Li-S9.3I battery demonstrates 400 stable cycles with a specific capacity retention of 87%. The design of this conductive, low-melting-point sulfur iodide material represents a substantial advancement in the chemistry of sulfur materials, and opens the door to the practical realization of SSLSBs.

Partially Ion-Paired Solvation Structure Design for Lithium-Sulfur Batteries under Extreme Operating Conditions.

Achieving increased energy density under extreme operating conditions remains a major challenge in rechargeable batteries. Herein, we demonstrate an all-fluorinated ester-based electrolyte comprising partially fluorinated carboxylate and carbonate esters. This electrolyte exhibits temperature-resilient physicochemical properties and moderate ion-paired solvation, leading to a half solvent-separated and half contact-ion pair in a sole electrolyte. As a result, facile desolvation and preferential reduction of anions/fluorinated co-solvents for LiF-dominated interphases are achieved without compromising ionic conductivity (>1 mS cm-1 even at -40 °C). These advantageous features were found to apply to both lithium metal and sulfur-based electrodes even under extreme operating conditions, allowing stable cycling of Li || sulfurized polyacrylonitrile (SPAN) full cells with high SPAN loading (>3.5 mAh cm-2 ) and thin Li anode (50 µm) at -40, 23 and 50 °C. This work offers a promising path for designing temperature-resilient electrolytes to support high energy density Li metal batteries operating in extreme conditions.

Toward a quantitative interfacial description of solvation for Li metal battery operation under extreme conditions.

The future application of Li metal batteries (LMBs) at scale demands electrolytes that endow improved performance under fast-charging and low-temperature operating conditions. Recent works indicate that desolvation kinetics of Li+ plays a crucial role in enabling such behavior. However, the modulation of this process has typically been achieved through inducing qualitative degrees of ion pairing into the system. In this work, we find that a more quantitative control of the ion pairing is crucial to minimizing the desolvation penalty at the electrified interface and thus the reversibility of the Li metal anode under kinetic strain. This effect is demonstrated in localized electrolytes based on strongly and weakly bound ether solvents that allow for the deconvolution of solvation chemistry and structure. Unexpectedly, we find that maximum degrees of ion pairing are suboptimal for ultralow temperature and high-rate operation and that reversibility is substantially improved via slight local dilution away from the saturation point. Further, we find that at the optimum degree of ion pairing for each system, weakly bound solvents still produce superior behavior. The impact of these structure and chemistry effects on charge transfer are then explicitly resolved via experimental and computational analyses. Lastly, we demonstrate that the locally optimized diethyl ether-based localized-high-concentration electrolytes supports kinetic strained operating conditions, including cycling down to -60 °C and 20-min fast charging in LMB full cells. This work demonstrates that explicit, quantitative optimization of the Li+ solvation state is necessary for developing LMB electrolytes capable of low-temperature and high-rate operation.

Locally Saturated Ether-Based Electrolytes With Oxidative Stability For Li Metal Batteries Based on Li-Rich Cathodes.

Li metal batteries applying Li-rich, Mn-rich (LMR) layered oxide cathodes present an opportunity to achieve high-energy density at reduced cell cost. However, the intense oxidizing and reducing potentials associated with LMR cathodes and Li anodes present considerable design challenges for prospective electrolytes. Herein, we demonstrate that, somewhat surprisingly, a properly designed localized-high-concentration electrolyte (LHCE) based on ether solvents is capable of providing reversible performance for Li||LMR cells. Specifically, the oxidative stability of the LHCE was found to heavily rely on the ratio between salt and solvating solvent, where local-saturation was necessary to stabilize performance. Through molecular dynamics (MD) simulations, this behavior was found to be a result of aggregated solvation structures of Li+/anion pairs. This LHCE system was found to produce significantly improved LMR cycling (95.8% capacity retention after 100 cycles) relative to a carbonate control as a result of improved cathode-electrolyte interphase (CEI) chemistry from X-ray photoelectron spectroscopy (XPS), and cryogenic transmission electron microscopy (cryo-TEM). Leveraging this stability, 4 mAh cm-2 LMR||2× Li full cells were demonstrated, retaining 87% capacity after 80 cycles in LHCE, whereas the control electrolyte produced rapid failure. This work uncovers the benefits, design requirements, and performance origins of LHCE electrolytes for high-voltage Li||LMR batteries.

Effect of Electrolyte Chemistry and Sulfur Content in Li||Sulfurized Polyacrylonitrile (SPAN) Batteries.

Sulfurized polyacrylonitrile (SPAN) is considered as a high-value cathode material, which leverages the high energy of S redox while mitigating the negative externalities that limit elemental S cycling. As such, the sulfur content in Li-SPAN batteries plays a critical role. In this work, we demonstrate that high-S loading SPAN cathodes, where the PAN backbone approaches the saturation point without signs of elemental S, are highly dependent on the electrolyte chemistry for long-term reversibility. Specifically, we find that a localized-high-concentration electrolyte (LHCE) further enhances the reversible capacity and cycling stability of SPAN cathode with optimized S content relative to a carbonate control, largely due to the formation of a compatible interphase. With this LHCE as the electrolyte and 43% sulfur ratio of SPAN as the cathode, a full cell applying N/P ratio = 1.82, a cathode loading of 6 mAh cm-2 (9.2 mg cm-2), and an electrolyte loading of 7 µL mg-1 SPAN can be cycled for 100 cycles with 433 mAh g-1 retained capacity and retains much of this reversibility even at 60 °C. This work reveals the molecular origin of optimized sulfur ratio in SPAN cathodes while providing guidance in electrolyte design for Li||SPAN cells with high capacity and cyclability.

Unravelling Ultrafast Li Ion Transport in Functionalized Metal-Organic Framework-Based Battery Electrolytes.

Nonaqueous fluidic transport and ion solvation properties under nanoscale confinement are poorly understood, especially in ion conduction for energy storage and conversion systems. Herein, metal-organic frameworks (MOFs) and aprotic electrolytes are studied as a robust platform for molecular-level insights into electrolyte behaviors in confined spaces. By employing computer simulations, along with spectroscopic and electrochemical measurements, we demonstrate several phenomena that deviate from the bulk, including modulated solvent molecular configurations, aggregated solvation structures, and tunable transport mechanisms from quasi-solid to quasi-liquid in functionalized MOFs. Technologically, taking advantage of confinement effects may prove useful for addressing stability concerns associated with volatile organic electrolytes while simultaneously endowing ultrafast transport of solvates, resulting in improved battery performance, even at extreme temperatures. The molecular-level insights presented here further our understanding of structure-property relationships of complex fluids at the nanoscale, information that can be exploited for the predictive design of more efficient electrochemical systems.

Application-Based Prospects for Dual-Ion Batteries.

Dual-ion batteries (DIBs) exhibit a distinct set of performance advantages and disadvantages due to their unique storage mechanism. However, the current cyclability/energy density tradeoffs of anion storage paired with the intrinsic required electrolyte loadings of conventional DIBs preclude their widespread adoption as an alternative to lithium-ion batteries (LIBs). Despite this, their reduced desolvation penalty and low-cost electrode materials may warrant their employment for low-temperature and/or grid storage applications. To expand beyond these applications, this Perspective reviews the prospects of solid salt storage and halogen intercalation-conversion as viable methods to increase DIB energy densities to a level on-par with LIBs. Fundamental limitations of conventional DIBs are examined, technology spaces are proposed where they can make meaningful impact over LIBs, and potential strategies are outlined to improve cell-level energy densities necessary for the widespread adoption of DIBs.

Ultralow-Temperature Li/CFx Batteries Enabled by Fast-Transport and Anion-Pairing Liquefied Gas Electrolytes.

Lithium fluorinated-carbon (Li/CFx ) is one of the most promising chemistries for high-energy-density primary energy-storage systems in applications where rechargeability is not required. Though Li/CFx demonstrates high energy density (>2100 Wh kg-1 ) under ambient conditions, achieving such a high energy density when exposed to subzero temperatures remains a challenge, particularly under high current density. Here, a liquefied gas electrolyte with an anion-pair solvation structure based on dimethyl ether with a low melting point (-141 °C) and low viscosity (0.12 mPa s, 20 °C), leading to high ionic conductivity (>3.5 mS cm-1 ) between -70 and 60 °C is reported. Besides that, through systematic X-ray photoelectron spectroscopy integrated with transmission electron microscopy characterizations, the interface of CFx is evaluated for low-temperature performance. The fast transport and anion-pairing solvation structure of the electrolyte are concluded to bring about reduced charge-transfer resistance at low temperatures, which results in significantly enhanced performance of Li/CFx cells (1690 Wh kg-1 , -60 °C based on active materials). Utilizing 50 mg cm-2 loading electrodes, the Li/CFx still displays 1530 Wh kg-1 at -60 °C. This work provides insights into the electrolyte design that may overcome the operational limits of batteries in extreme environments.

Solvent selection criteria for temperature-resilient lithium-sulfur batteries.

All-climate temperature operation capability and increased energy density have been recognized as two crucial targets, but they are rarely achieved together in rechargeable lithium (Li) batteries. Herein, we demonstrate an electrolyte system by using monodentate dibutyl ether with both low melting and high boiling points as the sole solvent. Its weak solvation endows an aggregate solvation structure and low solubility toward polysulfide species in a relatively low electrolyte concentration (2 mol L-1). These features were found to be vital in avoiding dendrite growth and enabling Li metal Coulombic efficiencies of 99.0%, 98.2%, and 98.7% at 23 °C, -40 °C, and 50 °C, respectively. Pouch cells employing thin Li metal (50 µm) and high-loading sulfurized polyacrylonitrile (3.3 mAh cm-2) cathodes (negative-to-positive capacity ratio = 2) output 87.5% and 115.9% of their room temperature capacity at -40 °C and 50 °C, respectively. This work provides solvent-based design criteria for a wide temperature range Li-sulfur pouch cells.

Predicting the Ion Desolvation Pathway of Lithium Electrolytes and Their Dependence on Chemistry and Temperature.

To better understand the influence of electrolyte chemistry on the ion-desolvation portion of charge-transfer beyond the commonly applied techniques, we apply free-energy sampling to simulations involving diethyl ether (DEE) and 1,3-dioxoloane/1,2-dimethoxyethane (DOL/DME) electrolytes, which display bulk solvation structures dominated by ion-pairing and solvent coordination, respectively. This analysis was conducted at a pristine electrode with and without applied bias at 298 and 213 K to provide insights into the low-temperature charge-transfer behavior, where it has been proposed that desolvation dominates performance. We find that, to reach the inner Helmholtz layer, ion-paired structures are advantageous and that the Li+ ion must reach a total coordination number of 3, which requires the shedding of 1 species in the DEE electrolyte or 2-3 species in DOL/DME. This work represents an effort to predict the distinct thermodynamic states as well as the most probable kinetic pathways of ion desolvation relevant for the charge transfer at electrochemical interphases.

A Fiber-Based 3D Lithium Host for Lean Electrolyte Lithium Metal Batteries.

3D hosts are promising to extend the cycle life of lithium metal anodes but have rarely been implemented with lean electrolytes thus impacting the practical cell energy density. To overcome this challenge, a 3D host that is lightweight and easy to fabricate with optimum pore size that enables full utilization of its pore volume, essential for lean electrolyte operations, is reported. The host is fabricated by casting a VGCF (vapor-grown carbon fiber)-based slurry loaded with a sparingly soluble rubidium nitrate salt as an additive. The network of fibers generates uniform pores of ≈3 µm in diameter with a porosity of 80%, while the nitrate additive enhances lithiophilicity. This 3D host delivers an average coulombic efficiency of 99.36% at 1 mA cm-2 and 1 mAh cm-2 for over 860 cycles in half-cell tests. Full cells containing an anode with 1.35-fold excess lithium paired with LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) cathodes exhibit capacity retention of 80% over 176 cycles at C/2 under a lean electrolyte condition of 3 g Ah-1 . This work provides a facile and scalable method to advance 3D lithium hosts closer to practical lithium-metal batteries.

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries.

Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g-1 vs. <0.03 mAh g-1) at -40 °C under reduced pressure of the electrolyte.

Tailoring Electrolyte Solvation for Li Metal Batteries Cycled at Ultra-Low Temperature.

Lithium metal batteries (LMBs) hold the promise to pushing cell level energy densities beyond 300 Wh kg-1 while operating at ultra-low temperatures (< -30°C). Batteries capable of both charging and discharging at these temperature extremes are highly desirable due to their inherent reduction of external warming requirements. Here we demonstrate that the local solvation structure of the electrolyte defines the charge-transfer behavior at ultra-low temperature, which is crucial for achieving high Li metal coulombic efficiency (CE) and avoiding dendritic growth. These insights were applied to Li metal full cells, where a high-loading 3.5 mAh cm-2 sulfurized polyacrylonitrile (SPAN) cathode was paired with a one-fold excess Li metal anode. The cell retained 84 % and 76 % of its room temperature capacity when cycled at -40 and -60 °C, respectively, which presented stable performance over 50 cycles. This work provides design criteria for ultra-low temperature LMB electrolytes, and represents a defining step for the performance of low-temperature batteries.

An ester electrolyte for lithium-sulfur batteries capable of ultra-low temperature cycling.

A novel lithium bis(fluorosulfonyl)imide in a methyl propionate/fluoroethylene carbonate (LiFSI MP/FEC) electrolyte was designed for high compatibility with the Li metal and sulfurized polyacrylonitrile (SPAN). The resulting Li||SPAN cells can charge and discharge at -20 °C and -40 °C with over 91% and 78% room temperature capacity retention.

Draining Over Blocking: Nano-Composite Janus Separators for Mitigating Internal Shorting of Lithium Batteries.

Catastrophic battery failure due to internal short is extremely difficult to detect and mitigate. In order to enable the next-generation lithium-metal batteries, a "fail safe" mechanism for internal short is highly desirable. Here, a novel separator design and approach is introduced to mitigate the effects of an internal short circuit by limiting the self-discharge current to prevent cell temperature rise. A nano-composite Janus separator-with a fully electronically insulating side contacting the anode and a partially electronically conductive (PEC) coating with tunable conductivity contacting the cathode-is implemented to intercept dendrites, control internal short circuit resistance, and slowly drain cell capacity. Galvanostatic cycling experiments demonstrate Li-metal batteries with the Janus separator perform normally before shorting, which then results in a gradual increase of internal self-discharge over >25 cycles due to PEC-mitigated shorting. This is contrasted by a sudden voltage drop and complete failure seen with a single layer separator. Potentiostatic charging abuse tests of Li-metal pouch cells result in dendrites completely penetrating the single-layer separator causing high short circuit current and large cell temperature increase; conversely, negligible current and temperature rise occurs with the Janus separator where post mortem electron microscopy shows the PEC layer successfully intercepts dendrites.

Exploiting Mechanistic Solvation Kinetics for Dual-Graphite Batteries with High Power Output at Extremely Low Temperature.

Improving the extremely low temperature operation of rechargeable batteries is vital to the operation of electronics in extreme environments, where systems capable of high-rate discharge are in short supply. Herein, we demonstrate the holistic design of dual-graphite batteries, which circumvent the sluggish ion-desolvation process found in typical lithium-ion batteries during discharge. These batteries were enabled by a novel electrolyte, which simultaneously provides high electrochemical stability and ionic conductivity at low temperature. The dual-graphite cells, when compared to industry-type graphite ∥ LiCoO2 full-cells demonstrated an 11 times increased capacity retention at -60 °C for a 10 C discharge rate, indicative of the superior kinetics of the "dual-ion" storage mechanism. These trends are further supported by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) measurements at reduced temperature. This work provides a new design strategy for extreme low-temperature batteries.

An Aqueous Dual-Ion Battery Cathode of Mn3 O4 via Reversible Insertion of Nitrate.

We report reversible electrochemical insertion of NO3 - into manganese(II, III) oxide (Mn3 O4 ) as a cathode for aqueous dual-ion batteries. Characterization by TGA, FTIR, EDX, XANES, EXAFS, and EQCM collectively provides unequivocal evidence that reversible oxidative NO3 - insertion takes place inside Mn3 O4 . Ex situ HRTEM and corresponding EDX mapping results suggest that NO3 - insertion de-crystallizes the structure of Mn3 O4 . Kinetic studies reveal fast migration of NO3 - in the Mn3 O4 structure. This finding may open a new direction for novel low-cost aqueous dual-ion batteries.

A ZnCl2 water-in-salt electrolyte for a reversible Zn metal anode.

We report a low-cost water-in-salt electrolyte, of 30 m ZnCl2, which enables a dendrite-free Zn metal anode to possess a high coulombic efficiency (CE). In asymmetric Zn‖Zn cells with a limited mass of plated Zn as the working electrode, the ZnCl2 WiSE improves the average CE of the Zn anode to 95.4% from 73.2% in 5 m ZnCl2.

Insights on the Proton Insertion Mechanism in the Electrode of Hexagonal Tungsten Oxide Hydrate.

This study reveals the transport behavior of lattice water during proton (de)insertion in the structure of the hexagonal WO3·0.6H2O electrode. By monitoring the mass evolution of this electrode material via electrochemical quartz crystal microbalance, we discovered (1) WO3·0.6H2O incorporates additional lattice water when immersing in the electrolyte at open circuit voltage and during initial cycling; (2) The reductive proton insertion in the WO3 hydrate is a three-tier process, where in the first stage 0.25 H+ is inserted per formula unit of WO3 while simultaneously 0.25 lattice water is expelled; then in the second stage 0.30 naked H+ is inserted, followed by the third stage with 0.17 H3O+ inserted per formula unit. Ex situ XRD reveals that protonation of the WO3 hydrate causes consecutive anisotropic structural changes: it first contracts along the c-axis but later expands along the ab planes. Furthermore, WO3·0.6H2O exhibits impressive cycle life over 20 000 cycles, together with appreciable capacity and promising rate performance.

Amorphous titanic acid electrode: its electrochemical storage of ammonium in a new water-in-salt electrolyte.

We report an amorphous titanic acid of TiO1.85(OH)0.30·0.28H2O as a new electrode for aqueous ammonium-ion batteries, which operates in a new water-in-salt electrolyte-25 m NH4CH3COO. The titanic acid electrode exhibits a specific capacity nearly 8 times that from the crystalline TiO2 electrode. In electrochemical reactions, the amorphous titanic acid provides abundant storage sites in its disordered structure and affords strong H-bonding toward the inserted NH4+ ions.