Cation Co-Intercalation with Anions: The Origin of Low Capacities of Graphite Cathodes in Multivalent Electrolytes.

Dual-ion batteries involving anion intercalation into graphite cathodes represent promising battery technologies for low-cost and high-power energy storage. However, the fundamental origins regarding much lower capacities of graphite cathodes in earth abundant and inexpensive multivalent electrolytes than in Li-ion electrolytes remain elusive. Herein, we reveal that the limited anion-storage capacity of a graphite cathode in multivalent electrolytes is rooted in the abnormal multivalent-cation co-intercalation with anions in the form of large-sized anionic complexes. This cation co-intercalation behavior persists throughout the stage evolution of graphite intercalation compounds and leads to a significant decrease of sites practically viable for capacity contribution inside graphite galleries. Further systematic studies illustrate that the phenomenon of cation co-intercalation into graphite is closely related to the high energy penalty of interfacial anion desolvation due to the strong cation-anion association prevalent in multivalent electrolytes. Leveraging this understanding, we verify that promoting ionic dissociation in multivalent electrolytes by employing high-permittivity and oxidation-tolerant co-solvents is effective in suppressing multivalent-cation co-intercalation and thus achieving increased capacity of graphite cathodes. For instance, introducing adiponitrile as a co-solvent to a Mg2+-based carbonate electrolyte leads to 83% less Mg2+ co-intercalation and a ∼29.5% increase in delivered capacity of the graphite cathode.

Rational Design of Functional Electrolytes Towards Commercial Dual-Ion Batteries.

Invited for this month's cover is the group of Weitao Zheng at the Jilin University. The image shows the working mechanism of dual-ion batteries (DIBs). The Review itself is available at 10.1002/cssc.202201375.

Rational Design of Functional Electrolytes Towards Commercial Dual-Ion Batteries.

Dual-ion batteries (DIBs) based on anion (de)intercalation into low-cost graphitic carbon cathodes hold great promise in grid-scale energy storage. Different from the electrolyte in rocking-chair batteries, which only serves as a charge transporter, both cations and anions in the electrolyte for DIBs participate in battery reactions. Hence, the impact of the electrolyte formulation on cycle life, energy density, as well as cost has become a subject of vital importance. This review discussed the challenges and recent progress of electrolytes for DIBs, with a particular focus on the exploration of electrolytes with high oxidation stability, high salt concentration, high ionic conductivity, and low cost. Moreover, the influence of varied ion concentrations at different state-of-charge levels on the electrolyte properties such as ionic conductivity and electrochemical stability is analyzed. Finally, perspectives on the current limitations and future research directions of electrolytes for DIBs are provided.

A PF6 - -Permselective Polymer Electrolyte with Anion Solvation Regulation Enabling Long-Cycle Dual-Ion Battery.

Graphitic carbon that allows reversible anion (de)intercalation is a promising cathode material for cost-efficient and high-voltage dual-ion batteries (DIBs). However, one notorious but overlooked issue is the incomplete interfacial anion desolvation, which not only reduces the oxidative stability of electrolytes, but also results in solvent co-intercalation into graphite layers. Here, an "anion-permselective" polymer electrolyte with abundant cationic quaternary ammonium motif is developed to weaken the PF6 - -solvent interaction and thus facilitates PF6 - desolvation. This strategy significantly inhibits solvent co-intercalation as well as enhances the oxidation resistance of electrolyte, ensuring the structural integrity of graphite. As a result, the as-assembled graphite||Li cell achieves a superior cyclability with an average Coulombic efficiency of 99.0% (vs 95.7% for baseline electrolyte) and 87.1% capacity retention after 2000 cycles even at a high cutoff potential of 5.4 V versus Li+ /Li. Besides, this polymer also forms a robust cathode electrolyte interface, working together to enable a long-life DIB. This strategy of tuning anion coordination environment provides a promising solution to regulate solvent co-intercalation chemistry for DIBs.

Bioinspired Antiaging Binder Additive Addressing the Challenge of Chemical Degradation of Electrolyte at Cathode/Electrolyte Interphase.

For layered transition metal oxides cathode-based lithium batteries, the chemical degradation of electrolytes leads to fast battery capacity decay, severely challenging their practical applications. This kind of chemical degradation of electrolytes is caused by the oxidation of reactive oxygen (e.g., singlet oxygen) and the attack of free radicals during cycling. To address this, we first report a biologically inspired antiaging strategy of developing the photostabilizer with singlet oxygen- and free radicals-scavenging abilities as a cathode binder additive. It is fully evidenced that this binder system consisting of the binder additive and a commercially available polyvinylidene difluoride can scavenge singlet oxygen and free radicals generated during high-voltage cycling, thus significantly restraining electrolyte decomposition. As a result, high-voltage layered transition metal oxides-based lithium batteries with reproducibly superior electrochemical performance, even under elevated temperatures, can be achieved. This bioinspired strategy to scavenge reactive oxygen and free radicals heralds a new paradigm for manipulating the cathode/electrolyte interphase chemistry of various rechargeable batteries involving layered transition metal oxides-based cathodes.

Dirac semimetal saturable absorber with actively tunable modulation depth.

In this Letter, we demonstrate an electrically contacted saturable absorber (SA) device based on topological Dirac semimetal Cd3As2. With a current-induced temperature change in the range of 297-336 K, the modulation depth of the device is found to be significantly altered from 33% to 76% (under the irradiation of a 1560 nm femtosecond laser). The broad tuning of the modulation depth is attributed to the strong temperature dependence of the carrier concentration close to room temperature. The simple tuning mechanism uncovered here, together with the compatibility with III-V compounds substrate, such as GaAs, points to the potential of fabricating broadband, electrically tunable, SESAM-like devices based on emerging bulk Dirac materials.