H₂‐Inhibited Organic Anodes for Fast and Long‐Life Aqueous Aluminum Ion Batteries with a 3.5‐Month Calendar Life

Abstract

Aqueous aluminum ion batteries are rarely constructed due to the unworkable Al metal and the preferential H2 evolution. Herein, organic anode with H2‐inhibition is optimized through tuning the polymerization degree and displays a high‐rate and reversible storage of Al ions based on an enolation between Al ions and the carbonyl double bonds on the conjugated structures. The superiority of the optimal sample is researched, which is attributed to the raised state of lowest unoccupied molecule orbital (LUMO) with the doner N–N bridge and relatively small steric hindrance of the dimmer. When paired with active carbon, a high cycling life of 5000 cycles with a retention of 99.2% is obtained. A full battery constructed by this dimer and δ‐MnO2 cathode delivers an average voltage of 1.0 V, high capacity of 263.8 mAh g‐1 based on the mass of δ‐MnO2, and high‐capacity retention of 88.8% after cycling for 300 cycles. More importantly, with a fully eliminated corrosion and passivation in AlCl3 and Al2(SO4)3 electrolytes, a long calendar stability of 104 days is achieved.

Reversible, Dendrite-Free, High-Capacity Aluminum Metal Anode Enabled by Aluminophilic Interface Layer

“…The dense and smooth morphology at ultrahigh areal capacities is ascribed to the effective regulation of the AIL on Al deposition. The AIL plays a critical role at the stage of Al initial nucleation and growth, which regulates the homogeneous Al deposition on the aluminophilic Pt sites to inhibit Al dendrite formation in the further growth . The dense Al deposition can maintain good electron-transport and mass-transport, thus reducing the generation of inactive Al and improving reversibility of Al plating/stripping.…”

“…The AIL plays a critical role at the stage of Al initial nucleation and growth, which regulates the homogeneous Al deposition on the aluminophilic Pt sites to inhibit Al dendrite formation in the further growth. 52 The dense Al deposition can maintain good electron-transport and masstransport, thus reducing the generation of inactive Al and improving reversibility of Al plating/stripping. Moreover, EDS mapping of the cross-section of the Pt-AIL@Ti anode reveals the ultrathin Pt-AIL between the Ti substrate and the deposited Al layer.…”

Regulated Hydrated Eutectic Electrolyte Enhancing Interfacial Chemical Stability for Highly Reversible Aqueous Aluminum‐Ion Battery with a Wide Temperature Range of −20 to 60 °C

“…e) Comparison of the wide electrochemical window of this work with recently reported AAIBs electrolytes. Al 2 (SO 4 ) 3 , [ 60 ] ɑ‐Al/Al 2 (SO 4 ) 3 , [ 34 ] Al(ClO 4 ) 3 ·9H 2 O/Succinonitrile, [ 40 ] Al(ClO 4 ) 3 ·9H 2 O/Methylurea. [ 13 ] f) In situ observation of HER process on the Al foil using HEE30 and BE at 0.2 mA cm −2 , respectively.…”

“…In contrast, the Al/Al symmetric cell based on the HEE30 electrolyte exhibits very low volume of H 2 . Figure S20a,b (Supporting Information) illustrates that the thickness of the symmetric Al/Al symmetric cell using BE electrolyte increases from 2.969 mm in the initial state [60] ɑ-Al/Al 2 (SO 4 ) 3 , [34] Al(ClO 4 ) 3 ·9H 2 O/Succinonitrile, [40] Al(ClO 4 ) 3 ·9H 2 O/Methylurea. [13] f) In situ observation of HER process on the Al foil using HEE30 and BE at 0.2 mA cm −2 , respectively.…”

Recent progress in aqueous aluminum-ion batteries

“…Since 1 M Al 2 (SO 4 ) 3 is acidic, AQ molecules gain two electrons from the external circuit during circulation, and with the help of protons in the electrolyte, through a one-step two-electron redox process to produce anthrahydroquinone (AQ-H2) and then achieve Al 3+ intercalation [64]. PTCDA-based material (PI-0.6) can realize reversible Al 3+ intercalation by the bonding of carbonyl groups to Al 3+ [65].…”