Fragmented electrochemically active composite particles for lithium-ion batteries

Abstract

A battery electrode composition contains a population of fractured composite particles, each of which contains silicon and carbon. In some embodiments, 90% or more of the fractured composite particles in the population are characterized by aspect ratios of 2.3 or less, and 50% or more of the fractured composite particles in the population are characterized by aspect ratios of 1.25 or more. In some embodiments, the population is characterized by a particle size distribution (PSD) as determined by laser particle size analysis (LPSA) and a volume-weighted particle size parameter of the fiftieth percentile D. 50 The PSD lies in a range of approximately 2.0 to approximately 17.0 µm.

Description

Reference to related patent applications

[0001] The present patent application claims priority over U.S. provisional application No. 63 / 477,727 entitled “Jagged Electrochemically-Active Composite Particles For Lithium-Ion Batteries”, filed on December 29, 2022, and U.S. non-provisional application No. 18 / 398,718 entitled “Jagged Electrochemically-Active Composite Particles For Lithium-Ion Batteries”, filed on December 28, 2023, both of which have been assigned to the successor in title of the present application and are expressly incorporated herein by reference in their entirety. Background area

[0002] Aspects of the present disclosure relate generally to energy storage devices, in particular battery technology and the like. background

[0003] Due in part to their relatively high energy density, relatively high specific energy, low weight and potentially long lifespan, advanced rechargeable batteries are desirable for a wide range of consumer electronics, electric vehicles, grid storage and other important applications.

[0004] Despite the increasing commercial prevalence of batteries, further development of these batteries is necessary, particularly for applications in low-emission or zero-emission, hybrid-electric or fully electric vehicles, consumer electronics, portable devices, energy-efficient cargo ships and locomotives, drones, aerospace applications, and power grids. Further improvements are especially desirable for various rechargeable batteries, such as rechargeable lithium and lithium-ion batteries, rechargeable sodium and sodium-ion batteries, and rechargeable potassium and potassium-ion batteries, to name just a few.

[0005] In certain types of rechargeable lithium-metal and lithium-ion batteries, charge-storing anodes can comprise silicon (Si)-containing anode particles with gravimetric capacities ranging from approximately 800 mAh / g to approximately 3000 mAh / g (per mass of the Si-containing anode particles in a Li-free state). A subset of such anodes includes anodes with an electrode layer exhibiting a capacity ranging from approximately 400 mAh / g to approximately 2800 mAh / g (per mass of the electrode layer, excluding the mass of the current collector, in a Li-free state). This class of charge-storing anodes offers significant potential for increasing the gravimetric and volumetric energy of rechargeable batteries.

[0006] In certain types of rechargeable batteries, charge-storing active anode materials can be fabricated as high-capacity (nano)composite powders (e.g., consisting at least partially of active material nanomaterials or nanostructures that may be embedded on and / or in a porous structure, such as a carbon-containing matrix material). These powders exhibit moderately high volume changes (e.g., about 8–180 vol%) during the first charge-discharge cycle and moderate volume changes (e.g., about 5–50 vol%) during subsequent charge-discharge cycles. A subset of such charge-storing anode particles includes anode particles with an average size (e.g., diameter or thickness) in the range of about 0.2 to about 40 µm (micrometers or µm), as measured by laser particle size distribution analysis (LPSA), laser image analysis, electron microscopy, optical microscopy, or other suitable methods.Such a class of charge-storing particles offers great opportunities for scalable manufacturing and the achievement of high energy density at the cell level and other performance characteristics.

[0007] Examples of electrode materials that exhibit moderately high volume changes (e.g., about 8–180 vol%) during the first charge-discharge cycle and moderate volume changes (e.g., about 5–50 vol%) during subsequent charge-discharge cycles include (nano)composites, which comprise active electrode materials of the so-called conversion type (which includes both the subclasses of so-called chemical conversion and so-called "true conversion") and of the so-called alloy type. In the case of metal-ion batteries (such as lithium-ion batteries), examples of such conversion-type active electrode materials include metal fluorides (such as lithium fluoride, iron fluoride, copper fluoride, bismuth fluoride, their mixtures and alloys, etc.).Metal chlorides, metal iodides, metal bromides, metal chalcogenides (such as sulfides, including lithium sulfide and other metal sulfides), sulfur, selenium, metal oxides (including, but not limited to, lithium oxide and silicon oxide), metal nitrides, metal phosphides (including lithium phosphide), metal hydrides, and others. In metal-ion batteries (e.g., lithium-ion batteries), examples of such alloy electrode materials include silicon, germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorus, silver, cadmium, indium, tin, lead, bismuth, and their alloys. These materials generally offer higher gravimetric and volumetric capacity than so-called intercalation electrodes, which are commonly used in commercially available metal-ion (e.g., lithium-ion) batteries. Alloy electrode materials are particularly advantageous for use in certain high-performance anodes for Li-ion batteries.Silicon-based alloy anodes can be particularly attractive for such applications.

[0008] An example of low-swelling particles is the mixture of active anode materials based on conversion silicon (or, more broadly, silicon-containing) with graphite, so-called silicon-graphite mixtures. In some examples of a mixed anode, the silicon-containing active anode material may be a silicon- and carbon-containing nanocomposite (referred to here as a Si-C composite or Si-C nanocomposite or Si-C composite (or nanocomposite) particle, even if such particles contain elements other than Si and C in relatively small amounts of less than about 10–20 atomic percent) and provide about 20 to 80% of the total mixed anode capacity, while the remainder of the capacity is provided by graphite. (In other examples, the Si-C composite (e.g., Si-C composite particles) may constitute more than about 80% or less than about 20% of the anode capacity.)Such anodes offer a much higher volumetric and gravimetric energy density than the intercalation-type graphite anodes commonly used in commercial lithium-ion batteries. Furthermore, the graphite in such a mixed anode can consist of natural or synthetic graphite, or a mixture of both. In some designs, it is advantageous to use natural graphite or a mixture of both because such graphite particles are able to absorb mechanical stresses caused by the significant swelling of silicon-based (e.g., Si-C) particles during lithium injection. These properties of Si-C nano-composite graphite mixtures can result in moderate volume changes during the first cycle and minimal volume changes during subsequent charge cycles.These properties are advantageous for anode particles with high charging capacity, which also reduces the manufacturing costs of such battery cells.

[0009] In some configurations, active electrode materials for use in electrochemical energy storage devices such as batteries, electrochemical capacitors, or hybrid devices may consist of carbon-containing composite particles. A subclass of such composite particles may include those in which conversion, alloying, intercalation, or pseudocapacitance-type materials are embedded or infiltrated within a carbon or carbon-containing matrix material. However, existing approaches for the synthesis or thermochemical processing of such carbon or carbon-containing matrix materials may suffer from low efficiency, low packing density, low throughput, insufficient control of uniformity, or other limitations.

[0010] Accordingly, there remains a need for improved batteries, components and other related materials and manufacturing processes. Brief description

[0011] The following is a simplified summary of one or more aspects disclosed herein. This summary should therefore not be considered a comprehensive overview of all aspects considered, nor should it be seen as identifying key or critical elements with respect to all aspects considered, or as defining the scope of any particular aspect. Accordingly, the purpose of this summary is simply to present, in simplified form, certain concepts relating to one or more aspects of the mechanisms disclosed herein, in order to precede the detailed descriptions that follow.

[0012] In one aspect, a battery electrode composition comprises a population of fractured composite particles, each of which comprises silicon and carbon; wherein: about 90% or more of the fractured composite particles in the population are characterized by aspect ratios of about 2.3 or less; about 50% or more of the fractured composite particles in the population are characterized by aspect ratios of about 1.25 or more; and the population is characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA) such that: a volume-weighted particle size parameter of the fiftieth percentile (D 50 ) the PSD of the population lies in a range of approximately 2.0 to approximately 17.0 µm.

[0013] In some aspects, approximately 90% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 2.1 or less.

[0014] In some aspects, approximately 50% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.35 or more.

[0015] In some aspects, approximately 10% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.3 or less.

[0016] In some aspects, the mass fraction of silicon in the fractured composite particles ranges from about 3 wt.% to about 80 wt.%.

[0017] In some aspects, the mass fraction of silicon ranges from about 33 wt.% to about 60 wt.%.

[0018] In some aspects, the specific surface area (SSA) of the population according to Brunauer-Emmett-Teller (BET) lies in a range of about 1 m². 2 / g up to about 18 m 2 / G.

[0019] In some aspects, the BET-SSA lies within a range of approximately 1 m. 2 / g up to about 10 m 2 / G.

[0020] In some aspects, the D50 value lies in a range of approximately 2.0 to approximately 8.0 µm.

[0021] In some aspects, the D50 value lies in a range of approximately 6.0 to approximately 17.0 µm.

[0022] In some aspects, the D50 value lies in a range of approximately 6.0 to approximately 9.0 µm.

[0023] In some aspects, the PSD of the population ranges from about 0.3 to about 1.8.

[0024] In some aspects, the volume-weighted particle size parameter of the tenth percentile (D) 10 ) the PSD of the population at least approximately 1.0 µm; and a value of the D10 the PSD of the population divided by the D 50 The PSD of the population ranges from 35% to 75%.

[0025] In some aspects, the battery electrode composition comprises a mixture of the fractured composite particles and graphite particles; and a mass fraction of the fractured composite particles in the battery electrode composition, excluding any binder, is in the range of about 10 wt.% to about 70 wt.%, or a mass fraction of the graphite particles in the battery electrode composition, excluding any binder, is in the range of about 30 wt.% to about 90 wt.%, or a combination thereof.

[0026] In some aspects, the D50 value of the PSD of the population lies in a range of approximately 6.0 to approximately 12.0 µm.

[0027] In some aspects, a volume-weighted particle size parameter of the tenth percentile (D) is suitable. 10) the PSD of the population in a range of approximately 1.0 to approximately 4.0 µm.

[0028] In some aspects, a volume-weighted particle size parameter of the ninetieth percentile (D) 90 ) the PSD of the population in a range of approximately 7.0 to approximately 25.0 µm.

[0029] In some aspects, the D 90 -value in a range of approximately 12.0 to approximately 20.0 µm.

[0030] In some aspects, a volume-weighted particle size parameter of the ninety-ninth percentile (D) is appropriate. 99 ) the PSD of the population in a range of approximately 15.0 to approximately 28.0 µm.

[0031] In some aspects, the PSD of the population ranges from about 0.6 to about 2.1.

[0032] In some aspects, the specific surface area (SSA) of the population according to Brunauer-Emmett-Teller (BET) lies in a range of about 1 m². 2 / g up to about 10 m 2 / G.

[0033] In some aspects, the fractured composite particles exhibit a specific lithiation capacity in the first cycle in a range of about 1600 mAh / g to about 2200 mAh / g.

[0034] In some aspects, the specific capacity of the mixture ranges from about 600 mAh / g to about 1200 mAh / g, normalized to a mass of the mixture.

[0035] In one aspect, a battery electrode comprises a battery electrode composition arranged on and / or in a current collector, wherein: the battery electrode comprises a binder.

[0036] In some aspects, the coating density of the battery electrode lies in a range of approximately 0.9 to approximately 1.7 g / cm². 3 .

[0037] In some aspects, it is a carbon-containing functional additive.

[0038] In some aspects, the carbon-containing functional additive is selected from: single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon black, expanded graphite, graphene oxide and graphene.

[0039] In some aspects, the mass fraction of the carbon-containing functional additive in the battery electrode is approximately 1 wt.% or less.

[0040] In some aspects, the D 50 -The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and the mass fraction of the binder in the battery electrode is in a range of approximately 7 wt.% to approximately 10 wt.%.

[0041] In some aspects, the D 50 -The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and the area-related binder loading of the battery electrode is in a range of approximately 9.0 mg / m² 2 up to approximately 13.0 mg / m³ 2, where the area-related binder loading is defined as a mass fraction of the binder in the battery electrode, divided by a product of (1) a mass fraction of the fractured composite particles in the battery electrode and (2) a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET).

[0042] In one aspect, a lithium-ion battery comprises an anode current collector; a cathode current collector; a battery electrode designed as an anode, the current collector of which is designed as an anode current collector; a cathode arranged on or in the cathode current collector; and an electrolyte that ionically couples the anode and the cathode.

[0043] In one aspect, a method for producing a battery electrode comprises (A1) providing a battery electrode composition, (A2) producing a slurry comprising the battery electrode composition and a binder; and (A3) pouring the slurry onto and / or into a current collector to form the battery electrode.

[0044] In one aspect, a method for manufacturing a lithium-ion battery comprises (B1) manufacturing a battery electrode, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (B2) manufacturing or providing a cathode arranged on and / or in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0045] In one aspect, a method for manufacturing a lithium-ion battery comprises (C1) providing a battery electrode, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (C2) manufacturing or providing a cathode arranged on and / or in a cathode current collector; and (C3) assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0046] One aspect concerns a battery electrode composition comprising a population of fractured composite particles, each of which includes silicon (Si) and carbon (C) (e.g., mainly graphitic carbon) and may include other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), and sulfur (S), to name a few. In some embodiments, the combined mass of Si and C may constitute approximately 75 to approximately 100 wt% of the total mass of the composite particles. Such composite particles are sometimes referred to here as Si-C composites. In some embodiments, such composite particles include nanoscale or nanostructured elements (e.g., nanoscale or nanostructured Si, nanoscale or nanostructured C), which may be referred to as nanocomposite particles.In some embodiments, the Si or Si-containing material in such nanocomposites may be present in the form of nanoparticles. In some embodiments, the mass-averaged size of the nanoparticles of Si or Si-containing material may be in the range of about 1 nm to about 200 nm (in some embodiments in the range of about 1 nm to about 10 nm; in other embodiments in the range of about 10 nm to about 30 nm; in still other embodiments in the range of about 30 nm to about 100 nm; in still other embodiments in the range of about 100 nm to about 200 nm), measured by means of image analysis using electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (RTEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, neutron scattering, and other suitable methods.In some embodiments, 90% or more of the fractured composite particles in the population are characterized by aspect ratios of 2.3 or less, or aspect ratios of 2.1 or less. In some embodiments, 50% or more of the fractured composite particles in the population are characterized by aspect ratios of 1.25 or more, or aspect ratios of 1.35 or more. In some embodiments, 10% or more of the fractured composite particles in the population are characterized by aspect ratios of 1.3 or less. The population may be characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA), image analysis of electron micrographs, or other suitable methods. In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D. 50) the PSD in a range of approximately 2.0 µm to approximately 16.0 µm, or in a range of approximately 2.0 to approximately 4.0 µm, or in a range of approximately 4.0 to approximately 6.0 µm, or in a range of approximately 6.0 to approximately 8.0 µm, or in a range of approximately 8.0 to approximately 16.0 µm. In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D) is used. 50 ) the PSD in a range of approximately 1.0 µm to approximately 17.0 µm or in a range of approximately 1.0 to approximately 4.0 µm or in a range of approximately 4.0 to approximately 6.0 µm or in a range of approximately 6.0 to approximately 9.0 µm or in a range of approximately 9.0 to approximately 17.0 µm.

[0047] Another aspect concerns a battery electrode composition comprising a population of nano-composite particles, each nano-composite particle containing silicon and carbon (such that the total mass of the silicon and carbon atoms constitutes 75 to 100 wt.% of the mass of the nano-composite particles), and the nano-composite particles exhibiting certain properties. In some embodiments, the mass fraction of silicon in the nano-composite particles ranges from approximately 3 wt.% to approximately 80 wt.% (in some embodiments from approximately 3 wt.% to approximately 20 wt.%; in other embodiments from approximately 20 wt.% to approximately 35 wt.%; in still other embodiments from approximately 35 wt.% to approximately 50 wt.%; in still other embodiments from approximately 50 wt.% to approximately 80 wt.%; in still other embodiments from approximately 33 wt.% to approximately 60 wt.%; in still other embodiments from approximately 5 wt.% to approximately 50 wt.%).-%; in other embodiments from approximately 7 wt.% to approximately 40 wt.%; in other embodiments from approximately 9 wt.% to approximately 30 wt.%). In some embodiments, the specific surface area (SSA) of the composite particles according to Brunauer-Emmett-Teller (BET) is in the range of approximately 1 m. 2 / g up to about 50 m 2 / g (in some embodiments from about 1 to about 3 m) 2 / g; in other embodiments of about 3 m 2 / g up to about 12 m 2 / g; in other embodiments of about 12 m 2 / g up to about 18 m 2 / g; in other embodiments of about 18 m 2 / g up to about 30 m 2 / g; in other embodiments of about 30 m 2 / g up to about 50 m 2 / G).

[0048] Another aspect concerns a battery electrode composition comprising a population of composite particles (e.g., nano-composite particles), where some or all of the composite particles contain silicon and carbon (such that the total mass of the Si and C atoms constitutes 75 to 100 wt% of the mass of the nano-composite particles). The population can be characterized by a particle size distribution (PSD), which in one example is determined by laser particle size distribution analysis (LPSA) on well-dispersed particle suspensions. It should be noted that other types of particle size distribution analysis (e.g., by SEM image analysis) can also be used (and in some experiments may even lead to more accurate measurements). In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D) is used. 50) the PSD in a range of approximately 1.0 µm to approximately 12.0 µm (in some embodiments from approximately 1.0 µm to approximately 2.0 µm; in other embodiments from approximately 2.0 µm to approximately 4.0 µm; in still other embodiments from approximately 4.0 µm to approximately 6.0 µm; in still other embodiments from approximately 6.0 µm to approximately 12.0 µm). A cumulative volume fraction, defined as the cumulative volume of the composite particles with particle sizes of a threshold particle size or less, divided by a total volume of all composite particles, can be estimated by LPSA. In some embodiments (e.g., when the D 50 (where the value is in a range of approximately 2.0 µm to approximately 4.0 µm), the cumulative volume fraction at the threshold particle size of 4.6 µm is 90 vol% or less, or 85 vol% or less, or 80 vol% or less. In other embodiments (e.g., when the D 50(where the value is in a range of approximately 4.0 µm to approximately 6.0 µm), the cumulative volume fraction at the threshold particle size of 7 µm is 90 vol% or less, or 85 vol% or less, or 80 vol% or less. In other embodiments (e.g., when the D 50 (where the value is in a range of approximately 6.0 µm to approximately 12.0 µm), the cumulative volume fraction at the threshold particle size of 15 µm is 90 vol% or less, or 85 vol% or less, or 80 vol% or less. Note that the presence of excessively large particles can impair the cell's performance characteristics (e.g., reduced cell stability, increased impedance, reduced rate performance, etc.). In some embodiments (e.g., when the D 50 (where the value is in a range of approximately 2.0 µm to approximately 4.0 µm), the cumulative volume fraction at the threshold particle size of 10 µm is 80 vol.% or more. In some embodiments (e.g., when the D 50(where the value is in a range of approximately 2.0 µm to approximately 4.0 µm), the cumulative volume fraction at the threshold particle size of 12 µm is 90 vol.% or more. In other embodiments (e.g., when the D 50 (where the value is in a range of approximately 4.0 µm to approximately 6.0 µm), the cumulative volume fraction at the threshold particle size of 15 µm is 80 vol.% or more. In other embodiments (e.g., when the D 50 (where the value is in a range of approximately 4.0 µm to approximately 6.0 µm), the cumulative volume fraction at the threshold particle size of 22 µm is 90 vol.% or more. In other embodiments (e.g., when the D 50 (where the value is in a range of approximately 6.0 µm to approximately 12.0 µm), the cumulative volume fraction at the threshold particle size of 28 µm is 80 vol.% or more. In other embodiments (e.g., when the D 50(where the value is in a range of approximately 6.0 µm to approximately 12.0 µm), the cumulative volume fraction at the threshold particle size of 32 µm is 90 vol% or more.

[0049] Another aspect concerns a battery electrode composition that includes a population of composite particles (e.g., nano-composite particles), where each of the composite particles contains silicon and carbon (e.g., mainly graphitic, sp 2 -bonded carbon) comprises (such that the total weight of the Si and C atoms contributes 75-100 wt% to the mass of the nano-composite particles). The population can be characterized by a particle size distribution (PSD), which in one example is determined by laser particle size distribution analysis (LPSA). In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D) is used. 50The surface area of ​​the PSD is in a range of approximately 6.0 µm to approximately 8.0 µm. In some embodiments, the specific surface area of ​​the composite particles, according to Brunauer-Emmett-Teller (BET), is in a range of approximately 1 m². 2 / g up to about 50 m 2 / g (in some embodiments from about 1 to about 3 m) 2 / g; in other embodiments of about 3 m 2 / g up to about 12 m 2 / g; in other embodiments of about 12 m 2 / g up to about 18 m 2 / g; in other embodiments of about 18 m 2 / g up to about 30 m 2 / g; in other embodiments of about 30 m 2 / g up to about 50 m 2 / G).

[0050] Another aspect concerns a battery electrode composition that includes a population of composite particles (e.g., nano-composite particles), where each of the composite particles contains silicon and carbon (mostly graphitic, sp 2-bonded carbon) comprises (such that the total mass of the Si and C atoms constitutes 75 to 100 wt.% of the mass of the nano-composite particles). In some embodiments, the battery electrode composition may include one or more carbon-containing functional additives (e.g., additives that improve the electrical conductivity or the rate performance of the electrode's mechanical properties). In some embodiments, the carbon-containing functional additive is selected from: carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs)), carbon nanofibers, carbon black, graphite, expandable graphite, graphene oxide (e.g., single-walled graphene oxide, multi-walled graphene oxide), and graphene (e.g., single-walled graphene, multi-walled graphene).In some embodiments, the battery electrode composition may contain one or more binders (in some embodiments, two or more binder components).

[0051] Another aspect relates to a battery electrode. In some embodiments, the battery electrode comprises one of the aforementioned battery electrode compositions, arranged on or within a current collector. In some embodiments, the battery electrode comprises a battery electrode composition and a binder. In some embodiments, the coating density of the battery electrode is in the range of approximately 0.8 to approximately 1.5 g / cm³. 3 or in a range of approximately 0.8 to approximately 1.7 g / cm³ 3 (in some versions from about 0.8 to about 0.9 g / cm³) 3 ; in other versions from about 0.9 to about 1.0 g / cm³ 3 ; in other versions, from about 1.0 to about 1.2 g / cm³ 3; in other versions, from about 1.2 to about 1.5 g / cm³ 3 ; in other versions ranging from approximately 0.9 to approximately 1.6 g / cm³ 3 ; in other versions, from approximately 0.9 to approximately 1.2 g / cm³ 3 ; in other versions, from approximately 0.9 to approximately 1.7 g / cm³ 3 In some embodiments, the battery electrode comprises a carbon-containing functional additive. In some embodiments, the carbon-containing functional additive can be selected from: carbon nanotubes (e.g., SWCNT, MWCNT), carbon nanofibers, carbon black, graphite, expandable graphite, graphene oxide (e.g., single-wall graphene oxide, multi-wall graphene oxide), and graphene (e.g., single-wall graphene, multi-wall graphene).

[0052] Another aspect relates to a battery electrode. In some embodiments, the battery electrode comprises one of the above-mentioned battery electrode compositions arranged on or in a current collector. In some embodiments, the battery electrode comprises a battery electrode composition and a binder. In some embodiments, the battery electrode composition comprises a population of fractured composite particles characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA). In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D) is present. 50 ) of the PSD in a range of approximately 6.0 to approximately 8.0 µm. In some embodiments, the mass fraction of the binder in the battery electrode is in a range of approximately 7 wt.% to approximately 10 wt.%.

[0053] The battery electrode (e.g., an anode comprising Si-C composite particles) can be characterized by an area-specific binder loading, defined as the mass fraction of the binder in the battery electrode divided by the product of (1) a mass fraction of the fragmented composite (e.g., nano-composite) particles in the battery electrode and (2) a specific surface area of ​​the particle population according to Brunauer-Emmett-Teller (BET). In some embodiments, the area-specific binder loading of the battery electrode (e.g., the anode comprising Si-C nano-composite particles) is in the range of approximately 2.0 mg / m². 2 up to approximately 15.0 mg / m³ 2 (e.g., in some versions of approximately 2.0 mg / m³) 2 up to approximately 5.0 mg / m³ 2 ; in other versions of approximately 5.0 mg / m³ 2 up to approximately 9.0 mg / m³ 2 ; in other versions of approximately 9.0 mg / m³ 2 up to approximately 13.0 mg / m³ 2 ).

[0054] Another aspect concerns a lithium-ion battery. In some embodiments, the lithium-ion battery comprises an anode current collector, a cathode current collector, one of the aforementioned battery electrodes arranged as the anode on or in the anode current collector, a cathode arranged on or in the cathode current collector, and an electrolyte that ionically couples the anode and the cathode.

[0055] Another aspect concerns a method for manufacturing a battery electrode, comprising steps (A1), (A2), and (A3). Step (A1) comprises providing one of the aforementioned battery electrode compositions. Step (A2) comprises preparing a slurry containing the battery electrode composition and a binder. Step (A3) comprises pouring the slurry onto or into a current collector to form the battery electrode, which may optionally include a compaction (calendering) process, namely, compacting the battery electrode to a desired value. The pouring of the slurry may also include evaporating the solvent from the slurry. In some embodiments, the coating density of the battery electrode (e.g., an anode comprising nano-composite Si-C particles) is in the range of approximately 0.8 to approximately 1.5 g / cm³. 3 (in some embodiments from about 0.8 to about 0.9 g / cm³) 3; in other embodiments from about 0.9 to about 1.0 g / cm³ 3 ; in other versions from about 1.0 to about 1.2 g / cm³ 3 ; in other versions from about 1.2 to about 1.5 g / cm³ 3 ; in other versions ranging from approximately 0.9 to approximately 1.6 g / cm³ 3 ; in other versions, from approximately 0.9 to approximately 1.2 g / cm³ 3 In some embodiments, a coating density in the range of approximately 0.9 to approximately 1.7 g / cm² is possible. 3In some embodiments, the battery electrode comprises a carbon-containing functional additive. In some embodiments, the carbon-containing functional additive can be selected from: carbon nanotubes (SWCNT or MWCNT or both), carbon nanofibers, carbon black, graphite, expandable graphite, and graphene. In some embodiments, the mass fraction of the binder in the battery electrode is in the range of approximately 7 wt.% to approximately 10 wt.%. The battery electrode can be characterized by an area-specific binder loading, which is defined as the mass fraction of the binder in the battery electrode divided by the product of (1) a mass fraction of the fractured composite particles in the battery electrode and (2) a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET). In some embodiments, the area-specific binder loading of the battery electrode (e.g.,the anode, which comprises Si-C nano-composite particles) in a range of approximately 2.0 mg / m. 2 up to approximately 15.0 mg / m³ 2 (e.g., in some versions of approximately 2.0 mg / m³) 2 up to approximately 5.0 mg / m³ 2 ; in other versions of approximately 5.0 mg / m³ 2 up to approximately 9.0 mg / m³ 2 ; in other versions of approximately 9.0 mg / m³ 2 up to approximately 13.0 mg / m³ 2 ).

[0056] Another aspect concerns a method for manufacturing a lithium-ion battery, comprising stages (B1), (B2), and (B3). Stage (B1) comprises manufacturing a battery electrode according to one of the preceding methods for manufacturing a battery electrode, wherein the battery electrode is configured as the anode and the current collector as the anode current collector. Stage (B2) comprises manufacturing or providing a cathode arranged on or in a cathode current collector. Stage (B3) comprises assembling a battery cell from the anode and the cathode (and, in some embodiments, a porous separator membrane or porous separator layer(s) between them) and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0057] Another aspect concerns a method for manufacturing a lithium-ion battery, comprising stages (C1), (C2), and (C3). Stage (C1) comprises providing one of the aforementioned battery electrodes, wherein the battery electrode is configured as an anode and the current collector as the anode current collector. Stage (C2) comprises manufacturing or providing a cathode arranged on or within a cathode current collector. Stage (C3) comprises assembling a battery cell from the anode and the cathode (and, in some embodiments, a porous separator membrane or porous separator layer(s) between them) and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0058] In one aspect, a battery electrode composition comprises a population of fractured composite particles, each of which comprises silicon and carbon; wherein: 90% or more of the fractured composite particles in the population are characterized by aspect ratios of 2.3 or less; 50% or more of the fractured composite particles in the population are characterized by aspect ratios of 1.25 or more; and the population is characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA) such that: a volume-weighted particle size parameter of the fiftieth percentile D 50 The PSD lies in a range of approximately 2.0 to approximately 8.0 µm.

[0059] In some aspects, approximately 90% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 2.1 or less.

[0060] In some aspects, approximately 50% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.35 or more.

[0061] In some aspects, approximately 10% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.3 or less.

[0062] In some aspects, the mass fraction of silicon in the fractured composite particles ranges from about 3 wt.% to about 80 wt.%.

[0063] In some aspects, the mass fraction of silicon ranges from approximately 35 wt.% to 70 wt.%.

[0064] In some aspects, the mass fraction of silicon ranges from approximately 35 wt.% to 50 wt.%.

[0065] In some aspects, the mass fraction of silicon ranges from approximately 40 wt.% to 55 wt.%.

[0066] In some aspects, the specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET) lies in a range of about 3 m². 2 / g up to about 18 m 2 / G.

[0067] In some aspects, the D 50 -value in a range of approximately 2.0 to approximately 4.0 µm.

[0068] In some aspects, the cumulative volume fraction, defined as the cumulative volume of the fractured composite particles with particle sizes of about 4.6 µm or less, divided by the total volume of all fractured composite particles, is about 90 vol% or less; and the particle sizes, cumulative volume and total volume are estimated by the LPSA.

[0069] In some aspects, the cumulative volume fraction is approximately 85% by volume or less.

[0070] In some aspects, the cumulative volume fraction is approximately 80 vol% or less.

[0071] In some aspects, the D50 in a range of approximately 6.0 to approximately 8.0 µm.

[0072] In some aspects, the specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET) lies in a range of about 3 m². 2 / g up to about 12 m 2 / G.

[0073] In one aspect, a battery electrode comprises the battery electrode composition according to claim 1, which is arranged on or in a current collector, wherein: the battery electrode comprises a binder.

[0074] In some aspects, the coating density of the battery electrode lies in a range of approximately 0.9 to approximately 1.0 g / cm². 3 .

[0075] In some aspects, the battery electrode also contains a carbon-based functional additive.

[0076] In some aspects, the carbon-containing functional additive is selected from: carbon nanotubes, carbon nanofibers, carbon black, graphite, expandable graphite, graphene oxide and graphene.

[0077] In some aspects, the D 50 -The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and the mass fraction of the binder in the battery electrode is in a range of approximately 7 wt.% to approximately 10 wt.%.

[0078] In some aspects, the D 50 -The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and the area-related binder loading of the battery electrode is in a range of approximately 9.0 mg / m² 2 up to approximately 13.0 mg / m³ 2, where the area-related binder loading is defined as a mass fraction of the binder in the battery electrode, divided by a product of (1) a mass fraction of the fractured composite particles in the battery electrode and (2) a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET).

[0079] In one aspect, a lithium-ion battery comprises an anode current collector; a cathode current collector; the battery electrode designed as the anode, whose current collector is designed as the anode current collector; a cathode arranged on or in the cathode current collector; and an electrolyte that ionically couples the anode and the cathode.

[0080] In one aspect, a process for manufacturing a battery electrode comprises (A1) providing the battery electrode composition, (A2) preparing a slurry comprising the battery electrode composition and a binder; and (A3) pouring the slurry onto or into a current collector to form the battery electrode. (Note: In some embodiments, this step may frequently include evaporating the solvent from the slurry and / or compacting the battery electrode to a desired value.)

[0081] In one aspect, a method for manufacturing a lithium-ion battery comprises (B1) manufacturing the battery electrode according to the method of (A1), (A2) and (A3), wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (B2) manufacturing or providing a cathode arranged on or in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode (and, in some embodiments, a porous separator membrane or porous separator layer(s) between them) and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0082] In one aspect, a method for manufacturing a lithium-ion battery comprises the following steps: (C1) providing the battery electrode, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (C2) manufacturing or providing a cathode arranged on or in a cathode current collector; and (C3) assembling a battery cell from the anode and the cathode (and, in some embodiments, a porous separator membrane or porous separator layer(s) between them) and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0083] Other purposes and benefits associated with the aspects disclosed here will be obvious to professionals based on the accompanying drawing and detailed description. Brief description of the drawing

[0084] The accompanying drawing serves as an aid in describing embodiments of the disclosure and is intended solely to illustrate these embodiments and not to limit them. Unless otherwise stated or implied by the context, different hatching, shading, and / or fill patterns in the drawing are used only to clarify the contrast between different components, elements, features, etc., and are not intended to convey the use of specific materials, colors, or other properties that may be defined outside of this disclosure for the specific pattern used. Fig. Figure 1 shows an example of a Li-ion battery in which the components, materials, processes and other techniques described here can be used. Fig.Figure 2 is a flowchart of a process for manufacturing a rechargeable Li-ion battery cell according to certain embodiments. Fig. Figure 3 is a flowchart of a process for producing anode (or cathode) particles according to certain embodiments, including carrying out an activation process on carbon particles. Fig. Figure 4 shows a schematic representation of a fractured particle 400 and a graphical representation 420 of a dependence of cumulative particle number distributions of fractured composite particles on the aspect ratios of the fractured composite particles. Fig. Figure 5 shows a SEM image (502) of fractured composite particles originating from a population with a D 50 -value of approximately 2.5 µm were recorded, and a SEM image (504) of jagged composite particles from a population with a D 50-value of approximately 7 µm were recorded. Fig. Figure 6 shows an SEM image 602 of fractured composite particles originating from a population with a D 50 -value of approximately 9 µm were recorded, and an SEM image 604 of jagged composite particles originating from a population with a D 50 -value of approximately 14 µm were recorded. Fig. Figure 7 shows a graphical representation of a dependency of a full width D. 90 - D 10 from D 50 for each of the exemplary populations of fractured composite particles and a graphical representation 704 of a dependence of the mass fraction of silicon in the composite particles on D 50 for each of the exemplary particle populations. Fig. Figure 8 shows SEM images (802, 804) of cross-sections of electrode coatings containing a population sample of fractured composite particles of D 50of approximately 4 µm or a population sample of fractured composite particles of D 50 of approximately 14 µm. Fig. Figure 9 shows a graphical representation of the dependence of a cycle lifetime on D. 50 for each of the example particle populations and a graphical representation 904 of a dependence of a normalized coating thickness change on D 50 for each of the example particle populations. Fig. Figure 10 shows a graphical representation of the dependence of a volumetric energy density on D. 50 for each of the example populations of fractured composite particles and a graphical representation 1004 of a dependence of a volumetric charge density on D 50 for each of the example populations of particles. Fig. Figure 11 shows a graphical representation 1102 of a dependence of a normalized high-rate discharge capacity density on D 50for each of the example populations of fractured composite particles and a graphical representation 1104 of a dependence of a discharge voltage on D 50 for each of the example populations of particles. Fig. Figure 12 shows a graphical representation 1202 of a dependence of a normalized capacity (expressed as a fraction of a reference capacity) as a function of the charging rate (charging rate C) for lithium-ion battery test cells, the populations of fractured composite particles of D 50 from about 3 µm to about 5 µm. Fig. Figure 13 shows a graphical representation 1302 of a dependence of a first-cycle efficiency on D 50 for each of the example particle populations and a graphical representation 1304 of a dependence of a formation efficiency on D 50 for each of the example particle populations. Fig.Figure 14 shows a graphical representation 1402 of a dependence of an internal resistance on D 50 for each of the example populations of fractured composite particles and a graphical representation 1404 of a dependence of a coating density on D 50 for each of the example populations of particles. Fig. Figure 15 shows a graphical representation 1502 of a dependence of a specific surface according to Brunauer-Emmett-Teller (BET-SSA) on D 50 for each of the example populations of fractured composite particles and a graphical representation 1504 of a dependence of an area-related binder loading on D 50 for each of the example particle populations. Fig. Figure 16 shows a graphical representation 1602, which illustrates the relationship between cycle lifetime values ​​and cumulative volume fractions (D). 50 -threshold of 4.6 µm) for populations of fractured composite particles with D 50-values ​​in a range of approximately 2.0 µm to approximately 4.0 µm. The cumulative volume fraction is defined as the cumulative volume of particles with D 50 -values ​​from a D 50 -threshold value or less, divided by the total volume of all particles. Fig. Figure 17 shows a graphical representation (1702) of the dependence of an area-related binder loading on the mass fraction of the binder in each test cell. The test cells contained populations of fractured composite particles with D 50 -values ​​of approximately 7.42 µm. The test cell of the control sample contained a particle population with a D 50 -value of approximately 5.35 µm. Fig. Figure 18 shows a graphical representation of the dependence of cycle lifetime on the mass fraction of the binder in each of the test cells. Fig.17 and a graphical representation 1804 of a dependence of a normalized coating thickness change on the binder mass fraction of each of the test cells of Fig. 17. Fig. Figure 19 shows a graphical representation from 1902 of a dependence of a volumetric energy density (VED) on the mass fraction of the binder for each of the test cells of Fig. 17 and a graphical representation from 1904 of a dependence of a volumetric charge density (VQD) on the mass fraction of the binder for each of the test cells of Fig. 17. Fig. Figure 20 shows a graphical representation from 2002 of the dependence of a discharge voltage on the mass fraction of the binder for each of the test cells. Fig. 17 and a graphical representation from 2004 of the dependence of the internal resistance on the mass fraction of the binder for each of the test cells of Fig. 17. Fig.Figure 21 shows a graphical representation 2102 of a dependence of a formation efficiency on the mass fraction of the binder for each of the test cells of Fig. 17 and a graphical representation 2104 of a dependence of an efficiency of the first cycle on the mass fraction of the binder for each of the test cells of Fig. 17. Fig. Figure 22 shows an SEM image (2201) of a population of fractured composite particles (including agglomerates of fractured particles) without any optimization of the population's particle size distribution (PSD), and an SEM image (2202) of a cross-section of an electrode coating comprising a mixture of the fractured particle population shown in 2201 and graphite particles as the active electrode material. 50 The population size is approximately 10 µm, and the population consists of fine particles (“fine grain”) and coarse particles. Fig.Figure 23 shows an SEM image (2301) of a population of fractured composite particles after optimization of the population's particle size distribution (PSD) and an SEM image (2302) of a cross-section of an electrode coating comprising a mixture of the fractured particles shown in 2301 and graphite particles. Before optimization of its PSD, the population had a D 50 -value of approximately 10 µm. The PSD optimization process included the removal of fine particles (the removed fine particles had a D 50 -value of approximately 1.5 µm) and the removal of coarse particles (the removed coarse particles had a D 50 -value of approximately 15 µm). Fig. Figure 24 shows the graphical representations 2401 and 2402 of the volume-weighted particle size distributions (PSDs) of example populations of fractured composite particles. Graphical representation 2401 shows the PSDs of example populations of the respective D 50-values ​​that exhibit relatively wide PSDs, before optimization of the respective PSDs. Graphical representation 2402 shows (1) the PSD of an example population before optimization of its PSD (D 50 -value of approximately 10.1 µm) and (2) the PSD of an example population after optimization of its PSD (D 50 -value of approximately 9.8 µm). PSD optimization involves the removal of fine and coarse particles. As a result of these PSD optimization processes, the PSD changes from a relatively broader PSD (e.g., larger span, larger FWHM) to a relatively narrower PSD (e.g., smaller span, smaller FWHM). Fig. 25 shows a Table 1 with selected characteristics (D 10 , D 50 , D 90 , D 99 , span, FWHM, D 10 / D 50, BET-SSA, and whether the population was not subjected to any optimization of its PSD (so-called “broad” PSD) or to an optimization of its PSD (so-called “narrow” PSD)) of example populations of fractured composite particles, as well as selected properties (estimated capacity of the active electrode material comprising the respective fractured composite particles and graphite particles, electrode coating density and cycle life) of electrode coatings and battery cells derived from the respective example populations of fractured composite particles. Fig. Figure 26 shows an SEM image (2601) of a population of spheroidal composite particles. In the example shown, the D 50 -Value of the population in a range of approximately 5 to approximately 7 µm. Fig.Figure 27 shows a graphical representation 2701, which shows the dependence of the BET-SSA values ​​of example populations of composite particles (fractured composite particles before PSD optimization (which have so-called “wide” PSDs), fractured composite particles after PSD optimization (which have so-called “narrow” PSDs) and spheroidal particles) on their respective D 50 -values ​​shown. In the example shown, the D 50 -Values ​​measured with LPSA. Fig. Figure 28 shows graphs 2802, 2804, and 2806 of selected PSD characteristic curves of example populations of fractured composite particles. Graph 2802 shows the dependence on D 99 -values ​​from the D 50-values ​​of the respective populations of fractured composite particles and illustrates the trends between populations that were not subjected to PSD optimization (so-called "wide" PSDs) and populations that were subjected to PSD optimization (so-called "narrow" PSDs). Graphic 2804 shows the dependence of D 90 -values ​​from the D 50 -values ​​of the respective populations of fractured composite particles and illustrates the trends between populations that were not subjected to PSD optimization (so-called "wide" PSDs) and populations that were subjected to PSD optimization (so-called "narrow" PSDs). Graphic 2806 shows the dependence of D 10 -values ​​from the D 50-values ​​of the respective populations of fractured composite particles and illustrates the trends between populations that were not subjected to PSD optimization (so-called “wide” PSDs) and populations that were subjected to PSD optimization (so-called “narrow” PSDs). Fig. Figure 29 shows the graphs 2901 and 2902, which show the dependence of the cycle life of Li-ion batteries produced using the respective example populations of fractured composite particles on the D 50-values ​​of the respective example populations are shown. Graphs 2901 and 2902 illustrate the trends between populations that were not subjected to PSD optimization (so-called "broad" PSDs) and populations that were subjected to PSD optimization (so-called "narrow" PSDs). In the examples shown, anodes containing a mixture of the fractured composite particles and graphite particles ("active material mixtures") were used for the Li-ion batteries. Graph 2901 shows the cycle life of Li-ion batteries with active material mixtures that have a Li-ion capacity of approximately 600 mAh / g. Graph 2902 shows the cycle life of lithium-ion batteries with active material mixtures that have a lithium-ion capacity of approximately 1000 mAh / g. Fig.Figure 30 shows the graphical representations 3002, 3004, 3006 and 3008, which illustrate the dependence of selected PSD characteristic curves of example populations of fractured composite particles on the D 50 -values ​​of the example populations show. In the in Fig. In the 30 examples shown, the PSDs of the respective populations were modified by comminution (either by jet milling or ball milling). Graphs 3002, 3004, 3006, and 3008 illustrate the trends between populations subjected to ball milling and populations subjected to jet milling. The PSD characteristics shown are the range for 3002, D 90 for 3004, D 10 for 3006 and the volume fraction of fine particles (defined as particles with a diameter of 1 µm and below, measured by LPSA) in the population for 3008. Detailed description

[0085] Aspects of the present invention are disclosed in the following description and the accompanying drawings, which relate to specific embodiments of the invention. The term "embodiments of the invention" does not require that all embodiments of the invention include the discussed feature, advantage, method, or mode of operation, and alternative embodiments may be developed without departing from the scope of the invention. Furthermore, known elements of the invention may not be described in detail or may be omitted so as not to obscure other, more important details.

[0086] Aspects of the present disclosure provide for processes for the production of advanced carbonaceous (e.g., mostly graphitic, sp 2-bonded carbon containing) composite particles for use in electrodes (e.g. anode or cathode electrodes) of rechargeable Li-ion or Na-ion or K-ion batteries, among other types of batteries, electrochemical capacitors and hybrid electrochemical energy storage devices.

[0087] Each numerical range described herein in relation to an embodiment of the present invention is intended not only to define the upper and lower limits of the associated numerical range, but also, as an implicit representation, to represent each discrete value within that range in units or increments corresponding to the precision level by which the upper and lower limits are characterized. For example, a numerical spacing range from 7 nm to 20 nm (i.e., a precision level in units or increments of one) comprises (in nm) a series of [7, 8, 9, 10, ..., 19, 20], as if the intermediate numbers 8 to 19 were explicitly specified in units or increments of one. In another example, a temperature range from about -120 °C to about -60 °C comprises a series of temperature ranges from about -120 °C to about -119 °C, from about -119 °C to about -118 °C, ...from approximately -61 °C to approximately -60 °C, as if the intermediate values ​​(in °C) between -120 °C and -60 °C were explicitly specified in incremental ranges. In another example, a numerical percentage range from 30.92% to 47.44% (i.e., a precision level in units or hundredths) (in %) encompasses a set of [30.92, 30.93, 30.94, ..., 47.43, 47.44], as if the intermediate values ​​between 30.92 and 47.44 were explicitly specified in units or hundredths. Therefore, each of the intermediate values ​​encompassed by a given numerical range is to be interpreted as if those intermediate values ​​had been explicitly specified, and each such intermediate value can thus represent its own upper and / or lower bound of a subrange falling within the wider range. Each sub-area (e.g.Any range that contains at least one intermediate number from the broader range as an upper and / or lower bound is to be understood as being implicitly specified by the explicit statement of the broader range. Another example: A numerical range with upper and lower bounds defined at different precision levels is to be interpreted in increments corresponding to the bound with the higher precision level. Thus, for example, B. a numerical percentage range from 30.92% to 47.4% (i.e., precision levels in units or increments of hundredths or tenths) (in %) a series of [30.92, 30.93, 30.94, ..., 47.39, 47.40] (in %) as if 47.4% (tenths) were specified as 47.40% (hundredths) and as if the intermediate numbers between 30.92 and 47.40 were explicitly stated in units or increments of hundredths.

[0088] It is clear that the accuracy of a given measurement, threshold, or other imprecise parameter can depend on various factors such as measuring instruments, environmental conditions, and so on. In the following, references to such measurements or thresholds can be interpreted as a corresponding value that implies pseudo-exact accuracy (e.g., a threshold of 80% encompasses 80.0000...%). Alternatively, references to such measurements or thresholds can be described by a qualifier that captures a pseudo-exact value(s) as well as a range extending above and / or below the pseudo-exact value(s). For example, the aforementioned threshold of 80% can be interpreted as "about," "approximately," "around," "≈," or "~" 80%, which encompasses "exactly" 80% (e.g., 80.0000...%) plus a range around 80%.In some embodiments, the range around a measurement or threshold described by the qualifier “about”, “approximately”, “around” or “~” may include the degree of accuracy for which the measurement or threshold in question can be measured using the most accurate instruments commercially available at the priority date of the application in question.

[0089] Although the following description includes specific examples related to Li-metal and Li-ion batteries (for reasons of brevity and convenience, and due to the current popularity of Li-technology), it is clear that various aspects are also applicable to other rechargeable and primary batteries (such as Na and Na-ion, Mg and Mg-ion, K and K-ion, Ca and Ca-ion and other metal and metal-ion batteries, alkaline batteries, flow batteries, etc.), as well as to electrochemical capacitors and hybrid energy storage devices.

[0090] While the following description includes specific examples related to composite materials that incorporate alloy-type active anode materials (such as Si, Sn, Sb, Al, etc.), it is clear that various aspects also apply to conversion-type active anode and cathode materials, intercalation-type active anode and cathode materials, pseudocapacitance-type active anode and cathode materials, and materials with mixed electrochemical energy storage mechanisms. It should be noted that the choice of high-performance alloy-type (conversion-type) anode material may differ for Na and Na⁺ ions, Mg and Mg⁺ ions, K and K⁺ ions, Ca and Ca⁺ ions, and Li or Li⁺ ions. For example, while Si may be a preferred alloy material for Li⁺ or Li⁺-ion batteries, Sn or Sb, or Sn- or Sb-containing alloys, may be a preferred alloy material for Na⁺ or Na⁺-ion batteries.

[0091] While the following description may also describe certain examples of material formulations in a Li-free state (e.g., silicon-containing nano-composite anodes or metal fluoride cathodes), it is clear that various aspects are also applicable to Li-containing electrodes and active materials (e.g., partially or fully lithiated Si-enclosing anodes or partially or fully lithiated Si-enclosing anode particles, partially or fully lithiated metal fluoride-enclosing cathodes (such as a mixture of LiF and metals such as Cu, Fe, Ni, Bi and various other metals and metal alloys and mixtures of such and other metals, etc.).) or partially or fully lithiated metal halides with cathode particles, partially or fully lithiated chalcogenides (such as Li₂S, Li₂S / metal mixtures, Li₂Se, Li₂Se / metal mixtures, Li₂S-Li₂Se mixtures, various other compositions with lithiated chalcogenides, etc.), partially or fully lithiated metal oxides (such as Li₂O, Li₂O / metal mixtures, etc.), partially or fully lithiated carbons, etc.). In some formulations, various material properties (e.g., at the particle level, at the interparticle level, at the electrode level, etc.) can change depending on whether the particles of active material are in a Li-free state, a partially lithiated state, or a fully lithiated state. Such Li-dependent material properties can include the pore volume of the particles, the pore volume of the electrodes, etc.Unless otherwise stated or implied, Li-dependent material properties (e.g., at the particle level, at the interparticle level, at the electrode level, etc.) are described as if the particles of active material were in a Li-free state. Furthermore, some of the examples below are characterized at the electrode level (e.g., as opposed to the particle level, interparticle level, or cell level, etc.). Unless otherwise stated or implied, references to electrode properties (e.g., electrode porosity, area-specific capacitance loading, gravimetric / volumetric capacitance, etc.) are understood to refer to the electrode components (e.g., particles of active material, binders, conductive additives, etc.) and not to the current collector.

[0092] The following description details various material properties for characterizing materials (e.g., molecules, particles, powders, slurries, electrodes, separators, electrolytes, battery cells, etc.) in different states. It should be noted that a person skilled in the art is generally able to select the most suitable measurement technique for a given measurement (and this is assumed here). Furthermore, in some cases, the most suitable measurement technique may be a combination of techniques. While the following table describes various measurement options for specific material types and specific material properties, certain embodiments of the disclosure may be set out in more detail in connection with a specific measurement technique and / or a specific commercially available measuring instrument, where justified.Note that while the table below describes measurements relating to particles of active material, similar measurements can also be performed on other particle types, such as precursor particles (e.g., carbon particles, etc.). Unless otherwise stated, the table below provides examples of how such material properties can be easily measured by a person skilled in the art using commercially available measuring instruments. Table of techniques and instruments for measuring material properties Type of material Characteristic Instrumentation for measurement Measurement technology Active material Coulomb efficiency Potentiostat A charge (current) is applied to an electrode containing the active material until a specific voltage limit is reached. The current is then reversed (discharge current) until a second voltage limit is reached. The ratio of the two charges passed through determines the Coulomb efficiency (CE). In the simplest case, the charging and discharging currents can be constant and often have absolute values ​​that are equal or close to each other. However, it should be clear that in some experiments, either the charging current or the discharging current, or both, can change during such experiments (e.g., they can initially be constant and then drop to a predetermined value upon reaching the voltage limit). Furthermore, the absolute values ​​of the charging and discharging currents can differ. Active material Partial vapor pressure (e.g. in Torr.) at manometer The partial vapor pressure of an active material in a mixture (e.g., of a temperature (e.g. in K) The vapor pressure of the active material (composite particles) at a specific temperature is calculated by multiplying the known vapor pressure of the active material by its molar fraction in the mixture. Particle-active material volume Gas pycnometer Gas pycnometers measure the skeletal volume of a material by gas displacement using the volume-pressure relationship of Boyle's law. A sample with a known mass is placed in the sample chamber and kept at a constant temperature. An inert gas, usually helium, is used as the displacement medium. Note: A change in volume percent can be calculated from two volume measurements of the particle of active material. Particle-active material Volume of the opening indicates the pore (e.g. in cc / cm) 3 / g) Nitrogen sorption / desorption isotherm The nitrogen sorption / desorption isotherm (typically at 77 K) is recorded and analyzed to estimate the total amount of adsorbed / desorbed gas, and the internal pore volume of the sample with known mass is estimated from these measurements. Furthermore, the pore size distribution (PSD) can be determined from the sorption / desorption isotherm using various analyses. such as nonlocal density functional theory (NLDFT). Particle-active material Volume average pore size and pore size distributions (e.g. in nm) PSA, Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Scanning Transmission Microscope (RTEM), Laser Microscope, Synchrotron X-rays, X-ray Microscope PSA using laser scattering, electron microscopy (SEM, TEM, RTEM) in combination with image analysis, laser microscopy (for larger particles and larger pores) in combination with image analysis, optical microscopy (for larger particles and larger pores), neutron scattering, X-ray scattering, and X-ray microscopy imaging can be used to measure pore sizes (average pore size or pore size distribution) in various size ranges (in addition to analyzing sorption / desorption isotherms). Particle-active material Closed internal pore volume (e.g. in cc / g or cm 3 / g) Gas pycnometer The closed porosity can be measured by analyzing the actual density values ​​measured with an argon gas pycnometer and comparing them with the theoretical density of the individual material components in Si-containing particles. Furthermore, the closed internal pore volume can be determined by comparing it with the neutron scattering results. The estimated total pore volume can be estimated using the nitrogen accessible pore volume estimated from the nitrogen sorption isotherm. Particle-active material Average size of closed internal volume (e.g., in nm) Gas pycnometer A pycnometer can be used to determine the amount of a specific medium (liquid or helium or other analytical gases) that is displaced by a solid. Particle-active material Size (e.g. in nm, µm, etc.) TEM, RTEM, SEM, X-rays, PS selection. Laser particle size distribution analysis (LPSA), laser image analysis, electron microscopy, optical microscopy or other suitable methods, transmission electron microscopy (TEM), scanning transmission electron microscopy (RTEM), scanning electron microscopy (SEM), X-ray microscopy, X-ray diffraction, neutron scattering and other suitable methods Particle-active material Composition (e.g. mass fraction or wt.%, mg, number of atoms, etc.) Scale Note 1: A weight percentage change can be calculated by comparing the mass fraction of a material in the particle relative to the total particle mass. Note 2: The capacity assigned to a given active The material to which a particle is attributed can be deduced from its composition, based on the known (e.g., theoretically or practically achievable) capacitance(s) of each active material. Note 3: The composition of the particle can be expressed as its weight (e.g., in mg). The composition can also be expressed by the number of atoms of a particular element (e.g., Fe, F, C, etc.). In the case of atoms, the number of atoms can be estimated from the weight of the atom in the particle (e.g., based on gas chromatography). Particle-active material Composition (e.g. mass fraction or wt.% of various atomic elements or molecules, atomic fraction or atom-% of the various elements, etc.) X-ray fluorescence (XRF), inductively coupled plasma optical emission spectroscopy (ICP-OES); energy-dispersive spectroscopy (EDS), wavelength-dispersive spectroscopy (WDS), electron energy loss spectroscopy (EELS), nuclear magnetic resonance (NMR); secondary ion- Mass spectrometry (SIMS); X-ray photoelectron spectroscopy (XPS); Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy (Raman) Particle-active material, battery half-cell Specific capacity Potentiostat An electrode containing an active anode or cathode material of interest is charged or discharged within specific potential limits using an electrochemical cell with a suitable reference electrode, usually lithium metal (by passing an electric current to the electrode). The total charge passed (e.g., in mAh) divided by the mass of the active material (e.g., in g) yields this quantity (e.g., in mAh / g). The active mass is calculated by multiplying the total mass of the electrode by the mass fraction of the active material. Both the reversible and irreversible capacitance during charging or discharging can be calculated in this way. Particle-active material BET SSA(z.B. in m 2 / g) BET instrument A sample is placed in a sealed chamber at 77 K, into which nitrogen is added. The process is initiated with increasing pressure. The pressure change of the nitrogen is used to calculate the surface area of ​​the sample. Particle-active material aspect ratio REM, TEM The dimensions and shape of the particles are usually measured using SEM or TEM or (in the case of large particles) using optical microscopy. Particle-active material True density of the particle (e.g. in g / cc or g / cm³) 3 ) Argon gas pycnometer The actual density can be measured with an argon gas pycnometer and compared with the theoretical density of the individual material components present in the particle. particle population of inert material Particle size distribution (e.g. in nm or µm) Dynamic light scattering particle size analyzer, scanning electron microscope Laser particle size distribution analysis (LPSA) of well-dispersed particle suspensions can be performed, either by image analysis of electron micrographs or by other suitable techniques. While various methods exist for measuring particle size distributions (PSDs), LPSA is quite efficient for some applications. It should be noted that other methods of particle size distribution analysis (e.g., by SEM image analysis) can also be used. (and in some experiments can even lead to more accurate measurements). With LPSA, particle size parameters of the PSD of a population can be measured, such as: a volume-weighted particle size parameter of the tenth percentile (e.g. abbreviated as D10), a volume-weighted particle size parameter of the fiftieth percentile (e.g. abbreviated as D50), a volume-weighted particle size parameter of the ninth percentile (e.g. abbreviated as D90), and a volume-weighted particle size parameter of the ninetieth percentile (e.g. abbreviated as D99). particle population of inert material Width (e.g. inm) PSA From these particle size parameters, parameters can be derived that relate to characteristic widths of the PSD, such as D50 - D10 (sometimes referred to here as left width), D90 - D50 (sometimes referred to here as right width) and D90 - D10 (sometimes referred to here as full width). particle population of inert material Cumulative volume share 1 Calculated using LPSA data A cumulative volume fraction, defined as the cumulative volume of the composite particles with particle sizes of a threshold particle size or Less, divided by the total volume of all composite particles, can be estimated by LPSA. particle population of inert material Composition (e.g., in wt.%) Scale The mass of the active materials added to the electrode, divided by the total mass of the electrode. particle population of inert material BET SSA(z.B. in m 2 / g) BET isotherm Obtained from nitrogen sorption-desorption data at cryogenic temperatures, such as 77 K electrolyte Salt concentration (e.g. in M ​​or mol-%) Scales, volumetric pipette The total volume of the solution is calculated either by summing the volumes of the components (measured with a volumetric pipette) or by dividing the mass of the components by their density. The molar mass of the salt is then used to calculate the total number of moles of salt in the solution. The number of moles of salt is then divided by the total volume to obtain the solvent concentration in M ​​(mol / L). electrolyte Solvent concentration (e.g., in moder, mol-%) Scales, volumetric pipette The total volume of the solution is calculated either by the sum of the volumes of the components (measured with a volumetric pipette) or by dividing the mass of the components by their density. The molar volume of each solvent This is then used to calculate the total number of solvent moles in the solution. The number of solvent moles is then divided by the total volume to obtain the solvent concentration in M ​​(mol / L). electrode Composition (e.g. as mass fraction or wt.%) Scale The mass fraction of a material (e.g., active material, particles of the active material, binder, etc.) in the electrode is calculated based on a measured or estimated mass of the material and a measured or estimated mass of the electrode, excluding the electrode current collector. Note: The mass of the individual components (e.g., particles of the active composite material, graphite particles, binder, functional additives, etc.) of the battery electrode composition can be measured before mixing to a slurry to estimate their mass in a cast electrode. The mass of the materials deposited on the cast electrode can be determined by comparing the weight of the cast electrode before and after. The material deposition can be measured. electrode Binder loading per unit area (e.g. in mg / m²) 2 ) Scale Mass fraction of the binder in the battery electrode, divided by a product of (1) a mass fraction of the particles of the active material (e.g. Si-C nano composite, etc.) in the battery electrode and (2) a specific surface area of ​​the particle population of the active material according to Brunauer-Emmett-Teller (BET). electrode Capacity allocated to the active material (proportion of the active material capacity) Calculated Measure the mass (weight) of the active material in the electrode and calculate the electrode capacitance based on the known theoretical capacitance of the active material. For example, the average weight fraction of the active material in each particle-active material can be measured and used to calculate the mass of the active material based on the mass of the particles of active material before mixing in the slurry. This process can be repeated if the electrode contains two or more active materials to calculate the relative capacitance allocation for each active material in the electrode. electrode Capacity attributable to particle-active material (capacity fraction of particle-active material) Potentiostat and scale Determine the average specific capacitance (in mAh / g) of the active material particles. The average specific capacitance can be estimated, for example, from the average weight fraction of the active material(s) in each particle and the associated known theoretical capacitance(s). Subsequently, the mass (weight) of the active material particles in the electrode is measured before mixing in the slurry, which can be used to calculate the capacitance to be attributed to the active material. This process can be repeated if the electrode contains two or more types of active material particles to calculate the relative capacitance assignment for each type of active material particle in the electrode. electrode Mass of inactive material in the electrode Scale The average weight fraction (wt%) of inactive material in each particle of active material can be measured and used to calculate the mass of inactive material based on the mass of the particles of active material prior to the measurement. used for mixing in the slurry. electrode Mass of particle-active material in the electrode Scale Measuring the particle active material before the type of particle active material is mixed into the slurry. electrode Area-related capacity loading (e.g. in mAh / cm²) 2 ) Potentiostat and scale The area-related capacitance loading is the weight of the coated active material per unit area (g / cm²). 2 )multiplied by the gravimetric capacity of the active material (not the electrode, but the active material itself without binder and without electrolyte; in mAh / g). electrode Coulomb efficiency Potentiostat The change in charge input to (or output from) an electrode divided by the charge output to (or output from) the electrode during a complete electrochemical cycle within specific voltage limits. Since the direction of charge flow is opposite at cathodes and anodes, the definition depends on the electrode. The Coulomb efficiency is measured for both materials by constructing a so-called half-cell, a An electrochemical cell consisting of a cathode or anode material of interest as the working electrode and a lithium metal foil serving as both the counter and reference electrode. Charge is then either added to or removed from the material in question until the cell voltage reaches a suitable limit. The process is then reversed until a second voltage limit is reached, and the charge passed through in both steps is used to calculate the Coulomb efficiency, as described above. Battery cell Installment payment Potentiostat This is the time required to charge or discharge a battery between a specific state of charge. It is measured by charging or discharging a battery and measuring the time until a certain amount of charge has passed through or until the battery's operating voltage reaches a specific value. Battery cell Cell discharge voltage (e.g. in V) Potentiostat A battery consisting of a corresponding anode and cathode is charged and discharged within certain voltage limits, and the The charge-weighted cell voltage during discharge is calculated. Battery cell Operating temperature Potentiostat and thermocouples Average temperature of the battery cell, measured at the positive / negative terminal / cell shaft, etc., during the charging / discharging process or at a specific voltage level or while a load is applied, etc. Battery half-cell Anode discharge (delithiation) potential (e.g. in V) Potentiostat An electrode containing an active anode material (or a mixture of active materials) of interest is charged and discharged within specific potential limits using an electrochemical cell with a suitable reference electrode, usually lithium metal (by passing an electric current to the electrode). The cell potential averaged over the charge during both discharges (corresponding to the delithiation of the anode) is calculated. Battery half-cell Cathode discharge (lithiation) potential (e.g., in V) Potentiostat An electrode containing an active cathode material (or a mixture of active materials) of interest is charged and discharged within specific potential limits using an electrochemical cell with a suitable reference electrode, usually lithium metal (by electrically (current is passed to the electrode). The cell potential averaged over the charge of both discharges (corresponding to the lithiation of the cathode) is calculated. Battery cell Volumetric Energy Density(VED) Potentiostat The VED is calculated by first calculating the energy per unit area of ​​the battery and then dividing the energy per unit area by the sum of the illustrative anode, cathode, separator and current collector thicknesses. Battery cell Internal resistance (impedance) Potentiostat The internal resistance (also referred to as impedance in many contexts) is measured by applying small current pulses to the battery cell and recording the instantaneous change in cell voltage.

[0093] In some of the embodiments described below, certain parameters (e.g., temperature, state of charge (SOC), etc.) are defined using relative terms such as low, reduced, high, increased, boosted, etc. With regard to temperature, unless otherwise specified, this term may refer to the storage temperature of the battery cell or the operating temperature of the battery cell, depending on the context of the particular example. With regard to SOC, unless otherwise specified, a high SOC may be defined as higher than approximately 70% SOC (e.g., approximately 70–80% SOC in some embodiments; approximately 80–90% SOC in some embodiments; approximately 90–100% SOC in some embodiments).

[0094] The following refers to various battery electrode compositions. Such battery electrode compositions may be in the form of a “dry” powder (e.g., before being mixed into or suspended in a slurry), in the slurry itself (e.g., in a suspended state), or in a cast electrode (e.g., cast onto and / or into a current collector to form an electrode, bound together with a suitable binder, dried, and optionally coated and / or calendered).

[0095] While the following description provides certain examples related to Si-C composite (e.g., nano-composite) anode active materials (e.g., nano-composite particles containing silicon (Si) and carbon (C) (e.g., mostly graphitic, sp 2-bonded carbon) and other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), to name just a few, and where a total mass of Si and C atoms can constitute about 75 wt.% to about 100 wt.% of the total mass of the composite material), it is understandable that various aspects may be applicable to other types of silicon-containing high-capacity active anode materials (including, but not limited to, for example, various silicon-containing or silicon oxide-containing or silicon nitride-containing or silicon oxynitride-containing or silicon phosphide-containing particles, or particles containing a mixture or alloy or other combinations of such active materials, various other types of Si-containing composites, including, but not limited to, core-shell or hierarchical or nano-composite particles, etc.).

[0096] While the following description may include certain examples related to some specific alloy and conversion-type chemistries of active anode and cathode materials for lithium-ion batteries (e.g., silicon-containing anodes or metal fluoride-containing or lithium sulfide-containing cathodes), it is clear that various aspects are also applicable to other lithium-ion battery chemistries (other conversion and alloy-type electrodes as well as various intercalation-type anodes and cathodes) and to other battery chemistries.In the case of metal-ion batteries (such as Li-ion batteries), examples of other suitable conversion-type electrodes include, but are not limited to, metal fluorides, metal chlorides, metal iodides, metal bromides, sulfur, metal sulfides (including but not limited to lithium sulfide), selenium, metal selenide (including but not limited to lithium sulfide), metal oxides, metal nitrides, metal phosphides, metal hydrides, their various mixtures, composites (including nano-composites) and alloys, and others.

[0097] While the following description may describe certain examples related to fractured (e.g., Si-containing, such as Si-C, etc.) nano-composite particles with a relatively small range of aspect ratios, it will be understood that various aspects are applicable to other forms of (e.g., Si-containing, such as Si-C, etc.) nano-composite particles, including, but not limited to, cylindrical or fibrous (e.g., Si-containing, such as Si-C, etc.) nano-composite particles (e.g., with aspect ratios in the range of about 1 to about 200; in some formulations from about 1 to about 5; in other formulations from about 5 to about 10; in other formulations from about 10 to about 200), spherical or spheroidal particles, to name just a few illustrative examples.

[0098] During the operation of a battery (e.g., a lithium-ion battery), the conversion materials change (convert) from one crystal structure to another (hence the name "conversion" type). This process also involves the breaking of chemical bonds and the formation of new ones. During the operation of (e.g., Li-ion) batteries, lithium ions are introduced into alloy-type materials, forming lithium alloys (hence the name "alloy"-type materials). Sometimes, alloy-type electrode materials are considered a subclass of conversion-type electrode materials.

[0099] In one or more embodiments of the present disclosure, a preferred anode for a battery cell may comprise a mixture of Si-C nanocomposite (e.g., particles) and graphite (e.g., particles) as the active anode material, a so-called mixed anode. In addition to the particles of active anode material, an anode may contain inactive material such as binders (e.g., polymer binders) and other functional additives (e.g., surfactants, electrically conductive additives). In some embodiments, the active anode material may constitute approximately 90 wt.% to approximately 98 wt.% of the anode. The particles of active anode material may, for example, constitute approximately 95.5 wt.% of the anode. In some embodiments, mixed anodes may comprise Si-C nanocomposites (e.g., particles) with a proportion of approximately 7 wt.% to approximately 75 wt.% of the anode, while the graphite (e.g., particles)The active anode material constitutes the remainder of the mass (weight) of the particles. In some embodiments where the active anode material particles constitute approximately 95.5 wt.% of the mixed anode, the mixed anode (including the active and inactive material particles) may comprise approximately 7 wt.% Si-C nanocomposite (e.g., particles) and approximately 88.5 wt.% graphite particles. In some embodiments where the active anode material particles constitute approximately 95.5 wt.% of the mixed anode, the mixed anode (including the active and inactive material particles) may comprise approximately 19 wt.% Si-C nanocomposite (e.g., particles) and approximately 76.5 wt.% graphite particles. In some embodiments, where the particles of active anode material constitute approximately 95.5 wt.% of the mixed anode, the mixed anode (including the particles of active and inactive material) may contain approximately 35 wt.The mixed anode may comprise approximately 50 wt% Si-C nano-composite (e.g., particles) and approximately 60.5 wt% graphite particles. In some embodiments where the active anode material particles constitute approximately 94.5 wt% of the mixed anode, the mixed anode (including the active and inactive material particles) may comprise approximately 50 wt% Si-C nano-composite (e.g., particles) and approximately 44.5 wt% graphite particles. In some embodiments where the active anode material particles constitute approximately 92.5 wt% of the mixed anode, the mixed anode (including the active and inactive material particles) may comprise approximately 69.4 wt% Si-C nano-composite (e.g., particles) and approximately 23.1 wt% graphite particles. In some designs, a higher proportion of Si-C composite particles in the mixed anode can benefit from a higher proportion of inactive material to achieve better cycle stability and other performance characteristics.

[0100] While the following descriptions may also describe certain examples of mixed anode formulations expressed as mass (wt%) of the Si-C nanocomposite (e.g., the particles), it is understood that various aspects of this disclosure are applicable to mixed anode formulations expressed as wt% Si in the anode. In some embodiments, a mixed anode composition of about 7 wt% Si-C nanocomposite (e.g., particles) may, for example, correspond to about 3-3.5 wt% Si in the mixed anode. In some embodiments, a mixed anode composition of about 19 wt% Si-C nanocomposite corresponds to about 8-9.5 wt% Si in the mixed anode. In some embodiments, a mixed anode composition of about 35 wt% Si-C nanocomposite (e.g., particles) corresponds to about 15-18 wt% Si in the mixed anode.In some embodiments, a mixed anode composition of approximately 50 wt.% Si-C nano-composite (e.g., particles) corresponds to approximately 21–30 wt.% Si in the mixed anode. In corresponding embodiments, mixed anodes can be obtained in which the mass (weight) of silicon is in the range of approximately 3 wt.% to approximately 30 wt.% of the total mass of the anode.

[0101] While the following descriptions may also describe certain examples of mixed anode formulations expressed as the mass (wt%) of the Si-C nanocomposite (e.g., the particles) relative to the total active material in the anode, it is understandable that various aspects of this disclosure are applicable to mixed anode formulations that attribute a fraction (e.g., %) of the total mixed anode capacity to the Si. In some embodiments, approximately 25% of the total mixed anode capacity is derived from the Si-C nanocomposite (e.g., particles) in a mixed anode composition of approximately 7 wt% Si-C nanocomposite (e.g., particles) and approximately 93 wt% graphite (e.g., particles). In some other embodiments, approximately 50% of the total capacity of the mixed anode is derived from the Si-C nano-composite material (e.g., particles) in a mixed anode composition of approximately 19 wt.In some embodiments, approximately 70% of the total capacity of the mixed anode is derived from the Si-C nanocomposite (e.g., particles) and approximately 81 wt% graphite (e.g., particles). In other embodiments, approximately 70% of the total capacity of the mixed anode is derived from the Si-C nanocomposite in a mixed anode composition of approximately 35 wt% Si-C nanocomposite (e.g., particles) and approximately 65 wt% graphite (e.g., particles). In other embodiments, approximately 80% of the total capacity of the mixed anode is derived from the Si-C nanocomposite (e.g., particles) in a mixed anode composition of approximately 50 wt% Si-C nanocomposite (e.g., particles) and approximately 50 wt% graphite (e.g., particles). Note that the percentage of the Si-C nano composite (e.g., the particles) in the total capacity of the mixed anode depends on both the weight percent of these particles (e.g., in relation to the total active material in the anode) and the specific capacity of the Si-C nano composite.Si-C nano-composite particles with higher specific capacity, for example, offer a higher percentage of the total capacity at the same wt.%.

[0102] While the following description may describe certain examples of suitable intercalation-type graphites for use in combination with Si-C nanocomposites (e.g., particles) in a mixture, it is understood that various aspects of this disclosure are applicable to synthetic soft-type graphite (or soft carbon in the broadest sense), synthetic hard-type graphite (or hard carbon in the broadest sense), and natural graphite (which may, for example, be coated with pitch coal); including, but not limited to, those exhibiting a discharge capacity of about 320 to about 372 mAh / g (e.g., in some formulations of about 320 to about 350 mAh / g; or in other formulations of about 350 to about 362 mAh / g; or in other formulations of about 362 to about 372 mAh / g).372 mAh / g); including, but not limited to, those exhibiting low, moderate and high swelling; including, but not limited to, those exhibiting good and poor compression; including, but not limited to, those exhibiting a specific surface area according to Brunauer-Emmett-Teller (BET) of approximately 1 to approximately 4 m². 2 exhibiting / g; including, but not limited to, those exhibiting a lithiation efficiency of approximately 90% or more; including, but not limited to, those exhibiting average particle sizes of approximately 8 µm to approximately 18 µm; including, but not limited to, those exhibiting true densities of approximately 1.5 g / cm³ 3 up to approximately 2.3 g / cm³ 3 exhibit (e.g., in some versions, approximately 1.5 to approximately 1.8 g / cm³) 3 , in other versions from about 1.8 to about 2.3 g / cm³ 3); including, but not limited to, those exhibiting poor, moderate or good cycle life when used alone in Li-ion battery anodes (e.g. without Si-C composites or other active particles); including, but not limited to, those that are coated and include coatings with a coating thickness that noticeably improves compression and swelling during cycling.

[0103] The following description includes certain examples of suitable intercalation-type cathodes (including high-voltage cathodes) in connection with lithium nickel cobalt aluminum oxides (NCA), lithium nickel cobalt manganese aluminum oxides (NCMA), lithium nickel oxides (LNO), lithium manganese cobalt oxides (LMO), lithium nickel manganese cobalt oxides (NCM), lithium cobalt oxide (LCO), lithium cobalt aluminum oxides (LCAO), lithium iron phosphate (LFP), lithium cobalt phosphate (LCP), lithium manganese phosphate (LMP), lithium manganese iron phosphate (LMFP), lithium nickel phosphate (LiNiPO4), and lithium vanadium fluorophosphate. (LiVFPO4), lithium iron fluorosulfate (LiFeSO4F), various Li excess materials (e.g. lithium excess (rock salt) transition metal oxides and oxyfluorides such as Li 1,211 Mon 0,467 Cr 0,3 O2, Li 1,3 Mn 0,4 Note 0,3 O2, Li 1,2 Mn 0,4 Ti 0,4 O2, Li 1,2 Mn 0,8 O2, Li 1,2Mn 0,7 W 0,07 O2, Li 1,2 Mn 0,8 O 1,95 F 0,1 , Li 1,2 Mn 0,75 Zr 0,05 O 1,95 F 0,1 , Li 1,2 Mn 0,7 Zr 0,05 W 0,035 O 1,95 F 0,1 , Li 1,2 Ni 0,333 Ti 0,333 Mon 0,133 O2 and many others), various high-capacity Li-ion-based materials with partial substitution of oxygen by fluorine or iodine (e.g., rock salt Li2Mn) 2 / 3 Note 1 / 3 O2F, Li2Mn 1 / 2 Ti 1 / 2 O2F, Li 1,5 N / a 0,5 MnO 2,85 I 0,12, ua) and many other types of Li-containing disordered, layered, tavorite, olivine or spinel-like active materials or mixtures thereof, containing at least oxygen or fluorine or sulfur and at least one transition metal, and other lithium transition metal (TM) oxides or phosphates or sulfates (or mixed) active cathode or anode materials based on the intercalation of lithium (Li) and changes in the TM oxidation state (including, but not limited to, those which may be doped or heavily doped; including, but not limited to, those which have a gradient in composition or a core-shell morphology; including, but not limited to, those which may be partially fluorinated or contain a significant proportion of fluorine in their composition (e.g., about 0.001-10 atomic %), etc.) described, however, it is understandable that various aspects are applicable to high-voltage lithium transition metal oxide (or phosphate or sulfate or mixed or other) cathodes in which TM and oxygen (O) are covalently bonded and both TM and O participate in electrochemical reduction-oxidation reactions (redox reactions) during charging and discharging (including, but not limited to, such oxide or phosphate or sulfate or mixed cathodes which may comprise at least about 0.25 atomic % of Mn, Fe, Ni, Co, Nb, Mg, Cr, Mo, Zr, W, Ta, Ti, Hf, Y, La, Sb, V, Sn, Si or Ge).

[0104] Fig.Figure 1 shows an example of a metal-ion battery (e.g., a lithium-ion battery) in which the electrode particles, components, materials, processes, and other techniques, or combinations thereof, described herein can be applied according to various embodiments. A cylindrical battery is shown for illustration, but other arrangements, including prismatic or pouch batteries (laminate batteries), can also be used. The example battery 100 comprises a negative electrode (anode electrode or anode) 102, a positive electrode (cathode electrode or cathode) 103, a separator 104 arranged between the anode 102 and the cathode 103, an electrolyte (implicitly shown) impregnating the separator 104, a battery casing 105, and a sealing element 106 sealing the battery casing 105. The electrolyte ionically couples the anode (negative electrode) and the cathode (positive electrode).The electrolyte is located between the anode electrode and the cathode electrode. In some embodiments, the battery 100 also includes an anode current collector and a cathode current collector. The anode is arranged on or in the anode current collector and the cathode on or in the cathode current collector.

[0105] Fig. Figure 2 shows a flowchart of a process 120 for manufacturing a Li-ion battery, such as the example battery 100 from Fig.1. In the example shown, process 120 comprises operations 122, 124, 132, 134, and 140. The flowchart includes an anode branch (left branch) with operations 122 and 124 and a cathode branch (right branch) with operations 132 and 134. In operation 122, anode particles (e.g., conventional anode particles, core-shell anode particles, or composite anode particles, including but not limited to silicon-containing composite particles (e.g., nano-composite particles) in which silicon-containing active material is embedded in pores of a particle core) are produced, and in operation 124, an anode is formed. Similarly, in operation 132, cathode particles (e.g.,conventional cathode particles or core-shell cathode particles or composite cathode particles, including but not limited to conversion-type cathode material comprising composite particles in which the active material of the conversion-type cathode material is deposited in the pores of a particle core) are produced, and a cathode is formed in process 134.

[0106] The electrodes used in lithium-ion batteries are generally manufactured by (i) forming a slurry containing active materials, conductive additives, binder solutions, and in some cases, surfactants or other functional additives; (ii) casting the slurry onto a metal foil (e.g., copper or copper alloy foil for most anodes and aluminum or aluminum alloy foil for most cathodes); and (iii) drying the cast electrodes to completely evaporate the solvent. In some embodiments, step (iii) may also include compacting the battery electrode to a desired density. It should be noted that a metal mesh, metal foam, or a very rough metal foil (e.g., with metal nanowires or metal nanosheets on the surface) may be used in some embodiments (e.g., for higher area-specific capacity charging or for faster charging, etc.).It should also be noted that in some designs, thin, metal-coated polymer sheets can be used (e.g., to improve safety or reduce the weight of the power collector, etc.). It should also be noted that in some designs, porous metal foils or metal composite films (e.g., nano-composite films) can be used (e.g., for improved properties, reduced weight, etc.).

[0107] Process 124 comprises the fabrication of an anode electrode, wherein the anode electrode contains the anode particles prepared in Process 122. For example, this Process 124 may include: (1) preparing an anode slurry containing the anode particles (e.g., from Process 122) and other anode slurry components, and (2) casting the anode slurry onto an anode current collector (e.g., a copper foil or copper alloy foil current collector). In some embodiments, this step may also include evaporating the solvent of the slurry and / or compacting the battery electrode to a desired value. Other components of the anode slurry may include, for example: other electrochemically active anode materials (e.g., natural or synthetic graphite, soft or hard carbon), electrically conductive additives (e.g.,Carbon nanotubes or carbon black or branched carbon or carbon nanofibers or graphite flakes or expandable graphite or graphene (e.g. single-wall graphene, multi-wall graphene) or graphene oxide (e.g. single-wall graphene oxide, multi-wall graphene oxide) or soft graphite or their various combinations, to name just a few), binders (e.g. polymer binders) and solvents (e.g. water or a suitable organic solvent).

[0108] Step 134 comprises the fabrication of a cathode electrode, wherein the cathode electrode contains the cathode particles produced in Step 132. For example, this Step 134 may include: (1) preparing a cathode slurry containing the cathode particles (e.g., from Step 132) and other cathode slurry components, and (2) casting the cathode slurry onto a cathode current collector (e.g., a current collector made of aluminum foil or aluminum alloy foil). In some embodiments, this step may also include evaporating the solvent of the slurry and / or compacting the battery electrode to a desired value. Other components of the cathode slurry may include, for example: other electrochemically active cathode materials, electrically conductive additives (e.g., carbon nanotubes or carbon black or branched carbon or carbon nanofibers or graphite flakes or graphene).single-walled graphene, multi-walled graphene) or graphene oxide (e.g. single-walled graphene oxide, multi-walled graphene oxide) or soft graphite or their various combinations, to name a few), binders (e.g. polymer binders) and solvents (e.g. water or a suitable organic solvent).

[0109] In process 140, the rechargeable lithium-ion battery cell is assembled from at least the anode electrode and the cathode electrode, with an electrolyte located between the anode and cathode electrodes. The electrolyte facilitates ionic conduction between the anode and the cathode. The electrolyte ionically couples the anode and the cathode. At the battery's operating temperatures, the electrolyte can be a liquid or a solid electrolyte (or a mixture of liquid and solid electrolyte). (In some embodiments, the solid electrolyte may, for example, be molten or semi-molten during melt infiltration and subsequently solidify.) In some embodiments, for example, when using a liquid electrolyte, a separator can be used to maintain a distance between the anode and the cathode electrodes.

[0110] Fig.Figure 3 is a flowchart of a process 150 for the production of anode particles and illustrates process 122 in detail. Process 150 comprises processes 152, 154, 156, 158, and 160. In some embodiments, the processes and systems described here may be particularly useful when employed as part of process 122 and / or process 132. In some embodiments, the electrode particles are produced using porous carbon or particles containing porous carbon (e.g., mostly using graphitic, sp 2 -bound carbon or porous graphitic, sp 2-bonded carbon-containing particles) with nanostructured or nanoscale particles of active material (e.g., with an average diameter or linear dimensions in the range of about 1 nm to about 200 nm (in some embodiments from about 1 nm to about 10 nm; in other embodiments from about 10 nm to about 30 nm; in still other embodiments from about 30 nm to about 100 nm; in still other embodiments from about 100 nm to about 200 nm), measured by image analysis of electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (RTEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, neutron scattering, and other suitable methods) that are formed in the pores of the porous carbon or the porous carbon-containing particles.In the case of anode particles for use in lithium-ion batteries, the particles of active material can be silicon-containing particles.

[0111] In process 152, carbon particles are provided. In some embodiments, carbon particles (e.g., mainly graphitic sp) can be used. 2 Carbon-bound carbon can be obtained by pyrolysis or carbonization (e.g., by heat treatment or hydrothermal treatment) of a suitable precursor particle, such as a polymer particle or a particle derived from biomass. In some embodiments, the carbon particles can be obtained from carbon-containing inorganic precursor particles (e.g., carbides or oxycarbides, etc.).

[0112] In some embodiments, inorganic sacrificial templates (including, but not limited to, various oxides or hydroxides or oxyhydroxides of various metals and semimetals - e.g. Zn, Mg, Si, Al, Ti, Ca, Mg, Sc etc. and their various combinations) or soft (organic) templates can be used for the formation of porous carbon particles.

[0113] In some embodiments, it may be advantageous for the porosity of the carbon or carbon-containing particles (e.g., the specific surface area and specific pore volume) to be quite high prior to the formation of the nanostructured or nanoscale particles containing the active material. In some embodiments, it is advantageous for the carbon or carbon-containing particles to have a Brunauer-Emmett-Teller (BET) specific surface area (SSA) (e.g., obtained from nitrogen sorption / desorption data at cryogenic temperatures, such as 77 K) of approximately 500 m².2 / g or more before the particles of active material form within them. In some embodiments, it is preferred that the carbon particles have a specific BET surface area in a range of about 500 m². 2 / g up to about 4500 m 2 / g or approximately 4800 m 2 / g exhibit (in some embodiments from about 500 to about 1000 m 2 / g; in other embodiments from about 1000 to about 2000 m 2 / g; in other embodiments from about 2000 to about 3000 m 2 / g; in other embodiments from about 3000 to about 3800 m 2 / g; in other embodiments from about 3800 to about 4800 m 2 / g), before the particles of active material form within them. In some embodiments, it is preferred that the carbon particles have a total volume of micro- and mesopores (macropore sizes above 50 nm not counted) in a range of about 0.5 cm³. 3 / g up to about 5 cm 3 / g exhibit (in some embodiments from about 0.5 to about 1 cm 3 / g; in other embodiments from about 1 to about 2 cm 3 / g; in other embodiments from about 2 to about 3.5 cm 3 / g; in other embodiments from about 3.5 to about 5 cm 3 / g;), before the particles of active material form within them. In some embodiments, such large surface areas can be achieved by physical or chemical activation of carbon or carbon-containing precursor particles, or by rapid annealing of carbon or carbon-containing precursor particles, or by using temporary template materials, or by other known suitable means. In some cases, the precursor particles themselves can be highly porous (e.g., aerogel particles). However, in some embodiments, it may be preferable to create or enhance the porosity in carbon or carbon precursor particles (e.g., by activating the carbon or carbon-containing particles, or by leaching non-carbon components from carbon-containing particles) before the particles of active material form within them, in order to adjust the porosity properties.Accordingly, process 154 includes carrying out a porosity improvement process (e.g., activation) on the carbon particles (e.g., from process 152).

[0114] Following the activation process (Process 154), other process steps are carried out, such as Process A in Process 156, Process B in Process 158, and Process C in Process 160. In the example shown, there are three process steps after the porosity enhancement process (e.g., an activation process) (Process 154), but in other implementations, there may be fewer or more than three process steps after activation. For illustrative purposes, Process 150 is described with regard to the formation of specific electrode particles (e.g., anode particles). The concepts of Process 150, which involve porosity enhancement (e.g., activation) of the carbon particles, can also be applied to other anode or cathode particles that require activation of the carbon particles.

[0115] In the Fig. The three examples shown are nanostructured or nanoscale silicon (Si) or silicon oxide (SiO) x) or silicon nitride (SiN y ) or silicon oxynitride (SiO₂) x N y ) or silicon phosphide (SiP) z ) Particles (0 <x<2; 0<y<1,3; 0<z<1) oder deren verschiedene Kombinationen, Legierungen und Mischungen in den Poren (und / oder auf der Oberfläche) von porösem Kohlenstoff oder porösen kohlenstoffhaltigen Partikeln (z. B. überwiegend graphitischem sp 2 -bound porous carbon or predominantly graphitic, sp 2-bonded carbon-containing particles). Process A (Process 156), for example, involves the formation of silicon-based active material particles in at least some of the pores of the porous carbon particles. The formation (e.g., by deposition or infiltration, or deposition / infiltration of a Si-containing precursor followed by conversion to the final Si or Si-containing material) of silicon-based active material particles in the porous carbon particles can, in some examples, be achieved by solution-based or vapor-based deposition methods, or by other suitable means. For brevity, the particles after completion of Process A are sometimes referred to as silicon-carbon composite particles (although in some embodiments, such composite particles may also contain elements other than Si and C).In some embodiments, such composite particles comprise nanoscale or nanostructured elements (e.g., nanoscale or nanostructured Si, nanoscale or nanostructured C), which may be referred to as nano-composite particles. In some embodiments, the Si or Si-containing material in such nano-composites may be present in the form of nanoparticles. In some embodiments, the mass-averaged size of the nanoparticles of Si or Si-containing material may be in the range of about 1 nm to about 200 nm (in some embodiments in the range of about 1 nm to about 10 nm; in other embodiments in the range of about 10 nm to about 30 nm; in still other embodiments in the range of about 30 nm to about 100 nm; in still other embodiments in the range of about 100 nm to about 200 nm), as measured by electron microscopy image analysis (e.g.,Transmission electron microscopy (TEM), scanning transmission electron microscopy (RTEM), scanning electron microscopy (SEM), X-ray microscopy, X-ray diffraction, neutron scattering and other suitable methods.

[0116] In the example shown, process B is carried out at step 158. Process B includes, for example, the formation of a protective layer on and within the silicon-carbon (Si-C) composite particles (starting at step 156). In some embodiments, the suitable average thickness of the protective layer can range from about 0.2 nm to about 50 nm (in some embodiments from about 0.2 nm to about 2 nm; in others from about 2 nm to about 5 nm; in others from about 5 nm to about 10 nm; in still others from about 10 nm to about 50 nm). In some embodiments, the actual density of the protective layer can be about 0.8 g / cm³. 3 up to approximately 4.8 g / cm³ 3 or approximately 5.8 g / cm³ 3sufficient (in some versions of approximately 0.8 g / cm³) 3 up to about 1.6 g / cm³ 3 ; in other versions of approximately 1.6 g / cm³ 3 up to about 3 g / cm² 3 ; in other versions of approximately 3 g / cm³ 3 up to approximately 4.5 g / cm³ 3 ; in other versions of approximately 4.5 g / cm³ 3 up to approximately 4.8 g / cm³ 3 or approximately 5.8 g / cm³ 3 ).

[0117] In some designs, the protective layer may consist of or be based on electronically conductive material such as carbon. In some designs, such a carbon coating may be doped (e.g., with B, P, N, O, and / or other elements). In some designs, the atomic fraction of the individual dopants may range from approximately 0.01 atomic percent to approximately 10.01 atomic percent (in some designs from approximately 0.01 atomic percent to approximately 0.1 atomic percent; in other designs from approximately 0.1 atomic percent to approximately 1 atomic percent; in other designs from approximately 1 atomic percent to approximately 5 atomic percent; in still other designs from approximately 5 atomic percent to approximately 10.01 atomic percent). In some designs, the protective layer may be largely impermeable to electrolyte solvents.

[0118] During the operation of a Li-ion battery cell (e.g., 100 in Fig.1) The protective coating can prevent direct contact between the silicon nanoparticles and an electrolyte solvent composition. In some designs, direct contact between the electrolyte solvent composition and the silicon nanoparticles can undesirably accelerate the degradation of the lithium-ion battery cell.

[0119] In the example shown, process C is carried out at step 160. Process C includes, for example, modifying the particle size distribution (PSD). Process C may include comminution of the protected silicon-carbon composite particles (from step 158). Comminution may be performed if the particle sizes are (on average) larger than the desired final particle size distribution (e.g., for slurry and electrode processing). Various methods for comminution are known in the art. Comminution may be carried out, for example, by one or more of the following methods: ball milling, jet milling, abrasive milling, pin milling, and hammer milling. In some embodiments, it may be advantageous to perform particle size selection during process C. In some cases, process C may include particle size selection in addition to comminution (e.g., after comminution).Process C may include sieving, particle size separation, centrifugation, other aerodynamic size classification, or other means. In some cases, process C may involve particle size selection without comminution. For example, it may be advantageous to retain some of the larger particles and discard the finer ones. Particle size selection may be carried out by any suitable method known to those skilled in the art, such as sieving, particle size separation, and aerodynamic size classification.

[0120] The process C (160) described above includes examples such as comminution and particle size selection to modify the particle size distribution (PSD) of a particle population. In some cases, it may be advantageous to apply additional or alternative methods for modifying or adjusting a PSD, such as mixing two or more particle populations, each population having a different PSD than the others. For example, particle populations with different PSDs can be obtained (e.g., sourced from one supplier or produced to different PSDs, including applying the comminution and / or particle size selection methods described above under different processing conditions).

[0121] The particle size distribution (PSD) that characterizes a particle population can be determined using laser particle size distribution analysis (LPSA), image analysis of electron microscopy images, or other suitable methods. For example, the particle size distribution (PSD) can be determined by laser particle size distribution analysis (LPSA) on well-dispersed particle suspensions. It should be noted that other methods of particle size distribution analysis (e.g., by SEM image analysis) can also be used (and in some experiments may even lead to more accurate measurements). While there are various methods for measuring PSDs, laser particle size distribution analysis (LPSA) is quite efficient for some applications. With LPSA, particle size parameters of a population's PSD can be measured, such as a volume-weighted particle size parameter of the tenth percentile (e.g., abbreviated as D). lO), a volume-weighted particle size parameter of the fiftieth percentile (e.g. abbreviated as D) 50 ), a volume-weighted particle size parameter of the ninetieth percentile (e.g. abbreviated as D) 90 ) and a volume-weighted particle size parameter of the ninety-ninth percentile (e.g. abbreviated as D) 99 Additionally, parameters relating to characteristic PSD widths, such as D, can be derived from these particle size parameters. 50 - D 10 (sometimes referred to here as left width), D 90 - D 50 (sometimes referred to here as right width), D 90 - D 10 (sometimes referred to here as full width) and (D 90 - D 10 / D 50(here sometimes referred to as the range). A cumulative volume fraction, defined as the cumulative volume of composite particles with particle sizes of a threshold particle size or smaller, divided by the total volume of all composite particles, can be estimated by LPSA. In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D) is used. 50 the PSD in a range of approximately 2.0 µm to approximately 16.0 µm or in a range of approximately 2.0 to approximately 4.0 µm or in a range of approximately 4.0 to approximately 6.0 µm or in a range of approximately 6.0 to approximately 8.0 µm or in a range of approximately 8.0 to approximately 16.0 µm.

[0122] After completion of the processes in process 150 (e.g., processes 152, 154, 156, 158, 160), the composite particles can be characterized by a specific surface area (SSA) according to Brunauer-Emmett-Teller (BET) (e.g., obtained from nitrogen sorption / desorption data at cryogenic temperatures, such as 77 K). In some embodiments, the BET-SSA of the composite particles is in the range of approximately 1 m². 2 / g up to about 50 m 2 / g (in some embodiments from about 1 to about 3 m) 2 / g; in other embodiments of about 3 m 2 / g up to about 12 m 2 / g; in other embodiments of about 12 m 2 / g up to about 18 m 2 / g; in other embodiments of about 18 m 2 / g up to about 30 m 2 / g; in other embodiments of about 30 m 2 / g up to about 50 m 2 / G).

[0123] Fig.Figure 4 (above) shows a schematic representation of a fractured particle (e.g., a fractured composite particle) 400, as it can be observed, for example, under a light microscope. Two parallel lines 402, 404 are tangent to respective parts of the fractured particle 400. A distance 406 between the parallel lines 402, 404 is sometimes called the minimum Feret diameter because this distance 406 is the shortest distance between all possible pairs of parallel lines that can be drawn tangentially to the respective parts of the fractured particle 400. Similarly, two parallel lines 412, 414 are tangent to the respective parts of the fractured particle 400.A distance 416 between the parallel lines 412, 414 is sometimes referred to as the maximum Feret diameter, since this distance 416 is the longest distance between all possible pairs of parallel lines that can be drawn tangentially to the respective parts of the fractured particle 400. An aspect ratio of a particle can be defined as the maximum Feret diameter of the particle divided by a minimum Feret diameter of the particle. Aspect ratios can be estimated by image analysis (e.g., using image analysis software) of particle populations viewed under a light microscope. The exemplary fractured composite particles described here were prepared according to method 150 of [reference missing]. Fig. 3 obtained, whereby carbon particles (152) were initially obtained.

[0124] Fig.Figure 4 (below) shows a graphical representation 420 of a dependence of cumulative distributions (expressed as a fraction of the number of particles in the total population of each) of two selected populations of jagged particles. For each population of jagged particles, an image analysis was performed to estimate an aspect ratio of the individual particles in the population. The population represented by graph line 432 contained approximately 2192 particles, and the population was defined by a D 50 -value of approximately 4.5 µm. The population represented by line 434 contained approximately 7485 particles, and the population was characterized by a D 50The value is approximately 5.5 µm. The cumulative distribution of a particle population, as a function of a given aspect ratio, expresses the proportion of particles in that population whose aspect ratios are less than or equal to the specified aspect ratio. The x-axis (422) shows the aspect ratios, and the y-axis (424) shows the cumulative distribution of the particle population. For example, consider one of the data points (442) along the graph line (432), which corresponds to an aspect ratio of approximately 1.5 and a cumulative distribution proportion of approximately 0.68. This means that approximately 68% of the particles in this population have an aspect ratio of 1.5 or less.

[0125] Scanning electron micrographs (SEM) of illustrative, exemplary fractured composite particles (or their agglomerates) are shown in Fig. 5 and Fig. 6 shown. Fig.Figure 5 shows an SEM image 502 of fractured composite particles originating from a population with D 50 of approximately 2.5 µm, and an SEM image 504 of jagged composite particles from a population with D 50 were recorded from approximately 7 µm. Fig. Figure 6 shows an SEM image 602 of fractured composite particles originating from a population with D 50 of approximately 9 µm, and an SEM image 604 of jagged composite particles from a population with D 50of approximately 14 µm. In the examples shown, the composite particles are jagged and not round (e.g., not spherical, not spheroidal, etc.). Many of the composite particles have quite low aspect ratios, e.g., less than about 10, less than about 5, or less than about 3. On the other hand, many of the composite particles have aspect ratios greater than about 1. In some embodiments, the aspect ratios of populations of jagged composite particles (including those shown in Figure 420 of Fig.4 example populations shown) are characterized by one or more of the following features: (1) about 90% or more of the fractured composite particles in the population are characterized by aspect ratios of about 2.3 or less, or about 2.2 or less, or about 2.1 or less; (2) about 50% or more of the fractured composite particles in the population are characterized by aspect ratios of about 1.25 or more, or about 1.3 or more, or about 1.35 or more; and (3) about 10% or more of the fractured composite particles in the population are characterized by aspect ratios of about 1.3 or less, or about 1.25 or less, or about 1.2 or less.

[0126] Fig. Figure 7 shows a graphical representation of a dependency of a full width D. 90 - D 10 from D 50for each of the example particle populations and a graphical representation 704 of a dependence of the mass fraction of silicon in the composite particles on D 50 for each of the example particle populations. The example populations exhibited D 50 Values ​​ranged between approximately 2.1 µm and approximately 14.1 µm. In the example populations shown, the full width D was... 90 - D 10between approximately 3.0 µm and approximately 31.7 µm. The mass fraction of silicon (Si) was estimated by thermogravimetric analysis (TGA) of a powder sample in a crucible heated in air to approximately 900 °C (at a rate of approximately 40 °C / min) and held for approximately 60 minutes. The sample was then allowed to cool to room temperature, and it was assumed that the resulting mass consisted entirely of silicon dioxide. Under this assumption, the amount of silicon that would have been present in the original powder sample was calculated. In the examples shown, the Si mass fractions ranged from approximately 38.5 wt% to approximately 46.4 wt%. In some embodiments, the Si mass fractions in the composite particles can range from approximately 35 wt% to approximately 50 wt%. In some embodiments, the silicon mass fraction in the composite particles can range from about 3 wt.% to about 80 wt.% (e.g., about 3 to about 20 wt.%).-%, approximately 20 to approximately 35 wt.%, approximately 35 to approximately 50 wt.%, approximately 50 to approximately 80 wt.%, etc.).

[0127] The electrode coatings for the illustrative examples were fabricated using each of the battery electrode compositions containing an appropriate population of fractured composite particles. In addition to the composite particles, a battery electrode composition may contain functional additives (e.g., additives that improve the electrical conductivity or the rate performance of the electrode's mechanical properties), such as carbon-containing functional additives. Examples of suitable carbon-containing functional additives include carbon nanotubes (single-walled carbon nanotubes, abbreviated SWCNTs, multi-walled carbon nanotubes, abbreviated MWCNTs), carbon nanofibers, carbon black, graphite, expandable graphite, graphene oxide, and graphene.Suspensions were prepared by thoroughly mixing the fractured nano-composite particles (or a mixture of fractured nano-composite particles and graphite in the case of mixed anodes) (e.g., with a mass fraction in the range of approximately 87 wt.% to approximately 94 wt.% or in the range of approximately 89 wt.% to approximately 92 wt.% of the suspension's solids content), a binder composition (e.g., with a mass fraction in the range of approximately 6 wt.% to approximately 13 wt.% or in the range of 8 wt.% to approximately 10 wt.% of the suspension's solids content), functional additives (e.g., in a mass fraction in the range of approximately 0 wt.% to approximately 0.1 wt.% of the suspension's solids content), and a solvent composition (e.g., in a mass fraction of 10 wt.% to approximately 40 wt.% of the suspension).The exemplary anode slurries were then poured onto a copper foil and dried at room temperature to form an electrode coating. Subsequently, the dried electrode coatings were calendered (using a constant force in our illustrative examples) to obtain a coating density within a specific range, e.g., approximately 0.75 g / cm². 3 up to approximately 1.00 g / cm² 3 (e.g. in the case of anodes that contain only Si-C nano-composite particles as the active material without graphite) or in a range of about 0.80 g / cm² 3 up to approximately 1.00 g / cm² 3 or in a range of approximately 0.85 g / cm³ 3 up to approximately 1.00 g / cm² 3 or in a range of approximately 0.90 g / cm² 3 up to approximately 1.00 g / cm² 3 It should be noted that a higher density (e.g., versions with approximately 1.0 to approximately 1.2 g / cm³) 3, versions with approximately 1.2 to approximately 1.5 g / cm³ 3 or more) can preferably be achieved for mixed anodes comprising small to large proportions of soft or hard graphite (generally soft or hard carbon) or their various mixtures (e.g., about 5-80% of the capacity provided by graphite and about 20-95% of the capacity provided by Si-C nano-composite or other Si-containing particles).

[0128] Fig. Figure 8 shows SEM images 802 and 804 of cross-sections of electrode coatings. SEM image 802 is a cross-sectional view of an electrode coating with a population sample of D. 50 of approximately 4 µm, and SEM image 804 is a cross-sectional view of an electrode coating with a population sample of D 50of approximately 14 µm. Comparing these two examples, the coating made of larger particles (804) exhibits larger pores than the coating made of smaller particles (802). Accordingly, the porosity of the coating tends to decrease and the density of the coating tends to increase as the particle size decreases (e.g., D decreases). 50 from approximately 14 µm to approximately 4 µm). Electrode coatings with the respective example particle populations (i.e., the populations shown in graphical representations 702, 704 in Fig. The 7 layers were applied to copper foils. The thickness of the electrode coating ranged from approximately 24.3 µm to approximately 43.5 µm.

[0129] Conventional active anode materials used in lithium-ion batteries are of the intercalation type. During charging or discharging, metal ions are intercalated into these materials, occupying the spaces between them. Such anodes undergo small or very small volume changes (e.g., less than about 8 vol.%) when used in electrodes. Polyvinylidene fluoride (also known as polyvinylidene difluoride (PVDF)), polyacrylic acid (PAA) (or its salts, derivatives, and copolymers) (sometimes blended with styrene-butadiene rubber (SBR)), and carboxymethylcellulose (CMC) (often blended with styrene-butadiene rubber (SBR)) are the three most commonly used binders for these electrodes. Carbon black is the most commonly used conductive additive in these electrodes.However, such anodes have relatively low gravimetric and volumetric capacities (typically less than 370 mAh / g rechargeable specific capacity in the case of graphite- or hard-carbon-based anodes and less than 600 mAh / cm). 3 Rechargeable volumetric capacitance at the electrode level, without considering the volume of the current collector foils).

[0130] Active anode materials of the alloy type (or more generally, the conversion type) for use in lithium-ion batteries offer higher gravimetric and volumetric capacities compared to intercalation-type anodes. For example, earth-rich silicon (Si) offers approximately 10 times the gravimetric capacity and approximately 3 times the volumetric capacity compared to an intercalation-type graphite (or graphite-like) anode. However, Si undergoes significant volume expansion (up to approximately 300 vol%) during the introduction of lithium, which can lead to thickness changes and mechanical failure of Si-containing anodes. Furthermore, Si (and some Li-Si alloys that can form during the lithiation of Si) have relatively low electrical conductivity and relatively low ionic conductivity (for lithium ions). The electronic and ionic conductivity of Si is lower than that of graphite.The formation of (nano)composite particles containing silicon (including, but not limited to, silicon-carbon composites, silicon-metal composites, silicon-polymer composites, silicon-ceramic composites, composites comprising various combinations of nanostructured silicon, carbon, polymer, ceramic, and metal, or other types of porous composites comprising nanostructured silicon or nanostructured or nanoscale silicon particles in various shapes and forms) can reduce volume changes during the insertion and removal of lithium ions, which in turn can lead to improved cycle stability in rechargeable lithium-ion cells. In some formulations, silicon can be doped or heavily doped with nitrogen (N), phosphorus (P), boron (B), or other elements, or allowed to be metal-modified. In addition to silicon-based composites, silicon oxides (SiO) can be used. x ) or oxynitrides (SiO₂) x N y) or nitrides (SiN y ) or phosphides (SiP y) or other Si-element-containing particles (including those partially reduced by Li or Mg) decrease volume changes and improve cycle stability, although usually at the cost of higher first-cycle losses or faster degradation, or both. In some embodiments, Si-encompassing anode particles can exhibit high gravimetric lithiation capacities in the range of approximately 800 mAh / g to approximately 3000 mAh / g (per mass of the Si-containing anode particles in a Li-free state; in some embodiments from approximately 800 mAh / g to approximately 1400 mAh / g; in other embodiments from approximately 1400 mAh / g to approximately 2200 mAh / g; in other embodiments from approximately 2200 mAh / g to approximately 2600 mAh / g; in other embodiments from approximately 2600 mAh / g to approximately 3000 mAh / g), measured in lithium half-cells in the potential range for lithiation in the first cycle from their open-circuit potential down to 0.01 V vs. Li / Li +at a constant current rate of approximately C / 10, where the potential is held at 0.01 V until the current drops to approximately C / 100, and during delthiation in the first cycle from 0.01 V to approximately 1.5 V against Li / Li +at a constant current rate of C / 10. This high specific capacity is advantageous for obtaining lighter batteries. However, lithium-ion battery cells with anodes containing high-capacity anode particles and non-optimized particle size distribution (PSD) can degrade undesirably quickly in conventional electrolytes (especially when processed with conventional binders and conductive additives at typical area-specific capacity loadings), particularly at elevated temperatures or when charged to high voltages (e.g., above approximately 4–4.3 V).A subgroup of anodes with silicon-containing anode particles includes anodes with an electrode layer that has a capacity in the range of approximately 400 mAh / g to approximately 2800 mAh / g (per mass of the electrode layer, excluding the mass of the current collector, in a lithium-free state); in some versions from approximately 400 mAh / g to approximately 500 mAh / g; in other versions from approximately 500 mAh / g to approximately 700 mAh / g; in other versions from approximately 700 mAh / g to approximately 1000 mAh / g; in other versions from approximately 1000 mAh / g to approximately 1200 mAh / g; in other versions from approximately 1200 mAh / g to approximately 1500 mAh / g; in other versions from approximately 1500 mAh / g to approximately 2000 mAh / g; in other versions from approximately 2000 mAh / g to approximately 2800 mAh / g). Such a class of charge-storing anodes offers great potential for increasing the gravimetric and volumetric energy of rechargeable batteries.However, lithium-ion battery cells with anodes containing high-capacity anode particles and non-optimized PSD can degrade undesirably quickly in conventional electrolytes and when processed with conventional binders and conductive additives at typical areal capacity charges, especially at elevated temperatures (e.g., battery operating temperatures, such as 50–80 °C or higher) or when charged to high voltages (e.g., above approximately 4–4.3 V). Besides silicon-containing anodes, other examples of such high-capacity anodes (e.g., nano-composite anodes) contain alloy-type (or, more broadly, conversion-type) active materials, including those containing germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorus, silver, cadmium, indium, tin, lead, bismuth, their alloys, and others.Besides anodes containing active materials in metallic form, other interesting types of high-capacity anodes (including nano-composite anodes) can include metal oxides (including silicon oxide, lithium oxide, etc.), metal nitrides (including silicon nitride, etc.), metal oxynitrides (including silicon oxynitride, etc.), metal phosphides (including lithium phosphide), metal hydrides, and others.

[0131] Lithium-ion cells with alloy-type (or more generally, conversion-type) active anode materials can degrade undesirably quickly in conventional electrolytes, especially at elevated temperatures or when charged to high voltages (e.g., above 4–4.3 V) and stored at such voltages and elevated temperatures (e.g., above 50–80 °C). In some designs, the degradation of lithium-ion cells with alloy-type (or, more broadly, conversion-type) active anode materials can be particularly rapid in large cells (e.g., cells with a cell capacity in the range of approximately 10 Ah to approximately 40 Ah), ultra-large cells (e.g., cells with a cell capacity in the range of approximately 40 Ah to approximately 400 Ah), or gigantic cells (e.g., cells with a cell capacity in the range of approximately 400 Ah to approximately 4,000 Ah or even more).Large, ultra-large, or gigantic cells can be particularly attractive for use in certain applications, such as electric transportation or grid storage. In some designs, the degradation of lithium-ion cells with alloy-type (or more generally, conversion-type) active anode materials can be particularly rapid in cells containing a medium (e.g., about 3–4 g / Ah) or low (e.g., about 2–3 g / Ah) amount of electrolyte, normalized to the cell's total capacity. However, using a medium or low amount of electrolyte can be especially attractive for reducing cell manufacturing costs or certain side reactions and maximizing cell energy density.One or more aspects of this disclosure make it possible to mitigate or overcome some or all of these limitations and to substantially improve the performance of such Li-ion cells through the use of certain disclosed electrolyte compositions. One or more aspects of this disclosure make it possible to mitigate or overcome some or all of these limitations and to substantially improve the performance of such Li-ion cells through the use of certain disclosed compositions and certain disclosed properties of active materials. One or more aspects of this disclosure make it possible to mitigate or overcome some or all of these limitations and to substantially improve the performance of such Li-ion cells through the use of certain disclosed PSDs of the particle active anode material (e.g., particle active material comprising alloying or conversion materials).

[0132] High-capacity (nano-)composite anode powders (including, but not limited to, those containing silicon) exhibiting moderately high volume changes (e.g., about 8 to about 180 vol%) during the first charge-discharge cycle, moderate volume changes (e.g., about 5 to about 50 vol%) during subsequent charge-discharge cycles, and an average size in the range of about 0.2 to about 40 µm (preferably about 0.4 to about 20 µm for some applications) can be particularly attractive for battery applications with regard to manufacturability and performance characteristics. In particular, a subclass of such anode powders with a specific surface area in the range of about 0.5 m² 2 / g up to about 50 m 2 / g (in some embodiments of about 0.5 m 2 / g to about 2 m 2 / g; in other embodiments of about 2 m 2 / g up to about 12 m 2 / g; in other embodiments of about 12 m2 / g up to about 50 m 2 / g) performed particularly well in some embodiments. In some embodiments, electrodes with a moderate area-related electrode capacitance loading (e.g., of about 2 to about 4 mAh / cm²) were used. 2 ) to high (e.g., from about 4 to about 12 mAh / cm²) 2 ) and ultra-high (over about 12 mAh / cm²) 2) are also particularly attractive for use in cells. In some configurations, a spheroidal (including near-spherical or spherical) or ellipsoidal (including flattened spheroidal) shape of these composite particles can be additionally very attractive for increasing the rate performance and volumetric capacity (density) of the electrodes. In other configurations, jagged, cylindrical, fibrous, or irregularly shaped composite particles can also be used effectively. Unfortunately, a non-optimized PSD of such particles can lead to poor performance in batteries.

[0133] However, higher electrode density and lower binder content are advantageous for increasing cell energy density and reducing costs in certain applications. Lower binder content can also be beneficial for increasing cell rate performance. Larger volume changes lead to poorer performance in some designs, which may be due to damage to the solid electrolyte interlayer (SEI) formed on the anode, uneven lithiation and delithiation of electrode particles within the electrodes, and other factors. Unfortunately, lithium and lithium-ion battery cells with such anodes, which result in a non-optimized PSD, require active (e.g.,These cells, which contain silicon-containing materials and conventional electrolytes, often employ such large quantities of conventional SEI-forming additives to maintain acceptable cycle stability that their use at elevated or low temperatures is not possible, their calendar life is undesirably limited, or such cells cannot be charged to high voltages (e.g., above approximately 4.1–4.3 V). The performance of such battery cells can become particularly poor when charged above 4.3–4.4 V, and even worse when charged above 4.5 V.

[0134] However, higher cell voltage, a wider operating temperature window, and longer cycle life are advantageous for most applications. Such cells can suffer from excessive capacity loss (e.g., more than 5%), large volume expansion (e.g., more than 10%), and significant gassing if exposed to high temperatures (e.g., more than 50–90°C) for extended periods (e.g., approximately 12–168 hours) while fully charged (e.g., approximately 90–100% state of charge, SOC). For most applications, it is often necessary for them to pass such elevated-temperature charging tests.In some designs, the degradation of Li-ion cells with high-capacity (nano-)composite anode powders with non-optimized PSD, exhibiting moderately high volume changes during the first charge-discharge cycle, moderate volume changes during subsequent charge-discharge cycles, and an average size in the range of approximately 0.2 to approximately 40 µm, can become particularly undesirably rapid, especially in large cells (e.g., cells with cell capacities in the range of approximately 10 Ah to approximately 40 Ah), very large cells (e.g., cells with cell capacities in the range of approximately 40 Ah to approximately 400 Ah), or gigantic cells (e.g., cells with cell capacities in the range of approximately 400 Ah to approximately 4,000 Ah or more). In some designs, Li-ion cells with such volume-changing anode particles can degrade particularly rapidly and undesirably quickly if the cells have a medium (e.g., about 3-4 g / Ah) or low (e.g.,containing approximately 2-3 g / Ah of electrolyte, normalized to the total cell capacity. One or more embodiments of the present disclosure make it possible to mitigate or overcome some or all of these limitations and to substantially improve the performance of such Li-ion cells through the use of certain disclosed electrolyte compositions.

[0135] One or more embodiments of the present disclosure overcome some or all of the challenges described above for various types of metal-ion cells (e.g., Li-ion cells) comprising high-capacity active nano-composite anode materials (e.g., materials comprising conversion-type or alloy-type active materials) that may contain Si in their composition, may undergo certain volume changes during cycling (e.g., moderately high volume changes (e.g., about 8 to about 160 or about 180 vol%) during the first charge-discharge cycle and moderate volume changes (e.g., about 5 to about 50 vol%) during subsequent charge-discharge cycles), may have an average particle size in the range of about 0.2 to about 40 µm and a specific surface area in the range of about 0.5 to about 50 m². 2 / g exhibit (in some versions from approx. 0.5 to approx. 2 m 2 / g; in other versions from approx. 2 to approx. 12 m 2 / g; in other versions from approximately 12 to approximately 50 m 2 / g), can be used with such electrodes in moderate (e.g. approx. 2 - approx. 4 mAh / cm²) 2 ) and high area-related capacity loads (e.g. approx. 4 - approx. 12 mAh / cm²) 2) with high packing density (electrolyte-filled electrode porosity in the range of approximately 5 to approximately 35 vol% after the first charge-discharge cycle) and relatively low binder content (e.g., approximately 0.5 to approximately 14 wt%), can contain a moderate or low amount of electrolyte per cell capacity (e.g., less than approximately 4 g / mAh), can be charged to moderately high (e.g., above approximately 4.1–4.3 V), high (e.g., above approximately 4.3–4.4 V), or very high (e.g., above approximately 4.5–4.8 V) voltages, can be exposed to temperatures above approximately 40 °C at a high state of charge (e.g., approximately 70–100% SOC) during testing or operation, and can be large cells (e.g., cells with a cell capacity in the range of approximately 10 Ah to approximately 40 Ah) or ultra-large cells (e.g., cells with a Cell capacities in the range of approximately 40 Ah to approximately 400 Ah) or gigantic cells (e.g. cells with a cell capacity in the range of approximately 400 Ah to approximately 4,000 Ah or even more) can be produced.

[0136] In some formulations, the swelling of binders in electrolytes depends not only on the composition of the binder but can also depend on the electrolyte composition. Furthermore, in some formulations, such swelling (and the resulting performance degradation) often correlates with a reduction in the elastic modulus when the binders are exposed to electrolytes. In this sense, the smaller the reduction in the modulus in certain electrolytes, the more stable the interface between binder-bound (nano-)composite active particles and conductive additives becomes. In some formulations, a reduction in the binder modulus of more than 15–20% can lead to a noticeable performance degradation. In one example, a reduction in the binder modulus of approximately twofold (2x) can result in a significant performance degradation.In another example, a reduction in modulus of five times or more (e.g., by a factor of 5 to 500) can lead to a very significant decrease in performance. Therefore, selecting an electrolyte composition that does not cause significant swelling of the binder can be highly advantageous for certain applications. In some examples, it may be preferable to select an electrolyte composition that reduces the modulus of the binder by less than about 30% (preferably by no more than about 10%) when exposed to an electrolyte. For anodes containing more than one binder composition, it may be preferable in some embodiments to select an electrolyte composition in which at least one binder reduces the modulus by no more than about 30% (preferably by no more than about 10%) when exposed to the electrolyte.

[0137] In one or more embodiments of the present disclosure, a preferred battery cell comprises lithium cobalt oxide (LCO) as the active cathode material. In one or more other embodiments of the present disclosure, a preferred battery cell comprises lithium nickel cobalt manganese oxide (NCM) as the active cathode material. In one or more other embodiments of the present disclosure, a preferred battery cell comprises lithium nickel cobalt manganese aluminum oxide (NCMA) as the active cathode material. In one or more other embodiments of the present disclosure, a preferred battery cell comprises lithium nickel cobalt aluminum oxide (NCA) as the active cathode material. In one or more other embodiments of the present disclosure, a preferred battery cell comprises a high-voltage spinel (e.g., lithium nickel manganese oxide (LNMO) or lithium manganese oxide (LMO)) as the active cathode material.In some embodiments, the active LCO, NCM, NCMA, NCA, LNMO, or LMO cathode materials may consist predominantly (e.g., to more than 50 wt%) of single-crystal powder (or of a powder with a particle size greater than approximately 500 nm; in some embodiments, greater than approximately 1 µm). In some of the preferred examples, a surface of LCO, NCM, NCMA, NCA, LMO, or LNMO may be coated with a layer of ceramic material. Illustrative examples of a preferred coating material for such cathodes include, among others, titanium oxide (e.g., TiO₂), aluminum oxide (e.g., Al₂O₃), tungsten oxide (e.g., WO₃), chromium oxide (e.g., Cr₂O₃), niobium oxide (e.g., NbO or NbO₂), and zirconium oxide (e.g., ZrO₂), as well as various mixtures thereof. In some versions, such ceramic materials may also contain lithium (Li) - e.g.as lithium titanium oxide, lithium aluminum oxide, lithium tungsten oxide, lithium chromium oxide, lithium niobium oxide, lithium zirconium oxide, and their various alloys, mixtures, and combinations. In other preferred examples, LCO, NCM, NCMA, NCA, LMFP, LMP, LMO, or LMNO may be doped with Al, Ti, Mg, Nb, Zr, Cr, Hf, Ta, W, Mo, or La. In some embodiments, aluminum or an aluminum alloy is preferred as the material for the cathode current collector. In some embodiments, a preferred battery cell includes a polymer separator. In some of the preferred examples, a polymer separator is made of or includes polyethylene, polypropylene, or a mixture thereof. In some of the preferred examples, a surface of a polymer separator is coated with a layer of ceramic material.Examples of preferred coating materials for polymer separators include titanium dioxide (TiO2), aluminum oxide (Al2O3), aluminum hydroxide or oxyhydroxide, zirconium oxide (ZrO2), magnesium oxide (MgO), or magnesium hydroxide or oxyhydroxide. In some embodiments, a preferred battery cell may incorporate a silicon-carbon nanocomposite (e.g., a nanocomposite or (nano)composite, as used here, consists at least partially of active material made of nanomaterials, nanostructures, or nanoparticles, regardless of whether the nanocomposite or (nano)composite itself is a nanomaterial) or silicon (SiO3). x, x ≥ 0) or natural or synthetic graphite or soft carbon or hard carbon or their various mixtures and combinations in their anode composition. In some of the preferred examples, the active anode material comprises a mixture of a silicon-carbon-containing nanocomposite (here sometimes abbreviated as Si-C nanocomposite) and graphite (e.g., wherein the graphite is distinct from the carbon portion of the Si-C nanocomposite). In some embodiments, a Si-C nanocomposite comprises composite particles that may contain Si nanoparticles embedded in pores (e.g., surface pores or internal pores such as closed internal pores or open internal pores) of a porous carbon framework particle. Such a porous carbon framework particle may consist of (e.g., bent or defective) graphene material and / or graphite material.In some designs, a preferred anode current collector may consist of copper or a copper alloy.

[0138] In one or more embodiments of the present disclosure, a preferred anode for a battery cell may comprise a mixture of Si-C nanocomposite (particles) and graphite (particles) as the active anode material, a so-called mixed anode. In addition to the active anode material, an anode may also contain inactive material such as binders (e.g., polymer binders) and other functional additives (e.g., surfactants, electrically conductive additives). In some embodiments, the active anode material (particles) may constitute approximately 90 wt.% to approximately 98 wt.% of the anode. For example, in some embodiments, the active anode material (particles) may constitute approximately 95.5 wt.% of the anode.

[0139] In some embodiments, a mixed anode may contain approximately 7 wt% to approximately 97 wt% Si-C nanocomposite (e.g., particles). While the descriptions below may also describe certain examples of mixed anode formulations expressed as the mass (wt%) of the Si-C nanocomposite (e.g., the particles) relative to the total weight of the Si-C composite and the graphite (e.g., the particles) in a mixture, it is understood that various aspects of this disclosure are applicable to mixed anode formulations expressed as wt% of the Si in the anode (e.g., including the weight of conductive and other additives, binders, Si-containing composites such as Si-C nanocomposites, and graphite). In some embodiments, a mixed anode composition of approximately 7 wt.% Si-C nano-composite (e.g. particles) corresponds to approximately 3-3.5 wt.% Si in the mixed anode.In some embodiments, a mixed anode composition of approximately 19 wt.% Si-C nanocomposite (e.g., particles) corresponds to approximately 8–10 wt.% Si in the mixed anode. In some embodiments, a mixed anode composition of approximately 35 wt.% Si-C nanocomposite (e.g., particles) can correspond to approximately 15–18 wt.% Si in the mixed anode. In some embodiments, a mixed anode composition of approximately 50 wt.% Si-C nanocomposite (e.g., particles) can correspond to approximately 21–30 wt.% Si in the mixed anode. In corresponding embodiments, mixed anodes can be obtained in which the mass (weight) of silicon is in the range of approximately 3 wt.% to approximately 30 wt.% of the total mass of the anode. The term "total mass of the anode" here refers only to the mass of the anode, excluding the anode current collector foil or separator.The masses of the current collector and the separator are excluded from the mass of the anode, even if the current collector and the separator are attached to the anode.

[0140] In some embodiments, a mixed anode may contain a Si-C nanocomposite (e.g., particles) that provides approximately 25% to approximately 99.5% of the total anode capacity. While the descriptions below may also describe certain examples of mixed anode formulations expressed as the mass (wt%) of the Si-C nanocomposite (e.g., the particles), it is understood that various aspects of this disclosure are applicable to mixed anode formulations that attribute a fraction (e.g., %) of the total mixed anode capacity to the Si capacity. For example, in some embodiments, approximately 25% of the total mixed anode capacity may be derived from the Si-C nanocomposite (e.g., particles) in a mixed anode composition of approximately 7 wt% Si-C nanocomposite (e.g., particles). In some other embodiments, approximately 50% of the total capacity of the mixed anode can be made from the Si-C nano-composite material (e.g.In some other embodiments, approximately 70% of the total capacity of the mixed anode can be obtained from the Si-C nano-composite (e.g., particles) in a mixed anode composition of approximately 19 wt.% Si-C nano-composite (e.g., particles). In some other embodiments, approximately 80% of the total capacity of the mixed anode can be obtained from the Si-C nano-composite (e.g., particles) in a mixed anode composition of approximately 50 wt.% Si-C nano-composite (e.g., particles).

[0141] In some embodiments, mixed anodes can comprise Si-C nano-composites (e.g. particles) with a proportion of about 7 wt.% to about 99 wt.% of the particles of active anode material, wherein the graphite particles make up the remainder of the mass (weight) of the particles of active anode material. In some embodiments, where the particles of active anode material constitute about 95.5 wt.% of the mixed anode, the mixed anode (including the particles of active and inactive material) may comprise about 7 wt.% Si-C nano-composite (e.g., particles) and about 88.5 wt.% graphite (e.g., particles), about 19 wt.% Si-C nano-composite (e.g., particles) and about 76.5 wt.% graphite (e.g., particles), about 35 wt.% Si-C nano-composite (e.g., particles) and about 60.5 wt.% graphite (e.g., particles), or about 50 wt.% Si-C nano-composite (e.g., particles) and about 45.5 wt.% graphite (e.g., particles).Particles, wherein the graphite particles are in all cases separate from the carbon portion of the Si-C nanocomposite). In some of the preferred examples, where the particles of active anode material constitute about 90 wt.% or more of the mixed anode, the composition of the active anode material may comprise a small proportion (e.g., about 1-20 wt.%, preferably about 1-10 wt.%, and even more preferably about 1-5 wt.%) of graphite (e.g., particles, wherein the graphite particles are distinct from the carbon portion of the Si-C nanocomposite).

[0142] In some of the illustrative examples, where the particles of active anode material constitute about 90 wt% of the anode, the composition of the particles of active anode material can consist almost entirely of Si-C nano-composite (e.g., particles) and is essentially free of graphite particles (e.g., < about 1 wt%) (e.g., where the graphite particles are distinct from the C part of the Si-C nano-composite).

[0143] In some of the illustrative examples, where the particles of active anode material constitute approximately 96.5 wt% of the anode, the composition of the particles of active anode material can consist almost entirely of graphite and is essentially free of Si-C nano-composite (e.g., < about 1 wt%).

[0144] In one or more embodiments of the present disclosure, an electrolyte containing esters and / or carbonates (e.g., cyclic carbonates, linear carbonates) can be used in a lithium-ion battery cell. The lithium-ion battery comprises an anode current collector (e.g., a foil of copper or a copper alloy), a cathode current collector (e.g., a foil of aluminum or an aluminum alloy), an anode arranged on or in the anode current collector, a cathode arranged on or in the cathode current collector, and one of the aforementioned electrolytes ionically coupling the anode and the cathode. In some examples, a separator (e.g., a separator foil or a coating) can be arranged between the anode and the cathode, with at least a portion of the electrolyte infiltrating or impregnating the separator. The anode can consist of any suitable anode material, as described herein.The anode can, for example, contain silicon-carbon composite particles, which combine silicon and carbon (e.g., mainly graphitic, sp. 2 -bonded carbon). In some embodiments, the mass of silicon can range from about 3 wt% to about 80 wt% of the total mass of the anode. In some cases, at least some of the silicon in the silicon-carbon composite particles can be present as nanoscale or nanostructured silicon. The anode can, for example, contain graphitic carbon particles containing carbon. In some cases, the graphitic carbon particles can be substantially free of silicon. In some cases, both the silicon-carbon composite particles and the graphitic carbon particles can be present in an anode.

[0145] In an illustrative example, a lithium-ion battery cell with a capacity of about 0.028 Ah may contain: (i) an anode with about 100% capacity of active Si-C nano-composite material (e.g., particles) (with a specific reversible capacity of about 1600 to about 1700 mAh / g, normalized to the weight of the active materials in the anode), which weighs about 40 to about 44 wt.(1) a silicon mass fraction in the Si-C composite particles, which are cast onto a Cu current collector film from a water-based suspension comprising a binder based on a polyacrylic acid (PAA) salt copolymer and about 0.1% carbon black as a conductive additive, (2) a cathode with high-voltage lithium cobalt oxide (LCO) active material (with a specific reversible capacity of about 170 mAh / g, normalized to the weight of the active materials in the cathode), cast onto an Al current collector film from a suspension in organic solvent comprising a polyacrylic acid (PAA)-based binder and a conductive carbon black additive, with an anode:cathode area-specific capacity ratio of about 1.15:1 and a reversible area-specific capacity loading of about 3.5 mAh / cm². 2, a charging voltage of about 4.4 V, (iii) a polymer-ceramic separator and (iv) an electrolyte ELY No. 1 containing: about 15 mol% FEC, about 44 mol% ethyl propionate (EP) (linear ester), about 7 mol% LiPF6, about 24 mol% non-fluorinated cyclic carbonates, about 7 mol% diethyl carbonate (DEC), and about 3 mol% other compounds.

[0146] Li-ion battery test cells (with LCO cathodes, as described above) containing the nano-composite particles from the example (with the entire anode capacity provided by Si-C nano-composite particles) were tested in a cycle life test. The test cells were fabricated, and an initial formation procedure was performed on the test cells. The charge / discharge test conditions included constant current and constant potential (CCCP) at 2C charging to 4.0 V and dropping to 1C, followed by CCCP at 1C charging to 4.2 V and dropping to 0.05 C, followed by 1C discharge. Graph 902 ( Fig. Figure 9) shows the number of cycles until 80% of the capacity at the start of cycling is reached (during cycling at 25 °C), sometimes referred to as cycle life (also as “N80”), as a function of D 50the respective population of fractured composite particles. The capacity at the start of cycling is defined as the capacity after completion of the third cycle. Some test cells with larger particles (e.g., with D 50 Cells with particles larger than approximately 10 µm exhibited poor cycle lifetimes (e.g., less than approximately 200 cycles). On the other hand, test cells with smaller particles (e.g., at D) showed 50 in a range of approximately 2.0 µm to approximately 8.0 µm) better cycle lifetime values ​​(e.g., more than 340 cycles or in a range of approximately 340 cycles to approximately 729 cycles). Accordingly, in some embodiments (e.g., when all or nearly all of the capacity is provided by Si-C composite particles), it can have beneficial effects (e.g., a better cycle lifetime) if populations of fractured composite particles with D 50Values ​​in a range of approximately 2.0 µm to approximately 8.0 µm can be used (especially if the cell charging rates are comparable or faster). For larger particles (e.g., at D 50 (larger than approximately 10 µm) a possible degradation pathway may involve mechanical failure of the electrode coating after several charge / discharge cycles, partly due to poor packing of the jagged composite particles in the coating (note, for example, the large interstitial pores between the particles in SEM image 804 of Fig. 8) Furthermore, larger particles may exhibit a higher charge transfer resistance and in some cases (e.g., in tests in cold climates or at low temperatures and / or in anodes designed to have moderate to high area-specific capacitance loadings (e.g., about 2-12 mAh / cm²) 2) etc.) lead to lithium superposition if the cells are charged quickly. With smaller particles (e.g., with D 50 (in a range of approximately 2.0 µm to approximately 8.0 µm) a possible degradation pathway may consist of the surface area (of the particles) exposed to the electrolyte increasing with decreasing particle size, leading to an increased occurrence of undesired side reactions between the electrolyte and the particles (e.g. excessive SEI growth).

[0147] The graphic representation 904 ( Fig. Figure 9) shows a dependence of a normalized coating thickness change of the anodes of test cells on D 50each of the example particle populations. The normalized coating thickness change is defined as the coating thickness change (expressed in µm) divided by the amount of lithium ions per unit area of ​​the electrode introduced into the electrode (anode) during the transition from the discharged to the charged state (expressed in mAh / cm²). 2) (e.g., during the so-called "formation" cycle). The coating thickness change is the difference in coating thickness between the charged state at cycle 4 and the electrode coating in the initial state. The coating thickness is measured on test cells using a high-precision digital contact sensor (with a resolution of approximately 0.1 µm) after they have undergone four charge / discharge cycles. The normalized coating thickness change can be considered a quantitative measure of the degree of swelling of an electrode coating, particularly the degree of swelling in the thickness direction. Figure 904 shows that the normalized thickness change (i.e., the degree of swelling in the direction of the electrode thickness, or z-swelling) decreases with decreasing D 50 tends to decrease. Accordingly, the normalized thickness change can be increased by using populations of fractured composite particles with D 50The thickness change can be reduced in a range of approximately 2.0 µm to approximately 8.0 µm, or in a range of approximately 2.0 µm to approximately 6.0 µm, or in a range of approximately 2.0 µm to approximately 5.0 µm, or in a range of approximately 2.0 µm to approximately 4.0 µm. The normalized thickness change can be reduced in a range of approximately 2.5 to approximately 3.0 µm / (mAh / cm²). 2 ) for populations with D 50 -values ​​in the range of approximately 2.0 µm to approximately 4.0 µm. Besides the particle size D 50Swelling can also depend on the properties of the binder, the particle size distribution, the capacity of the active particles and the Si content, the particle density, the shapes and aspect ratios of the particles, and the overall composition of the slurry (including, for example, the proportion and type of graphite when used in a mixed anode, the proportion and type of conductive additives, the proportion and type of binder, etc.). However, it has been observed that the general tendency for smaller Si-containing composite particles to exhibit less swelling is associated with D 50 The thickness must be consistent and therefore selected accordingly. The maximum permissible thickness change depends on the cell design. In general, however, less swelling can be advantageous to achieve better cell stability. In some cell designs, the anode swelling can preferably be less than 4.5 µm per mAh / cm². 2 (< about 4.5 cm 2µm / mAh). In other designs, the anode swelling can preferably be less than 3.5 µm per mAh / cm². 2 (< about 3.5 cm 2 µm / mAh). In other designs, the anode swelling can preferably be less than 3.0 µm per mAh / cm². 2 (< about 3.0 cm 2 µm / mAh). In other designs, the anode swelling can preferably be less than approximately 2.75 µm per mAh / cm². 2 (< about 2.75 cm 2 µm / mAh). In other designs, the anode swelling can preferably be less than approximately 2.5 µm per mAh / cm². 2 (<2.5 cm 2 µm / mAh).

[0148] Fig. Figure 10 shows a graphical representation of the dependence of a volumetric energy density (sometimes abbreviated as VED) of test cells on D. 50 each of the example particle populations and a graphical representation 1004 of a dependence of a volumetric charge density (sometimes abbreviated as VQD) of test cells of D 50each of the example particle populations. (Note that in these test cells, all or nearly all of the anode capacity was provided by Si-C composite particles, and no graphite was added to the anode.) VQD is defined as the anode capacity (after the fourth cycle) (expressed in mAh) divided by the anode volume (expressed in cm³). 3 VED is defined as the cell energy (after the fourth cycle) (expressed in Wh) divided by the cell's external volume (expressed in liters). Test cells with smaller particles tend to exhibit higher VED and VQD values. A test cell with a population of fractured composite particles with D 50 For example, values ​​of approximately 3.6 µm showed a VED of approximately 1095 Wh / 1 and a VQD of approximately 886 mAh / cm². 3 Accordingly, VED and / or VQD can be achieved by using a population of fractured composite particles with D 50Values ​​in the range of approximately 2.0 µm to approximately 8.0 µm, or in the range of approximately 2.0 µm to approximately 6.0 µm, or in the range of approximately 2.0 µm to approximately 5.0 µm, or in the range of approximately 2.0 µm to approximately 4.0 µm, may be increased. Several factors may contribute to the higher VED and VQD values ​​of the test cells with smaller, jagged composite particles. One factor, for example, may be the lower z-swelling in the test cells with smaller particles (see, for example, diagram 904 in [reference]). Fig. 9). Another factor could be, for example, the higher efficiency in the first cycle in test cells with smaller particles (see, for example, diagram 1302 in Fig. 13). Another factor could be, for example, the higher formation efficiency in test cells with smaller particles (see, e.g., diagram 1304 in Fig. 13). Another factor could be, for example, the lower internal resistance in test cells with smaller particles (see, for example, diagram 1402 in Fig.14). Another factor may be, for example, the higher coating density of the electrodes (anodes) in test cells with smaller particles (see, e.g., diagram 1404 in Fig. 14). Another factor could be, for example, the higher discharge voltage in test cells with smaller particles (see, e.g., diagram 1104 in Fig. 11) In addition to the particle size D 50 The VED can also depend on other factors, including the properties of the binder, the particle size distribution (PSD), the capacity of the active particles and the Si content, the particle density, the shapes and aspect ratios of the particles, and / or the overall composition of the slurry (including, for example, the proportion and type of graphite, the proportion and type of conductive additives, the proportion and type of binder, etc.). However, it has been found that the general trends in the dependence of the VED on D 50the Si-containing composite particles are consistent, so that in some versions of the D 50 The value must be chosen accordingly.

[0149] Fig. Figure 11 shows a graphical representation 1102 of a dependence of a normalized high-rate discharge capacity of test cells on D 50 each of the example particle populations and a graphical representation 1104 of a dependence of a discharge voltage of test cells on D 50each of the example particle populations. (Note that in these test cells, all or nearly all of the anode capacity was supplied by Si-C composite particles, and no graphite was added to the anode.) The normalized high-rate discharge capacity (in this case, at 2C discharge) is defined as the cell discharge capacity measured after 2C discharge divided by the cell discharge capacity measured after 0.5C discharge, with measurements taken after 20 cycles. Some test cells with populations of jagged composite particles with D 50-Values ​​in the range of approximately 2.0 µm to approximately 5.0 µm exhibited a normalized high-rate discharge capacity of more than approximately 90%. A higher normalized high-rate discharge capacity (e.g., approximately 90% or more) may be due to better impedance values ​​(e.g., lower impedance) and / or better ion diffusion values ​​due to thinner electrode coatings and / or shorter diffusion lengths at the particle. (For example, a smaller particle with a similar ion diffusivity to a larger particle may have shorter diffusion lengths.) The discharge voltage is defined as the discharge energy (Wh) divided by the discharge capacity (Ah). Some test cells with populations of fractured nano-composite particles with D 50-Values ​​in the range of approximately 2.0 µm to approximately 5.0 µm exhibited discharge voltages of more than approximately 3.5 V. Accordingly, the normalized high-rate discharge capacity and / or the discharge voltage can be increased by using populations of fractured nano-composite particles with D 50 -values ​​in a range of approximately 2.0 µm to approximately 8.0 µm, or in a range of approximately 2.0 µm to approximately 6.0 µm, or in a range of approximately 2.0 µm to approximately 5.0 µm. In addition to the particle size D 50The discharge voltage and high-rate discharge capacity can also depend on the binder properties, particle size distribution (PSD), active particle capacity and silicon content, particle density, shape of the silicon-containing nano-composite particles, particle shapes and aspect ratios, BET-SSA of the particles, and the overall composition of the slurry (including, for example, the proportion and type of graphite, the proportion and type of conductive additives, the proportion and type of binder, etc.), as well as other factors. The general trends of the discharge voltage and the dependence of the high-rate capacity of silicon-containing nano-composite particles with D 50 However, they were consistent, so that in some versions of the D 50 The value must be chosen accordingly to meet the required specifications for the cell design.

[0150] Fig.Figure 12 shows a graphical representation 1202 of a dependence of a normalized capacity (also referred to as % of the reference capacity) for lithium-ion battery test cells (with LCO cathodes, as described above), the populations of fractured nano-composite particles of D 50of approximately 3 µm and approximately 5 µm. (It should be noted that in these test cells, all or nearly all of the anode capacity was provided by Si-C composite particles, and no graphite was added to the anode.) The normalized capacity is defined as the charge capacity achieved at a given charge rate (expressed in mAh), normalized to the cycle-start capacity (capacity after completion of cycle 3) (expressed in mAh). For each charge condition, the cell was charged for at least 5 cycles to obtain an average capacity. Accordingly, the normalized capacity at faster charge rates (e.g., charge rates of more than approximately 2C, or more than approximately 3C, or more than approximately 4C, or more than approximately 5C) can be achieved by using a population of fractured composite particles with D 50-values ​​in the range of approximately 2.0 µm to 4.0 µm can be increased. A higher normalized capacitance may be due to better impedance metrics (e.g., lower impedance) and / or better ion diffusion metrics (e.g., higher ion diffusivity).

[0151] Fig. Figure 13 shows a graphical representation 1302 of a dependence of an efficiency of the test cells in the first cycle on D 50 each of the example particle populations and a graphical representation 1304 of a dependence of the formation efficiency of the test cells on D 50each of the example particle populations. (It should be noted that in these test cells, all or almost all of the anode capacity was provided by Si-C composite particles, and no graphite was added to the anode.) First-cycle efficiency is defined as the first-cycle discharge capacity divided by the first-cycle charge capacity. Some test cells with populations of fractured nano-composite particles with D 50 Values ​​in the range of approximately 2.0 µm to approximately 6.0 µm showed efficiencies of over 90% in the first cycle. The formation efficiency is defined as the discharge capacity at the beginning of the cycling (discharge capacity after completion of cycle 3) divided by the charge capacity of the first cycle. Some test cells with populations of fractured nano-composite particles with D 50Values ​​in the range of approximately 2.0 µm to approximately 6.0 µm exhibited a formation efficiency of more than 90%. Accordingly, the efficiency of the first cycle and / or the formation efficiency can be increased by enriching populations of fractured composite particles with D 50 Values ​​in a range of approximately 2.0 µm to approximately 6.0 µm are used. A higher efficiency in the first cycle (e.g., more than approximately 90%) and / or a higher formation efficiency (e.g., more than approximately 90%) may be due to better impedance metrics (e.g., lower impedance) and / or better ion diffusion metrics (e.g., higher ion diffusivity), which lead to a reduction in losses.

[0152] In addition to the particle size D 50The efficiency of the first cycle, the formation efficiency, and the normalized capacity may also depend on the binder properties, the particle size distribution (PSD), the capacity of the active particles and the Si content, the particle density, the shape of the Si-enclosing nano-composite particles, the presence of Li-trapping sites or (e.g., electronegative) elements in the composition of the Si-containing composite particles, the shapes and aspect ratios of the particles, the BET-SSA of the particles, and / or the overall composition of the slurry (including, for example, the proportion and type of graphite if used in mixed anodes; the proportion and type of conductive additives; the proportion and type of binder, etc.), among other factors.However, it was found that the general trends of the dependence of the normalized capacity (capacity maintenance), the first cycle efficiency and the formation efficiency on the Si-containing nano-composite particles of D. 50 are generally consistent, so that in some versions of the D 50 The value must be chosen accordingly to meet the required specifications for cell design.

[0153] Fig. Figure 14 shows a graphical representation of the dependence of an internal resistance of test cells on D. 50 each of the example particle populations and a graphical representation 1404 of a dependence of a coating density of electrode coatings on D 50each of the example particle populations. The internal resistance is determined as follows: A series of millisecond current pulses is applied to the cell at a state of charge of 0%, and the resulting voltages are measured. The average voltage is determined by averaging the respective voltages measured for each current pulse. The internal resistance is calculated by dividing the average voltage by the applied current. Test cells with smaller particles tended to exhibit lower internal resistance. For example, some test cells with populations of fractured nano-composite particles with D 50 -values ​​in the range of approximately 2.0 µm to approximately 6.0 µm showed internal resistance values ​​of less than approximately 10 Ω. For example, some test cells with populations of fractured nano-composite particles with D exhibited 50-values ​​in the range of approximately 2.0 µm to approximately 4.0 µm, internal resistance values ​​in the range of approximately 4 Ω to approximately 6 Ω. The coating density includes the fractured nano-composite particles, the binder, and any additives in the electrode, but not the current collector. The coating density is defined as the mass of the electrode divided by the volume of the electrode. Electrode coatings with smaller particles tended to exhibit a higher coating density. For example, some electrode coatings with populations of fractured nano-composite particles with D 50 -values ​​in a range of approximately 2.8 µm to approximately 6.0 µm; electrode coating density values ​​in a range of approximately 0.9 g / cm² 3 up to approximately 1.0 g / cm³ 3 For example, some electrode coatings with populations of fractured nano-composite particles with D 50-values ​​in a range of approximately 3.0 µm to approximately 5.0 µm; electrode coating density values ​​in a range of approximately 0.95 g / cm² 3 up to approximately 1.0 g / cm³ 3 on.

[0154] Note that the coating density and internal resistance are in addition to the D 50The particle size can also depend on the binder properties, the particle size distribution (PSD), the capacity of the active particles and the Si content, the particle density, the shape and composition of the Si-containing nano-composite particles, the conductivity of the surface of the Si-containing composite particles, the proportion of binder coating the outer surface of the particles, the shapes and aspect ratios of the particles, the BET-SSA value of the particles, the overall composition of the slurry (including, for example, the proportion and type of graphite if used in mixed anodes, the proportion and type of conductive additives, the proportion and type of binder, etc.), among other factors. The general trends in the dependence of the coating density and the internal resistivity on the Si-containing nano-composite particles of D 50 However, they proved to be generally consistent, so that in some versions of the D50 The value can be chosen accordingly to meet the required specifications for the cell design.

[0155] Fig. Figure 15 shows a graphical diagram 1502 of a dependence of a specific surface area according to Brunauer-Emmett-Teller (BET-SSA), as measured by analysis of N2 sorption-desorption isotherms at 77 K, of D 50 each of the example particle populations and a graphical diagram 1504 of a dependence of an area-related binder loading on D 50 Each of the example particle populations. The BET-SSA of each example population of fractured nano-composite particles was measured by nitrogen gas physisorption (around 77 K) on powder samples that had been degassed for 10 hours at 300 °C under vacuum. The BET-SSA value tends to increase as the particle size (e.g., D) increases. 50 ) decreases. For example, some populations of fractured nano-composite particles with D 50-values ​​in a range of approximately 2.0 µm to approximately 4.0 µm; BET-SSA values ​​in a range of approximately 8 to approximately 18 m 2 / g. For example, some populations of fractured nano-composite particles with D 50 -values ​​in a range of approximately 4.0 µm to approximately 6.0 µm; BET-SSA values ​​in a range of approximately 3 to approximately 14 m 2 / g. For example, some populations of fractured nano-composite particles with D 50 -values ​​in a range of approximately 6.0 µm to approximately 8.0 µm; BET-SSA values ​​in a range of approximately 3 to approximately 12 m 2The area-specific binder loading of an electrode coating is defined as the mass fraction of the binder in the electrode coating, divided by the product of (1) the mass fraction of the fractured composite particles in the electrode coating and (2) the BET-SSA value of the respective population of fractured composite particles. In graphical representation 1504, the area-specific binder loading is shown in mg / m². 2 specified. In the examples shown, the area-related binder loading tends to decrease as the particle size (e.g., D) decreases. 50 ) decreases. For smaller particles (e.g., D 50 (between approximately 2.0 µm and approximately 4.0 µm) there is a tendency towards less binder per unit surface area of ​​the composite particles due to their high BET-SSAs. For example, some populations of fractured composite particles with D 50-values ​​in a range of approximately 2.0 µm to approximately 4.0 µm to area-related binder loading values ​​for the corresponding electrode coatings in a range of approximately 5 to approximately 14 mg / m² 2 For example, some populations of fractured composite particles with D 50 -values ​​in a range of approximately 4.0 µm to approximately 6.0 µm to area-related binder loading values ​​for the corresponding electrode coatings in a range of approximately 6 to approximately 22 mg / m² 2 For example, some populations of fractured composite particles with D 50 -values ​​in a range of approximately 6.0 µm to approximately 8.0 µm to area-related binder loading values ​​for the corresponding electrode coatings in a range of approximately 8 to approximately 24 mg / m² 2The lower binder loading can have a beneficial effect on the impedance and / or ion diffusion metrics. In some embodiments, the area-specific binder loading of the battery electrode (e.g., the anode, which comprises Si-C nano-composite particles) is in the range of approximately 2.0 mg / m². 2 up to approximately 15.0 mg / m³ 2 (e.g., in some versions of approximately 2.0 mg / m³) 2 up to approximately 5.0 mg / m³ 2 ; in other versions of approximately 5.0 mg / m³ 2 up to approximately 9.0 mg / m³ 2 ; in other versions of approximately 9.0 mg / m³ 2 up to approximately 13.0 mg / m³ 2 ).

[0156] In some embodiments, lithium-ion battery cells have anodes containing smaller, jagged composite particles with D 50-values ​​in a range of about 2.0 µm to about 4.0 µm, exhibit advantageous properties such as lower z-swelling (e.g., Diagram 904), higher VED (e.g., Diagram 1002), higher VQD (e.g., Diagram 1004), faster discharge (e.g., Diagram 1102) and faster charge (e.g., Diagram 1202), higher discharge voltage (e.g., Diagram 1104), and lower internal resistance (e.g., Diagram 1402). However, in some embodiments, some lithium-ion battery cells with anodes containing larger, jagged composite particles with D 50 -values ​​in a range of approximately 4.0 µm to approximately 7.0 µm or in a range of approximately 4.0 µm to approximately 6.0 µm, exhibit a better cycle life than some lithium-ion battery cells with anodes that contain smaller, jagged composite particles with D 50 -values ​​in a range of approximately 2.0 µm to approximately 4.0 µm.

[0157] An additional feature that can be determined from a particle size distribution (PSD) of a particle population is a cumulative volume fraction, defined as the cumulative volume of particles with D 50 -values ​​of a D 50 -threshold value or less, divided by the total volume of all particles. In some of the examples considered here, the D 50 The threshold was set at 4.6 µm. Particle populations with D were analyzed. 50 -values ​​in a range of approximately 2.0 µm to approximately 4.0 µm were produced, with the corresponding cumulative volume fractions (D 50 -threshold of 4.6 µm) ranged between approximately 58% and approximately 96%. Lithium-ion battery test cells were fabricated with anodes containing each of these particle populations, and the cycle life was measured for each test. The results are shown in Figure 1602 in Fig.Figure 16 shows the dependence of the cycle lifetime (in Si-C composite anode / LCO cathode cells) on the respective cumulative volume fractions (D). 50-threshold of approximately 4.6 µm). Some examples with higher cumulative volume fractions (e.g., higher than approximately 80 vol%, or higher than approximately 85 vol%, or higher than approximately 90 vol%) exhibited shorter cycle lifetimes (e.g., less than approximately 500 cycles, less than approximately 450 cycles, or less than approximately 400 cycles). Higher cumulative volume fractions may indicate the presence of large quantities of finer particles (e.g., particle sizes of less than approximately 2.0 µm, less than approximately 1.0 µm, or less than approximately 0.5 µm), which may lead to a more frequent occurrence of undesired side reactions between the composite particles and the electrolyte. In some embodiments, cycle lifetime values ​​of more than approximately 500 cycles, more than approximately 550 cycles, or more than approximately 600 cycles can be achieved by adjusting the PSDs of populations of fractured composite particles.In some embodiments, the PSDs can be adjusted to achieve a cumulative volume fraction (4.6 µm threshold) of less than approximately 90% or less than approximately 85% or less than approximately 80% or in a range of approximately 60% to approximately 85% or in a range of approximately 60% to approximately 80% or in a range of approximately 70% to approximately 85% or in a range of approximately 70% to approximately 80% or in a range of approximately 65% ​​to approximately 85% or in a range of approximately 65% ​​to approximately 80%.

[0158] In the Fig. In the 16 described examples, composite particle populations with D were used. 50 -values ​​in a range of approximately 2.0 µm to approximately 4.0 µm with the corresponding cumulative volume fractions (D 50-threshold of approximately 4.6 µm) between approximately 58% and approximately 96% of the performance characteristics of lithium-ion battery cells (in Si-C composite anode / LCO cathode cells). In some embodiments, a volume-weighted particle size parameter of the fiftieth percentile (D) is used. 50 ) the PSD in a range of approximately 1.0 µm to approximately 12.0 µm (in some embodiments from approximately 1.0 µm to approximately 2.0 µm; in other embodiments from approximately 2.0 µm to approximately 4.0 µm; in still other embodiments from approximately 4.0 µm to approximately 6.0 µm; in still other embodiments from approximately 6.0 µm to approximately 12.0 µm). In some embodiments (e.g., when the D 50 (where the value is in a range of approximately 2.0 µm to approximately 4.0 µm), the cumulative volume fraction at the threshold particle size of approximately 4.6 µm is approximately 90 vol% or less, or approximately 85 vol% or less, or approximately 80 vol% or less. In other embodiments (e.g., when the D 50(where the value is in a range of approximately 4.0 µm to approximately 6.0 µm), the cumulative volume fraction at the threshold particle size of approximately 7 µm is approximately 90 vol% or less, or approximately 85 vol% or less, or approximately 80 vol% or less. In other embodiments (e.g., when the D 50 (where the particle size is in a range of approximately 6.0 µm to approximately 12.0 µm), the cumulative volume fraction at the threshold particle size of approximately 15 µm is approximately 90 vol% or less, or approximately 85 vol% or less, or approximately 80 vol% or less. It should be noted that the presence of excessively large particles can impair the cell's performance characteristics (e.g., reduced cell stability, increased impedance, reduced rate performance, etc.). In some embodiments (e.g., when the D 50(where the value is in a range of approximately 2.0 µm to approximately 4.0 µm), the cumulative volume fraction at the threshold particle size of approximately 10 µm is approximately 80 vol.% or more. In some embodiments (e.g., when the D 50 (where the value is in a range of approximately 2.0 µm to approximately 4.0 µm), the cumulative volume fraction at the threshold particle size of approximately 12 µm is approximately 90 vol.% or more. In other embodiments (e.g., when the D 50 (where the value is in a range of approximately 4.0 µm to approximately 6.0 µm), the cumulative volume fraction at the threshold particle size of approximately 15 µm is approximately 80 vol.% or more. In other embodiments (e.g., when the D 50 (where the value is in a range of approximately 4.0 µm to approximately 6.0 µm), the cumulative volume fraction at the threshold particle size of approximately 22 µm is approximately 90 vol.% or more. In other embodiments (e.g., when the D50(in a range of approximately 6.0 µm to approximately 12.0 µm), the cumulative volume fraction at the threshold particle size of approximately 28 µm is approximately 80 vol.% or more. In other embodiments (e.g., when the D 50 (where the particle size is in a range of approximately 6.0 µm to approximately 12.0 µm), the cumulative volume fraction at the threshold particle size of approximately 32 µm is approximately 90 vol% or more.

[0159] As can be seen in graphic 1502, the BET-SSA values ​​show a dependence on the D 50 -values ​​of the populations of fractured composite particles. Accordingly, as shown in 1504, the areal binder loading also shows a dependence on the D 50 -values ​​when the binder mass fraction in the electrode coating is kept in a range of approximately 6.5 to approximately 11.5 wt.%. Several lithium-ion battery cells with anodes containing a population of fractured nano-composite particles with D 50The particles, measuring approximately 7.42 µm, were produced with different binder mass fractions in the electrode (anode) coating and compared to a lithium-ion battery cell that has an anode with a population of jagged nano-composite particles with D 50 of approximately 5.35 µm. Fig. Figure 17 shows a graphic representation 1702, which illustrates the dependence of an area-related binder loading on the mass fraction of the binder for each of the selected particle populations. The binder mass fraction of the test cells with the D 50The binder mass fraction of approximately 7.42 µm was varied between approximately 6.5 wt.% and approximately 11.5 wt.%. In the example shown, a binder mass fraction of approximately 6.5 wt.% corresponds to a mass fraction of the fractured composite particles in the electrode of approximately 93.4 wt.%. In the example shown, a binder mass fraction of approximately 11.5 wt.% corresponds to a mass fraction of the fractured composite particles in the electrode of approximately 88.4 wt.%. The mass fraction of the binder in the test cell of the control sample with a D 50 The μ-value of approximately 5.35 µm corresponded to approximately 10.4 wt.%. The surface-related binder loading was in the range of approximately 8 mg / m². 2 up to approximately 16 mg / m³ 2 .

[0160] Fig. Figure 18 shows a graphical representation 1802 of a dependence of cycle lifetime on the mass fraction of the binder for each of the test cells of Fig. 17. The test cells (D 50Copper current collectors with a thickness of approximately 7.42 µm and binder mass fractions of approximately 10.4 wt.% and 11.5 wt.% exhibited a lithium coating during the charging process, indicating that at least part of the measured capacity is attributable to a lithium coating on the copper current collectors. In some embodiments, the lithium coating is preferably avoided for safety reasons. In some embodiments, the area-related binder loading (e.g., more than approximately 13 mg / m²) can be reduced. 2 ) corresponding to these binder mass fractions (e.g., approximately 10.4 wt.%, approximately 11.5 wt.%) are too high. In the other test cells (D 50 of approx. 7.42 µm, binder mass fractions of approx. 6.5 wt.%, approx. 7.5 wt.%, approx. 8.5 wt.% and approx. 9.5 wt.%) and in the test cell of the control sample (D 50 No lithium deposition was observed in the test cell (D) of approximately 5.35 µm, binder mass fraction of approximately 10.4 wt%. 50Test cells with a coating thickness of approximately 7.42 µm and a binder mass fraction of approximately 6.5 wt.% showed adhesion failure of the coating on the current collector, resulting in a short cycle life and possibly indicating that the amount of binder in this example was insufficient. Test cells with medium binder mass fractions (e.g., approximately 7.5 wt.%, approximately 8.5 wt.%, approximately 9.5 wt.%) with corresponding area-specific binder loading values ​​(e.g., in the range of approximately 9.0 mg / m²) 2 up to approximately 13 mg / m³ 2 ) exhibited cycle lifetime values ​​of more than 800 cycles. Accordingly, in some embodiments (e.g., D) 50in a range of approximately 6.0 µm to approximately 8.0 µm), binder mass fractions greater than approximately 6.6 wt.% or greater than approximately 7.0 wt.% or less than approximately 10.3 wt.% or less than approximately 10.0 wt.% or in a range of approximately 6.6 wt.% to approximately 10.3 wt.% or in a range of approximately 6.6 wt.% to approximately 10.0 wt.%, or in a range of approximately 7.0 wt.% to approximately 10.3 wt.%, or in a range of approximately 7.0 wt.% to approximately 10.0 wt.%, or in a range of approximately 7.0 wt.% to approximately 8.0 wt.%, or in a range of approximately 8.0 wt.% to approximately 9.0 wt.%, or in a range of approximately 9.0 wt.% to approximately 10.0 wt.%. In some embodiments (e.g., D 50 (in a range of approximately 6.0 µm to approximately 8.0 µm) area-related binder loading values ​​can be greater than approximately 9.0 mg / m². 2 or less than approximately 13.0 mg / m³ 2 or in a range of approximately 9.0 mg / m³ 2 up to approximately 13.0 mg / m³ 2or in a range of approximately 9.0 mg / m³ 2 up to approximately 10.0 mg / m³ 2 or in a range of approximately 10.0 mg / m³ 2 up to approximately 11.0 mg / m³ 2 or in a range of approximately 11.0 mg / m³ 2 up to approximately 12.0 mg / m³ 2 or in a range of approximately 12.0 mg / m³ 2 up to approximately 13.0 mg / m³ 2 to be given preference.

[0161] Fig. Figure 18 shows a graphical representation 1804 of a dependence of a normalized coating thickness change on the mass fraction of the binder for each of the test cells of Fig. 17. The normalized thickness change data are an indicator of the swelling of the electrode coating in the thickness direction (z-swelling). In the test cells shown (D 50 (of approximately 7.42 µm) the normalized coating thickness changes remain at less than approximately 3.0 µm (cm²). 2 / mAh) for binder mass fractions of approximately 7.0 wt.% to approximately 10.0 wt.%, comparable to other lithium-ion battery cells with populations of fractured composite particles of D 50 in a range of approximately 2.0 µm to approximately 4.0 µm (e.g. graphic representation 904).

[0162] Fig. Figure 19 shows a graphical representation from 1902 of a dependence of a volumetric energy density (VED) on the mass fraction of the binder for each of the test cells of Fig. 17 and a graphical representation from 1904 of a dependence of the volumetric charge density (VQD) on the mass fraction of the binder for each of the test cells of Fig. 17. VQD values ​​of more than 650 mAh / cm² 3 and VED values ​​of more than 950 Wh / 1 were measured in test cells (D 50 observed in the case of approximately 7.42 µm) with binder mass fractions of approximately 7.0 wt.% to approximately 10.0 wt.%.

[0163] Fig.Figure 20 shows a graphical diagram from 2002 illustrating the dependence of a discharge voltage on the mass fraction of the binder for each of the test cells. Fig. 17 and a graphical diagram from 2004 showing the dependence of an internal resistance on the mass fraction of the binder for each of the test cells of Fig. 17. Discharge voltage values ​​greater than approximately 3.5 V and internal resistance values ​​in the range of approximately 15 Ω to approximately 25 Ω were observed in test cells (D 50 observed in binder mass fractions of approximately 7.42 µm to approximately 10.0 wt.%.

[0164] Fig. Figure 21 shows a graphical diagram 2102 of a dependence of the efficiency of the first cycle on the mass fraction of the binder for each of the test cells of Fig. 17 and a graphical diagram 2104 of a dependence of a forming efficiency on the mass fraction of the binder for each of the test cells of Fig. 17. In test cells (D 50Formation efficiencies of more than approximately 83% and first-cycle efficiencies of more than approximately 83% were observed with binder mass fractions of approximately 7.42 µm and binder mass fractions of approximately 7.0 wt.% to approximately 10.0 wt.%.

[0165] In some designs (e.g., in mixed anodes with an anode capacity in the range of approximately 450 mAh / g to approximately 1600 mAh / g, normalized to the mass of the active materials, such as graphite and Si-C composites or other Si-containing anode materials; in some designs for the mixed anodes with a capacity in the range of approximately 500 mAh / g to approximately 1400 mAh / g, normalized to the mass of the active materials; in some designs for the mixed anodes with a capacity in the range of approximately 600 mAh / g to approximately 1200 mAh / g, normalized to the mass of the active materials), it can be advantageous to have a narrow particle size distribution (PSD) of the Si-containing composite (e.g., Si-C nano-composite) particles.It was found that the high proportion of fines (undesirably small particles) in the Si-C composite powder increases the external surface area of ​​these particles, their BET-SSA value, and the surface area of ​​these particles exposed to the electrolyte during cycling. This leads to a larger volume fraction of SEI formed during formation and storage, faster degradation during cycling, faster degradation during battery storage at room temperature and elevated temperatures, excessive gas formation during formation, and other undesirable results. In particular, it was found that in some formulations, it may be advantageous if the D. 10The diffraction value (measured by laser scattering or another suitable technique) of the Si-C nanocomposites (for use in a mixed anode) is greater than approximately 1 µm for spheroidal (e.g., spherical or nearly spherical) particles and greater than approximately 2 µm for jagged (or cylindrical) particles. In some embodiments, it may be advantageous if the D 10 The BET-SSA value of the fractured (or cylindrical) particles is in the range of approximately 2 to approximately 7 µm (in some embodiments from approximately 2 to approximately 3 µm; in other embodiments from approximately 3 to approximately 4 µm; in other embodiments from approximately 4 to approximately 5 µm; in other embodiments from approximately 5 to approximately 6 µm; in still other embodiments from approximately 5 to approximately 6 µm). In some embodiments, it has been found that it can be advantageous if the BET-SSA of the Si-C nano-composite powder (for use in a mixed anode) is in the range of approximately 1 to approximately 11 µm. 2 / g lies (in some versions from about 1 to about 2 m) 2 / g; in other versions from about 2 to about 4 m 2 / g; in other versions from about 4 to about 6 m 2 / g; in other versions from about 6 to about 8 m 2 / g; in other versions from about 8 to about 11 m 2 / g; in other versions from about 3 to about 7 m 2 / G).

[0166] Interestingly, it was found in some versions that the optimal PSD and the optimal D 50 , D 90 , and D 99 The Si-C composite particles for the mixed anodes may differ from those for the anode containing only Si-C composite material as active materials.

[0167] To achieve good performance in batteries, it has been found that Si-C nanocomposites (in mixed anodes) must exhibit moderately small volume changes during cycling and thus contain internal pores (e.g., a total pore volume in the range of approximately 5 to approximately 50 vol%, as estimated by powder density measurements or argon gas pycnometry or another suitable technique). However, mixed anodes must be compacted (calendered) to achieve high volumetric capacity and adequate power in the cells. Lower weight fractions of Si-C composites in the mixed anode often necessitate a higher calendering pressure (compaction pressure).Such high pressures can lead to cracking in the Si-C composites, exposing part of the internal surface and pores to the ambient air (and the electrolyte in a battery), which can result in excessive side reactions with the electrolyte. While large Si-C composites exhibit a lower BET, excessively large Si-C composite particles can suffer more from such mechanical damage during calendering. Furthermore, we have found that excessively large Si-C composite particles increase the roughness of the mixed anode (especially in anodes with lower area-specific capacitance loading), decrease its volumetric capacitance, increase the unevenness of the area-specific capacitance distribution, significantly reduce the mechanical stability of the anode during cycling (e.g., leading to detachment from the current collector or separation of the active material), and cause separator damage, etc.which can cause and reduce cycle stability.

[0168] Particularly in some designs (e.g., in mixed anodes with an anode capacity in the range of approximately 450 mAh / g to approximately 1600 mAh / g, normalized to the mass of the active materials, such as graphite and Si-C composites or other Si-containing anode materials; in some designs for mixed anodes with a capacity in the range of approximately 500 mAh / g to approximately 1400 mAh / g, normalized to the mass of the active materials; in some designs for mixed anodes with a capacity in the range of approximately 600 mAh / g to approximately 1200 mAh / g, normalized to the mass of the active materials), it has been found that it can be advantageous if the D 90-value (measured using laser scattering or another suitable technique) of the Si-C nano-composite powders (for use in a mixed anode) less than about 40 µm for spheroidal (e.g.spherical or nearly spherical) particles (in some versions less than about 30 µm; in other versions less than about 25 µm; in other versions less than about 20 µm; in other versions less than about 15 µm) less than about 40 µm for jagged particles (in some versions less than about 30 µm; in other versions less than about 25 µm; in other versions less than about 20 µm; in other versions less than about 15 µm) and less than 60 µm for cylindrical particles (in some versions less than about 50 µm; in other versions less than about 40 µm; in other versions less than about 30 µm; in other versions less than about 25 µm; in other versions less than about 20 µm; in other versions less than approximately 15 µm). In some versions, it has been noted that it may be advantageous if the D. 99-value (measured by laser scattering or another suitable technique) of the Si-C nano-composites (for use in a mixed anode) less than about 50 µm for spheroidal (e.g.spherical or nearly spherical particles (in some embodiments less than about 40 µm; in other embodiments less than about 35 µm; in other embodiments less than about 30 µm; in other embodiments less than about 25 µm; in other embodiments less than about 20 µm), less than about 50 µm for jagged particles (in some embodiments less than about 40 µm; in other embodiments less than about 35 µm; in other embodiments less than about 30 µm; in other embodiments less than about 25 µm; in other embodiments less than about 20 µm) and less than 80 µm for cylindrical particles (in some embodiments less than about 60 µm; in other embodiments less than about 50 µm; in other embodiments less than about 40 µm; in other embodiments less than approximately 30 µm; in other embodiments less than approximately 20 µm).It should be noted that lithium-ion batteries for motor vehicles generally have a higher capacity-to-surface charge and therefore the electrodes are usually thicker than those in lithium-ion batteries for consumer electronics applications (e.g., laptops, mobile phones, fitness trackers, etc.) or private drone applications. Thicker electrodes also allow for larger capacities. 50 , D 90 or D 99 be accepted.

[0169] To achieve good performance in lithium-ion batteries, in some embodiments the full width at half the maximum (FWHM) of the particle size distribution of Si-C nano-composite powders (in mixed anodes with an anode capacity in the range of about 450 mAh / g to about 1600 mAh / g, normalized to the mass of the active materials, such as graphite and Si-C composites or other Si-containing anode materials; in some embodiments for the mixed anodes with a capacity in the range of about 500 mAh / g to about 1400 mAh / g, normalized to the mass of the active materials; in some embodiments for the mixed anodes with a capacity in the range of about 600 mAh / g to about 1200 mAh / g, normalized to the mass of the active materials) is preferably in the range of about 3 to about 12 µm (in some embodiments from about 4 to about 8 µm; in some versions from about 5 to about 7 µm; in some versions from about 3 to about 5 µm;in some versions from about 7 to about 9 µm; in some versions from about 9 to about 12 µm).;

[0170] To achieve good performance in lithium-ion batteries, it turned out that in some designs the range ((D 90 -D 10 ) / D 50) the particle size distribution of Si-C nano-composite powders (in mixed anodes with an anode capacity in the range of about 450 mAh / g to about 1600 mAh / g, normalized to the mass of the active materials, such as graphite and Si-C composites or other Si-containing anode materials); in some embodiments for the mixed anodes with a capacity in the range of about 500 mAh / g to about 1400 mAh / g, normalized to the mass of the active materials; in some embodiments for the mixed anodes with a capacity in the range of about 600 mAh / g to about 1200 mAh / g, normalized to the mass of the active materials), preferably below about 3 (in some embodiments preferably below about 2; in other embodiments preferably below about 1; in other embodiments preferably below about 0.8).In some embodiments, the range of the particle size distribution of Si-C nano-composite powders (in such mixed anodes) can preferably be in the range of about 0.3 to about 3 (in some embodiments preferably from about 0.3 to about 2; in other embodiments preferably from about 0.3 to about 1.0; in other embodiments preferably from about 0.3 to about 0.8; in other embodiments preferably from about 0.4 to about 1.2).

[0171] Fig.Figure 22 shows an SEM image (2201) of a population of fractured composite particles (including agglomerates of fractured particles) without any optimization of the population's particle size distribution (PSD). The particles shown in SEM image 2201 include fine particles (so-called "fines") and coarse particles. Some of the particles may be agglomerates of smaller particles. The definition of fine particles depends on the specific application but can be defined as particles with a diameter (e.g., measured by LPSA) at or below a threshold value (e.g., about 0.5 µm, about 1.0 µm, about 1.5 µm, about 2.0 µm, etc.). The definition of coarse particles depends on the specific application, but can be defined as particles with a diameter (e.g., measured with LPSA) at and above a threshold value (e.g., about 5 µm, about 7 µm, about 8 µm, about 10 µm, about 15 µm, about 20 µm, about 30 µm, about 40 µm, about 50 µm, etc.).The composite particles in SEM image 2201 have jagged, irregular shapes and can exhibit a range of aspect ratios. These composite particles are in the form in which they were prepared, and the population PSD was not optimized. The D. 50 The population size is approximately 10 µm.

[0172] Fig.Figure 22 shows an SEM image (2202) of a cross-section of an electrode coating containing a mixture of the fractured particle population shown in Figure 2201 and graphite particles as the active electrode material. A slurry containing the electrode's active material was poured onto a copper current collector, and the solvent in the slurry was dried. The electrode coating was calendered with a force of 14 tons. Despite the calendering, the cross-sectional image (2202) shows that some of the particles protrude from the surface of the electrode coating. Such an effect can be observed, for example, when the composite particle population includes particles with diameters larger than the thickness of the electrode coating. It has been found that the use of composite particles, as in the example of Figure 2201, Fig.22 frequently leads to suboptimal (often insufficiently good or unacceptable) performance in mixed-anode lithium-ion batteries (especially in lithium-ion batteries for vehicles and consumer electronics). The term "mixed anode" refers to anodes in which the active electrode material is a mixture of composite particles and graphite particles.

[0173] Fig. Figure 23 shows a SEM image (2301) of a population of fractured composite particles after optimization of the population's particle size distribution (PSD). Before optimization of its PSD, the population had a D 50 -value of approximately 10 µm. The PSD optimization process included the removal of fine particles (the removed fine particles had a D 50 -value of approximately 1.5 µm) and the removal of coarse particles (the removed coarse particles had a D 50(value of approximately 15 µm). For the results shown, the removal of fine and coarse particles was achieved by sieving. In other cases, other methods for particle size selection (e.g., sieving, centrifugation, other aerodynamic size classification, or other methods) can be used. In SEM image 2301, the number of fine and coarse particles has decreased compared to SEM image 2201. The variance of the PSD is smaller in population 2301 (after PSD optimization) than in population 2201 (without PSD optimization). Population 2301 appears to have a more uniform size compared to population 2201.

[0174] Fig.Figure 23 shows an SEM image (2302) of a cross-section of an electrode coating containing a mixture of the jagged particles and graphite particles shown in Figure 2301 as the active electrode material. A slurry containing the active electrode material was poured onto a copper current collector, and the solvent of the slurry was dried. The electrode coating was calendered with a force of 14 tons. In contrast to cross-sectional image 2202, no particle protrusions are visible in cross-sectional image 2302. The surface of the electrode coating appears to be smooth. It has been shown that the use of composite particles, as in the example of Figure 2301, is advantageous. Fig. 23 often leads to superior (often very good, sufficiently good or acceptable) performance in mixed anode Li-ion batteries (especially in Li-ion batteries for motor vehicles and consumer electronics).

[0175] Fig.Figure 24 shows graphs 2401 and 2402 of the volume-weighted particle size distributions (PSDs) (expressed in volume percent) of example populations of fractured composite particles. Graph 2401 shows the PSDs of example populations of the respective D 50 -values ​​that exhibit relatively wide PSDs, before optimization of the respective PSDs. Graphical representation 2402 shows (1) the PSD of an example population before optimization of its PSD (D 50 (of approximately 10.1 µm) and (2) the PSD of an example population after optimization of its PSD (D 50 (of approximately 9.8 µm). The PSD optimization processes include the removal of fine and coarse particles. As a result of these PSD optimization processes, the PSD has changed from a relatively broader PSD (e.g., larger span, larger FWHM) to a relatively narrower PSD (e.g., smaller span, smaller FWHM). As in Fig.Figure 24 shows that the FWHM refers to the full width at half the maximum of the PSD distribution.

[0176] Table 1 ( Fig. 25) summarizes selected features (D 10 , D 50 , D 90 , D 99 , span, FWHM, D 10 / D 50 , BET-SSA) of example populations of fractured composite particles. Graphic 2401 shows the PSDs of (1) a population with a D 50 -value of approximately 3.65 µm, which corresponds to composite particle sample No. 1 in Table 1; (2) a population with a D 50 -value of approximately 5.03 µm, which corresponds to composite particle sample No. 2 in Table 1; (3) a population with a D 50 -value of approximately 8.02 µm, which corresponds to composite particle sample No. 3 in Table 1; and (4) a population with a D 50-value of approximately 13.31 µm, which corresponds to composite particle sample No. 5 in Table 1. As can be seen from Table 1, these population samples (Nos. 1, 2, 3, and 5) have not undergone any optimization of their PSD (so-called "broad" PSD). Graphic 2401 shows that populations of fractured composite particles with a range of D 50 -values ​​(e.g., in the example shown, in the range between approximately 3.65 and approximately 13.31 µm) with a relatively wide range (e.g., in a range from approximately 1.9 to approximately 2.07) can be obtained by adjusting the conditions for the synthesis of the composite particles and the comminution of larger particles into smaller particles. Populations that have not undergone PSD optimization (e.g., the samples shown in 2401) may have been subjected to comminution to achieve a desired average particle size (e.g., D). 50 ) to obtain, but were not freed from fine and coarse particles.

[0177] Graphic 2402 shows the PSDs of (1) a population with a D 50 -value of approximately 9.82 µm, which corresponds to the composite particle sample No. 8 in Table 1, and (2) a population with a D 50-value of approximately 10.16 µm, corresponding to composite particle sample No. 4 in Table 1. Graph 2402 compares the range of a population of fractured composite particles that was not subjected to PSD optimization (sample No. 4 with a range of approximately 1.97 and an FWHM of approximately 23.0 µm) with the range of a population of fractured composite particles that was subjected to PSD optimization (sample No. 8 with a range of approximately 0.67 and an FWHM of approximately 6.0 µm). Accordingly, graph 2402 illustrates the considerable effects of PSD optimization (e.g., the removal of fine and coarse particles) on the range and FWHM value of the fractured composite particle populations.

[0178] In Table 1 ( Fig.25) Population samples Nos. 1, 2, 3, 4, and 5 were not subjected to any PSD optimization process and are designated as having “wide” PSDs. Population samples Nos. 6, 7, 8, and 9 underwent PSD optimization processes and are designated as having “narrow” PSDs. Each population sample was used to fabricate mixed anodes of two types: Type A and Type B. Each population sample of fractured Si-C composite particles exhibited a specific lithiation capacity in the first cycle of approximately 1900 mAh / g (corresponding to a Si mass fraction in the Si-C composite particles of approximately 51 wt%, with the remainder of the Si-C composite particles containing carbon). In the examples shown, the active material of the mixed anode electrode consists of a mixture of graphite particles and the corresponding fractured composite particles.For electrodes of type A, the active material of the electrode exhibited a first-cycle lithiation capacity of approximately 600 mAh and consisted of approximately 16 wt% of the corresponding fractured composite particles and approximately 84 wt% of graphite particles. For electrodes of type B, the active material of the electrode exhibited a first-cycle lithiation capacity of approximately 1000 mAh and consisted of approximately 42 wt% of the corresponding fractured composite particles and approximately 58 wt% of graphite particles. For each electrode type (type A, type B) of each population sample, a coating density measured after calendering is given in Table 1. Li-ion battery cells were fabricated for each electrode type of each population sample, and their performance characteristics were evaluated. A cycle lifetime is given for Li-ion battery cells of each electrode type and each composite particle population. In some embodiments of a mixed anode (e.g.,(a mixture of Si-C composite particles and graphite particles) the mass fraction of the Si-C composite particles (e.g., fractured Si-C composite particles) in the battery electrode composition (excluding binder) can be in a range of approximately 10 wt.% to approximately 70 wt.% (e.g., approximately 10 to approximately 20 wt.%, approximately 20 to approximately 30 wt.%, approximately 30 to approximately 40 wt.%, approximately 40 to approximately 50 wt.%, approximately 50 to approximately 60 wt.%, or approximately 60 to approximately 70 wt.%). In some embodiments of a mixed anode (e.g., a mixture of Si-C composite particles and graphite particles), the mass fraction of the graphite particles in the battery electrode composition (excluding binder) can be in a range of about 30 wt.% to about 90 wt.% (e.g., about 30 to about 40 wt.%, about 40 to about 50 wt.%, about 50 to about 60 wt.%, about 60 to about 70 wt.%, about 70 to about 80 wt.%, or about 80 to about 90 wt.%).

[0179] Details regarding the fabrication and testing of the electrodes and Li-ion battery cells listed in Table 1 are as follows. For type A electrodes (~600 mAh / g), a water-based slurry containing a binder based on a polyacrylic acid (PAA) salt copolymer (approx. 4 wt%), single-walled carbon nanotubes (approx. 0.05 wt%), and an active material for the anode electrode (approx. 95.95 wt%) was applied to a 10 µm thick copper foil with an area-specific capacitance loading of approx. 4.1 mAh / cm². 2 The active electrode material (approximately 100 parts by weight) was a mixture of Si-C composite particles (approximately 16 parts by weight) and graphite particles (approximately 84 parts by weight). The type A electrodes were calendered with a force of 16 tons to achieve coating densities in the range of approximately 1.53 to approximately 1.76 g / cm². 3To achieve this, a water-based slurry containing a binder based on a polyacrylic acid (PAA) salt copolymer (approx. 6.6 wt%), single-walled carbon nanotubes (approx. 0.1 wt%), and an active material for the anode electrode (approx. 93.3 wt%) was applied to a 10 µm thick copper foil with an area-specific capacitance loading of approx. 4.1 mAh / cm² for type B electrodes (~1000 mAh / g). 2 The active electrode material (approximately 100 parts by weight) was a mixture of Si-C composite particles (approximately 42 parts by weight) and graphite particles (approximately 58 parts by weight). The type B electrodes were calendered with a force of 14 tons to achieve coating densities in the range of approximately 1.27 to approximately 1.42 g / cm². 3 to achieve this. The electrodes were then assembled into single-layer pouch cells (area of ​​approximately 6.25 cm²). 2) with an NCM811 cathode (made of a lithium nickel manganese cobalt oxide (NCM) with the approximate composition Li[Ni 0,8 Co 0,1 Mn 0,1 ]O2), a 10 µm ceramic separator, and an electrolyte formulation containing 13.92 wt% LiPF6 (as the primary lithium salt), 13.33 wt% fluoroethylene carbonate (FEC), 5.04 wt% ethylene carbonate (EC), 3.85 wt% ethyl methyl carbonate (EMC), 62.49 wt% dimethyl carbonate (DMC), 0.52 wt% vinylene carbonate (VC), and 0.85 wt% lithium difluorophosphate (LFO). After the electrolyte formulation was added to the Li-ion battery cell, the cell was cycled under the following charge / discharge test conditions. The charge / discharge test conditions include constant current and constant potential (CCCP) at 2C charge to 4.0V and drop to 1C, followed by CCCP at 1C charge to 4.2V and drop to 0.05C, followed by 1C discharge.

[0180] Table 1 ( Fig.Figure 25) shows the cycle lifetime of Li-ion battery cells obtained from the individual particle populations and electrode types. For each composite particle population, cells with type A electrodes (~600 mAh / g) exhibited higher cycle lifetime values ​​than cells with type B electrodes (~1000 mAh / g). Cycle lifetime values ​​of more than 1900 cycles were measured for three of the “narrow” PSD samples: (1) Population No. 7, electrode type A, D 10 of approximately 4.69 µm, D 50 of approximately 6.77 µm, a ratio D 10 / D 50 of approximately 69%, range of approximately 0.74, BET-SSA of approximately 6.7 m 2 / g, 2251 cycles; (2) Population No. 8, Electrode type A, D 10 of approximately 7.05 µm, D 50 of approximately 9.82 µm, a ratio D 10 / D 50 of approximately 72%, range of approximately 0.67, BET-SSA of approximately 3.7 m 2 / g, 2276 cycles; and (3) Population No. 9, Electrode Type A, D 10 of approximately 11.61 µm, D 50of approximately 16.8 µm, a ratio D 10 / D 50 of approximately 69%, range of approximately 0.74, BET-SSA of approximately 2.8 m 2 / g, 1919 cycles. The cycle lifetime of another “narrow” PSD sample was not as good, e.g., population no. 6, electrode type A, D 10 of approximately 0.9 µm, D 50 of approximately 2.69 µm, a ratio D 10 / D 50 of approximately 33%, range of approximately 1.58, BET-SSA of approximately 14.5 m 2 / g, 983 cycles. Population No. 6 has a smaller D 10 -value, a smaller D 50 -value, a larger range, and a larger BET-SSA than the other “narrow” PSD populations No. 7, No. 8, and No. 9. For further comparison, the “wide” PSD populations used in Type A electrodes exhibited cycle lifetime values ​​in the range of approximately 973 cycles to 1380 cycles. The “wide” PSD populations exhibited a D 10-value in a range from 1.1 µm to 3.01 µm (corresponding to ratios D) 10 / D 50 in a range of 23 to 30%), a range in a range of about 1.9 to about 2.07 and BET-SSA in a range of about 5.8 to 14.3 m 2 / g. In some embodiments, beneficial effects on cycle life (and other battery characteristics) can be observed when the range is less than approximately 2.1, less than approximately 1.9, less than approximately 1.8, less than approximately 1.5, less than approximately 1.2, less than approximately 1.0, or less than approximately 0.8. Furthermore, in some embodiments, the range can be greater than approximately 0.3, greater than approximately 0.5, or greater than approximately 0.6. In some embodiments, beneficial effects on lifetime (and other battery characteristics) can be observed when the BET-SSA of the composite particles is less than approximately 15 m. 2 / g, less than about 12 m 2 / g, less than about 10 m 2 / g, less than about 8 m 2 / g, less than about 7 m 2 / g, less than about 6 m 2 / g, less than about 5 m 2 / g, less than about 4 m 2 / g, or less than about 3 m 2 The value is / g. Furthermore, in some embodiments, the BET-SSA can be larger than approximately 1 m. 2 / g, larger than about 2 m 2 / g, larger than about 5 m 2 / g or larger than about 8 m 2 / g. In some versions, positive effects on lifespan (and other battery properties) can be observed when the D 10 -value greater than approximately 0.5 µm, greater than approximately 1.0 µm, greater than approximately 1.5 µm, or greater than approximately 2.0 µm. In some designs, beneficial effects on cycle life (and other battery characteristics) can be observed when the ratio D is greater than approximately 0.5 µm. 10 / D 50greater than approximately 35%, greater than approximately 45%, greater than approximately 55%, or greater than approximately 65%. Furthermore, the ratio D 10 / D 50 in some embodiments less than about 80% or less than about 75%.

[0181] Fig. Figure 26 shows an SEM image (2601) of a population of spheroidal composite particles. In the example shown, the D 50 The population size is in the range of approximately 5 to approximately 7 µm. The term "spheroidal" here refers to a round shape that is almost spherical or globular, as can be seen, for example, in SEM image 2601.

[0182] Fig.Figure 27 shows a graphical representation 2701, which shows the dependence of the BET-SSA values ​​of example populations of composite particles (fractured composite particles before PSD optimization (which have so-called “wide” PSDs), fractured composite particles after PSD optimization (which have so-called “narrow” PSDs) and spheroidal particles) on their respective D 50 -values ​​shown. Examples of spheroidal particles are in Fig. 26 is shown. In the example shown, the D 50 Values ​​measured with LPSA. Graphic 2701 illustrates the trends between the fractured composite particles with "wide" PSDs, the fractured composite particles with "narrow" PSDs, and the spheroidal particles, which exhibit relatively narrow PSDs. For a given D 50For particle sizes (e.g., 8 µm, 10 µm, 12 µm), the spheroidal particles (with relatively narrow PSDs) exhibit the lowest BET-SSA values, followed by jagged particles with "narrow" PSDs that have undergone PSD optimization, and then jagged particles with "wide" PSDs that have not undergone PSD optimization. Smaller BET-SSA values ​​may indicate smaller external surface areas of the Si-C powders (Si-C composite particles). The use of composite particles with a smaller external surface area can lead to better performance of lithium-ion batteries when used in mixed anodes (e.g., longer calendar lifetime and / or longer cycle stability and / or better high-temperature stability, etc.). However, if the particle sizes of the Si-C composite particles (e.g., the D) are smaller, the performance of the Si-C composite particles may be lower. 50 or especially the D 90 or the D 99If the surface area of ​​the Si-C composite particles becomes too large, the performance of the lithium-ion battery can decrease despite smaller BET-SSA values ​​and / or smaller external surface areas of the Si-C composite particles. In some cases, excessively large D 90 - and D 99 -values ​​more harmful than excessively large D 50 These are values ​​for the performance of lithium-ion batteries with mixed anodes. In some embodiments, the D 50The particle size of the fractured (or cylindrical) composite particles should preferably be in the range of approximately 5 to approximately 15 µm (in some embodiments from approximately 5 to approximately 7 µm; in other embodiments from approximately 7 to approximately 9 µm; in other embodiments from approximately 9 to approximately 11 µm; in other embodiments from approximately 11 to approximately 13 µm; in other embodiments from approximately 13 to approximately 15 µm; in yet other embodiments from approximately 8 to approximately 12 µm; in yet other embodiments from approximately 6 to approximately 10 µm; in yet other embodiments from approximately 6 to approximately 12 µm; in yet other embodiments from approximately 6 to approximately 9 µm). In some embodiments, it may be advantageous if the D 50 -value of the jagged (or cylindrical) composite particles is in a range of about 2 to about 17 µm.

[0183] Fig.Figure 28 shows graphs 2802, 2804, and 2806 of selected PSD characteristic curves of example populations of fractured composite particles. Graph 2802 shows the dependence on D 99 -values ​​from the D 50 -values ​​of the respective populations of fractured composite particles and illustrates the trends between populations that were not subjected to PSD optimization (so-called "wide" PSDs) and populations that were subjected to PSD optimization (so-called "narrow" PSDs). Graphic 2804 shows the dependence of D 90 -values ​​from the D 50 -values ​​of the respective populations of fractured composite particles and illustrates the trends between populations that were not subjected to PSD optimization (so-called "wide" PSDs) and populations that were subjected to PSD optimization (so-called "narrow" PSDs). Graphic 2806 shows the dependence of D10\ -values ​​from the D 50 -values ​​of the respective populations of fractured composite particles and illustrates the trends between populations that were not subjected to PSD optimization (so-called “wide” PSDs) and populations that were subjected to PSD optimization (so-called “narrow” PSDs).

[0184] Fig. Figure 29 shows graphs 2901 and 2902, which show the dependence of the cycle life of lithium-ion batteries (with Si-C nano-composite and graphite mixed anodes / NCM cathodes) fabricated with the respective example populations of fractured composite particles in the anode on the D 50 -values ​​of the respective example populations are shown. The manufacture and testing of the electrodes and battery cells are described herein with reference to the in Fig. 24 and Table 1 ( Fig.25) described the results presented. Graphs 2901 and 2902 illustrate the trends between populations that did not undergo PSD optimization (so-called “broad” PSDs) and populations that did undergo PSD optimization (so-called “narrow” PSDs). In the examples shown, anodes containing a mixture of the fractured composite particles and graphite particles (“active material mixtures”) were used for the Li-ion batteries. Graph 2901 shows cycle lifetime (N80) data for lithium-ion batteries with type A electrodes (~600 mAh / g active electrode material capacity). Graph 2902 shows cycle lifetime (N80) data for lithium-ion batteries with type B electrodes (~1000 mAh / g active electrode material capacity).

[0185] For a specific value of D 50For the composite particle population and for a specific electrode type (~600 mAh / g or ~1000 mAh / g active electrode material capacity), lithium-ion battery cells with "narrow" PSDs that underwent PSD optimization exhibited higher cycle life (N80) data than lithium-ion battery cells with "wide" PSDs that did not undergo PSD optimization. The improvement in cycle life (N80) through the use of "narrow" PSDs is particularly pronounced for type A electrodes (~600 mAh / g active electrode material capacity), where an increase in N80 of more than 60% was observed, exceeding 2400 cycles in some cases. The improvement in cycle life through the use of "narrower" PSDs is also observed with type B electrodes, where cycle life values ​​(N80) increase by more than 60% in some cases. At a specific value of D 50The composite particle population typically resulted in a longer cycle life (N80) for Li-ion battery cells with a mixed anode of lower capacity (~600 mAh / g capacity of the active electrode material) compared to Li-ion battery cells with a mixed anode of higher capacity (~1000 mAh / g capacity of the active electrode material). Fig. 29). If the D 50 As the N80 values ​​increase from approximately 2–3 µm, improved cycling stability (e.g., a longer cycle lifetime (N80)) is initially observed, likely due to factors such as the less frequent occurrence of side reactions between the electrolyte and the composite particles (e.g., through reduced growth of SEI or solid-electrolyte interphase). This trend of increasing cycle lifetime (N80) is observed until optimal ranges (e.g., approximately 6 to 9 µm, 6 to 10 µm, 6 to 12 µm) are reached at the D 50-values ​​are reached. If the D 50 -values ​​above the optimal D 50 Beyond certain ranges, mechanical and other problems can arise that limit the cycle life, and the cycle life decreases to some extent. In some embodiments, the use of composite particles with "narrow" PSDs can significantly improve cycle stability (e.g., cycle life).

[0186] Fig. Figure 30 shows the graphical representations 3002, 3004, 3006 and 3008, which illustrate the dependence of selected PSD properties of example populations of fractured composite particles on the D 50 -values ​​of the example populations show. In the in Fig.In the 30 examples shown, the PSDs of the respective populations were modified by comminution (either by jet milling or ball milling). Graphs 3002, 3004, 3006, and 3008 illustrate the trends between the populations subjected to ball milling and those subjected to jet milling. The PSD properties shown represent the range for 3002, D 90 for 3004, D 10 for 3006 and the volume fraction of fine particles (or “fine fractions”, defined as particles with a diameter of 1 µm and below, measured by LPSA) in the population for 3008. In general, both jet milling and ball milling have proven to be effective tools for reducing the size of larger particles in composite particle populations with D 50-values ​​in a range of approximately 3 µm to approximately 12 µm. There are also some differences between jet milling and ball milling. For the in Fig. The following observations can be made regarding the 30 examples shown: (1) Graphic representation 3002 shows that for D 50 -Values ​​in the range of approximately 3 µm to approximately 7 µm during ball milling tend to result in populations with a larger range than during jet milling for a given D 50 -value. (2) Graphic 3004 shows that for D 50 -Values ​​in the range of approximately 3 µm to approximately 7 µm during ball milling tend to indicate populations with a larger D 90 -values ​​arise during jet milling for a specific D 50 -value. (3) Graphic 3006 shows that for D 50 Values ​​in the range of approximately 3 µm to approximately 6 µm during ball milling tend to indicate populations with a smaller D 10-values ​​arise during jet milling for a specific D 50 -value. (4) Graphic 3008 shows that for D 50 -Values ​​in the range of approximately 3 µm to approximately 5 µm during ball milling tend to result in populations with a higher volume fraction of fines than during jet milling for a given D 50 -Value.

[0187] Some aspects of this revelation may also be applicable to cells containing other intercalation-type cathode materials (e.g., lithium iron phosphate (LFP), lithium manganese oxide (LMO), lithium manganese nickel oxide (LMNO), lithium iron manganese phosphate (LFMP), etc.) and to cells with other conventional intercalation-type anode materials (e.g., carbon-containing – such as synthetic or artificial graphites, soft carbons, hard carbons, and their various mixtures), and may offer advantages in the form of improved rate performance or improved stability, especially for electrodes with medium and high capacity loading (e.g., more than about 3–4 mAh / cm²). 2 ).

[0188] Battery cell modules or battery cell packs may advantageously comprise cells with the electrode and / or electrolyte compositions described in this disclosure. Such cell modules or packs may offer improved performance characteristics, simplified designs, better safety features, or lower costs.

[0189] The detailed description above indicates that various features are grouped into examples. This type of disclosure should not be interpreted as implying that the example clauses contain more features than are explicitly mentioned in the individual clauses. Rather, the various aspects of the disclosure may encompass fewer features than those of a single disclosed example clause. Therefore, the following clauses should be considered part of the description, with each clause potentially serving as a separate example. While each dependent clause within the clauses may refer to a specific combination with one of the other clauses, the aspect(s) of that dependent clause are not limited to that specific combination.It is clear that other example clauses may also include a combination of the aspect(s) of the dependent clause with the subject matter of another dependent or independent clause, or a combination of any feature with other dependent and independent clauses. The various aspects disclosed here expressly include these combinations unless expressly stated otherwise or it is readily apparent that a particular combination is not intended (e.g., contradictory aspects, such as defining an element as both an electrical insulator and an electrical conductor). Furthermore, it is provided that aspects of one clause may be included in any other independent clause, even if the clause is not directly dependent on the independent clause.

[0190] Examples of implementation are described in the following numbered clauses:

[0191] Clause 1. Battery electrode composition, comprising: a population of fractured composite particles, each of the fractured composite particles comprising silicon and carbon; wherein: 90% or more of the fractured composite particles in the population are characterized by aspect ratios of 2.3 or less; 50% or more of the fractured composite particles in the population are characterized by aspect ratios of 1.25 or more; and the population is characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA) such that: a volume-weighted particle size parameter of the fiftieth percentile D 50 The PSD lies in a range of approximately 2.0 to approximately 8.0 µm.

[0192] Clause 2. Battery electrode composition according to Clause 1, wherein: approximately 90% or more of the jagged composite particles in the population are characterized by aspect ratios of approximately 2.1 or less.

[0193] Clause 3. Battery electrode composition according to one of Clauses 1 to 2, wherein: about 50% or more of the jagged composite particles in the population are characterized by aspect ratios of about 1.35 or more.

[0194] Clause 4. Battery electrode composition according to one of Clauses 1 to 3, wherein: about 10% or more of the jagged composite particles in the population are characterized by aspect ratios of about 1.3 or less.

[0195] Clause 5. Battery electrode composition according to one of Clauses 1 to 4, wherein: a mass fraction of the silicon in the fractured composite particles is in a range of about 3 wt.% to about 80 wt.%.

[0196] Clause 6. Battery electrode composition according to Clause 5, wherein: the mass fraction of silicon is in a range of approximately 35 wt.% to approximately 50 wt.%.

[0197] Clause 7. Battery electrode composition according to one of clauses 1 to 6, wherein: a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET) in a range of about 3 m 2 / g up to about 18 m 2 / g lies.

[0198] Clause 8. Battery electrode composition according to one of clauses 1 to 7, wherein: the D 50 -value lies in a range of approximately 2.0 to approximately 4.0 µm.

[0199] Clause 9. Battery electrode composition according to Clause 8, wherein: a cumulative volume fraction, defined as a cumulative volume of the fractured composite particles with particle sizes of about 4.6 µm or less, divided by a total volume of all fractured composite particles, is about 90 vol% or less; and the particle sizes, cumulative volume and total volume are estimated by the LPSA.

[0200] Clause 10. Battery electrode composition according to Clause 9, wherein: the cumulative volume fraction is approximately 85 vol% or less.

[0201] Clause 11. Battery electrode composition according to Clause 10, wherein: the cumulative volume fraction is approximately 80 vol% or less.

[0202] Clause 12. Battery electrode composition according to one of clauses 1 to 11, wherein: the D 50 -value lies in a range of approximately 6.0 to approximately 8.0 µm.

[0203] Clause 13. Battery electrode composition according to Clause 12, wherein: a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET) in a range of about 3 m 2 / g up to about 12 m 2 / g lies.

[0204] Clause 14. Battery electrode comprising: the battery electrode composition according to claim 1, which is arranged on or in a current collector, wherein: the battery electrode comprises a binder.

[0205] Clause 15. Battery electrode according to Clause 14, wherein: a coating density of the battery electrode in a range of approximately 0.9 to approximately 1.0 g / cm² 3 lies.

[0206] Clause 16. Battery electrode according to Clause 15, which additionally contains one or more carbon-containing functional additive(s).

[0207] Clause 17. Battery electrode composition according to Clause 16, wherein the carbon-containing functional additive(s) is / are selected from one, two or more of the following: carbon nanotubes (including, but not limited to, single-walled carbon nanotubes and / or multi-walled carbon nanotubes), carbon nanofibers, carbon black, graphite, expandable graphite, graphene oxide and graphene.

[0208] Clause 18. Battery electrode according to one of clauses 14 to 17, wherein: the D 50 -The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and the mass fraction of the binder in the battery electrode is in a range of approximately 7 wt.% to approximately 10 wt.%.

[0209] Clause 19. Battery electrode according to one of clauses 14 to 18, wherein: the D 50-The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and an area-related binder loading of the battery electrode is in a range of approximately 99.0 mg / m² 2 up to approximately 13.0 mg / m³ 2 lies, where the area-related binder loading is defined as a mass fraction of the binder in the battery electrode, divided by a product of (1) a mass fraction of the fractured composite particles in the battery electrode and (2) a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET).

[0210] Clause 20. Lithium-ion battery comprising: an anode current collector; a cathode current collector; the battery electrode according to Clause 14, which is configured as the anode, wherein its current collector is configured as the anode current collector; a cathode arranged on or in the cathode current collector; and an electrolyte ionically coupling the anode and the cathode.

[0211] Clause 21. Method for manufacturing a battery electrode, the method comprising: (A1) providing the battery electrode composition of Clause 1; (A2) manufacturing a slurry containing the battery electrode composition and a binder; and (A3) pouring the slurry onto or into a current collector to form the battery electrode.

[0212] Clause 22. Method for manufacturing a lithium-ion battery, the method comprising: (B1) manufacturing the battery electrode according to the method of Clause 21, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (B2) manufacturing or providing a cathode arranged on or in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0213] Clause 23. Method for manufacturing a lithium-ion battery, the method comprising: (C1) providing the battery electrode of Clause 14, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (C2) manufacturing or providing a cathode arranged on or in a cathode current collector; and (C3) assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0214] Further examples of implementation are described in the following numbered additional clauses:

[0215] Additional Clause 1. Battery electrode composition, comprising: a population of fractured composite particles, each of the fractured composite particles comprising silicon and carbon; wherein: about 90% or more of the fractured composite particles in the population are characterized by aspect ratios of about 2.3 or less; about 50% or more of the fractured composite particles in the population are characterized by aspect ratios of about 1.25 or more; and the population is characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA), such that: a volume-weighted particle size parameter of the fiftieth percentile (D 50 ) the PSD of the population lies in a range of approximately 2.0 to approximately 17.0 µm.

[0216] Additional clause 2. Battery electrode composition according to additional clause 1, wherein: approximately 90% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 2.1 or less.

[0217] Additional clause 3. Battery electrode composition according to one of the additional clauses 1 to 2, wherein: approximately 50% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.35 or more.

[0218] Additional clause 4. Battery electrode composition according to one of the additional clauses 1 to 3, wherein: about 10% or more of the fractured composite particles in the population are characterized by aspect ratios of about 1.3 or less.

[0219] Additional clause 5. Battery electrode composition according to one of the additional clauses 1 to 4, wherein: a mass fraction of the silicon in the fractured composite particles is in a range of about 3 wt.% to about 80 wt.%.

[0220] Additional clause 6. Battery electrode composition according to additional clause 5, wherein: the mass fraction of silicon is in a range of approximately 33 wt.% to approximately 60 wt.%.

[0221] Additional clause 7. Battery electrode composition according to one of the additional clauses 1 to 6, wherein: a specific surface area (SSA) of the population according to Brunauer-Emmett-Teller (BET) in a range of about 1 m 2 / g up to about 18 m 2 / g lies.

[0222] Additional clause 8. Battery electrode composition according to additional clause 7, wherein: the BET-SSA in an area of ​​approximately 1 m 2 / g up to about 10 m 2 / g lies.

[0223] Additional clause 9. Battery electrode composition according to one of the additional clauses 1 to 8, wherein: the D50 value is in a range of approximately 2.0 to approximately 8.0 µm.

[0224] Additional clause 10. Battery electrode composition according to one of the additional clauses 1 to 9, wherein: the D50 value is in a range of approximately 6.0 to approximately 17.0 µm.

[0225] Additional clause 11. Battery electrode composition according to additional clause 10, wherein: the D50 value is in a range of approximately 6.0 to approximately 9.0 µm.

[0226] Additional clause 12. Battery electrode composition according to one of the additional clauses 1 to 11, wherein: a range of the PSD of the population is in a range of about 0.3 to about 1.8.

[0227] Additional clause 13. Battery electrode composition according to one of the additional clauses 1 to 12, wherein: a volume-weighted particle size parameter of the tenth percentile (D 10) the PSD of the population is at least approximately 1.0 µm; and a value of the D 10 the PSD of the population divided by the value of D 50 The PSD of the population lies in a range of 35% to 75%.

[0228] Additional Clause 14. Battery electrode composition according to one of Additional Clauses 1 to 13, wherein: the battery electrode composition comprises a mixture of the fractured composite particles and graphite particles; and a mass fraction of the fractured composite particles in the battery electrode composition, excluding any binder, is in the range of about 10 wt.% to about 70 wt.%, or a mass fraction of the graphite particles in the battery electrode composition, excluding any binder, is in the range of about 30 wt.% to about 90 wt.%, or a combination thereof.

[0229] Additional clause 15. Battery electrode composition according to additional clause 14, wherein the D50 value of the PSD of the population is in a range of approximately 6.0 to approximately 12.0 µm.

[0230] Additional clause 16. Battery electrode composition according to one of the additional clauses 14 to 15, wherein a volume-weighted particle size parameter of the tenth percentile (D 10 ) the PSD of the population lies in a range of approximately 1.0 to approximately 4.0 µm.

[0231] Additional clause 17. Battery electrode composition according to one of the additional clauses 14 to 16, wherein a volume-weighted particle size parameter of the ninetieth percentile (D 90 ) the PSD of the population lies in a range of approximately 7.0 to approximately 25.0 µm.

[0232] Additional clause 18. Battery electrode composition according to additional clause 17, wherein the D 90 in a range of approximately 12.0 to approximately 20.0 µm.

[0233] Additional clause 19. Battery electrode composition according to one of the additional clauses 14 to 18, wherein a volume-weighted particle size parameter of the ninety-ninth percentile (D 99 ) the PSD of the population lies in a range of approximately 15.0 to approximately 28.0 µm.

[0234] Additional clause 20. Battery electrode composition according to one of the additional clauses 14 to 19, wherein the PSD of the population ranges from about 0.6 to about 2.1.

[0235] Additional clause 21. Battery electrode composition according to one of the additional clauses 14 to 20, wherein a specific surface area (SSA) of the population according to Brunauer-Emmett-Teller (BET) in a range of about 1 m 2 / g up to about 10 m 2 / g lies.

[0236] Additional clause 22. Battery electrode composition according to one of the additional clauses 14 to 21, wherein the fractured composite particles have a specific lithiation capacity in the first cycle in the range of about 1600 mAh / g to about 2200 mAh / g.

[0237] Additional clause 23. Battery electrode composition according to one of the additional clauses 14 to 22, wherein a specific capacity of the mixture is in the range of about 600 mAh / g to about 1200 mAh / g, normalized to a mass of the mixture.

[0238] Additional clause 24. Battery electrode, comprising: the battery electrode composition of additional clause 1, arranged on and / or in a current collector, wherein: the battery electrode comprises a binder.

[0239] Additional clause 25. Battery electrode according to additional clause 24, wherein: a coating density of the battery electrode in a range of approximately 0.9 to approximately 1.7 g / cm² 3 lies.

[0240] Additional clause 26. Battery electrode according to one of the additional clauses 24 to 25, which further comprises: a carbon-containing functional additive.

[0241] Additional clause 27. Battery electrode according to additional clause 26, wherein the carbon-containing functional additive is selected from: single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon black, expandable graphite, graphene oxide and graphene.

[0242] Additional clause 28. Battery electrode according to additional clause 27, wherein a mass fraction of the carbon-containing functional additive in the battery electrode is approximately 1 wt.% or less.

[0243] Additional clause 29. Battery electrode according to one of the additional clauses 24 to 28, wherein: the D 50-The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and the mass fraction of the binder in the battery electrode is in a range of approximately 7 wt.% to approximately 10 wt.%.

[0244] Additional clause 30. Battery electrode according to any of the additional clauses 24 to 29, wherein: the D 50 -The PSD value of the population is in a range of approximately 6.0 to approximately 8.0 µm; and an area-related binder loading of the battery electrode is in a range of approximately 9.0 mg / m² 2 up to approximately 13.0 mg / m³ 2 lies, where the area-related binder loading is defined as a mass fraction of the binder in the battery electrode, divided by a product of (1) a mass fraction of the fractured composite particles in the battery electrode and (2) a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET).

[0245] Additional Clause 31. Lithium-ion battery comprising: an anode current collector; a cathode current collector; the battery electrode of Additional Clause 24, which is configured as an anode, wherein its current collector is configured as an anode current collector; a cathode arranged on or in the cathode current collector; and an electrolyte ionically coupling the anode and the cathode.

[0246] Additional Clause 32. Method for manufacturing a battery electrode, the method comprising: (A1) providing the battery electrode composition of Additional Clause 1; (A2) manufacturing a slurry containing the battery electrode composition and a binder; and (A3) pouring the slurry onto and / or into a current collector to form the battery electrode.

[0247] Additional Clause 33. Method for manufacturing a lithium-ion battery, the method comprising: (B1) manufacturing the battery electrode according to the method of Additional Clause 32, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (B2) manufacturing or providing a cathode arranged on and / or in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0248] Additional Clause 34. Method for manufacturing a lithium-ion battery, the method comprising: (C1) providing the battery electrode of Additional Clause 24, wherein the battery electrode is configured as the anode and the current collector as the anode current collector; (C2) manufacturing or providing a cathode arranged on and / or in a cathode current collector; and (C3) assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

[0249] This description is intended to enable a person skilled in the art to manufacture or use embodiments of the present invention. However, it is clear that the present invention is not limited to the specific formulations, process steps, and materials disclosed herein, since various modifications of these embodiments are readily apparent to those skilled in the art. This means that the general principles defined herein can also be applied to other embodiments without departing from the spirit or scope of the invention. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] US 63 / 477,727

[0001] US 18 / 398,718

[0001] Cited non-patent literature

[0000] Jagged Electrochemically-Active Composite Particles For Lithium-Ion Batteries” (Jagged electrochemically active composite particles for lithium-ion batteries), submitted on December 29, 2022

[0001] Jagged Electrochemically-Active Composite Particles For Lithium-Ion Batteries” (Jagged electrochemically active composite particles for lithium-ion batteries), submitted on December 28, 2023

[0001]

Claims

[1] Battery electrode composition, comprising: a population of fractured composite particles, each of which contains silicon and carbon; where: approximately 90% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 2.3 or less; approximately 50% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.25 or more; and the population is characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA), such that: a volume-weighted particle size parameter of the fiftieth percentile (D 50 ) the PSD of the population lies in a range of approximately 2.0 to approximately 17.0 µm. [2] Battery electrode composition according to claim 1, wherein: approximately 90% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 2.1 or less. [3] Battery electrode composition according to claim 1, wherein: approximately 50% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.35 or more. [4] Battery electrode composition according to claim 1, wherein: approximately 10% or more of the fractured composite particles in the population are characterized by aspect ratios of approximately 1.3 or less. [5] Battery electrode composition according to claim 1, wherein: The mass fraction of silicon in the fractured composite particles is in a range of approximately 3 wt.% to approximately 80 wt.%. [6] Battery electrode composition according to claim 5, wherein: The mass fraction of silicon is in a range of approximately 33 wt.% to approximately 60 wt.%. [7] Battery electrode composition according to claim 1, wherein: a specific surface area (SSA) of the population according to Brunauer-Emmett-Teller (BET) in an area of ​​about 1 m 2 / g up to about 18 m 2 / g lies. [8] Battery electrode composition according to claim 7, wherein: the BET-SSA in an area of ​​approximately 1 m 2 / g up to about 10 m 2 / g lies. [9] Battery electrode composition according to claim 1, wherein: the D 50 -value lies in a range of approximately 2.0 to approximately 8.0 µm. [10] Battery electrode composition according to claim 1, wherein: the D 50 -value lies in a range of approximately 6.0 to approximately 17.0 µm. [11] Battery electrode composition according to claim 10, wherein: the D 50-value lies in a range of approximately 6.0 to approximately 9.0 µm. [12] Battery electrode composition according to claim 1, wherein: The PSD of the population ranges from approximately 0.3 to approximately 1.

8. [13] Battery electrode composition according to claim 1, wherein: a volume-weighted particle size parameter of the tenth percentile (D 10 ) the PSD of the population is at least approximately 1.0 µm; and a value of D 10 the PSD of the population divided by the D 50 The PSD value of the population lies in a range of 35% to 75%. [14] Battery electrode composition according to claim 1, wherein: the battery electrode composition comprises a mixture of fractured composite particles and graphite particles; and a mass fraction of the fractured composite particles in the battery electrode composition, excluding any binder, is in a range of approximately 10 wt.% to approximately 70 wt.%, or a mass fraction of the graphite particles in the battery electrode composition, excluding any binder, is in a range of approximately 30 wt.% to approximately 90 wt.%, or a combination thereof. [15] Battery electrode composition according to claim 14, wherein the D 50 The PSD value of the population lies in a range of approximately 6.0 to approximately 12.0 µm. [16] Battery electrode composition according to claim 14, wherein a volume-weighted particle size parameter of the tenth percentile (D 10 ) the PSD of the population lies in a range of approximately 1.0 to approximately 4.0 µm. [17] Battery electrode composition according to claim 14, wherein a volume-weighted particle size parameter of the ninetieth percentile (D 90) the PSD of the population lies in a range of approximately 7.0 to approximately 25.0 µm. [18] Battery electrode composition according to claim 17, wherein the D 90 -value lies in a range of approximately 12.0 to approximately 20.0 µm. [19] Battery electrode composition according to claim 14, wherein a volume-weighted particle size parameter of the ninety-ninth percentile (D 99 ) the PSD of the population lies in a range of approximately 15.0 to approximately 28.0 µm. [20] Battery electrode composition according to claim 14, wherein the PSD of the population is in a range of about 0.6 to about 2.

1. [21] Battery electrode composition according to claim 14, wherein a specific surface area (SSA) of the Brunauer-Emmett-Teller (BET) population in a range of about 1 m 2 / g up to about 10 m 2 / g lies. [22] Battery electrode composition according to claim 14, wherein the fractured composite particles have a specific lithiation capacity in the first cycle in the range of about 1600 mAh / g to about 2200 mAh / g. [23] Battery electrode composition according to claim 14, wherein a specific capacity of the mixture is in the range of about 600 mAh / g to about 1200 mAh / g, normalized to a mass of the mixture. [24] Battery electrode, comprising: the battery electrode composition according to claim 1, which is arranged on and / or in a current collector, where: the battery electrode contains a binding agent. [25] Battery electrode according to claim 24, wherein the coating density of the battery electrode is in a range of about 0.9 to about 1.7 g / cm². 3 lies. [26] Battery electrode according to claim 24, further comprising: a carbon-containing functional additive. [27] Battery electrode according to claim 26, wherein the carbon-containing functional additive is selected from: single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon black, expandable graphite, graphene oxide and graphene. [28] Battery electrode according to claim 27, wherein a mass fraction of the carbon-containing functional additive in the battery electrode is about 1 wt.% or less. [29] Battery electrode according to claim 24, wherein: the D 50 -The PSD value of the population lies in a range of approximately 6.0 to approximately 8.0 µm; and The mass fraction of the binder in the battery electrode is in the range of approximately 7 wt.% to approximately 10 wt.%. [30] Battery electrode according to claim 24, wherein: the D 50 -The PSD value of the population lies in a range of approximately 6.0 to approximately 8.0 µm; and an area-related binder loading of the battery electrode in the range of approximately 9.0 mg / m² 2 up to approximately 13.0 mg / m³ 2 lies, where the area-related binder loading is defined as a mass fraction of the binder in the battery electrode, divided by a product of (1) a mass fraction of the fractured composite particles in the battery electrode and (2) a specific surface area of ​​the population according to Brunauer-Emmett-Teller (BET). [31] Lithium-ion battery, consisting of: an anode current collector; a cathode current collector; the battery electrode according to claim 24, which is designed as an anode, wherein its current collector is designed as the anode current collector; a cathode that is arranged on or in the cathode current collector; and an electrolyte that ionically couples the anode and the cathode. [32] Method for producing a battery electrode, the method comprising: (A1) Provision of the battery electrode composition according to claim 1; (A2) Producing a slurry containing the battery electrode composition and a binder; and (A3) Pouring the slurry onto and / or into a current collector to form the battery electrode. [33] Method for manufacturing a lithium-ion battery, the method comprising: (B1) Manufacturing the battery electrode according to the method of claim 32, wherein the battery electrode is configured as the anode and the current collector is configured as the anode current collector; (B2) Manufacturing or providing a cathode arranged on and / or in a cathode current collector; and (B3) Assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery. [34] Method for manufacturing a lithium-ion battery, the method comprising: (C1) Provision of the battery electrode according to claim 24, wherein the battery electrode is configured as the anode and the current collector is configured as the anode current collector; (C2) Manufacturing or providing a cathode arranged on and / or in a cathode current collector; and (C3) Assembling a battery cell from the anode and the cathode and filling a space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form the lithium-ion battery.

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