Coordinatively Cross-Linked Binders for Silicon-Based Electrodes for Li-Ion Batteries: Beneficial Impact on Mechanical Properties and Electrochemical Performance.

A simple and versatile preparation of Zn(II)-poly(carboxylates) reticulated binders by the addition of Zn(II) precursors (ZnSO4, ZnO, or Zn(NO3)2) into a preoptimized poly(carboxylic acids) binder solution is proposed. These binders lead systematically to a significantly improved electrochemical performance when used for the formulation of silicon-based negative electrodes. The formation of carboxylate-Zn(II) coordination bonds formation is investigated by rheology and FTIR and NMR spectroscopies. Mechanical characterizations reveal that the coordinated binder offers a better electrode coating cohesion and adhesion to the current collector, as well as higher hardness and elastic modulus, which are even preserved in the presence of a carbonate solvent (i.e., in battery operation conditions). Ultimately, as shown from operando dilatometry experiments, the electrode expansion during lithiation is reduced, mitigating electrode mechanical failure. Such coordinatively reticulated electrodes outperform their uncoordinated counterparts with an improved capacity retention of over 30% after 60 cycles.

Nanoscale Morphological Characterization of Coordinated Binder and Solid Electrolyte Interphase in Silicon-Based Electrodes for Li-Ion Batteries.

The physical crosslinking of polymeric binders through coordination chemistry significantly improves the electrochemical performance of silicon-based negative electrodes. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy is used to probe the nanoscale morphology of such electrodes. This technique reveals the homogeneous coordination of carboxylated binder with Zn cations and its layering on the silicon surface. The solid electrolyte interphase (SEI) formed after the first cycle is denser with Zn-coordinated binder and preferentially observed on binder-depleted zones. The superiority of coordinated binders can be attributed to their capacity to better stabilize the electrode and the SEI layer due to improved mechanical properties. This results in a lower SEI impedance, a higher first cycle coulombic efficiency, and a 40% improvement of capacity retention after 50 cycles for highly loaded electrodes of over 6 mAh cm-2 .

Influence of the Polyacrylic Acid Binder Neutralization Degree on the Initial Electrochemical Behavior of a Silicon/Graphite Electrode.

The role of the physicochemical properties of the water-soluble polyacrylic acid (PAA) binder in the electrochemical performance of highly loaded silicon/graphite 50/50 wt % negative electrodes has been examined as a function of the neutralization degree x in PAAH1-xLix at the initial cycle in an electrolyte not containing ethylene carbonate. Electrode processing in the acidic PAAH binder at pH 2.5 leads to a deep copper corrosion, resulting in a significant electrode cohesion and adhesion to the current collector surface, but the strong binder rigidity may explain the big cracks occurring on the electrode surface at the first cycle. The nonuniform binder coating on the material surface leads to an important degradation of the electrolyte, explaining the lowest initial Coulombic efficiency and the lowest reversible capacity among the studied electrodes. When processed in neutral pH, the PAAH0.22Li0.78 binder forms a conformal artificial solid electrolyte interphase layer on the material surface, which minimizes the electrolyte reduction at the first cycle and then maximizes the initial Coulombic efficiency. However, the low mechanical resistance of the electrode and its strong cracking explain its low reversible capacity. Electrodes prepared at intermediate pH 4 combine the positive assets of electrodes prepared at acidic and neutral pH. They lead to the best initial performance with a notable areal capacity of 7.2 mA h cm-2 and the highest initial Coulombic efficiency of around 90%, a value much larger than the usual range reported for silicon/graphite anodes. All data obtained with complementary characterization techniques were discussed as a function of the PAA polymeric chain molecular conformation, microstructure, and surface adsorption or grafting, emphasizing the tremendous role of the binder in the electrode initial performance.

Optimization of the cathode material for nitrate removal by a paired electrolysis process.

Ni, Cu, Cu(90)Ni(10) and Cu(70)Ni(30) were evaluated as cathode materials for the conversion of nitrate to nitrogen by a paired electrolysis process using an undivided flow-through electrolyzer. Firstly, corrosion measurements revealed that Ni and Cu(70)Ni(30) electrodes have a much better corrosion resistance than Cu and Cu(90)Ni(10) in the presence of chloride, nitrate and ammonia. Secondly, nitrate electroreduction experiments showed that the cupro-nickel electrodes are the most efficient for reducing nitrate to ammonia with a selectivity of 100%. Finally, paired electrolysis experiments confirmed the efficiency of Cu(70)Ni(30) and Cu(90)Ni(10) cathodes for the conversion of nitrate to nitrogen. During a typical electrolysis, the concentration of nitrate varied from 620ppm to less than 50ppm NO(3)(-) with an N(2) selectivity of 100% and a mean energy consumption of 20kWh/kg NO(3)(-) (compared to ∼35 and ∼220kWh/kg NO(3)(-) with Cu and Ni cathodes, respectively).

Nitrate removal by a paired electrolysis on copper and Ti/IrO(2) coupled electrodes - influence of the anode/cathode surface area ratio.

In this study, nitrate removal in alkaline media by a paired electrolysis with copper cathode and Ti/IrO(2) anode enabled the conversion of nitrate to nitrogen. Optimum conditions for carrying out reduction of nitrate to ammonia and subsequent oxidation of the produced ammonia to nitrogen were found. At the copper cathode, electroreduction of nitrate to ammonia was optimal near -1.4 V vs Hg/HgO. At the Ti/IrO(2) anode, a pH value of 12, the presence of chloride and a potential fixed around 2.3 V vs Hg/HgO permitted the production of hypochlorite, leading to the oxidation of ammonia to nitrogen with a N(2) selectivity of 100%. Controlling the cathode/anode surface area ratio, and thus the current density, appeared to be a very efficient way of shifting electrode potentials to optimal values, consequently favoring the conversion of nitrate to nitrogen during a paired galvanostatic electrolysis. A cathode/anode surface area ratio of 2.25 was shown to be the most efficient to convert nitrate to nitrogen.