Serrated electrochemically active composite particles for lithium-ion batteries

Abstract

The battery electrode composition includes a population of sawtooth composite particles, each of the sawtooth composite particles comprising silicon and carbon. In some embodiments, at least 90% of the sawtooth composite particles in the population are characterized by an aspect ratio of 2.3 or less, and at least 50% of the sawtooth composite particles in the population are characterized by an aspect ratio of 1.25 or more. In some embodiments, the population is characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA), and a 50th percentile volume-weighted particle size parameter D of the PSD is 50 is in the range of about 2.0 to about 17.0 μm.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 477,727, filed December 29, 2022, and entitled "JAGGED ELECTROCHEMICALLY-ACTIVE COMPOSITE PARTICLES FOR LITHIUM-ION BATTERIES," and U.S. Non-Provisional Patent Application No. 18 / 398,718, filed December 28, 2023, and entitled "JAGGED ELECTROCHEMICALLY-ACTIVE COMPOSITE PARTICLES FOR LITHIUM-ION BATTERIES," both of which are assigned to the present assignee and are expressly incorporated by reference herein in their entireties.

[0002] Aspects of the present disclosure relate generally to energy storage devices, and more particularly to battery technology and the like. [Background technology]

[0003] Advanced rechargeable batteries are desirable for a wide range of consumer electronics, electric vehicles, grid storage and other important applications due in part to their relatively high energy density, relatively high specific energy, light weight and potential for long life.

[0004] However, despite the increasing commercial adoption of batteries, further development of these batteries is needed, particularly for low or no-emission applications, hybrid electric or all-electric vehicles, consumer electronics, wearable devices, energy-efficient cargo ships and locomotives, drones, aerospace applications, and the power grid. In particular, further improvements are desired for various rechargeable batteries, such as rechargeable Li and Li-ion batteries, rechargeable Na and Na-ion batteries, and rechargeable K and K-ion batteries, to name a few.

[0005] In certain types of Li metal and Li-ion rechargeable batteries, charge storage anodes can include silicon (Si)-containing anode particles having gravimetric capacities (per mass of Si-containing anode particles in the absence of Li) of about 800 mAh / g to about 3000 mAh / g. A subset of this anode includes anodes in which the electrode layer exhibits a capacity (per mass of electrode layer, not including the mass of the current collector, in the absence of Li) ranging from about 400 mAh / g to about 2800 mAh / g. This class of charge storage anodes offers significant potential for enhancing the gravimetric and volumetric energy of rechargeable batteries.

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

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

[0008] Examples of low-swelling particles include so-called silicon-graphite blends, which are mixtures of converted silicon-based (or broadly silicon-containing) anode active materials and graphite. In some examples of blend anodes, the Si-containing anode active material may be a Si-containing and C-containing nanocomposite (referred to herein as a Si-C composite, Si-C nanocomposite, or Si-C composite (or nanocomposite) particle, even if the particle contains relatively small amounts of elements other than Si and C, less than about 10-20 atomic %), contributing about 20-80% of the total blend anode capacity, with the remainder of the capacity coming from graphite. (In other examples, the Si-C composite (e.g., Si-C composite particle) may contribute more than about 80% or less than about 20% of the anode's capacity.) Such anodes offer much higher volumetric and gravimetric energy densities than intercalated graphite anodes commonly used in commercial Li-ion batteries. Furthermore, in such blend anodes, the graphite can be composed of natural graphite, artificial graphite, or a mixture of natural and artificial graphite. In some designs, using natural graphite or a mixture of natural and artificial graphite is more advantageous because such graphite particles can accommodate the stresses imposed by highly swollen Si-based (e.g., Si-C) particles (during Li intercalation). These properties of Si-C nanocomposite-graphite blends can provide an overall moderate volume change during the first cycle and a low volume change during subsequent charging cycles. These properties are advantageous for high-capacity-loading anode particles, which may also reduce the manufacturing costs of the battery cell.

[0009] In some designs, the active electrode material for use in an electrochemical energy storage device, such as a battery or electrochemical capacitor, or hybrid device, may be a carbon-containing composite particle. Subclasses of such composite particles may include composite particles in which conversion-type, alloy-type, intercalation-type, or pseudocapacitive materials are entrapped or infiltrated within a carbon or carbon-containing matrix material. However, existing approaches to the synthesis or thermochemical processing of such carbon or carbon-containing matrix materials suffer from low efficiency, low packing density, low throughput, or poor control over uniformity or other limitations.

[0010] Thus, there remains a need for improvements in batteries, components and other related materials and manufacturing processes. Summary of the Invention

[0011] The following provides a simplified summary of one or more aspects of the presently disclosed mechanisms. Accordingly, the following summary is not intended to be an exhaustive overview of all possible aspects, nor is it intended to identify key or essential elements of all possible aspects or to outline the scope associated with any particular aspect. Accordingly, the following summary is solely intended to present certain concepts of one or more aspects of the presently disclosed mechanisms in a simplified manner, as a prelude to the detailed description that follows.

[0012] In one aspect, a battery electrode composition includes a population of jagged composite particles, each of the jagged composite particles comprising silicon and carbon, wherein about 90% or more of the jagged composite particles in the population are characterized by an aspect ratio of about 2.3 or less, and about 50% or more of the jagged composite particles in the population are characterized by an aspect ratio of about 1.25 or more, and the population has a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA) where the 50th percentile volume-weighted particle size parameter (D) of the PSD of the population is 50 ) is in the range of about 2.0 to about 17.0 μm.

[0013] In some embodiments, about 90% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 2.1 or less.

[0014] In some embodiments, about 50% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.35 or greater.

[0015] In some embodiments, about 10% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.3 or less.

[0016] In some embodiments, the mass fraction of silicon in the sawtooth composite particles ranges from about 3% to about 80% by weight.

[0017] In some embodiments, the mass fraction of silicon ranges from about 33% to about 60% by weight.

[0018] In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the population is about 1 m 2 / g ~ approx. 18m 2 / g range.

[0019] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g~about 10m 2 / g range.

[0020] In some embodiments, D 50 is in the range of about 2.0 to about 8.0 μm.

[0021] In some embodiments, D 50 is in the range of about 6.0 to about 17.0 μm.

[0022] In some embodiments, D 50 is in the range of about 6.0 to about 9.0 μm.

[0023] In some embodiments, the span of the PSD of the population is in the range of about 0.3 to about 1.8.

[0024] In some embodiments, the 10th percentile volume-weighted particle size parameter (D) of the PSD of the population 10 ) is at least about 1.0 μm, and the PSD of the population is D 50 The PSD of the population divided by D 10 The value is in the range of 35% to 75%.

[0025] In some embodiments, the battery electrode composition comprises a blend of sawtooth composite particles and graphite particles, wherein the mass fraction of the sawtooth composite particles in the battery electrode composition, excluding any binder, is in the range of about 10% to about 70% by weight, or the mass fraction of the graphite particles in the battery electrode composition, excluding any binder, is in the range of about 30% to about 90% by weight, or a combination thereof.

[0026] In some embodiments, the D of the PSD of the population 50 is in the range of about 6.0 to about 12.0 μm.

[0027] In some embodiments, the 10th percentile volume-weighted particle size parameter (D) of the PSD of the population 10 ) is in the range of about 1.0 to about 4.0 μm.

[0028] In some embodiments, the 90th percentile volume-weighted particle size parameter (D) of the PSD of the population 90 ) is in the range of about 7.0 to about 25.0 μm.

[0029] In some embodiments, D 90 is in the range of about 12.0 to about 20.0 μm.

[0030] In some embodiments, the 99th percentile volume-weighted particle size parameter (D) of the PSD of the population 99 ) is in the range of about 15.0 to about 28.0 μm.

[0031] In some embodiments, the span of the PSD of the population is in the range of about 0.6 to about 2.1.

[0032] In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the population is about 1 m 2 / g~about 10m 2 / g range.

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

[0034] In some embodiments, the specific capacity of the blended mixture, when normalized by the mass of the blended mixture, is in the range of about 600 mAh / g to about 1200 mAh / g.

[0035] In one embodiment, a battery electrode includes a battery electrode composition disposed on and / or within a current collector, the battery electrode including a binder.

[0036] In some embodiments, the coating density of the battery electrode is about 0.9 to about 1.7 g / cm 3 is in the range.

[0037] In some embodiments, the battery electrode includes a carbon-containing functional additive.

[0038] In some embodiments, 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 embodiments, the mass fraction of the carbon-containing functional additive in the battery electrode is about 1 wt % or less.

[0040] In some embodiments, the D of the PSD of the population 50 is in the range of about 6.0 to about 8.0 μm, and the mass fraction of the binder in the battery electrode is in the range of about 7 wt % to about 10 wt %.

[0041] In some embodiments, the D of the PSD of the population 50 is in the range of about 6.0 to about 8.0 μm, and the area binder loading of the battery electrode is about 9.0 mg / m2 ~About 13.0mg / m 2 The areal binder loading is defined as the mass fraction of binder in the battery electrode divided by the product of (1) the mass fraction of the serrated composite particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the ensemble.

[0042] In one aspect, a lithium-ion battery includes an anode current collector, a cathode current collector, a battery electrode configured as an anode, with the current collector configured as the anode current collector, a cathode disposed on or within the cathode current collector, and an electrolyte ionically bonding the anode and cathode.

[0043] In one aspect, a method of making a battery electrode includes the steps of: (A1) providing a battery electrode composition; (A2) making a slurry comprising the battery electrode composition and a binder; and (A3) casting the slurry onto and / or into a current collector to form a battery electrode.

[0044] In one aspect, a method of manufacturing a lithium-ion battery includes the steps of: (B1) manufacturing a battery electrode, where the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (B2) manufacturing or providing a cathode disposed on and / or within a cathode current collector; and (B3) assembling a battery cell from the anode and cathode and filling a space between the anode and cathode with an electrolyte that ionically bonds the anode and cathode to form a lithium-ion battery.

[0045] In one aspect, a method of manufacturing a lithium-ion battery includes the steps of: (C1) providing a battery electrode, where the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on and / or within a cathode current collector; and (C3) assembling a battery cell from the anode and cathode and filling a space between the anode and cathode with an electrolyte that ionically bonds the anode and cathode to form a lithium-ion battery.

[0046] One aspect is directed to a battery electrode composition comprising a population of sawtooth composite particles, each of which comprises silicon (Si) and carbon (C) (e.g., predominantly graphitic carbon) and may also comprise 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 contribute from about 75% to about 100% by weight of the total mass of the composite particle. Such composite particles may also be referred to herein as Si-C composites. In some embodiments, such composite particles may comprise nanosized or nanostructured elements (e.g., nanosized or nanostructured Si, nanosized or nanostructured C), and may also be referred to as nanocomposite particles. In some embodiments, the Si or Si-containing materials present in such nanocomposites may be in the form of nanoparticles. In some examples, the mass average size of the Si or Si-containing material nanoparticles ranges from about 1 nm to about 200 nm (in some designs, from about 1 nm to about 10 nm, in other designs, from about 10 nm to about 30 nm, in still other designs, from about 30 nm to about 100 nm, and in still other designs, from about 100 nm to about 200 nm), as measured using image analysis by electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, neutron scattering, and other suitable techniques. In some embodiments, 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of 2.3 or less, or an aspect ratio of 2.1 or less. In some embodiments, 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of 1.25 or greater, or an aspect ratio of 1.35 or greater. In some embodiments, 10% or more of the serrated composite particles in the population are characterized by an aspect ratio of 1.3 or less. The population may be characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA), image analysis of electron microscope images, or other suitable techniques. In some embodiments, the 50th percentile volume-weighted particle size parameter (D) of the PSD is determined by the 50th percentile volume-weighted particle size parameter (D). 50) is in the range of about 2.0 μm to about 16.0 μm, about 2.0 to about 4.0 μm, about 4.0 to about 6.0 μm, about 6.0 to about 8.0 μm, or about 8.0 to about 16.0 μm. In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is in the range of about 1.0 μm to about 17.0 μm, about 1.0 to about 4.0 μm, about 4.0 to about 6.0 μm, about 6.0 to about 9.0 μm, or about 9.0 to about 17.0 μm.

[0047] Another aspect is directed to a battery electrode composition comprising a population of nanocomposite particles, each of which comprises Si and C (such that the combined mass of the Si and C atoms contributes 75-100 wt% of the nanocomposite particle's mass), wherein the nanocomposite particles have particular properties. In some embodiments, the mass fraction of silicon in the nanocomposite particles ranges from about 3 wt% to about 80 wt% (about 3 wt% to about 20 wt% in some designs, about 20 wt% to about 35 wt% in other designs, about 35 wt% to about 50 wt% in still other designs, about 50 wt% to about 80 wt% in still other designs, about 33 wt% to about 60 wt% in still other designs, about 5 wt% to about 50 wt% in still other designs, about 7 wt% to about 40 wt% in still other designs, and about 9 wt% to about 30 wt% in still other designs). In some embodiments, the composite particles have a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 1 m 2 / g~about 50m 2 / g (approximately 1m in some designs) 2 / g ~ approx. 3m 2 / g, and approximately 3m for other designs 2 / g ~ approx. 12m 2 / g, and in other designs, approximately 12 m 2 / g ~ approx. 18m 2 / g, and in other designs, approximately 18m 2 / g ~ approx. 30m 2 / g, and in other designs, approximately 30m 2 / g~about 50m 2 / g).

[0048] Yet another aspect is directed to a battery electrode composition comprising a population of composite (e.g., nanocomposite) particles, some or all of which comprise silicon and carbon (such that the combined mass of Si and C atoms contributes 75-100 wt% of the mass of the nanocomposite particles). The population is characterized by a particle size distribution (PSD), in one example, determined by laser particle size distribution analysis (LPSA) on a well-dispersed particle suspension. However, other types of particle size distributions (e.g., by SEM image analysis) may also be utilized (and may provide more accurate measurements in some experiments). In some embodiments, the 50th percentile volume-weighted particle size parameter (D) of the PSD is used. 50 ) is in the range of about 1.0 μm to about 12.0 μm (about 1.0 μm to about 2.0 μm in some designs, about 2.0 μm to about 4.0 μm in other designs, about 4.0 μm to about 6.0 μm in still other designs, and about 6.0 μm to about 12.0 μm in still other designs). The cumulative volume fraction, defined as the cumulative volume of composite particles having particle sizes equal to or less than the threshold particle size divided by the total volume of all composite particles, can be estimated by LPSA. In some embodiments (e.g., D 50 In other embodiments (e.g., when D is in the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction is 90 vol. % or less, 85 vol. % or less, or 80 vol. % or less relative to the threshold particle size of 4.6 μm. 50 In still other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction is 90 vol.% or less, 85 vol.% or less, or 80 vol.% or less relative to the 7 μm threshold particle size. 50 In some embodiments (e.g., when D is in the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction is 90 vol.% or less, 85 vol.% or less, or 80 vol.% or less relative to a threshold particle size of 15 μm. Note that the presence of excessively large particles can degrade cell performance characteristics (e.g., cell stability can be reduced, its impedance can increase, rate capability can be reduced, etc.). 50 In some embodiments (e.g., when D is in the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction is 80% or more by volume for a threshold particle size of 10 μm.50 In other embodiments (e.g., when D is in the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction is 90% or more by volume for a threshold particle size of 12 μm. 50 In other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction is 80% or more by volume for a threshold particle size of 15 μm. 50 In other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction is 90% or more by volume for a threshold particle size of 22 μm. 50 In still other embodiments (e.g., when D is in the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction is 80% or more by volume for a threshold particle size of 28 μm. 50 is in the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction is 90% by volume or more for a threshold particle size of 32 μm.

[0049] Yet another embodiment is directed to a battery electrode composition comprising a population of composite (e.g., nanocomposite) particles, each of the composite particles comprising silicon and carbon (predominantly graphitic sp 2 The population is characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA). In some embodiments, the 50th percentile volume-weighted particle size parameter (D) of the PSD is used. 50 ) is in the range of about 6.0 μm to about 8.0 μm. In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area of ​​the composite particles is about 1 m 2 / g~about 50m 2 / g (approximately 1m in some designs) 2 / g ~ approx. 3m 2 / g, and approximately 3m for other designs 2 / g ~ approx. 12m 2 / g, and in other designs, approximately 12 m 2 / g ~ approx. 18m 2 / g, and in other designs, approximately 18m 2 / g ~ approx. 30m2 / g, and in other designs, approximately 30m 2 / g~about 50m 2 / g).

[0050] Yet another embodiment is directed to a battery electrode composition comprising a population of composite (e.g., nanocomposite) particles, each of the composite particles comprising silicon and carbon (predominantly graphitic sp 2 The battery electrode composition may include one or more carbon-containing functional additives (e.g., additives that enhance the electrical conductivity or rate capability of the electrode's mechanical properties). In some embodiments, the carbon-containing functional additives are selected from carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs)), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide (e.g., single-layer graphene oxide, multi-layer graphene oxide), and graphene (e.g., single-layer graphene, multi-layer graphene). In some embodiments, the battery electrode composition may include one or more binders (and in some designs, two or more binder compositions).

[0051] Yet another aspect is directed to a battery electrode. In some embodiments, the battery electrode comprises any of the aforementioned battery electrode compositions disposed on or within a current collector. In some embodiments, the battery electrode comprises a battery electrode composition and a binder. In some embodiments, the battery electrode has a coating density of about 0.8 to about 1.5 g / cm. 3 or about 0.8 to about 1.7 g / cm 3 range (approx. 0.8 to approx. 0.9 g / cm in some designs) 3 , and about 0.9 to about 1.0 g / cm for other designs. 3 , and in other designs, about 1.0 to about 1.2 g / cm 3 , and about 1.2 to about 1.5 g / cm in other designs. 3 , and about 0.9 to about 1.6 g / cm in other designs. 3 , and about 0.9 to about 1.2 g / cm in other designs. 3, and about 0.9 to about 1.7 g / cm in other designs. 3 ) In some embodiments, the battery electrode comprises a carbon-containing functional additive. In some examples, the carbon-containing functional additive can be selected from carbon nanotubes (e.g., SWCNT, MWCNT), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide (e.g., single-layer graphene oxide, multi-layer graphene oxide), and graphene (e.g., single-layer graphene, multi-layer graphene).

[0052] Yet another aspect is directed to a battery electrode. In some embodiments, the battery electrode comprises any of the aforementioned battery electrode compositions disposed on or within 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 sawtooth composite particles characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA). In some embodiments, the 50th percentile volume-weighted particle size parameter (D) of the PSD is 50 ) is in the range of about 6.0 μm to about 8.0 μm. In some embodiments, the mass fraction of the binder in the battery electrode is in the range of about 7 wt % to about 10 wt %.

[0053] A battery electrode (e.g., an anode comprising Si-C nanocomposite particles) can be characterized by an areal binder loading, which is defined as the mass fraction of binder in the battery electrode divided by the product of (1) the mass fraction of sawtooth composite (e.g., nanocomposite) particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the particle population. In some embodiments, the areal binder loading of a battery electrode (e.g., an anode comprising Si-C nanocomposite particles) is about 2.0 mg / m 2 ~Approx. 15.0mg / m 2 (e.g., about 2.0 mg / m in some designs) 2 ~about 5.0mg / m 2 , and about 5.0 mg / m for other designs. 2 ~about 9.0mg / m 2 , and about 9.0 mg / m for other designs.2 ~About 13.0mg / m 2 ) range.

[0054] Yet another aspect is directed to a lithium-ion battery. In some embodiments, the lithium-ion battery includes an anode current collector, a cathode current collector, any one of the aforementioned battery electrodes configured as an anode disposed on or within the anode current collector, a cathode disposed on or within the cathode current collector, and an electrolyte ionically bonding the anode and cathode.

[0055] Yet another aspect is directed to a process for producing a battery electrode, comprising steps (A1), (A2), and (A3). Step (A1) comprises providing any of the battery electrode compositions described above. Step (A2) comprises producing a slurry comprising the battery electrode composition and a binder. Step (A3) comprises casting the slurry onto or into a current collector to form a battery electrode, which may optionally include a densification (calendering) operation, i.e., densifying the battery electrode to a desired value. Casting the slurry may also include evaporating the slurry solvent. In some embodiments, the coating density of the battery electrode (e.g., an anode comprising nanocomposite Si-C particles) is about 0.8 to about 1.5 g / cm. 3 (Some designs are approximately 0.8 to 0.9 g / cm 3 , and about 0.9 to about 1.0 g / cm for other designs. 3 , and about 1.0 to about 1.2 g / cm for other designs. 3 , and about 1.2 to about 1.5 g / cm for other designs. 3 , and about 0.9 to about 1.6 g / cm in other designs. 3 , and about 0.9 to about 1.2 g / cm in other designs. 3 In some embodiments, the coating density is in the range of about 0.9 to about 1.7 g / cm 3In some embodiments, the battery electrode comprises a carbon-containing functional additive. In some examples, the carbon-containing functional additive may be selected from carbon nanotubes (SWCNTs or MWCNTs, or both), carbon nanofibers, carbon black, graphite, expanded graphite, and graphene. In some embodiments, the mass fraction of the binder in the battery electrode is in the range of about 7 wt % to about 10 wt %. The battery electrode may be characterized by an areal binder loading, defined as the mass fraction of the binder in the battery electrode divided by the product of (1) the mass fraction of the sawtooth composite particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the population. In some embodiments, the areal binder loading of a battery electrode (e.g., an anode comprising Si-C nanocomposite particles) is about 2.0 mg / m 2 ~Approx. 15.0mg / m 2 (e.g., about 2.0 mg / m in some designs) 2 ~about 5.0mg / m 2 , and about 5.0 mg / m for other designs. 2 ~about 9.0mg / m 2 , and about 9.0 mg / m for other designs. 2 ~About 13.0mg / m 2 ) range.

[0056] Yet another aspect is directed to a process for manufacturing a lithium-ion battery, comprising steps (B1), (B2), and (B3). Step (B1) comprises fabricating a battery electrode according to any one of the aforementioned processes for fabricating a battery electrode, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector. Step (B2) comprises fabricating or providing a cathode disposed on or within a cathode current collector. Step (B3) comprises assembling a battery cell from the anode and cathode (and, in some designs, a porous separator membrane or layer therebetween) and filling the space between the anode and cathode with an electrolyte that ionically bonds the anode and cathode to form a lithium-ion battery.

[0057] Yet another aspect is directed to a process for manufacturing a lithium-ion battery, comprising steps (C1), (C2), and (C3). Step (C1) comprises providing any of the battery electrodes described above, where the battery electrode is configured as an anode and the current collector is configured as an anode current collector. Step (C2) comprises fabricating or providing a cathode disposed on or within a cathode current collector. Step (C3) comprises assembling a battery cell from the anode and cathode (and, in some designs, a porous separator membrane or layer therebetween) and filling the space between the anode and cathode with an electrolyte that ionically bonds the anode and cathode to form a lithium-ion battery.

[0058] In one aspect, a battery electrode composition includes a population of sawtooth composite particles, each of the sawtooth composite particles comprising silicon and carbon, wherein 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of 2.3 or less, and 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of 1.25 or more, and the population has a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA) where the 50th percentile volume-weighted particle size parameter D of the PSD is 50 is characterized by a PSD in the range of about 2.0 to about 8.0 μm.

[0059] In some embodiments, about 90% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 2.1 or less.

[0060] In some embodiments, about 50% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.35 or greater.

[0061] In some embodiments, about 10% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.3 or less.

[0062] In some embodiments, the mass fraction of silicon in the sawtooth composite particles ranges from about 3% to about 80% by weight.

[0063] In some embodiments, the mass fraction of silicon ranges from about 35% to about 70% by weight.

[0064] In some embodiments, the mass fraction of silicon ranges from about 35% to about 50% by weight.

[0065] In some embodiments, the mass fraction of silicon ranges from about 40% to about 55% by weight.

[0066] In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area of ​​the population is about 3 m 2 / g ~ approx. 18m 2 / g range.

[0067] In some embodiments, D 50 is in the range of about 2.0 to about 4.0 μm.

[0068] In some embodiments, the cumulative volume fraction, defined as the cumulative volume of sawtooth composite particles having a particle size of about 4.6 μm or less divided by the total volume of all of the sawtooth composite particles, is about 90% by volume or less, wherein the particle size, cumulative volume, and total volume are estimated by LPSA.

[0069] In some embodiments, the cumulative volume fraction is less than or equal to about 85% by volume.

[0070] In some embodiments, the cumulative volume fraction is less than or equal to about 80% by volume.

[0071] In some embodiments, D 50 is in the range of about 6.0 to about 8.0 μm.

[0072] In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area of ​​the population is about 3 m 2 / g ~ approx. 12m 2 / g range.

[0073] In one aspect, a battery electrode includes a battery electrode composition disposed on or within a current collector, the battery electrode including a binder.

[0074] In some embodiments, the coating density of the battery electrode is about 0.9 to about 1.0 g / cm 3 is in the range.

[0075] In some embodiments, the battery electrode further comprises a carbon-containing functional additive.

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

[0077] In some embodiments, the D of the PSD of the population 50 is in the range of about 6.0 to about 8.0 μm, and the mass fraction of the binder in the battery electrode is in the range of about 7 wt % to about 10 wt %.

[0078] In some embodiments, the D of the PSD of the population 50 is in the range of about 6.0 to about 8.0 μm, and the area binder loading of the battery electrode is about 9.0 mg / m 2 ~About 13.0mg / m 2 The areal binder loading is defined as the mass fraction of binder in the battery electrode divided by the product of (1) the mass fraction of the serrated composite particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the ensemble.

[0079] In one aspect, a lithium-ion battery includes an anode current collector, a cathode current collector, a battery electrode configured as an anode, with the current collector configured as the anode current collector, a cathode disposed on or within the cathode current collector, and an electrolyte ionically bonding the anode and cathode.

[0080] In one aspect, a method of manufacturing a battery electrode includes the steps of: (A1) providing a battery electrode composition; (A2) preparing a slurry comprising the battery electrode composition and a binder; and (A3) casting the slurry onto or into a current collector to form the battery electrode (although in some designs this step often includes evaporating the slurry solvent and / or densifying the battery electrode to a desired level).

[0081] In one aspect, a method of manufacturing a lithium-ion battery includes the steps of: (B1) fabricating a battery electrode according to the methods of (A1), (A2), and (A3), wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (B2) fabricating or providing a cathode disposed on or within a cathode current collector; and (B3) assembling a battery cell from the anode and cathode (and in some designs a porous separator membrane or layer therebetween) and filling the space between the anode and cathode with an electrolyte that ionically bonds the anode and cathode to form a lithium-ion battery.

[0082] In one aspect, a method of manufacturing a lithium-ion battery includes the steps of: (C1) providing a battery electrode, where the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on or within a cathode current collector; and (C3) assembling a battery cell from the anode and cathode (and in some designs a porous separator membrane or layer therebetween) and filling the space between the anode and cathode with an electrolyte that ionically bonds the anode and cathode to form a lithium-ion battery.

[0083] Other objects and advantages associated with the embodiments disclosed herein will become apparent to those skilled in the art based on the accompanying drawings and detailed description.

[0084] The accompanying drawings are presented to aid in the explanation of embodiments of the present disclosure and are provided solely for the purpose of illustrating the embodiments, not for the purpose of limitation thereof. Unless otherwise noted or suggested by context, the various hatching, shading, and / or fill patterns in the drawings are meant only to depict contrast between different components, elements, features, etc., and are not meant to convey the use of particular substances / materials, colors, or other characteristics that may be defined as outside the present disclosure for the particular patterns employed. [Brief explanation of the drawings]

[0085] [Figure 1] 1 illustrates an exemplary Li-ion battery in which the components, substances / materials, processes and other techniques described herein may be implemented. [Figure 2] FIG. 1 is a flow diagram of a process for manufacturing a Li-ion rechargeable battery cell according to certain embodiments. [Figure 3] FIG. 1 is a flow diagram of a process for making anode (or cathode) particles according to certain embodiments, which includes performing an activation process on carbon particles. [Figure 4] 4 shows a schematic diagram of a sawtooth particle 400 and a graphical plot 420 of the dependence of cumulative particle number distribution of sawtooth composite particles on aspect ratio of the sawtooth composite particles. [Figure 5] Shown are SEM images of sawtooth composite particles (502) obtained from a population with a D50 of about 2.5 μm and SEM images of sawtooth composite particles (504) obtained from a population with a D50 of about 7 μm. [Figure 6] Shown are SEM images 602 of sawtooth composite particles obtained from a population with a D50 of about 9 μm and SEM images 604 of sawtooth composite particles obtained from a population with a D50 of about 14 μm. [Figure 7] Shown is a graphical plot 702 of the dependence of overall width D90-D10 on D50 for each of the exemplary sawtooth composite particle populations and a graphical plot 704 of the dependence of mass fraction of silicon in the composite particles on D50 for each of the exemplary particle populations. [Figure 8]Shown are SEM images (802, 804) of cross sections of electrode coatings with a sample of sawtooth composite particle population with a D50 of about 4 μm and a sample of sawtooth composite particle population with a D50 of about 14 μm, respectively. [Figure 9] A graphical plot 902 of the dependence of cycle life on D50 for each of the exemplary particle populations and a graphical plot 904 of the dependence of normalized coating thickness change on D50 for each of the exemplary particle populations are shown. [Figure 10] A graphical plot 1002 of the dependence of volumetric energy density on D50 for each of the exemplary sawtooth composite particle populations and a graphical plot 1004 of the dependence of volumetric charge density on D50 for each of the exemplary particle populations are shown. [Figure 11] A graphical plot 1102 of the dependence of normalized high rate discharge capacity density on D50 for each of the exemplary sawtooth composite particle populations and a graphical plot 1104 of the dependence of discharge voltage on D50 for each of the exemplary particle populations are shown. [Figure 12] 12 shows a graphical plot 1202 of the dependence of normalized capacity (expressed as a fraction of base capacity) as a function of charge rate (charge C rate) for lithium ion battery test cells containing sawtooth composite particle populations of D50 of about 3 μm and about 5 μm. [Figure 13] A graphical plot 1302 of the dependence of first cycle efficiency on D50 for each of the exemplary particle populations and a graphical plot 1304 of the dependence of formation efficiency on D50 for each of the exemplary particle populations are shown. [Figure 14] A graphical plot 1402 of the dependence of internal resistance on D50 for each of the exemplary sawtooth composite particle populations and a graphical plot 1404 of the dependence of coating density on D50 for each of the exemplary particle populations are shown. [Figure 15] A graphical plot 1502 of the dependence of Brunauer-Emmett-Teller specific surface area (BET-SSA) on D50 for each of the exemplary sawtooth composite particle populations and a graphical plot 1504 of the dependence of areal binder loading on D50 for each of the exemplary particle populations are shown. [Figure 16]16 shows a graphical plot 1602 illustrating cycle life values ​​versus cumulative volume fraction (D50 threshold of 4.6 μm) for a sawtooth composite particle population with D50 values ​​ranging from about 2.0 μm to about 4.0 μm, where cumulative volume fraction is defined as the cumulative volume of particles with D50 values ​​at or below the threshold D50 value divided by the total volume of all particles. [Figure 17] A graphical plot 1702 of the dependence of areal binder loading on binder mass fraction for each test cell is shown. The test cells were constructed with a sawtooth composite particle population with a D50 value of approximately 7.42 μm. The control sample test cell was constructed with a particle population with a D50 value of approximately 5.35 μm. [Figure 18] 18 shows a graphical plot 1802 of the dependence of cycle life on binder mass fraction for each of the test cells of FIG. 17 and a graphical plot 1804 of the dependence of normalized coating thickness change on binder mass fraction for each of the test cells of FIG. [Figure 19] 19 shows a graphical plot 1902 of the dependence of volumetric energy density (VED) on binder mass fraction for each of the test cells of FIG. 17 and a graphical plot 1904 of the dependence of volumetric charge density (VQD) on binder mass fraction for each of the test cells of FIG. [Figure 20] 17. A graphical plot 2002 of the dependence of discharge voltage on binder mass fraction for each of the test cells of FIG. 17 and a graphical plot 2004 of the dependence of internal resistance on binder mass fraction for each of the test cells of FIG. 17 are shown. [Figure 21] 17A and 17B show a graphical plot 2102 of the dependence of the formation efficiency on the binder mass fraction for each of the test cells of FIG. 17A and a graphical plot 2104 of the dependence of the first cycle efficiency on the binder mass fraction for each of the test cells of FIG. [Figure 22] 22 shows an SEM image (2201) of a population of sawtooth composite particles (including agglomerates of sawtooth particles) without optimizing the particle size distribution (PSD) of the population, and an SEM image (2202) of a cross section of an electrode coating containing a mixture of graphite particles and the population of sawtooth particles shown in 2201 as the electrode active material. The D50 of the population is approximately 10 μm, and the population includes fine particles ("fines") and coarse particles. [Figure 23] 23 shows an SEM image (2301) of a population of sawtooth composite particles after optimizing the particle size distribution (PSD) of the population, and an SEM image (2302) of a cross section of an electrode coating containing a mixture of sawtooth particles shown in 2301 and graphite particles. Prior to the PSD optimization, the population had a D50 of approximately 10 μm. The PSD optimization process included the removal of fine particles (the removed fine particles had a D50 of approximately 1.5 μm) and coarse particles (the removed coarse particles had a D50 of approximately 15 μm). [Figure 24] Illustrated are graphical plots 2401 and 2402 of the volume-weighted particle size distribution (PSD) of an exemplary population of sawtooth composite particles. Graphical plot 2401 shows the PSD of the exemplary population at each D50 value, which indicates a relatively wide PSD, before any optimization of the respective PSD. Graphical plot 2402 shows (1) the PSD of the exemplary population (D50 of approximately 10.1 μm) before optimization of its PSD and (2) the PSD of the exemplary population (D50 of approximately 9.8 μm) after any optimization of its PSD. PSD optimization includes the removal of fine particles and the removal of coarse particles. As a result of these PSD optimization processes, the PSD changes from a relatively wide PSD (e.g., large span, large FWHM) to a relatively narrow PSD (e.g., small span, small FWHM). [Figure 25] Table 1 provides a tabulation of selected properties of exemplary populations of sawtooth composite particles (D10, D50, D90, D99, span, FWHM, D10 / D50, BET-SSA, and whether the population has undergone optimization of its PSD (so-called "wide" PSD) or its PSD (so-called "narrow" PSD)), as well as selected properties of electrode coatings and battery cells derived from each exemplary population of sawtooth composite particles (estimated capacity, electrode coating density, and cycle life of each electrode active material including sawtooth composite particles and graphite particles). [Figure 26] An SEM image of a population of spheroidal composite particles (2601) is shown. In the example shown, the D50 value of the population is in the range of about 5 to about 7 μm. [Figure 27]2 shows a graphical plot 2701 illustrating the dependence of BET-SSA values ​​of an exemplary population of composite particles (serrated composite particles before PSD optimization (exhibiting a so-called "wide" PSD), serrated composite particles after PSD optimization (exhibiting a so-called "narrow" PSD), and spheroidal particles) on their respective D50 values. In the illustrated example, the D50 values ​​were measured by LPSA. [Figure 28] Graphical plots 2802, 2804, and 2806 are shown of selected PSD properties of exemplary populations of sawtooth composite particles. Graphical plot 2802 shows the dependence of D90 values ​​on D50 values ​​for each population of sawtooth composite particles, illustrating the trend between populations that have not undergone PSD optimization (so-called "wide" PSDs) and populations that have undergone PSD optimization (so-called "narrow" PSDs). Graphical plot 2804 shows the dependence of D90 values ​​on D50 values ​​for each population of sawtooth composite particles, illustrating the trend between populations that have not undergone PSD optimization (so-called "wide" PSDs) and populations that have undergone PSD optimization (so-called "narrow" PSDs). Graphical plot 2806 shows the dependence of D10 values ​​on D50 values ​​for each population of sawtooth composite particles, illustrating the trend between populations that have not undergone PSD optimization (so-called "wide" PSDs) and populations that have undergone PSD optimization (so-called "narrow" PSDs). [Figure 29] Illustrated are graph plots 2901 and 2902 illustrating the dependence of cycle-life performance of Li-ion batteries fabricated using each exemplary population of sawtooth composite particles on the D50 value of each exemplary population. Graphic plots 2901 and 2902 show trends between populations that have not undergone PSD optimization (so-called "wide" PSD) and populations that have undergone PSD optimization (so-called "narrow" PSD). In the illustrated example, the Li-ion batteries employed anodes including a mixture of sawtooth composite particles and graphite particles ("active material mixture"). Graphic plot 2901 illustrates the cycle-life performance of a Li-ion battery employing an active material mixture exhibiting a Li-ion capacity of approximately 600 mAh / g. Graphic plot 2902 illustrates the cycle-life performance of a Li-ion battery employing an active material mixture exhibiting a Li-ion capacity of approximately 1000 mAh / g. [Figure 30]30 shows graphical plots 3002, 3004, 3006, and 3008 illustrating the dependence of selected PSD properties of exemplary populations of serrated composite particles on the D50 value of the exemplary population. In the example shown in FIG. 30, the PSD of each population was modified by milling (jet milling or ball milling). Graphical plots 3002, 3004, 3006, and 3008 show trends between the ball milled and jet milled populations. The PSD properties shown are span (3002), D90 (3004), D10 (3006), and the volume fraction of fine particles (defined as particles with a diameter of 1 μm or less as measured by LPSA) in the population (3008). DETAILED DESCRIPTION OF THE INVENTION

[0086] Aspects of the invention are disclosed in the following description and related drawings directed to specific embodiments of the invention. The term "embodiments of the invention" does not require that all embodiments of the invention include the described features, advantages, processes, or modes of operation, and alternative embodiments may be devised without departing from the scope of the invention. Additionally, well-known elements of the invention may not be described in detail or may be omitted so as not to obscure other more relevant details.

[0087] Embodiments of the present disclosure relate to highly carbon-containing (e.g., primarily graphitic sp) composites for use in electrodes (e.g., anode or cathode electrodes) of Li-ion, Na-ion, or K-ion rechargeable batteries, electrochemical capacitors, and hybrid electrochemical energy storage devices, among other battery types. 2 A process for producing bonded carbon-containing composite particles is provided.

[0088] Any numerical ranges described herein with respect to any embodiment of the present invention not only define the upper and lower limits of the associated numerical range, but are also intended as an implicit disclosure of each discrete value within that range in units or increments consistent with the level of precision by which the upper and lower limits are characterized. For example, a numerical distance range (i.e., a level of precision in units or increments of 1) of 7 nm to 20 nm encompasses the set (in nm) of [7, 8, 9, 10, . . . , 19, 20], as if the intervening numbers 8 to 19 in units or increments of 1 were explicitly disclosed. As another example, a temperature range of about -120°C to about -60°C encompasses the set (in °C) of temperature ranges of about -120°C to about -119°C, about -119°C to about -118°C, . . . , about -61°C to about -60°C, as if the intervening numbers (in °C) of -120°C to -60°C were explicitly disclosed in the incremental range. In yet another example, a numerical percentage range (i.e., a level of precision in hundredths or increments) of 30.92% to 47.44% encompasses (in %) the set [30.92, 30.93, 30.94, . . . , 47.43, 47.44], as if the intervening numbers between 30.92 and 47.44 in hundredths or increments were expressly disclosed. Accordingly, any intervening numbers encompassed by any disclosed numerical range are intended to be construed as if those intervening numbers were explicitly disclosed, whereby any such intervening numbers may constitute their own upper and / or lower limits of subranges falling within broader ranges. Each subrange (e.g., each range that includes at least one intervening number of the broader range as an upper and / or lower limit) is thereby intended to be construed as implicitly disclosed by the explicit disclosure of the broader range. In yet another example, a numerical range having upper and lower limits defined with different levels of precision should be interpreted in increments corresponding to the limit values ​​having the higher level of precision.For example, a numerical percentage range of 30.92% to 47.4% (i.e., levels of precision in hundredths and tenths of a percent, respectively) encompasses the set [30.92, 30.93, 30.94, . . . , 47.39, 47.40] (in %) as if 47.4% (tenths) were stated as 47.40% (hundredths), and as if the intervening numbers between 30.92 and 47.40 in hundredths of a percent or increments were explicitly disclosed.

[0089] It should be understood that the level of precision of any particular measurement, threshold, or other imprecise parameter may vary based on various factors, such as the measurement equipment, environmental conditions, etc. Accordingly, hereinafter, references to such measurements or thresholds may be interpreted as the respective values ​​assuming a pseudo-precise level of precision (e.g., an 80% threshold would consist of 80.0000...%). Alternatively, references to such measurements or thresholds may be described via modifiers that capture the pseudo-precise value as well as a range extending above and / or below the pseudo-precise value. For example, the 80% threshold noted above may be described as "about," "approximately," "around," "approximately ...

number

[0090] While the following description may describe specific examples in the context of Li metal and Li-ion batteries (for brevity and convenience, and due to the current prevalence of Li technology), it should be understood that various embodiments may be 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 electrochemical capacitors and hybrid energy storage devices.

[0091] While the following description may describe specific examples in the context of composites containing alloy-type anode active materials (e.g., Si, Sn, Sb, Al, etc.), it should be understood that various embodiments may be applicable to conversion-type anode and cathode active materials, intercalation-type anode and cathode active materials, pseudocapacitive anode and cathode active materials, and materials that may exhibit combined electrochemical energy storage mechanisms. It should be noted that the selection of high-capacity alloy-type (conversion-type) anode materials 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, Si may be a preferred alloy-type material for Li or Li-ion batteries, while Sn or Sb, or Sn- or Sb-containing alloys, may be preferred alloy-type materials for Na or Na-ion batteries.

[0092] While the following description may describe specific examples of material formulations in a Li-free state (e.g., as in silicon-containing nanocomposite anodes or metal fluoride cathodes), it should be understood that various embodiments may be applicable to lithium-containing electrodes and active materials (e.g., partially or fully lithiated Si-containing anodes or partially or fully lithiated Si-containing anode particles; cathodes comprising partially or fully lithiated metal fluorides (e.g., mixtures of LiF with metals such as Cu, Fe, Ni, Bi, various other metals and metal alloys, and mixtures thereof and other metals, etc.) or cathode particles comprising partially or fully lithiated metal halides (e.g., mixtures of LiF with metals such as Cu, Fe, Ni, Bi, various other metals and metal alloys, and mixtures thereof and other metals, etc.); partially or fully lithiated chalcogenides (e.g., LiS, LiS / metal mixtures, LiSe, LiSe / metal mixtures, LiS-LiSe mixtures, various other compositions containing lithiated chalcogenides, etc.); partially or fully lithiated metal oxides (e.g., LiO, LiO / metal mixtures, etc.); partially or fully lithiated carbon, etc.), among others. In some designs, various material properties (e.g., at the particle level, interparticle level, electrode level, etc.) may vary based on whether the active material particles are in a Li-free, partially lithiated, or fully lithiated state. Such Li-dependent material properties may include particle pore volume, electrode pore volume, etc. Hereinafter, unless otherwise stated or implied, references to such Li-dependent material properties (e.g., at the particle level, interparticle level, electrode level, etc.) may be considered to be provided as if the active material particles were in a Li-free state. Furthermore, some examples below are characterized at the electrode level (e.g., as opposed to the particle level, interparticle level, cell level, etc.). Hereinafter, unless otherwise stated or implied, references to such electrode-level properties (e.g., electrode porosity, areal capacity loading, or weight / volume capacity, etc.) may be considered to refer to the electrode components (e.g., active material particles, binder, conductive additives, etc.), excluding the current collector.

[0093] In the following description, various material properties are described to characterize materials in various states (e.g., molecules, particles, powders, slurries, electrodes, separators, electrolytes, battery cells, etc.). It should be noted that one skilled in the art can generally select (and is assumed herein to select) the optimal measurement technique for any particular measurement. Furthermore, in some cases, the optimal measurement technique may include a combination of techniques. While the following tables characterize various measurement type options for particular material types and particular material properties, where appropriate, particular embodiments of the present disclosure may be characterized more specifically in the context of particular measurement techniques and / or particular commercially available equipment. It should be noted that while the following tables characterize measurements on active material particles, similar measurements may also be performed on other particle types, such as precursor particles (e.g., carbon particles, etc.). Therefore, unless otherwise noted, the following tables provide examples of how such material properties may be readily measured by one skilled in the art using commercially available equipment. [Table 1] JPEG2026504787000004.jpg225159 JPEG2026504787000005.jpg237159 JPEG2026504787000006.jpg225159 JPEG2026504787000007.jpg235159 JPEG2026504787000008.jpg235159 JPEG2026504787000009.jpg236159 JPEG2026504787000010.jpg230159 JPEG2026504787000011.jpg231159 JPEG2026504787000012.jpg236159 JPEG2026504787000013.jpg80159

[0094] In some embodiments described below, certain parameters (e.g., temperature, state of charge (SOC), etc.) are specified in terms of relative terms such as low, reduced, high, increased, elevated, etc. With respect to temperature, unless otherwise specified, the relative terms may be characterized relative to a battery cell storage temperature or a battery cell use temperature, depending on the context of the relevant example. With respect to SOC, unless otherwise specified, a high SOC may be defined as greater than about 70% SOC (e.g., about 70-80% SOC in some designs, about 80-90% SOC in some designs, and about 90-100% SOC in some designs).

[0095] Reference below is made to various battery electrode compositions, which may be in the form of a "dry" powder (e.g., before being mixed or suspended in a slurry), the slurry itself (e.g., in suspension), or a cast electrode (e.g., cast onto and / or into a current collector, bound together with a suitable binder, dried, and optionally coated and / or calendered to form an electrode).

[0096] The following description is directed to Si-C composite (e.g., nanocomposite) anode active materials (e.g., silicon (Si) and carbon (C) (e.g., primarily graphitic sp 2 While specific examples are described in the context of nanocomposite particles comprising Si atoms (compounds of silicon and carbon atoms), and optionally containing other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), and sulfur (S), where the combined mass of the Si and C atoms may contribute from about 75% to about 100% by weight of the total mass of the composite particle, it should be appreciated that various embodiments may be applicable to other types of high capacity silicon-containing anode active materials (including, but not limited to, various silicon-containing particles, silicon oxide-containing particles, silicon nitride-containing particles, silicon oxynitride-containing particles, silicon phosphide-containing particles, or particles comprising mixtures, alloys, or other combinations of such active materials, various other types of Si-containing composites, including, but not limited to, core-shell particles, hierarchical particles, or nanocomposite particles).

[0097] While the following description may describe specific examples of anode and cathode active materials in the context of some specific alloy and conversion chemistries for Li-ion batteries (such as silicon-containing anodes or metal fluoride- or lithium sulfide-containing cathodes), it should be understood that various embodiments may be applicable to other Li-ion battery chemistries (other conversion and alloy-type electrodes and various insertion-type anodes and cathodes) and 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 selenides (including, but not limited to, lithium sulfide), metal oxides, metal nitrides, metal phosphides, metal hydrides, various mixtures, composites (including nanocomposites), and alloys thereof.

[0098] While the following description may describe specific examples in the context of sawtooth (e.g., Si-containing, such as Si—C) nanocomposite particles having aspect ratios in a relatively small range, it should be understood that various embodiments may be applicable to other shaped (e.g., Si-containing, such as Si—C) nanocomposite particles, including, but not limited to, cylindrical or fibrous (e.g., Si-containing, such as Si—C) nanocomposite particles, spherical or spheroidal particles (e.g., aspect ratios ranging from about 1 to about 200, in some designs from about 1 to about 5, in other designs from about 5 to about 10, and in other designs from about 10 to about 200), to provide some illustrative examples.

[0099] During battery operation (such as in a Li-ion battery), conversion materials change (transform) from one crystalline structure to another (hence the term "conversion" type). This process involves the breaking of chemical bonds and the formation of new chemical bonds. During (e.g., Li-ion) battery operation, Li ions are inserted into alloy-type materials to form lithium alloys (hence the term "alloy" type). "Alloy" type electrode materials are sometimes considered a subclass of "conversion" type electrode materials.

[0100] In one or more embodiments of the present disclosure, a suitable anode for a battery cell may include a mixture of Si-C nanocomposite (e.g., particles) and graphite (e.g., particles) as the anode active material, a so-called blend anode. In addition to the anode active material particles, the anode may include inactive materials such as a binder (e.g., a polymer binder) and other functional additives (e.g., surfactants, conductive additives). In some examples, the anode active material may be in the range of about 90% to about 98% by weight of the anode. For example, the anode active material particles may be about 95.5% by weight of the anode. In some examples, the blend anode may include Si-C nanocomposite (e.g., particles) in the range of about 7% to about 75% by weight of the anode, with graphite (e.g., particles) making up the remainder of the mass (weight) of the anode active material particles. In some embodiments where the anode active material particles are about 95.5% by weight of the blend anode, the blend anode (including the active material particles and inactive material) can include about 7% by weight of Si-C nanocomposite (e.g., particles) and about 88.5% by weight of graphite particles. In some embodiments where the anode active material particles are about 95.5% by weight of the blend anode, the blend anode (including the active material particles and inactive material) can include about 19% by weight of Si-C nanocomposite (e.g., particles) and about 76.5% by weight of graphite particles. In some embodiments where the anode active material particles are about 95.5% by weight of the blend anode, the blend anode (including the active material particles and inactive material) can include about 35% by weight of Si-C nanocomposite (e.g., particles) and about 60.5% by weight of graphite particles. In some embodiments where the anode active material particles are about 94.5% by weight of the blend anode, the blend anode (including the active material particles and inactive material) can include about 50% by weight of Si-C nanocomposite (e.g., particles) and about 44.5% by weight of graphite particles. In some embodiments where the anode active material particles are about 92.5% by weight of the blend anode, the blend anode (including the active material particles and inactive material) can include about 69.4% by weight of Si-C nanocomposite (e.g., particles) and about 23.1% by weight of graphite particles.In some designs, a higher fraction of Si—C composite particles in the blend anode may benefit from a higher fraction of inactive material to achieve superior cycling stability and other performance characteristics.

[0101] While the following description may describe specific examples of blended anode formulations expressed as the mass (wt%) of Si-C nanocomposite (e.g., particles), it should be understood that various aspects of the present disclosure may be applicable to blended anode formulations expressed as the wt% of Si in the anode. In some examples, a blended anode composition of about 7 wt% Si-C nanocomposite (e.g., particles) may correspond to, for example, about 3-3.5 wt% Si in the blended anode. In some examples, a blended anode composition of about 19 wt% Si-C nanocomposite (e.g., particles) corresponds to about 8-9.5 wt% Si in the blended anode. In some examples, a blended anode composition of about 35 wt% Si-C nanocomposite (e.g., particles) corresponds to about 15-18 wt% Si in the blended anode. In some examples, a blended anode composition of about 50 wt% Si-C nanocomposite (e.g., particles) corresponds to about 21-30 wt% Si in the blended anode. In each example, a blended anode can be obtained in which the mass (weight) of silicon ranges from about 3 wt % to about 30 wt % of the total mass of the anode.

[0102] While the following description may describe specific examples of blend anode formulations expressed as the mass (wt%) of Si-C nanocomposite (e.g., particles) relative to the total active material in the anode, it should be understood that various aspects of the present disclosure may be applicable to blend anode formulations in which a fraction (e.g., %) of the blend anode's total capacity is attributed to the capacity of Si. In some examples, about 25% of the blend anode's total capacity is obtained from Si-C nanocomposite (e.g., particles) in a blend anode composition of about 7 wt% Si-C nanocomposite (e.g., particles) and about 93 wt% graphite (e.g., particles). In some other examples, about 50% of the blend anode's total capacity is obtained from Si-C nanocomposite (e.g., particles) in a blend anode composition of about 19 wt% Si-C nanocomposite (e.g., particles) and about 81 wt% graphite (e.g., particles). In some other examples, about 70% of the total capacity of the blend anode is obtained from the Si-C nanocomposite (e.g., particles) in a blend anode composition of about 35 wt% Si-C nanocomposite (e.g., particles) and about 65 wt% graphite (e.g., particles). In some other examples, about 80% of the total capacity of the blend anode is obtained from the Si-C nanocomposite (e.g., particles) in a blend anode composition of about 50 wt% Si-C nanocomposite (e.g., particles) and about 50 wt% graphite (e.g., particles). Note that the percentage of the total capacity of the blend anode provided by the Si-C nanocomposite (e.g., particles) depends on both the weight percentage of such particles (e.g., relative to the total active material in the anode) and the specific capacity of the Si-C nanocomposite. For example, a Si-C nanocomposite with a higher specific capacity will provide a higher fraction (%) of total capacity for the same weight percentage.

[0103] While the following description may set forth specific examples of intercalated graphites suitable for use in combination with Si-C nanocomposites (e.g., particles) in blends, various embodiments of the present disclosure are directed to intercalated graphites, including, but not limited to, those exhibiting discharge capacities of about 320 to about 372 mAh / g (e.g., about 320 to about 350 mAh / g in some designs, about 350 to about 362 mAh / g in other designs, or about 362 to about 372 mAh / g in other designs), including, but not limited to, those exhibiting low swelling, moderate swelling, and high swelling, including, but not limited to, those exhibiting good or poor compressibility, including, but not limited to, those exhibiting about 1 to about 4 m 2 / g, including but not limited to, those exhibiting a Brunauer-Emmett-Teller (BET) specific surface area of ​​about 90% or greater, including but not limited to, those exhibiting an average particle size of about 8 μm to about 18 μm, including but not limited to, those exhibiting an average particle size of about 1.5 g / cm 3 ~Approx. 2.3g / cm 3 (For example, some designs have a value of about 1.5 to about 1.8 g / cm 3 , and about 1.8 to about 2.3 g / cm for other designs. 3 ), including, but not limited to, those that exhibit poor, moderate, or good cycle life when used alone (e.g., without Si—C composite or other active particles) in anodes of Li-ion batteries, including, but not limited to, those that are coated and have a coating thickness to significantly improve compressibility and springiness during cycling, and it should be understood that this may be applicable to soft-type synthetic graphite (i.e., soft carbon in the broad sense), hard-type synthetic graphite (i.e., hard carbon in the broad sense), and natural graphite (which may be coated, for example, with pitch carbon).

[0104] The following description includes lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese aluminum oxide (NCMA), lithium nickel oxide (LNO), lithium manganese oxide (LMO), lithium nickel manganese cobalt oxide (NCM), lithium cobalt oxide (LCO), lithium cobalt aluminum oxide (LCAO), lithium iron phosphate (LFP), lithium cobalt phosphate (LCP), lithium manganese phosphate (LMP), lithium manganese iron phosphate (LMFP), lithium nickel phosphate (LiNiPO4), lithium vanadium fluorophosphate (LiVFPO4), lithium iron fluorosulfate (LiFeSO4F), various Li-rich materials (e.g., Li 1.211 Mo 0.467 Cr 0.3 O2, Li 1.3 Mn 0.4 Nb 0.3 O2, Li 1.2 Mn 0.4 Ti 0.4 O2, Li 1.2 Mn 0.8 O2, Li 1.2 Mn 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 Mo 0.133 Lithium-rich (rock-salt) transition metal oxides and oxyfluorides such as LiMnO and many others), various high-capacity Li-ion based materials with partial substitution of oxygen for fluorine or iodine (e.g., rock-salt LiMn, among others). 2 / 3 Nb 1 / 3 O2F, Li2Mn 1 / 2 Ti 1 / 2 O2F, Li1.5 Na 0.5 MnO 2.85 I 0.12 ), as well as numerous other types of Li-containing disordered, layered, tavorite-type, olivine-type, or spinel-type cathode or anode active materials, including at least oxygen, fluorine, or sulfur, and at least one transition metal and other lithium TM oxide, phosphate, sulfate (or mixed) cathode or anode active materials, including, but not limited to, those that may be doped or heavily doped, including, but not limited to, those with a gradient in composition or a core-shell morphology, and including, but not limited to, those that may be partially fluorinated or contain some significant fraction (e.g., about 0.001-10 atomic %) of fluorine in their composition. While specific examples of suitable intercalation-type cathodes (including high-voltage cathodes) may be described in the context of lithium-type active materials or mixtures thereof, it should be understood that various embodiments may be applicable to high-voltage lithium transition metal oxide (or phosphate, sulfate, mixed, or other) cathodes in which the TM and oxygen (O) are covalently bonded and both participate in electrochemical oxidation-reduction (redox) reactions during charge and discharge (including, but not limited to, oxides, phosphates, sulfates, or mixed cathodes that may contain at least about 0.25 atomic % Mn, Fe, Ni, Co, Nb, Mg, Cr, Mo, Zr, W, Ta, Ti, Hf, Y, La, Sb, V, Sn, Si, or Ge).

[0105] FIG. 1 illustrates an exemplary metal-ion (e.g., Li-ion) battery, to which the electrode particles, components, materials, processes, and other techniques described herein, or combinations thereof, may be applied according to various embodiments. While a cylindrical battery is shown here for illustrative purposes, other types of configurations, including prismatic or pouch-type (laminated) batteries, may also be used as desired. The exemplary battery 100 includes a negative electrode (anode electrode or anode) 102, a positive electrode (cathode electrode or cathode) 103, a separator 104 interposed between the anode 102 and the cathode 103, an electrolyte (implied) impregnating the separator 104, a battery case 105, and a sealing member 106 sealing the battery case 105. The electrolyte ionically bonds the anode (negative electrode) and the cathode (positive electrode). The electrolyte is interposed 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 disposed on or within the anode current collector, and the cathode is disposed on or within the cathode current collector.

[0106] 2 shows a flow diagram of a process 120 for fabricating a Li-ion battery, such as the example battery 100 of FIG. 1. In the illustrated example, process 120 includes operations 122, 124, 132, 134, and 140. The flow diagram includes an anode branch (left branch) that includes operations 122 and 124 and a cathode branch (right branch) that includes operations 132 and 134. In operation 122, anode particles (e.g., conventional anode particles or core-shell anode particles, or composite anode particles including, but not limited to, Si-containing composite (e.g., nanocomposite) particles whereby Si-containing active material is deposited within the pores of the particle core) are produced, and in operation 124, an anode is formed. Similarly, in process 132, cathode particles (e.g., conventional cathode particles or core-shell cathode particles, or composite cathode particles including, but not limited to, conversion cathode material, including composite particles whereby conversion cathode material active material is deposited within the pores of the particle core) are produced, and in process 134, a cathode is formed.

[0107] Electrodes used in Li-ion batteries are generally fabricated by (i) forming a slurry containing active material, conductive additives, a binder solution, and optionally surfactants or other functional additives, (ii) casting the slurry onto a metal foil (e.g., Cu or Cu alloy foil for most anodes and Al or Al alloy foil for most cathodes), and (iii) drying the cast electrode to completely evaporate the solvent. In some embodiments, step (iii) may also include densifying the battery electrode to a desired value. Note that metal mesh, metal foam, or highly rough metal foil (e.g., with metal nanowires or metal nanosheets on its surface) may be used in some designs (e.g., for higher areal capacity loading or to achieve faster charging). Note that metal-coated thin polymer sheets may also be used in some designs (e.g., to achieve improved safety or lighter current collectors). Note that porous metal foils or composite (e.g., nanocomposite) metal foils may also be used in some designs (e.g., for improved performance, lighter weight, etc.).

[0108] Process 124 includes fabricating an anode electrode, which includes the anode particles produced in process 122. For example, process 124 may include (1) fabricating an anode slurry including 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 designs, this stage often includes evaporating the slurry solvent and / or densifying the battery electrode to a desired value. For example, other anode slurry components can include other electrochemically active anode materials (e.g., natural or synthetic graphite, soft carbon or hard carbon), conductive additives (e.g., carbon nanotubes, carbon black, branched carbon, carbon nanofibers, graphite flakes, expanded graphite, graphene (e.g., single-layer graphene, multi-layer graphene), graphene oxide (e.g., single-layer graphene oxide, multi-layer graphene oxide), soft graphite, or various combinations thereof, to name a few), binders (e.g., polymeric binders), and solvents (e.g., water or suitable organic solvents).

[0109] Process 134 includes fabricating a cathode electrode, which includes the cathode particles produced in process 132. For example, process 134 may include (1) fabricating a cathode slurry including the cathode particles (e.g., from process 132) and other cathode slurry components, and (2) casting the cathode slurry onto a cathode current collector (e.g., an aluminum foil or aluminum alloy foil current collector). In some designs, this stage often includes evaporating the slurry solvent and / or densifying the battery electrode to a desired value. For example, other cathode slurry components can include other electrochemically active cathode materials, conductive additives (e.g., carbon nanotubes, carbon black, branched carbon, carbon nanofibers, graphite flakes, graphene (e.g., single-layer graphene, multi-layer graphene), graphene oxide (e.g., single-layer graphene oxide, multi-layer graphene oxide), soft graphite, or various combinations thereof, to name a few), binders (e.g., polymer binders), and solvents (e.g., water or suitable organic solvents).

[0110] In process 140, a Li-ion rechargeable battery cell is assembled from at least an anode electrode and a cathode electrode with an electrolyte interposed between the anode and cathode electrodes. The electrolyte provides ionic conductivity between the anode and cathode. The electrolyte ionically bonds the anode and cathode. The electrolyte may include a liquid electrolyte or a solid electrolyte (or a mixture of liquid and solid electrolytes) at the battery's operating temperature (e.g., in some designs, the solid electrolyte may be molten or semi-molten during melt infiltration and subsequently solidified). In some embodiments, such as those in which a liquid electrolyte is used, a separator may be used to maintain a space between the anode and cathode electrodes.

[0111] 3 is a flow diagram of a process 150 for manufacturing anode particles, illustrating operation 122 in more detail. Process 150 includes operations 152, 154, 156, 158, and 160. In some designs, the processes and systems described herein may be particularly useful when implemented as part of operation 122 and / or operation 132. In some embodiments, electrode particles are fabricated using porous carbon or porous carbon-containing particles (e.g., often graphitic sp 2 Bonded carbon or porous graphite sp 2 The porous carbon or porous carbon-containing particles may be fabricated using anode particles (e.g., porous carbon-containing particles) and have nanostructured or nanosized active material particles (e.g., having average diameters or linear dimensions in the range of about 1 nm to about 200 nm (in some designs, about 1 nm to about 10 nm, in other designs, about 10 nm to about 30 nm, in still other designs, about 30 nm to about 100 nm, and in still other designs, about 100 nm to about 200 nm) as measured using image analysis of electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, neutron scattering, and other suitable techniques)) formed within the pores of the porous carbon or porous carbon-containing particles. In the case of anode particles for use in Li-ion batteries, the active material particles may be silicon-containing particles.

[0112] In operation 152, carbon particles are provided. In some designs, carbon (e.g., often graphitic sp 2 The carbon particles can be obtained by pyrolysis or carbonization (e.g., by thermal or hydrothermal treatment) of suitable precursor particles, such as polymer particles or biomass-derived particles. In some designs, the carbon particles can be obtained by carbon-containing inorganic precursor particles (e.g., carbides or oxycarbides).

[0113] In some designs, inorganic sacrificial templates (including but not limited to various oxides, hydroxides or oxyhydroxides of various metals and metalloids, such as Zn, Mg, Si, Al, Ti, Ca, Mg, Sc, etc., and various combinations thereof) or soft (organic) templates may be used for the formation of porous carbon particles.

[0114] In some designs, it may be preferred that the porosity (e.g., specific surface area and specific pore volume) of the carbon or carbon-containing particles be very high prior to the formation of nanostructured or nanosized active material particles therein. In some examples, the carbon or carbon-containing particles are etched to a thickness of about 500 m prior to the formation of the active material particles therein. 2 Preferably, the carbon particles exhibit a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of at least about 500 m / g (e.g., as obtained from nitrogen adsorption-desorption data at cryogenic temperatures, such as about 77 K). In some embodiments, the carbon particles are heated to about 500 m / g prior to the formation of active material particles thereon. 2 / g~about 4500m 2 / g or approximately 4800m 2 / g (approx. 500 to approx. 1000 m in some designs) 2 / g, and about 1000 to about 2000m for other designs 2 / g, and about 2000 to 3000 m for other designs 2 / g, and about 3000 to about 3800 m for other designs 2 / g, and in other designs, about 3800 to about 4800 m 2 / g). In some embodiments, the carbon particles preferably exhibit a total micro- and mesopore volume (not including macropores 50 nm or larger) in the range of about 0.5 cc / g to about 5 cc / g (about 0.5 to about 1 cc / g in some designs, about 1 to about 2 cc / g in other designs, about 2 to about 3.5 cc / g in other designs, and about 3.5 to about 5 cc / g in other designs) prior to the formation of active material particles therein. In some designs, such high surface areas can be obtained by performing physical or chemical activation of carbon or carbon-containing precursor particles, by rapid annealing of carbon or carbon-containing precursor particles, by using temporary template materials, or by other known suitable means. In some cases, the precursor particles themselves may be highly porous (e.g., aerogel particles). Nevertheless, in some designs, it may be preferable to tailor porosity characteristics by creating or enhancing porosity in the carbon or carbon precursor particles (e.g., by performing activation on the carbon or carbon-containing particles or by leaching non-carbon components of the carbon-containing particles) prior to the formation of active material particles therein. Accordingly, treatment 154 includes subjecting the carbon particles (e.g., by treatment 152) to a porosity-enhancing (e.g., activation) process.

[0115] After the activation step (step 154), other process steps are performed, such as process A at step 156, process B at step 158, and process C at step 160. In the illustrated example, there are three process steps after the porosity-enhancing (e.g., activation) process (step 154), although in other embodiments there may be fewer or more than three process steps after activation. For illustrative purposes, process 150 is described with respect to the formation of specific electrode (e.g., anode) particles. The concepts of process 150, which involves enhancing the porosity (e.g., activation) of carbon particles, may be applicable to other anode particles or with cathode particles requiring carbon particle activation.

[0116] In the example shown in FIG. 3, nanostructured or nanosized silicon (Si), silicon oxide (SiOx ), silicon nitride (SiN y ), silicon oxynitride (SiO x N y ), or silicon phosphide (SiP z ), particles (0 < x < 2, 0 < y < 1.3, 0 < z < 1) or various combinations, alloys and mixtures thereof are formed within the pores (and / or on the surface) of porous carbon or porous carbon-containing particles (e.g., in many cases, graphitic sp 2 -bonded porous carbon or particles containing mostly graphitic sp 2 -bonded carbon). For example, Process A (Treatment 156) involves the formation of silicon-based active material particles in at least a part of the pores of porous carbon particles. The formation of silicon-based active material particles in porous carbon particles (e.g., by deposition, infiltration or deposition / infiltration of Si-containing precursors followed by their subsequent conversion to the final Si or Si-based material) can be achieved in some examples by solution-based or vapor-based deposition processes or by other suitable means. For the sake of simplicity, the particles at the completion of Process A may be referred to as silicon-carbon composite particles (with the understanding that elements other than Si and C may be present in such composite particles in some designs). In some embodiments, this composite particle contains nano-sized or nano-structured elements (e.g., nano-sized or nano-structured Si, nano-sized or nano-structured C), and may be referred to as a nanocomposite particle in some cases. In some examples, the Si or Si-containing material present in such a nanocomposite may be in the form of nanoparticles. In some examples, the mass average size of the Si or Si-containing material nanoparticles may range from about 1 nm to about 200 nm (about 1 nm to about 10 nm in some designs, about 10 nm to about 30 nm in other designs, about 30 nm to about 100 nm in still other designs, and about 100 nm to about 200 nm in yet other designs) when measured using image analysis of electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, neutron scattering and other suitable techniques.

[0117] In the illustrated example, process B is performed in operation 158. For example, process B includes forming a protective coating on or within the silicon-carbon (Si-C) composite particles (via operation 156). In some designs, a suitable average thickness of the protective coating may range from about 0.2 nm to about 50 nm (from about 0.2 nm to about 2 nm in some designs, from about 2 nm to about 5 nm in other designs, from about 5 nm to about 10 nm in other designs, and from about 10 nm to about 50 nm in still other designs). In some designs, the true density of the protective coating can range from about 0.8 g / cc to about 4.8 g / cc or about 5.8 g / cc (about 0.8 g / cc to about 1.6 g / cc in some designs, about 1.6 g / cc to about 3 g / cc in other designs, about 3 g / cc to about 4.5 g / cc in other designs, and about 4.5 g / cc to about 4.8 g / cc or about 5.8 g / cc in still other designs).

[0118] In some designs, the protective coating may include or be based on a conductive material such as carbon. In some designs, such carbon coatings may be doped (e.g., with B, P, N, O, and / or other elements). In some designs, the atomic fraction of an individual dopant may range from about 0.01 atomic % to about 10.01 atomic % (about 0.01 atomic % to about 0.1 atomic % in some designs, about 0.1 atomic % to about 1 atomic % in other designs, about 1 atomic % to about 5 atomic % in other designs, and about 5 atomic % to about 10.01 atomic % in still other designs). In some designs, the protective coating may be substantially impermeable to the electrolyte solvent.

[0119] During 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 the electrolyte solvent composition, which in some designs can undesirably accelerate degradation of the Li-ion battery cell.

[0120] In the illustrated example, process C is performed in operation 160. For example, process C includes changing the particle size distribution (PSD). Process C may include performing milling on the protected silicon-carbon composite particles (from operation 158). Milling may be performed if the particle size is larger (on average) than the final desired particle size distribution (e.g., for slurry and electrode processing). Various processes for performing milling are known in the art. For example, milling can be performed by one or more of ball milling, jet milling, friction milling, pin milling, and hammer milling. In some embodiments, it may be preferable to perform particle size selection during process operation C. In some cases, process C may include particle size selection (e.g., post-milling particle size selection) in addition to milling (e.g., by sieving, screening, centrifugation, other aerodynamic size classification, or other means). In some cases, process C may include particle size selection without milling. For example, it may be preferable to retain some of the larger particle sizes and discard the finer particle sizes. Particle size selection can be carried out by any one of the suitable processes known to those skilled in the art, such as screening, sieving and aerodynamic sizing.

[0121] The above process operation C (160) includes examples of changing the particle size distribution (PSD) of a population of particles, such as milling and particle size selection. In some cases, it may be preferable to employ additional or alternative processes to change or adjust the PSD, such as blending two or more populations of particles, each population having a different PSD than the others in the population. For example, particle populations of different PSDs may be obtained (e.g., obtained from a supplier or manufactured to have different PSDs, including employing the aforementioned processes of milling and / or particle size selection under different processing conditions).

[0122] The particle size distribution (PSD) that characterizes a particle population can be determined by laser particle size distribution analysis (LPSA), image analysis of electron microscope images, or other suitable techniques. In one example, the particle size distribution (PSD) can be determined by laser particle size distribution analysis (LPSA) on a well-dispersed particle suspension. However, other types of particle size distributions (e.g., by SEM image analysis) may also be used (and may even provide a more accurate measurement in some experiments). There are various processes for measuring PSD, but for some applications, laser particle size distribution analysis (LPSA) is very efficient. Using LPSA, the 10th percentile volume-weighted particle size parameter (e.g., D for short) can be determined. 10 ), the 50th percentile volume-weighted particle size parameter (e.g., D for short) 50 ), the 90th percentile volume-weighted particle size parameter (e.g., D for short) 90 ), and the 99th percentile volume-weighted particle size parameter (e.g., D for short) 99 ) particle size parameters of the PSD of the population can be measured. 50 -D 10 (Here it is sometimes called left width), D 90 -D 50 (Here it is sometimes called right width), D 90 -D 10 (Here, this is sometimes called the overall width) and (D 90 -D 10 ) / D 50 Parameters related to the characteristic width of the PSD, such as the particle size parameter (sometimes referred to herein as the span), can be derived from these particle size parameters. The cumulative volume fraction, defined as the cumulative volume of composite particles with particle sizes equal to or less than a threshold particle size divided by the total volume of all of the composite particles, can be estimated by LPSA. In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is in the range of about 2.0 μm to about 16.0 μm, about 2.0 to about 4.0 μm, about 4.0 to about 6.0 μm, about 6.0 to about 8.0 μm, or about 8.0 to about 16.0 μm.

[0123] Upon completion of treatments in process 150 (e.g., treatments 152, 154, 156, 158, 160), the composite particles may be characterized by a Brunauer-Emmett-Teller (BET) specific surface area (SSA) (e.g., obtained from nitrogen adsorption-desorption data at cryogenic temperatures, such as about 77 K). In some embodiments, the BET-SSA of the composite particles is greater than or equal to about 1 m. 2 / g~about 50m 2 / g (approx. 1 to 3 m in some designs) 2 / g, and approximately 3m for other designs 2 / g ~ approx. 12m 2 / g, and in other designs, approximately 12 m 2 / g ~ approx. 18m 2 / g, and in other designs, approximately 18m 2 / g ~ approx. 30m 2 / g, and in other designs, approximately 30m 2 / g~about 50m 2 / g).

[0124] FIG. 4 (top) shows a schematic diagram of a sawtooth particle (e.g., a sawtooth composite particle) 400, as may be observed, for example, under an optical microscope. Two parallel lines 402, 404 are tangent to each portion of the sawtooth particle 400. The distance 406 between the parallel lines 402, 404 is sometimes referred to as the minimum Feret diameter because this distance 406 is the smallest distance between all possible pairs of parallel lines that may be drawn tangent to each portion of the sawtooth particle 400. Similarly, two parallel lines 412, 414 are tangent to each portion of the sawtooth particle 400. The distance 416 between the parallel lines 412, 414 is sometimes referred to as the minimum Feret diameter because this distance 416 is the largest distance between all possible pairs of parallel lines that may be drawn tangent to each portion of the sawtooth particle 400. The aspect ratio of a particle may be defined as the maximum Feret diameter of the particle divided by the minimum Feret diameter of the particle. The aspect ratio may be estimated by performing image analysis (e.g., running image analysis software) on a population of particles viewed under an optical microscope. The exemplary sawtooth composite particles described herein were obtained by following process 150 of FIG. 3, which begins with step 152 of obtaining carbon particles.

[0125] Figure 4 (bottom) shows a graphical plot 420 of the dependence of the cumulative distribution (expressed as a fraction of the number of particles in each population) of two selected populations of sawtooth particles. Image analysis was performed on each population of sawtooth particles to estimate the aspect ratio for each particle in the population. The population represented by plot line 432 contains approximately 2192 particles, and the population has a D of approximately 4.5 μm. 50 The population represented by plot line 434 contained approximately 7485 particles and had a D of approximately 5.5 μm. 50The cumulative distribution of a particle population represents the fraction of particles in each population that have an aspect ratio equal to or less than a particular aspect ratio, expressed as a fraction of the particular aspect ratio. The x-axis 422 represents the aspect ratio, and the y-axis 424 represents the cumulative distribution of the particle population. For example, consider one of the data points 442 along the plot line 432, which corresponds to an aspect ratio of about 1.5 and a cumulative distribution fraction of about 0.68. This means that about 68% of the particles in this population have an aspect ratio of about 1.5 or less.

[0126] Scanning electron microscope (SEM) images of illustrative example sawtooth composite particles (or their aggregates) are shown in Figures 5 and 6. Figure 5 shows a D of about 2.5 μm. 50 SEM image of sawtooth composite particles taken from a population of 502 and approximately 7 μm D 50 FIG. 6 shows an SEM image 504 of a sawtooth composite particle obtained from a population of approximately 9 μm D 50 SEM image of sawtooth composite particles obtained from a population of 602 and D of approximately 14 μm 50 6 shows an SEM image 604 of sawtooth composite particles obtained from a population of 100 particles. In the example shown, the composite particles are sawtooth and non-round (e.g., not spherical, not spheroidal, etc.). Many of the composite particles have very low aspect ratios, such as less than about 10, less than about 5, or less than about 3. Meanwhile, many of the composite particles have aspect ratios greater than about 1. In some examples, the aspect ratio of a population of sawtooth composite particles (including the exemplary population shown in graph plot 420 of FIG. 4 ) can be characterized by one or more of the following: (1) about 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 2.3 or less, about 2.2 or less, or about 2.1 or less; (2) about 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.25 or more, about 1.3 or more, or about 1.35 or more; and (3) about 10% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.3 or less, about 1.25 or less, or about 1.2 or less.

[0127] FIG. 7 shows the D of each of the exemplary particle populations. 50 Overall width D 90 -D10 7. A graphical plot 702 of the dependence of D on the 50 7 shows a graphical plot 704 of the dependence of the mass fraction of silicon in the composite particles on D. The exemplary population has a D of about 2.1 μm to about 14.1 μm. 50 In the illustrated example group, the overall width D 90 -D 10 The Si mass fraction ranged from about 3.0 μm to about 31.7 μm. Silicon (Si) mass fraction was estimated by thermogravimetric analysis (TGA) of powder samples in a crucible heated in air to about 900°C (at a ramp rate of about 40°C / min) and held for about 60 minutes. The sample was then cooled to room temperature, and the resulting mass was assumed to be entirely silicon oxide. Under this assumption, the amount of silicon that would have been present in the original powder sample was calculated. In the illustrative example shown, the Si mass fraction ranged from about 38.5 wt% to about 46.4 wt%. In some examples, the Si mass fraction in the composite particles can range from about 35 wt% to about 50 wt%. In some examples, 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%, about 20 to about 35 wt%, about 35 to about 50 wt%, about 50 to about 80 wt%, etc.).

[0128] Illustrative example electrode coatings were prepared using each of the battery electrode compositions containing the respective populations of sawtooth composite particles. In addition to the composite particles, the battery electrode compositions may contain functional additives, such as carbon-containing functional additives (e.g., additives that enhance the rate capability of the electrode's electrical conductivity or mechanical properties). Examples of suitable carbon-containing functional additives include carbon nanotubes (single-walled carbon nanotubes, abbreviated as SWCNT, multi-walled carbon nanotubes, abbreviated as MWCNT), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide, and graphene. A slurry was prepared by thoroughly mixing sawtooth nanocomposite particles (or a mixture of sawtooth nanocomposite particles and graphite in the case of a blend anode) (e.g., at a mass fraction in the range of about 87 wt % to about 94 wt % or about 89 wt % to about 92 wt % of the solids content of the slurry), a binder composition (e.g., at a mass fraction in the range of about 6 wt % to about 13 wt % or about 8 wt % to about 10 wt % of the solids content of the slurry), a functional additive (e.g., at a mass fraction in the range of about 0 wt % to about 0.1 wt % of the solids content of the slurry), and a solvent composition (e.g., at a mass fraction of 10 wt % to about 40 wt % of the slurry). The illustrative anode slurry was then cast onto a copper foil and dried at room temperature to form an electrode coating. The dried electrode coating was subsequently calendered (in our illustrative example, by using a constant force) to a specific range, e.g., about 0.75 g / cm. 3 ~Approx. 1.00g / cm 3 in the range of about 0.80 g / cm (e.g., for an anode containing exclusively Si-C nanocomposite particles as the active material without graphite). 3 ~Approx. 1.00g / cm 3 range, approximately 0.85 g / cm 3 ~Approx. 1.00g / cm 3 or about 0.90 g / cm 3 ~Approx. 1.00g / cm 3 Coating densities in the range of about 1.0 to about 1.2 g / cm were obtained. 3 Designed for approximately 1.2 to 1.5 g / cm 3The above design can be suitably achieved for blend anodes comprising low to high fractions of soft or hard graphite (broadly speaking, soft or hard carbon) or various mixtures thereof (e.g., about 5-80% of the capacity provided by graphite and about 20-95% of the capacity provided by Si-C nanocomposite or other Si-containing particles).

[0129] Figure 8 shows SEM images 802, 804 of a cross section of the electrode coating. SEM image 802 shows a D of approximately 4 μm. 50 804 is a cross-sectional view of an electrode coating containing a population sample of approximately 14 μm D 50 8A and 8B are cross-sectional views of electrode coatings containing a population sample of 1000 particles. Comparing these two examples, the coating with larger particles (804) exhibits larger pores than the coating with smaller particles (802). Thus, as particle size decreases (e.g., D 50 As the particle size decreases (from about 14 μm to about 4 μm), coating porosity tends to decrease and coating density tends to increase. Electrode coatings containing each exemplary particle population (i.e., the populations characterized by graph plots 702 and 704 in FIG. 7) were coated onto copper foil. Electrode coating thicknesses ranged from about 24.3 μm to about 43.5 μm.

[0130] Conventional anode active materials utilized in Li-ion batteries are of the intercalation type. Metal ions are inserted into and occupy interstitial sites in the material during charging or discharging of the battery. These anodes undergo small or very small volume changes (e.g., less than about 8% by volume) when used in an electrode. Polyvinylidene fluoride (also called polyvinylidene difluoride (PVDF)), polyacrylic acid (PAA) (or its salts, derivatives, and copolymers) (sometimes blended with styrene-butadiene rubber SBR), and carboxymethyl cellulose (CMC) (often blended with styrene-butadiene rubber SBR) are the three most common binders used in these electrodes. Carbon black is the most common conductive additive used in these electrodes. Meanwhile, such anodes have relatively low gravimetric and volumetric capacities (typically less than about 370 mAh / g rechargeable specific capacity for graphite or hard carbon-based anodes, and about 600 Ah / cm at the electrode level without considering the volume of the current collector foil). 3 (rechargeable volume capacity less than 10 ...

[0131] Alloy-type (or, more broadly, conversion-type) anode active materials for use in Li-ion batteries offer higher gravimetric and volumetric capacities than intercalation-type anodes. For example, earth-abundant silicon (Si) offers approximately 10 times higher gravimetric capacity and approximately 3 times higher volumetric capacity than intercalation-type graphite (or graphite-like) anodes. On the other hand, Si suffers from significant volume expansion (up to approximately 300% by volume) upon Li intercalation, which can induce thickness changes and mechanical failure of Si-containing anodes. Furthermore, Si (and any Li-Si alloy compounds that may form upon lithiation of Si) suffer from relatively low electrical and ionic (Li-ion) conductivity. The electronic and ionic conductivity of Si is lower than that of graphite. The formation of (nano)composite Si-containing particles (including, but not limited to, Si-carbon composites, Si-metal composites, Si-polymer composites, Si-ceramic composites, composites containing various combinations of nanostructured Si, carbon, polymer, ceramic, and metal, or other types of porous composites containing nanostructured Si or nanostructured or nanosized Si particles of various shapes and morphologies) may reduce the volume change upon Li-ion insertion and extraction, which in turn may lead to better cycling stability in rechargeable Li-ion cells. In some designs, Si may be doped or heavily doped with nitrogen (N), phosphorus (P), boron (B), or other elements, or alloyed with metals. In addition to Si-based composites, silicon oxide (SiO x ), silicon oxynitride (SiO x N y ), silicon nitride (SiN y ), silicon phosphide (SiP y ) or other Si-element-containing particles (including those partially reduced with Li or Mg) may reduce volume change and improve cycling stability, generally at the expense of higher first-cycle losses or faster degradation, or both. In some designs, Si-containing anode particles exhibit first-cycle lithiation vs. Li / Li (at a constant current rate of about C / 10 with the potential held at 0.01 V from their open circuit potential difference to 0.01 V at a constant current rate of about C / 10, with the potential held at 0.01 V until the current drops to about C / 100).+ , and first cycle delithiation from 0.01 V to about 1.5 V at about C / 10 constant current rate vs. Li / Li +These anodes can exhibit high gravimetric lithiation capacities in the range of about 800 mAh / g to about 3000 mAh / g (per mass of Si-containing anode particles in the Li-free state, in some designs, about 800 mAh / g to about 1400 mAh / g; in other designs, about 1400 mAh / g to about 2200 mAh / g; in other designs, about 2200 mAh / g to about 2600 mAh / g; and in other designs, about 2600 mAh / g to about 3000 mAh / g) as measured in lithium half-cells over a potential range of about 1000 V to about 4000 V. Such high specific capacities are advantageous for achieving lighter batteries. However, Li-ion battery cells having anodes containing high-capacity anode particles with a non-optimized particle size distribution (PSD) can exhibit undesirably fast degradation in conventional electrolytes (especially when processed with conventional binders and conductive additives at typical areal capacity loadings), particularly at elevated temperatures or upon charging to high voltages (e.g., above about 4 to 4.3 V). A subset of anodes having Si-containing anode particles includes anodes having electrode layers that exhibit capacities in the range of about 400 mAh / g to about 2800 mAh / g (about 400 mAh / g to about 500 mAh / g in some designs, about 500 mAh / g to about 700 mAh / g in other designs, about 700 mAh / g to about 1000 mAh / g in other designs, about 1000 mAh / g to about 1200 mAh / g in other designs, about 1200 mAh / g to about 1500 mAh / g in other designs, about 1500 mAh / g to about 2000 mAh / g in other designs, and about 2000 mAh / g to about 2800 mAh / g in other designs, without taking into account the mass of the current collector and per mass of the electrode layer). This class of charge storage anodes offers high potential for increasing the gravimetric and volumetric energy of rechargeable batteries. However, Li-ion battery cells having anodes containing high capacity anode particles with a non-optimized PSD can exhibit undesirably rapid degradation, especially at high temperatures (e.g., battery operating temperatures, e.g., above about 50-80°C) or upon charging to high voltages (e.g., above about 4-4.3 V), when processed with conventional binders and conductive additives in conventional electrolytes and at typical areal capacity loads.In addition to Si-containing anodes, other examples of such high capacity (e.g., nanocomposite) anodes comprising alloy-type (or more broadly, conversion-type) active materials include, but are not limited to, those comprising germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorus, silver, cadmium, indium, tin, lead, bismuth, alloys thereof, and others. In addition to anodes comprising active materials in metallic form, other types of high capacity (including nanocomposite) anodes of interest 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.

[0132] Li-ion cells having alloy-type (or, more broadly, conversion-type) anode active materials can exhibit undesirably rapid degradation in conventional electrolytes, particularly at high temperatures, or when charged to high voltages (e.g., above about 4-4.3 V) and stored at those voltages at high temperatures (e.g., above about 50-80°C). In some designs, degradation of Li-ion cells having alloy-type (or, more broadly, conversion-type) anode active materials can be particularly undesirably rapid for larger cells (e.g., cells with cell capacities ranging from about 10 Ah to about 40 Ah), extra-large cells (e.g., cells with cell capacities ranging from about 40 Ah to about 400 Ah), or giant cells (e.g., cells with cell capacities ranging from about 400 Ah to about 4000 Ah or more). However, large, extra-large, or giant cells may be particularly promising for use in some electrical transportation or grid storage applications. In some designs, degradation of Li-ion cells with alloy-type (or more broadly, conversion-type) anode active materials can be particularly undesirably rapid for cells containing moderate (e.g., about 3-4 g / Ah) or low (e.g., about 2-3 g / Ah) amounts of electrolyte when normalized by total cell capacity. However, using moderate or low amounts of electrolyte can be particularly promising for reducing cell fabrication costs or certain side reactions and maximizing the cell's energy density. One or more embodiments of the present disclosure can mitigate or overcome some or all of the above limitations and substantially enhance the performance of these Li-ion cells by using specific disclosed electrolyte compositions. One or more embodiments of the present disclosure can mitigate or overcome some or all of the above limitations and substantially enhance the performance of these Li-ion cells by using specific disclosed compositions of active materials and specific disclosed properties. One or more embodiments of the present disclosure enable the use of certain disclosed PSDs of anode active material particles (e.g., active material particles including alloyed or conversion-type active materials) to mitigate or overcome some or all of the above limitations and substantially enhance the performance of such Li-ion cells.

[0133] High-capacity (nano)composite anode powders (including, but not limited to, those containing Si) exhibit a moderately high volume change rate (e.g., about 8 to about 180% by volume) during the first charge-discharge cycle, a moderate voltage change rate (e.g., about 5 to about 50% by volume) during subsequent charge-discharge cycles, and an average size in the range of about 0.2 to about 40 μm (more preferably about 0.4 to about 20 μm for some applications), which may be particularly promising for battery applications in terms of manufacturability and performance characteristics. In particular, average sizes in the range of about 0.5 μm 2 / g~about 50m 2 / g range (approximately 0.5m for some designs) 2 / g ~ approx. 2m 2 / g, and approximately 2m for other designs 2 / g ~ approx. 12m 2 / g, and in other designs, approximately 12 m 2 / g~about 50m 2 A subclass of such anode powders having a specific surface area of ​​about 1000 mAh / cm2 / g has worked particularly well in some embodiments. In some designs, moderate electrode area capacity loadings (e.g., about 2 to about 4 mAh / cm2) are preferred. 2 ) to high electrode area capacity loading (e.g., about 4 to about 12 mAh / cm 2 ) and very high electrode area capacity loading (e.g., about 12 mAh / cm 2 Electrodes with morphologies of 0.1 to 0.5 mm or greater (e.g., 0.1 to 0.5 mm) are also particularly promising for use in cells. In some designs, spheroidal (including near-spherical or spherical) or ellipsoidal (including oblate spheroidal) shapes of these composite particles may be even more promising for increasing the rate capability and volumetric capacity (density) of the electrode. In other designs, sawtooth-shaped, cylindrical, fibrous, or irregularly shaped composite particles may also be effectively used. Unfortunately, the non-optimized PSD of such particles results in poor battery performance.

[0134] On the other hand, higher electrode density and lower binder content are advantageous for increasing cell energy density and reducing cost in certain applications. Lower binder content can also be advantageous for increasing cell rate performance. A larger volume change rate can reduce performance in some designs, which may be related to damage to the solid electrolyte interfacial (SEI) layer formed on the anode, uneven lithiation and delithiation of electrode particles within the electrode, and other factors. Unfortunately, Li and Li-ion battery cells with anodes having non-optimized PSDs of active (e.g., Si-containing) materials and conventional electrolytes often require the use of large amounts of conventional SEI-forming additives to maintain acceptable cycling stability, which can inhibit their use at high or low temperatures, undesirably limit their calendar life, or prevent such cells from being charged to high voltages (e.g., above about 4.1-4.3 V). The performance of such battery cells can be particularly poor when the cells are charged to above about 4.3-4.4 V, and even poorer when the cells are charged to above about 4.5 V.

[0135] On the other hand, higher cell voltages, wider operating temperature windows, and longer cycle life are advantageous for most applications. Such cells may suffer from excessive capacity degradation (e.g., greater than about 5%) at full charge (e.g., about 90-100% SOC) over extended periods (e.g., about 12-168 hours), significant volume expansion (e.g., greater than about 10%), and significant gas evolution when exposed to high temperatures (e.g., greater than about 50-90°C). Passing such high-temperature charging tests is often required for most applications. In some designs, Li-ion cells containing high-capacity (nano)composite anode powders with a non-optimized PSD exhibiting a moderately high volume change during the first charge / discharge cycle, moderate volume change during subsequent charge / discharge cycles, and an average size in the range of about 0.2 to about 40 μm may degrade undesirably fast, especially for large cells (e.g., cells with a cell capacity in the range of about 10 Ah to about 40 Ah), ultra-large cells (e.g., cells with a cell capacity in the range of about 40 Ah to about 400 Ah), or giant cells (e.g., cells with a cell capacity in the range of about 400 Ah to about 4000 Ah or more). In some designs, Li-ion cells with such volume-changing anode particles may degrade undesirably fast, especially for cells containing moderate (e.g., about 3 to 4 g / Ah) or low (e.g., about 2 to 3 g / Ah) amounts of electrolyte when normalized by the total cell capacity. One or more embodiments of the present disclosure may alleviate or overcome some or all of the above limitations by using specific disclosed electrolyte compositions, thereby substantially enhancing the performance of such Li-ion cells.

[0136] One or more embodiments of the present disclosure overcome some or all of the above-mentioned problems of various types of metal ion (e.g., Li-ion) cells with high-capacity nanocomposite anode active materials (e.g., materials including conversion-type or alloy-type active materials). The high-capacity nanocomposite anode active materials may include Si in their composition, may have a certain volume change rate during cycling (e.g., a moderately high volume change rate (e.g., about 8 to about 160 or about 180 vol%) during the first charge / discharge cycle and a moderate volume change rate (e.g., about 5 to about 50 vol%) during subsequent charge / discharge cycles), and have an average particle size in the range of about 0.2 to about 40 μm and a particle size of about 0.5 to about 50 μm. 2 Specific surface area in the range of / g (approximately 0.5 to approximately 2 m in some designs) 2 / g, and about 2 to about 12 m for other designs 2 / g, and other designs range from about 12 to about 50 m 2 / g) and have a high packing density (electrode porosity filled with electrolyte in the range of about 5 to about 35% by volume after the first charge-discharge cycle) and a relatively low binder content (e.g., about 0.5 to about 14% by weight) resulting in a moderate areal capacity loading (e.g., about 2 to about 4 mAh / cm 2 ) and high areal capacity loading (e.g., about 4 to about 12 mAh / cm 2 ), may contain a moderate or small amount of electrolyte per cell capacity (e.g., less than about 4 g / mAh), may be charged to a moderately high voltage (e.g., about 4.1-4.3 V or more), a high voltage (e.g., about 4.3-4.4 V or more), or a very high voltage (e.g., about 4.5-4.8 V or more), may be exposed to temperatures of about 40°C or more at a high state of charge (e.g., about 70-100% SOC) during testing or operation, and may be manufactured as large cells (e.g., cells with a cell capacity in the range of about 10 Ah to about 40 Ah), ultra-large cells (e.g., cells with a cell capacity in the range of about 40 Ah to about 400 Ah), or giant cells (e.g., cells with a cell capacity in the range of about 400 Ah to about 4000 Ah or more).

[0137] In some designs, binder swelling in the electrolyte may depend not only on the binder composition but also on the electrolyte composition. Furthermore, in some designs, such swelling (and resulting performance degradation) often correlates with a decrease in modulus upon binder exposure to the electrolyte. In this sense, the smaller the decrease in modulus in a particular electrolyte, the more stable the binder-bound (nano)composite active particle / conductive additive interface. In some designs, a decrease in binder modulus of more than about 15-20% can result in significant performance degradation. In one example, a decrease in binder modulus by about 2x (x2) can result in significant performance degradation. In a further example, a decrease in modulus by about 5x or more (e.g., about 5x to 500x) can result in very significant performance degradation. Therefore, selecting an electrolyte composition that does not induce significant binder swelling may be highly preferred for certain applications. In some cases, it may be preferable to select an electrolyte composition that reduces the binder modulus by less than about 30% (more preferably by about 10% or less) when exposed to the electrolyte. For anodes containing two or more binder compositions, it may be preferable in some designs to select an electrolyte composition in which at least one binder does not reduce the modulus by more than about 30% (more preferably, reduces the modulus by about 10% or less) when exposed to the electrolyte.

[0138] In one embodiment of the present disclosure, a suitable battery cell includes lithium cobalt oxide (LCO) as the cathode active material. In one or more other embodiments of the present disclosure, a suitable battery cell includes lithium nickel cobalt manganese oxide (NCM) as the cathode active material. In one or more other embodiments of the present disclosure, a suitable battery cell includes lithium nickel cobalt manganese aluminum oxide (NCMA) as the cathode active material. In one or more other embodiments of the present disclosure, a suitable battery cell includes lithium nickel cobalt aluminum oxide (NCA) as the cathode active material. In one or more other embodiments of the present disclosure, a suitable battery cell includes a high-voltage spinel (e.g., lithium nickel manganese oxide (LNMO) or lithium manganese oxide (LMO)) as the cathode active material. In some designs, the LCO, NCM, NCMA, NCA, LNMO, or LMO cathode active material may comprise a majority (e.g., greater than 50 wt%) of single crystal powder (or powder with a grain size of about 500 nm or greater, and in some designs about 1 μm or greater). In some suitable examples, the surface of the LCO, NCM, NCMA, NCA, LMO, or LMNO may be coated with a layer of ceramic material. Illustrative examples of suitable coating materials for such cathodes include, but are not limited to, titanium oxide (e.g., TiO), aluminum oxide (e.g., AlO), tungsten oxide (e.g., WO), chromium oxide (e.g., CrO), niobium oxide (e.g., NbO or NbO), and zirconium oxide (e.g., ZrO), as well as various mixtures thereof. In some designs, such ceramic materials may further include lithium (Li), for example, as lithium titanium oxide, lithium aluminum oxide, lithium tungsten oxide, lithium chromium oxide, lithium niobium oxide, lithium zirconium oxide, and various alloys, mixtures, and combinations thereof. In other suitable examples, the 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 designs, the preferred cathode current collector material is aluminum or an aluminum alloy. In some designs, the preferred battery cell includes a polymer separator.In some preferred examples, the polymer separator is made of or includes polyethylene, polypropylene, or a mixture thereof. In some preferred examples, the surface of the polymer separator is coated with a layer of ceramic material. Examples of suitable coating materials for the polymer separator may include, but are not limited to, titanium oxide (TiO2), aluminum oxide (Al2O3), aluminum hydroxide or oxyhydroxide, zirconium oxide (ZrO2), magnesium oxide (MgO), or magnesium hydroxide or oxyhydroxide. In some designs, suitable battery cells include silicon and carbon-containing nanocomposites (e.g., as used herein, a nanocomposite or (nano)composite is at least partially composed of active material nanomaterials, nanostructures, or nanoparticles, regardless of whether the nanocomposite or (nano)composite is itself a nanomaterial), silicon (SiO2), or a combination thereof. x , x≧0), natural or synthetic graphite, soft or hard carbon, or various mixtures and combinations thereof, may be included in the anode composition. In some suitable examples, the anode active material includes a mixture of silicon and carbon-containing nanocomposite (sometimes abbreviated herein as Si-C nanocomposite) and graphite (e.g., the graphite is different from the C portion of the Si-C nanocomposite). In some examples, the Si-C nanocomposite includes composite particles that may include Si nanoparticles embedded within the pores (e.g., surface pores or interior pores, such as closed or open interior pores) of the porous carbon scaffold particles. Such porous carbon scaffold particles may include (e.g., curved or defective) graphene and / or graphite materials. In some designs, a suitable anode current collector may include copper or a copper alloy.

[0139] In one or more embodiments of the present disclosure, a suitable anode for a battery cell may include a mixture of Si-C nanocomposite particles and graphite particles as the anode active material, a so-called blend anode. In addition to the anode active material, the anode may include inactive materials such as binders (e.g., polymer binders) and other functional additives (e.g., surfactants, conductive additives). In some examples, the anode active material particles may range from about 90% to about 98% by weight of the anode. For example, the anode active material particles may be about 95.5% by weight of the anode in some designs.

[0140] In some designs, the blend anode may contain from about 7 wt. % Si-C nanocomposite to about 97 wt. % Si-C nanocomposite (e.g., particles), based on the total weight of the Si-C composite and graphite (e.g., particles) in the blend. While the following description may describe specific examples of blend anode formulations expressed as the mass (wt. %) of the Si-C nanocomposite (e.g., particles), it should be understood that various aspects of the present disclosure may be applicable to blend anode formulations expressed as the weight % of Si in the anode (e.g., including the weight of conductive and other additives, binders, Si-containing composites such as the Si-C nanocomposite, and graphite). For example, in some examples, a blend anode composition of about 7 wt. % Si-C nanocomposite (e.g., particles) corresponds to about 3-3.5 wt. % Si in the blend anode. In some examples, a blend anode composition of about 19 wt. % Si-C nanocomposite (e.g., particles) corresponds to about 8-10 wt. % Si in the blend anode. In some examples, a blend anode composition of about 35 wt% Si-C nanocomposite (e.g., particles) can correspond to about 15-18 wt% Si in the blend anode. In some examples, a blend anode composition of about 50 wt% Si-C nanocomposite (e.g., particles) can correspond to about 21-30 wt% Si in the blend anode. In each example, a blend anode can be obtained in which the mass (weight) of silicon ranges from about 3 wt% to about 30 wt% of the total anode mass. Here, the term "total anode mass" is used to refer to the mass of the anode alone, excluding the anode current collector foil or separator. The mass of the current collector and separator is excluded from the anode mass, even if the current collector and separator are attached to the anode.

[0141] In some designs, the blend anode may include Si-C nanocomposites (e.g., particles) that contribute about 25% to about 99.5% of the total anode capacity. While the following description may describe specific examples of blend anode formulations expressed as the mass (wt%) of Si-C nanocomposites (e.g., particles), it should be understood that various aspects of the present disclosure may be applicable to blend anode formulations that attribute a fraction (e.g., %) of the total capacity of the blend anode to the capacity of Si. For example, in some examples, at a blend anode composition of about 7 wt% Si-C nanocomposites (e.g., particles), about 25% of the total capacity of the blend anode may be obtained from the Si-C nanocomposites (e.g., particles). In some other examples, at a blend anode composition of about 19 wt% Si-C nanocomposites (e.g., particles), about 50% of the total capacity of the blend anode may be obtained from the Si-C nanocomposites (e.g., particles). In some other examples, at about 35 wt. % Si-C nanocomposite (e.g., particles) blend anode compositions, about 70% of the total capacity of the blend anode can be obtained from the Si-C nanocomposite (e.g., particles). In some other examples, at about 50 wt. % Si-C nanocomposite (e.g., particles) blend anode compositions, about 80% of the total capacity of the blend anode can be obtained from the Si-C nanocomposite (e.g., particles).

[0142] In some examples, the blend anode can include a Si—C nanocomposite (e.g., particles) ranging from about 7% to about 99% by weight of the anode active material particles and graphite particles making up the remainder of the mass (weight) of the anode active material particles. In some embodiments in which the anode active material particles are about 95.5% by weight of the blended anode, the blended anode (including the active material particles and inactive material) can include about 7% by weight Si—C nanocomposite (e.g., particles) and about 88.5% by weight graphite (e.g., particles), about 19% by weight Si—C nanocomposite (e.g., particles) and about 76.5% by weight graphite (e.g., particles), about 35% by weight Si—C nanocomposite (e.g., particles) and about 60.5% by weight graphite (e.g., particles), or about 50% by weight Si—C nanocomposite (e.g., particles) and about 45.5% by weight graphite (e.g., particles; in all cases the graphite particles are different from the C portion of the Si—C nanocomposite). In some preferred examples where the anode active material particles are about 90 wt % or greater of the blended anode, the anode active material composition can include a small (e.g., about 1-20 wt %, preferably 1-10 wt %, even more preferably about 1-5 wt %) fraction of graphite (e.g., particles, graphite particles different from part C of a Si-C nanocomposite).

[0143] In some illustrative examples where the anode active material particles are about 90% by weight of the anode, the anode active material particle composition may consist almost entirely of Si—C nanocomposite (e.g., particles) and be substantially free (e.g., less than about 1% by weight) of graphite particles (e.g., the graphite particles are distinct from the C portion of the Si—C nanocomposite).

[0144] In some illustrative examples where the anode active material particles are about 96.5% by weight of the anode, the anode active material particle composition may consist almost entirely of graphite, with substantially no Si—C nanocomposite present (e.g., less than about 1% by weight).

[0145] In one or more embodiments of the present disclosure, an electrolyte including an ester and / or a carbonate (e.g., cyclic carbonate, linear carbonate) may be employed in a lithium-ion battery cell. A lithium-ion battery includes an anode current collector (e.g., copper or copper alloy foil), a cathode current collector (e.g., aluminum or aluminum alloy foil), an anode disposed on or within the anode current collector, a cathode disposed on or within the cathode current collector, and any of the above-described electrolytes ionically bonding the anode and cathode. In some examples, a separator (e.g., separator membrane or coating) may be disposed between the anode and cathode, with at least a portion of the electrolyte permeating or impregnating the separator. The anode may include any suitable anode material as described herein. For example, the anode may be a composite of silicon and carbon (e.g., a predominantly graphitic sp 2 The anode may include silicon-carbon composite particles comprising silicon-carbon composite particles (e.g., silicon-carbon composite particles, graphitic carbon particles ... silicon-carbon composite particles, graphitic carbon particles, silicon-carbon composite particles, graphitic carbon particles, silicon-carbon composite particles, silicon-carbon composite particles, graphitic carbon particles, silicon-carbon composite particles, silicon-carbon composite particles, graphitic carbon particles, silicon-carbon composite particles, silicon-carbon composite particles, graphitic

[0146] In one illustrative example, a Li-ion battery cell having a capacity of about 0.028 Ah has (i) about 100 volume % Si-C nanocomposite active material (e.g., particles), corresponding to about 40 to about 44 weight % silicon mass fraction in the Si-C composite particles cast onto a Cu current collector foil from an aqueous suspension containing a polyacrylic acid (PAA) salt copolymer-based binder and about 0.1% carbon black conductive additive (about 1600 to about 1700 wt % when normalized by the weight of the active material in the anode). (ii) an anode (having a specific reversible capacity of about 170 mAh / g when normalized to the weight of the active material in the cathode) having a high voltage lithium cobalt oxide (LCO) active material cast on an Al current collector foil from an organic solvent suspension containing a polyacrylic acid (PAA) based binder and a carbon black conductive additive, wherein the anode:cathode areal capacity ratio is about 1.15:1 and the areal reversible capacity loading is about 3.5 mAh / cm 2 and a charging voltage of about 4.4 V; (iii) a polymer-ceramic separator; and (iv) an electrolyte ELY#1 comprising about 15 mol% FEC, about 44 mol% ethyl propionate (EP) (linear ester), about 7 mol% LiPF, about 24 mol% non-fluorinated cyclic carbonate, about 7 mol% diethyl carbonate (DEC), and about 3 mol% other compounds.

[0147] Li-ion battery test cells (with LCO cathodes as described above) containing exemplary nanocomposite particles (with the total anode capacity provided by the Si-C nanocomposite particles) were tested in cycle life tests. Test cells were fabricated and the initial formation procedure was performed on the test cells. The charge / discharge test conditions were constant current constant potentiostatic (CCCP) with a 2C charge to 4.0 V, ramped down to 1 C, followed by CCCP with a 1C charge to 4.2 V, ramped down to 0.05 C, followed by a 1C discharge. Graphical plot 902 (FIG. 9) shows the D of each respective population of sawtooth composite particles. 50As a function of σ, cycle life is also referred to as the number of cycles (also called "N80") to reach 80% of the cycling onset capacity (during cycling at 25°C). The cycling onset capacity is defined as the capacity at the completion of the third cycle. Larger particles (e.g., D > about 10 μm) 50 Some test cells with smaller particles (e.g., D in the range of about 2.0 μm to about 8.0 μm) showed low cycle life values ​​(e.g., less than about 200 cycles). 50 Some test cells with Si-C composite particles (e.g., Si-C composite particles) exhibited good cycle life values ​​(e.g., greater than about 340 cycles or in the range of about 340 cycles to about 729 cycles). Thus, in some examples (e.g., where all or nearly all of the capacity is provided by the Si-C composite particles), the D values ​​(especially at comparable or faster cell charge rates) in the range of about 2.0 μm to about 8.0 μm are 50 There may be beneficial effects (e.g., better cycle life) in employing a sawtooth composite particle population having a D 50 ), one potential degradation pathway could be mechanical failure of the electrode coating after multiple charge / discharge cycles due in part to poor packing of the sawtooth composite particles within the coating (e.g., consider the large interstitial pores between particles in SEM image 804 of FIG. 8). Additionally, larger particles may exhibit higher charge transfer resistance, in some cases (e.g., when tested in cold climates or at low temperatures and / or when the anode is subjected to moderate to high areal capacitance loadings (e.g., about 2-12 mA / cm). 2 ) can induce Li plating when the cell is rapidly charged. 50 ), one potential degradation pathway could be that the surface area exposed to the electrolyte increases with decreasing particle size, leading to a greater occurrence of undesired side reactions between the electrolyte and the particles (e.g., excessive SEI growth).

[0148] Graphical plot 904 (FIG. 9) shows the D of each of the exemplary particle populations.50 1 shows the dependence of the normalized coating thickness change of the anode of the test cell on the amount of lithium ions inserted into the electrode (anode) per unit area of ​​the electrode (in mAh / cm). 2 The normalized coating thickness change is defined as the difference between the coating thickness during the charge state in cycle 4 and the as-prepared electrode coating. The coating thickness is measured using a high-precision digital contact sensor (with a resolution of approximately 0.1 μm) on the test cell after it has undergone four charge / discharge cycles. The normalized coating thickness change can be considered a quantitative measure of the degree of swelling of the electrode coating, especially in the thickness direction. The graph plot 904 shows the difference between the coating thickness during the charge state in cycle 4 and the as-prepared electrode coating. 50 This shows that as D decreases, the normalized thickness change (i.e., swelling in the electrode thickness direction, i.e., the degree of z-swelling) tends to decrease. Therefore, the normalized thickness change is in the range of D from about 2.0 μm to about 8.0 μm, from about 2.0 μm to about 6.0 μm, from about 2.0 μm to about 5.0 μm, or from about 2.0 μm to about 4.0 μm. 50 The normalized thickness variation can be reduced by employing a sawtooth composite particle population with a D value ranging from about 2.0 μm to about 4.0 μm. 50 For populations with values ​​of about 2.5 to about 3.0 μm / (mAh / cm 2 ) range. The swelling can be 50 In addition to the size of the D, it may also depend on the binder properties, particle size distribution, capacity and Si fraction of the active particles, particle density, particle shape and aspect ratio, and overall slurry composition (including, for example, the graphite fraction and type when used in a blend anode, the conductive additive fraction and type, the binder fraction and type, etc.). On the other hand, the D of the smaller Si-containing composite particles 50 The general trend of smaller swelling for D was found to be consistent. 50must be selected accordingly. The maximum allowable thickness change depends on the cell configuration. On the other hand, generally, smaller swelling can be beneficial to achieve improved cell stability. In some cell designs, the anode swelling is preferably less than 4.5 μm / (mAh / cm 2 ) less than (< about 4.5 cm 2 In other designs, the swelling of the anode is preferably 3.5 μm / (mAh / cm 2 ) less than (< about 3.5 cm 2 In other designs, the anode swelling is preferably 3.0 μm / (mAh / cm 2 ) less than (< about 3.0 cm 2 In other designs, the anode swelling is preferably 2.75 μm / (mAh / cm 2 ) less than (< about 2.75 cm 2 In yet other designs, the anode swelling may be preferably 2.5 μm / (mAh / cm 2 ) less than (< about 2.5 cm 2 μm / mAh).

[0149] FIG. 10 shows the D of each of the exemplary particle populations. 50 A graphical plot 1002 of the dependence of the volumetric energy density (sometimes abbreviated as VED) of the test cell on D for each of the exemplary particle populations. 50 10 shows a graphical plot 1004 of the dependence of the volumetric charge density (sometimes abbreviated as VQD) of test cells on the anode capacity (note that in these test cells, all or nearly all of the anode capacity was provided by the Si-C composite particles, and no graphite was added to the anode). VQD is the anode capacity (after the fourth cycle) (expressed in mAh) relative to the anode volume (cm). 3 VED is defined as the cell energy (after 4 cycles) (expressed in Wh) divided by the external volume of the cell (expressed in liters). Test cells with smaller particles tend to show higher VED and VQD values. For example, a D of about 3.6 μm 50The test cell with the sawtooth composite particle population had a VED of about 1095 Wh / l and a VEE of about 886 mAh / cm 3 Therefore, the VED and / or VQD exhibited a D in the range of about 2.0 μm to about 8.0 μm, about 2.0 μm to about 6.0 μm, about 2.0 μm to about 5.0 μm, or about 2.0 μm to about 4.0 μm. 50 The VED and VQD values ​​can be increased by employing a sawtooth composite particle population with higher VED and VQD values. Several factors may contribute to the higher VED and VQD values ​​exhibited by the smaller sawtooth composite particle test cells. For example, one factor may be reduced z-swell in the smaller particle test cells (see, e.g., plot 904 in FIG. 9 ). For example, another factor may be higher first cycle efficiency in the smaller particle test cells (see, e.g., plot 1302 in FIG. 13 ). For example, yet another factor may be higher formation efficiency in the smaller particle test cells (see, e.g., plot 1304 in FIG. 13 ). For example, yet another factor may be lower internal resistance in the smaller particle test cells (see, e.g., plot 1402 in FIG. 14 ). For example, yet another factor may be higher electrode (anode) coverage density in the smaller particle test cells (see, e.g., plot 1404 in FIG. 14 ). For example, yet another factor may be the higher discharge voltage in the test cell for smaller particles (see, for example, plot 1104 in FIG. 11). 50 In addition to size, it may also depend on binder properties, particle size distribution (PSD), active particle capacity and Si fraction, particle density, particle shape and aspect ratio, and / or overall slurry composition (including, for example, graphite fraction and type, conductive additive fraction and type, binder fraction and type, etc.), among other factors. 50 The general trend of VED dependence on D was found to be consistent, so that for some designs, D 50 must be selected accordingly.

[0150] FIG. 11 shows the D of each of the exemplary particle populations. 50A graphical plot 1102 of the dependence of the normalized high rate discharge capacity of the test cell on the D of each of the exemplary particle populations. 50 11 shows a graphical plot 1104 of the dependence of the discharge voltage of the test cells on the Si-C composite particles (note that in these test cells, all or nearly all of the anode capacity was provided by the Si-C composite particles, and no graphite was added to the anode). The normalized high rate discharge (in this case, 2C discharge) capacity is defined as the discharge capacity of the cell measured after a 2C discharge divided by the discharge capacity of the cell measured after a 0.5C discharge, assuming that the measurement is performed after 20 cycles. 50 Some test cells with sawtooth composite particle populations having a D value exhibited a normalized high rate discharge capacity greater than about 90%. A higher normalized high rate discharge capacity (e.g., greater than about 90%) may be due to a better impedance metric (e.g., lower impedance) and / or a better ion diffusion metric due to a thinner electrode coating and / or a reduced diffusion length of the particles (e.g., smaller particles with similar ion diffusivity to larger particles may have a reduced diffusion length scale). The discharge voltage is defined as the discharge energy (Wh) divided by the discharge capacity (Ah). For D particles ranging from about 2.0 μm to about 5.0 μm, 50 Some test cells having sawtooth nanocomposite particle populations with D values ​​exhibited discharge voltages greater than about 3.5 V. Therefore, the normalized rate discharge capacity and / or discharge voltage were significantly higher for D values ​​in the range of about 2.0 μm to about 8.0 μm, the range of about 2.0 μm to about 6.0 μm, or the range of about 2.0 μm to about 5.0 μm. 50 The discharge voltage and high rate discharge capacity can be increased by employing a sawtooth composite particle population having a value of 50 In addition to size, it may also depend on, among other factors, binder properties, particle size distribution (PSD), active particle capacity and Si fraction, particle density, Si-containing nanocomposite particle design, particle shape and aspect ratio, particle BET-SSA, and overall slurry composition (including, for example, graphite fraction and type, conductive additive fraction and type, binder fraction and type, etc.). On the other hand, Si-containing nanocomposite particle D 50The general trend of the dependence of discharge voltage and high-rate capacity on D was found to be consistent, so that in some designs, D 50 must be selected accordingly to meet the required cell design specifications.

[0151] Figure 12 shows the D 50 12 shows a graphical plot 1202 of the dependence of normalized capacity (also referred to as percentage (%) of reference capacity) for lithium-ion battery test cells (with LCO cathodes as described above) containing a sawtooth nanocomposite particle population of 1.0 μm to 4.0 μm (note that in these test cells, all or nearly all of the anode capacity was provided by the Si-C composite particles, and no graphite was added to the anode). Normalized capacity is defined as the charge capacity (expressed in mAh) obtained for a given charge rate normalized to the cycling start capacity (capacity at the completion of cycle 3) (expressed in mAh). For each respective charging condition, the cells were cycled for a minimum of five cycles to obtain an average capacity. Thus, the normalized capacity at faster charge rates (e.g., charge rates greater than about 2 C, greater than about 3 C, greater than about 4 C, or greater than about 5 C) is significantly higher for D particles in the range of about 2.0 μm to 4.0 μm. 50 The higher normalized capacity can be attributed to a better impedance metric (e.g., lower impedance) and / or a better ion diffusion metric (e.g., higher ion diffusivity).

[0152] FIG. 13 shows the D of each of the exemplary particle populations. 50 A graphical plot 1302 of the dependence of the first cycle efficiency of the test cell on D for each of the exemplary particle populations. 50 13 shows a graphical plot 1304 of the dependence of the formation efficiency of test cells on the D (note that in these test cells, all or nearly all of the anode capacity was provided by the 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. D ranges from about 2.0 μm to about 6.0 μm. 50Some test cells with sawtooth nanocomposite particle populations with D values ​​exhibited first cycle efficiencies greater than about 90%. The formation efficiency is defined as the discharge capacity at the start of cycling (the discharge capacity at the completion of cycle 3) divided by the first cycle charge capacity. 50 Some test cells with sawtooth nanocomposite particle populations having a D value of about 2.0 μm to about 6.0 μm exhibited formation efficiencies greater than about 90%. Therefore, first cycle efficiency and / or formation efficiency were significantly higher in the D range of about 2.0 μm to about 6.0 μm. 50 Higher first cycle efficiencies (e.g., greater than about 90%) and / or higher formation efficiencies (e.g., greater than about 90%) can be attributed to better impedance metrics (e.g., lower impedance) and / or better ion diffusion metrics (e.g., higher ion diffusivity), resulting in reduced losses.

[0153] First cycle efficiency, formation efficiency and normalized capacity are calculated using particle D 50 In addition to size, it may also depend on, among other factors, binder properties, particle size distribution (PSD), capacity and Si fraction of the active particles, particle density, design of the Si-containing nanocomposite particles, presence of Li trapping sites or (e.g., electronegative) elements in the composition of the Si-containing composite particles, particle shape and aspect ratio, BET-SSA of the particles, and / or overall slurry composition (including, for example, graphite fraction and type, conductive additive fraction and type, binder fraction and type, etc., when used in a blend anode). On the other hand, Si-containing nanocomposite particle D 50 The general trends in the dependence of normalized capacity (capacity retention), first cycle efficiency, and formation efficiency on D were found to be fairly consistent, so that for some designs, D 50 must be selected accordingly to meet the required cell design specifications.

[0154] FIG. 14 shows the D of each of the exemplary particle populations. 50 A graphical plot 1402 of the dependence of the internal resistance of the test cell on D for each of the exemplary particle populations.50 14 shows a graphical plot 1404 of the dependence of electrode coating density on . The internal resistance is determined as follows: a series of millisecond-long current pulses are applied to a cell at 0% charge and the resulting voltage is measured. The average voltage is determined by averaging the respective voltages measured for each of the current pulses. The internal resistance is the average voltage divided by the applied current. Test cells with smaller particles tended to exhibit lower internal resistance. For example, D in the range of about 2.0 μm to about 6.0 μm. 50 Some test cells with sawtooth nanocomposite particle populations having a D value of less than about 10 Ω exhibited internal resistance values ​​of less than about 10 Ω. For example, the D values ​​ranged from about 2.0 μm to about 4.0 μm. 50 Some test cells with sawtooth nanocomposite particle populations exhibited internal resistance values ​​ranging from about 4 Ω to about 6 Ω. The coating density includes the sawtooth nanocomposite particles, binder, and any additives in the electrode, but excludes the current collector. 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 higher coating densities. For example, electrode coatings with D ranging from about 2.8 μm to about 6.0 μm exhibited higher coating densities. 50 Some electrode coatings having a sawtooth nanocomposite particle population with a value of about 0.9 g / cm 3 ~Approx. 1.0g / cm 3 For example, the electrode coating density ranged from about 3.0 μm to about 5.0 μm. 50 Some electrode coatings having a sawtooth nanocomposite particle population with a value of about 0.95 g / cm 3 ~Approx. 1.0g / cm 3 The electrode coating density values ​​ranged from 0.01 to 0.01.

[0155] The coating density and internal resistance are 50In addition to size, it may also depend on, among other factors, binder properties, particle size distribution (PSD), capacity and Si fraction of the active particles, particle density, design and composition of the Si-containing nanocomposite particles, surface conductivity of the Si-containing composite particles, fraction of binder covering the outer surface region of the particles, shape and aspect ratio of the particles, BET-SSA of the particles, and overall slurry composition (including, for example, fraction and type of graphite when used in a blend anode, fraction and type of conductive additive, fraction and type of binder, etc.). Meanwhile, the Si-containing nanocomposite particle D 50 The general trend of the dependence of coating density and internal resistance on D was found to be fairly consistent, so that for some designs, D 50 can be selected accordingly to meet the required cell design specifications.

[0156] FIG. 15 shows the D of each of the exemplary particle populations. 50 1502 is a graphical plot of the dependence of the Brunauer-Emmett-Teller specific surface area (BET-SSA) as measured by analyzing N adsorption-desorption isotherms at 77 K on the D of each of the exemplary particle populations. 50 15 shows a graphical plot 1504 of the dependence of areal binder loading on the BET-SSA of each exemplary population of sawtooth nanocomposite particles. The BET-SSA of each exemplary population of sawtooth nanocomposite particles was measured by nitrogen gas physisorption (approximately 77 K) of powder samples degassed in vacuum at 300° C. for 10 hours. The BET-SSA is a function of particle size (e.g., D 50 ) decreases. For example, in the range of about 2.0 μm to about 4.0 μm, 50 Some sawtooth nanocomposite particle populations have values ​​of about 8 to about 18 m 2 / g. For example, the D range of about 4.0 μm to about 6.0 μm 50 Some sawtooth nanocomposite particle populations have values ​​of about 3 to about 14 m 2 / g. For example, the D range of about 6.0 μm to about 8.0 μm 50 Some sawtooth nanocomposite particle populations have a particle size of about 3 to about 12 m. 2 / g. The areal binder loading of the electrode coating is defined as the mass fraction of binder in the electrode coating divided by the product of (1) the mass fraction of sawtooth composite particles in the electrode coating and (2) the BET-SSA value of each sawtooth composite particle population. In the graphical plot 1504, the areal binder loading is expressed in mg / m 3 In the illustrated example, the areal binder loading is expressed in units of particle size (e.g., D 50 ) tends to decrease as the particle size decreases. 50 ) tend to have less binder per unit surface area of ​​the composite particles due to their high BET-SSA. For example, D in the range of about 2.0 μm to about 4.0 μm 50 Some serrated composite particle populations have a particle size of about 5 to about 14 mg / m 2 For example, a D range of about 4.0 μm to about 6.0 μm results in areal binder loading values ​​for the corresponding electrode coating. 50 Some serrated composite particle populations have a particle size of about 6 to about 22 mg / m 2 For example, a D range of about 6.0 μm to about 8.0 μm results in areal binder loading values ​​for the corresponding electrode coating. 50 Some serrated composite particle populations have a particle size of about 8 to about 24 mg / m 2 This results in areal binder loading values ​​for corresponding electrode coverages in the range of 0.01 mg / m². There may be beneficial effects of low areal binder loading on impedance metrics and / or ion diffusion metrics. In some embodiments, the areal binder loading of a battery electrode (e.g., an anode comprising Si—C nanocomposite particles) is about 2.0 mg / m². 2 ~Approx. 15.0mg / m 2 (e.g., about 2.0 mg / m in some designs) 2 ~about 5.0mg / m 2 , and about 5.0 mg / m for other designs. 2 ~about 9.0mg / m 2 , and about 9.0 mg / m for other designs. 2 ~About 13.0mg / m 2 ) range.

[0157] In some embodiments, D ranges from about 2.0 μm to about 4.0 μm. 50 Lithium ion battery cells with anodes including smaller sawtooth composite particles having a D value of 0.01 μm exhibit favorable properties such as smaller z-swell (e.g., plot 904), higher V (e.g., plot 1002), higher V (e.g., plot 1004), faster discharge (e.g., plot 1102), faster charge (e.g., plot 1202), higher discharge voltage (e.g., plot 1104), and lower internal resistance (e.g., plot 1402). On the other hand, in some embodiments, anodes including smaller sawtooth composite particles having a D value of 0.01 μm in the range of about 4.0 μm to about 7.0 μm or about 4.0 μm to about 6.0 μm exhibit favorable properties such as smaller z-swell (e.g., plot 904), higher V (e.g., plot 1002), higher V (e.g., plot 1004), faster discharge (e.g., plot 1102), faster charge (e.g., plot 1202), higher discharge voltage (e.g., plot 1104), and lower internal resistance (e.g., plot 1402). 50 Some lithium-ion battery cells with anodes containing larger serrated composite particles with a D value in the range of about 2.0 μm to about 4.0 μm have 50 The results show better cycle life than some lithium-ion battery cells with anodes containing smaller sawtooth composite particles having a value of 0.1%.

[0158] An additional property that can be determined from the particle size distribution (PSD) of a particle population is the cumulative volume fraction, which is the threshold D 50 D below the value 50 It is defined as the cumulative volume of particles with a value divided by the total volume of all particles. In some of the examples considered here, the threshold D 50 The particle population was set to a D value of 4.6 μm in the range of about 2.0 μm to about 4.0 μm. 50 values ​​and the corresponding cumulative volume fraction (D of 4.6 μm) 50 The threshold (D) ranged from about 58% to 96%. Lithium-ion battery test cells were prepared using anodes containing each of these particle populations, and cycle life was measured for each test. The results are shown in graph plot 1602 of FIG. 16. Graph plot 1602 shows the respective cumulative volume fractions (D of about 4.6 μm). 50Figure 1 shows the dependence of cycle life (in Si-C composite anode / LCO cathode cells) on the PSD threshold. Some examples with higher cumulative volume fractions (e.g., greater than about 80 vol%, greater than about 85 vol%, or greater than about 90 vol%) exhibited shorter cycle lives (e.g., less than about 500 cycles, less than about 450 cycles, or less than about 400 cycles). A higher cumulative volume fraction indicates the presence of a large amount of finer particles (e.g., particle sizes less than about 2.0 μm, less than about 1.0 μm, or less than about 0.5 μm), which may result in more frequent undesired side reactions between the composite particles and the electrolyte. In some examples, cycle life values ​​greater than about 500 cycles, greater than about 550 cycles, or greater than about 600 cycles can be achieved by adjusting the PSD of the sawtooth composite particle population. In some embodiments, the PSD can be adjusted to obtain a cumulative volume fraction (4.6 μm threshold) of less than about 90%, less than about 85%, less than about 80%, in the range of about 60% to about 85%, in the range of about 60% to about 80%, in the range of about 70% to about 85%, in the range of about 70% to about 80%, in the range of about 65% to about 85%, or in the range of about 65% to about 80%.

[0159] In the example described above with respect to FIG. 16, D in the range of about 2.0 μm to about 4.0 μm 50 value and the corresponding cumulative volume fraction (D of approximately 4.6 μm) 50 Composite particle populations with PSD (50th percentile volume-weighted particle size parameter (D)) in the range of about 58% to 96% have been tested for lithium-ion battery cell performance characteristics (in Si-C composite anode / LCO cathode cells). In some embodiments, the 50th percentile volume-weighted particle size parameter (D) of the PSD was measured. 50 ) is in the range of about 1.0 μm to about 12.0 μm (about 1.0 μm to about 2.0 μm in some designs, about 2.0 μm to about 4.0 μm in other designs, about 4.0 μm to about 6.0 μm in still other designs, and about 6.0 μm to about 12.0 μm in still other designs). In some embodiments (e.g., D 50 In other embodiments (e.g., when D is in the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction is about 90 vol. % or less, about 85 vol. % or less, or about 80 vol. % or less, with a threshold particle size of about 4.6 μm. 50In still other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction is about 90% by volume or less, about 85% by volume or less, or about 80% by volume or less, with a threshold particle size of about 7 μm. 50 In some embodiments (e.g., when D is in the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction is about 90 vol. % or less, about 85 vol. % or less, or about 80 vol. % or less, with a threshold particle size of about 15 μm. Note that the presence of excessively large particles can degrade cell performance characteristics (e.g., reduced cell stability, increased impedance, reduced rate capability, etc.). 50 In some embodiments (e.g., when D is in the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction is about 80% by volume or greater, with a threshold particle size of about 10 μm. 50 In other embodiments (e.g., when D is in the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction is about 90% by volume or greater, with a threshold particle size of about 12 μm. 50 In other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction is about 80% by volume or greater, with a threshold particle size of about 15 μm. 50 In other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction is about 90% by volume or greater, with a threshold particle size of about 22 μm. 50 In still other embodiments (e.g., when D is in the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction is about 80% by volume or greater, with a threshold particle size of about 28 μm. 50 is in the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction is about 90% by volume or more, with a threshold particle size of about 32 μm.

[0160] As shown in the graph plot 1502, the BET-SSA values ​​are the D of the sawtooth composite particle population. 50 Therefore, as shown in 1504, the areal binder loading also exhibits a dependence on the D when the binder mass fraction in the electrode coating is maintained in the range of about 6.5 to about 11.5 wt.%. 50The dependence on the value of D is approximately 7.42 μm. 50 Several lithium-ion battery cells were prepared with anodes containing a sawtooth nanocomposite particle population having a D of about 5.35 μm, varying the binder mass fraction in the electrode (anode) coating. 50 The results were compared with a lithium-ion battery cell having an anode including a sawtooth nanocomposite particle population having a D of about 7.42 μm. FIG. 17 shows a graphical plot 1702 illustrating the dependence of areal binder loading on binder mass fraction for each of the selected particle populations. 50 The binder mass fraction of the test cells having a D of about 5.35 μm was varied between about 6.5 wt % and about 11.5 wt %. In the illustrated example, a binder mass fraction of about 6.5 wt % corresponds to a mass fraction of sawtooth composite particles in the electrode of about 93.4 wt %. In the illustrated example, a binder mass fraction of about 11.5 wt % corresponds to a mass fraction of sawtooth composite particles in the electrode of about 88.4 wt %. 50 The binder mass fraction of the control sample test cell having a binder loading of about 8 mg / m was about 10.4 wt.%. 2 ~about 16mg / m 2 was in the range of

[0161] FIG. 18 shows a graphical plot 1802 of the dependence of cycle life on binder mass fraction for each of the test cells of FIG. 17. Test cells with binder mass fractions of about 10.4 wt % and about 11.5 wt % (D of about 7.42 μm) 50 ) indicates lithium plating during charging, indicating that at least a portion of the measured capacity is due to lithium plating on the copper current collector. In some designs, lithium plating is preferably avoided for safety reasons. In some examples, areal binder loadings (e.g., about 13 mg / m) corresponding to these binder mass fractions (e.g., about 10.4 wt. %, about 11.5 wt. %) are also shown. 2 The other test cells (D of about 7.42 μm) may be too high. 50 , about 6.5 wt%, about 7.5 wt%, about 8.5 wt%, and about 9.5 wt% binder mass fractions) and a control sample test cell (D of about 5.35 μm50 , about 10.4 wt.% binder mass fraction). No lithium plating was observed in the test cell with a binder mass fraction of about 6.5 wt.% (D of about 7.42 μm). 50 ) indicates poor adhesion of the coating to the current collector, resulting in a reduced cycle life, possibly indicating that the amount of binder was insufficient in this example. The corresponding areal binder loading value (e.g., about 9.0 mg / m 2 ~about 13mg / m 2 Test cells with moderate binder mass fraction values ​​(e.g., about 7.5 wt%, about 8.5 wt%, about 9.5 wt%) along with binder mass fraction values ​​in the range of about 6.0 μm to about 8.0 μm exhibited cycle life values ​​of over 800 cycles. 50 In some embodiments (e.g., a D in the range of about 6.0 μm to about 8.0 μm) of about 6.0 μm to about 8.0 μm, a binder mass fraction of more than about 6.6 wt %, more than about 7.0 wt %, less than about 10.3 wt %, less than about 10.0 wt %, about 6.6 wt % to about 10.3 wt %, about 6.6 wt % to about 10.0 wt %, about 7.0 wt % to about 10.3 wt %, about 7.0 wt % to about 10.0 wt %, about 7.0 wt % to about 8.0 wt %, about 8.0 wt % to about 9.0 wt %, or about 9.0 wt % to about 10.0 wt % may be suitable. 50 ) is approximately 9.0 mg / m 2 Ultra, about 13.0mg / m 2 Less than about 9.0 mg / m 2 ~About 13.0mg / m 2 range, approximately 9.0 mg / m 2 ~about 10.0mg / m 2 range, approximately 10.0 mg / m 2 ~Approx. 11.0mg / m 2 range, approximately 11.0 mg / m 2 ~Approx. 12.0mg / m 2 or about 12.0 mg / m 2 ~About 13.0mg / m 2 Area binder loading values ​​in the range of may be suitable.

[0162] FIG. 18 shows a graphical plot 1804 of the dependence of normalized coating thickness change on binder mass fraction for each of the test cells of FIG. 17. The normalized thickness change data is indicative of swelling of the electrode coating in the thickness direction (z-swelling). The test cell shown (D of about 7.42 μm) 50 ), the normalized coating thickness change is about 3.0 μm (cm ) for binder mass fractions of about 7.0 wt.% to about 10.0 wt.%. 2 / mAh) and D in the range of about 2.0 μm to about 4.0 μm 50 This is comparable to other lithium ion battery cells (e.g., graph plot 904) having a sawtooth composite particle population of 1000 .mu.m.

[0163] 19 shows a graphical plot 1902 of the dependence of volumetric energy density (VED) on binder mass fraction for each of the test cells of FIG. 17 and a graphical plot 1904 of the dependence of volumetric charge density (VQD) on binder mass fraction for each of the test cells of FIG. 17. 3 VQD values ​​higher than about 1.0 wt. % and VED values ​​higher than about 950 Wh / l were observed in test cells having a binder mass fraction of about 7.0 wt. % to about 10.0 wt. % (D of about 7.42 μm). 50 ) was confirmed.

[0164] FIG. 20 shows a graphical plot 2002 of the dependence of discharge voltage on binder mass fraction for each of the test cells of FIG. 17 and a graphical plot 2004 of the dependence of internal resistance on binder mass fraction for each of the test cells of FIG. 17. Discharge voltage values ​​greater than about 3.5 V and internal resistance values ​​in the range of about 15 Ω to about 25 Ω were observed for test cells having a binder mass fraction of about 7.0 wt % to about 10.0 wt % (D of about 7.42 μm). 50 ) was confirmed.

[0165] FIG. 21 shows a graphical plot 2102 of the dependence of first cycle efficiency on binder mass fraction for each of the test cells of FIG. 17 and a graphical plot 2104 of the dependence of formation efficiency on binder mass fraction for each of the test cells of FIG. 17. Formation efficiency values ​​greater than about 83% and first cycle efficiency values ​​greater than about 83% were observed for test cells having binder mass fractions of about 7.0 wt % to about 10.0 wt % (with a D of about 7.42 μm). 50 ) was confirmed.

[0166] In some designs (e.g., in blend anodes having anode capacities ranging from about 450 mAh / g to about 1600 mAh / g when normalized to the mass of the active materials, such as graphite and Si-C composite or other Si-containing anode materials; in some designs, for blend anodes having capacities ranging from about 500 mAh / g to about 1400 mAh / g when normalized to the mass of the active materials; and in some designs, for blend anodes having capacities ranging from about 600 mAh / g to about 1200 mAh / g when 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 nanocomposite) particles. A high fraction of fines (undesirably small particles) in Si composite powders has been found to increase the external surface area of ​​such particles, their BET-SSA, and the surface area of ​​these particles exposed to the electrolyte during cycling, resulting in a high volume fraction of SEI formed during formation and storage, rapid degradation during cycling, rapid degradation during battery storage at room and elevated temperatures, excessive gassing during formation, and other undesirable consequences. In particular, some designs have been found to increase the D (as measured using laser scattering or other suitable techniques) of Si-C nanocomposites (for use in blend anodes). 10 It has been found that it can be advantageous for D to be greater than about 1 μm for spheroidal (e.g., spherical or near-spherical) particles and greater than about 2 μm for sawtooth (or cylindrical) particles. In some designs, D for sawtooth (or cylindrical) particles 10It may be suitable for the BET-SSA of the Si-C nanocomposite powder (for use in blend anodes) to be in the range of about 1 to about 11 μm. 2 / g (approx. 1 to 2 m in some designs) 2 / g, and about 2 to 4 m for other designs 2 / g, and about 4 to 6 m for other designs 2 / g, and about 6 to 8 m for other designs 2 / g, and about 8 to 11 m for other designs 2 / g, and about 3 to about 7 m for other designs 2 / g) can be advantageous.

[0167] Interestingly, in some designs, the optimum PSD and optimum D of the Si-C composite particles were 50 , D 90 and D 99 It was found that the can be different for blend anodes relative to anodes containing only Si-C composites as active materials.

[0168] It has been found that to achieve good battery performance, the Si-C nanocomposite (in the blend anode) must exhibit a reasonably small volume change during cycling and therefore contain internal porosity (e.g., a total pore volume ranging from about 5% to about 50% by volume, as estimated using powder density measurements, argon gas pycnometry, or other suitable techniques). Meanwhile, the blend anode must be densified (calendered) to achieve high volumetric capacity and sufficient performance in the cell. A low weight percent of the Si-C composite in the blend anode often requires high calendering (densification) pressures. Such high pressures can induce cracking of the Si-C composites, exposing their interior surface regions and portions of the internal pores to the ambient air (and the battery electrolyte), which can lead to excessive side reactions with the electrolyte. While large Si-C composites exhibit a smaller BET, oversized Si-C composite particles may be more susceptible to mechanical damage during such calendering. Furthermore, it has been found that excessively large Si-C composite particles can increase the roughness of the blend anode (especially for anodes exhibiting lower areal capacity loading), reduce its volumetric capacity, increase the non-uniformity of the areal capacity distribution, significantly reduce the mechanical stability of the anode during cycling (e.g., resulting in delamination from the current collector or separation of the active material), and induce damage to the separator, etc., thereby reducing cycling stability.

[0169] In particular, in some designs (e.g., blend anodes having anode capacities ranging from about 450 mAh / g to about 1600 mAh / g when normalized to the mass of the active materials, such as graphite and Si-C composite or other Si-containing anode materials; in some designs, for blend anodes having capacities ranging from about 500 mAh / g to about 1400 mAh / g when normalized to the mass of the active materials; and in some designs, for blend anodes having capacities ranging from about 600 mAh / g to about 1200 mAh / g when normalized to the mass of the active materials), the D (as measured using laser scattering or other suitable technique) of Si-C nanocomposite powders (for use in blend anodes) may be significantly higher than the D (as measured using laser scattering or other suitable technique). 90 It has been found that, for spheroidal (e.g., spherical or near-spherical) particles, it may be advantageous to have a diameter of less than about 40 μm (less than about 30 μm in some designs, less than about 25 μm in other designs, less than about 20 μm in other designs, and less than about 15 μm in other designs), for sawtooth particles, it may be advantageous to have a diameter of less than about 40 μm (less than about 30 μm in some designs, less than about 25 μm in other designs, less than about 20 μm in other designs, and less than about 15 μm in other designs), for cylindrical particles, it may be advantageous to have a diameter of less than 60 μm (less than about 50 μm in some designs, less than about 40 μm in other designs, less than about 30 μm in other designs, less than about 25 μm in other designs, less than about 20 μm in other designs, and less than about 15 μm in other designs). In some designs, the D (as measured using laser scattering or other suitable technique) of a Si—C nanocomposite (for use in a blend anode) may be 99However, it has been found that for spheroidal (e.g., spherical or approximately spherical) particles, it can be advantageous to have a diameter of less than about 50 μm (less than about 40 μm in some designs, less than about 35 μm in other designs, less than about 30 μm in other designs, less than about 25 μm in other designs, and less than about 20 μm in other designs), for serrated particles, it can be advantageous to have a diameter of less than about 50 μm (less than about 40 μm in some designs, less than about 35 μm in other designs, less than about 30 μm in other designs, less than about 25 μm in other designs, and less than about 20 μm in other designs), and for cylindrical particles, it can be advantageous to have a diameter of less than about 80 μm (less than about 60 μm in some designs, less than about 50 μm in other designs, less than about 40 μm in other designs, less than about 30 μm in other designs, and less than about 20 μm in other designs). It should be noted that in automotive applications, Li-ion batteries generally exhibit a larger areal capacity load, and therefore the electrodes are generally thicker than those for Li-ion batteries intended for consumer electronics (e.g., laptops, mobile phones, fitness trackers, etc.) or consumer drone applications. Thicker electrodes result in a larger D 50 , D 90 or D 99 may be acceptable.

[0170] To achieve good performance in Li-ion batteries, in some designs, the full width at half maximum (FWHM) of the particle size distribution of the Si-C nanocomposite powder has been found to be in the range of about 3 to about 12 μm (in some designs, about 4 to about 8 μm, in some designs, about 5 to about 7 μm, in some designs, about 3 to about 5 μm, in some designs, about 7 to about 9 μm, and in some designs, about 9 to about 12 μm) (for blend anodes having anode capacities in the range of about 450 mAh / g to about 1600 mAh / g when normalized to the mass of the active material, such as graphite and Si-C composite or other Si-containing anode material; in some designs, for blend anodes having capacities in the range of about 500 mAh / g to about 1400 mAh / g when normalized to the mass of the active material; and in some designs, for blend anodes having capacities in the range of about 600 mAh / g to about 1200 mAh / g when normalized to the mass of the active material).

[0171] To achieve good performance in Li-ion batteries, some designs involve adjusting the particle size distribution span (D 90 -D 10 ) / D 50 ) has been found to be preferably less than about 3 (in some designs, more preferably less than about 2; in other designs, more preferably less than about 1; and in other designs, more preferably less than about 0.8) (for blend anodes having anode capacities in the range of about 450 mAh / g to about 1600 mAh / g when normalized to the mass of the active materials, such as graphite and Si—C composite or other Si-containing anode materials; in some designs, for blend anodes having capacities in the range of about 500 mAh / g to about 1400 mAh / g when normalized to the mass of the active materials; and in some designs, for blend anodes having capacities in the range of about 600 mAh / g to about 1200 mAh / g when normalized to the mass of the active materials). In some designs, the span of the particle size distribution of the Si-C nanocomposite powder (in such blended anodes) may preferably range from about 0.3 to about 3 (in some designs, more preferably from about 0.3 to about 2; in other designs, more preferably from about 0.3 to about 1.0; in other designs, more preferably from about 0.3 to about 0.8; and in other designs, more preferably from about 0.4 to about 1.2).

[0172] FIG. 22 shows an SEM image (2201) of a population of sawtooth composite particles (including agglomerates of sawtooth particles) without optimizing the particle size distribution (PSD) of the population. The particles shown in SEM image 2201 include fine particles (also known as "fines") and coarse particles. Some of the particles may be agglomerates of smaller particles. The definition of fine particles depends on the specific embodiment, but can be defined as particles having a diameter (e.g., as measured by LPSA) equal to or less than 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 embodiment, but can be defined as particles having a diameter (e.g., as measured by LPSA) equal to or greater than 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 a sawtooth, irregular shape and may exhibit a range of aspect ratios. These composite particles are in their as-prepared morphology and the PSD of the population is not optimized. 50 is about 10 μm.

[0173] FIG. 22 shows an SEM image (2202) of a cross section of an electrode coating containing a blend of a population of sawtooth particles and graphite particles as the electrode active material, shown as 2201. A slurry containing the electrode active material was cast onto a copper current collector, and the slurry solvent was allowed to dry. The electrode coating was calendered under 14 tons of force. Despite the calendering process, the cross-sectional image (2202) shows some particles protruding from the electrode coating surface. For example, this effect can be observed when the population of composite particles contains particles with diameters larger than the thickness of the electrode coating. The use of composite particles, such as those in the example of FIG. 22, has been found to frequently result in suboptimal (often not sufficiently good or unacceptable) performance in Li-ion batteries with blended anodes, particularly in Li-ion batteries for automobiles and consumer electronics. Herein, the term “blend anode” refers to an anode in which the electrode active material contains a blend of composite particles and graphite particles.

[0174] Figure 23 shows an SEM image (2301) of a population of sawtooth composite particles after optimization of the particle size distribution (PSD) of the population. Before undergoing optimization of its PSD, the population had a D of approximately 10 μm. 50 The PSD optimization process was performed to remove particles (removed particles were approximately 1.5 μm D 50 and removal of coarse particles (the removed coarse particles were approximately 15 μm in diameter). 50 (shown). For the results shown, removal of fines and removal of coarse particles were performed by sieving. In other embodiments, other particle size selection processes (e.g., screening, centrifugation, other aerodynamic sizing, or other processes) may be employed. In SEM image 2301, the number of fine and coarse particles has been reduced when compared to SEM image 2201. The deviation in PSD is smaller in the 2301 population (after PSD optimization) than in the 2201 population (without PSD optimization). The 2301 population appears to be more uniformly sized than the 2201 population.

[0175] FIG. 23 shows an SEM image (2302) of a cross section of an electrode coating containing a blend of sawtooth particles and graphite particles as the electrode active material, shown at 2301. A slurry containing the electrode active material was cast onto a copper current collector, and the slurry solvent was allowed to dry. The electrode coating was calendered under a force of 14 tons. Unlike cross section image 2202, particle protrusions are not visible in cross section image 2302. The electrode coating surface appears smooth. The use of composite particles such as those in the example of FIG. 23 has been found to frequently result in excellent (often very good, and often sufficiently good or acceptable) performance in Li-ion batteries with blend anodes, particularly in automotive and consumer electronics Li-ion batteries.

[0176] 24 shows graphical plots 2401 and 2402 of the volume-weighted particle size distribution (PSD) (expressed as volume %) of an exemplary population of sawtooth composite particles. Graphical plot 2401 shows the respective D s showing a relatively broad PSD, prior to any optimization of the respective PSD. 50 The graph plot 2402 shows the PSD of an example population of values. (1) Its PSD (D of about 10.1 μm)50 ) the PSD of the example population before optimization, and (2) its PSD (D of approximately 9.8 μm) 50 24 shows the PSD of an example ensemble after optimization of the PSD distribution. The PSD optimization process includes fine particle removal and coarse particle removal. As a result of these PSD optimization processes, the PSD was changed from a relatively wide PSD (e.g., wider span, wider FWHM) to a relatively narrow PSD (e.g., narrower span, wider FWHM). As shown in FIG. 24, FWHM is the full width at half maximum of the PSD distribution.

[0177] Table 1 (Figure 25) lists selected properties (D 10 , D 50 , D 90 , D 99 , Span, FWHM, D 10 / D 50 , BET-SSA). Graph plot 2401 shows (1) a D of approximately 3.65 μm, which corresponds to composite particle sample #1 in Table 1; 50 (2) a population having a D of approximately 5.03 μm, corresponding to composite particle sample #2 in Table 1 50 (3) a population having a D of approximately 8.02 μm, corresponding to composite particle sample #3 in Table 1 50 and (4) a population having a D of about 13.31 μm, corresponding to composite particle sample #5 in Table 1. 50 As shown in Table 1, these population samples (#1, #2, #3, and #5) have not undergone optimization of their PSDs (so-called "wide" PSDs). Graph plot 2401 shows the PSDs of populations with a relatively wide span (e.g., a range of about 1.9 to about 2.07). 50 A population of sawtooth composite particles having a range of values ​​(e.g., in the illustrated example, ranging from about 3.65 to about 13.31 μm) can be obtained by adjusting the conditions for synthesis of the composite particles and milling the larger particles into smaller particles. A population that has not undergone PSD optimization (e.g., the sample shown at 2401) can be obtained by adjusting the conditions for synthesis of the composite particles and milling the larger particles into smaller particles. 50 ), but may not be subjected to removal of fines and coarse particles.

[0178] Graphical plot 2402 shows (1) a D of approximately 9.82 μm corresponding to composite particle sample #8 in Table 1; 50 and (2) a population having a D of about 10.16 μm, corresponding to composite particle sample #4 in Table 1. 50 Graph plot 2402 compares the span of a population of sawtooth composite particles that has not undergone PSD optimization (sample #4, with a span of about 1.97 and a FWHM of about 23.0 μm) with the span of a population of sawtooth composite particles that has undergone PSD optimization (sample #8, with a span of about 0.67 and a FWHM of about 6.0 μm). Thus, graph plot 2402 shows the dramatic impact of performing PSD optimization (e.g., fines removal, coarse particle removal) on the span and FWHM of the population of sawtooth composite particles.

[0179] In Table 1 ( FIG. 25 ), population samples #1, #2, #3, #4, and #5 were not subjected to the PSD optimization process and therefore have a “wide” PSD. Population samples #6, #7, #8, and #9 were subjected to the PSD optimization process and therefore have a “narrow” PSD. Each population sample was used to fabricate two types of blend anode electrodes: Type A and Type B. Each population sample of sawtooth composite Si-C particles exhibited a specific first cycle lithiation capacity of approximately 1900 mAh / g (corresponding to a Si mass fraction of approximately 51 wt. % in the Si-C composite particles, with the remainder of the Si-C composite particles comprising carbon). In the illustrated example, the blend anode electrode active material included a blend of graphite particles and the respective sawtooth composite particles. In Type A electrodes, the electrode active material exhibited a first cycle lithiation capacity of approximately 600 mAh and contained approximately 16 wt. % of the respective sawtooth composite particles and approximately 84 wt. % of the graphite particles. For Type B electrodes, the electrode active material exhibited a first-cycle lithiation capacity of approximately 1000 mAh and contained approximately 42 wt. % of each sawtooth composite particle and approximately 58 wt. % graphite particles. For each electrode type (Type A, Type B) of each population sample, the coating density measured after calendaring is reported in Table 1. For each electrode type of each population sample, Li-ion battery cells were fabricated and performance characteristics were evaluated. Cycle life is reported for Li-ion battery cells of each electrode type and each composite particle population. In some examples of blend anodes (e.g., blended mixtures of Si-C composite particles and graphite particles), the mass fraction of the Si-C composite particles (e.g., sawtooth Si-C composite particles) in the battery electrode composition (excluding any binder) can be in the range of about 10 wt % to about 70 wt % (e.g., about 10 to about 20 wt %, about 20 to about 30 wt %, about 30 to about 40 wt %, about 40 to about 50 wt %, about 50 to about 60 wt %, or about 60 to about 70 wt %).In some examples of blend anodes (e.g., blended mixtures of Si-C composite particles and graphite particles), the mass fraction of the graphite particles in the battery electrode composition (excluding any binder) can be in the 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 %).

[0180] The details of the preparation and testing of the electrodes and Li-ion battery cells reported in Table 1 are as follows: For Type A (approximately 600 mAh / g) electrodes, an aqueous slurry containing a polyacrylic acid (PAA) salt copolymer-based binder (approximately 4 wt%), single-walled carbon nanotubes (approximately 0.05 wt%), and anode active material (approximately 95.95 wt%) was deposited on a 10 μm thick copper foil to provide approximately 4.1 mAh / cm 2 The electrode active material (about 100 parts by weight) was a blend of Si-C composite particles (about 16 parts by weight) and graphite particles (about 84 parts by weight). The Type A electrodes were calendered under a force of 16 tons to obtain an areal capacitance loading of about 1.53 to about 1.76 g / cm. 3 For the Type B (approximately 1000 mAh / g) electrode, a water-based slurry containing a polyacrylic acid (PAA) salt copolymer-based binder (approximately 6.6 wt%), single-walled carbon nanotubes (approximately 0.1 wt%), and anode active material (approximately 93.3 wt%) was applied to a 10 μm-thick copper foil to achieve a coating density of approximately 4.1 mAh / cm. 2 The electrode active material (about 100 parts by weight) was a blend of Si-C composite particles (about 42 parts by weight) and graphite particles (about 58 parts by weight). The Type B electrodes were calendered under a force of 14 tons to a coating density of about 1.27 to about 1.42 g / cm. 3 The coating density was achieved in the range of 0.01 to 0.01. The electrode was then coated with NCM811 (approximate composition Li[Ni 0.8 Co 0.1 Mn 0.1A single-layer pouch complete cell (approximately 6.25 cm) was fabricated with a lithium nickel manganese cobalt oxide (NCM) cathode, a 10 μm ceramic separator, and an electrolyte formulation containing 13.92 wt% LiPF (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). 2 After the electrolyte formulation was added to the Li-ion battery cell, the cell was cycled under the following charge / discharge test conditions: constant current constant potentiostatic (CCCP) at 2 C charge to 4.0 V, then ramped down to 1 C, followed by CCCP at 1 C charge to 4.2 V, then ramped down to 0.05 C, followed by 1 C discharge.

[0181] Table 1 (FIG. 25) reports the cycle-life performance of Li-ion battery cells obtained from each composite particle population and electrode type. For each composite particle population, cells with type A electrodes (approximately 600 mAh / g) exhibited higher cycle-life values ​​than cells with type B electrodes (approximately 1000 mAh / g). Cycle-life values ​​higher than 1900 cycles were observed for three "narrow" PSD samples: (1) Population #7, electrode type A, approximately 4.69 μm D 10 , D of about 6.77 μm 50 , about 69% ratio D 10 / D 50 , span of about 0.74, about 6.7m 2 / g BET-SSA, 2251 cycles, (2) Population #8, Electrode Type A, D of approximately 7.05 μm 10 , D of about 9.82 μm 50 , about 72% ratio D 10 / D 50 , span of about 0.67, about 3.7m 2 / g BET-SSA, 2276 cycles, and (3) Population #9, Electrode Type A, D of approximately 11.61 μm 10 , D of about 16.8 μm 50 , about 69% ratio D 10 / D50 , span of about 0.74, about 2.8m 2 / g BET-SSA, 1919 cycles. Cycle life values ​​for other "narrow" PSD samples are, for example, population #6, electrode type A, D of about 0.9 μm. 10 , D of about 2.69 μm 50 , about 33% ratio D 10 / D 50 , span of approximately 1.58, approximately 14.5m 2 / g BET-SSA, 983 cycles, etc. Population #6 had a smaller D than the other "narrow" PSD populations #7, #8, and #9. 10 , small D 50 , indicating a wide span and large BET-SSA. For further comparison, a "wide" PSD population performed on Type A electrodes showed cycle life values ​​ranging from approximately 973 cycles to 1380 cycles. The "wide" PSD population exhibited a D ranging from 1.1 μm to 3.01 μm. 10 (Ratio D in the range of 23-30% 10 / D 50 ), spans ranging from about 1.9 to about 2.07, and about 5.8 to 14.3 m 2 / g. In some examples, beneficial effects on cycle life (and other battery properties) may be observed when the span is less than about 2.1, less than about 1.9, less than about 1.8, less than about 1.5, less than about 1.2, less than about 1.0, or less than about 0.8. Furthermore, in some examples, the span may be greater than about 0.3, greater than about 0.5, or greater than about 0.6. In some examples, beneficial effects on cycle life (and other battery properties) may be observed when the BET-SSA of the composite particles is greater than about 15 m / g. 2 / g or less, approx. 12m 2 / g or less, approximately 10m 2 / g, approximately 8m 2 / g, approximately 7m 2 / g or less, approximately 6m 2 / g or less, approximately 5m 2 / g, approximately 4m 2 / g or less, or about 3m 2 / g. Further, in some embodiments, the BET-SSA may be found to be less than about 1 m2 / g, and approximately 2m 2 / g, approximately 5m 2 / g or greater than about 8m 2 In some embodiments, the beneficial effect on cycle life (and other battery characteristics) can be greater than D 10 In some embodiments, beneficial effects on cycle life (and other battery characteristics) may be observed when the ratio D 10 / D 50 may be identified when the ratio D is greater than about 35%, greater than about 45%, greater than about 55%, or greater than about 65%. 10 / D 50 may be less than about 80% or less than about 75%.

[0182] Figure 26 shows an SEM image (2601) of a population of spheroidal composite particles. In the example shown, the D 50 Values ​​range from about 5 to about 7 μm. Here, the term "spheroidal" is employed to refer to a near-spherical or spherically rounded shape, as exemplified in SEM image 2601.

[0183] Figure 27 shows the respective D 50 27 shows a graphical plot 2701 illustrating the dependence of BET-SSA values ​​for an example population of composite particles (serrated composite particles before PSD optimization (exhibiting a so-called "wide" PSD), serrated composite particles after PSD optimization (exhibiting a so-called "narrow" PSD), and spheroidal particles) on the PSD value. An example of spheroidal particles is shown in FIG. 26. In the illustrated example, D 50 The values ​​were measured by LPSA. Graphical plot 2701 shows the trends between sawtooth composite particles with a "wide" PSD, sawtooth composite particles with a "narrow" PSD, and spheroidal particles exhibiting a relatively narrow PSD. 50For various particle sizes (e.g., 8 μm, 10 μm, 12 μm), spheroidal particles (with a relatively narrow PSD) exhibited the smallest BET-SSA values, followed by sawtooth particles with a "narrow" PSD that had undergone PSD optimization, and then by sawtooth particles with a "wide" PSD that had not undergone PSD optimization. A smaller BET-SSA value may indicate a smaller external surface area of ​​the Si-C powder (Si-C composite particles). The use of composite particles with a smaller external surface area may result in superior Li-ion battery performance (e.g., longer calendar life, longer cycle stability, and / or better high-temperature stability) when used in a blend anode. On the other hand, the particle size of the Si-C composite particles (e.g., the D of the Si-C composite particles) 50 or especially D 90 Or D 99 If D becomes too large, Li-ion battery performance may be degraded despite the small BET-SSA value and / or small external surface area of ​​the Si-C composite particles. 90 and D 99 is excessive D 50 In some designs, the D of the sawtooth (or cylindrical) composite particles can be more detrimental to the performance of Li-ion batteries with blend anodes. 50 In some designs, it may be preferable for the D of the sawtooth (or cylindrical) composite particle to be in the range of about 5 to about 15 μm (about 5 to about 7 μm in some designs, about 7 to about 9 μm in other designs, about 9 to about 11 μm in other designs, about 11 to about 13 μm in other designs, about 13 to about 15 μm in other designs, about 8 to about 12 μm in still other designs, about 6 to about 10 μm in still other designs, about 6 to about 12 μm in still other designs, and about 6 to about 9 μm in still other designs). 50 It may be preferable for the thickness to be in the range of about 2 to about 17 μm.

[0184] 28 shows graphical plots 2802, 2804, and 2806 of selected PSD characteristics of exemplary populations of sawtooth composite particles. Graphical plot 2802 shows the D 50 D for value 99The graph plot 2804 shows the dependence of D values ​​on the D for each population of sawtooth composite particles, illustrating trends between populations that have not undergone PSD optimization (so-called "wide" PSD) and populations that have undergone PSD optimization (so-called "narrow" PSD). 50 D for value 90 The graph plot 2806 shows the dependence of D values ​​on the D for each population of sawtooth composite particles, illustrating trends between populations that have not undergone PSD optimization (so-called "wide" PSD) and populations that have undergone PSD optimization (so-called "narrow" PSD). 50 D for value 10 The dependence of values ​​is shown, showing trends between populations that have not undergone PSD optimization (so-called "wide" PSD) and populations that have undergone PSD optimization (so-called "narrow" PSD).

[0185] Figure 29 shows the D of each example population. 50 29A-29C show graph plots 2901 and 2902 illustrating the dependence of cycle life performance of Li-ion batteries (fabricated with Si-C nanocomposite and graphite blend anodes / NCM cathodes) fabricated using each exemplary population of sawtooth composite particles in the anode on the value of . The electrode and battery cell fabrication and testing were as described herein with reference to FIG. 24 and the results shown in Table 1 (FIG. 25). Graph plots 2901 and 2902 show trends between populations that did not undergo PSD optimization (so-called "wide" PSD) and populations that did undergo PSD optimization (so-called "narrow" PSD). In the illustrated example, the Li-ion battery employed an anode comprising a mixture of sawtooth composite particles and graphite particles ("active material mixture"). Graph plot 2901 shows cycle life (N80) data for a Li-ion battery employing a Type A electrode (electrode active material capacity of approximately 600 mAh / g). Graphical plot 2902 shows cycle life data (N80) for a Li-ion battery employing a Type B electrode (electrode active material capacity of approximately 1000 mAh / g).

[0186] D of composite particle ensemble 50For specific values ​​of and specific electrode types (electrode active material capacity of about 600 mAh / g or about 1000 mAh / g), Li-ion battery cells employing a "narrow" PSD that has undergone PSD optimization exhibited greater cycle life data (N80) than Li-ion battery cells employing a "wide" PSD that has not undergone PSD optimization. The improvement in cycle life (N80) employing a "narrow" PSD is significant for Type A electrodes (electrode active material capacity of about 600 mAh / g), for which N80 is observed to increase by more than 60% in some cases to over 2400 cycles. The improvement in cycle life by employing a "narrow" PSD is also observed for Type B electrodes, for which cycle life values ​​(N80) are observed to increase by more than 60% in some cases. 50 For a particular value of , a Li-ion battery cell with a lower capacity blend anode (about 600 mAh / g electrode active material capacity) typically results in a longer cycle life (N80) than a Li-ion battery cell with a higher capacity blend anode (about 1000 mAh / g electrode active material capacity) (Figure 29). 50 As the diameter increases from about 2-3 μm, better cycling stability (e.g., longer cycle life (N80)) is initially observed, likely due to a lower incidence of side reactions between the electrolyte and the composite particles (e.g., as exemplified by a smaller growth of the SEI, i.e., solid electrolyte interface). This trend of increasing cycle life (N80) is consistent with the D 50 The value is checked until an optimal range (e.g., about 6 to about 9 μm, about 6 to about 10 μm, about 6 to about 12 μm) is reached. 50 The optimum value is D 50 As the PSD increases beyond this range, mechanical and other problems that limit cycle life may occur, resulting in a decrease in cycle life to some extent. In some embodiments, the use of composite particles with a "narrow" PSD can significantly increase cycle stability (e.g., cycle life).

[0187] FIG. 30 shows selected PSD characteristics of an exemplary population of sawtooth composite particles, as well as the D 5030 shows graphical plots 3002, 3004, 3006, and 3008 illustrating the dependence of the PSD on the value of the PSD. In the example shown in FIG. 30, the PSD of each population was modified by milling (jet milling or ball milling). Graphical plots 3002, 3004, 3006, and 3008 show the trends between the ball milled and jet milled populations. The PSD characteristics shown are plotted with span 3002 and D 90 to 3004, D 10 The volume fraction of fine particles (or "fines," defined as particles with a diameter of 1 μm or less as measured by LPSA) in the population is shown in 3006 and 3008. In general, both jet milling and ball milling are effective tools for the fragmentation of larger particles, producing particles with a diameter in the range of about 3 μm to about 12 μm. 50 Jet milling has been shown to result in a complex particle population with a D value in the range of about 3 μm to about 7 μm. Jet milling and ball milling also have some differences. For the example shown in FIG. 30, the following can be observed: (1) The graph plot 3002 shows a D value in the range of about 3 μm to about 7 μm. 50 For values, ball milling is performed at a specific D 50 (2) The graph plot 3004 shows that jet milling tends to produce a population with a wider span than jet milling for D values ​​in the range of about 3 μm to about 7 μm. 50 For values, ball milling is performed at a specific D 50 value, D larger than jet milling 90 (3) Graph plot 3006 shows that the D ranges from about 3 μm to about 6 μm. 50 For values, ball milling is performed at a specific D 50 value, D smaller than jet milling 10 (4) Graph plot 3008 shows that the D ranges from about 3 μm to about 5 μm. 50 For values, ball milling is performed at a specific D 50 values, it shows that jet milling tends to produce a population with a higher volume fraction of fines than jet milling.

[0188] Some aspects of the present disclosure are also 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 cells containing other conventional intercalation-type (e.g., carbonaceous, such as synthetic or artificial graphite, soft carbon, hard carbon, and various mixtures thereof) anode materials, particularly at medium and high capacity loads (e.g., about 3-4 mAh / cm). 2 This may provide the benefit of improved rate performance or improved stability for electrodes (above).

[0189] Battery cell modules or battery cell packs may advantageously include cells having the electrode and / or electrolyte compositions provided in this disclosure. Such cell modules or packs may offer improved performance characteristics, simplified design, better safety features, or lower cost.

[0190] In the above detailed description, it can be seen that various features are grouped together in each example. Aspects of this disclosure should not be understood as intending that an example clause have more features than are expressly set forth in each clause. Rather, various aspects of the present disclosure may include fewer than all features of each example clause disclosed. Accordingly, the following clauses are hereby considered to be incorporated into the detailed description, with each clause standing on its own as a separate example. Although each dependent clause may refer to a specific combination with one of the other clauses in that clause, the aspects of that dependent clause are not limited to that specific combination. It should be understood that other example clauses may also include combinations of the dependent clause aspects with the subject matter of any other dependent or independent clause, or combinations of any features with other dependent and independent clauses. The various aspects disclosed herein explicitly include combinations unless it is expressly stated or readily inferable 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). It is further contemplated that aspects of a clause may be included in any other dependent clause even if the clause is not directly dependent on an independent clause.

[0191] Examples are described in the following numbered clauses:

[0192] Clause 1. A battery electrode composition comprising: a population of sawtooth composite particles, each of the sawtooth composite particles comprising silicon and carbon, wherein 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of 2.3 or less, and 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of 1.25 or more, the population having a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA), wherein a 50th percentile volume-weighted particle size parameter D of the PSD is 50 1. A battery electrode composition characterized by a PSD such that the PSD is in the range of about 2.0 to about 8.0 μm.

[0193] Clause 2. The battery electrode composition of clause 1, wherein about 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 2.1 or less.

[0194] Clause 3. The battery electrode composition of clause 1 or 2, wherein about 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.35 or greater.

[0195] Clause 4. The battery electrode composition of any one of clauses 1 to 3, wherein about 10% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.3 or less.

[0196] Clause 5. The battery electrode composition of any one of clauses 1 to 4, wherein the mass fraction of the silicon in the sawtooth composite particles is in the range of about 3% by weight to about 80% by weight.

[0197] Clause 6. The battery electrode composition of clause 5, wherein the mass fraction of the silicon is in the range of about 35% to about 50% by weight.

[0198] Clause 7. The Brunauer-Emmett-Teller (BET) specific surface area of ​​said population is about 3 m 2 / g ~ approx. 18m 2 7. The battery electrode composition of any one of clauses 1 to 6, wherein the composition is in the range of 1 / g.

[0199] Article 8. Paragraph D 50 8. The battery electrode composition of any one of clauses 1 to 7, wherein the average particle size is in the range of about 2.0 to about 4.0 μm.

[0200] Clause 9. The battery electrode composition of clause 8, wherein a cumulative volume fraction, defined as the cumulative volume of said sawtooth composite particles with a particle size of about 4.6 μm or less divided by the total volume of all of said sawtooth composite particles, is about 90 volume % or less, wherein said particle size, said cumulative volume, and said total volume are estimated by said LPSA.

[0201] Clause 10. The battery electrode composition of clause 9, wherein the cumulative volume fraction is less than or equal to about 85% by volume.

[0202] Clause 11. The battery electrode composition of clause 10, wherein the cumulative volume fraction is less than or equal to about 80 volume percent.

[0203] Article 12. Paragraph D 50 12. The battery electrode composition of any one of clauses 1 to 11, wherein the average particle size is in the range of about 6.0 to about 8.0 μm.

[0204] Clause 13. The Brunauer-Emmett-Teller (BET) specific surface area of ​​said population is about 3 m 2 / g ~ approx. 12m 2 13. The battery electrode composition of claim 12, wherein the composition is in the range of 1 / g.

[0205] Clause 14. A battery electrode comprising the battery electrode composition of clause 1 disposed on or within a current collector, the battery electrode including a binder.

[0206] Clause 15. The coating density of the battery electrode is about 0.9 to about 1.0 g / cm 3 15. The battery electrode of claim 14, wherein the electrode is in the range of

[0207] Clause 16. The battery electrode of clause 15, further comprising a carbon-containing functional additive.

[0208] Clause 17. The battery electrode of clause 16, wherein the carbon-containing functional additive is selected from 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, expanded graphite, graphene oxide, and graphene.

[0209] Article 18. The D of the PSD of the Group 50 Item 18. The battery electrode of any one of items 14 to 17, wherein the average particle size is in the range of about 6.0 to about 8.0 μm, and the mass fraction of the binder in the battery electrode is in the range of about 7 wt % to about 10 wt %.

[0210] Article 19. The D of the PSD of the Group 50 is in the range of about 6.0 to about 8.0 μm, and the area binder loading of the battery electrode is about 9.0 mg / m 2 ~About 13.0mg / m 2 19. The battery electrode of any one of clauses 14 to 18, wherein the areal binder loading is defined as the mass fraction of the binder in the battery electrode divided by the product of (1) the mass fraction of the serrated composite particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the population.

[0211] Clause 20. A lithium ion battery comprising: an anode current collector; a cathode current collector; the battery electrode of clause 14 configured as an anode, the current collector configured as the anode current collector; a cathode disposed on or within the cathode current collector; and an electrolyte ionically bonding the anode and the cathode.

[0212] Clause 21. A method of manufacturing a battery electrode, comprising: (A1) providing the battery electrode composition of clause 1; (A2) producing a slurry comprising the battery electrode composition and a binder; and (A3) casting the slurry onto or into a current collector to form the battery electrode.

[0213] Clause 22. A method for manufacturing a lithium ion battery, comprising: (B1) manufacturing the battery electrode according to the method described in Clause 21, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (B2) manufacturing or providing a cathode disposed on or within 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 bonds the anode and the cathode to form the lithium ion battery.

[0214] Clause 23. A method of manufacturing a lithium ion battery, comprising: (C1) providing a battery electrode according to clause 14, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on or within a cathode current collector; and (C3) assembling the anode and the cathode into a battery cell and filling a space between the anode and the cathode with an electrolyte that ionically bonds the anode and the cathode to form the lithium ion battery.

[0215] Further examples are described in the numbered appendices below.

[0216] Addendum 1. A battery electrode composition comprising a population of sawtooth composite particles, each of the sawtooth composite particles comprising silicon and carbon, wherein about 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 2.3 or less, and about 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.25 or more, the population having a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA) where the 50th percentile volume-weighted particle size parameter (D) of the PSD of the population is greater than or equal to 1.25. 50 ) is in the range of about 2.0 to about 17.0 μm 1. A battery electrode composition characterized by:

[0217] Additional Clause 2. The battery electrode composition of Additional Clause 1, wherein about 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 2.1 or less.

[0218] Additional Clause 3. The battery electrode composition of Additional Clause 1 or 2, wherein about 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.35 or greater.

[0219] Additional Clause 4. The battery electrode composition of any one of Additional Clauses 1 to 3, wherein about 10% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.3 or less.

[0220] Additional Clause 5. The battery electrode composition of any one of Additional Clauses 1 to 4, wherein the mass fraction of the silicon in the sawtooth composite particles is in the range of about 3% by weight to about 80% by weight.

[0221] Additional Clause 6. The battery electrode composition of Additional Clause 5, wherein the mass fraction of the silicon is in the range of about 33% to about 60% by weight.

[0222] Addendum 7. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of said population is approximately 1 m 2 / g ~ approx. 18m 2 / g。 Battery electrode composition of any one of clauses 1 to 6, wherein the composition of claim 1.

[0223] Additional Article 8. The BET-SSA is approximately 1 m 2 / g~about 10m 2 / g。 Battery electrode composition of Addendum 7, in the range of.

[0224] Additional Clause 9. Paragraph D 50 9. The battery electrode composition of any one of Additional Clauses 1 to 8, wherein the average particle size is in the range of about 2.0 to about 8.0 μm.

[0225] Additional Clause 10. Paragraph D 50 10. The battery electrode composition of any one of Additional Clauses 1 to 9, wherein the average particle size is in the range of about 6.0 to about 17.0 μm.

[0226] Additional Clause 11. Paragraph D 50 The battery electrode composition of Addendum 10, wherein the average particle size is in the range of about 6.0 to about 9.0 μm.

[0227] Additional Clause 12. The battery electrode composition of any one of Additional Clauses 1 to 11, wherein the span of the PSD of the population is in the range of about 0.3 to about 1.8.

[0228] Addendum 13. The 10th percentile volume-weighted particle size parameter (D) of said PSD of said population 10 ) is at least about 1.0 μm, and the D 50 The PSD of the population divided by the D 10 13. The battery electrode composition of any one of Addendum 1 to 12, wherein the value of is in the range of 35% to 75%.

[0229] Additional Clause 14. The battery electrode composition of any one of Additional Clauses 1 to 13, comprising a blend of the sawtooth composite particles and graphite particles, wherein the mass fraction of the sawtooth composite particles in the battery electrode composition, excluding any binder, is in the range of about 10% to about 70% by weight, or the mass fraction of the graphite particles in the battery electrode composition, excluding any binder, is in the range of about 30% to about 90% by weight, or a combination thereof.

[0230] Additional Article 15. The D of the PSD of the Group 50 is in the range of about 6.0 to about 12.0 μm.

[0231] Addendum 16. The 10th percentile volume-weighted particle size parameter (D) of said PSD of said population 10 16. The battery electrode composition of Addendum 14 or 15, wherein the average particle size is in the range of about 1.0 to about 4.0 μm.

[0232] Addendum 17. The 90th percentile volume-weighted particle size parameter (D) of said PSD of said population 90 17. The battery electrode composition of any one of Addendum 14 to 16, wherein the average particle size is in the range of about 7.0 to about 25.0 μm.

[0233] Additional Clause 18. Paragraph D 90 is in the range of about 12.0 to about 20.0 μm.

[0234] Addendum 19. The 99th percentile volume-weighted particle size parameter (D) of said PSD of said population 99 19. The battery electrode composition of any one of Additional Clauses 14 to 18, wherein the average particle size is in the range of about 15.0 to about 28.0 μm.

[0235] Addendum 20. The battery electrode composition of any one of Addendums 14 to 19, wherein the span of the PSD of the population is in the range of from about 0.6 to about 2.1.

[0236] Addendum 21. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of said population is approximately 1 m 2 / g~about 10m 2 21. The battery electrode composition of any one of Addendum 14 to 20, wherein the composition is in the range of / g.

[0237] Additional Clause 22. The battery electrode composition of any one of Additional Clauses 14 to 21, wherein the sawtooth composite particles exhibit a specific first cycle lithiation capacity in the range of about 1600 mAh / g to about 2200 mAh / g.

[0238] Addendum 23. The battery electrode composition of any one of Addendums 14 to 22, wherein the specific capacity of the blended mixture, when normalized to the mass of the blended mixture, is in the range of about 600 mAh / g to about 1200 mAh / g.

[0239] Addendum 24. A battery electrode comprising the battery electrode composition of Addendum 1 disposed on and / or within a current collector, the battery electrode including a binder.

[0240] Additional Clause 25. The coating density of the battery electrode is about 0.9 to about 1.7 g / cm 3 2. The battery electrode of Addendum 24, wherein the electrode is in the range of

[0241] Addendum 26. The battery electrode of Addendum 24 or 25, further comprising a carbon-containing functional additive.

[0242] Addendum 27. The battery electrode of Addendum 26, wherein 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.

[0243] Addendum 28. The battery electrode of Addendum 27, wherein the mass fraction of the carbon-containing functional additive in the battery electrode is about 1 wt % or less.

[0244] Additional Clause 29. The D of the PSD of the Group 50 29. The battery electrode of any one of Additional Clauses 24 to 28, wherein the average particle size is in the range of about 6.0 to about 8.0 μm, and the mass fraction of the binder in the battery electrode is in the range of about 7 wt % to about 10 wt %.

[0245] Additional Clause 30. The D of the PSD of the Group 50 is in the range of about 6.0 to about 8.0 μm, and the area binder loading of the battery electrode is about 9.0 mg / m 2 ~About 13.0mg / m 2 30. The battery electrode of any one of Addendum 24 to 29, wherein the areal binder loading is defined as the mass fraction of the binder in the battery electrode divided by the product of (1) the mass fraction of the serrated composite particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the population.

[0246] Addendum 31. A lithium ion battery comprising: an anode current collector; a cathode current collector; a battery electrode according to Addendum 24 configured as an anode, the current collector configured as the anode current collector; a cathode disposed on or within the cathode current collector; and an electrolyte ionically bonding the anode and the cathode.

[0247] Addendum 32. A method of manufacturing a battery electrode, comprising: (A1) providing a battery electrode composition according to Addendum 1; (A2) producing a slurry comprising the battery electrode composition and a binder; and (A3) casting the slurry onto and / or into a current collector to form the battery electrode.

[0248] Addendum 33. A method of manufacturing a lithium-ion battery, the method comprising: (B1) manufacturing the battery electrode according to the method of Addendum 32, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (B2) manufacturing or providing a cathode disposed on and / or within a cathode current collector; and (B3) assembling the anode and the cathode into a battery cell and filling a space between the anode and the cathode with an electrolyte that ionically bonds the anode and the cathode to form the lithium-ion battery.

[0249] Addendum 34. A method of manufacturing a lithium ion battery, the method comprising the steps of: (C1) providing a battery electrode according to Addendum 24, the battery electrode configured as an anode and the current collector configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on and / or within a cathode current collector; and (C3) assembling the anode and the cathode into a battery cell and filling a space between the anode and the cathode with an electrolyte that ionically bonds the anode and the cathode to form the lithium ion battery.

[0250] This description is provided to enable any person skilled in the art to make or use embodiments of the invention. However, since various modifications to these embodiments will be readily apparent to those skilled in the art, it should be understood that the invention is not limited to the particular formulations, process steps, and substances / materials disclosed herein. Indeed, the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.

Claims

1. 1. A battery electrode composition comprising: a population of jagged composite particles, each of the jagged composite particles comprising silicon and carbon; at least about 90% of the serrated composite particles in the population are characterized by an aspect ratio of about 2.3 or less; about 50% or more of the serrated composite particles in the population are characterized by an aspect ratio of about 1.25 or greater; The population has a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA), The 50th percentile volume-weighted particle size parameter (D ５０ ) is in the range of about 2.0 to about 17.0 μm; Battery electrode composition.

2. 10. The battery electrode composition of claim 1, wherein about 90% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 2.1 or less.

3. 10. The battery electrode composition of claim 1, wherein about 50% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.35 or greater.

4. 10. The battery electrode composition of claim 1, wherein about 10% or more of the sawtooth composite particles in the population are characterized by an aspect ratio of about 1.3 or less.

5. 10. The battery electrode composition of claim 1, wherein the mass fraction of the silicon in the sawtooth composite particles ranges from about 3% to about 80% by weight.

6. 6. The battery electrode composition of claim 5, wherein the mass fraction of the silicon ranges from about 33% to about 60% by weight.

7. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the mass is about 1 m ２ / g ~ approx. 18m ２ 10. The battery electrode composition of claim 1, wherein the SiO2 content is in the range of 0.1 wt. / g.

8. The BET-SSA is about 1 m ２ / g ~ approx. 10m ２ 8. The battery electrode composition of claim 7, wherein the SiO2 content is in the range of 0.1 wt. / g.

9. The above D ５０ 10. The battery electrode composition of claim 1, wherein the average particle size is in the range of about 2.0 to about 8.0 μm.

10. The above D ５０ 10. The battery electrode composition of claim 1, wherein the average particle size is in the range of about 6.0 to about 17.0 μm.

11. The above D ５０ 11. The battery electrode composition of claim 10, wherein the average particle size is in the range of about 6.0 to about 9.0 μm.

12. 10. The battery electrode composition of claim 1, wherein the span of the PSD of the population is in the range of about 0.3 to about 1.

8.

13. The 10th percentile volume-weighted particle size parameter (D １０ ) is at least about 1.0 μm; The D of the PSD of the population ５０ The D of the PSD of the population divided by １０ 10. The battery electrode composition of claim 1, wherein the value of is in the range of 35% to 75%.

14. a blend of the sawtooth composite particles and graphite particles; 10. The battery electrode composition of claim 1, wherein the mass fraction of the sawtooth composite particles in the battery electrode composition, excluding any binder, is in the range of about 10 wt% to about 70 wt%, or the 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.

15. The D of the PSD of the population ５０ 15. The battery electrode composition of claim 14, wherein the average particle size is in the range of about 6.0 to about 12.0 μm.

16. The 10th percentile volume-weighted particle size parameter (D １０ 15. The battery electrode composition of claim 14, wherein the average particle size is in the range of about 1.0 to about 4.0 μm.

17. The 90th percentile volume-weighted particle size parameter (D ９０ 15. The battery electrode composition of claim 14, wherein the average particle size is in the range of about 7.0 to about 25.0 μm.

18. The above D ９０ 18. The battery electrode composition of claim 17, wherein the average particle size is in the range of about 12.0 to about 20.0 μm.

19. The 99th percentile volume-weighted particle size parameter (D ９９ 15. The battery electrode composition of claim 14, wherein the average particle size is in the range of about 15.0 to about 28.0 μm.

20. 15. The battery electrode composition of claim 14, wherein the span of the PSD of the population is in the range of about 0.6 to about 2.

1.

21. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the mass is about 1 m ２ / g ~ approx. 10m ２ 15. The battery electrode composition of claim 14, wherein the SiO2 content is in the range of 0.15 wt. / g.

22. 15. The battery electrode composition of claim 14, wherein the sawtooth composite particles exhibit a specific first cycle lithiation capacity in the range of about 1600 mAh / g to about 2200 mAh / g.

23. 15. The battery electrode composition of claim 14, wherein the specific capacity of the blended mixture, when normalized by the mass of the blended mixture, is in the range of about 600 mAh / g to about 1200 mAh / g.

24. A battery electrode, 10. The battery electrode composition of claim 1 disposed on and / or within a current collector. Including, A battery electrode including a binder.

25. The coating density of the battery electrode is about 0.9 to about 1.7 g / cm ３ 25. The battery electrode of claim 24, wherein the .lambda.

26. 25. The battery electrode of claim 24, further comprising a carbon-containing functional additive.

27. 27. The battery electrode of claim 26, wherein 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.

28. 30. The battery electrode of claim 27, wherein the mass fraction of the carbon-containing functional additive in the battery electrode is about 1 wt% or less.

29. The D of the PSD of the population ５０ is in the range of about 6.0 to about 8.0 μm, 25. The battery electrode of claim 24, wherein the mass fraction of the binder in the battery electrode ranges from about 7% to about 10% by weight.

30. The D of the PSD of the population ５０ is in the range of about 6.0 to about 8.0 μm, The battery electrode has an areal binder loading of about 9.0 mg / m ２ ~Approx. 13.0mg / m ２ and the areal binder loading is defined as the mass fraction of the binder in the battery electrode divided by the product of (1) the mass fraction of the serrated composite particles in the battery electrode and (2) the Brunauer-Emmett-Teller (BET) specific surface area of ​​the population.

31. A lithium-ion battery, an anode current collector; a cathode current collector; 25. The battery electrode of claim 24 configured as an anode, wherein the current collector is configured as the anode current collector; a cathode disposed on or within the cathode current collector; an electrolyte ionically bonding the anode and the cathode; A lithium-ion battery comprising:

32. 1. A method of manufacturing a battery electrode, comprising: (A1) providing a battery electrode composition according to claim 1; (A2) preparing a slurry containing the battery electrode composition and a binder; (A3) casting the slurry onto and / or into a current collector to form the battery electrode; A method for providing the above.

33. 1. A method for manufacturing a lithium ion battery, comprising: (B1) A step of manufacturing the battery electrode according to the method of claim 32, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (B2) fabricating or providing a cathode disposed on and / or within a cathode current collector; (B3) assembling the anode and the cathode into a battery cell and filling a space between the anode and the cathode with an electrolyte that ionically bonds the anode and the cathode to form the lithium ion battery; A method for manufacturing a lithium ion battery comprising:

34. 1. A method for manufacturing a lithium ion battery, comprising: (C1) providing a battery electrode according to claim 24, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on and / or within a cathode current collector; (C3) assembling the anode and the cathode into a battery cell, and filling a space between the anode and the cathode with an electrolyte that ionically bonds the anode and the cathode to form the lithium ion battery; A method for manufacturing a lithium ion battery comprising:

Images