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b-science.net is present at the International Battery Seminar and Exhibit in Orlando FL (USA) this week with poster P14 titled
'Benchmarking of All-Solid / Semi-Solid Electrolytes Based on the Global Patent Literature'.
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Lithium-ion batteries – electrolytes – solid & semi-solid
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An all-solid-state battery was developed with a layered structure as shown in the Figure.
The battery includes a negative electrode current collector (1), a solid electrolyte
layer 2A containing a first sulfide solid electrolyte and a second sulfide solid
electrolyte, a solid electrolyte layer 2B containing a third sulfide solid
electrolyte, a positive electrode active material layer (3), and a positive electrode
current collector (4) in this order in the thickness direction (DT). A protective
layer (5) containing Li and Sn is formed between the negative electrode current
collector and the solid electrolyte layer 2A when the battery is charged.
Solid electrolyte layer 2A contains 10 mass% of the first sulfide solid
electrolyte (Li10SnP2S12 having a LGPS crystalline
phase) and 90 mass% of the second sulfide solid electrolyte (Li3PS4
containing LiI). The third sulfide solid electrolyte in layer 2B consists of the same
Li3PS4 containing LiI as used for the second sulfide solid
electrolyte, having no reduction peak at 0.3-1.0 V vs. Li/Li+).
These cells exhibit a discharge capacity of 150 mAh/g in the first
cycle and a capacity retention
rate of 91.3% after 20 cycles, as compared to 132 mAh/g and 85.6% for comparative
cells with a single sulfide layer (Li3PS4
containing LiI).
The favorable performance is attributed to the formation of a
lithium-tin alloy layer during cycling, which likely functions as a protective interface
between the negative electrode current collector and the solid electrolyte. This
protective layer prevents the decomposition of the sulfide solid electrolyte during
cycling while maintaining high ionic conductivity.
This work illustrates how Sn-containing sulfides that form metallic Sn at low potential allow for the formation
of a protective interface layer that enables a favorable current density distribution, when combined with a second sulfide
layer that is electrochemically more stable at low potentials.
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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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Lithium-ion batteries – negative electrode (excluding Li metal electrodes)
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A porous carbon framework with a total pore volume of 0.8-1.2
cm3/g, a PD50 pore diameter of 2 nm, and a D50 particle
diameter of 2.5-10 μm that contain 500-5,000 ppm calcium and
1,000-16,000 ppm phosphorus was prepared, based on phosphoric acid activation of a biomass
feedstock (such as lignin obtained from a wood pulping process), without subsequent washing steps. Silicon was deposited within
the micropores through chemical vapor infiltration using monosilane (380-400°C),
resulting in nanoscale silicon domains (<50 nm) occupying 45-55% of
the internal pore volume. The silicon-impregnated frameworks were annealed
(600-650°C under nitrogen), passivated with oxygen-containing gas, and coated with
pyrolytic carbon (550°C, acetylene), resulting in a material that contains ≈5 atom% Ca vs. Si.
In half-cells during the first charge, the
applied potential caused lithium insertion into silicon while
simultaneously forming an intermetallic phase with calcium. This in-situ formation
of a silicon-calcium-lithium intermetallic phase occurs without requiring
additional manufacturing steps beyond the standard formation cycling protocol.
In half-cell tests, the material exhibits a reversible capacity of 1,120 mAh/g with a first cycle efficiency of
89.6% and capacity retention of 95% after 50 cycles at 0.1 C charge/discharge, while a Ca-free comparative material
exhibits 997 mAh/g, 78.5%, and 83%, respectively.
This work illustrates that the use of a Ca- & P-containing porous carbon framework results in improved
electrochemical performance of Si-carbon composite materials.
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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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Lithium-ion batteries – positive electrode
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A secondary particle cathode active material was prepared from NiSO4,
CoSO4, and MnSO4 with a molar ratio of 92:4:4. These
precursors were mixed with LiOH (1:1 Li:precursor ratio), along with ZrO2 (0.003 mol, which might refer to 0.3 mol%)
and Al(OH)3 (0.01 mol, which might refer to 1 mol%). Presumably, a co-precipitation reaction was carried out.
The mixture was sintered (700°C, 35 h, oxygen).
The resulting material was pulverized and large particles
were removed by sieving to produce the Zr/Al-doped active material.
After washing, the dried material was coated with boron by mixing with boric acid (500-1,000
ppm) in a cylindrical reactor (35 Hz, 25 min). The mixture was sintered (300°C, 15 h, oxygen).
The final product exhibits a crystallite size of 73 nm (measured by XRD) and
Ni2+ occupying lithium sites at 3.49 atom%. In half-cells,
the material exhibits a discharge capacity of 238.0 mAh/g (4.3-2.5 V vs. Li+/Li, 0.1 C charge discharge)
and maintains 92.0% capacity after 50 cycles at 45°C (4.3-3.0 V vs. Li+/Li, 0.5 C charge / 1.0 C discharge).
This work illustrates promising electrochemical characteristics for a Zr/Al-doped high-Ni NMC material with a B-based coating.
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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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Fuel cells (PEMFC / SOFC / PAFC / AEMFC) – electrochemically active materials
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A carbon-supported platinum catalyst synthesis method was developed to control
platinum nanocrystal morphology through temperature manipulation. The process
involves a mixture of platinum(II) acetylacetonate (Pt(acac)2), reduced
graphene oxide as carbon source, formic acid, and ethylene glycol as solvent.
Two synthesis approaches were investigated: a one-step heating process at a single
temperature and a multi-step heating process. The one-step process at 80-120°C
produced irregular nanospheres, while heating at 150-210°C yielded nanocubes. The
multi-step heating process (80°C for 3 h, followed by 130°C for 24 h, then 210°C for
6 h) formed tetrahedra-shaped nanocrystals chemically bonded to the carbon
support.
TEM images in Figures 2A-2D show platinum tetrahedra nanocrystals formed during the
multi-step heating process at different temperatures. Figures 2A-2C demonstrate the
tetrahedron shapes from different synthesized samples, highlighting the high
reproducibility of the method. Figure 2D shows various orientations of tetrahedra on
reduced graphene oxide, unlike cubes which have only one projection in TEM
imaging.
Electrochemical measurements demonstrated that carbon-supported platinum nanocubes
exhibit superior oxygen reduction reaction (ORR) performance compared to
commercial Pt/C catalysts (Figure 4B, 401-403: Pt nanocube-RGO catalysts,
404: commercial Pt on carbon catalyst), with improved durability due to chemical bonding between
the platinum nanoparticles and the carbon support.
This
approach demonstrates Pt catalyst morphology control through a multi-step heating process, without relying on complex surfactants or ligands.
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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-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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- Metal-air batteries: XLSX
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- Na-ion batteries: XLSX
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Prior patent updates
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2025-02-25
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2025-02-04
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2025-01-14
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2024-12-23
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2024-12-03
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