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Lithium-ion batteries – electrolytes – solid & semi-solid
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Li6PS5Cl (LPSCl) was surface-modified with
sodium 3-mercapto-1-propanesulfonate (3M1P, see Figure) through ball-milling
(30 min, room temperature) to form a composite sulfide electrolyte
(LPSCl@3M1P).
The LPSCl@3M1P powder was pressed into pellets (diameter :
12 mm, 370 MPa). Lithium foils were attached to both sides to form
symmetric Li|LPSCl@3M1P|Li cells. The cells were tested at stack
pressures of 2 MPa and 30 MPa.
As shown in the Figure, the critical current density (CCD) exhibits
2.4 mA/cm-2 at 2 MPa and 4.0 mA/cm-2
at 30 MPa for LPSCl@3M1P cells, as compared to 0.3 mA/cm-2
and 0.6 mA/cm-2 for bare LPSCl at the same pressures,
respectively. The symmetric Li|LPSCl@3M1P|Li cells cycled for >500 h
at 0.5 mA/cm-2, as compared to ≈50 h for Li|LPSCl|Li
cells.
Full cells were assembled with NCM811-based positive electrodes. The
positive electrode formulation comprised NCM811 / LPSCl / vapor-grown
carbon fibers (VGCF, 64 : 33 : 3 by mass, loading : 4 mg/cm2). Cells
were cycled at 0.1 C charge / discharge (voltage range: 2.5-4.25 V,
60°C). The Li|LPSCl@3M1P|NCM811 cells exhibit a capacity retention
of 84% after 200 cycles, as compared to lower retention for
comparative Li|LPSCl|NCM811 cells (specific value not identified).
According to an X-ray photoelectron spectroscopy (XPS) analysis,
LPSCl@3M1P surfaces show reduced Li2S formation after
100 cycles (≈38% of
total area) as compared to LPSCl surfaces (≈82% of total area),
demonstrating suppressed electrolyte decomposition.
Surface morphology analysis reveals smooth electrolyte surfaces for
LPSCl@3M1P after 40 cycles, in contrast to porous surfaces observed
for bare LPSCl. Cross-sectional focused ion beam scanning electron
microscopy (FIB-SEM) images show dense, void-free lithium layers
with intimate electrolyte contact for LPSCl@3M1P systems. The
deposited lithium exhibits hexagonally shaped crystals with (0001)
facets oriented parallel to the substrate, which promotes uniform
lithium deposition during cycling.
This work illustrates substantial electrochemical benefits upon
surface modification of sulfide electrolytes with additive 3M1P,
specifically in terms of allowing for uniform lithium metal deposition.
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Lithium-ion batteries – negative electrode (excluding Li metal electrodes)
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Multilayer graphene (5-8 layers) was mixed with deionized water to form a
dispersion. Sodium tungstate was added to adjust the pH to 6-7. The
dispersion was ultrasonicated, and the solid sample was separated by
filtration.
The solid sample was placed in a tube furnace and heated to 720°C under
nitrogen atmosphere for 2 h to obtain multilayer graphene secondary
particles.
The multilayer graphene secondary particles were placed in a CVD (chemical vapor deposition)
furnace.
Water vapor was introduced (8 L/min, 7.2 MPa, 4.1 h) to create nanopores on
the graphene layers. The resulting porous graphene exhibits a BET specific
surface area of 1,342 m2/g, a pore volume of 0.72 cm3/g,
and an average nanopore diameter of 5.3 nm.
The porous graphene was placed in a tube furnace under nitrogen atmosphere
(15 L/min). Monosilane gas (3 L/min) was introduced, and CVD
was performed (630°C, 10 h) to deposit nano-silicon within the
nanopores.
After silicon deposition, ethylene gas was introduced, and a carbon coating
layer was formed on the surface (900°C, 3 h).
The resulting silicon-carbon composite material exhibited a BET specific
surface area of 0.15 m2/g, a tap density of 0.8 g/cm3
(5 T pressure), a volume-average particle size Dv50 of 9.1 μm, and
an Si content of 45 mass%.
Negative electrodes were prepared by mixing the silicon-carbon composite
material, graphite, single-walled carbon nanotubes, Super C conductive
carbon black, and lithium polyacrylate (40 : 54.5 : 0.5 : 2 : 3 by mass)
in deionized water, followed by coating on Cu foil, drying, and calendering.
In full cells (NMC-based positive electrodes), the material exhibits a
capacity retention of 80% after 1,998 cycles (0.5 C charge / 0.33 C
discharge).
Figure: EDS (energy-dispersive X-ray spectroscopy) mapping image and
elemental composition of the silicon-carbon composite material cross-section,
illustrating the distribution of Si and C elements. The analysis
confirms that silicon was uniformly deposited within the nanopores of the
graphene layers rather than between graphene layers.
元素: Element
质量含量%: Mass content %
总量: Total
电子图像: Electron image
This work illustrates promising cycling stability
as a result of homogeneous Si deposition on a graphene material with
carefully tailored pore size distribution.
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Lithium-ion batteries – positive electrode
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LiMn0.4Fe0.6PO4 was coated with a
composite layer consisting of bacterial cellulose, lithium polyacrylate, and
PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate).
Bacterial cellulose (fiber diameter: 50-100 nm) was crushed, washed with
sodium hydroxide solution (3 mass%, 25 min), and acid-washed with
hydrochloric acid solution (0.5 mol/L) to pH 7. The pre-treated cellulose
was dispersed in lithium polyacrylate (Li-PAA) aqueous solution (ultrasonication)
to obtain a fiber dispersion.
LMFP (D50: 1.3 μm) was dispersed in ethanol / water (1 : 1 by volume,
60 g/L) and added to the fiber dispersion. PEDOT:PSS solution (pH 5.0,
adjusted with ammonia) was added, followed by stirring (20 min) to
obtain a mixed slurry. Mass ratio of bacterial cellulose : Li-PAA : PEDOT:PSS
was 4.5 : 1.5 : 6, with total coating mass of
4.7 mass%.
The slurry was spray-dried and subjected to gradient annealing. The
annealing protocol included a low-temperature stage (250°C, 1 h), a
mid-temperature stage (400°C, 2.5 h, argon atmosphere), and a
high-temperature stage (600°C, 3 h, Ar / H2 = 95 : 5 by
volume).
The resulting material exhibits a discharge capacity of
148 mAh/g (1 C) and 131 mAh/g (5 C) in half-cells, along with
a capacity retention of 96.9% after 200 cycles (1 C charge / discharge,
2.0-4.35 V vs. Li+/Li), as compared to 139.5 mAh/g (1 C),
116.5 mAh/g (5 C), and 89.2% for a comparative material coated only with
bacterial cellulose and Li-PAA (without PEDOT:PSS).
This work illustrates that annealed PEDOT:PSS / Li-PAA / cellulose
form a coating on LMFP that enables promising power performance
and cycling stability.
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Fuel cells (PEMFC / SOFC / PAFC / AEMFC) – electrochemically active materials
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SOLID OXIDE FUEL CELL
Applicant:
NISSAN MOTOR /
WO 2025181907 A1
A metal-supported solid oxide fuel cell (SOFC) was developed with enhanced
oxidation resistance. The metal support is formed from an Fe-Cr alloy
(stainless steel) with added Si or Al.
Stainless steel powder with 1 mass% Si was prepared as the metal support
powder. The powder is formed into a sheet (50-500 μm thickness), then
laminated with the bonding layer, fuel electrode layer, and electrolyte layer green
sheets. The assembly is fired in a reducing atmosphere, followed by a heat
treatment at 800-1,200°C in an oxidizing atmosphere to form an oxide film
containing Al or Si on the surface of the base material.
The metal support exhibits a porous structure (thickness: 100-500 μm).
Metallic reforming catalyst particles (Ni, Ru, Pt, Rh
or Co) are supported on the oxide film to enable internal reforming
functionality.
A bonding layer is provided between the metal support and fuel electrode
layer. The bonding layer is formed from Fe-Cr alloy with porous structure but
contains lower concentrations of Al and Si compared to the metal support,
enabling strong adhesion between the metal support and fuel electrode layer
while maintaining oxidation resistance of the metal support itself.
The Figure shows the cross-sectional structure, with (a) showing the overall
cell structure and (b) showing details of the metal support layers. The oxide
film prevents oxidation of the base material in high-temperature,
high-moisture reforming environments.
During operation, fuel with S/C exceeding 1 is supplied to the metal support.
The fuel is reformed via steam reforming in the metal support, generating
hydrogen. Resistance measurements after operation at 600°C with H2/H2O
(50:50 vol%) exhibit a resistance change rate of 1/2 compared to a metal
support without Si addition, confirming that the oxide film suppresses
oxidation.
1: fuel cell
2: metal support
3: fuel electrode layer
4: electrolyte layer
5: air electrode layer
6: bonding layer
7: base material
8: oxide film
9: reforming catalyst particles
This work illustrates that incorporating 1 mass% Si into the metal support of
SOFC reduces undesired oxidation and resistance increases.
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Triweekly patent lists for other categories (Excel files are included for premium users)
-
- Lithium metal batteries (excluding Li-S, Li-Air): XLSX
-
- 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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2025-09-23
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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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2025-07-01
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