Sawtooth-shaped electrochemically active composite particles for lithium ion batteries

Abstract

A battery electrode composition includes a population of serrated composite particles, wherein each serrated composite particle includes silicon and carbon. In some embodiments, about 90% or more of the serrated composite particles in the population of particles are characterized by an aspect ratio of about 2.3 or less, and about 50% or more of the serrated composite particles in the population of particles are characterized by an aspect ratio of about 1.25 or greater. In some embodiments, the population of particles is characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA), and a fifty percentile volume weighted particle size parameter D50 of the PSD is in a range of from about 2.0 [mu] m to about 17.0 [mu] m.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims the benefit of U.S. Provisional Application No. 63 / 477,727, filed on December 29, 2022, entitled “SERRATED ELECTROCHEMICALLY ACTIVE COMPOSITE PARTICLES FOR LITHIUM ION BATTERIES,” and U.S. Non-Provisional Application No. 18 / 398,718, filed on December 28, 2023, entitled “SERRATED ELECTROCHEMICALLY ACTIVE COMPOSITE PARTICLES FOR LITHIUM ION BATTERIES,” both of which are assigned to the present assignee and are expressly incorporated herein by reference in their entireties. Technical Field

[0002] field

[0003] Various aspects of the present invention relate generally to energy storage devices, and more particularly to battery technology and the like. Background Art

[0004] background

[0005] Due in part to their relatively high energy density, relatively high specific energy, light weight, and potentially long life, advanced rechargeable batteries are ideal for a wide range of consumer electronics, electric vehicles, grid storage, and other important applications.

[0006] However, despite their increasing commercial popularity, these batteries still require further development, particularly for applications in low-emission or zero-emission, hybrid electric or all-electric vehicles, consumer electronics, wearable devices, energy-efficient cargo ships and locomotives, drones, aerospace applications, and power grids. In particular, further improvements are needed for various rechargeable batteries, such as rechargeable lithium and lithium-ion batteries, rechargeable sodium and sodium-ion batteries, and rechargeable potassium and potassium-ion batteries, among others.

[0007] In certain types of lithium metal and lithium ion rechargeable batteries, the charge storage anode can include silicon (Si)-containing anode particles having a gravimetric capacity in the range of about 800 mAh / g to about 3000 mAh / g (per mass of the silicon-containing anode particles in a lithium-free state). A subset of such anodes includes anodes whose electrode layers exhibit a capacity in the range of about 400 mAh / g to about 2800 mAh / g (per mass of the electrode layer in a lithium-free state, excluding the mass of the current collector). This type of charge storage anode offers significant potential for increasing the gravimetric and volumetric energy of rechargeable batteries.

[0008] In certain types of rechargeable batteries, the charge storage anode active material can be produced as a high-capacity (nano)composite powder (e.g., composed at least in part of active nanomaterials or nanostructures that can be embedded on and / or in a porous structure, such as a carbonaceous matrix material) that exhibits a moderately high volume change (e.g., about 8-180 vol.%) during the first charge-discharge cycle and a moderate volume change (e.g., about 5-50 vol.%) 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) ranging from about 0.2 to about 40 μm (micrometers) as measured using laser particle size distribution analysis (LPSA), laser image analysis, electron microscopy, optical microscopy, or other suitable techniques. Such charge storage particles offer great promise for scalable manufacturing and achieving high cell-level energy density and other performance characteristics.

[0009] Examples of electrode materials that exhibit a moderately high volume change (e.g., about 8-180 vol.%) during the first charge-discharge cycle and a moderate volume change (e.g., about 5-50 vol.%) during subsequent charge-discharge cycles include (nano) composite materials, which include so-called conversion-type (including so-called chemical conversion and so-called "true conversion" sub-classes) and so-called alloy-type active electrode materials. In the case of metal ion batteries (such as lithium ion batteries), examples of such conversion-type active electrode materials include, but are not limited to, metal fluorides (such as lithium fluoride, iron fluoride, copper fluoride, bismuth fluoride, and mixtures and alloys thereof, etc.), metal chlorides, metal iodides, metal bromides, metal chalcogenides (such as sulfides, including lithium sulfide and other metal sulfides), sulfur, selenium, metal oxides (including but not limited to lithium oxide and silicon oxide), metal nitrides, metal phosphides (including lithium phosphide), metal hydrides, etc. In the case of metal ion batteries (such as lithium ion batteries), examples of such alloy electrode materials include, but are not limited to, silicon, germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorus, silver, cadmium, indium, tin, lead, bismuth, and alloys thereof. These materials generally provide higher weight and volumetric capacities than the so-called intercalation electrodes commonly used in commercial metal ion (such as lithium ion) batteries. Alloy electrode materials are particularly advantageous for use in certain high-capacity anodes for lithium ion batteries. Silicon-based alloy anodes may be particularly attractive for such applications.

[0010] One example of a low-swelling particle can include a mixture of a converted silicon-based (or, more broadly, silicon-containing) anode active material and graphite, a so-called silicon-graphite blend. In some examples of blended anodes, the silicon-containing anode active material can be a silicon- and carbon-containing nanocomposite (referred to herein as a silicon-carbon composite or silicon-carbon nanocomposite or silicon-carbon composite (or nanocomposite) particles, even if these particles contain relatively little of elements other than silicon and carbon—less than about 10-20 at.%)—and provides about 20% to 80% of the total blended anode capacity, with the remainder coming from graphite. (In other examples, the silicon-carbon composite (e.g., silicon-carbon composite particles) can account for more than about 80% or less than about 20% of the anode capacity.) Such anodes offer significantly higher volumetric and gravimetric energy densities than the intercalated graphite anodes commonly used in commercial lithium-ion batteries. Furthermore, in such blended anodes, the graphite can be composed of natural graphite, synthetic graphite, or a mixture of natural and synthetic graphite. In some designs, it is advantageous to use natural graphite or a mixture of natural graphite and artificial graphite because such graphite particles can accommodate the stresses caused by the high swelling (during lithium insertion) of silicon-based (e.g., silicon-carbon) particles. This characteristic of the blend of silicon-carbon nanocomposite and graphite can provide a moderate volume change of the particle population during the first cycle and a low volume change during subsequent charging cycles. This characteristic is advantageous for high-capacity loading of anode particles, which can also reduce the manufacturing cost of such battery cells.

[0011] In some designs, the active electrode material for an electrochemical energy storage device (such as a battery, electrochemical capacitor, or hybrid device) can be a carbon-containing composite material particle. A subclass of such composite particles can include composite particles in which a conversion, alloy, embedded, or pseudocapacitive material is confined or infiltrated within a carbon matrix material or within a carbon-containing matrix material. However, existing composite or thermochemical processing methods for such carbon-matrix materials or carbon-containing matrix materials may have problems such as low efficiency, low packing density, low yield, or insufficient control over uniformity, or other limitations.

[0012] Therefore, there remains a need for improved batteries, components, and other related materials and manufacturing processes. Summary of the Invention

[0013] The following is a simplified description of one or more aspects disclosed herein. Therefore, the following description should not be considered an extensive overview of all contemplated aspects, nor should it be considered to identify important or critical elements related to all contemplated aspects, or to describe the scope of any particular aspect. Therefore, the sole purpose of the following description is to present certain concepts related to one or more aspects of the mechanisms disclosed herein in a simplified form before providing the detailed description presented later.

[0014] In one aspect, a battery electrode composition includes a population of jagged composite particles, wherein each jagged composite particle comprises 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; about 50% or more of the jagged composite particles in the population are characterized by an aspect ratio of about 1.25 or greater; and the population is characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA) such that a fiftieth percentile volume-weighted particle size parameter (D 50 ) is in the range of about 2.0 μm to about 17.0 μm.

[0015] In some aspects, about 90% or more of the jagged composite particles in a population of particles are characterized by an aspect ratio of about 2.1 or less.

[0016] In some aspects, about 50% or more of the jagged composite particles in a population of particles are characterized by an aspect ratio of about 1.35 or greater.

[0017] In some aspects, about 10% or more of the jagged composite particles in a population of particles are characterized by an aspect ratio of about 1.3 or less.

[0018] In some aspects, the mass fraction of silicon in the jagged composite particles ranges from about 3 wt.% (weight percent) to about 80 wt.%.

[0019] In some aspects, the mass fraction of silicon is in a range from about 33 wt. % to about 60 wt. %.

[0020] In some aspects, the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the particle population is about 1 m 2 / g to about 18m 2 / g range.

[0021] In some aspects, BET-SSA is present at about 1 m 2 / g to about 10m 2 / g range.

[0022] In some respects, D 50 In the range of about 2.0 μm to about 8.0 μm.

[0023] In some respects, D 50 In the range of about 6.0 μm to about 17.0 μm.

[0024] In some respects, D 50 In the range of about 6.0 μm to about 9.0 μm.

[0025] In some aspects, the span of the PSD of the population of particles is in the range of about 0.3 to about 1.8.

[0026] In some aspects, the tenth percentile volume-weighted particle size parameter (D 10 ) is at least about 1.0 μm; and the PSD of the particle population has a D 10 Divide D by the PSD of the particle group 50 The values ​​obtained were in the range of 35% to 75%.

[0027] In some aspects, the battery electrode composition comprises a blended mixture of jagged composite particles and graphite particles; and the mass fraction of the jagged composite particles (excluding any binder) in the battery electrode composition is in the range of about 10 wt.% to about 70 wt.%, and / or the mass fraction of the graphite particles (excluding any binder) in the battery electrode composition is in the range of about 30 wt.% to about 90 wt.%.

[0028] In some aspects, the PSD of a particle population is D 50 In the range of about 6.0 μm to about 12.0 μm.

[0029] In some aspects, the tenth percentile volume-weighted particle size parameter (D 10 ) is in the range of about 1.0 μm to about 4.0 μm.

[0030] In some aspects, the 90th percentile volume-weighted particle size parameter (D 90 ) is in the range of about 7.0 μm to about 25.0 μm.

[0031] In some respects, D 90 In the range of about 12.0 μm to about 20.0 μm.

[0032] In some aspects, the 99th percentile volume-weighted particle size parameter (D 99 ) is in the range of about 15.0 μm to about 28.0 μm.

[0033] In some aspects, the span of the PSD of the population of particles is in the range of about 0.6 to about 2.1.

[0034] In some aspects, the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the particle population is about 1 m 2 / g to about 10m 2 / g range.

[0035] In some aspects, the jagged composite particles exhibit a first cycle lithiation specific capacity in a range from about 1600 mAh / g to about 2200 mAh / g.

[0036] In some aspects, the specific capacity of the blended mixture is in a range from about 600 mAh / g to about 1200 mAh / g when normalized by the mass of the blended mixture.

[0037] In one aspect, a battery electrode includes a battery electrode composition disposed on and / or in a current collector, wherein the battery electrode comprises a binder.

[0038] In some aspects, the coating density of the battery electrode is about 0.9 g / cm 3 to about 1.7g / cm 3 within the range.

[0039] In some aspects, a carbon-containing functional additive is also included.

[0040] In some aspects, the carbon-containing functional additive is selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon black, exfoliated graphite, graphene oxide, and graphene.

[0041] In some aspects, the mass fraction of the carbon-containing functional additive in the battery electrode is about 1 wt. % or less.

[0042] In some aspects, the PSD of a particle population is D 50 in the range of about 6.0 μm 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. %.

[0043] In some aspects, the PSD of a particle population is D 50 in the range of about 6.0 μm to about 8.0 μm; and the areal binder loading of the battery electrode is about 9.0 mg / m 2 to about 13.0 mg / m 2 where 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 particle population.

[0044] In one aspect, a lithium ion battery includes: an anode current collector; a cathode current collector; a battery electrode configured as an anode, whose current collector is configured as the anode current collector; a cathode disposed on or in the cathode current collector; and an electrolyte ionically coupling the anode and cathode.

[0045] In one aspect, a method for manufacturing a battery electrode includes: (A1) providing a battery electrode composition; (A2) preparing a slurry comprising the battery electrode composition and a binder; and (A3) casting the slurry on and / or in a current collector to form a battery electrode.

[0046] In one aspect, a method of manufacturing a lithium-ion battery includes: (B1) manufacturing a battery electrode, 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 in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode and filling the space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form a lithium-ion battery.

[0047] In one aspect, a method of manufacturing a lithium-ion battery includes: (C1) providing a battery electrode, 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 in 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 couples the anode and cathode to form a lithium-ion battery.

[0048] One aspect relates to a battery electrode composition comprising a population of serrated composite particles, wherein each serrated composite particle comprises silicon (Si) and carbon (C) (e.g., primarily graphite carbon), and may contain other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), etc., to name a few. In some embodiments, the total mass of Si and C may be from about 75 wt.% to about 100 wt.% of the total mass of the composite particles. Such composite particles are sometimes referred to herein as Si-C composites. In some embodiments, such composite particles comprise nanosized or nanostructured elements (e.g., nanosized or nanostructured Si, nanosized or nanostructured C) - which may be referred to as nanocomposite particles. In some embodiments, the Si or Si-containing material present in such nanocomposite materials may be in the form of nanoparticles. In some embodiments, the mass average size of the Si or Si-containing material nanoparticles can be 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; in still other designs, about 100 nm to about 200 nm), as measured using electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM)), X-ray microscopy, X-ray diffraction, image analysis of neutron scattering, and other suitable techniques. In some embodiments, 90% or more of the jagged composite particles in a population of particles 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 jagged composite particles in a population of particles 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 jagged composite particles in a population of particles are characterized by an aspect ratio of 1.3 or less. The particle population can be characterized by particle size distribution (PSD) determined by laser particle size analysis (LPSA), image analysis of electron microscopy images, or other suitable techniques. 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, or in the range of about 2.0 μm to about 4.0 μm, or in the range of about 4.0 μm to about 6.0 μm, or in the range of about 6.0 μm to about 8.0 μm, or in the range of about 8.0 μm 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, or in the range of about 1.0 μm to about 4.0 μm, or in the range of about 4.0 μm to about 6.0 μm, or in the range of about 6.0 μm to about 9.0 μm, or in the range of about 9.0 μm to about 17.0 μm.

[0049] Another aspect relates to a battery electrode composition comprising a population of nanocomposite particles, wherein each nanocomposite particle comprises Si and C (such that the total mass of Si and C atoms is 75 wt.% to 100 wt.% of the mass of the nanocomposite particle), and the nanocomposite particles have certain properties. In some embodiments, the mass fraction of silicon in the nanocomposite particles is in the range of about 3 wt.% to about 80 wt.% (in some designs, about 3 wt.% to about 20 wt.%; in other designs, about 20 wt.% to about 35 wt.%; in still 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, about 9 wt.% to about 30 wt.%). In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the composite particles is about 1 m 2 / g to about 50m 2 / g range (in some designs, about 1m 2 / g to about 3m 2 / g; in other designs, about 3m 2 / g to about 12m 2 / g; in some other designs, about 12m 2 / g to about 18m 2 / g; in some other designs, about 18m 2 / g to about 30m 2 / g; in some other designs, about 30m 2 / g to about 50m 2 / g).

[0050] Yet another aspect relates to a battery electrode composition comprising a population of composite (e.g., nanocomposite) particles, wherein some or all of the composite particles comprise silicon and carbon (such that the total mass of silicon and carbon atoms comprises 75 wt.% to 100 wt.% of the mass of the nanocomposite particles). In one example, the population of particles can be characterized by a particle size distribution (PSD) as measured by laser particle size analysis (LPSA) of a well-dispersed particle suspension. Note that other types of particle size distributions (e.g., by SEM image analysis) can also be utilized (and may even result in more accurate measurements in some experiments). In some embodiments, the fiftieth percentile volume-weighted particle size parameter (D 50 ) is in the range of about 1.0 μm to about 12.0 μm (in some designs, about 1.0 μm to about 2.0 μm; in other designs, about 2.0 μm to about 4.0 μm; in still other designs, about 4.0 μm to about 6.0 μm; in still other designs, about 6.0 μm to about 12.0 μm). The cumulative volume fraction can be estimated by LPSA, which is defined as the cumulative volume of composite particles having a particle size of the threshold particle size or less divided by the total volume of all composite particles. In some embodiments (e.g., when D 50 In the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction at the threshold particle size of 4.6 μm is 90 vol.% (volume percentage) or less, or 85 vol.% or less, or 80 vol.% or less. In other embodiments (e.g., when D 50 In some other embodiments (e.g., when D 50 In the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction at the threshold particle size of 15 μm is 90 vol.% or less, or 85 vol.% or less, or 80 vol.% or less. Note that the presence of oversized particles may degrade the performance characteristics of the battery cell (e.g., reduce the stability of the battery cell, increase its impedance, reduce rate performance, etc.). In some embodiments (e.g., when D 50 In the range of about 2.0 μm to about 4.0 μm), the cumulative volume fraction at the threshold particle size of 10 μm is 80 vol.% or greater. In some embodiments (e.g., when D 50 In other embodiments (e.g., when D 50In other embodiments (e.g., when D 50 In other embodiments (e.g., when D 50 In some other embodiments (e.g., when D 50 In the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction at a threshold particle size of 32 μm is 90 vol. % or greater.

[0051] Yet another aspect relates to a battery electrode composition comprising a population of composite (e.g., nanocomposite) particles, wherein each composite particle comprises silicon and carbon (e.g., primarily sp 2 The particle size distribution (PSD) of the nanocomposite particles can be characterized by a particle size distribution (PSD) as determined by laser particle size analysis (LPSA). In some embodiments, the 50th percentile volume weighted particle size parameter (D 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 in the range of about 1 m 2 / g to about 50m 2 / g range (in some designs, about 1m 2 / g to about 3m 2 / g; in other designs, about 3m 2 / g to about 12m 2 / g; in some other designs, about 12m 2 / g to about 18m 2 / g; in some other designs, about 18m 2 / g to about 30m 2 / g; in some other designs, about 30m 2 / g to about 50m 2 / g).

[0052] Yet another aspect relates to a battery electrode composition comprising a population of composite (e.g., nanocomposite) particles, wherein each composite particle comprises silicon and carbon (primarily sp 2%. In some embodiments, the battery electrode composition may include one or more carbon-containing functional additives (e.g., additives that enhance the conductivity, rate capability, or mechanical properties of the electrode). In some embodiments, the carbon-containing functional additive is selected from the group consisting of carbon nanotubes (e.g., single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs)), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide (e.g., single-walled graphene oxide and multi-walled graphene oxide), and graphene (e.g., single-walled graphene and multi-walled graphene). In some embodiments, the battery electrode composition may include one or more binders (in some designs, two or more binder components).

[0053] Yet another aspect relates to a battery electrode. In some embodiments, the battery electrode comprises any of the foregoing battery electrode compositions disposed on or in a current collector. In some embodiments, the battery electrode comprises a battery electrode composition and a binder. In some embodiments, the coating density of the battery electrode is about 0.8 g / cm 3 to about 1.5g / cm 3 in the range of about 0.8 g / cm 3 to about 1.7g / cm 3 In some designs, about 0.8 g / cm 3 to about 0.9g / cm 3 ; in other designs, approximately 0.9 g / cm 3 to about 1.0g / cm 3 ; in some other designs, about 1.0 g / cm 3 to about 1.2g / cm 3 ; in some other designs, about 1.2 g / cm 3 to about 1.5g / cm 3 In still other designs, about 0.9 g / cm 3 to about 1.6g / cm 3 In still other designs, about 0.9 g / cm 3 to about 1.2g / cm 3 In some other designs, about 0.9g / cm 3 to about 1.7g / cm 3 In some embodiments, the battery electrode comprises a carbon-containing functional additive. In some embodiments, the carbon-containing functional additive may be selected from the group consisting of carbon nanotubes (e.g., SWCNTs and MWCNTs), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide (e.g., single-walled graphene oxide and multi-walled graphene oxide), and graphene (e.g., single-walled graphene and multi-walled graphene).

[0054] Yet another aspect relates to a battery electrode. In some embodiments, the battery electrode comprises any of the foregoing battery electrode compositions disposed on or in a current collector. In some embodiments, the battery electrode comprises a battery electrode composition and a binder. In some embodiments, the battery electrode composition comprises a population of jagged composite particles characterized by a particle size distribution (PSD) as determined by laser particle size distribution analysis (LPSA). In some embodiments, the 50th percentile volume weighted particle size parameter (D 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.%.

[0055] A battery electrode (e.g., an anode comprising silicon-carbon nanocomposite particles) can be characterized by an areal binder loading, where 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 jagged 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 the battery electrode (e.g., an anode comprising silicon-carbon nanocomposite particles) is about 2.0 mg / m 2 to about 15.0 mg / m 2 range (e.g., in some designs, approximately 2.0 mg / m 2 to about 5.0 mg / m 2 In other designs, approximately 5.0 mg / m 2 to about 9.0 mg / m 2 In some other designs, approximately 9.0 mg / m 2 to about 13.0 mg / m 2 ).

[0056] Yet another aspect relates to a lithium-ion battery. In some embodiments, the lithium-ion battery includes an anode current collector, a cathode current collector, any of the aforementioned battery electrodes configured as an anode disposed on or in the anode current collector, a cathode disposed on or in the cathode current collector, and an electrolyte ionically coupling the anode and cathode.

[0057] Yet another aspect relates to a process for manufacturing a battery electrode, comprising stages (A1), (A2), and (A3). Stage (A1) comprises providing any one of the above-described battery electrode compositions. Stage (A2) comprises preparing a slurry comprising the battery electrode composition and a binder. Stage (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 of 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 silicon-carbon particles) is about 0.8 g / cm 3 to about 1.5g / cm 3 In some designs, about 0.8 g / cm 3 to about 0.9g / cm 3 ; in other designs, approximately 0.9 g / cm 3 to about 1.0g / cm 3 ; in other designs, approximately 1.0 g / cm 3 to about 1.2g / cm 3 ; in other designs, approximately 1.2 g / cm 3 to about 1.5g / cm 3 In still other designs, about 0.9 g / cm 3 to about 1.6g / cm 3 In still other designs, about 0.9 g / cm 3 to about 1.2g / cm 3 In some embodiments, the coating density can be about 0.9 g / cm 3 to about 1.7g / cm 3 In some embodiments, the battery electrode comprises a carbon-containing functional additive. In some embodiments, the carbon-containing functional additive may be selected from the group consisting of 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 area binder loading, which 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 particle population. In some embodiments, the battery electrode (e.g., an anode comprising silicon-carbon nanocomposite particles) has an area binder loading of about 2.0 mg / m 2 to about 15.0 mg / m 2 range (e.g., in some designs, approximately 2.0 mg / m 2 to about 5.0 mg / m2 In other designs, approximately 5.0 mg / m 2 to about 9.0 mg / m 2 In still other designs, about 9.0 mg / m 2 to about 13.0 mg / m 2 ).

[0058] Yet another aspect relates to a method for manufacturing a lithium-ion battery, comprising stages (B1), (B2), and (B3). Stage (B1) comprises manufacturing a battery electrode according to any of the above-described processes for manufacturing a battery electrode, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector. Stage (B2) comprises manufacturing or providing a cathode disposed on or in a cathode current collector. Stage (B3) comprises assembling a battery cell from an anode and a cathode (and, in some designs, a porous separator or porous separator layer disposed between the anode and cathode), and filling the space between the anode and cathode with an electrolyte that ionically couples the anode and cathode to form a lithium-ion battery.

[0059] Yet another aspect relates to a method for manufacturing a lithium-ion battery, comprising stages (C1), (C2), and (C3). Stage (C1) comprises providing any of the battery electrodes described above, wherein the battery electrode is configured as an anode and the current collector is configured as an anode current collector. Stage (C2) comprises manufacturing or providing a cathode disposed on or in a cathode current collector. Stage (C3) comprises assembling a battery cell from an anode and a cathode (and, in some designs, a porous separator or porous separator layer disposed between the anode and cathode), and filling the space between the anode and cathode with an electrolyte that ionically couples the anode and cathode to form a lithium-ion battery.

[0060] In one aspect, a battery electrode composition includes a population of jagged composite particles, wherein each jagged composite particle comprises silicon and carbon; wherein: 90% or more of the jagged composite particles in the population are characterized by an aspect ratio of 2.3 or less; 50% or more of the jagged composite particles in the population are characterized by an aspect ratio of 1.25 or greater; and the population is characterized by a particle size distribution (PSD) as determined by laser particle size analysis (LPSA) such that a 50th percentile volume-weighted particle size parameter D of the PSD is 0.05. 50 In the range of about 2.0 μm to about 8.0 μm.

[0061] In some aspects, about 90% or more of the jagged composite particles in a population of particles are characterized by an aspect ratio of about 2.1 or less.

[0062] In some aspects, about 50% or more of the jagged composite particles in a population of particles are characterized by an aspect ratio of about 1.35 or greater.

[0063] In some aspects, about 10% or more of the jagged composite particles in a population of particles are characterized by an aspect ratio of about 1.3 or less.

[0064] In some aspects, the mass fraction of silicon in the jagged composite particles ranges from about 3 wt.% to about 80 wt.%.

[0065] In some aspects, the mass fraction of silicon is in a range from about 35 wt. % to about 70 wt. %.

[0066] In some aspects, the mass fraction of silicon is in a range from about 35 wt. % to about 50 wt. %.

[0067] In some aspects, the mass fraction of silicon is in a range from about 40 wt. % to about 55 wt. %.

[0068] In some aspects, the Brunauer-Emmett-Teller (BET) specific surface area of ​​the particle population is about 3 m 2 / g to about 18m 2 / g range.

[0069] In some respects, D 50 In the range of about 2.0 μm to about 4.0 μm.

[0070] In some aspects, the cumulative volume fraction (defined as the cumulative volume of jagged composite particles having a particle size of about 4.6 μm or less divided by the total volume of all jagged composite particles) is about 90 vol. % or less; and the particle size, cumulative volume, and total volume are estimated by LPSA.

[0071] In some aspects, the cumulative volume fraction is about 85 vol. % or less.

[0072] In some aspects, the cumulative volume fraction is about 80 vol. % or less.

[0073] In some respects, D 50 In the range of about 6.0 μm to about 8.0 μm.

[0074] In some aspects, the Brunauer-Emmett-Teller (BET) specific surface area of ​​the particle population is about 3 m 2 / g to about 12m 2 / g range.

[0075] In one aspect, a battery electrode comprises the battery electrode composition of claim 1 disposed on or in a current collector, wherein the battery electrode comprises a binder.

[0076] In some aspects, the coating density of the battery electrode is about 0.9 g / cm 3 to about 1.0g / cm 3 within the range.

[0077] In some aspects, the battery electrode further comprises a carbon-containing functional additive.

[0078] In some aspects, the carbon-containing functional additive is selected from the group consisting of: carbon nanotubes, carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide, and graphene.

[0079] In some aspects, the PSD of a particle population is D 50 in the range of about 6.0 μm 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. %.

[0080] In some aspects, the PSD of a particle population is D 50 in the range of about 6.0 μm to about 8.0 μm; and the areal binder loading of the battery electrode is about 9.0 mg / m 2 to about 13.0 mg / m 2 where 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 particle population.

[0081] In one aspect, a lithium ion battery includes: an anode current collector; a cathode current collector; the battery electrode configured as an anode, whose current collector is configured as the anode current collector; a cathode disposed on or in the cathode current collector; and an electrolyte ionically coupling the anode and cathode.

[0082] In one aspect, a method of making a battery electrode comprises: (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 a battery electrode (note that in some designs, this stage may typically include evaporating the slurry solvent and / or densifying the battery electrode to a desired value).

[0083] In one aspect, a method of manufacturing a lithium-ion battery comprises: (B1) manufacturing a battery electrode by the methods according to (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) manufacturing or providing a cathode disposed on or in a cathode current collector; and (B3) assembling a battery cell from an anode and a cathode (and, in some designs, a porous separator or porous separator layer located between the anode and cathode) and filling the space between the anode and cathode with an electrolyte that ionically couples the anode and cathode to form a lithium-ion battery.

[0084] In one aspect, a method of manufacturing a lithium-ion battery includes: (C1) providing a battery electrode, 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 in a cathode current collector; and (C3) assembling a battery cell from an anode and a cathode (and, in some designs, a porous separator or porous separator layer disposed between the anode and cathode) and filling the space between the anode and cathode with an electrolyte that ionically couples the anode and cathode to form a lithium-ion battery.

[0085] Other objects and advantages associated with the aspects disclosed herein will be apparent to those skilled in the art based on the accompanying drawings and detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0086] The accompanying drawings are presented to assist in describing embodiments of the present invention and are provided solely for the purpose of illustrating the embodiments and not for limiting the same. Unless the context indicates or implies otherwise, the different hatching, shading, and / or fill patterns in the drawings are intended solely to provide a contrast between different components, elements, features, etc. and are not intended to convey specific materials, colors, or other characteristics that may be used for the particular pattern employed that are not limited to the present invention.

[0087] Figure 1 An exemplary lithium-ion battery is shown in which the components, materials, processes, and other techniques described herein may be implemented.

[0088] Figure 2 is a flow chart of a method of manufacturing a rechargeable lithium-ion battery cell according to certain embodiments.

[0089] Figure 3 is a flow chart of a process for making anode (or cathode) particles, including subjecting the carbon particles to an activation process, according to certain embodiments.

[0090] Figure 4 A schematic diagram of a jagged particle 400 and a graph 420 showing the correlation of the cumulative particle number distribution of the jagged composite particles with the aspect ratio of the jagged composite particles are shown.

[0091] Figure 5 Shown from D 50 SEM image 502 of jagged composite particles taken from a particle group of about 2.5 μm and a 50 SEM image 504 of jagged composite material particles taken of a cluster of particles approximately 7 μm in size.

[0092] Figure 6 Shown from D 50 SEM image 602 of jagged composite particles taken from a particle group of about 9 μm and a 50 SEM image 604 of jagged composite particles taken from a cluster of particles approximately 14 μm in size.

[0093] Figure 7 The full width D of each exemplary serrated composite particle population is shown. 90 -D 10 With D 50 702, and the mass fraction of silicon in the composite particles versus D for each exemplary particle population. 50 Graph 704 of the correlation.

[0094] Figure 8 SEM images 802, 804 of cross sections of electrode coatings are shown, the electrode coatings comprising D 50 The jagged composite particle group sample of about 4 μm and D 50 A sample of a jagged composite particle group of approximately 14 μm.

[0095] Figure 9 The cycle life of each exemplary particle population is shown versus D 50 Graph 902 of the correlation of the normalized coating thickness variation and D for each exemplary particle population. 50 Graph 904 of the correlation.

[0096] Figure 10 The volumetric energy density and D of each exemplary serrated composite particle population are shown. 50 Graph 1002 of the correlation of volume charge density and D for each exemplary particle population. 50 Graph 1004 of the correlation.

[0097] Figure 11 The normalized high rate discharge capacity density and D for each exemplary serrated composite particle population are shown. 50 Graph 1102 of the correlation of discharge voltage and D for each exemplary particle population. 50 Graph 1104 of the correlation.

[0098] Figure 12 Shown for the inclusion of D 50 Graph 1202 of the normalized capacity (expressed as a fraction of the reference capacity) versus the charge rate (C-rate) for lithium-ion battery test cells of approximately 3 μm and approximately 5 μm jagged composite particle populations.

[0099] Figure 13 The first cycle efficiency and D of each exemplary particle population are shown. 50 Graph 1302 of the correlation of the formation efficiency of each exemplary particle population with D 50 Graph 1304 of the correlation.

[0100] Figure 14 The internal resistance and D of each exemplary serrated composite particle group are shown. 50 Graph 1402 of the correlation of coating density and D for each exemplary particle population. 50 Graph 1404 of the correlation.

[0101] Figure 15 The Brunauer-Emmett-Teller specific surface area (BET-SSA) and D 50 Graph 1502 of the correlation of area binder loading and D for each exemplary particle population. 50 Graph 1504 of the correlation.

[0102] Figure 16 A graph 1602 is shown, which represents D 50 The cycle life value and cumulative volume fraction (D 50 The cumulative volume fraction is defined as D 50 The value is the threshold D 50 The cumulative volume of particles with a value of 0 or less is divided by the total volume of all particles.

[0103] Figure 17 Graph 1702 shows the correlation of area adhesive loading and adhesive mass fraction for each test unit. The test units include D 50 The control sample test unit includes D 50 The particle size is about 5.35 μm.

[0104] Figure 18 Shown Figure 17 A graph 1802 showing the correlation between the cycle life of each test unit and the mass fraction of the adhesive, and Figure 17Graph 1804 showing the correlation between the normalized coating thickness variation and the binder mass fraction for each test unit.

[0105] Figure 19 Shown Figure 17 Graph 1902 showing the correlation between the volume energy density (VED) of each test unit and the binder mass fraction; and Figure 17 Graph 1904 showing the dependence of the volume charge density (VQD) of each test cell on the binder mass fraction.

[0106] Figure 20 Shown Figure 17 Graph 2002 showing the correlation between the discharge voltage of each test unit and the binder mass fraction and Figure 17 Graph 2004 showing the correlation between the internal resistance of each test unit and the mass fraction of the adhesive.

[0107] Figure 21 Shown Figure 17 Graph 2102 showing the correlation between the formation efficiency of each test unit and the mass fraction of the binder and Figure 17 Graph 2104 showing the correlation between the first cycle efficiency of each test unit and the binder mass fraction.

[0108] Figure 22 An SEM image 2201 of a population of jagged composite particles (including agglomerates of jagged particles) is shown without any optimization of the particle size distribution (PSD) of the particle population, and an SEM image 2202 of a cross-section of an electrode coating comprising a mixture of the jagged particle population shown in 2201 and graphite particles as the electrode active material. 50 It is about 10 μm, and the particle group includes fine particles ("fine particles") and coarse particles.

[0109] Figure 23 2301 shows an SEM image of a jagged composite particle group after optimizing the particle size distribution (PSD) of the particle group, and an SEM image of a cross-section of an electrode coating comprising a mixture of jagged particles and graphite particles shown in 2301. Before optimizing its PSD, the particle group had a PSD of 50 The PSD optimization process includes the removal of fine particles (the D 50 about 1.5μm) and remove coarse particles (the D 50 about 15μm).

[0110] Figure 24Graphs 2401 and 2402 show volume weighted particle size distributions (PSDs) for exemplary populations of jagged composite particles. Graph 2401 shows the volume weighted particle size distributions (PSDs) for an exemplary population of jagged composite particles before any optimization of the respective PSDs. 50 Graph 2402 shows: (1) the PSD of an exemplary particle population before any optimization of its PSD (D 50 about 10.1 μm) and (2) the PSD of the exemplary particle population after its PSD is optimized (D 50 The PSD optimization includes fine particle removal and coarse particle removal. Due to these PSD optimization processes, the PSD changes from a relatively wide PSD (e.g., a larger span, a larger full width at half maximum (FWHM)) to a relatively narrow PSD (i.e., a smaller span, a smaller FWHM).

[0111] Figure 25 Table 1 is shown, which lists selected properties of an exemplary particle population of serrated composite particles (D 10 、D 50 、D 90 、D 99 , span, FWHM, D 10 / D 50 , BET-SSA, and whether the particle population has not undergone any optimization of its PSD (so-called "broad" PSD) or has undergone optimization of its PSD (so-called "narrow" PSD)), as well as selected characteristics of electrode coatings and battery cells obtained from various exemplary particle populations of jagged composite particles (estimated capacity of electrode active material containing corresponding jagged composite particles and graphite particles, electrode coating density and cycle life).

[0112] Figure 26 An SEM image 2601 of a population of spherical composite particles is shown. In the example shown, the D 50 The values ​​range from about 5 μm to about 7 μm.

[0113] Figure 27 Graph 2701 is shown, which shows the BET-SSA values ​​of an exemplary particle population of composite particles (jagged composite particles before PSD optimization (exhibiting so-called "wide" PSD), jagged composite particles after PSD optimization (exhibiting so-called "narrow" PSD), and spherical particles) and their corresponding D 50 In the example shown, D 50 The values ​​were measured by LPSA.

[0114] Figure 28Graphs 2802, 2804, and 2806 illustrate selected PSD characteristics of exemplary particle populations of jagged composite particles. Graph 2802 illustrates the PSD characteristics of various particle populations of jagged composite particles. 99 Value and D 50 The correlation of the values ​​of PSD for each particle population that has not undergone PSD optimization (so-called "wide" PSD) and the particle population that has undergone PSD optimization (so-called "narrow" PSD) is shown in Figure 2804. 90 Value and D 50 The correlation of the values ​​of PSD for each particle population of jagged composite particles is shown, illustrating the trend between the particle population that has not undergone PSD optimization (so-called "wide" PSD) and the particle population that has undergone PSD optimization (so-called "narrow" PSD). 10 Value and D 50 The correlation of the values ​​illustrates the trend between the population of particles that did not undergo PSD optimization (so-called “broad” PSD) and the population of particles that did undergo PSD optimization (so-called “narrow” PSD).

[0115] Figure 29 Graphs 2901 and 2902 are shown, which represent the cycle life performance of lithium ion batteries made using various exemplary particle groups of serrated composite particles and the D of each exemplary particle group. 50 The correlation of the values. Graphs 2901 and 2902 show the trends between a population of particles that have not undergone PSD optimization (so-called "wide" PSD) and a population of particles that have undergone PSD optimization (so-called "narrow" PSD). In the example shown, a lithium-ion battery employed an anode comprising a mixture of jagged composite particles and graphite particles ("active material mixture"). Graph 2901 shows the cycle life performance of a lithium-ion battery using an active material mixture having a lithium ion capacity of approximately 600 mAh / g. Graph 2902 shows the cycle life performance of a lithium-ion battery using an active material mixture having a lithium ion capacity of approximately 1000 mAh / g.

[0116] Figure 30 Graphs 3002, 3004, 3006, and 3008 are shown, which represent selected PSD characteristics of an exemplary population of jagged composite particles versus D for the exemplary population. 50 The relevance of the value. Figure 30 In the example shown, the PSD of each particle population was altered by comminution (jet milling or ball milling). Graphs 3002, 3004, 3006, and 3008 show the trends between the particle population that underwent ball milling and the particle population that underwent jet milling. The PSD characteristics shown are the span of 3002, the D of 3004, and the PSD of 3005. 90 、3006D10 and the volume fraction of fine particles (defined as particles with a diameter of 1 μm and below as measured by LPSA) in the particle population of 3008. DETAILED DESCRIPTION

[0117] Various aspects of the present invention are disclosed in the following description of specific embodiments of the invention and the associated drawings. The term "embodiments of the invention" does not require that all embodiments of the invention include the discussed features, advantages, processes, or modes of operation, and alternative embodiments may be devised without departing from the scope of the invention. Furthermore, well-known elements of the invention may not be described in detail or may be omitted to avoid obscuring other, more relevant details.

[0118] Aspects of the present invention provide for the production of advanced carbon-containing (e.g., primarily sp-containing) 2 The present invention relates to a method for producing bonded graphitic carbon (graphitic carbon) composite particles for use in electrodes (e.g., anode electrodes or cathode electrodes) of lithium-ion, sodium-ion, or potassium-ion rechargeable batteries and other types of batteries, in electrochemical capacitors, and in hybrid electrochemical energy storage devices.

[0119] Any numerical range described herein with respect to any embodiment of the present invention is intended to define not only the upper and lower limits of the relevant numerical range, but also implicitly disclose each discrete value within the range in units or increments consistent with the level of precision characterizing the upper and lower limits. For example, a numerical distance range of 7 nm to 20 nm (i.e., with a level of precision in units of 1 or increments of 1) includes the set of [7, 8, 9, 10, ..., 19, 20] (in nm), just as the intermediate numbers 8 to 19 are explicitly disclosed in units of 1 or increments of 1. In another example, a temperature range of about -120°C to about -60°C includes the set of temperature ranges (in °C): about -120°C to about -119°C, about -119°C to about -118°C, ..., about -61°C to about -60°C, just as the intermediate numbers (in °C) between -120°C and -60°C are explicitly disclosed in increments. In yet another example, a numerical percentage range from 30.92% to 47.44% (i.e., a level of precision in percents or increments) encompasses the set (in %) [30.92, 30.93, 30.94, ..., 47.43, 47.44] as if the intervening numbers between 30.92% and 47.44% in percents or increments were explicitly disclosed. Thus, it is intended that any intervening numbers included in any disclosed numerical range be interpreted as if they had been explicitly disclosed, and any such intervening numbers may therefore constitute their own upper and / or lower limits for sub-ranges within the broader range. Thus, it is intended that each sub-range (e.g., each range that includes at least one intervening number from the broader range as an upper and / or lower limit) be interpreted as implicitly disclosed by virtue of the explicit disclosure of the broader range. In another example, numerical ranges with upper and lower limits defined at different levels of precision are to be interpreted in increments corresponding to the limits with the higher levels of precision. For example, the numerical percentage range from 30.92% to 47.4% (i.e., with precision levels in units or increments of one hundredth and one tenth, respectively) encompasses the set (in %) [30.92, 30.93, 30.94, ..., 47.39, 47.40] just as if 47.4% (a precision level of one tenth) were stated as 47.40% (a precision level of one hundredth), and as if intermediate numbers between 30.92 and 47.40 were expressly disclosed in units or increments of one hundredth.

[0120] It is understood that the level of precision of any particular measurement, threshold, or other imprecise parameter may vary depending on various factors, such as the measurement instrument, environmental conditions, etc. Therefore, references to these measurements or thresholds below may be interpreted as corresponding values ​​exhibiting a pseudo-precise level of precision (e.g., a threshold of 80% includes 80.0000…%). Alternatively, references to these measurements or thresholds may be described by a modifier that defines the pseudo-precise value plus a range extending above and / or below the pseudo-precise value. For example, the 80% threshold described above may be interpreted as "about," "approximately," "near," "≈," or "~" 80%, which includes "exactly" 80% (e.g., 80.0000…%) plus a range around 80%. In some designs, the range encompassed by the modifiers "about," "approximately," "near," or "~" around the measurement or threshold may include the level of precision of the corresponding measurement or threshold that can be measured using the most accurate commercially available instrument as of the priority date of this application.

[0121] While the following description may describe certain examples in the context of lithium metal and lithium ion batteries (for brevity and convenience, and due to the current popularity of lithium technology), it will be appreciated that various aspects may also be applicable to other rechargeable and primary batteries (e.g., sodium and sodium ion batteries, magnesium and magnesium ion batteries, potassium and potassium ion batteries, calcium and calcium ion batteries, and other metal and metal ion batteries, alkaline batteries, flow batteries, etc.), as well as electrochemical capacitors and hybrid energy storage devices.

[0122] While the following description may describe certain examples in the context of composite materials comprising alloy-type anode active materials (e.g., silicon (Si), tin (Sn), antimony (Sb), aluminum (Al), etc.), it should be understood that various aspects may also 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 hybrid electrochemical energy storage mechanisms. Note that the choice of high-capacity alloy-type (conversion-type) anode materials may vary for sodium and sodium ions, magnesium and magnesium ions, potassium and potassium ions, calcium and calcium ions, and lithium or lithium ions. For example, while silicon may be a preferred alloy-type material for lithium or lithium-ion batteries, tin or antimony or alloys containing tin or antimony may be preferred alloy-type materials for sodium or sodium-ion batteries.

[0123] Although the following description may also describe certain examples of material formulations in a lithium-free state (e.g., as in a silicon-containing nanocomposite anode or metal fluoride cathode), it should be understood that various aspects may be applicable to lithium-containing electrodes and active materials (e.g., partially or fully lithiated silicon-containing anodes, or partially or fully lithiated silicon-containing anode particles, partially or fully lithiated metal fluoride cathodes (e.g., mixtures of LiF with metals such as Cu, Fe, Ni, Bi, various other metals and metal alloys, and mixtures of these and other metals, etc.), or partially or fully lithiated metal halide cathode particles, partially or fully lithiated chalcogenides (e.g., Li2S, Li2S / metal mixtures, Li2Se, Li2Se / metal mixtures, Li2S-Li2Se mixtures, various other compositions containing lithiated chalcogenides, etc.), partially or fully lithiated metal oxides (e.g., Li2O, Li2O / metal mixtures, etc.), partially or fully lithiated carbon, etc.). In some designs, various material properties (e.g., at the particle level, inter-particle level, electrode level, etc.) may vary depending on whether the active material particles are in a lithium-free state, a partially lithiated state, or a fully lithiated state. Such lithium-related material properties may include particle pore volume, electrode pore volume, etc. Below, unless otherwise stated or implied, it can be assumed that references to such lithium-related material properties (e.g., at the particle level, inter-particle level, electrode level, etc.) are as if the active material particles are in a lithium-free state. In addition, some of the examples below are characterized at the electrode level (e.g., as opposed to the particle level or inter-particle level or cell level, etc.). Below, unless otherwise stated or implied, it can be assumed that references to such electrode-level properties (e.g., electrode porosity or areal capacity loading or weight / volume capacity, etc.) refer to the electrode components (e.g., active material particles, binder, conductive additives, etc.) excluding the current collector.

[0124] 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.). Note that one of ordinary skill in the art is generally able to select (and is assumed herein to have selected) the most appropriate measurement technique for any particular measurement. Furthermore, in some cases, the most appropriate measurement technique may include a combination of multiple techniques. While the following table characterizes various measurement type options for specific material types and specific material properties, certain embodiments of the present invention may be more specifically characterized in the context of specific measurement techniques and / or specific commercial instruments, if necessary. Note that while the following table characterizes measurement results with respect to active material particles, similar measurements can also be performed on other particle types, such as precursor particles (e.g., carbon particles, etc.). Therefore, unless otherwise stated, the following table provides examples of how one of ordinary skill in the art can easily measure these material properties using commercial instruments: Table of techniques and instruments for measuring material properties

[0125] In some embodiments described below, certain parameters (e.g., temperature, state of charge (SOC), etc.) are defined using relative terms such as low, reduced, high, increased, and elevated. With respect to temperature, unless otherwise noted, such relative terms may be characterized relative to a battery cell storage temperature or a battery cell operating temperature, depending on the context of the example. With respect to SOC, unless otherwise noted, a high SOC may be defined as an SOC greater than approximately 70% (e.g., in some designs, approximately 70-80% SOC; in some designs, approximately 80-90% SOC; in some designs, approximately 90-100% SOC).

[0126] Reference is made below to various battery electrode compositions. Such battery electrode compositions may be in the form of a "dry" powder (e.g., prior to mixing into or suspending in a slurry), in the slurry itself (e.g., in suspension), or in a cast electrode (e.g., cast onto and / or into a current collector to form an electrode, bound together with a suitable binder, dried, and optionally coated and / or calendered).

[0127] Although the following description may describe a silicon-carbon composite (eg, nanocomposite) anode active material (eg, comprising silicon (Si) and carbon (C) (eg, primarily sp 2 % to about 100 wt. % of the total mass of the composite particles), but it should be understood that various aspects can be applicable to other types of high capacity silicon-containing anode active materials (including but not limited to: for example, various silicon-containing or silicon oxide-containing or silicon nitride-containing or silicon oxynitride-containing or silicon phosphide-containing particles, or particles comprising mixtures or alloys or other combinations of such active materials, various other types of silicon-containing composite materials, including but not limited to core-shell or hierarchical or nanocomposite particles, etc.).

[0128] While the following description may describe certain examples in the context of some specific alloy and conversion chemistries for anode and cathode active materials for lithium-ion batteries (e.g., silicon-containing anodes, or metal fluoride-containing or lithium sulfide-containing cathodes), it should be understood that various aspects may be applicable to other chemistries for lithium-ion batteries (other conversion and alloy electrodes and various intercalation anodes and cathodes) and other battery chemistries. In the case of metal-ion batteries (such as lithium-ion batteries), examples of other suitable conversion 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, and the like.

[0129] While the following description may describe certain examples in the context of jagged (e.g., Si-containing, such as Si-C, etc.) nanocomposite particles having a relatively small range of aspect ratios, it should be understood that various aspects can be applicable to nanocomposite particles of other shapes (e.g., Si-containing, such as Si-C, etc.), including but not limited to cylindrical or fibrous (e.g., Si-containing, such as Si-C, etc.) nanocomposite particles (e.g., aspect ratios in the range of about 1 to about 200; in some designs, aspect ratios of about 1 to about 5; in other designs, aspect ratios of about 5 to about 10; in other designs, aspect ratios of about 10 to about 200), spherical or spherical particles, to name a few illustrative examples.

[0130] During the operation of a battery (e.g., a lithium-ion battery), a conversion material changes (converts) from one crystal structure to another (hence the term "conversion" type). This process is accompanied by the breaking of chemical bonds and the formation of new bonds. During the operation of a (e.g., lithium-ion) battery, lithium ions are inserted into the alloy-type material to form a lithium alloy (hence the term "alloy" type). Sometimes, "alloy"-type electrode materials are considered a subclass of "conversion"-type electrode materials.

[0131] In one or more embodiments of the present invention, a preferred anode for a battery cell may include a mixture of Si-C nanocomposite materials (e.g., particles) and graphite (e.g., particles) as the anode active material, a so-called blended anode. In addition to the anode active material particles, the anode may also include inactive materials, such as binders (e.g., polymer binders) and other functional additives (e.g., surfactants, conductive additives). In some embodiments, the anode active material may be in the range of about 90 wt.% (weight percent) to about 98 wt.% of the anode. For example, the anode active material particles may account for about 95.5 wt.% of the anode. In some embodiments, the blended anode may include Si-C nanocomposite materials (e.g., particles) accounting for about 7 wt.% to about 75 wt.% of the anode and graphite (e.g., particles) constituting the remaining mass (weight) of the anode active material particles. In some embodiments where the anode active material particles account for about 95.5 wt.% of the blended anode, the blended anode (comprising active material particles and inactive materials) may include about 7 wt.% of Si-C nanocomposite materials (e.g., particles) and about 88.5 wt.% of graphite particles. In some embodiments where the anode active material particles comprise approximately 95.5 wt.% of the blended anode, the blended anode (comprising active material particles and inactive material) may comprise approximately 19 wt.% Si-C nanocomposite (e.g., particles) and approximately 76.5 wt.% graphite particles. In some embodiments where the anode active material particles comprise approximately 95.5 wt.% of the blended anode, the blended anode (comprising active material particles and inactive material) may comprise approximately 35 wt.% Si-C nanocomposite (e.g., particles) and approximately 60.5 wt.% graphite particles. In some embodiments where the anode active material particles comprise approximately 94.5 wt.% of the blended anode, the blended anode (comprising active material particles and inactive material) may comprise approximately 50 wt.% Si-C nanocomposite (e.g., particles) and approximately 44.5 wt.% graphite particles. In some embodiments where the anode active material particles comprise about 92.5 wt.% of the blended anode, the blended anode (comprising active material particles and inactive material) may comprise about 69.4 wt.% Si-C nanocomposite (e.g., particles) and about 23.1 wt.% graphite particles. In some designs, a higher fraction of Si-C composite particles in the blended anode may benefit from a higher fraction of inactive material to achieve superior cycling stability and other performance characteristics.

[0132] Although the following description may also describe certain examples of blended anode formulations expressed in terms of mass (wt.%) of Si-C nanocomposite materials (e.g., particles), it should be understood that various aspects of the present invention may be applicable to blended anode formulations expressed in terms of wt.% of Si in the anode. In some embodiments, a blended anode composition having about 7 wt.% Si-C nanocomposite materials (e.g., particles) may correspond to, for example, about 3-3.5 wt.% Si in the blended anode. In some embodiments, a blended anode composition having about 19 wt.% Si-C nanocomposite materials corresponds to about 8-9.5 wt.% Si in the blended anode. In some embodiments, a blended anode composition having about 35 wt.% Si-C nanocomposite materials (e.g., particles) corresponds to about 15-18 wt.% Si in the blended anode. In some embodiments, a blended anode composition having about 50 wt.% Si-C nanocomposite materials (e.g., particles) corresponds to about 21-30 wt.% Si in the blended anode. In various embodiments, a blended anode can be obtained wherein the mass (weight) of silicon is in a range from about 3 wt.% to about 30 wt.% of the total mass of the anode.

[0133] While the following description may also describe certain examples of blended anode formulations expressed as a mass percentage (wt.%) of Si-C nanocomposite (e.g., particles) relative to all active materials in the anode, it should be understood that various aspects of the present invention can be applied to blended anode formulations in which a portion (e.g., a percentage (%)) of the total capacity of the blended anode is attributed to the capacity of silicon. In some embodiments, about 25% of the total capacity of the blended anode is obtained from the Si-C nanocomposite (e.g., particles) in a blended anode composition having about 7 wt.% Si-C nanocomposite (e.g., particles) and about 93 wt.% graphite (e.g., particles). In some other embodiments, about 50% of the total capacity of the blended anode is obtained from the Si-C nanocomposite (e.g., particles) in a blended anode composition having about 19 wt.% Si-C nanocomposite (e.g., particles) and about 81 wt.% graphite (e.g., particles). In some other embodiments, about 70% of the total capacity of the blended anode is obtained from the Si-C nanocomposite in a blended anode composition having about 35 wt.% Si-C nanocomposite (e.g., particles) and about 65 wt.% graphite (e.g., particles). In some other embodiments, about 80% of the total capacity of the blended anode is obtained from the Si-C nanocomposite (e.g., particles) in a blended anode composition having 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 blended anode provided by the Si-C nanocomposite (e.g., particles) depends on the weight percentage of such particles (e.g., relative to all active materials in the anode) and the specific capacity of the Si-C nanocomposite. For example, for the same weight percentage, higher specific capacity Si-C nanocomposite particles will provide a higher percentage of the total capacity.

[0134] While the following description may describe certain examples of suitable intercalated graphites for use in conjunction with Si-C nanocomposites (e.g., particles) in blends, it should be understood that various aspects of the present invention may be applicable to soft synthetic graphites (or, broadly, soft carbon), hard synthetic graphites (or, broadly, hard carbon), and natural graphites (which may, for example, be pitch carbon coated), including but not limited to those graphites exhibiting a discharge capacity of about 320 to about 372 mAh / g (e.g., in some designs, about 320 to about 350 mAh / g; or in other designs, about 350 to about 362 mAh / g; or in other designs, about 362 to about 372 mAh / g;); including but not limited to those graphites exhibiting low, medium, and high swelling; including but not limited to those graphites exhibiting good compression and poor compression; including but not limited to those graphites exhibiting about 1 m 2 / g to about 4m 2 / g Brunauer-Emmett-Teller (BET) specific surface area; including but not limited to those graphites that exhibit a lithiation efficiency of about 90% or more; including but not limited to those graphites with an average particle size of about 8 μm to about 18 μm; including but not limited to those graphites that exhibit about 1.5 g / cm 3 to about 2.3g / cm 3 (For example, in some designs, about 1.5 g / cm 3 To approximately 1.8g / cm 3 ; in other designs, approximately 1.8 g / cm 3 To approximately 2.3g / cm 3 ) of the true density of the graphite; including but not limited to those graphites that exhibit poor, moderate or good cycle life when used alone in lithium ion battery anodes (e.g., without Si-C composites or other active particles); including but not limited to those graphites that are coated and include a coating having a coating thickness to significantly improve compression and elasticity during cycling.

[0135] Although the following description may be found in 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 ferric sulfate fluoride (LiFeSO4F), various lithium-excess materials (e.g., lithium-excess (rock salt) transition metal oxides and oxyfluorides such as 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 0.7Zr 0.05 W 0.035 O 1.95 F 0.1 、Li 1.2 Ni 0.333 Ti 0.333 Mo 0.133 O2 and many other materials), various high-capacity lithium-ion based materials with partial substitution of oxygen for fluorine or iodine (e.g., rock salt Li2Mn 2 / 3 Nb 1 / 3 O2F、Li2Mn 1 / 2 Ti 1 / 2 O2F、Li 1.5 Na 0.5 MnO 2.85 I 0.12 Certain examples of suitable intercalation cathodes (including high voltage cathodes) that rely on lithium (Li) intercalation and variations in TM oxidation state (including but not limited to those that may be doped or heavily doped; including but not limited to those that have gradients in composition or core-shell morphology; including but not limited to those that may be partially fluorinated or contain significant amounts of TM in their composition) are described in the context of numerous other types of lithium-containing disordered layered Tavorite-type olivine or spinel-type active materials or mixtures thereof (which contain at least oxygen or fluorine or sulfur and at least one transition metal and other lithium transition metal (TM) oxides or phosphates or sulfates (or mixed) cathode or anode active materials). % fluorine (e.g., those containing about 0.001-10 at. %), etc.), but it should be understood that various aspects can be applicable to high voltage lithium transition metal oxide (or phosphate or sulfate or mixed or other) cathodes in which TM and oxygen (O) are covalently bound and TM and O participate in electrochemical reduction-oxidation (redox) reactions during both charge and discharge (including but not limited to those oxides or phosphates or sulfates or mixed cathodes that may contain at least about 0.25 at. % of Mn, Fe, Ni, Co, Nb, Mg, Cr, Mo, Zr, W, Ta, Ti, Hf, Y, La, Sb, V, Sn, Si or Ge).

[0136] Figure 1An exemplary metal ion (e.g., lithium ion) battery is shown, in which the electrode particles, components, materials, methods, and other techniques, or combinations thereof, described herein can be applied according to various embodiments. For illustrative purposes, a cylindrical battery is shown here, but other types of arrangements, including prismatic or pouch (laminated) batteries, may also be used as needed. An exemplary battery 100 includes a negative electrode (anode electrode or anode) 102, a positive electrode (cathode electrode or cathode) 103, a separator 104 placed between the anode 102 and the cathode 103, an electrolyte (implicitly shown) impregnating the separator 104, a battery housing 105, and a seal 106 that seals the battery housing 105. The electrolyte couples the anode (negative electrode) and the cathode (positive electrode) ionically. The electrolyte is placed between the anode electrode and the cathode electrode. In some embodiments, the battery 100 also includes an anode current collector and a cathode current collector. The anode is arranged on or in the anode current collector, and the cathode is arranged on or in the cathode current collector.

[0137] Figure 2 shows the use for making Figure 1 FIG1 is a flow chart of a process 120 for a lithium-ion battery of an exemplary battery 100 of FIG1 . In the example shown, process 120 includes operations 122, 124, 132, 134, and 140. The flow chart includes an anode branch (left branch) and a cathode branch (right branch), the anode branch including operations 122 and 124, and the cathode branch including 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, wherein Si-containing active material is deposited within the pores of the particle core) are prepared; in operation 124, the anode is formed. Similarly, in operation 132, cathode particles (e.g., conventional cathode particles or core-shell cathode particles or composite cathode particles, including but not limited to composite particles comprising a conversion cathode material, wherein the conversion cathode active material is deposited within the pores of the particle core) are prepared; in operation 134, the cathode is formed.

[0138] Electrodes used in lithium-ion batteries are typically produced by: (i) forming a slurry containing active material, conductive additives, a binder solution, and in some cases, a surfactant or other functional additive; (ii) casting the slurry onto a metal foil (e.g., Cu or Cu alloy foil for most anodes, Al or Al alloy foil for most cathodes); and (iii) drying the cast electrode to completely evaporate the solvent. In some embodiments, stage (iii) may also include densifying the battery electrode to a desired value. Note that metal mesh, metal foam, or very rough metal foil (e.g., including metal nanowires or metal nanosheets on its surface) can be used in some designs (e.g., for higher areal capacity loading or to achieve faster charging, etc.). It should also be noted that metal-coated thin polymer sheets can also be used in some designs (e.g., to improve safety or reduce current collector weight, etc.). It should also be noted that porous metal foil or composite (e.g., nanocomposite) metal foil can be used in some designs (e.g., to improve performance, reduce weight, etc.).

[0139] Operation 124 includes fabricating an anode electrode, wherein the anode electrode comprises the anode particles prepared in operation 122. For example, operation 124 may include: (1) preparing an anode slurry comprising the anode particles (e.g., from operation 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 may typically include evaporating the slurry solvent and / or densifying the battery electrode to a desired value. For example, the other anode slurry components may include: other electrochemically active anode active materials (e.g., natural or synthetic graphite, soft carbon, or hard carbon), conductive additives (e.g., carbon nanotubes or carbon black or branched carbon or carbon nanofibers or graphite flakes or expanded graphite or graphene (e.g., single-walled graphene, multi-walled graphene) or graphene oxide (e.g., single-walled graphene oxide, multi-walled graphene oxide) or soft graphite or various combinations thereof, to name a few), a binder (e.g., a polymer binder), and a solvent (e.g., water or a suitable organic solvent).

[0140] Operation 134 includes fabricating a cathode electrode, wherein the cathode electrode comprises the cathode particles prepared in operation 132. For example, operation 134 may include: (1) preparing a cathode slurry comprising the cathode particles (e.g., from operation 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 may typically include evaporating the slurry solvent and / or densifying the battery electrode to a desired value. For example, the other cathode slurry components may include: other electrochemically active cathode active materials, conductive additives (e.g., carbon nanotubes or carbon black or branched carbon or carbon nanofibers or graphite flakes or graphene (e.g., single-walled graphene, multi-walled graphene) or graphene oxide (e.g., single-walled graphene oxide, multi-walled graphene oxide) or soft graphite or various combinations thereof, to name a few), a binder (e.g., a polymer binder), and a solvent (e.g., water or a suitable organic solvent).

[0141] In operation 140, a lithium-ion rechargeable battery cell is assembled from at least an anode electrode and a cathode electrode, wherein an electrolyte is placed between the anode electrode and the cathode electrode. The electrolyte provides ionic conduction between the anode and the cathode. The electrolyte couples the anode and the cathode ions. The electrolyte may include a liquid electrolyte or a solid electrolyte (or a mixture of a liquid electrolyte and a solid electrolyte) at the battery operating temperature (for example, in some designs, the solid electrolyte may be molten or semi-molten during the melt infiltration process and may subsequently solidify). In some embodiments, such as in embodiments using a liquid electrolyte, a separator may be used to maintain the space between the anode electrode and the cathode electrode.

[0142] Figure 3 1 is a flow chart of a process 150 for preparing anode particles, and illustrates operation 122 in greater 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, the electrode particles are made using porous carbon or particles containing porous carbon (e.g., primarily using particles containing sp 2 Bonded graphitic carbon or sp 2In some embodiments, the active material particles are prepared from particles of porous graphitic carbon (e.g., particles of bonded porous graphitic carbon), wherein nanostructures or nanosized active material particles are formed in the pores of the porous carbon or the particles containing the porous carbon (e.g., having an average diameter or linear dimension ranging from 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; 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). In the case of anode particles for lithium-ion batteries, the active material particles may be silicon-containing particles.

[0143] In operation 152, carbon particles are provided. In some designs, the carbon (e.g., primarily sp 2 Bonded graphitic carbon) particles can be obtained by pyrolysis or carbonization (e.g., by thermal or hydrothermal treatment) of suitable precursor particles (e.g., polymer particles or biomass-derived particles). In some designs, carbon particles can be obtained from carbon-containing inorganic precursor particles (e.g., carbides or oxycarbides, etc.).

[0144] In some designs, inorganic sacrificial templates (including but not limited to various oxides or hydroxides or oxyhydroxides of various metals and semimetals such as Zn, Mg, Si, Al, Ti, Ca, Mg, Sc, etc. and various combinations thereof) or soft (organic) templates can be used to form porous carbon particles.

[0145] 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 forming the nanostructures or nanosized active material particles therein. In some embodiments, it may be preferred that the carbon or carbon-containing particles exhibit a porosity of about 500 m / s prior to forming the active material particles therein. 2 / g or greater Brunauer-Emmett-Teller (BET) specific surface area (SSA) (e.g., obtained from nitrogen adsorption-desorption data at low temperature, such as about 77 K). In some embodiments, it is preferred that the carbon particles have a BET SSA of about 500 m / g before forming active material particles therein. 2 / g to about 4500m 2 / g or about 4800m 2 / g range (in some designs, about 500m 2 / g to about 1000m 2 / g; in other designs, about 1000m 2 / g to about 2000m 2 / g; in other designs, about 2000m 2 / g to about 3000m 2 / g; in other designs, about 3000m 2 / g to about 3800m 2 / g; in some other designs, about 3800m 2 / g to about 4800m 2 / g). In some embodiments, it is preferred that the carbon particles exhibit a total micropore and mesopore volume (excluding macropores greater than 50 nm) in the range of about 0.5 cc / g to about 5 cc / g (in some designs, about 0.5 cc / g to about 1 cc / g; in other designs, about 1 cc / g to about 2 cc / g; in other designs, about 2 cc / g to about 3.5 cc / g; in other designs, about 3.5 cc / g to about 5 cc / g) before forming the active material particles therein. In some designs, such a high surface area can be obtained by physically or chemically activating the carbon or carbon-containing precursor particles, or by rapid annealing of the carbon or carbon-containing precursor particles, or by using a temporary template material, or by other known suitable methods. In some cases, the precursor particles themselves can be highly porous (e.g., aerogel particles). However, in some designs, it may be preferred to create or enhance porosity in the carbon or carbon precursor particles (e.g., by activating the carbon or carbon-containing particles, or by leaching out non-carbon components of the carbon-containing particles) before forming the active material particles therein to adjust the porosity characteristics. Thus, operation 154 includes performing a porosity enhancement (eg, activation) process on the carbon particles (eg, from operation 152 ).

[0146] After the activation operation (operation 154), other process operations are performed, such as process A in operation 156, process B in operation 158, and process C in operation 160. In the example shown, there are three process operations after the porosity enhancement (e.g., activation) process (operation 154), but in other embodiments, there may be fewer or more than three process operations after activation. For illustrative purposes, process 150 is described with respect to the formation of certain electrode (e.g., anode) particles. The concepts of process 150, including porosity enhancement (e.g., activation) of carbon particles, can be applied to other anode particles or cathode particles that require carbon particle activation.

[0147] exist Figure 3 In the example shown, nanostructured or nanosized silicon (Si) or silicon oxide (SiO x ) or silicon nitride (SiN y ) or silicon oxynitride (SiO x N y ) or silicon phosphide (SiP zParticles (0 < x < 2; 0 < y < 1.3; 0 < z < 1) or various combinations, alloys, and mixtures thereof are formed within (and / or on the surface of) the pores of porous carbon or particles containing porous carbon (e.g., predominantly porous graphite carbon containing sp 2 bonded or predominantly graphite carbon containing sp 2 bonded). For example, Process A (Operation 156) includes forming silicon-based active material particles at least in some of the pores of the porous carbon particles. In some examples, the formation of silicon-based active material particles in the porous carbon particles (e.g., by depositing or infiltrating or depositing / infiltrating a silicon-containing precursor followed by conversion to the final silicon or silicon-based material) can be achieved by solution-based or vapor-based deposition processes or other suitable methods. For the sake of brevity, the particles after completion of Process A are sometimes referred to as silicon-carbon composite particles (it is understood that in some designs, elements other than silicon and carbon may be present in such composite particles). In some embodiments, such composite particles contain nano-sized or nanostructured elements (e.g., nano-sized or nanostructured silicon, nano-sized or nanostructured carbon), which can be referred to as nanocomposite particles. In some embodiments, the silicon or silicon-containing material present in such nanocomposites can be in the form of nanoparticles. In some embodiments, the mass average size of the silicon or silicon-containing material nanoparticles can be 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 some other designs, about 30 nm to about 一百纳米; in yet some 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).

[0148] It should be noted that the Chinese "一百纳米" in the original text seems to be an incorrect expression. I translated it as "100 nm" according to the context. If this is not what you intended, please correct the original text for a more accurate translation.In the example shown, process B is performed in operation 158. For example, process B includes forming a protective coating on and in the silicon-carbon (Si-C) composite material particles (from operation 156). In some designs, a suitable average thickness of the protective coating can be in a range of about 0.2 nm to about 50 nm (in some designs, about 0.2 nm to about 2 nm; in other designs, about 2 nm to about 5 nm; in other designs, about 5 nm to about 10 nm; and in still other designs, about 10 nm to about 50 nm). In some designs, the true density of the protective coating can be in the range of about 0.8 g / cc to about 4.8 g / cc or about 5.8 g / cc (in some designs, about 0.8 g / cc to about 1.6 g / cc; in other 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 still other designs, about 4.5 g / cc to about 4.8 g / cc or about 5.8 g / cc).

[0149] In some designs, the protective coating may comprise a conductive material such as carbon or be based on a conductive material such as carbon. In some designs, such a carbon coating may be doped (e.g., doped with B, P, N, O, and / or other elements). In some designs, the atomic fraction of the various dopants may be in the range of about 0.01 at.% to about 10.01 at.% (in some designs, about 0.01 at.% to about 0.1 at.%; in other designs, about 0.1 at.% to about 1 at.%; in other designs, about 1 at.% to about 5 at.%; in still other designs, about 5 at.% to about 10.01 at.%). In some designs, the protective coating may be largely impermeable to the electrolyte solvent.

[0150] In lithium-ion battery cells (e.g. Figure 1 During operation of the battery, the protective coating can prevent direct contact between the silicon nanoparticles and the electrolyte solvent composition. In some designs, direct contact between the electrolyte solvent composition and the silicon nanoparticles may undesirably accelerate degradation of the lithium-ion battery cell.

[0151] In the example shown, process C is performed in operation 160. For example, process C includes changing the particle size distribution (PSD). Process C can include crushing the protected silicon-carbon composite particles (which come from operation 158). When the particle size (average) is greater than the final desired particle size distribution (for example, for slurry and electrode processing), crushing can be performed. There are many methods known in the art for crushing. For example, crushing can be performed by one or more of the following methods: ball milling, jet milling, attrition milling, pin milling, and hammer milling. In some embodiments, it may be preferred to perform particle size selection during process operation C. In some cases, in addition to crushing, process C may also include particle size selection (for example, particle size selection after crushing) (for example, by screening or sieving or centrifugation or other pneumatic particle size classification or other means). In some cases, process C may include particle size selection without crushing. For example, it may be preferred to retain some larger particle sizes and discard finer particle sizes. Particle size selection can be performed by any suitable method known to those skilled in the art, such as screening, sieving, and pneumatic particle size classification.

[0152] The process operation C (160) described above includes examples of modifying the particle size distribution (PSD) of a particle population, such as by performing comminution and particle size selection. In some cases, it may be desirable to employ additional or alternative processes to modify or adjust the PSD, such as by blending two or more particle populations, each of which has a different PSD than the other particle populations. For example, particle populations having different PSDs may be obtained (e.g., obtained from a supplier or manufactured with different PSDs, including by employing the comminution and / or particle size selection processes described above under different processing conditions).

[0153] 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 performing laser particle size distribution analysis (LPSA) on a well-dispersed particle suspension. Note that other types of particle size distributions (e.g., by SEM image analysis) can also be utilized (which may even lead to more accurate measurements in some experiments). Although there are many ways to measure PSD, laser particle size distribution analysis (LPSA) is very efficient in certain applications. Using LPSA, particle size parameters of the PSD of a particle population can be measured, such as: the tenth percentile volume weighted particle size parameter (e.g., abbreviated as D 10 ); the 50th percentile volume-weighted particle size parameter (e.g., abbreviated as D 50 ); the 90th percentile volume-weighted particle size parameter (e.g., abbreviated as D 90 ); and the ninety-ninth percentile volume-weighted particle size parameter (e.g., abbreviated as D99 ). In addition, parameters related to the characteristic width of the PSD can be derived from these granularity parameters, such as D 50 -D 10 (sometimes referred to herein as left width), D 90 -D 50 (sometimes referred to herein as right width), D 90 -D 10 (sometimes referred to herein as full width) and (D 90 -D 10 ) / D 50 (Sometimes referred to herein as span). The cumulative volume fraction can be estimated by LPSA, which is defined as the cumulative volume of composite particles having a particle size of a threshold particle size or less divided by the total volume of all composite particles. 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, or in the range of about 2.0 μm to about 4.0 μm, or in the range of about 4.0 μm to about 6.0 μm, or in the range of about 6.0 μm to about 8.0 μm, or in the range of about 8.0 μm to about 16.0 μm.

[0154] After completing the operations in process 150 (e.g., operations 152, 154, 156, 158, 160), the composite particles can be characterized by Brunauer-Emmett-Teller (BET) specific surface area (SSA) (e.g., obtained from nitrogen adsorption-desorption data at low temperatures, such as about 77 K). In some embodiments, the BET-SSA of the composite particles is about 1 m 2 / g to about 50m 2 / g (in some designs, about 1m 2 / g to about 3m 2 / g; in other designs, about 3m 2 / g to about 12m 2 / g; in some other designs, about 12m 2 / g to about 18m 2 / g; in some other designs, about 18m 2 / g to about 30m 2 / g; in some other designs, about 30m 2 / g to about 50m 2 / g).

[0155] Figure 4(Top) shows a schematic diagram of a jagged particle (e.g., a jagged composite particle) 400, which can be observed, for example, under an optical microscope. Two parallel lines 402, 404 are tangent to corresponding portions of the jagged 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 shortest distance between all possible pairs of parallel lines drawn tangent to corresponding portions of the jagged particle 400. Similarly, two parallel lines 412, 414 are tangent to corresponding portions of the jagged particle 400. The distance 416 between the parallel lines 412, 414 is sometimes referred to as the maximum Feret diameter because this distance 416 is the longest distance between all possible pairs of parallel lines drawn tangent to corresponding portions of the jagged particle 400. The aspect ratio of a particle can be defined as the maximum Feret diameter of the particle divided by the minimum Feret diameter of the particle. The aspect ratio can be estimated by image analysis (e.g., running image analysis software) of a population of particles observed under an optical microscope. The exemplary jagged composite particles described herein are obtained by following Figure 3 The process 150 of obtaining carbon particles begins by obtaining carbon particles (152).

[0156] Figure 4 (Bottom) A graph 420 shows the correlation of the cumulative distributions (expressed as fractions of the number of particles in the entire corresponding particle population) of two selected jagged particle populations. Image analysis was performed on each jagged particle population to estimate the aspect ratio of each particle in the particle population. The particle population represented by line 432 contains approximately 2192 particles and is characterized by D 50 The particle group represented by line 434 contains about 7485 particles, and the particle group is characterized by D 50 The cumulative distribution of a particle population represents the fraction of particles in each population that have an aspect ratio less than or equal to the specified aspect ratio as a function of the specified aspect ratio. The x-axis 422 shows the aspect ratio, and the y-axis 424 shows the cumulative distribution of the particle population. For example, consider one of the data points 442 along plot 432, which corresponds to an aspect ratio of approximately 1.5 and a cumulative distribution fraction of approximately 0.68. This means that approximately 68% of the particles in that population have an aspect ratio of approximately 1.5 or less.

[0157] Figure 5 and Figure 6 Scanning electron microscope (SEM) images of exemplary jagged composite particles (or agglomerates thereof) are shown. Figure 5 Shown from D 50 SEM image 502 of a jagged composite material particle obtained from a population of particles approximately 2.5 μm and a SEM image 502 of a jagged composite material obtained from a population of particles approximately 2.5 μm 50SEM image 504 of a jagged composite particle obtained from a population of particles approximately 7 μm. Figure 6 Shown from D 50 SEM image 602 of a jagged composite material particle obtained from a population of particles approximately 9 μm and obtained from D 50 604 shows an SEM image of a jagged composite particle obtained from a population of particles having a diameter of about 14 μm. In the example shown, the composite particles are jagged and not round (e.g., not spherical, not spherical, etc.). Many of the composite particles have a very low aspect ratio, such as less than about 10, less than about 5, or less than about 3. On the other hand, many of the composite particles have an aspect ratio greater than about 1. In some embodiments, the population of jagged composite particles (including Figure 4 The aspect ratio of the exemplary particle population (illustrated in FIG420 ) can be characterized by one or more of the following: (1) about 90% or more of the jagged composite particles in the particle population are characterized by an aspect ratio of about 2.3 or less, or about 2.2 or less, or about 2.1 or less; (2) about 50% or more of the jagged composite particles in the particle population are characterized by an aspect ratio of about 1.25 or greater, or about 1.3 or greater, or about 1.35 or greater; and (3) about 10% or more of the jagged composite particles in the particle population are characterized by an aspect ratio of about 1.3 or less, or about 1.25 or less, or about 1.2 or less.

[0158] Figure 7 The full width D of each exemplary particle population is shown. 90 -D 10 With D 50 702, and the mass fraction of silicon in the composite particles versus D for each exemplary particle population. 50 Graph 704 of the correlation of D for an exemplary particle population. 50 The range of is between about 2.1 μm and about 14.1 μm. In the exemplary particle population shown, the full width D 90 -D 10The silicon (Si) mass fraction is estimated by thermogravimetric analysis (TGA) of a powder sample heated in air to approximately 900°C (at a heating rate of approximately 40°C / min) for approximately 60 minutes in a crucible. The sample is then cooled to room temperature, and the resulting material is assumed to be entirely silicon oxide. Under this assumption, the amount of silicon already present in the original powder sample is calculated. In the illustrative example shown, the silicon mass fraction ranges from approximately 38.5 wt.% to approximately 46.4 wt.%. In some embodiments, the silicon mass fraction in the composite material particles may range from approximately 35 wt.% to approximately 50 wt.%. In some embodiments, the silicon mass fraction in the composite material particles may range from approximately 3 wt.% to approximately 80 wt.% (e.g., from approximately 3 wt.% to approximately 20 wt.%, from approximately 20 wt.% to approximately 35 wt.%, from approximately 35 wt.% to approximately 50 wt.%, from approximately 50 wt.% to approximately 80 wt.%, etc.).

[0159] Each of the battery electrode compositions containing the corresponding serrated composite particle populations was used to prepare an electrode coating for the illustrative examples. In addition to the composite particles, the battery electrode composition may also contain functional additives (e.g., additives that enhance the conductivity, rate performance, or mechanical properties of the electrode), such as carbon-containing functional additives. Examples of suitable carbon-containing functional additives include carbon nanotubes (single-walled carbon nanotubes, abbreviated as SWCNTs; multi-walled carbon nanotubes, abbreviated as MWCNTs), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide, and graphene. The slurry is prepared by thoroughly mixing the jagged nanocomposite particles (or, in the case of a blended anode, a mixture of jagged nanocomposite particles and graphite) (e.g., having a mass fraction in the range of about 87 wt.% to about 94 wt.% of the slurry solids content, or in the range of about 89 wt.% to about 92 wt.%), a binder composition (e.g., having a mass fraction in the range of about 6 wt.% to about 13 wt.% of the slurry solids content, or in the range of 8 wt.% to about 10 wt.%), a functional additive (e.g., having a mass fraction in the range of about 0 wt.% to about 0.1 wt.% of the slurry solids content), and a solvent composition (e.g., having a mass fraction in the range of 10 wt.% to about 40 wt.% of the slurry). The exemplary anode slurry is then cast onto a copper foil and dried at room temperature to form an electrode coating. Subsequently, the dried electrode coating is calendared (in our exemplary embodiment, by using a constant force) to obtain a coating density within a specific range, for example, about 0.75 g / cm 3 to about 1.00g / cm 3 in the range of about 0.80 g / cm (e.g., in the case where the anode comprises only Si-C nanocomposite particles as active material without any graphite), or in the range of about 0.80 g / cm3 to about 1.00g / cm 3 in the range of about 0.85 g / cm 3 to about 1.00g / cm 3 in the range of about 0.90 g / cm 3 to about 1.00g / cm 3 Note that higher densities (e.g., having a density of about 1.0 g / cm2) may be preferably obtained for blended anodes containing small to large proportions of soft graphite or hard graphite (broadly, soft carbon or hard carbon) or various mixtures thereof (e.g., graphite provides about 5-80% of the capacity, while Si-C nanocomposites or other silicon-containing particles provide about 20-95% of the capacity). 3 to about 1.2g / cm 3 Design, with approximately 1.2g / cm 3 to about 1.5g / cm 3 or higher design).

[0160] Figure 8 SEM images 802, 804 of a cross section of an electrode coating are shown. The SEM image 802 is a cross section of a 50 The cross-sectional view of the electrode coating of the particle group sample of about 4 μm, and the SEM image 804 is a ... 50 Cross-sectional view of an electrode coating for a sample of a population of particles approximately 14 μm. Comparing the two examples, the coating with the larger particles (804) shows larger pores than the coating with the smaller particles (802). Therefore, as the particle size decreases (e.g., D 50 As the coating porosity decreases from about 14 μm to about 4 μm, the coating porosity tends to decrease and the coating density tends to increase. Figure 7 The electrode coating has a thickness ranging from about 24.3 μm to about 43.5 μm.

[0161] Conventional anode active materials used in lithium-ion batteries are of the intercalation type. During the charge or discharge process of the battery, metal ions are intercalated and occupy the interstitial positions of these materials. When used in electrodes, the volume change of such anodes is small or very small (e.g., less than about 8 vol.%). Polyvinylidene fluoride (also known as polyvinylidene difluoride, PVDF), polyacrylic acid (PAA) (or its salts, derivatives and copolymers) (sometimes mixed with styrene-butadiene rubber (SBR)) and carboxymethyl cellulose (CMC) (usually mixed with styrene-butadiene rubber (SBR)) are the three most commonly used binders in these electrodes. Carbon black is the most commonly used conductive additive in these electrodes. However, such anodes exhibit relatively small gravimetric and volumetric capacities (typically less than about 370 mAh / g of rechargeable specific capacity in the case of graphite-based or hard carbon-based anodes, and less than about 600 mAh / cm at the electrode level without considering the volume of the current collector foil). 3 rechargeable volume capacity).

[0162] Alloy-type (or more broadly, conversion-type) anode active materials for lithium-ion batteries offer higher gravimetric and volumetric capacities than intercalation-type anodes. For example, silicon (Si), which is abundant on Earth, has approximately 10 times the gravimetric capacity and approximately 3 times the volumetric capacity of intercalation-type graphite (or graphite-like) anodes. However, during lithium insertion, silicon undergoes significant volume expansion (up to approximately 300 vol.%), which may result in thickness changes and mechanical failure of silicon-containing anodes. In addition, silicon (and some lithium-silicon alloy compounds that may be formed during the lithiation of silicon) has relatively low electronic conductivity and relatively low ionic (lithium ion) conductivity. The electronic and ionic conductivities of silicon are lower than those of graphite. Forming (nano) composite silicon-containing particles (including but not limited to silicon-carbon composites, silicon-metal composites, silicon-polymer composites, silicon-ceramic composites, composites containing various combinations of nanostructured silicon, carbon, polymers, ceramics and metals, or other types of porous composites - which contain nanostructured silicon or nanostructured silicon particles or nanosized silicon particles in various shapes and forms) can reduce the volume change during lithium ion insertion and extraction, which in turn can lead to better cycling stability of rechargeable lithium ion battery cells. In some designs, silicon can be doped or heavily doped with nitrogen (N), phosphorus (P), boron (B) or other elements, or allowed to be doped with metals. In addition to silicon-based composites, silicon oxide (SiO x ) or silicon oxynitride (SiO x N y ) or silicon nitride (SiN y ) or silicon phosphide (SiP y) or other silicon-containing particles (including those partially reduced by Li or Mg, etc.) can also reduce volume changes and improve cycling stability, but generally at the expense of higher first cycle losses or faster degradation, or both. In some designs, the silicon-containing anode particles can exhibit a high gravimetric lithiation capacity in the range of about 800 mAh / g to about 3000 mAh / g (per mass of silicon-containing anode particles in the lithium-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; in other designs, about 2600 mAh / g to about 3000 mAh / g), as measured in a lithium half-cell over the following potential range: for first cycle lithiation, at a constant current rate of about C / 10 from its open circuit potential to a potential relative to Li / Li + The potential was maintained at 0.01 V until the current dropped to about C / 100, and for the first cycle delithiation, the current was increased from 0.01 V to 0.01 V relative to Li / Li at a constant current rate of C / 10. +The 0.01 V to about 1.5 V change in the specific capacity is advantageous for lighter batteries. However, lithium-ion battery cells with anodes containing high-capacity anode particles with unoptimized particle size distribution (PSD) may exhibit undesirably rapid degradation in conventional electrolytes (especially when processed with conventional binders and conductive additives at typical areal capacity loadings), especially at high temperatures or when charged to high voltages (e.g., above about 4-4.3 V). A subset of anodes having silicon-containing anode particles includes anodes whose electrode layer exhibits a capacity in the range of about 400 mAh / g to about 2800 mAh / g (per mass of the electrode layer in the lithium-free state, excluding the mass of the current collector; in some designs, about 400 mAh / g to about 500 mAh / g; in other 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, about 2000 mAh / g to about 2800 mAh / g). This type of charge storage anode offers great potential for increasing the gravimetric and volumetric energy of rechargeable batteries. However, lithium-ion battery cells having anodes containing high-capacity anode particles that are not PSD-optimized may exhibit undesirably rapid degradation in conventional electrolytes when treated with conventional binders and conductive additives at typical areal capacity loadings, particularly at high temperatures (e.g., battery operating temperatures, e.g., about 50-80° C. or higher) or when charged to high voltages (e.g., above about 4-4.3 V). In addition to silicon-containing anodes, other examples of such high-capacity (e.g., nanocomposite) anodes containing alloy-type (or more broadly, conversion-type) active materials include, but are not limited to, those containing germanium, antimony, aluminum, magnesium, zinc, gallium, arsenic, phosphorus, silver, cadmium, indium, tin, lead, bismuth, and alloys thereof, among others. In addition to anodes containing active materials in metallic form, other interesting types of high-capacity (containing nanocomposite) anodes may also contain 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 the like.

[0163] Lithium-ion battery cells with alloy-type (or more broadly, conversion-type) anode active materials may exhibit undesirably rapid degradation in conventional electrolytes, particularly at elevated temperatures or when charged to high voltages (e.g., greater than about 4-4.3 V) and stored at such voltages at elevated temperatures (e.g., greater than about 50-80° C.). In some designs, degradation of lithium-ion battery cells with alloy-type (or more broadly, conversion-type) anode active materials may become particularly undesirably rapid 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 even greater). However, large, ultra-large, or giant cells may be particularly attractive in some electric transportation or grid storage applications. In some designs, when normalized by the total cell capacity, the degradation of lithium-ion battery cells having alloy-type (or more broadly, conversion-type) anode active materials may become particularly undesirably rapid for battery cells containing moderate amounts (e.g., about 3-4 g / Ah) or low amounts (e.g., about 2-3 g / Ah) of electrolyte. However, using moderate or low amounts of electrolyte may be particularly attractive for reducing battery cell manufacturing costs or certain side reactions and maximizing the energy density of the battery cell. One or more aspects of the present invention enable mitigating or overcoming some or all of these limitations and significantly improving the performance of such lithium-ion battery cells by using certain disclosed electrolyte compositions. One or more aspects of the present invention enable mitigating or overcoming some or all of these limitations and significantly improving the performance of such lithium-ion battery cells by using certain disclosed compositions and certain disclosed properties of active materials. One or more aspects of the present invention enable mitigating or overcoming some or all of these limitations and significantly improving the performance of such lithium-ion battery cells by using certain disclosed PSDs of anode active material particles (e.g., active material particles containing alloying or conversion-type active materials).

[0164] High capacity (nano) composite anode powders (including but not limited to powders containing silicon) that exhibit moderately high volume changes during the first charge-discharge cycle (e.g., about 8 vol.% to about 180 vol.%) and moderate volume changes during subsequent charge-discharge cycles (e.g., about 5 vol.% to about 50 vol.%), and average sizes in the range of about 0.2 μm to about 40 μm (more preferably, for some applications, in the range of about 0.4 μm to about 20 μm) are particularly attractive for battery applications in terms of manufacturability and performance characteristics. In particular, in some embodiments, the specific surface area is about 0.5 m 2 / g to about 50m2 / g (in some designs, about 0.5m 2 / g to about 2m 2 / g; in other designs, about 2m 2 / g to about 12m 2 / g; in some other designs, about 12m 2 / g to about 50m 2 A subclass of this anode powder in the range of 100 mAh / cm2 / g performs particularly well. In some designs, the electrode area capacity loading ranges from moderate (e.g., about 2 mAh / cm2 / g) to 2 to about 4 mAh / cm 2 ) to high (e.g., about 4 mAh / cm 2 to about 12 mAh / cm 2 ) and ultra-high (above about 12 mAh / cm 2 ) are also particularly attractive for use in battery cells. In some designs, spherical (including nearly spherical or spherical) or ellipsoidal (including oblate spheroidal) shapes of these composite particles may be particularly attractive for improving the rate performance and volumetric capacity (density) of the electrode. In other designs, jagged composite particles, cylindrical composite particles, fibrous composite particles, or irregularly shaped composite particles may still be effectively used. Unfortunately, the unoptimized PSD of such particles may result in poor battery performance.

[0165] However, in some applications, higher electrode density and lower binder content are beneficial for increasing battery cell energy density and reducing cost. Lower binder content may also be beneficial for improving battery cell rate performance. Larger volume changes lead to poor performance of some designs, which may be related to damage to the solid electrolyte interface (SEI) layer formed on the anode, uneven lithiation and delithiation of electrode particles within the electrode, and / or other factors. Unfortunately, lithium batteries and lithium-ion batteries with such anodes and conventional electrolytes containing active (e.g., silicon-containing) materials with unoptimized PSDs typically require the use of very large amounts of conventional solid electrolyte interface (SEI) building additives to maintain acceptable cycling stability, which prevents the battery cells from being used at high or low temperatures, or undesirably limits their calendering life, and does not allow such battery cells to be charged to high voltages (e.g., above about 4.1-4.3V). When such battery cells are charged above about 4.3-4.4V, their performance may become particularly poor, and even worse when charged above about 4.5V.

[0166] However, higher cell voltages, wider operating temperature windows, and longer cycle life are advantageous for most applications. When exposed to high temperatures (e.g., above about 50-90°C) for extended periods (e.g., about 12-168 hours) at a fully charged state (e.g., a state of charge (SOC) of about 90-100%), such cells may suffer from excessive capacity degradation (e.g., above about 5%), large volume expansion (e.g., above about 10%), and significant gassing. Most applications require passing this high-temperature charging test. In some designs, degradation of lithium-ion battery cells containing high-capacity (nano)composite anode powders with non-optimized PSDs—such powders exhibiting moderately high volume changes during the first charge-discharge cycle, moderate volume changes during subsequent charge-discharge cycles, and having an average size in the range of about 0.2 μm to about 40 μm—may be particularly undesirably rapid for large cells (e.g., cells with cell capacities in the range of about 10 Ah to about 40 Ah), or very large cells (e.g., cells with cell capacities in the range of about 40 Ah to about 400 Ah), or giant cells (e.g., cells with cell capacities in the range of about 400 Ah to about 4000 Ah, or even greater)—may be particularly undesirably rapid for large cells (e.g., cells with cell capacities in the range of about 10 Ah to about 40 Ah), or very large cells (e.g., cells with cell capacities in the range of about 400 Ah to about 4000 Ah), or even larger cells (e.g., cells with cell capacities in the range of about 400 Ah to about 4000 Ah, or even greater). In some designs, degradation of lithium-ion battery cells containing such volume-changing anode particles may 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. One or more embodiments of the present invention enable mitigation or overcoming of some or all of these limitations and significantly improve the performance of such lithium-ion battery cells through the use of certain disclosed electrolyte compositions.

[0167] One or more embodiments of the present invention overcome some or all of the above-mentioned challenges of various types of metal ion (e.g., lithium ion) battery cells that include high capacity nanocomposite anode active materials (e.g., materials including conversion-type or alloying-type active materials) that may include silicon in their composition, that may undergo some volume change during cycling (e.g., moderately high volume change during the first charge-discharge cycle (e.g., about 8 vol.% to about 160 vol.% or about 180 vol.%), and moderate volume change during subsequent charge-discharge cycles (e.g., about 5 vol.% to about 50 vol.%)), have an average particle size in the range of about 0.2 μm to about 40 μm, and have a specific surface area of ​​about 0.5 m 2 / g to about 50m 2 / g range (in some designs, about 0.5m 2 / g to about 2m 2 / g; in other designs, about 2m 2 / g to about 12m 2 / g; in some other designs, about 12m 2 / g to about 50m 2 / g), can be used with medium area capacity loading (e.g., about 2 mAh / cm 2 to about 4 mAh / cm 2 ) and high areal capacity loading (e.g., about 4 mAh / cm 2 to about 12 mAh / cm 2 ) has a high packing density (the porosity of the electrode filled with electrolyte is in the range of about 5 vol.% to about 35 vol.% after the first charge-discharge cycle) and a relatively low binder content (e.g., about 0.5 wt.% to about 14 wt.%), can contain a moderate or small amount of electrolyte per cell capacity (e.g., less than about 4 g / mAh), can be charged to moderately high (e.g., above about 4.1-4.3 V) or high (e.g., above about 4.3-4.4 V) or very high (e.g., above about 4.5 -4.8V), can be exposed to a temperature above about 40°C at a high state of charge (e.g., SOC of about 70-100%) during testing or operation, and can be produced as a large battery cell (e.g., a battery cell with a battery cell capacity in the range of about 10Ah to about 40Ah), or an ultra-large battery cell (e.g., a battery cell with a battery cell capacity in the range of about 40Ah to about 400Ah), or a giant battery cell (e.g., a battery cell with a battery cell capacity in the range of about 400Ah to about 4000Ah or even larger).

[0168] In some designs, the swelling of the adhesive in the electrolyte may depend not only on the adhesive composition but also on the electrolyte composition. Furthermore, in some designs, this swelling (and the resulting performance degradation) is often associated with a decrease in the elastic modulus of the adhesive when exposed to the electrolyte. In this sense, the smaller the decrease in modulus in certain electrolytes, the more stable the (nano)composite active particle / conductive additive interface connected by the adhesive. In some designs, a decrease in the adhesive modulus of more than about 15-20% may result in a significant decrease in performance. In one example, a decrease in the adhesive modulus of about two times (2x) may result in a significant decrease in performance. In another example, a decrease in the modulus of about five times or more (e.g., about 5x-500x) may result in a very significant decrease in performance. Therefore, for some applications, it may be highly preferable to select an electrolyte composition that does not cause significant adhesive swelling. In some examples, it may be preferable to select an electrolyte composition that reduces the adhesive modulus by less than about 30% (more preferably, no more than about 10%) when exposed to the electrolyte. In anodes comprising more than one binder composition, in some designs it may be preferred to select an electrolyte composition in which the modulus of at least one binder does not decrease by more than about 30% (more preferably, does not decrease by more than about 10%) when exposed to the electrolyte.

[0169] In one or more embodiments of the present invention, the preferred battery cell comprises lithium cobalt oxide (LCO) as the cathode active material. In another one or more embodiments of the present invention, the preferred battery cell comprises lithium nickel cobalt manganese oxide (NCM) as the cathode active material. In another one or more embodiments of the present invention, the preferred battery cell comprises lithium nickel cobalt manganese aluminum oxide (NCMA) as the cathode active material. In another one or more embodiments of the present invention, the preferred battery cell comprises lithium nickel cobalt aluminum oxide (NCA) as the cathode active material. In another one or more embodiments of the present invention, the preferred battery cell comprises 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 large amount (e.g., greater than 50 wt.%) of single crystal powder (or powder with a particle size greater than about 500 nm; in some designs, the particle size is greater than about 1 μm). In some preferred examples, the surface of the LCO, NCM, NCMA, NCA, LMO or LMNO may be coated with a layer of ceramic material. Illustrative examples of preferred coating materials for such cathodes include, but are not limited to, titanium oxide (e.g., TiO2), aluminum oxide (e.g., Al2O3), tungsten oxide (e.g., WO), chromium oxide (e.g., Cr2O3), niobium oxide (e.g., NbO or NbO2), and zirconium oxide (e.g., ZrO2), and various mixtures thereof. In some designs, such ceramic materials may also contain lithium (Li), such 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 preferred examples, LCO, NCM, NCMA, NCA, LMFP, LMP, LMO, or LMNO may be doped with Al, Ti, Mg, Nb, Zr, Cr, Hf, Ta, W, Mo, or La. In some 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 contains, 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 preferred coating materials for polymer separators may include, but are not limited to, titanium oxide (TiO2), aluminum oxide (Al2O3), aluminum hydroxide or aluminum oxyhydroxide, zirconium oxide (ZrO2), magnesium oxide (MgO) or magnesium hydroxide or magnesium oxyhydroxide. In some designs, preferred battery cells may include silicon-containing and carbon-containing nanocomposites (e.g., as used herein, nanocomposites or (nano)composites are at least partially composed of active nanomaterials or nanostructures or nanoparticles, regardless of whether the nanocomposites or (nano)composites themselves are nanomaterials) or silicon (SiOx , x≥0) or natural or synthetic graphite or soft carbon or hard carbon or various mixtures and combinations thereof. In some preferred examples, the anode active material includes a mixture of silicon- and carbon-containing nanocomposites (sometimes abbreviated herein as silicon-carbon nanocomposites) and graphite (e.g., graphite is different from the carbon portion of the silicon-carbon nanocomposite). In some embodiments, the silicon-carbon nanocomposite includes composite particles, which may include silicon nanoparticles embedded in the pores (e.g., surface pores or internal pores, such as internal closed pores or internal open pores) of porous carbon scaffold particles. Such porous carbon scaffold particles may include (e.g., curved or defective) graphene materials and / or graphite materials. In some designs, the preferred anode current collector may include copper or a copper alloy.

[0170] In one or more embodiments of the present invention, the preferred anode of the battery cell may include a mixture of silicon-carbon nanocomposite (particles) and graphite (particles) as the anode active material, a so-called blended anode. In addition to the anode active material, the anode may also include inactive materials such as binders (e.g., polymer binders) and other functional additives (e.g., surfactants, conductive additives). In some embodiments, the anode active material (particles) may be in the range of about 90 wt.% to about 98 wt.% of the anode. For example, in some designs, the anode active material (particles) may be about 95.5 wt.% of the anode.

[0171] In some designs, the blended anode can contain from about 7 wt.% silicon-carbon nanocomposite to about 97 wt.% silicon-carbon nanocomposite (e.g., particles). Although the following description may also describe certain examples of blended anode formulations, these formulations are expressed as the mass (wt.%) of silicon-carbon nanocomposite (e.g., particles) relative to the total weight of silicon-carbon composite and graphite (e.g., particles) in the blend, it should be understood that various aspects of the present invention can be applied to blended anode formulations expressed as the wt.% of silicon in the anode (e.g., including the weight of conductive additives and other additives, binders, silicon-containing composites such as silicon-carbon nanocomposite and graphite). For example, in some embodiments, a blended anode composition having about 7 wt.% silicon-carbon nanocomposite (e.g., particles) corresponds to about 3-3.5 wt.% silicon in the blended anode. In some embodiments, a blended anode composition having about 19 wt.% silicon-carbon nanocomposite (e.g., particles) corresponds to about 8-10 wt.% silicon in the blended anode. In some embodiments, a blended anode composition having about 35 wt.% of a silicon-carbon nanocomposite material (e.g., particles) may correspond to about 15-18 wt.% of silicon in the blended anode. In some embodiments, a blended anode composition having about 50 wt.% of a silicon-carbon nanocomposite material (e.g., particles) may correspond to about 21-30 wt.% of silicon in the blended anode. In various embodiments, a blended anode may be obtained in which the mass (weight) of silicon is in the range of about 3 wt.% to about 30 wt.% of the total mass of the anode. Here, the term "total mass of the anode" refers only to the mass of the anode excluding any anode current collector foil or separator. Even if the current collector and separator are attached to the anode, the mass of the current collector and separator are not included in the mass of the anode.

[0172] In some designs, the blended anode may include a silicon-carbon nanocomposite material (e.g., particles), wherein the silicon-carbon nanocomposite material provides about 25% to about 99.5% of the total anode capacity. Although the following description may also describe certain examples of blended anode formulations expressed in terms of mass (wt.%) of silicon-carbon nanocomposite materials (e.g., particles), it should be understood that various aspects of the present invention may be applicable to blended anode formulations in which a portion (e.g., wt.%) of the total capacity of the blended anode is attributed to the capacity of silicon. For example, in some embodiments, about 25% of the total capacity of the blended anode can be obtained from a silicon-carbon nanocomposite material (e.g., particles) in a blended anode composition having about 7 wt.% of silicon-carbon nanocomposite materials (e.g., particles). In some other embodiments, about 50% of the total capacity of the blended anode can be obtained from a silicon-carbon nanocomposite material (e.g., particles) in a blended anode composition having about 19 wt.% of silicon-carbon nanocomposite materials (e.g., particles). In some other embodiments, about 70% of the total capacity of the blended anode can be obtained from the silicon-carbon nanocomposite material (e.g., particles) in the blended anode composition having about 35 wt.% silicon-carbon nanocomposite material (e.g., particles). In some other embodiments, about 80% of the total capacity of the blended anode can be obtained from the silicon-carbon nanocomposite material (e.g., particles) in the blended anode composition having about 50 wt.% silicon-carbon nanocomposite material (e.g., particles).

[0173] In some embodiments, the blended anode may comprise a silicon-carbon nanocomposite (e.g., particles) and graphite particles, wherein the silicon-carbon nanocomposite is in the range of about 7 wt.% to about 99 wt.% of the anode active material particles, with the graphite particles constituting the remaining mass (weight) of the anode active material particles. In some embodiments where the anode active material particles comprise about 95.5 wt.% of the blended anode, the blended anode (comprising active material particles and inactive material) may comprise about 7 wt.% silicon-carbon nanocomposite (e.g., particles) and about 88.5 wt.% graphite (e.g., particles), about 19 wt.% silicon-carbon nanocomposite (e.g., particles) and about 76.5 wt.% graphite (e.g., particles), about 35 wt.% silicon-carbon nanocomposite (e.g., particles) and about 60.5 wt.% graphite (e.g., particles), or about 50 wt.% silicon-carbon nanocomposite (e.g., particles) and about 45.5 wt.% graphite (e.g., particles, wherein in all cases, the graphite particles are separated from the carbon portion of the silicon-carbon nanocomposite). In some preferred examples where the anode active material particles comprise about 90 wt. % or more of the blended anode, the anode active material composition can include a small amount (e.g., about 1-20 wt. %, preferably about 1-10 wt. %, and even more preferably about 1-5 wt. %) of graphite (e.g., particles, wherein the graphite particles are different from the carbon portion of the silicon-carbon nanocomposite).

[0174] In some illustrative examples where the anode active material particles comprise about 90 wt. % of the anode, the anode active material particle composition can consist almost entirely of silicon-carbon nanocomposite (e.g., particles) and be substantially free (e.g., less than about 1 wt. %) of graphite particles (e.g., the graphite particles are distinct from the carbon portion of the silicon-carbon nanocomposite).

[0175] In some illustrative examples where the anode active material particles comprise about 96.5 wt. % of the anode, the anode active material particle composition may consist almost entirely of graphite and be substantially free of silicon-carbon nanocomposite (eg, less than about 1 wt. %).

[0176] In one or more embodiments of the present invention, an electrolyte comprising an ester and / or carbonate (e.g., cyclic carbonate, linear carbonate) may be used in a lithium-ion battery cell. The lithium-ion battery comprises an anode current collector (e.g., copper foil or copper alloy foil), a cathode current collector (e.g., aluminum foil or aluminum alloy foil), an anode disposed on or in the anode current collector, a cathode disposed on or in the cathode current collector, and any of the above electrolytes that couple the anode and cathode ionically. In some examples, a diaphragm (e.g., a separator or coating) may be disposed between the anode and the cathode, wherein at least some of the electrolyte permeates or impregnates the diaphragm. The anode may comprise any suitable anode material described herein. For example, the anode may comprise silicon-carbon composite particles comprising silicon and carbon (e.g., primarily sp 2 In some embodiments, the mass of silicon can range from about 3 wt.% to about 80 wt.% of the total mass of the anode. In some cases, at least some of the silicon can be present in the silicon-carbon composite particles as nanosized or nanostructured silicon. For example, the anode can include graphitic carbon particles containing carbon. In some cases, the graphitic carbon particles can be substantially free of silicon. In some cases, both silicon-carbon composite particles and graphitic carbon particles can be present in the anode.

[0177] In one illustrative example, a lithium-ion battery cell having a capacity of approximately 0.028 Ah can include: (i) an anode having approximately 100% capacity of a silicon-carbon nanocomposite active material (e.g., particles) (having a specific reversible capacity of approximately 1600 mAh / g to approximately 1700 mAh / g when normalized by the weight of the active material in the anode), corresponding to a silicon mass fraction of approximately 40 wt.% to approximately 44 wt.% in the silicon-carbon composite particles cast onto a copper current collector foil from an aqueous suspension comprising a polyacrylic acid (PAA) salt copolymer-based binder and approximately 0.1% carbon black conductive additive; and (ii) a cathode having a high-voltage lithium cobalt oxide (LCO) active material (having a specific reversible capacity of approximately 170 mAh / g when normalized by the weight of the active material in the cathode) cast onto an aluminum current collector foil from an organic solvent suspension comprising a polyacrylic acid (PAA)-based binder and a carbon black conductive additive, wherein the anode to cathode areal capacity ratio is approximately 1.15:1 and the areal reversible capacity loading is approximately 3.5 mAh / cm 2 , with 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) (straight-chain ester), about 7 mol% LiPF6, about 24 mol% non-fluorinated cyclic carbonate, about 7 mol% diethyl carbonate (DEC), and about 3 mol% other compounds.

[0178] A lithium-ion battery test cell (as described above, with an LCO cathode) containing exemplary nanocomposite particles (where all of the anode capacity was provided by the silicon-carbon nanocomposite particles) was tested in a cycle life test. The test cell was fabricated and an initial formation process was performed on the test cell. The charge / discharge test conditions included charging at 2C to 4.0V and ramping down to 1C under constant current and constant potential (CCCP), then charging at 1C to 4.2V and ramping down to 0.05C under CCCP, followed by a 1C discharge. Graph 902 ( Figure 9 ) shows the D of each corresponding serrated composite particle group. 50 The number of cycles to reach 80% of the starting capacity (during cycling at 25°C) is sometimes referred to as the cycle life (also referred to as "N80"). The starting capacity is defined as the capacity at the completion of the third cycle. Some materials with larger particles (e.g., D 50 Test units with particles larger than about 10 μm exhibited poor cycle life values ​​(e.g., less than about 200 cycles). On the other hand, test units with smaller particles (e.g., D 50In the range of about 2.0 μm to about 8.0 μm) the test unit showed better cycle life values ​​(e.g., greater than 340 cycles or in the range of about 340 cycles to about 729 cycles). Therefore, in some embodiments (e.g., where all or substantially all of the capacity is provided by the silicon-carbon composite particles), the D 50 A population of jagged composite particles having a size in the range of about 2.0 μm to about 8.0 μm may produce beneficial effects (e.g., better cycle life) (particularly at similar or faster battery cell charging rates). For larger particles (e.g., D 50 larger than about 10 μm), one potential degradation pathway could be mechanical failure of the electrode coating after multiple charge / discharge cycles, which can be attributed in part to poor packing of jagged composite particles in the coating (e.g., considering Figure 8 804). In addition, larger particles may exhibit higher charge transfer resistance and, in some cases (e.g., when tested in cold climates or at low temperatures and / or when the anode is constructed to exhibit moderate to high areal capacity loading (e.g., about 2-12 mAh / cm 2 ), etc.), when the battery cell is rapidly charged, lithium plating may be induced. For smaller particles (e.g., D 50 In the range of about 2.0 μm to about 8.0 μm), one possible degradation pathway may be that the surface area (of the particles) exposed to the electrolyte increases with decreasing particle size, leading to more undesirable side reactions between the electrolyte and the particles (e.g., SEI overgrowth).

[0179] Figure 904( Figure 9 ) shows the normalized coating thickness variation of the anode of the test cell in dependence on the D50 of each exemplary particle population. The normalized coating thickness variation is defined as the coating thickness variation (in μm) divided by the amount of lithium ions per unit area of ​​the electrode (anode) inserted in the electrode (in mAh / cm) from the discharged state to the charged state. 2 denoted by (e.g., during the so-called "forming" cycle). The coating thickness variation is the difference in coating thickness between the charged state at cycle 4 and the as-prepared electrode coating. After undergoing four charge / discharge cycles, the coating thickness was measured on the test cell using a high-precision digital contact sensor (resolution of approximately 0.1 μm). The normalized coating thickness variation can be considered as a quantitative measure of the degree of swelling of the electrode coating, particularly in the thickness direction. Graph 904 shows that the normalized thickness variation (i.e., the degree of swelling in the thickness direction of the electrode, or z-swelling) increases with D 50 Therefore, by adopting D 50The normalized thickness variation can be reduced by selecting a jagged composite particle population having a value in the range of about 2.0 μm to about 8.0 μm, or in the range of about 2.0 μm to about 6.0 μm, or in the range of about 2.0 μm to about 5.0 μm, or in the range of about 2.0 μm to about 4.0 μm. 50 For a population of particles with a value in the range of about 2.0 μm to about 4.0 μm, the normalized thickness variation may be about 2.5 to about 3.0 μm / (mAh / cm 2 ) range. Except for the particle D 50 In addition to size, swelling may also depend on binder properties, particle size distribution, active particle capacity and silicon fraction, particle density, particle shape and aspect ratio, and overall slurry composition (including, for example, the fraction and type of graphite when used in a blended anode; the fraction and type of conductive additives; the fraction and type of binder, etc.). However, it was found that smaller silicon-containing composite particles D 50 The general trend is towards smaller swelling, so the anode must be selected accordingly. The maximum allowable thickness variation depends on the cell structure. However, in general, smaller swelling may be beneficial for improved cell stability. In some cell designs, anode swelling of less than 4.5 μm (mAh / cm 2 )(less than about 4.5cm 2 In other designs, the anode swelling may preferably be less than 3.5 μm / (mAh / cm 2 )(less than about 3.5cm 2 In other designs, the anode swelling may preferably be less than 3.0 μm / (mAh / cm 2 )(less than about 3.0cm 2 In other designs, the anode swelling may preferably be less than about 2.75 μm / (mAh / cm 2 )(less than about 2.75cm 2 In some other designs, the anode swelling may preferably be less than about 2.5 μm / (mAh / cm 2 )(less than 2.5cm 2 μm / mAh).

[0180] Figure 10 The volumetric energy density (sometimes abbreviated as VED) of the test cell is shown versus the D for each exemplary particle population. 50 1002, and the volume charge density (sometimes abbreviated VQD) of the test cell versus D for each exemplary particle population. 50(Note that in these test cells, all or nearly all of the anode capacity was provided by the silicon-carbon composite particles and no graphite was added to the anode.) VQD is defined as the anode capacity (after the fourth cycle) in mAh divided by the anode volume in cm 3 VED is defined as the cell energy (after the fourth cycle) in Wh divided by the cell's external volume in liters (l). Test cells with smaller particles tend to exhibit higher VED and VQD values. For example, D 50 The test unit of the jagged composite particle group with a value of about 3.6 μm showed a VED of about 1095 Wh / l and a capacity of about 886 mAh / cm 3 Therefore, by adopting D 50 The VED and / or VQD values ​​may be increased by using a population of jagged composite particles having values ​​in the range of about 2.0 μm to about 8.0 μm, or in the range of about 2.0 μm to about 6.0 μm, or in the range of about 2.0 μm to about 5.0 μm, or in the range of about 2.0 μm to about 4.0 μm. Several factors may cause the test cells having smaller jagged composite particles to exhibit higher VED and VQD values. For example, one factor may be a reduction in z-swelling in the test cells having smaller particles (e.g., see Figure 9 For example, another factor could be the higher first cycle efficiency in the test unit with smaller particles (see, for example, Figure 13 For example, yet another factor may be the higher formation efficiency in the test cell with smaller particles (see, for example, Figure 13 For example, yet another factor may be the lower internal resistance in the test cell with smaller particles (see, for example, Figure 14 For example, yet another factor could be the higher electrode (anode) coating density in the test cell with smaller particles (see, for example, Figure 14 For example, yet another factor may be the higher discharge voltage in the test cell with smaller particles (see, for example, Figure 11 Figure 1104 in Figure 1104). In addition to the D 50 In addition to size, VED may also depend on binder properties, particle size distribution (PSD), active particle capacity and silicon fraction, particle density, particle shape and aspect ratio and / or overall slurry composition (e.g., including: graphite fraction and type; conductive additive fraction and type; binder fraction and type, etc.), among other factors. However, it was found that VED was significantly different from the D of silicon-containing composite particles. 50 The overall trend of the correlation is consistent, so in some designs, D must be selected accordingly.50 .

[0181] Figure 11 The normalized high rate discharge capacity of the test cell is shown versus the D of each exemplary particle population. 50 1102, and the discharge voltage of the test cell versus the D of each exemplary particle population. 50 (Note that in these test cells, all or nearly all of the anode capacity was provided by the silicon-carbon 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 cell discharge capacity measured after a 2C discharge divided by the cell discharge capacity measured after a 0.5C discharge, where the measurement is made after 20 cycles. 50 Test units of the jagged composite particle population with values ​​ranging from about 2.0 μm to about 5.0 μm exhibited a normalized high rate discharge capacity greater than about 90%. The higher normalized high rate discharge capacity (e.g., about 90% or greater) may be attributed to better impedance metrics (e.g., lower impedance) and / or better ion diffusion metrics due to thinner electrode coatings and / or reduced diffusion lengths at the particles (e.g., smaller particles with similar ion diffusivities to larger particles may have reduced diffusion length scales). The discharge voltage is defined as the discharge energy (Wh) divided by the discharge capacity (Ah). Some with D 50 The test cells of the jagged nanocomposite particle population with a value in the range of about 2.0 μm to about 5.0 μm exhibited a discharge voltage greater than about 3.5 V. 50 A population of jagged composite particles having a D value in the range of about 2.0 μm to about 8.0 μm, or in the range of about 2.0 μm to about 6.0 μm, or in the range of about 2.0 μm to about 5.0 μm can increase the normalized high rate discharge capacity and / or discharge voltage. 50 In addition to size, the discharge voltage and high rate discharge capacity may also depend on the binder properties, particle size distribution (PSD), the capacity and silicon fraction of active particles, particle density, design of silicon-containing nanocomposite particles, shape and aspect ratio of particles, BET-SSA of particles, and overall slurry composition (e.g., including: fraction and type of graphite; fraction and type of conductive additives; fraction and type of binder, etc.), among other factors. However, it was found that the discharge voltage and high rate capacity were significantly related to the D of silicon-containing nanocomposite particles. 50 The overall trend of the correlation is consistent, so in some designs, D must be selected accordingly. 50 to meet the required battery cell design specifications.

[0182] Figure 12Graph 1202 shows the correlation of normalized capacity (also referred to as percentage (%) of reference capacity) for a lithium-ion battery test cell (as described above, having an LCO cathode) containing D 50 The cells were cycled at least five times for each corresponding charge condition to obtain the average capacity. Therefore, by using D 50 A population of jagged composite particles having a diameter in the range of about 2.0 μm to 4.0 μm can increase the normalized capacity at faster charge rates (e.g., charge rates greater than about 2 C, or greater than about 3 C, or greater than about 4 C, or greater than about 5 C). The higher normalized capacity may be attributed to better impedance metrics (e.g., lower impedance) and / or better ion diffusion metrics (e.g., higher ion diffusivity).

[0183] Figure 13 The first cycle efficiency of the test unit is shown versus the D of each exemplary particle population. 50 1302, and the formation efficiency of the test unit and the D of each exemplary particle population. 50 (Note that in these test cells, all or nearly all of the anode capacity was provided by the silicon-carbon composite particles and no graphite was added to the anode.) The first cycle efficiency is defined as the first cycle discharge capacity divided by the first cycle charge capacity. 50 Test units of the jagged nanocomposite particle population with values ​​ranging from about 2.0 μm to about 6.0 μm exhibited a first cycle efficiency greater than about 90%. The formation efficiency is defined as the discharge capacity at the beginning of the cycle (the discharge capacity at the completion of cycle 3) divided by the first cycle charge capacity. Some having D 50 The test units of the jagged nanocomposite particle population having a value in the range of about 2.0 μm to about 6.0 μm exhibited a formation efficiency greater than about 90%. 50 A population of jagged composite particles having a size in the range of about 2.0 μm to about 6.0 μm can improve first cycle efficiency and / or formation efficiency. The higher first cycle efficiency (e.g., greater than about 90%) and / or higher formation efficiency (e.g., greater than about 90%) may be attributed to better impedance metrics (e.g., lower impedance) and / or better ion diffusion metrics (e.g., higher ion diffusivity), which results in reduced losses.

[0184] In addition to the particles D 50 In addition to size, first cycle efficiency, formation efficiency, and normalized capacity may also depend on binder properties, particle size distribution (PSD), capacity and silicon fraction of active particles, particle density, design of silicon-containing nanocomposite particles, presence of lithium capture sites or (e.g., electronegative) elements in the composition of silicon-containing composite particles, particle shape and aspect ratio, BET-SSA of particles and / or overall slurry composition (e.g., including: when used in a blended anode, the fraction and type of graphite; the fraction and type of conductive additives; the fraction and type of binder, etc.), as well as other factors. However, it was found that normalized capacity (capacity retention), first cycle efficiency, and formation efficiency were significantly related to the D of silicon-containing nanocomposite particles. 50 The overall trend of the correlation is basically consistent, so in some designs, D must be selected accordingly. 50 to meet the required battery cell design specifications.

[0185] Figure 14 The internal resistance of the test cell and the D of each exemplary particle population are shown. 50 1402, and the coating density of the electrode coating versus D for each exemplary particle population. 50 Graph 1404 of the correlation. The internal resistance is determined by applying a series of millisecond-long current pulses to the battery cell at 0% state of charge and measuring the resulting voltage. The average voltage is determined by averaging the individual voltages measured for each current pulse. The internal resistance is the average voltage divided by the applied current. Test cells with smaller particles tend to exhibit lower internal resistance. For example, some cells with D 50 Test units of the jagged nanocomposite particle population having a value in the range of about 2.0 μm to about 6.0 μm exhibited an internal resistance value of less than about 10 Ω. For example, some having D 50 Test cells with jagged nanocomposite particle populations ranging from about 2.0 μm to about 4.0 μm exhibited internal resistance values ​​ranging from about 4 Ω to about 6 Ω. The coating density includes the jagged nanocomposite particles, binder, and any additives in the electrode, but excludes the current collector. The coating density is defined as the mass of the electrode divided by the volume of the electrode. Electrode coatings with smaller particles tend to exhibit higher coating densities. For example, a coating with D 50 Some electrode coatings for populations of jagged nanocomposite particles with values ​​ranging from about 2.8 μm to about 6.0 μm exhibited a value of about 0.9 g / cm 3 to about 1.0g / cm 3 For example, some electrode coatings with D 50 Electrode coatings of a population of jagged nanocomposite particles having a particle size in the range of about 3.0 μm to about 5.0 μm exhibited a particle size of about 0.95 g / cm 3to about 1.0g / cm 3 Electrode coating density values ​​within the range.

[0186] Note that, in addition to the particle D 50 In addition to size, coating density and internal resistance may also depend on binder properties, particle size distribution (PSD), capacity and silicon fraction of active particles, particle density, design and composition of silicon-containing nanocomposite particles, conductivity of the silicon-containing composite particle surface, fraction of binder coating the surface area of ​​the particle, shape and aspect ratio of the particle, BET-SSA of the particle, overall slurry composition (e.g., including: fraction and type of graphite when used in a blended anode; fraction and type of conductive additive; fraction and type of binder, etc.), and other factors. However, it was found that coating density and internal resistance were significantly related to the D of the silicon-containing nanocomposite particles. 50 The overall trend of the correlation is basically consistent, so in some designs, D can be selected accordingly. 50 to meet the required battery cell design specifications.

[0187] Figure 15 The Brunauer-Emmett-Teller specific surface area (BET-SSA) measured by analyzing the N2 adsorption-desorption isotherm at 77K is shown versus the D of each exemplary particle population. 50 Graph 1502 of the correlation of area binder loading with D for each exemplary particle population. 50 Graph 1504 of the correlation of BET-SSA. The BET-SSA of each exemplary population of jagged nanocomposite particles was measured by nitrogen physical adsorption (at about 77 K) of a powder sample vacuum-gassed at 300° C. for 10 hours. The BET-SSA increases with particle size (e.g., D 50 ) decreases and tends to increase. For example, some D 50 The population of jagged nanocomposite particles with values ​​ranging from about 2.0 μm to about 4.0 μm exhibited a 2 / g to about 18m 2 / g range. For example, some D 50 The population of jagged nanocomposite particles with values ​​ranging from about 4.0 μm to about 6.0 μm exhibited a 2 / g to about 14m 2 / g range. For example, some D 50 The population of jagged nanocomposite particles having a value in the range of about 6.0 μm to about 8.0 μm exhibited a value of about 3 μm. 2 / g to about 12m 2The 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 the serrated composite particles in the electrode coating and (2) the BET-SSA value of the corresponding serrated composite particle population. In graph 1504, the areal binder loading is expressed in mg / m 2 In the example shown, as the particle size (e.g. D 50 ) decreases, the area binder loading tends to decrease. In smaller particles (e.g., D 50 Between about 2.0 μm and about 4.0 μm), there is a tendency for the binder per unit surface area of ​​the composite particles to decrease due to the high BET-SSA of the composite particles. For example, some D 50 A population of jagged composite particles having a value in the range of about 2.0 μm to about 4.0 μm results in an area binder loading value of about 5 mg / m2 for the corresponding electrode coating. 2 to about 14 mg / m 2 For example, some D 50 A population of jagged composite particles having a value in the range of about 4.0 μm to about 6.0 μm results in an area binder loading value of about 6 mg / m2 for the corresponding electrode coating. 2 to about 22 mg / m 2 For example, some D 50 A population of jagged composite particles having a value in the range of about 6.0 μm to about 8.0 μm results in an area binder loading value of about 8 mg / m2 for the corresponding electrode coating. 2 to about 24 mg / m 2 Lower areal binder loadings may have a beneficial effect on impedance metrics and / or ion diffusion metrics. In some embodiments, the areal binder loading of a battery electrode (e.g., an anode comprising silicon-carbon nanocomposite particles) is about 2.0 mg / m 2 to about 15.0 mg / m 2 (For example, in some designs, approximately 2.0 mg / m 2 to about 5.0 mg / m 2 In other designs, approximately 5.0 mg / m 2 to about 9.0 mg / m 2 In some other designs, about 9.0 mg / m 2 to about 13.0 mg / m 2 ) within the scope of .

[0188] In some embodiments, having a 50Lithium ion battery cells having anodes with smaller jagged composite particles having values ​​ranging from about 2.0 μm to about 4.0 μm exhibit advantageous properties such as less z swelling (e.g., graph 904), higher VED (e.g., graph 1002), higher VQD (e.g., graph 1004), faster discharge (e.g., graph 1102), faster charge (e.g., graph 1202), higher discharge voltage (e.g., graph 1104), and lower internal resistance (e.g., graph 1402). However, in some embodiments, compared to cells having anodes containing D 50 Compared to some lithium ion battery cells having anodes containing smaller jagged composite particles having a value in the range of about 2.0 μm to about 4.0 μm, 50 Some lithium ion battery cells having anodes with larger jagged composite particles having values ​​in the range of about 4.0 μm to about 7.0 μm or in the range of about 4.0 μm to about 6.0 μm exhibited better cycle life.

[0189] Another property that can be determined from the particle size distribution (PSD) of a particle population is the cumulative volume fraction, which is defined as D 50 The value is the threshold D 50 The cumulative volume of particles with a value of D or lower is divided by the total volume of all particles. In some examples considered herein, the threshold D 50 The value is set to 4.6 μm. 50 The cumulative volume fraction (D 50 The threshold value is 4.6 μm) in the range of about 58% to about 96%. Lithium-ion battery test cells were made with anodes containing each of these particle groups, and the cycle life of each test was measured. The results are shown in Figure 2. Figure 16 Graph 1602 shows the cycle life (in a silicon-carbon composite anode / LCO cathode cell) versus the respective cumulative volume fractions (D 50The threshold value is about 4.6 μm). Some examples with higher cumulative volume fractions (e.g., greater than about 80 vol.%, or greater than about 85 vol.%, or greater than about 90 vol.%) exhibit shorter cycle lives (e.g., less than about 500 cycles, or less than about 450 cycles, or less than about 400 cycles). Higher cumulative volume fractions may indicate the presence of a larger number of finer particles (e.g., with a particle size less than about 2.0 μm, or less than about 1.0 μm, or less than about 0.5 μm), which may result in more frequent undesirable side reactions between the composite particles and the electrolyte. In some embodiments, by adjusting the PSD of the jagged composite particle population, cycle life values ​​of greater than about 500 cycles, or greater than about 550 cycles, or greater than about 600 cycles can be achieved. In some embodiments, the PSD can be adjusted to obtain a cumulative volume fraction (4.6 μm threshold) of less than about 90%, or less than about 85%, or less than about 80%, or in the range of about 60% to about 85%, or in the range of about 60% to about 80%, or in the range of about 70% to about 85%, or in the range of about 70% to about 80%, or in the range of about 65% to about 85%, or in the range of about 65% to about 80%.

[0190] In About Figure 16 In the above example, D 50 The value is in the range of about 2.0 μm to about 4.0 μm, the corresponding cumulative volume fraction (D 50 The lithium-ion battery cell performance characteristics of a composite particle population having a threshold of about 4.6 μm (in a silicon-carbon composite anode / LCO cathode battery cell) in the range of about 58% to about 96% are shown. In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is in the range of about 1.0 μm to about 12.0 μm (in some designs, about 1.0 μm to about 2.0 μm; in other designs, about 2.0 μm to about 4.0 μm; in still other designs, about 4.0 μm to about 6.0 μm; in still other designs, about 6.0 μm to about 12.0 μm). In some embodiments (e.g., when D 50 In other embodiments (e.g., when D 50 In some other embodiments (e.g., when D 50In the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction at a threshold particle size of about 15 μm is about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less. Note that the presence of overly large particles may degrade battery performance characteristics (e.g., reduce battery cell stability, increase its impedance, reduce rate performance, etc.). In some embodiments (e.g., when D 50 In some embodiments (e.g., when D 50 In other embodiments (e.g., when D 50 In other embodiments (e.g., when D 50 In other embodiments (e.g., when D 50 In some other embodiments (e.g., when D 50 In the range of about 6.0 μm to about 12.0 μm), the cumulative volume fraction at a threshold particle size of about 32 μm is about 90 vol. % or higher.

[0191] As shown in graph 1502, the BET-SSA value shows that the D 50 Therefore, as shown in 1504, if the binder mass fraction in the electrode coating is maintained in the range of about 6.5 wt.% to about 11.5 wt.%, the area binder loading also shows a correlation with D 50 The correlation of the values ​​of D was obtained by using different binder mass fractions in the electrode (anode) coating. 50 Several lithium-ion battery cells were prepared by anodes containing a population of jagged nanocomposite particles of approximately 7.42 μm and combined with a 50 A comparison was made with lithium-ion battery cells containing anodes containing a population of jagged nanocomposite particles of approximately 5.35 μm. Figure 17 A graph 1702 is shown showing the correlation of areal binder loading with the binder mass fraction for each selected particle population. 50The binder mass fraction of the test cells of approximately 7.42 μm varied between approximately 6.5 wt.% and approximately 11.5 wt.%. In the example shown, a binder mass fraction of approximately 6.5 wt.% corresponds to a mass fraction of the jagged composite particles in the electrode of approximately 93.4 wt.%. In the example shown, a binder mass fraction of approximately 11.5 wt.% corresponds to a mass fraction of the jagged composite particles in the electrode of approximately 88.4 wt.%. 50 The control sample test unit with a size of about 5.35 μm had a binder mass fraction of about 10.4 wt.%. The area binder loading was about 8 mg / m 2 to about 16 mg / m 2 within the range.

[0192] Figure 18 Shown Figure 17 Graph 1802 shows the correlation between the cycle life of each test unit and the binder mass fraction. Test units with a binder mass fraction of about 10.4 wt.% and about 11.5 wt.% (D 50 About 7.42 μm) exhibited lithium plating during charging, indicating that at least part of the measured capacity is attributable to lithium plating on the copper current collector. In some designs, lithium plating is preferably avoided for safety reasons. In some embodiments, the area binder loading (e.g., greater than about 13 mg / m) corresponding to these binder mass fractions (e.g., about 10.4 wt.%, about 11.5 wt.%) 2 ) may be too high. In other test units (D 50 about 7.42 μm, with a binder mass fraction of about 6.5 wt.%, about 7.5 wt.%, about 8.5 wt.% and about 9.5 wt.%) and a control sample test unit (D 50 No lithium deposition was observed in the test unit with a binder mass fraction of about 6.5 wt.% (D 50 The coatings with intermediate binder mass fraction values ​​(e.g., about 7.5 wt.%, about 8.5 wt.%, about 9.5 wt.%) and corresponding areal binder loading values ​​(e.g., at about 9.0 mg / m 2 to about 13 mg / m 2 ) exhibited cycle life values ​​greater than 800 cycles. 50In the range of about 6.0 μm to about 8.0 μm), preferably, the binder mass fraction is greater than about 6.6 wt.%, or greater than about 7.0 wt.%, or less than about 10.3 wt.%, or less than about 10.0 wt.%, or in the range of about 6.6 wt.% to about 10.3 wt.%, or in the range of about 6.6 wt.% to about 10.0 wt.%, or in the range of about 7.0 wt.% to about 10.3 wt.%, or in the range of about 7.0 wt.% to about 10.0 wt.%, or in the range of about 7.0 wt.% to about 8.0 wt.%, or in the range of about 8.0 wt.% to about 9.0 wt.%, or in the range of about 9.0 wt.% to about 10.0 wt.%. In some embodiments (e.g., D 50 In the range of about 6.0 μm to about 8.0 μm), preferably, the area adhesive loading value is greater than about 9.0 mg / m 2 , or less than about 13.0 mg / m 2 , or about 9.0 mg / m 2 to about 13.0 mg / m 2 in the range of, or about 9.0 mg / m 2 to about 10.0 mg / m 2 in the range of, or about 10.0 mg / m 2 to about 11.0 mg / m 2 in the range of, or about 11.0 mg / m 2 to about 12.0 mg / m 2 in the range of, or about 12.0 mg / m 2 to about 13.0 mg / m 2 within the range.

[0193] Figure 18 Shown Figure 17 Graph 1804 of the normalized coating thickness variation versus binder mass fraction for each test unit. The normalized thickness variation data indicates swelling of the electrode coating in the thickness direction (z swelling). In the test unit shown (D 50 The normalized coating thickness variation is maintained at less than about 3.0 μm (cm) for binder mass fractions of about 7.0 wt.% to about 10.0 wt.%. 2 / mAh), which is consistent with D 50 Other lithium-ion battery cells are comparable (eg, graph 904 ) for a population of jagged composite particles in the range of about 2.0 μm to about 4.0 μm.

[0194] Figure 19 Shown Figure 17 A graph 1902 showing the correlation between the volume energy density (VED) of each test unit and the mass fraction of the binder, and Figure 17 Graph 1904 shows the correlation between the volume charge density (VQD) of each test unit and the binder mass fraction. 50 Greater than about 650 mAh / cm was observed in a 100 μm (about 7.42 μm) binder mass fraction of about 7.0 wt.% to about 10.0 wt.%). 3 A VQD value of greater than about 950Wh / l and a VED value of greater than about 950Wh / l.

[0195] Figure 20 Shown Figure 17 A graph 2002 showing the correlation between the discharge voltage of each test unit and the binder mass fraction, and Figure 17 Graph 2004 shows the correlation between the internal resistance of each test unit and the mass fraction of the binder. In the test unit (D 50 A discharge voltage value greater than about 3.5 V and an internal resistance value ranging from about 15Ω to about 25Ω were observed in the sample (about 7.42 μm).

[0196] Figure 21 Shown Figure 17 A graph 2102 showing the correlation between the first cycle efficiency of each test unit and the mass fraction of the adhesive, and Figure 17 Graph 2104 shows the correlation between the formation efficiency of each test unit and the mass fraction of the binder. In the test unit (D 50 Formation efficiency values ​​greater than about 83% and first cycle efficiency values ​​greater than about 83% were observed for the 100 nm CMOS process (approximately 7.42 μm).

[0197] In some designs (e.g., in blended anodes having a capacity of about 450 mAh / g to about 1600 mAh / g when normalized by the mass of active material, wherein the active material is, for example, graphite and a silicon-carbon composite or other silicon-containing anode material; in some designs, for blended anodes having a capacity of about 500 mAh / g to about 1400 mAh / g when normalized by the mass of active material; in some designs, for blended anodes having a capacity of about 600 mAh / g to about 1200 mAh / g when normalized by the mass of active material), a narrow particle size distribution (PSD) of the silicon-containing composite (e.g., silicon-carbon nanocomposite) particles may be advantageous. A high proportion of fine particles (undesirably small particles) in the silicon-carbon composite powder has been found to increase the external surface area of ​​these particles, the BET-SSA of these particles, and the surface area of ​​these particles exposed to the electrolyte during cycling, and can lead to a larger volume fraction of SEI formed during formation and storage, faster degradation during cycling, faster degradation during battery storage at room temperature and elevated temperatures, excessive gassing during formation, and other undesirable consequences. In particular, in some designs, it has been found that it may be advantageous for the silicon-carbon nanocomposite (for blended anodes) to have a D of 0.001 for spherical (e.g., spherical or nearly spherical) particles. 10 (measured using laser scattering or other suitable techniques) exceeds about 1 μm, while for jagged (or cylindrical) particles, D 10 More than about 2 μm. In some designs, the D 10 Preferably, the BET-SSA of the silicon-carbon nanocomposite powder (for blended anodes) is in the range of about 1 μm to about 7 μm (in some designs, about 2 μm to about 3 μm; in other designs, about 3 μm to about 4 μm; in other designs, about 4 μm to about 5 μm; in other designs, about 5 μm to about 6 μm; in still other designs, about 5 μm to about 6 μm). In some designs, it has been found that it may be advantageous to have a BET-SSA of the silicon-carbon nanocomposite powder (for blended anodes) in the range of about 1 μm to about 7 μm. 2 / g to about 11m 2 / g range (in some designs, about 1m 2 / g to about 2m 2 / g; in other designs, about 2m 2 / g to about 4m 2 / g; in other designs, about 4m 2 / g to about 6m 2 / g; in other designs, about 6m 2 / g to about 8m 2 / g; in other designs, about 8m 2 / g to about 11m 2 / g; in other designs, about 3m 2 / g to about 7m2 / g).

[0198] Interestingly, in some designs, the optimal PSD and optimal D of the Si-C composite particles of the blended anode were found to be higher than that of the anode containing only Si-C composite as active material. 50 、D 90 and D 99 May be different.

[0199] In order to obtain good performance in the battery, it was found that the silicon-carbon nanocomposite (in the blended anode) needs to exhibit a moderately small volume change during cycling and therefore contain internal pores (e.g., a total pore volume in the range of about 5 vol.% to about 50 vol.%, estimated using powder density measurements or argon pycnometers or other suitable techniques). However, the blended anode needs to be densified (calendered) to obtain high volumetric capacity and sufficient performance in the battery cell. The smaller the weight percentage (wt.%) of the silicon-carbon composite in the blended anode, the higher the calendering (densification) pressure is generally required. Such high pressures may cause the silicon-carbon composite to crack, exposing part of its internal surface area and internal pores to the ambient air (and the electrolyte in the battery), which may lead to excessive side reactions with the electrolyte. Although the BET of large silicon-carbon composites is small, silicon-carbon composite particles that are too large may suffer more of this mechanical damage during the calendering process. In addition, we found that silicon-carbon composite particles that are too large may increase the roughness of the blended anode (especially for anodes that exhibit smaller areal capacity loading), may reduce its volumetric capacity, may increase the inhomogeneity of the areal capacity distribution, may significantly reduce the mechanical stability of the anode during cycling (e.g., causing collector delamination or active material separation), may cause damage to the separator, etc., and it was found that this would reduce the cycling stability.

[0200] In particular, in some designs (e.g., in blended anodes having an anode capacity of about 450 mAh / g to about 1600 mAh / g when normalized by the mass of active material, wherein the active material is, for example, graphite and a silicon-carbon composite or other silicon-containing anode material; in some designs, for blended anodes having a capacity of about 500 mAh / g to about 1400 mAh / g when normalized by the mass of active material; in some designs, for blended anodes having a capacity of about 600 mAh / g to about 1200 mAh / g when normalized by the mass of active material), it was found that it may be advantageous for the silicon-carbon nanocomposite powder (for the blended anode) to have a D of about 100 mAh / g for spherical (e.g., spherical or nearly spherical) particles. 90less than about 40 μm (in some 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, less than about 15 μm) (measured using laser scattering or other suitable technique), and for jagged particles, D 90 less than about 40 μm (in some 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, less than about 15 μm), while for cylindrical particles, D 90 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, less than about 25 μm; in other designs, less than about 20 μm; in other designs, less than about 15 μm). In some designs, it has been found that it may be advantageous for the silicon-carbon nanocomposite (for blended anodes) to have a D of less than about 60 μm for spherical (e.g., spherical or nearly spherical) particles. 99 less than about 50 μm (in some designs, less than about 40 μm; in other 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, less than about 20 μm) (measured using laser scattering or other suitable technique), and for jagged particles, D 99 less than about 50 μm (in some designs, less than about 40 μm; in other 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, less than about 20 μm), while for cylindrical particles, D 99 Less than about 80 μm (in some designs, less than about 60 μm; in other 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, less than about 20 μm). Note that in automotive applications, lithium-ion batteries typically exhibit greater areal capacity loading, so the electrodes are typically thicker than lithium-ion batteries in consumer applications (such as laptops, mobile phones, fitness trackers, etc.) or consumer drone applications. Thicker electrodes can allow for larger D 50 、D 90 or D 99 .

[0201] To achieve good performance in lithium-ion batteries, in some designs, it was found that the full width at half maximum (FWHM) of the particle size distribution of the silicon-carbon nanocomposite powder (e.g., in blended anodes having an anode capacity of about 450 mAh / g to about 1600 mAh / g when normalized by the mass of active material, wherein the active material is, for example, graphite and a silicon-carbon composite or other silicon-containing anode material; in some designs, for blended anodes having a capacity of about 500 mAh / g to about 1400 mAh / g when normalized by the mass of active material; in some designs, for blended anodes having a capacity of about 600 mAh / g to about 1200 mAh / g when normalized by the mass of active material) is preferably in the range of about 3 μm to about 12 μm (in some designs, about 4 μm to about 8 μm; in some designs, about 5 μm to about 7 μm; in some designs, about 3 μm to about 5 μm; in some designs, about 7 μm to about 9 μm; in some designs, about 9 μm to about 12 μm).

[0202] To achieve good performance in lithium-ion batteries, the particle size distribution of silicon-carbon nanocomposite powders was found to span (D 90 -D 10 ) / D 50 ) (in blended anodes having a capacity of about 450 mAh / g to about 1600 mAh / g when normalized by the mass of active material, wherein the active material is, for example, graphite and a silicon-carbon composite or other silicon-containing anode material; in some designs, for blended anodes having a capacity of about 500 mAh / g to about 1400 mAh / g when normalized by the mass of active material; in some designs, for blended anodes having a capacity of about 600 mAh / g to about 1200 mAh / g when normalized by the mass of active material) preferably less than about 3 (in some designs, more preferably less than about 2; in other designs, more preferably less than about 1; in other designs, more preferably less than about 0.8). In some designs, the span of the particle size distribution of the silicon-carbon nanocomposite powder (in such a blended anode) may preferably be in the range of about 0.3 to about 3 (in some designs, more preferably about 0.3 to about 2; in other designs, more preferably about 0.3 to about 1.0; in other designs, more preferably about 0.3 to about 0.8; in other designs, more preferably about 0.4 to about 1.2).

[0203] Figure 22An SEM image (2201) of a population of jagged composite particles (including agglomerates of jagged particles) is shown, wherein no optimization of the particle size distribution (PSD) of the population has been performed. The particles shown in SEM image 2201 include fine particles (so-called "fines") and coarse particles. Some 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 below a threshold value (e.g., about 0.5 μm, about 1.0 μm, about 1.5 μm, about 2.0 μm, etc.). The definition of coarse particles depends on the specific embodiment, but can be defined as particles having a diameter (e.g., as measured by LPSA) equal to or above a threshold value (e.g., about 5 μm, about 7 μm, about 8 μm, about 10 μm, about 15 μm, about 20 μm, about 30 μm, about 40 μm, about 50 μm, etc.). The composite particles in SEM image 2201 have a jagged, irregular shape and can exhibit a range of aspect ratios. These composite particles are in their prepared form and the PSD of the particle population has not been optimized. 50 About 10μm.

[0204] Figure 22 An SEM image (2202) of a cross section of an electrode coating is shown, the electrode coating comprising a blended mixture of the jagged particle group shown in 2201 and graphite particles as the electrode active material. The slurry comprising the electrode active material is cast onto a copper current collector and the slurry solvent is allowed to dry. The electrode coating is calendered under a force of 14 tons. Despite the calendering process, the cross-sectional image 2202 shows that some particles protrude from the surface of the electrode coating. This effect can be observed, for example, if the composite particle group includes particles having a diameter greater than the thickness of the electrode coating. It has been found that in lithium-ion batteries with blended anodes (particularly in automotive and consumer lithium-ion batteries), the use of a Figure 22 The composite particles in the examples often result in suboptimal (usually insufficient or unacceptable) performance. Here, the term "blended anode" refers to an anode whose electrode active material comprises a blended mixture of composite particles and graphite particles.

[0205] Figure 23 An SEM image (2301) of a jagged composite particle group after optimization of the particle size distribution (PSD) of the particle group is shown. 50 The PSD optimization process includes the removal of fine particles (the D 50 about 1.5μm) and removal of coarse particles (D 50is approximately 15 μm). For the results shown, the removal of fine and coarse particles was accomplished by screening. In other embodiments, other particle size selection processes may be used (e.g., screening or centrifugation or other pneumatic particle size classification or other processes). In SEM image 2301, the number of fine and coarse particles is reduced compared to SEM image 2201. The PSD variance in the particle population of 2301 (after PSD optimization) is less than the PSD variance in the particle population of 2201 (without PSD optimization). The particle population of 2301 appears to be more uniform in size compared to the particle population of 2201.

[0206] Figure 23 An SEM image (2302) of a cross section of an electrode coating is shown, the electrode coating comprising a blended mixture of the jagged particles shown in 2301 and graphite particles as the electrode active material. The slurry comprising the electrode active material is cast onto a copper current collector and the slurry solvent is allowed to dry. The electrode coating is rolled under a force of 14 tons. No particle protrusions are observed in the cross section image 2302 compared to the cross section image 2202. The surface of the electrode coating appears to be smooth. It has been found that in lithium ion batteries with blended anodes (particularly in automotive and consumer grade lithium ion batteries), the use of Figure 23 The composite particles in the examples generally result in excellent (usually very good, good enough, or acceptable) performance.

[0207] Figure 24 Graphs 2401 and 2402 show volume weighted particle size distributions (PSDs) (expressed in vol.%) for an exemplary population of jagged composite particles. Graph 2401 shows the volume weighted particle size distributions (PSDs) for an exemplary population of jagged composite particles, expressed in vol. %. Graph 2401 shows the volume weighted particle size distributions (PSDs) for an exemplary population of jagged composite particles, expressed in vol. %, for an exemplary population of jagged composite particles, ... 50 Graph 2402 shows: (1) the PSD of an exemplary particle population before any optimization of its PSD (D 50 about 10.1 μm); and (2) the PSD of the exemplary particle population after its PSD is optimized (D 50 The PSD optimization process includes fine particle removal and coarse particle removal. As a result of these PSD optimization processes, the PSD has changed from a relatively wide PSD (e.g., a larger span, a larger full width at half maximum (FWHM)) to a relatively narrow PSD (i.e., a smaller span, a smaller FWHM). Figure 24 As shown, FWHM refers to the full width at half maximum of the PSD distribution.

[0208] Table 1 Figure 25 ) summarizes selected properties of an exemplary population of serrated composite particles (D 10 、D 50 、D90 、D 99 , span, FWHM, D 10 / D 50 , BET-SSA). Graph 2401 shows: (1) D 50 The PSD of the particle group of about 3.65 μm corresponds to the composite particle sample #1 in Table 1; (2) D 50 The PSD of the particle group is about 5.03 μm, corresponding to the composite particle sample #2 in Table 1; (3) D 50 The PSD of the particle population is about 8.02 μm, corresponding to the composite particle sample #3 in Table 1; and (4) D 50 The PSD of the particle population is about 13.31 μm, corresponding to the composite particle sample #5 in Table 1. As shown in Table 1, these particle population samples (#1, #2, #3, and #5) have not undergone any optimization of their PSD (so-called "wide" PSD). Graph 2401 shows that by adjusting the synthesis conditions of the composite particles and the conditions for crushing larger particles into smaller particles, a relatively wide range of PSDs (e.g., in the range of about 1.9 to about 2.07) can be obtained. 50 A population of jagged composite particles having a range of values ​​(e.g., in the example shown, a range of about 3.65 μm to about 13.31 μm). A population of particles that has not undergone PSD optimization (e.g., the sample shown in 2401) may have been comminuted to obtain a desired average particle size (e.g., D 50 ), but fine and coarse particles have not been removed.

[0209] Graph 2402 shows: (1) D 50 The PSD of the particle population is approximately 9.82 μm, corresponding to the composite particle sample #8 in Table 1; and (2) D 50 The PSD of the particle population is approximately 10.16 μm, corresponding to the composite particle sample #4 in Table 1. Graph 2402 compares the span of a jagged composite particle population that has not undergone PSD optimization (sample #4, span of approximately 1.97 and full width at half maximum of approximately 23.0 μm) and the span of a jagged composite particle population that has undergone PSD optimization (sample #8, span of approximately 0.67 and full width at half maximum of approximately 6.0 μm). Thus, graph 2402 shows that performing PSD optimization (e.g., removing fine particles, removing coarse particles) has a significant impact on the span and FWHM of the jagged composite particle population.

[0210] In Table 1 ( Figure 25), particle group samples #1, #2, #3, #4 and #5 have not undergone the PSD optimization process and are referred to as having a "wide" PSD. Particle group samples #6, #7, #8 and #9 have undergone the PSD optimization process and are referred to as having a "narrow" PSD. Each particle group sample is used to make two types of blended anode electrodes: Type A and Type B. Each particle group sample of the serrated composite silicon-carbon particles exhibits a first cycle lithiation capacity of approximately 1900 mAh / g (corresponding to a mass fraction of silicon in the silicon-carbon composite material particles of approximately 51 wt.%, with the remaining silicon-carbon composite material particles containing carbon). In the example shown, the blended anode electrode active material comprises a blended mixture of graphite particles and corresponding serrated composite material particles. In the Type A electrode, the electrode active material exhibits a first cycle lithiation capacity of approximately 600 mAh and comprises approximately 16 wt.% of the corresponding serrated composite material particles and approximately 84 wt.% of graphite particles. In the B-type electrode, the electrode active material exhibited a first cycle lithiation capacity of about 1000 mAh and contained about 42 wt.% of the corresponding serrated composite particles and about 58 wt.% of graphite particles. For each electrode type (type A, type B) of each particle group sample, the coating density measured after calendering is shown in Table 1. For each electrode type of each particle group sample, a lithium-ion battery cell was manufactured and its performance characteristics were evaluated. The cycle life of the lithium-ion battery cell for each electrode type and each composite particle group was recorded. In some embodiments of the blended anode (e.g., a blended mixture of silicon-carbon composite particles and graphite particles), the mass fraction of the silicon-carbon composite particles (e.g., serrated silicon-carbon 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 wt.% to about 20 wt.%, about 20 wt.% to about 30 wt.%, about 30 wt.% to about 40 wt.%, about 40 wt.% to about 50 wt.%, about 50 wt.% to about 60 wt.%, or about 60 wt.% to about 70 wt.%). In some embodiments of the blended anode (e.g., a blended mixture of silicon-carbon 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 wt.% to about 40 wt.%, about 40 wt.% to about 50 wt.%, about 50 wt.% to about 60 wt.%, about 60 wt.% to about 70 wt.%, about 70 wt.% to about 80 wt.%, or about 80 wt.% to about 90 wt.%).

[0211] The manufacturing and testing details of the electrodes and lithium-ion battery cells listed in Table 1 are as follows. For the Type A (about 600 mAh / g) electrode, an aqueous slurry containing a polyacrylic acid (PAA) salt copolymer-based binder (about 4 wt.%), single-walled carbon nanotubes (about 0.05 wt.%), and an anode electrode active material (about 95.95 wt.%) was coated on a 10-μm thick copper foil at an areal capacity loading of about 4.1 mAh / cm 2 The electrode active material (about 100 parts by weight) is a blended mixture of silicon-carbon composite particles (about 16 parts by weight) and graphite particles (about 84 parts by weight). The Type A electrode was calendared with an applied force of 16 tons to obtain a coating density in the range of about 1.53 g / cm 3 to about 1.76 g / cm 3 For the Type B (about 1000 mAh / g) electrode, an aqueous slurry containing a polyacrylic acid (PAA) salt copolymer-based binder (about 6.6 wt.%), single-walled carbon nanotubes (about 0.1 wt.%), and an anode electrode active material (about 93.3 wt.%) was coated on a 10-μm thick copper foil at an areal capacity loading of about 4.1 mAh / cm 2 The electrode active material (about 100 parts by weight) is a blended mixture of silicon-carbon composite particles (about 42 parts by weight) and graphite particles (about 58 parts by weight). The Type B electrode was calendared with an applied force of 14 tons to obtain a coating density in the range of about 1.27 g / cm 3 to about 1.42 g / cm 3 Then the electrodes were assembled into single-layer pouch full cells (with an area of about 6.25 cm 2 ) having a cathode of NCM811 (a lithium nickel cobalt manganese oxide (NCM) with a composition approximately Li[Ni 0.8 Co 0.1 Mn 0.1 O2), a 10-μm ceramic separator, and an electrolyte formulation containing 13.92 wt.% of LiPF6 (as the primary lithium salt), 13.33 wt.% of fluoroethylene carbonate (FEC), 5.04 wt.% of ethylene carbonate (EC), 3.85 wt.% of ethyl methyl carbonate (EMC), 62.49 wt.% of dimethyl carbonate (DMC), 0.52 wt.% of vinylene carbonate (VC), and 0.85 wt.% of lithium difluorophosphate (LFO). After adding the electrolyte formulation to the lithium-ion battery cells, the cells were cycled under the following charge / discharge test conditions. The charge / discharge test conditions included charging at 2C to 4.0V and gradually decreasing to 1C under constant current and constant potential (CCCP), then charging at 1C to 4.2V and gradually decreasing to 0.05C, and then discharging at 1C.

[0212] Table 1 ( Figure 25) reports the cycle life performance of lithium-ion battery cells obtained from each composite particle population and each electrode type. For each composite particle population, the battery cells with type A (about 600 mAh / g) electrodes have greater cycle life values ​​than the battery cells with type B (about 1000 mAh / g) electrodes. Cycle life values ​​greater than 1900 cycles were measured for the following three "narrow" PSD samples: (1) Particle population #7, electrode types A, D 10 About 4.69μm, D 50 About 6.77μm, D 10 / D 50 The ratio is about 69%, the span is about 0.74, and the BET-SSA is about 6.7m 2 / g, 2251 cycles; (2) Particle group #8, electrode type A, D 10 About 7.05μm, D 50 About 9.82μm, D 10 / D 50 The ratio is about 72%, the span is about 0.67, and the BET-SSA is about 3.7m 2 / g, 2276 cycles; and (3) particle group #9, electrode types A, D 10 About 11.61μm, D 50 About 16.8μm, D 10 / D 50 The ratio is about 69%, the span is about 0.74, and the BET-SSA is about 2.8m 2 / g, 1919 cycles. The cycle life values ​​of another “narrow” PSD sample are not as good, such as particle group #6, electrode type A, D 10 About 0.9μm, D 50 About 2.69μm, D 10 / D 50 The ratio is about 33%, the span is about 1.58, and the BET-SSA is about 14.5m 2 / g, 983 cycles. Compared with other “narrow” PSD particle groups #7, #8 and #9, particle group #6 showed a smaller D 10 , smaller D 50 , larger span and larger BET-SSA. For further comparison, the “wide” PSD particle population implemented in type A electrodes exhibited cycle life values ​​ranging from about 973 cycles to 1380 cycles. 10 In the range of 1.1 μm to 3.01 μm (corresponding to D 10 / D 50 ratio is in the range of 23% to 30%), span is in the range of about 1.9 to about 2.07, BET-SSA is in the range of about 5.8m2 / g to 14.3m 2 In some embodiments, 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, a beneficial effect on cycle life (and other battery characteristics) may be observed. In addition, in some embodiments, the span may be greater than about 0.3, greater than about 0.5, or greater than about 0.6. In some embodiments, when the BET-SSA of the composite material particles is less than about 15 m 2 / g, less than about 12m 2 / g, less than about 10m 2 / g, less than about 8m 2 / g, less than about 7m 2 / g, less than about 6m 2 / g, less than about 5m 2 / g, less than about 4m 2 / g or less than about 3m 2 / g, a beneficial effect on cycle life (and other battery characteristics) can be observed. In addition, in some embodiments, the BET-SSA can be greater than about 1m 2 / g, greater than about 2m 2 / g, greater than about 5m 2 / g, or greater than about 8m 2 / g. In some embodiments, when D 10 When D is greater than about 0.5 μm, greater than about 1.0 μm, greater than about 1.5 μm, or greater than about 2.0 μm, beneficial effects on cycle life (and other battery characteristics) may be observed. 10 / D 50 When the ratio is greater than about 35%, greater than about 45%, greater than about 55%, or greater than about 65%, a beneficial effect on cycle life (and other battery characteristics) may be observed. 10 / D 50 The ratio may be less than about 80% or less than about 75%.

[0213] Figure 26 An SEM image (2601) of a population of spherical composite particles is shown. In the example shown, the D 50 The value is in the range of about 5 μm to about 7 μm. Here, the term “spherical” refers to a nearly spherical or spherical round shape, as illustrated in the SEM image 2601 .

[0214] Figure 27Graph 2701 is shown, which shows the BET-SSA values ​​of an exemplary population of composite particles (jagged composite particles before PSD optimization (exhibiting so-called "broad" PSD), jagged composite particles after PSD optimization (exhibiting so-called "narrow" PSD), and spherical particles) versus their respective D 50 An example of a spherical particle is Figure 26 In the example shown, D 50 The values ​​are measured by LPSA. Graph 2701 shows the trend between jagged composite particles with a "wide" PSD, jagged composite particles with a "narrow" PSD, and spherical particles that exhibit a relatively narrow PSD. For a particular D 50 values ​​(e.g., 8 μm, 10 μm, 12 μm), spherical particles (with relatively narrow PSD) exhibit the smallest BET-SSA values, followed by jagged particles with "narrow" PSD that have undergone PSD optimization, and then jagged particles with "wide" PSD that have not undergone PSD optimization. Smaller BET-SSA values ​​may indicate that the silicon-carbon powder (silicon-carbon composite particles) has a smaller surface area. When used in blended anodes, the use of composite particles with a smaller surface area may result in excellent lithium-ion battery performance (e.g., longer calendering life and / or longer cycle stability and / or better high temperature stability, etc.). However, when the particle size of the silicon-carbon composite particles (e.g., D of the silicon-carbon composite particles) is smaller than that of the silicon-carbon composite particles, the BET-SSA value may be greater than that of the spherical particles (e.g., D of the silicon-carbon composite particles). 50 , or more specifically, D 90 or D 99 ) becomes too large, the lithium-ion battery performance may be reduced despite the small BET-SSA value and / or small surface area of ​​the silicon-carbon composite particles. In some cases, an excessively large D may be insufficient for the performance of lithium-ion batteries with a blended anode. 90 and D 99 Maybe D is too large 50 In some designs, the D of the jagged (or cylindrical) composite particles 50 Preferably, the diameter of the zigzag (or cylindrical) composite particles is in the range of about 5 μm to about 15 μm (in some designs, about 5 μm to about 7 μm; in other designs, about 7 μm to about 9 μm; in other designs, about 9 μm to about 11 μm; in other designs, about 11 μm to about 13 μm; in other designs, about 13 μm to about 15 μm; in still other designs, about 8 μm to about 12 μm; in still other designs, about 6 μm to about 10 μm; in still other designs, about 6 μm to about 12 μm; in still other designs, about 6 μm to about 9 μm). In some designs, the D of the zigzag (or cylindrical) composite particles is about 1 μm to about 1 μm. 50 Preferably, it is in the range of about 2 μm to about 17 μm.

[0215] Figure 28 Graphs 2802, 2804, and 2806 illustrate selected PSD characteristics of exemplary particle populations of jagged composite particles. Graph 2802 illustrates the PSD characteristics of various particle populations of jagged composite particles. 99 Value and D 50 The correlation of the values ​​of θ and θ illustrates the trend between the particle population that did not undergo PSD optimization (so-called "wide" PSD) and the particle population that did undergo PSD optimization (so-called "narrow" PSD). 90 Value and D 50 The correlation of the values ​​of θ and θ illustrates the trend between the particle population that did not undergo PSD optimization (so-called "wide" PSD) and the particle population that did undergo PSD optimization (so-called "narrow" PSD). 10 Value and D 50 The correlation of the values ​​illustrates the trend between the population of particles that have not undergone PSD optimization (so-called “broad” PSD) and the population of particles that have undergone PSD optimization (so-called “narrow” PSD).

[0216] Figure 29 Graphs 2901 and 2902 are shown showing the cycle life performance of lithium-ion batteries (made of blended anodes / NCM cathodes of silicon-carbon nanocomposite and graphite) made using various exemplary particle groups of jagged composite particles in the anode versus the D of the various exemplary particle groups. 50 The electrodes and battery cells were fabricated and tested as described herein. Figure 24 and Table 1( Figure 25 ). Graphs 2901 and 2902 show the trends between a population of particles that did not undergo PSD optimization (so-called "wide" PSD) and a population of particles that did undergo PSD optimization (so-called "narrow" PSD). In the example shown, a lithium-ion battery employed an anode comprising a mixture of jagged composite particles and graphite particles ("active material mixture"). Graph 2901 shows cycle life (N80) data for a lithium-ion battery employing an A-type electrode (electrode active material capacity of approximately 600 mAh / g). Graph 2902 shows cycle life data (N80) for a lithium-ion battery employing a B-type electrode (electrode active material capacity of approximately 1000 mAh / g).

[0217] For a specific D 50values ​​and specific electrode types (electrode active material capacity of about 600 mAh / g or about 1000 mAh / g), lithium-ion battery cells using "narrow" PSDs that have undergone PSD optimization show greater cycle life data (N80) than lithium-ion battery cells using "wide" PSDs that have not undergone PSD optimization. For type A electrodes (electrode active material capacity of about 600 mAh / g), the use of "narrow" PSDs significantly improves the cycle life (N80); in some cases, an increase of more than 60% in N80 is observed, exceeding 2400 cycles. Improved cycle life using "narrow" PSDs is also observed in type B electrodes; in some cases, an increase of more than 60% in cycle life values ​​(N80) is observed. For D 50 For a specific value of N, lithium-ion battery cells with lower capacity blended anodes (about 600 mAh / g of electrode active material capacity) generally have longer cycle life (N80) than lithium-ion battery cells with higher capacity blended anodes (about 1000 mAh / g of electrode active material capacity) ( Figure 29 ). With D 50 The value starts to increase from about 2 to 3 μm, and initially better cycling stability (e.g., longer cycle life (N80)) is observed, which may be due to factors such as less frequent side reactions between the electrolyte and the composite particles (e.g., as exemplified by smaller SEI (or solid electrolyte interface) growth). A trend of increasing cycle life (N80) is observed until D 50 The optimal range of the value is (e.g., about 6 μm to about 9 μm, about 6 μm to about 10 μm, about 6 μm to about 12 μm). 50 The value increases to the optimal D 50 Outside this range, mechanical and other problems that limit cycle life may occur, and the cycle life may be reduced to some extent. In some embodiments, using composite particles with a "narrow" PSD can significantly improve cycle stability (e.g., cycle life).

[0218] Figure 30 Graphs 3002, 3004, 3006, and 3008 are shown showing selected PSD characteristics of an exemplary population of jagged composite particles versus D for the exemplary population. 50 The relevance of the value. Figure 30 In the example shown, the PSD of each particle population was altered by comminution (jet milling or ball milling). Graphs 3002, 3004, 3006, and 3008 show the trends between the particle population that underwent ball milling and the particle population that underwent jet milling. The PSD characteristics shown are the span of 3002, the D of 3004, and the PSD of 3005. 90 、3006D 10and the volume fraction of fine particles (or “fines”, defined as particles with a diameter of 1 μm and less as measured by LPSA) in the particle population of 3008. In general, both jet milling and ball milling have been found to be effective tools for comminuting larger particles, producing D 50 A population of composite particles with a value ranging from about 3 μm to about 12 μm. There are also some differences between jet milling and ball milling. For example, Figure 30 As shown, the following observations can be made: (1) Graph 3002 shows that for D 50 In the case where the value is in the range of about 3 μm to about 7 μm, for a specific D 50 value, ball milling tends to produce particle groups with larger spans than jet milling; (2) Graph 3004 shows that for D 50 In the case where the value is in the range of about 3 μm to about 7 μm, for a specific D 50 Compared with jet milling, ball milling tends to produce a larger D 90 (3) Graph 3006 shows that for D 50 In the case where the value is in the range of about 3 μm to about 6 μm, for a specific D 50 Compared with jet milling, ball milling tends to produce particles with smaller D 10 (4) Graph 3008 shows that for D 50 In the case where the value is in the range of about 3 μm to about 5 μm, for a specific D 50 values, ball milling tends to produce a particle population with a higher volume fraction of fine particles compared to jet milling.

[0219] Some aspects of the present invention may also be applicable to battery cells containing other intercalation cathode materials (e.g., lithium iron phosphate (LFP), lithium manganese oxide (LMO), lithium manganese nickel oxide (LMNO), lithium iron manganese phosphate (LFMP), etc.) and battery cells containing other traditional intercalation anode materials (e.g., carbonaceous graphite such as synthetic graphite or artificial graphite, soft carbon, hard carbon, and various mixtures thereof), and may provide benefits of improved rate performance or improved stability, particularly for cells with moderate and high capacity loading (e.g., greater than about 3-4 mAh / cm 2 ) electrodes.

[0220] A battery cell module or battery cell group may advantageously include battery cells having the electrode and / or electrolyte composition provided in the present invention. Such a cell module or cell group may provide improved performance characteristics, simplified design, better safety features, or lower cost.

[0221] In the above detailed description, it can be seen that different features are grouped together in the examples. This disclosure should not be understood as an intention to express that the exemplary clauses have more features than those explicitly mentioned in each clause. On the contrary, various aspects of the invention may include fewer features than all the features of the disclosed individual exemplary clauses. Therefore, the following clauses should be considered to be included in the specification, where each clause itself can serve as a separate example. Although each dependent clause can refer to a specific combination with one of the other clauses in each clause, the aspects of the dependent clause are not limited to that specific combination. It should be understood that other exemplary clauses may also include a combination of aspects of the dependent clause with the subject matter of any other dependent clause or independent clause, or a combination of any feature with other dependent and independent clauses. The various aspects disclosed herein explicitly include these combinations, unless it is expressly stated or can be easily inferred that a particular combination is not desired (for example, contradictory aspects, such as defining an element as both an electrical insulator and an electrical conductor). In addition, various aspects of a clause may also be included in any other independent clause, even if the clause is not directly subordinate to the independent clause.

[0222] Implementation examples are described in the following numbered clauses:

[0223] Item 1: A battery electrode composition comprising a population of jagged composite particles, wherein each jagged composite particle comprises silicon and carbon; wherein: 90% or more of the jagged composite particles in the population are characterized by an aspect ratio of 2.3 or less; 50% or more of the jagged composite particles in the population are characterized by an aspect ratio of 1.25 or greater; and the population is characterized by a particle size distribution (PSD) as measured by laser particle size analysis (LPSA) such that a 50th percentile volume-weighted particle size parameter D of the PSD is 50 In the range of about 2.0 μm to about 8.0 μm.

[0224] Item 2: The battery electrode composition of Item 1, wherein: about 90% or more of the jagged composite particles in the population of particles are characterized by an aspect ratio of about 2.1 or less.

[0225] Clause 3: The battery electrode composition of any one of clauses 1 to 2, wherein: about 50% or more of the jagged composite particles in the population of particles are characterized by an aspect ratio of about 1.35 or greater.

[0226] Item 4: The battery electrode composition of any one of Items 1 to 3, wherein: about 10% or more of the jagged composite particles in the population of particles are characterized by an aspect ratio of about 1.3 or less.

[0227] Item 5: The battery electrode composition of any one of Items 1 to 4, wherein: the mass fraction of silicon in the jagged composite particles is in the range of about 3 wt.% to about 80 wt.%.

[0228] Item 6: The battery electrode composition of Item 5, wherein the mass fraction of silicon is in the range of about 35 wt.% to about 50 wt.%.

[0229] Item 7: The battery electrode composition according to any one of Items 1 to 6, wherein: the Brunauer-Emmett-Teller (BET) specific surface area of ​​the particle group is about 3 m 2 / g to about 18m 2 / g range.

[0230] Clause 8: The battery electrode composition according to any one of clauses 1 to 7, wherein: D 50 In the range of about 2.0 μm to about 4.0 μm.

[0231] Item 9: A battery electrode composition according to Item 8, wherein: the cumulative volume fraction is about 90 vol.% or less, wherein the cumulative volume fraction is defined as the cumulative volume of the jagged composite particles having a particle size of about 4.6 μm or less divided by the total volume of all jagged composite particles; and the particle size, cumulative volume and total volume are estimated by LPSA.

[0232] Item 10: The battery electrode composition of Item 9, wherein: the cumulative volume fraction is about 85 vol.% or less.

[0233] Item 11: The battery electrode composition of Item 10, wherein: the cumulative volume fraction is about 80 vol.% or less.

[0234] Clause 12: The battery electrode composition according to any one of clauses 1 to 11, wherein: D 50 In the range of about 6.0 μm to about 8.0 μm.

[0235] Item 13: The battery electrode composition according to Item 12, wherein: the Brunauer-Emmett-Teller (BET) specific surface area of ​​the particle group is about 3 m 2 / g to about 12m 2 / g range.

[0236] Item 14: A battery electrode comprising the battery electrode composition of claim 1 disposed on or in a current collector, wherein the battery electrode comprises a binder.

[0237] Item 15: The battery electrode according to Item 14, wherein: the coating density of the battery electrode is about 0.9 g / cm 3 to about 1.0g / cm 3 within the range.

[0238] Item 16: The battery electrode according to Item 15, further comprising a carbon-containing functional additive.

[0239] Item 17: A battery electrode according to Item 16, wherein: the carbon-containing functional additive is selected from one, two or more of the following: carbon nanotubes (including but not limited to single-walled carbon nanotubes and / or multi-walled carbon nanotubes), carbon nanofibers, carbon black, graphite, expanded graphite, graphene oxide and graphene.

[0240] Item 18: A battery electrode according to any one of Items 14 to 17, wherein: the PSD of the particle population has a D 50 The thickness of the battery electrode is in the range of about 6.0 μm 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.%.

[0241] Item 19: A battery electrode according to any one of Items 14 to 18, wherein: the PSD of the particle population has a D 50 in the range of about 6.0 μm to about 8.0 μm; and the battery electrode has an area binder loading of about 9.0 mg / m 2 to about 13.0 mg / m 2 in the range of , 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 particle population.

[0242] Item 20: A lithium-ion battery comprising: an anode current collector; a cathode current collector; the battery electrode of Item 14 configured as an anode, the anode current collector configured as the anode current collector; a cathode disposed on or in the cathode current collector; and an electrolyte ionically coupling the anode and cathode.

[0243] Item 21: A method for manufacturing a battery electrode, the method comprising: (A1) providing a battery electrode composition according to Item 1; (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 a battery electrode.

[0244] Item 22: A method of manufacturing a lithium-ion battery, the method comprising: (B1) manufacturing a battery electrode by the method according to Item 21, wherein the battery electrode is configured as an anode and the current collector of the anode is configured as an anode current collector; (B2) manufacturing or providing a cathode disposed on or in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode and filling the space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form a lithium-ion battery.

[0245] Item 23: A method of manufacturing a lithium-ion battery, the method comprising: (C1) providing a battery electrode according to item 14, wherein the battery electrode is configured as an anode and the current collector of the anode is configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on or in a cathode current collector; and (C3) assembling a battery cell from the anode and the cathode and filling the space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form a lithium-ion battery.

[0246] Further implementing examples are described in the following numbered additional clauses:

[0247] Additional clause 1: A battery electrode composition comprising a population of jagged composite particles, wherein each jagged composite particle comprises 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; about 50% or more of the jagged composite particles in the population are characterized by an aspect ratio of about 1.25 or greater; and the population is characterized by a particle size distribution (PSD) as determined by laser particle size analysis (LPSA) such that a fiftieth percentile volume-weighted particle size parameter (D 50 ) is in the range of about 2.0 μm to about 17.0 μm.

[0248] Additional clause 2: The battery electrode composition of additional clause 1, wherein: about 90% or more of the jagged composite particles in the population of particles are characterized by an aspect ratio of about 2.1 or less.

[0249] Additional clause 3: The battery electrode composition of any one of additional clauses 1 to 2, wherein: about 50% or more of the jagged composite particles in the population of particles are characterized by an aspect ratio of about 1.35 or greater.

[0250] Additional clause 4: The battery electrode composition of any one of additional clauses 1 to 3, wherein: about 10% or more of the jagged composite particles in the population of particles are characterized by an aspect ratio of about 1.3 or less.

[0251] Additional clause 5: The battery electrode composition according to any one of additional clauses 1 to 4, wherein the mass fraction of silicon in the serrated composite particles is in the range of about 3 wt.% to about 80 wt.%.

[0252] Additional clause 6: The battery electrode composition according to additional clause 5, wherein the mass fraction of silicon is in the range of about 33 wt.% to about 60 wt.%.

[0253] Additional clause 7: A battery electrode composition according to any one of additional clauses 1 to 6, wherein: the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the particle group is about 1 m 2 / g to about 18m 2 / g range.

[0254] Additional clause 8: The battery electrode composition according to additional clause 7, wherein: BET-SSA is about 1m 2 / g to about 10m 2 / g range.

[0255] Additional clause 9: The battery electrode composition according to any one of additional clauses 1 to 8, wherein: D 50 In the range of about 2.0 μm to about 8.0 μm.

[0256] Additional clause 10: The battery electrode composition according to any one of additional clauses 1 to 9, wherein: D 50 In the range of about 6.0 μm to about 17.0 μm.

[0257] Additional clause 11: The battery electrode composition according to additional clause 10, wherein: D 50 In the range of about 6.0 μm to about 9.0 μm.

[0258] Additional clause 12: The battery electrode composition of any one of additional clauses 1 to 11, wherein: the span of the PSD of the particle population is in the range of about 0.3 to about 1.8.

[0259] Additional clause 13: A battery electrode composition according to any one of additional clauses 1 to 12, wherein: the tenth percentile volume-weighted particle size parameter (D 10 ) is at least about 1.0 μm; and the PSD of the particle population has a D 10 Divide the D by the PSD of the particle group 50 The values ​​obtained were in the range of 35% to 75%.

[0260] Additional clause 14: A battery electrode composition according to any one of additional clauses 1 to 13, wherein: the battery electrode composition comprises a blended mixture of jagged composite particles and graphite particles; and the mass fraction of the jagged composite particles in the battery electrode composition, excluding any binder, is in the range of about 10 wt.% to about 70 wt.%, and / 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.%.

[0261] Additional clause 15: The battery electrode composition according to additional clause 14, wherein: the PSD of the particle group has a D 50 In the range of about 6.0 μm to about 12.0 μm.

[0262] Additional clause 16: A battery electrode composition according to any one of additional clauses 14 to 15, wherein: the tenth percentile volume-weighted particle size parameter (D 10 ) is in the range of about 1.0 μm to about 4.0 μm.

[0263] Additional clause 17: A battery electrode composition according to any one of additional clauses 14 to 16, wherein: the 90th percentile volume-weighted particle size parameter (D 90 ) is in the range of about 7.0 μm to about 25.0 μm.

[0264] Additional clause 18: The battery electrode composition according to additional clause 17, wherein: D 90 In the range of about 12.0 μm to about 20.0 μm.

[0265] Additional clause 19: A battery electrode composition according to any one of additional clauses 14 to 18, wherein: the 99th percentile volume-weighted particle size parameter (D 99 ) is in the range of about 15.0 μm to about 28.0 μm.

[0266] Additional clause 20: The battery electrode composition of any one of additional clauses 14 to 19, wherein: the span of the PSD of the particle population is in the range of about 0.6 to about 2.1.

[0267] Additional clause 21: A battery electrode composition according to any one of additional clauses 14 to 20, wherein: the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the particle population is about 1 m 2 / g to about 10m 2 / g range.

[0268] Additional clause 22: The battery electrode composition of any one of additional clauses 14 to 21, wherein: the jagged composite particles exhibit a first cycle lithiation specific capacity in the range of about 1600 mAh / g to about 2200 mAh / g.

[0269] Additional clause 23: The battery electrode composition of any one of additional clauses 14 to 22, wherein: when normalized by the mass of the blended mixture, the specific capacity of the blended mixture is in the range of about 600 mAh / g to about 1200 mAh / g.

[0270] Additional clause 24: A battery electrode comprising the battery electrode composition according to additional clause 1 disposed on and / or in a current collector, wherein the battery electrode comprises a binder.

[0271] Additional clause 25: The battery electrode according to additional clause 24, wherein: the coating density of the battery electrode is about 0.9 g / cm 3 to about 1.7g / cm 3 within the range.

[0272] Additional clause 26: The battery electrode according to any one of additional clauses 24 to 25, further comprising a carbon-containing functional additive.

[0273] Additional clause 27: The battery electrode according to additional clause 26, wherein: the carbon-containing functional additive is selected from: single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon black, expanded graphite, graphene oxide and graphene.

[0274] Additional clause 28: The battery electrode according to additional clause 27, wherein the mass fraction of the carbon-containing functional additive in the battery electrode is about 1 wt.% or less.

[0275] Additional clause 29: A battery electrode according to any one of additional clauses 24 to 28, wherein: the PSD of the particle population has a value of D 50 The thickness of the battery electrode is in the range of about 6.0 μm 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.%.

[0276] Additional clause 30: A battery electrode according to any one of additional clauses 24 to 29, wherein: the PSD of the particle population has a value of D 50 in the range of about 6.0 μm to about 8.0 μm; and the battery electrode has an area binder loading of about 9.0 mg / m 2 to about 13.0 mg / m 2in the range of , 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 particle population.

[0277] Additional clause 31: A lithium-ion battery comprising: an anode current collector; a cathode current collector; a battery electrode according to clause 24 configured as an anode, the anode current collector being configured as the anode current collector; a cathode disposed on or in the cathode current collector; and an electrolyte ionically coupling the anode and cathode.

[0278] Additional clause 32: A method for manufacturing a battery electrode, the method comprising: (A1) providing a battery electrode composition according to Additional clause 1; (A2) preparing a slurry comprising the battery electrode composition and a binder; and (A3) casting the slurry on and / or in a current collector to form a battery electrode.

[0279] Additional clause 33: A method for manufacturing a lithium-ion battery, the method comprising: (B1) manufacturing a battery electrode by the method described in additional clause 32, the battery electrode being configured as an anode and the current collector of the anode being configured as an anode current collector; (B2) manufacturing or providing a cathode disposed on and / or in a cathode current collector; and (B3) assembling a battery cell from the anode and the cathode and filling the space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form a lithium-ion battery.

[0280] Additional clause 34: A method of manufacturing a lithium-ion battery, the method comprising: (C1) providing a battery electrode according to additional clause 24, the battery electrode being configured as an anode and the current collector of the anode being configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on and / or in a cathode current collector; and (C3) assembling a battery cell from the anode and the cathode and filling the space between the anode and the cathode with an electrolyte that ionically couples the anode and the cathode to form a lithium-ion battery.

[0281] This description is provided to enable those skilled in the art to make or use the embodiments of the present invention. However, it should be understood that the present invention is not limited to the specific formulations, process steps, and materials disclosed herein, as various modifications to these embodiments will be apparent to those skilled in the art. In other words, the general principles defined herein can be applied to other embodiments without departing from the spirit or scope of the present invention.

Claims

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

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

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

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

5. The battery electrode composition according to claim 1, wherein: The mass fraction of silicon in the jagged composite particles is in the range of about 3 wt. % to about 80 wt. %.

6. The battery electrode composition according to claim 5, wherein: The mass fraction of silicon is in the range of about 33 wt. % to about 60 wt. %.

7. The battery electrode composition according to claim 1, wherein: The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the particle group is about 1 m 2 / g to about 18m 2 / g range.

8. The battery electrode composition according to claim 7, wherein: BET-SSA is about 1m 2 / g to about 10m 2 / g range.

9. The battery electrode composition according to claim 1, wherein: D 50 In the range of about 2.0 μm to about 8.0 μm.

10. The battery electrode composition according to claim 1, wherein: D 50 In the range of about 6.0 μm to about 17.0 μm.

11. The battery electrode composition according to claim 10, wherein: D 50 In the range of about 6.0 μm to about 9.0 μm.

12. The battery electrode composition according to claim 1, wherein: The PSD of the particle population has a span in the range of about 0.3 to about 1.

8.

13. The battery electrode composition according to claim 1, wherein: The tenth percentile volume-weighted particle size parameter (D 10 ) is at least about 1.0 μm; and The PSD of the particle group is D 10 Divide the D by the PSD of the particle group 50 The values ​​obtained were in the range of 35% to 75%.

14. The battery electrode composition according to claim 1, wherein: The battery electrode composition comprises a blended mixture of serrated composite particles and graphite particles; and The mass fraction of the jagged composite particles in the battery electrode composition, excluding any binder, is in the range of about 10 wt.% to about 70 wt.%, and / 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.%.

15. The battery electrode composition according to claim 14, wherein: The PSD of the particle group is D 50 In the range of about 6.0 μm to about 12.0 μm.

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

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

18. The battery electrode composition according to claim 17, wherein: D 90 In the range of about 12.0 μm to about 20.0 μm.

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

20. The battery electrode composition according to claim 14, wherein: The PSD of the particle population has a span in the range of about 0.6 to about 2.

1.

21. The battery electrode composition of claim 14, wherein: The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the particle group is about 1 m 2 / g to about 10m 2 / g range.

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

23. The battery electrode composition of claim 14, wherein: When normalized by the mass of the blended mixture, the specific capacity of the blended mixture ranges from about 600 mAh / g to about 1200 mAh / g.

24. A battery electrode comprising: The battery electrode composition according to claim 1, provided on and / or in a current collector, wherein: The battery electrode includes a binder.

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

26. The battery electrode according to claim 24, further comprising: Carbon-containing functional additives.

27. The battery electrode according to claim 26, wherein: The carbon-containing functional additive is selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, carbon black, expanded graphite, graphene oxide and graphene.

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

29. The battery electrode according to claim 24, wherein: The PSD of the particle group is D 50 in the range of about 6.0 μm 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. %.

30. The battery electrode according to claim 24, wherein: The PSD of the particle group is D 50 in the range of about 6.0 μm to about 8.0 μm; and The areal binder loading of the battery electrode was approximately 9.0 mg / m 2 to about 13.0 mg / m 2 in the range of , 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 particle population.

31. A lithium-ion battery comprising: anode current collector; cathode current collector; The battery electrode according to claim 24 configured as an anode, wherein the current collector of the anode is configured as the anode current collector; a cathode disposed on or in the cathode current collector; as well as An electrolyte that ionically couples the anode and cathode.

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

33. A method of manufacturing a lithium ion battery, the method comprising: (B1) manufacturing a battery electrode by the method according to claim 32, wherein the battery electrode is configured as an anode, and the current collector of the anode is configured as an anode current collector; (B2) manufacturing or providing a cathode disposed on and / or in a cathode current collector; as well as (B3) Assembling a battery cell from an anode and a cathode, and filling the space between the anode and cathode with an electrolyte that ionically couples the anode and cathode to form a lithium-ion battery.

34. A method of manufacturing a lithium ion battery, the method comprising: (C1) Providing the battery electrode according to claim 24, wherein the battery electrode is configured as an anode, and the current collector of the anode is configured as an anode current collector; (C2) manufacturing or providing a cathode disposed on and / or in a cathode current collector; as well as (C3) Assembling a battery cell from an anode and a cathode, and filling the space between the anode and cathode with an electrolyte that ionically couples the anode and cathode to form a lithium-ion battery.

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