Aqueous Organic Hydrogen Gas Proton Batteries with Ultrahigh-Rate and Ultralow-Temperature Performance.

Aqueous proton batteries (APBs) have emerged as one of the most promising batteries for large-scale energy storage technology. However, they usually show an undesirable electrochemical performance. Herein, we demonstrate a novel aqueous catalytic hydrogen gas powered organic proton (HOP) battery, which is driven by hydrogen evolution/oxidation redox reactions via commercial nanocatalysts on the anode and coordination/decoordination reactions of C═O with H+ on the cathode. The HOP battery shows an excellent rate capacity of 190.1 mAh g-1 at 1 A g-1 and 71.4 mAh g-1 at 100 A g-1. It also delivers a capacity of 96.6 mAh g-1 after 100000 cycles and operates at temperatures down to -70 °C. Moreover, the HOP battery is fabricated in a large-scale pouch cell with an extended capacity, exhibiting its potential for practical energy storage applications. This work provides new insights into the building of sustainable APBs, which will broaden the horizons of high-performance aqueous batteries.

Super Hydrous Solvated Structure of Chaotropic Ca2+ Contributes Superior Anti-Freezing Aqueous Electrolytes and Stabilizes the Zn anode.

The further development of aqueous zinc (Zn)-ion batteries (AZIBs) is constrained by the high freezing points and the instability on Zn anodes. Current improvement strategies mainly focus on regulating hydrogen bond (HB) donors (H) of solvent water to disrupt HBs, while neglecting the environment of HB-acceptors (O). Herein, we propose a mechanism of chaotropic cation-regulated HB-acceptor via a "super hydrous solvated" structure. Chaotropic Ca2+ can form a solvated structure via competitively binding O atoms in H2O, effectively breaking the HBs among H2O molecules, thereby reducing the glass transition temperature of hybrid 1 mol L-1 (M) ZnCl2+4 M CaCl2 electrolyte (-113.2 °C). Meanwhile, the high hydratability of Ca2+ contributes to the water-poor solvated structure of Zn2+, suppressing side reactions and uneven Zn deposition. Benefiting from the anti-freezing electrolyte and high reversible Zn anode, the Zn||Pyrene-4,5,9,10-tetraone (PTO) batteries deliver an ultrahigh capacity of 183.9 mAh g-1 at 1.0 A g-1 over 1600-time stable cycling at -60 °C. This work presents a cheap and efficient aqueous electrolyte to simultaneously improve low-temperature performances and Zn stability, broadening the design concepts for antifreeze electrolytes.

Localized Alkaline Environment via In Situ Electrostatic Confinement for Enhanced CO2-to-Ethylene Conversion in Neutral Medium.

Electrocatalytic CO2 reduction reaction (CO2RR) is one of the most promising routes to facilitate carbon neutrality. An alkaline electrolyte is typically needed to promote the production of valuable multi-carbon molecules (such as ethylene). However, the reaction between CO2 and OH- consumes a significant quantity of CO2/alkali and causes the rapid decay of CO2RR selectivity and stability. Here, we design a catalyst-electrolyte interface with an effective electrostatic confinement of in situ generated OH- to improve ethylene electrosynthesis from CO2 in neutral medium. In situ Raman measurements indicate the direct correlation between ethylene selectivity and the intensities of surface Cu-CO and Cu-OH species, suggesting the promoted C-C coupling with the surface enrichment of OH-. Thus, we report a CO2-to-ethylene Faradaic efficiency (FE) of 70% and a partial current density of 350 mA cm-2 at -0.89 V vs the reversible hydrogen electrode. Furthermore, the system demonstrated a 50 h stable operation at 300 mA cm-2 with an average ethylene FE of ∼68%. This study offers a universal strategy to tune the reaction micro-environment, and a significantly improved ethylene FE of 64.5% was obtained even in acidic electrolytes (pH = 2).

High-entropy Electrolyte Enables High Reversibility and Long Lifespan for Magnesium Metal Anodes.

The stable cycling of Mg-metal anodes is limited by several problems, including sluggish electrochemical kinetics and passivation at the Mg surface. In this study, we present a high-entropy electrolyte composed of lithium triflate (LiOTf) and trimethyl phosphate (TMP) co-added to magnesium bis(trifluoromethane sulfonyl)imide (Mg(TFSI)2 /1,2-dimethoxyethane (DME) to significantly improve the electrochemical performance of Mg-metal anodes. The as-formed high-entropy Mg2+ -2DME-OTf- -Li+ -DME-TMP solvation structure effectively reduced the Mg2+ -DME interaction in comparison with that observed in traditional Mg(TFSI)2 /DME electrolytes, thereby preventing the formation of insulating components on the Mg-metal anode and promoting its electrochemical kinetics and cycling stability. Comprehensive characterization revealed that the high-entropy solvation structure brought OTf- and TMP to the surface of the Mg-metal anode and promoted the formation of a Mg3 (PO4 )2 -rich interfacial layer, which is beneficial for enhancing Mg2+ conductivity. Consequently, the Mg-metal anode achieved excellent reversibility with a high Coulombic efficiency of 98 % and low voltage hysteresis. This study provides new insights into the design of electrolytes for Mg-metal batteries.

Regulating Frozen Electrolyte Structure with Colloidal Dispersion for Low Temperature Aqueous Batteries.

Electrolyte freezing under low temperatures is a critical challenge for the development of aqueous batteries (ABs). While lowering the freezing point of the electrolyte has caught major research efforts, limited attention has been paid to the structural evolution during the electrolyte freezing process and regulating the frozen electrolyte structure for low temperature ABs. Here, we reveal the formation process of interconnected liquid regions for ion transport in frozen electrolytes with various in situ variable-temperature technologies. More importantly, the low-temperature performance of ABs was significantly improved with the colloidal electrolyte design using graphene oxide quantum dots (GOQDs), which effectively inhibits the growth of ice crystals and expands the interconnected liquid regions for facial ion transport. This work provides new insights and a promising strategy for the electrolyte design of low-temperature ABs.

Hydrogen Bond Shielding Effect for High-Performance Aqueous Zinc Ion Batteries.

Manganese oxides are highly desirable for the cathode of rechargeable aqueous zinc ion batteries (AZIBs) owing to their low cost and high abundance. However, the terrible structure stability of manganese oxide limits its practical application. Here, it is demonstrated that the hydrogen-bond shielding effect can improve the electrochemical performance of manganese oxide. Briefly, (NH4 )0.125 MnO2 (NHMO) is prepared by introducing NH4 + into the tunnel structure of α-MnO2 . The robust hydrogen bonds between N-H and host O atoms can stabilize the lattice structure of α-MnO2 and suppress the dissolution of Mn element. More importantly, it can also accelerate ions mobility kinetics by weakening the electrostatic interaction of host O atoms. Thus, the fabricated Zn||NHMO battery possesses impressive cycling life (99.5% of capacity retention over 10 000 cycles) and rate capability (109 mA h g-1 of discharge capacity at 6000 mA g-1 ). Comprehensive analyses reveal the essences of interfacial charge and bulk ions transfer. This finding opens new opportunities for the development of high-performance AZIBs.

Intrinsic Nonflammable Ether Electrolytes for Ultrahigh-Voltage Lithium Metal Batteries Enabled by Chlorine Functionality.

The issues of inherent low anodic stability and high flammability hinder the deployment of the ether-based electrolytes in practical high-voltage lithium metal batteries. Here, we report a rationally designed ether-based electrolyte with chlorine functionality on ether molecular structure to address these critical challenges. The chloroether-based electrolyte demonstrates a high Li Coulombic efficiency of 99.2 % and a high capacity retention >88 % over 200 cycles for Ni-rich cathodes at an ultrahigh cut-off voltage of 4.6 V (stable even up to 4.7 V). The chloroether-based electrolyte not only greatly improves electrochemical stabilities of Ni-rich cathodes under ultrahigh voltages with interphases riched in LiF and LiCl, but possesses the intrinsic nonflammable safety feature owing to the flame-retarding ability of chlorine functional groups. This study offers a new approach to enable ether-based electrolytes for high energy density, long-life and safe Li metal batteries.

Layered Ca0.28 MnO2 ·0.5H2 O as a High Performance Cathode for Aqueous Zinc-Ion Battery.

Aqueous zinc-ion batteries are promising candidates for grid-scale energy storage because of their intrinsic safety, low cost, and high energy intensity. However, lack of suitable cathode materials with both excellent rate performance and cycling stability hinders further practical application of aqueous zinc-ion batteries. Here, a nanoflake-self-assembled nanorod structure of Ca0.28 MnO2 ·0.5H2 O as Zn-insertion cathode material is designed. The Ca0.28 MnO2 ·0.5H2 O exhibits a reversible capacity of 298 mAh g-1 at 175 mA g-1 and long-term cycling stability over 5000 cycles with no obvious capacity fading, which indicates that the per-insertion of Ca ions and water can significantly improve reversible insertion/extraction stability of Zn2+ in Mn-based layered type material. Further, its charge storage mechanism, especially hydrogen ions, is elucidated. A comprehensive study suggests that the intercalation of hydrogen ions in the first discharge plat is controled by both pH value and type of anion of electrolyte. Further, it can stabilize the Ca0.28 MnO2 ·0.5H2 O cathode and facilitate the following insertion of Zn2+ in 1 m ZnSO4 /0.1 m MnSO4 electrolyte. This work can enlighten and promote the development of high-performance rechargeable aqueous zinc-ion batteries.

Aqueous Batteries Operated at -50 °C.

Insufficient ionic conductivity and freezing of the electrolyte are considered the main problems for electrochemical energy storage at low temperatures (low T). Here, an electrolyte with a freezing point lower than -130 °C is developed by using dimethyl sulfoxide (DMSO) as an additive with molar fraction of 0.3 to an aqueous solution of 2 m NaClO4 (2M-0.3 electrolyte). The 2M-0.3 electrolyte exhibits sufficient ionic conductivity of 0.11 mS cm-1 at -50 °C. The combination of spectroscopic investigations and molecular dynamics (MD) simulations reveal that hydrogen bonds are stably formed between DMSO and water molecules, facilitating the operation of the electrolyte at ultra-low T. Using DMSO as the electrolyte additive, the aqueous rechargeable alkali-ion batteries (AABs) can work well even at -50 °C. This work provides a simple and effective strategy to develop low T AABs.

Molecular anchoring of free solvents for high-voltage and high-safety lithium metal batteries.

Constraining the electrochemical reactivity of free solvent molecules is pivotal for developing high-voltage lithium metal batteries, especially for ether solvents with high Li metal compatibility but low oxidation stability ( <4.0 V vs Li+/Li). The typical high concentration electrolyte approach relies on nearly saturated Li+ coordination to ether molecules, which is confronted with severe side reactions under high voltages ( >4.4 V) and extensive exothermic reactions between Li metal and reactive anions. Herein, we propose a molecular anchoring approach to restrict the interfacial reactivity of free ether solvents in diluted electrolytes. The hydrogen-bonding interactions from the anchoring solvent effectively suppress excessive ether side reactions and enhances the stability of nickel rich cathodes at 4.7 V, despite the extremely low Li+/ether molar ratio (1:9) and the absence of typical anion-derived interphase. Furthermore, the exothermic processes under thermal abuse conditions are mitigated due to the reduced reactivity of anions, which effectively postpones the battery thermal runaway.

Highly reversible zinc metal anode enabled by strong Brønsted acid and hydrophobic interfacial chemistry.

Uncontrollable zinc (Zn) plating and hydrogen evolution greatly undermine Zn anode reversibility. Previous electrolyte designs focus on suppressing H2O reactivity, however, the accumulation of alkaline byproducts during battery calendar aging and cycling still deteriorates the battery performance. Here, we present a direct strategy to tackle such problems using a strong Brønsted acid, bis(trifluoromethanesulfonyl)imide (HTFSI), as the electrolyte additive. This approach reformulates battery interfacial chemistry on both electrodes, suppresses continuous corrosion reactions and promotes uniform Zn deposition. The enrichment of hydrophobic TFSI- anions at the Zn|electrolyte interface creates an H2O-deficient micro-environment, thus inhibiting Zn corrosion reactions and inducing a ZnS-rich interphase. This highly acidic electrolyte demonstrates high Zn plating/stripping Coulombic efficiency up to 99.7% at 1 mA cm-2 ( > 99.8% under higher current density and areal capacity). Additionally, Zn | |ZnV6O9 full cells exhibit a high capacity retention of 76.8% after 2000 cycles.

Non-Noble Metal High-Entropy Alloy-Based Catalytic Electrode for Long-Life Hydrogen Gas Batteries.

The development of efficient, stable, and low-cost bifunctional catalysts for the hydrogen evolution/oxidation reaction (HER/HOR) is critical to promote the application of hydrogen gas batteries in large scale energy storage systems. Here we demonstrate a non-noble metal high-entropy alloy grown on Cu foam (NNM-HEA@CF) as a self-supported catalytic electrode for nickel-hydrogen gas (Ni-H2) batteries. Experimental and theoretical calculation results reveal that the NNM-HEA catalyst greatly facilitates the HER/HOR catalytic process through the optimized electronic structures of the active sites. The assembled Ni-H2 battery with NNM-HEA@CF as the anode shows excellent rate capability and exceptional cycling performance of over 1800 h without capacity decay at an areal capacity of 15 mAh cm-2. Furthermore, a scaled-up Ni-H2 battery fabricated with an extended capacity of 0.45 Ah exhibits a high cell-level energy density of ∼109.3 Wh kg-1. Moreover, its estimated cost reaches as low as ∼107.8 $ kWh-1 based on all key components of electrodes, separator and electrolyte, which is reduced by more than 6 times compared to that of the commercial Pt/C-based Ni-H2 battery. This work provides an approach to develop high-efficiency non-noble metal-based bifunctional catalysts for hydrogen batteries in large-scale energy storage applications.

Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery.

Novel small sulfur heterocyclic quinones (6a,16a-dihydrobenzo[b]naphtho[2',3':5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone (4S6Q) and benzo[b]naphtho[2',3':5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone (4S4Q)) are developed by molecule structural design method and as cathode for aqueous zinc-organic batteries. The conjugated thioether (-S-) bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extended π-conjugated plane and constructed flexible molecular skeleton. Hence, the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L-1 (M) Zn(ClO4)2 electrolyte. For instance, the Zn//4S6Q battery obtains 240 and 208.6 mAh g-1 of discharge capacity at 150 mA g-1 and 30 A g-1, respectively. The excellent rate capability is ascribed to the fast reaction kinetics. This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g-1. Additionally, the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations. Impressively, the battery can normally work at - 60 °C benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g-1, which is 86.2% of discharge capacity at 25 °C. The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.

Solvent versus Anion Chemistry: Unveiling the Structure-Dependent Reactivity in Tailoring Electrochemical Interphases for Lithium-Metal Batteries.

Electrolytes are critical for the reversibility of various electrochemical energy storage systems. The recent development of electrolytes for high-voltage Li-metal batteries has been counting on the salt anion chemistry for building stable interphases. Herein, we investigate the effect of the solvent structure on the interfacial reactivity and discover profound solvent chemistry of designed monofluoro-ether in anion-enriched solvation structures, which enables enhanced stabilization of both high-voltage cathodes and Li-metal anodes. Systematic comparison of different molecular derivatives provides an atomic-scale understanding of the unique solvent structure-dependent reactivity. The interaction between Li+ and the monofluoro (-CH2F) group significantly influences the electrolyte solvation structure and promotes the monofluoro-ether-based interfacial reactions over the anion chemistry. With in-depth analyses of the compositions, charge transfer, and ion transport at interfaces, we demonstrated the essential role of the monofluoro-ether solvent chemistry in tailoring highly protective and conductive interphases (with enriched LiF at full depths) on both electrodes, as opposed to the anion-derived ones in typical concentrated electrolytes. As a result, the solvent-dominant electrolyte chemistry enables a high Li Coulombic efficiency (∼99.4%) and stable Li anode cycling at a high rate (10 mA cm-2), together with greatly improved cycling stability of 4.7 V-class nickel-rich cathodes. This work illustrates the underlying mechanism of the competitive solvent and anion interfacial reaction schemes in Li-metal batteries and offers fundamental insights into the rational design of electrolytes for future high-energy batteries.

High-safety and high-efficiency electrolyte design for 4.6 V-class lithium-ion batteries with a non-solvating flame-retardant.

Nonflammable electrolytes are critical for the safe operation of high-voltage lithium-ion batteries (LIBs). Although organic phosphates are effective flame retardants, their poor electrochemical stability with a graphite (Gr) anode and Ni-rich cathodes would lead to the deterioration of electrode materials and fast capacity decay. Herein, we develop a safe and high-performance electrolyte formulation for high-voltage (4.6 V-class) LIBs using flame-retarding ethoxy(pentafluoro) cyclotriphosphazene (PFPN) as a non-solvating diluent for the high-concentration carbonate-ether hybrid electrolyte. In contrast to conventional nonflammable additives with restricted dosage, the high level of PFPN (69% mass ratio in our electrolyte design) could significantly increase the electrolyte flash point and protect the favored anion-rich inner solvation sheath because of its non-solvating feature, thus preventing solvent co-intercalation and structural damage to the Gr anode. The nonflammable electrolyte could also form a stable LiF-rich cathode electrolyte interphase (CEI), which enables superior electrochemical performances of Gr‖LiNi0.8Mn0.1Co0.1O2 (NMC811) full cells at high voltages (∼82.0% capacity retention after 1000 cycles at 4.5 V; 89.8% after 300 cycles at 4.6 V) and high temperatures (50 °C). This work sheds light on the electrolyte design and interphase engineering for developing practical safe high-energy-density LIBs.

Strongly Solvating Ether Electrolytes for High-Voltage Lithium Metal Batteries.

Ethers are promising electrolytes for lithium (Li) metal batteries (LMBs) because of their unique stability with Li metal. Although intensive research on designing anion-enriched electrolyte solvation structures has greatly improved their electrochemical stabilities, ether electrolytes are approaching an anodic bottleneck. Herein, we reveal the strong correlation between electrolyte solvation structure and oxidation stability. In contrast to previous designs of weakly solvating solvents for enhanced anion reactivities, the triglyme (G3)-based electrolyte with the largest Li+ solvation energy among different linear ethers demonstrates greatly improved stability on Ni-rich cathodes under an ultrahigh voltage of 4.7 V (93% capacity retention after 100 cycles). Ether electrolytes with a stronger Li+ solvating ability could greatly suppress deleterious oxidation side reactions by decreasing the lifetime of free labile ether molecules. This study provides critical insights into the dynamics of the solvation structure and its significant influence on the interfacial stability for future development of high-efficiency electrolytes for high-energy-density LMBs.

Plastic Monolithic Mixed-Conducting Interlayer for Dendrite-Free Solid-State Batteries.

Solid-state electrolytes (SSEs) hold a critical role in enabling high-energy-density and safe rechargeable batteries with Li metal anode. Unfortunately, nonuniform lithium deposition and dendrite penetration due to poor interfacial solid-solid contact are hindering their practical applications. Here, solid-state lithium naphthalenide (Li-Naph(s)) is introduced as a plastic monolithic mixed-conducting interlayer (PMMCI) between the garnet electrolyte and the Li anode via a facile cold process. The thin PMMCI shows a well-ordered layered crystalline structure with excellent mixed-conducting capability for both Li+ (4.38 × 10-3  S cm-1 ) and delocalized electrons (1.01 × 10-3  S cm-1 ). In contrast to previous composite interlayers, this monolithic material enables an intrinsically homogenous electric field and Li+ transport at the Li/garnet interface, thus significantly reducing the interfacial resistance and achieving uniform and dendrite-free Li anode plating/stripping. As a result, Li symmetric cells with the PMMCI-modified garnet electrolyte show highly stable cycling for 1200 h at 0.2 mA cm-2 and 500 h at a high current density of 1 mA cm-2 . The findings provide a new interface design strategy for solid-state batteries using monolithic mixed-conducting interlayers.

An Overcrowded Water-Ion Solvation Structure for a Robust Anode Interphase in Aqueous Lithium-Ion Batteries.

The water-in-salt electrolyte (WISE) features intimate interactions between a cation and anion, which induces the formation of an anion-derived solid electrolyte interphase (SEI) and expands the aqueous electrolyte voltage window to >3.0 V. Although further increasing the salt concentration (even to >60 molality (m)) can gradually improve water stability, issues about cost and practical feasibility are concerned. An alternative approach is to intensify ion-solvent interactions in the inner solvation structure by shielding off outward electrostatic attractions from nearby ions. Here, we design an "overcrowded" electrolyte using the non-polar, hydrogen-bonding 1,4-dioxane (DX) as an overcrowding agent, thereby achieving a robust LiF-enriched SEI and wide electrolyte operation window (3.7 V) with a low salt concentration (<2 m). As a result, the electrochemical performance of aqueous Li4Ti5O12/LiMn2O4 full cells can be substantially improved (88.5% capacity retention after 200 cycles, at 0.57 C). This study points out a promising strategy to develop low-cost and stable high-voltage aqueous batteries.