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Lithium-ion batteries – electrolytes – solid & semi-solid
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Li2S,
P2S5, LiBr and LiI were mixed with
tetramethylethylenediamine (TMEDA, complexing agent) and cyclohexane (molar
ratio Li2S : P2S5 : LiBr : LiI =
6 : 2 : 1 : 1), followed by bead-milling (60 min, zirconia
beads, 0.5 mm diameter, 8 m/s peripheral speed, 20°C), followed by vacuum
drying to obtain an amorphous complex. The complex was heat-treated (110°C,
6 h, reduced pressure), followed by another heat treatment (180°C, 2 h,
reduced pressure) to obtain a crystalline sulfide solid electrolyte with an
ion conductivity of 5.0 × 10-3 S/cm.
The above sulfide electrolyte and 4-tert-butylphenyl
glycidyl ether (organic modifier, 5 mass% with respect to sulfide
electrolyte) were added to a high-speed shear mixer (FM mixer, fluid mixer).
The organic modifier was added dropwise (10 min) during low-speed stirring
(2.0 m/s peripheral speed), followed by high-speed stirring (30 min,
6.1 m/s peripheral speed, cumulative energy: 11.8 Wh/kg).
The resulting modified sulfide solid electrolyte exhibits an ion conductivity
of 1.8 × 10-3 S/cm, along with particle sizes
D10, D50 and D90 of 0.18 μm, 1.9 μm and
13.4 μm, respectively (measured through laser diffraction / scattering
particle size distribution). The water content was 1,060 mass ppm (Karl
Fischer measurement, 200°C), and the organic solvent content was below
detection limits.
Comparative cells with the same sulfide electrolyte that was modified through
traditional slurry-based processing (stirring in cyclohexane for 24 h,
followed by vacuum drying or spray drying) exhibit an ion conductivity of
1.7 × 10-3 S/cm, D50 of 2.4 μm, water content
of 1,260-2,800 mass ppm and organic solvent content of 0.1-0.3 mass%.
Cyclic voltammetry measurements (CV, 25°C, 0.1 mV/s sweep speed, InLi
negative electrode, potential range: +2.1 to +5.0 V) illustrate an oxidation
current of 0.40 mA for the modified sulfide electrolyte prepared through dry
crushing, as compared to 0.51-0.53 mA for comparative samples prepared
through slurry-based processing. This indicates improved electrochemical
stability and reduced resistance increase during cell cycling.
This work suggests that dry crushing in the presence of organic
modifiers is superior to traditional slurry-based modification methods,
resulting in lower water content, reduced organic solvent contamination,
and improved electrochemical stability.
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Lithium-ion batteries – negative electrode (excluding Li metal electrodes)
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Polyethyleneimine (300 g) was dissolved in an ethanol / water solution,
followed by the addition of resorcinol. Melamine
was dissolved in water, ultrasonically dispersed, and added to the reaction
solution. Formaldehyde solution (3 M) was added, followed by the
addition of potassium hydroxide. The resulting solution was
filtered, dried, ball-milled, and carbonized to obtain nitrogen-doped
phenolic resin-based carbon microspheres.
The nitrogen-doped porous carbon microsphere powder was placed in
a rotary kiln and purged with an inert gas. The temperature was increased
to 850°C at 3°C/min under continuous inert gas flow. Water vapor was
introduced at 3 L/min for 2 h for activation. The activated porous carbon
was crushed and sieved to narrow the particle size distribution, yielding
nitrogen-doped porous carbon material.
The nitrogen-doped porous carbon powder was placed in a fluidized
bed reactor and purged with protective gas until the oxygen content was
below 200 ppm. The reactor was heated to 650°C at 3°C/min. Monosilane gas was
introduced at 3 L/min, while diborane gas was introduced at 0.5 L/min. The
reaction was maintained for 5 h to obtain nitrogen-doped porous carbon
filled with boron-doped nano-silicon in the pores.
Under continuous protective gas flow, the temperature was increased to
820°C at 3°C/min. Acetylene gas was introduced at 4 L/min for 1 h to form
an amorphous carbon coating layer, yielding a silicon-carbon material (see
Figure below).
In half-cells, the material exhibits a
discharge capacity of 2,140 mAh/g, a first cycle efficiency of
92.2%, and an electrical resistivity of 2.09 Ω·cm at 20 kN pressure, as
compared to 1,940 mAh/g, 90.3%, and 5.29 Ω·cm for a comparative
material without nitrogen doping.
This work illustrates how nitrogen doping of carbon and boron doping of Si can lead to favorable 1st cycle efficiency
and electrical conductivity in silicon-carbon composite negative electrode materials.
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Lithium-ion batteries – positive electrode
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LiMn0.6Fe0.36Ti0.02Mg0.02PO4
with a dual coating (LiNi0.5Mn1.5O4 and
carbon) was synthesized. Ti and Mg co-doped lithium manganese iron phosphate
(LMFP) was prepared by mixing FePO4, MnC2O4,
Li2CO3, NH4H2PO4,
TiO2 and MgO (molar ratio according to target stoichiometry) in
deionized water, followed by stirring (300 rpm, 2 h). The slurry was sand milled
using 0.6-0.8 mm zirconia beads (3 h), spray-dried (inlet temperature: 200°C,
outlet temperature: 110°C) and heat-treated (5°C/min to 650°C, 8 h).
The air-milled LMFP was mixed in a high-speed mixer with Li2CO3,
MnO and NiO precursors (according to LiNi0.5Mn1.5
O4 stoichiometry, 1.4 mass% coating layer with respect to core +
coating). The mixture was blended at 1,000 rpm, 1,500 rpm and 2,000 rpm (10 min
each), followed by a heat treatment (ramp at 2°C/min to 900°C, hold 10 h) to
form the LiNi0.5Mn1.5O4 coating layer through
heterogeneous nucleation on the LMFP surface.
The coated material was placed in a rotary furnace and purged with nitrogen
(2 h). The furnace was heated at 5°C/min to 1,000°C while maintaining nitrogen
flow. At 1,000°C, the gas was switched to a mixture of 20 volume% methane and
80 volume% argon. The material was exposed to this atmosphere (5 h) to form a
carbon coating layer via chemical vapor deposition (CVD). The resulting material
(see Figure below) exhibits a particle size Dv50 of 450 nm and a carbon content
of 1.2 mass%.
The material exhibits a powder compaction density of 2.55 g/cm3
(at 30 kN pressure) and a powder resistivity of 30 Ω·cm. In half-cells,
the material exhibits a 0.1 C discharge capacity of 160 mAh/g, a 0.33 C
discharge capacity of 154 mAh/g, a 1 C discharge capacity of 151 mAh/g, and a
capacity retention after 1,000 cycles of 98.9% (1 C charge / discharge, 25°C).
The positive electrode layer exhibits a compaction density of 2.4 g/cm3.
In comparison, the uncoated Ti and Mg co-doped LMFP exhibits a 0.1 C discharge
capacity of 150 mAh/g, a powder compaction density of 2.25 g/cm3, and
a capacity retention after 1,000 cycles of 89.2%.
This work illustrates very promising and well-rounded performance for a Ti and Mg co-doped LMFP material coated with
LiNi0.5Mn1.5O4.
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Fuel cells (PEMFC / SOFC / PAFC / AEMFC) – electrochemically active materials
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A nitrogen-doped porous carbon support material was synthesized for use in polymer
electrolyte membrane fuel cells (PEMFC).
Carbon support material 1 (BET specific surface area: 594.5 m2/g, pore
volume: 1.3 cm3/g, average pore size: 7.8 nm, oxygen content: 2.7 at%)
was heat-treated (900°C, 3 h, H2 / Ar atmosphere with 20 vol% H2,
300 sccm flow rate) to reduce oxygen-containing functional groups on the
carbon surface.
The surface-reduced carbon support was mixed with poly(4-vinyl pyridine) (P4VP, Mn =
40,000 g/mol) in dimethylformamide (DMF) at a mass ratio of 10 : 1 (carbon : P4VP).
The mixture was ultrasonicated (40 kHz, 100 W, 10 min) to prepare a uniform
dispersion with 90 mass% carbon content. The dispersion was centrifuged (5,000 rpm,
90 min) to recover the P4VP-coated carbon composite, which was dried (90°C, 10 h)
and heat-treated (700°C, 5 h, Ar atmosphere) to produce the nitrogen-doped porous
carbon support.
The resulting material exhibits a nitrogen content of 1.2 at%, with
pyridinic N accounting for 44.0% and pyrrolic N accounting for 31.9% of total
nitrogen species. The pyridinic N to pyrrolic N ratio is 1.38. The material
exhibits a positive zeta potential of 12.9 mV in ethanol, as compared to
-59.2 mV for the untreated carbon support. The oxygen content decreased to 0.7
at%, with C=O bonding oxygen accounting for 32.1% of total oxygen.
The Ntot/Otot ratio is 1.65.
Platinum nanoparticles were deposited on the nitrogen-doped carbon support
(platinum loading: 20 mass%) to prepare a fuel cell cathode catalyst. Membrane
electrode assemblies (MEA) were fabricated with a Nafion 117 membrane and
commercial Pt/C anode catalyst (Tanaka Precious Metals, TEC10E50E, 46.8 mass% Pt).
Single cell performance was evaluated at 80°C with humidified H2 and air
(40% relative humidity). The catalyst exhibits an initial cell voltage of 0.639 V
at 0.8 A/cm2, as compared to 0.621 V for a catalyst prepared with 160K
molecular weight P4VP and 0.615 V for a catalyst prepared without surface reduction
treatment. After an accelerated stress test (30,000 cycles, 0.6-0.95 VRHE),
the voltage degradation was 3.3%, as compared to 12.4% and 13.8% for the
comparative catalysts, respectively. The electrochemically active surface area
(ECSA) degradation rate was 47.4%, substantially lower than 50.1% and 58.9% for the
comparative catalysts.
This work illustrates a method to prepare nitrogen-doped porous carbon
support with controlled pyridinic and pyrrolic nitrogen functionalities
for PEMFC cathode catalysts that enables favorable initial cell voltage and durability.
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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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2025-10-14
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2025-09-23
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2025-09-02
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2025-08-12
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2025-07-22
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