Designing Breathing Air-electrode and Enhancing the Oxygen Electrocatalysis by Thermoelectric Effect for Efficient Zn-air Batteries

The sluggish kinetics and mutual interference of oxygen evolution and reduction reactions in the air electrode resulted in large charge/discharge overpotential and low energy efficiency of Zn-air batteries. In this work, we designed a breathing air-electrode configuration in the battery using P-type Ca₃Co₄O₉ and N-type CaMnO₃ as charge and discharge thermoelectrocatalysts, respectively. The Seebeck voltages generated from thermoelectric effect of Ca₃Co₄O₉ and CaMnO₃ synergistically compensated the charge and discharge overpotentials. The carrier migration and accumulation on the cold surface of Ca₃Co₄O₉ and CaMnO₃ optimized the electronic structure of metallic sites and thus enhanced their intrinsic catalytic activity. The oxygen evolution and reduction overpotentials were enhanced by 101 and 90 mV, respectively, at temperature gradient of 200 °C. The breathing Zn-air battery displayed a remarkable energy efficiency of 68.1 %. This work provides an efficient avenue towards utilizing waste heat for improving the energy efficiency of Zn-air battery.     

Bifunctional Interphase with Target-Distributed Desolvation Sites and Directionally Depositional Ion Flux for Sustainable Zinc Anode

Aqueous zinc batteries (AZBs) feature high safety and low cost, but intricate anodic side reactions and dendrite growth severely restrict their commercialization. Herein, ethylenediaminetetraacetic acid (EDTA) grafted metal organic framework (MOF-E) is proposed as a dually-functional anodic interphase for sustainable Zn anode. Specifically, the target-distributed EDTA serves as an ion-trapped tentacle to accelerate the desolvation and ionic transport by powerful chemical coordination, while the MOFs offer suitable ionic channels to induce oriented deposition. As a result, MOF-E interphase fundamentally suppresses side reactions and guides horizontally arranged Zn deposition with (002) preferred orientations. The Zn|MOF-E@Cu cell exhibits a markedly improved Coulombic efficiency of 99.7 % over 2500 cycles, and the MOF-E@Zn|KVOH (KV₁₂O_30-y ⋅ nH₂O) cell yields a steady circulation of 5000 cycles@90.47 % at 8 A g⁻¹.     

Atomically Dispersed FeN2P2 Motif with High Activity and Stability for Oxygen Reduction Reaction Over the Entire pH Range

The past decade has witnessed the great potential of Fe-based single-atom electrocatalysis in catalyzing oxygen reduction reaction (ORR). However, it remains a grand challenge to substantially improve their intrinsic activity and long-term stability in acidic electrolytes. Herein, we report a facile chemical vapor deposition strategy, by which high-density Fe atoms (3.97 wt%) are coordinated with square-planar para-positioned nitrogen and phosphorus atoms in a hierarchical carbon framework. The as-crafted atomically dispersed Fe catalyst (denoted Fe-SA/PNC) manifests an outstanding activity towards ORR over the entire pH range. Specifically, the half-wave potential of 0.92 V, 0.83 V, and 0.86 V vs. reversible hydrogen electrode (RHE) are attained in alkaline, neutral, and acidic electrolytes, respectively, representing the high performance among reported catalysts to date. Furthermore, after 30,000 durability cycles, the Fe-SA/PNC remains to be stable with no visible performance decay when tested in 0.1 M KOH and 0.5 M H₂SO₄, and only a minor negative shift of 40 mV detected in 0.1 M HClO₄, significantly outperforming commercial Pt/C counterpart. The coordination motif of Fe-SA/PNC is validated by density functional theory (DFT) calculations. This work provides atomic-level insight into improving the activity and stability of non-noble metal ORR catalysts, opening up an avenue to craft the desired single-atom electrocatalysts.     

Strengthening Aqueous Electrolytes without Strengthening Water

Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions—25 wt.% LiCl and 62 wt.% H₃PO₄—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 LiMn₂O₄ 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.     

Facile Processing of Unsubstituted π-Conjugated Aromatic Polymers through Water-solubilization Using Aromatic Micelles

π-Conjugated aromatic polymers (πCAPs) are central components of functional materials yet suffer from insolubility without multiple covalent substituents on their backbones. We herein disclose a new strategy for the facile processing of unsubstituted heterocyclic πCAPs (i.e., poly(para-phenylene-2,6-benzobisoxazole) and poly(benzimidazobenzo-phenanthroline)), independent of the polymer length, via non-covalent encircling with aromatic micelles, composed of bent aromatic amphiphiles, in water. The UV/Visible studies reveal that the efficiencies of the present encircling method are ≈10 to 50-fold higher than those using conventional amphiphiles under the same conditions. The AFM and SEM analyses of the resultant aqueous polymer composites show that otherwise insoluble πCAPs form fine bundles (e.g., ≈1 nm in thickness) in the tubular aromatic micelles, through efficient π-stacking interactions. In the same way, pristine poly(para-phenylene) can be dissolved in water, displaying enhanced fluorescence (10-fold), relative to the polymer solid. Two types of unsubstituted πCAPs are likewise co-encircled in water, indicated by UV/Visible analysis. Importantly, aqueous processing of the encircled πCAPs into free-standing single- or multicomponent films with submicrometer thickness is demonstrated through a simple filtration-annealing protocol.     

Reconstructing Hydrogen Bond Network Enables High Voltage Aqueous Zinc-Ion Supercapacitors

High-voltage aqueous rechargeable energy storage devices with safety and high specific energy are hopeful candidates for the future energy storage system. However, the electrochemical stability window of aqueous electrolytes is a great challenge. Herein, inspired by density functional theory (DFT), polyethylene glycol (PEG) can interact strongly with water molecules, effectively reconstructing the hydrogen bond network. In addition, N, N-dimethylformamide (DMF) can coordinate with Zn²⁺, assisting in the rapid desolvation of Zn²⁺ and stable plating/stripping process. Remarkably, by introducing PEG400 and DMF as co-solvents into the electrolyte, a wide electrochemical window of 4.27 V can be achieved. The shift in spectra indicate the transformation in the number and strength of hydrogen bonds, verifying the reconstruction of hydrogen bond network, which can largely inhibit the activity of water molecule, according well with the molecular dynamics simulations (MD) and online electrochemical mass spectroscopy (OEMS). Based on this electrolyte, symmetric Zn cells survived up to 5000 h at 1 mA cm⁻², and high voltage aqueous zinc ion supercapacitors assembled with Zn anode and activated carbon cathode achieved 800 cycles at 0.1 A g⁻¹. This work provides a feasible approach for constructing high-voltage alkali metal ion supercapacitors through reconstruction strategy of hydrogen bond network.     

Vanadium Oxides with Amorphous-Crystalline Heterointerface Network for Aqueous Zinc-Ion Batteries

Rechargeable aqueous Zn-VO_x batteries are attracting attention in large scale energy storage applications. Yet, the sluggish Zn²⁺ diffusion kinetics and ambiguous structure–property relationship are always challenging to fulfil the great potential of the batteries. Here we electrodeposit vanadium oxide nanobelts (VO-E) with highly disordered structure. The electrode achieves high capacities (e.g., ≈5 mAh cm⁻², 516 mAh g⁻¹), good rate and cycling performances. Detailed structure analysis indicates VO-E is composed of integrated amorphous-crystalline nanoscale domains, forming an efficient heterointerface network in the bulk electrode, which accounts for the good electrochemical properties. Theoretical calculations indicate that the amorphous-crystalline heterostructure exhibits the favorable cation adsorption and lower ion diffusion energy barriers compared to the amorphous and crystalline counterparts, thus accelerating charge carrier mobility and electrochemical activity of the electrode.     

Impact of the Chlorination of Lithium Argyrodites on the Electrolyte/Cathode Interface in Solid-State Batteries

Lithium argyrodite-type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li₆PS₅Cl and Li_5.5PS_4.5Cl_1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time-of-flight secondary ion mass spectrometry indicate that the Li_5.5PS_4.5Cl_1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance.     

Up/Down Tuning of Poly(ionic liquid)s in Aqueous Two-Phase Systems

Thermally induced reversible up/down migration of poly(ionic liquid)s (PILs) in aqueous two-phase systems (ATPSs) was achieved for the first time in this study. Novel ATPSs were fabricated using azobenzene (Azo)- and benzyl (Bn)-modified PILs, and their upper and lower phases could be easily tuned using the grafting degree (GD) of the Azo and Bn groups. Bn-PIL with higher GD_Bn could go up into the upper phase and Azo-PIL come down to the lower phase when the temperature increased (>65 °C); this behavior was reversed at lower temperatures. Moreover, a reversible two-phase/single-phase transition was realized under UV irradiation. Experimental and simulation results revealed that the difference in the hydration capacity between Bn-PIL and Azo-PIL accounted for their unique phase-separation behavior. A versatile platform for fabricating ATPSs with tunable stimuli-responsive behavior can be realized based on our findings, which can broaden their applications in the fields of smart separation systems and functional material development.     

Potentiometric determination of the 'formal' hydrolysis ratio of aluminium species in aqueous solutions

The ‘formal’ hydrolysis ratio (h = C(OH⁻)_added/C(Al)_total) of hydrolysed aluminium-ions is an important parameter required for the exhaustive and quantitative speciation-fractionation of aluminium in aqueous solutions. This paper describes a potentiometric method for determination of the formal hydrolysis ratio based on an automated alkaline titration procedure. The method uses the point of precipitation of aluminium hydroxide as a reference (h = 3.0) in order to calculate the initial formal hydrolysis ratio of hydrolysed aluminium-ion solutions. Several solutions of pure hydrolytic species including aluminium monomers (AlCl₃), Al₁₃ polynuclear cluster ([Al₁₃O₄(OH)₂₄(H₂O)₁₂]⁷⁺), Al₃₀ polynuclear cluster ([Al₃₀O₈(OH)₅₆(H₂O)₂₆]¹⁸⁺) and a suspension of nanoparticulate aluminium hydroxide have been used as ‘reference standards’ to validate the proposed potentiometric method. Other important variables in the potentiometric determination of the hydrolysis ratio have also been optimised including the concentration of aluminium and the type and strength of alkali (Trizma-base, NH₃, NaHCO₃, Na₂CO₃ and KOH). The results of the potentiometric analysis have been cross-verified by quantitative ²⁷Al solution nuclear magnetic resonance (²⁷Al NMR) measurements. The ‘formal’ hydrolysis ratio of a commercial basic aluminium chloride has been measured as an example of a practical application of the developed technique.