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Lithium-ion batteries – electrolytes – solid & semi-solid
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A solid-state battery was developed with additive materials designed to
reduce operating pressure while maintaining performance. The battery
comprises positive and negative electrodes separated by a solid electrolyte
layer containing Li6PS5Cl (LPSCl) particles and novel additive materials.
The additive materials follow the general formula A-B-C, where A
represents either a thiol group (S-H) or a leaving group, B is a
substituted or unsubstituted C3-C20 perfluoro alkane group, and C is a
sulfonate, phosphate, or salt thereof (see example in Figure). The thiol or leaving group is
configured to interact with sulfur atoms in the sulfide-containing
electrolyte particles through covalent bonding or non-covalent attachment.
Ball-milling was used to combine LPSCl powder (particle size: 0.1-50
μm) with additive materials in weight ratios ranging from 1 : 1 to 25 : 1.
During ball-milling, the additive molecules attach to
sulfide particle surfaces and fill spaces between neighboring particles.
The additive materials exhibit lower hardness (0.001-0.01 GPa) compared
to the sulfide particles (0.1-1 GPa), providing flexibility during battery
cycling.
Tests were carried out at pressures of 1-5 MPa.
Although no experimental results were identified, this work suggests that molecules like the one shown in the Figure
enable reduced operating pressures in sulfide-based solid-state Li-ion batteries.
Given that 'generic' LPSCl powder was used, it can be expected that combining an optimized sulfide electrolyte powder
and optimized electrodes
with the right additive will allow for reaching operating pressures below 1 MPa or even below 0.5 MPa.
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Lithium-ion batteries – negative electrode (excluding Li metal electrodes)
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Coconut shell-derived carbon was subjected to
steam activation treatment (1,000°C) to form mesoporous carbon. The material
was then mixed with KOH at a mass ratio of 1 : 3
and heated to 1,000°C (ramp rate: 10°C/min, hold: 2 h) under nitrogen
atmosphere. The resulting activated carbon exhibits branch-shaped pores with a
BET surface area of 1,940 m2/g and a pore volume of 1
cm3/g.
The porous carbon was heated to 400°C (30 min) under nitrogen
flow. Moisture-containing nitrogen gas was introduced, followed by heating to
415°C and monosilane gas introduction for silicon deposition (4 h). The
material was cooled to 25°C under nitrogen flow.
Silicon oxidation was performed by introducing oxygen diluted with nitrogen
(1 : 20 by volume) while maintaining the temperature below 50°C. The oxidation
process continued for 2 h, forming Si-O bonds and creating amorphous
low-valence nanosilicon oxide with primarily 0- to 2-valent silicon, with
2-valent silicon being dominant (material temperature: 30°C).
The resulting negative electrode active material exhibits a silicon content
of 58 mass%, and a carbon content of 42 mass%. 29Si CP/MAS-NMR analysis exhibits a peak maximum at
-91 ppm, indicating abundant Si-O-Si structures. XRD analysis reveals
silicon grain sizes of 1.4 nm using Scherrer's equation.
Half-cell tests demonstrate a discharge capacity of 2,015 mAh/g, a first
cycle efficiency of 78%, and a capacity retention of 90% after 1,000 cycles
(0.7 C charge/0.5 C discharge).
Figure: TEM cross-sectional image showing silicon (white regions)
dispersed in network structure throughout the porous carbon matrix (dark
regions), with branch-shaped pore architecture enabling controlled silicon
oxidation and volume expansion accommodation.
This work illustrates that Shinetsu Chemical has also started research on depositing silicon on carbon scaffolds
through CVD methods, while carefully controlling silicon oxidation to form low-valence silicon oxide.
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Lithium-ion batteries – positive electrode
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A hydroxide precursor Ni0.996Zr0.004(OH)2 was
synthesized through co-precipitation (65°C, pH 11). Nickel sulfate and
zirconium sulfate were dissolved in water (molar ratio Ni : Zr = 249 : 1,
total metal concentration 2 mol/L). The metal salt solution feed rate was
gradually increased from 0.3 L/h to 5 L/h as the precursor particle size
grew larger during synthesis.
The solution was mixed with sodium hydroxide (4 mol/L) and ammonia water
under stirring conditions. The reaction pH was controlled at 11, and the
process continued until the precursor reached a D50 of 10 μm. The
precipitate was washed with dilute alkali solution (2.5 mass% NaOH),
followed by deionized water washing (60°C), then centrifuged and dried.
This precursor was mixed with lithium hydroxide (Li : transition metal
molar ratio = 1.03) under oxygen atmosphere heat treatment. A two-stage
thermal process was applied: first stage heating at 5°C/min to 500°C
(5 h), then 3°C/min to 640°C (15 h). The resulting material exhibits the composition
LiNi0.996Zr0.004O2 with a
Li2ZrO3 grain boundary coating layer formed by
precipitation of excess zirconium beyond the lattice solubility limit.
The material exhibits primary particles arranged in a radial pattern
extending from the secondary particle center, as shown in the SEM image
below. This unique morphology is maintained after heat treatment due to
the low solubility product constant of Zr (Ksp = 1 × 10-50),
which refines the precursor primary particles and inhibits grain growth
during sintering.
In half-cell measurements, the material exhibits a 0.1 C discharge capacity of
238.9 mAh/g and a capacity retention
after 100 cycles of 90.4% (1 C charge / discharge), as compared to
230.7 mAh/g and 83.7% for unmodified LiNiO2, respectively.
The 5 C rate discharge capacity reaches 180.3 mAh/g, demonstrating improved
high-rate performance attributed to enhanced lithium-ion diffusion through
the radial primary particle arrangement and reduced grain boundary
resistance from the Li2ZrO3 coating layer.
This work illustrates an active material that is very close to pure lithium nickel oxide (>99%), but with a Zr-based
grain boundary coating that improves cycling stability and rate capability alongside an impressive 0.1 C discharge capacity
of 238.9 mAh/g.
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Fuel cells (PEMFC / SOFC / PAFC / AEMFC) – electrochemically active materials
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A catalyst ink manufacturing method was developed that prevents sedimentation of
catalyst particles in fuel cell applications. The method involves stirring catalyst
particles (metal catalyst supported on carbon carrier), solvent, and ionomer using
beads with diameters ≤2 mm.
The catalyst particles contain platinum (Pt) and Pt alloys with cobalt and nickel
supported on carbon carriers (solid carbon, hollow carbon, or high-crystallinity
carbon carriers). The solvent consists of water and ethanol mixtures, used along with
fluorine-based ionomers.
The stirring process was conducted using bead mills with rotation speeds ≥300 rpm.
Two bead sizes were tested: 1 mm diameter beads (Example 1) and 2 mm diameter beads
(Example 2). The mixing time was optimized to prevent over-dispersion while achieving
target particle sizes.
Example 1 utilized 1 mm diameter beads and achieved an average catalyst
particle diameter of 1.5 μm after 3 h of stirring (300 rpm). The catalyst ink
composition includes 9.0 mass% solid content with a water/ethanol ratio of 60:40
mass%. The ionomer-to-carbon ratio (I/C) was maintained at 0.8.
Sedimentation tests show that the catalyst ink prepared with 1 mm beads remains
stable without separation for ≈7 days. In contrast, catalyst ink prepared with 2 mm
beads shows sedimentation after 6 days, though it remains stable for at least 3
days.
A comparative example using conventional mixing (Filmix by Primix, 180 s) resulted
in an average particle diameter of ≈2.5 μm, with ink separation occurring within 1
day.
The Figure below illustrates how the average particle diameter decreases with
stirring time for both bead sizes, with over-dispersion occurring after 6 h of
mixing.
過分散: over-dispersion
撹拌混合時間: stirring/mixing time
触媒粒子径: catalyst particle diameter
This work illlustrates how the use of ball-milling procedures with the right energy input can improve
the dispersion stability of catalyst inks, which in turn could lead to improved lot-to-lot consistency
of catalyst characteristics upon up-scaling.
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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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2025-09-02
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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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2025-06-10
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