Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution.

Traditional cathode chemistry of Li-ion batteries relies on the transport of Li-ions within the solid structures, with the transition metal ions and anions acting as the static components. Here, we demonstrate that a solid solution of F- and PO43- facilitates the reversible conversion of a fine mixture of iron powder, LiF, and Li3PO4 into iron salts. Notably, in its fully lithiated state, we use commercial iron metal powder in this cathode, departing from electrodes that begin with iron salts, such as FeF3. Our results show that Fe-cations and anions of F- and PO43- act as charge carriers in addition to Li-ions during the conversion from iron metal to a solid solution of iron salts. This composite electrode delivers a reversible capacity of up to 368 mAh/g and a specific energy of 940 Wh/kg. Our study underscores the potential of amorphous composites comprising lithium salts as high-energy battery electrodes.

The Influence of Ions on the Electrochemical Stability of Aqueous Electrolytes.

The electrochemical stability window of water is known to vary with the type and concentration of dissolved salts. However, the underlying influence of ions on the thermodynamic stability of aqueous solutions has not been fully understood. Here, we investigated the electrolytic behaviors of aqueous electrolytes as a function of different ions. Our findings indicate that ions with high ionic potentials, i.e., charge density, promote the formation of their respective hydration structures, enhancing electrolytic reactions via an inductive effect, particularly for small cations. Conversely, ions with lower ionic potentials increase the proportion of free water molecules-those not engaged in hydration shells or hydrogen-bonding networks-leading to greater electrolytic stability. Furthermore, we observe that the chemical environment created by bulky ions with lower ionic potentials impedes electrolytic reactions by frustrating the solvation of protons and hydroxide ions, the products of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. We found that the solvation of protons plays a more substantial role than that of hydroxide, which explains a greater shift for OER than for HER, a puzzle that cannot be rationalized by the notion of varying O-H bond strengths of water. These insights will help the design of aqueous systems.

Electrolyte Interphases in Aqueous Batteries.

The narrow electrochemical stability window of water poses a challenge to the development of aqueous electrolytes. In contrast to non-aqueous electrolytes, the products of water electrolysis do not contribute to the formation of a passivation layer on electrodes. As a result, aqueous electrolytes require the reactions of additional components, such as additives and co-solvents, to facilitate the formation of the desired solid electrolyte interphase (SEI) on the anode and cathode electrolyte interphase (CEI) on the cathode. This review highlights the fundamental principles and recent advancements in generating electrolyte interphases in aqueous batteries.

Reversible Cl/Cl- redox in a spinel Mn3O4 electrode.

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn3O4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn2+ cations inserted in the first discharge and trapped in the Mn3O4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl- redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl3]- and [Cl5]-, inside the Zn2+-trapped Mn3O4, and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.

KI-Assisted Formation of Spindle-like Prussian White Nanoparticles for High-Performance Potassium-Ion Battery Cathodes.

Prussian white (PW) is considered as a promising cathode material for potassium-ion batteries (KIBs) due to its low cost and high theoretical capacity. However, the high water content and structural defects and the strict synthesis conditions of PW lead to its unsatisfactory cycling performance and low specific capacity, hindering its practical applications. Herein, a template-engaged reduction method is proposed, using MIL-88B(Fe) as a self-template and KI as the reducing agent to prepare K-rich PW with low defects and water content. Furthermore, the hierarchical porous spindle-like morphology can be inherited from the precursor, furnishing sufficient active sites and reducing the ion diffusion path. Consequently, when applied as a KIB cathode material, spindle-like PW (K1.72Fe[Fe(CN)6]0.96·0.342H2O) manifested remarkable potassium storage properties. Notably, a full cell assembled by the spindle-like PW cathode and graphite anode exhibited a large energy density of ∼216.7 Wh kg-1, demonstrating its huge potential for energy storage systems.

Li2 MnO3 : A Catalyst for a Liquid Cl2 Electrode in Low-Temperature Aqueous Batteries.

Li2 MnO3 has been contemplated as a high-capacity cathode candidate for Li-ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low-temperature electrochemical properties of Li2 MnO3 in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g-1 at a potential of 1.0 V versus Ag/AgCl at -78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li2 MnO3 cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li2 MnO3 but the reversible Cl2 (l)/Cl- (aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li2 MnO3 to promote the Cl2 /Cl- redox at low temperatures.

Ball Milling-Enabled Fe2.4+ to Fe3+ Redox Reaction in Prussian Blue Materials for Long-Life Aqueous Sodium-Ion Batteries.

Aqueous Na-ion batteries using Prussian blue materials have inherent advantages in safety, material sustainability, and economic cost. However, it is challenging to obtain long-term cycling stability because many redox reactions have poor intrinsic stability in water. Here, we demonstrate reversible Fe2.4+ to Fe3+ redox reaction of Prussian blue electrodes cycled in a 17 m NaClO4 water-in-salt electrolyte. The cubic phase c-Na1.17Fe[Fe(CN)6]·0.35H2O) derived from monoclinic Prussian blue (m-Na1.88Fe[Fe(CN)6]·0.7H2O) through ball milling delivers excellent cycling stability of >18,000 cycles with >90% capacity retention at the 10C rate. The specific capacity is ∼75 and ∼67 mAh/g at 1C and 10C rates, respectively. Systematic characterizations including electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy have verified the phase transition and iron oxidation state evolution, revealing the mechanism that enables the material's high rate and long durability as the battery cathode.

Strengthening Aqueous Electrolytes without Strengthening Water.

Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions-25 wt.% LiCl and 62 wt.% H3 PO4 -cooled to -78 °C exhibit a significantly widened stability window. Integrated experimental and simulation results reveal that, upon cooling, Li+ ions become less hydrated and pair up with Cl- , ice-like water clusters form, and H⋅⋅⋅Cl- bonding strengthens. Surprisingly, this low-temperature solvation structure does not strengthen water molecules' O-H bond, bucking the conventional wisdom that increasing water's stability requires stiffening the O-H covalent bond. We propose a more general mechanism for water's low temperature inertness in the electrolyte: less favorable solvation of OH- and H+ , the byproducts of hydrogen and oxygen evolution reactions. To showcase this stability, we demonstrate an aqueous Li-ion battery using LiMn2 O4 cathode and CuSe anode with a high energy density of 109 Wh/kg. These results highlight the potential of aqueous batteries for polar and extraterrestrial missions.

Anion chemistry in energy storage devices.

Anions serve as an essential component of electrolytes, whose effects have long been ignored. However, since the 2010s, we have seen a considerable increase of anion chemistry research in a range of energy storage devices, and it is now understood that anions can be well tuned to effectively improve the electrochemical performance of such devices in many aspects. In this Review, we discuss the roles of anion chemistry across various energy storage devices and clarify the correlations between anion properties and their performance indexes. We highlight the effects of anions on surface and interface chemistry, mass transfer kinetics and solvation sheath structure. Finally, we conclude with a perspective on the challenges and opportunities of anion chemistry for enhancing specific capacity, output voltage, cycling stability and anti-self-discharge ability of energy storage devices.

Correlation between Redox Potential and Solvation Structure in Biphasic Electrolytes for Li Metal Batteries.

The activity of lithium ions in electrolytes depends on their solvation structures. However, the understanding of changes in Li+ activity is still elusive in terms of interactions between lithium ions and solvent molecules. Herein, the chelating effect of lithium ion by forming [Li(15C5)]+ gives rise to a decrease in Li+ activity, leading to the negative potential shift of Li metal anode. Moreover, weakly solvating lithium ions in ionic liquids, such as [Li(TFSI)2 ]- (TFSI = bis(trifluoromethanesulfonyl)imide), increase in Li+ activity, resulting in the positive potential shift of LiFePO4 cathode. This allows the development of innovative high energy density Li metal batteries, such as 3.8 V class Li | LiFePO4 cells, along with introducing stable biphasic electrolytes. In addition, correlation between Li+ activity, cell potential shift, and Li+ solvation structure is investigated by comparing solvated Li+ ions with carbonate solvents, chelated Li+ ions with cyclic and linear ethers, and weakly solvating Li+ ions in ionic liquids. These findings elucidate a broader understanding of the complex origin of Li+ activity and provide an opportunity to achieve high energy density lithium metal batteries.

Reversible Copper Cathode for Nonaqueous Dual-Ion Batteries.

Most reported cathodes of nonaqueous dual-ion batteries (DIBs) host anions via insertion reactions. It is necessary to explore new cathode chemistry to increase the battery energy density. To date, transition metals have yet to be investigated for nonaqueous DIBs, albeit they may offer high capacity in anodic conversion reactions. Here, we report that bulk copper powder exhibits a high reversible capacity of 762 mAh g-1 at 3.2 V vs. Li+ /Li and relatively stable cycling in common organic electrolytes. The operation of the copper electrode is coupled with the transfer of anion charge carriers. An anion exchange membrane separator is employed to prevent Cu2+ from crossing from the catholyte to the anode side. We designed an unbalanced electrolyte with a more concentrated anolyte than a catholyte. This addresses the concentration overpotential ensued during charge and facilitates the high specific capacity and enhanced reversibility. This finding provides a promising direction for high-energy DIBs.

Copper metal electrode reversibly hosts fluoride in a 16 m KF aqueous electrolyte.

Fluoride is a promising charge carrier for batteries due to its high charge/mass ratio and small radius. Here, we report commercial copper powder exhibits a reversible capacity of up to 222 mA h g-1 in a saturated electrolyte of 16 m KF. This electrolyte suppresses dissolution of CuF2, the charged product. Furthermore, the KF solid comprised in the Cu electrode facilitates a high initial capacity. Our results showcase the potential of aqueous fluoride batteries using copper as an electrode.

From Copper to Basic Copper Carbonate: A Reversible Conversion Cathode in Aqueous Anion Batteries.

Dual-ion batteries that use anions and cations as charge carriers represent a promising energy-storage technology. However, an uncharted area is to explore transition metals as electrodes to host carbonate in conversion reactions. Here we report the reversible conversion reaction from copper to Cu2 CO3 (OH)2 , where the copper electrode comprising K2 CO3 and KOH solid is self-sufficient with anion-charge carriers. This electrode dissociates and associates K+ ions during battery charge and discharge. The copper active mass and the anion-bearing cathode exhibit a reversible capacity of 664 mAh g-1 and 299 mAh g-1 , respectively, and relatively stable cycling in a saturated mixture electrolyte of K2 CO3 and KOH. The results open an avenue to use carbonate as a charge carrier for batteries to serve for the consumption and storage of CO2 .

Acid-in-Clay Electrolyte for Wide-Temperature-Range and Long-Cycle Proton Batteries.

Proton conduction underlies many important electrochemical technologies. A family of new proton electrolytes is reported: acid-in-clay electrolyte (AiCE) prepared by integrating fast proton carriers in a natural phyllosilicate clay network, which can be made into thin-film (tens of micrometers) fluid-impervious membranes. The chosen example systems (sepiolite-phosphoric acid) rank top among the solid proton conductors in terms of proton conductivities (15 mS cm-1 at 25 °C, 0.023 mS cm-1 at -82 °C), electrochemical stability window (3.35 V), and reduced chemical reactivity. A proton battery is assembled using AiCE as the solid electrolyte membrane. Benefitting from the wider electrochemical stability window, reduced corrosivity, and excellent ionic selectivity of AiCE, the two main problems (gassing and cyclability) of proton batteries are successfully solved. This work draws attention to the element cross-over problem in proton batteries and the generic "acid-in-clay" solid electrolyte approach with superfast proton transport, outstanding selectivity, and improved stability for room- to cryogenic-temperature protonic applications.

A Graphite∥PTCDI Aqueous Dual-Ion Battery.

A full cell chemistry of aqueous dual-ion battery (DIB) was reported, comprising the graphite cathode and 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as the anode. This DIB employed a mixture aqueous electrolyte: 5 m tributylmethylammonium (TBMA) chloride plus 5 m MgCl2 , where [MgCl3 ]- and TBMA+ serve as the charge carriers for cathode and anode of the DIB, respectively. This novel full cell exhibited a specific capacity of around 41 mAh g-1 based on the total active mass of both electrodes with an average operation voltage of 1.45 V and stable cycling for 400 cycles.

The Quest for Stable Potassium-Ion Battery Chemistry.

Potassium-ion batteries (KIBs) have attracted wide interest for energy storage because of the abundance of the electrode materials involved; however, their electrochemical performances are far behind what can be achieved from lithium-ion batteries (LIBs) or sodium-ion batteries (SIBs). Herein, key promising electrode and electrolyte materials for potassium-ion batteries are identified, the coupled electrochemical reactions in the cell are investigated, and the compatibility between different materials is demonstrated to play the most important role. K2 Mn[Fe(CN)6 ] cathode can deliver a high capacity of ≈125 mAh g-1 and exceptional cycling stability over 61 000 cycles (≈9 months) if the side reactions from the anode can be prevented. Graphite is a good anode material but is subjected to degradation in traditional carbonate electrolytes. New concentrated electrolytes are developed and evaluated. A stable KIB system is demonstrated by coupling a stable K2 Mn[Fe(CN)6 ] cathode, a prepotassiated graphite anode with a concentrated electrolyte to achieve a high energy density of ≈260 Wh kg-1 (based on the active mass of cathode and anode) and good cycling of over 1000 cycles.

Fe-Ion Bolted VOPO4 ∙2H2 O as an Aqueous Fe-Ion Battery Electrode.

Iron ion batteries using Fe2+ as a charge carrier have yet to be widely explored, and they lack high-performing Fe2+ hosting cathode materials to couple with the iron metal anode. Here, it is demonstrated that VOPO4 ∙2H2 O can reversibly host Fe2+ with a high specific capacity of 100 mAh g-1 and stable cycling performance, where 68% of the initial capacity is retained over 800 cycles. In sharp contrast, VOPO4 ∙2H2 O's capacity of hosting Zn2+ fades precipitously over tens of cycles. VOPO4 ∙2H2 O stores Fe2+ with a unique mechanism, where upon contacting the electrolyte by the VOPO4 ∙2H2 O electrode, Fe2+ ions from the electrolyte get oxidized to Fe3+ ions that are inserted and trapped in the VOPO4 ∙2H2 O structure in an electroless redox reaction. The trapped Fe3+ ions, thus, bolt the layered structure of VOPO4 ∙2H2 O, which prevents it from dissolution into the electrolyte during (de)insertion of Fe2+ . The findings offer a new strategy to use a redox-active ion charge carrier to stabilize the layered electrode materials.

Reversible electrochemical conversion from selenium to cuprous selenide.

Using elemental selenium as an electrode, the redox-active Cu2+/Cu+ ion is reversibly hosted via the sequential conversion reactions of Se → CuSe → Cu3Se2 → Cu2Se. The four-electron redox process from Se to Cu2Se produces a high initial specific capacity of 1233 mA h g-1 based on the mass of selenium alone or 472 mA h g-1 based on the mass of Cu2Se, the fully discharged product.