Triweekly Patent Update – Free Version

The electrolyte sheet is divided into a solid electrolyte base layer and a thin electron blocking layer facing the negative electrode. The blocking layer conducts Li⁺ but not electrons, preventing lithium ions from being reduced to metal within the electrolyte and nucleating dendrites there.

The blocking layer comprises Cs_xM_y[Mo_a(CN)_b(NO)_c]·nH₂O, in which M is a divalent metal (here Fe), the cyanide- and nitrosyl-coordinated molybdenum anion forms the host framework, and n is the lattice water content. Cs_1.1Fe_0.95[Mo(CN)₅(NO)]·4H₂O was precipitated from aqueous Cs[Mo(CN)₅(NO)], CsCl and FeCl₂·4H₂O at 80°C. The powder was dispersed in n-hexane and electrodeposited (0.5 mA cm^-2, 25°C, 4 h) onto a 60 μm base layer of Li₆PS₅Cl and styrene-butadiene rubber (SBR) (98 : 2), forming a 10 μm blocking layer.

The blocking layer exhibits an electronic conductivity of 1 × 10^-10 S/cm, an ionic conductivity of 7.45 × 10^-3 S/cm at 45°C, and an elastic modulus of 49.8 GPa against 20 GPa for the base layer. Cells with Li_1.2Ni_0.13Co_0.13Mn_0.54O₂/InCl₃ (1 : 1) positive electrodes and silicon-carbon negative electrodes exhibit a first-cycle coulombic efficiency of 94.2% and a 200-cycle capacity retention of 87.4% (0.33 C, 2.0–4.8 V, 15 MPa), compared to 79.5% and 73.8% for cells whose electrolyte sheet is the Li₆PS₅Cl–SBR layer alone. Dendrite penetration after 200 cycles occurred in 4% of cells, versus 40% without the blocking layer.

Zinc acetate and benzimidazole were stirred in a methanol / toluene / ammonium hydroxide medium for 3 h to form ZIF-11, a zeolitic imidazolate framework (ZIF) belonging to the metal-organic framework (MOF) family. The framework was washed with methanol and carbonized under argon at 950°C for 2 h to form a carbon body.

The carbon body was mixed with KOH at a mass ratio of 1 : 3 and heat-treated at 800°C for 2 h to form the carbon porous body, which exhibits a BET specific surface area of 1,450 m²/g, a mean pore diameter of ≈1.67 nm, and a total pore volume of 0.62 cm³/g. The particles exhibit a uniform polyhedral habit with diameters of 3–7 μm (SEM).

Monosilane (SiH₄) was introduced at 50 sccm at 425°C for 2 h to deposit silicon within the pores of the carbon porous body. The resulting silicon-carbon composite exhibits a BET specific surface area of 1.9 m²/g, indicating that the pore volume is largely filled. The silicon content of the composite is not reported.

In half-cells against lithium metal, the composite exhibits a discharge capacity of 1,610 mAh/g, an initial efficiency of 89.7%, and a capacity retention of 89.7% (0.5 C; cycle number not reported), as compared to 950 mAh/g / 88.1% / 88.1% at a carbon body : KOH ratio of 1 : 1 (carbon porous body: 720 m²/g), 1,838 mAh/g / 80.5% / 80.5% at 1 : 5 (2,310 m²/g; composite: 243 m²/g), and 550 mAh/g / 64.4% / 20.1% without the KOH heat-treatment step (390 m²/g).

Figure: SEM image of the carbon porous body at 10,000× magnification, showing the polyhedral crystal habit inherited from the ZIF-11 framework and the uniform 3–7 μm particle size obtained without a classification step.

NiSO₄, MnSO₄, and CoSO₄ (molar ratio Ni : Mn : Co = 15 : 75 : 10) were dissolved in deionized water (40°C) to 35 mass%, and the solution was cooled to 20°C within 1 s to precipitate a solid. Filtration gave the metal salt (Ni_0.15Mn_0.75Co_0.1)SO₄, present as non-spherical secondary particles in which Ni, Mn, and Co are homogeneously distributed as a single phase (XRD). Vacuum drying (110°C) and heat treatment (800°C, 10 h, air) converted it to the oxide precursor (Ni_0.15Mn_0.75Co_0.1)O₂, without the chelating agent, base addition, or pH control of co-precipitation.

The precursor was mixed with Li₂CO₃ (Li : (Ni+Co+Mn) = 1.55 : 1) and heat-treated (650°C, 5 h, air) to give 0.5Li₂MnO₃·0.5LiNi_0.3Mn_0.5Co_0.2O₂. In half-cells (0.1 C, 4.65–2.5 V vs. Li⁺/Li, 45°C), the material exhibits an initial discharge capacity of 300.3 mAh/g, as compared to 295.1 mAh/g for material from a co-precipitated precursor of the same metal ratio (ammonia chelating agent, NaOH, pH 11.0, 24 h).

A membrane-electrode assembly (MEA) composition for proton exchange membrane fuel cells (PEMFC) combines a perfluorosulfonic acid (PFSA) ionomer with a polymer of intrinsic microporosity (PIM) carrying a proton conductive end group. Claims specify 60–99 mass% ionomer with 1–40 mass% PIM, a PIM ion exchange capacity (IEC) of ≥0.4 mmol/g and a number average molecular weight (Mn) of 10,000–30,000 g/mol.

PIM-1 and 3-azidopropane sulfonate (1 : 3 mass ratio) were reacted with NH₄Cl in N-methyl-2-pyrrolidone (NMP) at 120°C for 24 h and acidified (10 mass% aqueous HCl, 60°C, 1 h), giving an end-sulfonated PIM with Mn 20,800 g/mol and IEC 0.7 mmol/g. It was blended with Nafion at a 1 : 5 PIM : Nafion mass ratio and cast to a 26 µm membrane.

Oxygen permeability reaches 5.81 barrer versus 2.28 barrer for Nafion alone and 4.41 barrer for a variant with benzenesulfonic acid grafted onto PIM-1 rather than substituted at the chain end. In-plane proton conductivity (80°C, 50% relative humidity) is 23.8 mS/cm, above 15.1 mS/cm for the grafted variant and 12.3 mS/cm for unfunctionalized PIM-1, but below 33.3 mS/cm for Nafion alone. Haze falls to 38.74% from the grafted variant's 68.1%, indicating better PIM dispersion. No fuel cell polarization data is disclosed.