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Lithium-ion batteries – electrolytes – solid & semi-solid
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A solid state electrolyte based on a single-phase crystalline solution of
LiCB11H12 and LiCB11H11F
(40 : 60 molar ratio) was prepared through mechanochemical synthesis.
The precursor powders were ball-milled (400 rpm, 10 h) in zirconia jars
under inert atmosphere. The
resulting material exhibits an orthorhombic crystal structure with expanded
lattice parameters compared to pure LiCB11H12,
as confirmed by X-ray diffraction analysis.
Electrochemical testing in asymmetric Cu/Li half-cells exhibits a
coulombic efficiency of 99.5% for lithium metal plating and stripping
(0.2 mA/cm2, 25°C, 2 N⋅m torque). The electrolyte maintains
stable cycling performance exceeding 99% coulombic efficiency for over
100 cycles.
In symmetric Li/Li cells, the electrolyte exhibits low overpotential
(< 0.03 V vs. Li) during lithium plating and stripping for over 2,000 h.
Full cells with lithium metal negative electrodes and
LiNi0.8Co0.15Al0.05O2
(NCA) positive electrodes exhibit 94% capacity retention after 100 cycles
(C/20 charge / discharge).
The electrolyte demonstrates a significantly reduced elastic modulus of
≈6 GPa compared to traditional solid state electrolytes (typically > 25 GPa),
enabling room-temperature battery assembly through simple uniaxial
compression without elevated temperatures or pressures.
This work further illustrates the potential of boron-based solid-state electrolytes at the interface to lithium metal electrodes.
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Lithium-ion batteries – negative electrode (excluding Li metal electrodes)
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A dual-layer negative electrode was prepared with optimized SiOx (x = 0.96)-graphite
formulations to improve battery cell cycling and high-temperature storage
performance.
First negative electrode layer formulation: the layer positioned directly
on the copper current collector contains
artificial graphite and natural graphite (80 : 20 mass ratio, average particle
size: 18 μm), SiOx (x = 0.96), acetylene
black conductive additive, styrene-butadiene rubber (SBR) binder, and
carboxymethyl cellulose (CMC) thickener (87 : 9.5 : 1 : 1.5 : 1 mass ratio).
Individual carbon particle void fraction: 20% (percentage of void area relative to total
cross-sectional area of carbon-based particles, according to SEM cross-section analysis).
Second negative electrode layer formulation: the outer layer contains
artificial graphite (average particle size: 15 μm), SiOx
(x = 0.96), acetylene black, SBR binder, and CMC thickener
(87 : 9.5 : 1 : 1.5 : 1 mass ratio). Individual carbon particle void fraction: 25%.
The silicon content is 5.0 mass% with respect to the total negative electrode active
material. The coating weight is 140 mg/1,540 mm2 with a compacted
density of 1.45 g/cm3 (0% state of charge). The silicon-based
material exhibits a BET specific surface area of 1.4 m2/g and an average
particle size of 6 μm.
The electrolyte was formulated with ethyl acetate (25 mass%), ethylene carbonate
(27 mass%), and dimethyl carbonate (30 mass%).
Lithium salts include LiPF6 (8 mass%) and LiTFSI
(6 mass%) with a mass ratio of 0.75. Fluoroethylene carbonate (FEC, 2 mass%)
and vinylene carbonate (VC, 2 mass%) were added as SEI-forming additives.
The positive electrode contains LiFePO4, polyvinylidene
fluoride (PVDF) binder, and Super P conductive additive (97 : 2 : 1 mass ratio).
The coating weight is 280 mg/1540 mm2 with a compacted density of
2.7 g/cm3 (0% state of charge).
Battery cells were assembled with a 7 μm polyethylene separator coated with
polyvinylidene fluoride (PVDF, 1.2 g/m2). The electrolyte exhibits
1.4 × 10-2 S/cm ionic conductivity at room temperature.
In cycling tests, the optimized dual-layer formulation exhibits 1,294
cycles to 90% state of health under fast charging conditions (multi-step
charging from 10% to 80% SOC at 3.7-1.9 C rates, followed by 1 C discharge).
High-temperature storage (60°C, 90 days) resulted in 15.5% volume expansion,
as compared to 25.4% for a comparative cell with 18.0 mass% silicon content.
The dual-layer structure with different carbon particle sizes and void fractions
facilitates lithium-ion transport while mitigating silicon volume expansion
during cycling.
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Lithium-ion batteries – positive electrode
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An aqueous solution of NiCl2·6 H2O, CoCl2·6 H2O,
and MnCl2·4 H2O was prepared (molar ratio
Ni : Co : Mn = 93.5 : 4.5 : 2.0, total transition metal concentration: 100 g/l).
The solution was pumped through a nozzle into a tube-shaped reactor
heated by natural gas burners (800°C). During pyrolysis in the flame, the droplets
were converted to a composite oxide precursor containing chloride
(10-10,000 ppm). The particulate material was collected at the reactor bottom
through gravity (see Figure).
The precursor was mixed with LiOH·H2O (molar ratio Li / TM = 1.05 : 1.00)
and optionally Al(OH)3 dopant. The mixture was heated to 500°C (3 h,
heating rate: 3°C/min), then calcined at 830°C (12 h, oxygen stream), followed
by natural cooling.
The base cathode active material was coated with 2 mol-% Co(OH)2 and
heated to 700°C (3 h) to form the final coated
Li1+xTM1-xO2 material (x = -0.05 to +0.05,
chloride content: 100-1,000 ppm).
The process avoids generating stoichiometric amounts of alkali sulfates compared
to conventional precipitation methods. It is claimed without electrochemical data that the resulting cathode active material
exhibits improved electrochemical properties including reduced capacity fade
upon cycling.
This work illustrates substantial process optimization efforts by BASF to employ chloride instead of
sulfate precursors for high-nickel NMC cathode material manufacturing.
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Fuel cells (PEMFC / SOFC / PAFC / AEMFC) – electrochemically active materials
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A graphyne-based
functional layer was developed for proton exchange membrane
fuel cells (PEMFCs) to suppress gas crossover and enhance durability.
The graphyne layer was positioned between the cathode catalyst layer and the
polymer electrolyte membrane (PEM). The layer consists of graphyne flakes
bound by Nafion ionomer (weight ratio ionomer : graphyne of 0.5 : 1 to 5 : 1).
Layer thicknesses rang from 0.1 to 5.0 μm. The materials form stacked
configurations with flakes oriented substantially parallel to maximize gas
diffusion tortuosity.
Energy barrier calculations demonstrate that three layers of ABC-stacked
γ-graphyne require ≈2 eV for H2 molecule passage, effectively
preventing hydrogen crossover under normal operating conditions. The graphyne
barrier also blocks O2 crossover and Pt2+ cation
migration from the catalyst layers.
In membrane electrode assembly (MEA) configurations, the graphyne layer was
integrated as a discrete component between layers. The material maintains
proton conductivity comparable to Nafion while suppressing crossover of
H2 into the cathode and O2 out of the cathode.
This configuration enhances both cell performance and durability by preventing
degradation reactions from peroxide formation (O2 at the anode)
and cationic Pt reduction (H2 at the cathode).
This work illustrates how graphyne layers could serve as highly selective proton-conducting
layers. It will be interesting to see if reliability and cost targets can be met with this approach.
No quantitative performance results were identified in the patent.
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The premium version includes another two patent discussions, plus an Excel list with 50-100 commercially relevant recent patent families.
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Triweekly patent lists for other categories (Excel files are included for premium users)
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- Lithium metal batteries (excluding Li-S, Li-Air): XLSX
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- Lithium-air batteries: XLSX
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- Lithium-ion batteries – electrolytes – liquid: XLSX
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- Lithium-ion batteries – separators: XLSX
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- Lithium-sulfur batteries: XLSX
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- Na-ion batteries: XLSX
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Prior patent updates
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2025-07-01
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2025-06-10
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2025-05-20
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2025-04-29
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2025-04-08
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