Lithium-ion batteries with high-performance anodes containing graphite and silicon-based nanocomposites

Abstract

The battery anode includes a binder, a conductive additive, and an active material blend including silicon (Si)-containing active material particles and graphite active material particles. In some embodiments, the battery anode has a capacity of about 2 mAh / cm 2 ~about 16mAh / cm 2 The silicon (Si)-containing active material particles exhibit a specific capacity ranging from about 800 mAh / g to about 3000 mAh / g, and the silicon (Si)-containing active material particles contribute from about 25% to about 99% of the total capacity of the battery anode.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This patent application claims the benefit of U.S. Provisional Patent Application No. 63 / 483,680, filed February 7, 2023, and entitled "LITHIUM-ION BATTERIES WITH HIGH-PERFORMANCE ANODES COMPRISING GRAPHITE(S) AND SILICON-BASED NANOCOMPOSITES," and U.S. Non-Provisional Patent Application No. 18 / 434,744, filed February 6, 2024, and entitled "LITHIUM-ION BATTERIES WITH HIGH-PERFORMANCE ANODES COMPRISING GRAPHITE(S) AND SILICON-BASED NANOCOMPOSITES," both of which are assigned to the present assignee and are expressly incorporated by reference herein in their entireties.

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

[0003] Advanced rechargeable batteries are desirable for a wide range of consumer electronics, electric vehicles, grid storage, and other important applications, due in part to their relatively high energy density, relatively high specific energy, light weight, and potential for long life. However, despite the increasing commercial adoption of batteries, further development of these batteries is needed for low- or no-emission applications, hybrid-electric or all-electric vehicles, home appliances, wearable devices, energy-efficient cargo ships and locomotives, drones, aerospace applications, and power grids. Further improvements are desired for various rechargeable batteries, such as rechargeable Li and Li-ion batteries, Na and Na-ion batteries, K and K-ion batteries, and dual-ion batteries, to name a few.

[0004] In certain types of Li metal and Li-ion rechargeable batteries, charge storage anodes can include silicon (Si)-containing anode particles having gravimetric capacities (per mass of Si-containing anode particles in the absence of Li) of about 800 mAh / g to about 3000 mAh / g. A subset of such anodes includes anodes in which the electrode layer exhibits a capacity (per mass of electrode layer, not including the mass of the current collector, in the absence of Li) ranging from about 400 mAh / g to about 2800 mAh / g. This class of charge storage anodes offers significant potential for enhancing the gravimetric and volumetric energy of rechargeable batteries.

[0005] In certain types of rechargeable batteries, charge storage anode active materials can be fabricated as high-capacity (nano)composite powders that exhibit a moderately high volume change (e.g., about 8-180% by volume) during the first charge-discharge cycle and a moderate volume change (e.g., about 5-50% by volume) during subsequent charge-discharge cycles. A portion 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 microns (micrometers, i.e., μm), as measured using laser particle size distribution analysis (LPSA), laser image analysis, electron microscopy, optical microscopy, or other suitable techniques. This class of charge storage particles offers great promise for scalable manufacturing and achieving high cell-level energy density and other performance characteristics.

[0006] Examples of high-performance anodes can include so-called silicon-graphite blends, which are mixtures of novel silicon-based (or broadly defined as silicon-containing) anode active materials and graphite-based active materials. In some examples of blend anodes, the Si-containing anode active material may be a Si-containing and C-containing nanocomposite (herein referred to as a Si-C composite, Si-C nanocomposite, or Si-C composite (or nanocomposite) particle, even if the particle contains relatively small amounts of elements other than Si and C, less than about 10-20 atomic %, and the C is separate from the graphite-based active material), providing about 20-99% of the capacity, with the remainder of the capacity coming from the graphite-based active material. Such anodes offer much higher volumetric and gravimetric energy densities than intercalation-type graphite-only anodes commonly used in commercial Li-ion batteries. Furthermore, in such blend anodes, the graphite-based active material can be natural graphite, artificial graphite, or a mixture of natural and artificial graphite. The Si—C nanocomposite-graphite blend anode can provide an overall moderate volume change during the first cycle and a low volume change during subsequent charging cycles.

[0007] However, when blend anodes are fabricated using graphite, which is typically used in Li-ion batteries, and new Si-based (or broadly silicon-containing, e.g., nanocomposite) anode active materials, the blend anodes typically suffer from insufficient stability, excessive volume change, insufficient electrical and ionic conductivity, low packing density, insufficient volumetric capacity, and other limitations.

[0008] Thus, there remains a need for improvements in batteries, components and other related materials and manufacturing processes. Summary of the Invention

[0009] The following provides a simplified summary of one or more aspects of the presently disclosed mechanisms. Accordingly, the following summary is not intended to be an exhaustive overview of all possible aspects, nor is it intended to identify key or essential elements of all possible aspects or to outline the scope associated with any particular aspect. Accordingly, the following summary is solely intended to present certain concepts of one or more aspects of the presently disclosed mechanisms in a simplified manner, as a prelude to the detailed description that follows.

[0010] In one embodiment, a battery anode includes a binder, a conductive additive, and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, and the battery anode has a capacity of about 2 mAh / cm 2 ~about 16mAh / cm 2 the Si-containing active material particles exhibit a specific capacity in the range of about 800 mAh / g to about 3000 mAh / g, the Si-containing active material particles contribute about 25% to about 99% of the total capacity of the battery anode, and at least a portion of the graphite active material particles are characterized by a Raman spectrum, in which the full width at half maximum (FWHM) of the D band is about 30 cm. -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1 and the D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, is in the range of about 0.02 to about 1.12.

[0011] In some embodiments, the D / G peak intensity ratio is in the range of about 0.12 to about 0.30.

[0012] In some embodiments, the 2D1 / G peak intensity ratio, defined as the intensity of the 2D1 peak divided by the intensity of the G peak in the Raman spectrum, is in the range of about 0.10 to about 0.90.

[0013] In some embodiments, at least a portion of the graphite active material particles are characterized by an X-ray diffraction (XRD) spectrum in which the FWHM of the (002) reflection peak is within the range of about 0.220 degrees to about 5.620 degrees.

[0014] In some embodiments, the FWHM of the (002) reflection peak is in the range of 0.220 degrees to about 0.620 degrees.

[0015] In some embodiments, the average crystallite size of at least a portion of the graphite active material particles, as estimated by applying Scherrer's rule to the (002) reflection peak, is in the range of about 1 nm to about 40 nm.

[0016] In some embodiments, the average crystallite size is within the range of about 15 nm to about 30 nm.

[0017] In some embodiments, the average pressure (Cx) required to deform at least a portion of the graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

[0018] In some embodiments, the average pressure ranges from about 1 MPa to about 18 MPa.

[0019] In some embodiments, at least a portion of the graphite active material particles have a tap density in the range of about 0.10 g / cc to about 1.25 g / cc.

[0020] In some embodiments, the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0021] In some embodiments, the pycnometric density of at least a portion of the graphite active material particles ranges from about 2.15 g / cc to about 2.35 g / cc.

[0022] In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is in the range of about 2 μm to about 22 μm.

[0023] In some embodiments, the above D 50 The range is from about 12 μm to about 17 μm.

[0024] In some embodiments, the 90th percentile volume-weighted particle size parameter (D 90 ) is in the range of about 4 μm to about 30 μm.

[0025] In some embodiments, the above D 90 The range is from about 19 μm to about 26 μm.

[0026] In some embodiments, the 10th percentile volume-weighted particle size parameter (D 10 ) is in the range of about 0.5 μm to about 15 μm.

[0027] In some embodiments, the above D 10 The range is from about 7 μm to about 11 μm.

[0028] In some embodiments, at least a portion of the graphite active material particles have a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m 2 / g~about 450m 2 / g range.

[0029] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g~about 5m 2 / g range.

[0030] In some embodiments, the weight fraction of at least a portion of the graphite active material particles in the battery anode ranges from about 1% to about 50% by weight of the active material blend.

[0031] In some embodiments, the weight fraction ranges from about 2% to about 20% by weight of the active material blend.

[0032] In some embodiments, the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt % or less of the total mass of the Si-containing active material particles.

[0033] In some embodiments, the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a total amount ranging from 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0034] In some embodiments, the Si-containing active material particles comprise Si—C nanocomposite particles.

[0035] In some embodiments, at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0036] In one aspect, a lithium-ion battery includes a battery anode, a cathode, a separator electrically separating the battery anode and cathode, and an electrolyte ionically bonding the battery anode and cathode.

[0037] In one embodiment, a battery anode comprises a binder, a conductive additive, and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, wherein the mass fraction of Si in the Si-containing active material particles is in the range of about 20 wt% to about 80 wt%, and the mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 60:40 to about 98:2, and at least a portion of the graphite active material particles are characterized by a Raman spectrum in which the full width at half maximum (FWHM) of the D band is about 30 cm. -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1and the D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, is in the range of about 0.02 to about 1.12, and the average pressure (Cx) required to deform at least a portion of the graphite active material particles by 10% during a microcompression hardness test is in the range of about 1 MPa to about 18 MPa.

[0038] In some embodiments, the weight ratio of Si-containing active material particles to graphite active material particles ranges from about 75:25 to about 95:5.

[0039] In some embodiments, the average pressure ranges from about 7 MPa to about 18 MPa.

[0040] In some embodiments, the average pressure ranges from about 10 MPa to about 18 MPa.

[0041] In some embodiments, the D / G peak intensity ratio is in the range of about 0.12 to about 0.30.

[0042] In some embodiments, at least a portion of the graphite active material particles have a tap density in the range of about 0.10 g / cc to about 1.25 g / cc.

[0043] In some embodiments, the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0044] In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is in the range of about 2 μm to about 22 μm.

[0045] In some embodiments, the above D 50 The range is from about 11 μm to about 17 μm.

[0046] In some embodiments, the above D 50 The range is from about 12 μm to about 17 μm.

[0047] In some embodiments, the 90th percentile volume-weighted particle size parameter (D 90 ) is in the range of about 4 μm to about 30 μm.

[0048] In some embodiments, the above D 90 The range is from about 19 μm to about 30 μm.

[0049] In some embodiments, the above D 90 The range is from about 19 μm to about 26 μm.

[0050] In some embodiments, the 10th percentile volume-weighted particle size parameter (D 10 ) is in the range of about 0.5 μm to about 15 μm.

[0051] In some embodiments, the above D 10 The range is about 5 μm to about 11 μm.

[0052] In some embodiments, the above D 10 The range is from about 7 μm to about 11 μm.

[0053] In some embodiments, at least a portion of the graphite active material particles have a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m 2 / g~about 450m 2 / g range.

[0054] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g~about 5m 2 / g range.

[0055] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g ~ approx. 3m 2 / g range.

[0056] In some embodiments, the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt % or less of the total mass of the Si-containing active material particles.

[0057] In some embodiments, the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a total amount ranging from 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0058] In some embodiments, the Si-containing active material particles comprise Si-C nanocomposite particles.

[0059] In some embodiments, at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0060] In some embodiments, the battery anode has a current density of about 2 mAh / cm 2 ~about 16mAh / cm 2 It has a reversible capacity load in the range of

[0061] In one aspect, a lithium-ion battery includes a battery anode, a cathode, a separator electrically separating the battery anode and cathode, and an electrolyte ionically bonding the battery anode and cathode.

[0062] In one embodiment, a battery anode comprises a binder, a conductive additive, and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, wherein a mass fraction of Si in the Si-containing active material particles is in a range of about 20 wt% to about 80 wt%, and a mass ratio of the Si-containing active material particles to the graphite active material particles is in a range of about 7:93 to about 40:60, and at least a portion of the graphite active material particles are characterized by a Raman spectrum, in which the full width at half maximum (FWHM) of the D band is about 30 cm. -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1and the D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, is in the range of about 0.02 to about 1.12, and the average pressure (Cx) required to deform at least a portion of the graphite active material particles by 10% during a microcompression hardness test is in the range of about 20 MPa to about 30 MPa.

[0063] In some embodiments, the mass ratio of Si-containing active material particles to graphite active material particles ranges from about 10:90 to about 30:70.

[0064] In some embodiments, the average pressure ranges from about 24 MPa to about 30 MPa.

[0065] In some embodiments, the D / G peak intensity ratio is in the range of about 0.08 to about 0.30.

[0066] In some embodiments, at least a portion of the graphite active material particles have a tap density in the range of about 0.10 g / cc to about 1.25 g / cc.

[0067] In some embodiments, the tap density ranges from about 0.90 g / cc to about 1.20 g / cc.

[0068] In some embodiments, the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0069] In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is in the range of about 2 μm to about 22 μm.

[0070] In some embodiments, the above D 50 The range is from about 11 μm to about 17 μm.

[0071] In some embodiments, the above D 50 The range is from about 12 μm to about 17 μm.

[0072] In some embodiments, the 90th percentile volume-weighted particle size parameter (D 90 ) is in the range of about 4 μm to about 30 μm.

[0073] In some embodiments, the above D 90 The range is from about 19 μm to about 30 μm.

[0074] In some embodiments, the 10th percentile volume-weighted particle size parameter (D 10 ) is in the range of about 0.5 μm to about 15 μm.

[0075] In some embodiments, the above D 10 The range is about 5 μm to about 11 μm.

[0076] In some embodiments, at least a portion of the graphite active material particles have a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m 2 / g~about 450m 2 / g range.

[0077] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g~about 5m 2 / g range.

[0078] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g ~ approx. 3m 2 / g range.

[0079] In some embodiments, the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt % or less of the total mass of the Si-containing active material particles.

[0080] In some embodiments, the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a total amount ranging from 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0081] In some embodiments, the Si-containing active material particles comprise Si—C nanocomposite particles.

[0082] In some embodiments, at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0083] In some embodiments, the battery anode has a current density of about 2 mAh / cm 2 ~about 16mAh / cm 2 It has a reversible capacity load in the range of

[0084] In one aspect, a lithium-ion battery includes a battery anode, a cathode, a separator electrically separating the battery anode and cathode, and an electrolyte ionically bonding the battery anode and cathode.

[0085] In one embodiment, a battery anode includes a binder, a conductive additive, and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, and the battery anode has a capacity of about 2 mAh / cm 2 ~about 16mAh / cm 2 the Si-containing active material particles exhibit a specific capacity in the range of about 800 mAh / g to about 3000 mAh / g, the Si-containing active material particles contribute about 25% to about 99% of the total capacity of the battery anode, and at least a portion of the graphite active material particles are characterized by a Raman spectrum, in which the full width at half maximum (FWHM) of the D band is about 30 cm. -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1 and the D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, is in the range of about 0.02 to about 1.12.

[0086] In some embodiments, the D / G peak intensity ratio is in the range of about 0.12 to about 0.30.

[0087] In some embodiments, the 2D1 / G peak intensity ratio, defined as the intensity of the 2D1 peak divided by the intensity of the G peak in the Raman spectrum, is in the range of about 0.10 to about 0.90.

[0088] In some embodiments, at least some of the graphite active material particles are characterized by an X-ray diffraction (XRD) spectrum with a FWHM of the (002) reflection in the range of about 0.220 degrees to about 5.620 degrees.

[0089] In some embodiments, the FWHM of the (002) reflection is in the range of about 0.220 degrees to about 0.620 degrees.

[0090] In some embodiments, the average crystallite size of at least some of the graphite active material particles, as estimated by applying Scherrer's rule to the (002) reflection, is in the range of about 1 nm to about 40 nm.

[0091] In some embodiments, the average crystallite size is within the range of about 15 nm to about 30 nm.

[0092] In some embodiments, the average pressure (Cx) required to deform at least a portion of the graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

[0093] In some embodiments, the average pressure ranges from about 1 MPa to about 18 MPa.

[0094] In some embodiments, at least some of the graphite active material particles have a tap density in the range of about 0.10 g / cc to about 1.25 g / cc.

[0095] In some embodiments, the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0096] In some embodiments, the pycnometric density of at least some of the graphite active material particles ranges from about 2.15 g / cc to about 2.35 g / cc.

[0097] In some embodiments, the 50th percentile volume-weighted particle size parameter D of at least some of the graphite active material particles 50 However, the range is about 2 μm to about 22 μm.

[0098] In some embodiments, the above D 50 The range is from about 12 μm to about 17 μm.

[0099] In some embodiments, the 90th percentile volume-weighted particle size parameter D of at least some of the graphite active material particles 90 However, the range is about 4 μm to about 30 μm.

[0100] In some embodiments, the above D 90 The range is from about 19 μm to about 26 μm.

[0101] In some embodiments, the 10th percentile volume-weighted particle size parameter D of at least some of the graphite active material particles 10 However, the range is about 0.5 μm to about 15 μm.

[0102] In some embodiments, the above D 10 The range is from about 7 μm to about 11 μm.

[0103] In some embodiments, at least some of the graphite active material particles have a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m 2 / g~about 450m 2 / g range.

[0104] In some embodiments, the BET-SSA has a molecular weight of about 1 m 2 / g~about 5m 2 / g range.

[0105] In some embodiments, the weight fraction of at least a portion of the graphite active material particles in the battery anode ranges from about 1% to about 50% by weight of the active material blend.

[0106] In some embodiments, the weight fraction ranges from about 2% to about 20% by weight of the active material blend.

[0107] In some embodiments, the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt % or less of the total mass of the Si-containing active material particles.

[0108] In some embodiments, the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a total amount ranging from 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0109] In some embodiments, the Si-containing active material particles comprise Si—C nanocomposite particles.

[0110] In some embodiments, at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0111] In one aspect, a lithium-ion battery includes a battery anode, a cathode, a separator electrically separating the battery anode and cathode, and an electrolyte ionically bonding the battery anode and cathode.

[0112] Other objects and advantages associated with the embodiments disclosed herein will become apparent to those skilled in the art based on the accompanying drawings and detailed description.

[0113] The following provides a simplified summary of one or more aspects disclosed herein. As such, the following summary should not be considered an exhaustive overview of all possible aspects, nor should it be considered to identify key or essential elements of all possible aspects, nor should the following summary be considered to outline the scope associated with any particular aspect. As such, the following summary is solely intended to present certain concepts of one or more aspects of the mechanisms disclosed herein in a simplified manner, as a prelude to the detailed description presented below.

[0114] The accompanying drawings are presented to aid in the explanation of embodiments of the present disclosure and are provided solely for the purpose of illustrating the embodiments, not for the purpose of limitation thereof. Unless otherwise noted or suggested by context, the various hatching, shading, and / or fill patterns in the drawings are meant only to depict contrast between different components, elements, features, etc., and are not meant to convey the use of particular substances / materials, colors, or other characteristics that may be defined as outside the present disclosure for the particular patterns employed. [Brief explanation of the drawings]

[0115] [Figure 1] 1 illustrates an exemplary Li-ion battery in which the components, materials, processes and / or techniques disclosed herein may be implemented. [Figure 2] Table 1 is provided, listing exemplary graphite particles and / or other electrochemically active material particles and the measured average pressure, designated Cx, required to deform each particle by 10% in MPa. [Figure 3] Table 2 is provided, listing exemplary graphite particle samples and the measured tap density of each graphite particle sample. [Figure 4] Table 3 is provided, listing exemplary graphite particle samples and density measurements for each graphite particle sample obtained using nitrogen (N2) gas pycnometry. [Figure 5A] 1 shows a scanning electron microscope (SEM) image of exemplary graphite sample G1. [Figure 5B] 1 shows a scanning electron microscope (SEM) image of exemplary graphite sample G2. [Figure 5C] 1 shows a scanning electron microscope (SEM) image of exemplary graphite sample G3. [Figure 5D] 1 shows a scanning electron microscope (SEM) image of exemplary graphite sample G4. [Figure 5E] 1 shows a scanning electron microscope (SEM) image of exemplary graphite sample G5. [Figure 5F] 1 shows a scanning electron microscope (SEM) image of exemplary graphite sample G6. [Figure 6] Table 4 is provided, listing exemplary graphite particle samples and the values ​​of the 10th percentile volume-weighted particle size parameter D10, the 50th percentile volume-weighted particle size parameter D50, and the 90th percentile volume-weighted particle size parameter D90 of the particle size distribution (PSD) for each graphite particle sample. [Figure 7] Table 5 is provided, which lists exemplary graphite particle samples and the Brunauer-Emmett-Teller (BET) specific surface area (SSA) values ​​for each graphite particle sample. [Figure 8A] 1 shows a graphical plot of X-ray diffraction data for exemplary graphite samples G1, G2, G3, G4, and G6. [Figure 8B] Table 6 is provided, listing exemplary graphite particle samples and selected X-ray diffraction data for each graphite particle sample. [Figure 9A] 1 shows Raman spectra for exemplary graphite samples G1, G3, G4 and G6. [Figure 9B] Table 7 is provided, listing exemplary graphite particle samples and selected Raman data for the D and G spectral features for each graphite particle sample. [Figure 9C] Table 8 is provided, listing exemplary graphite particle samples and selected Raman data for 2D1 and G spectral features for each graphite particle sample. [Figure 10A] 1 shows a graphical plot of the cycle life, expressed as the estimated number of cycles (N80) to reach 80% of the initial cycling gravimetric charge capacity, of lithium ion battery test cells whose anodes are blend anodes comprising Si—C nanocomposite particles and each exemplary graphite particle. [Figure 10B] 1 shows a graphical plot of the capacity of lithium-ion battery test cells ("full cells") in which each anode is one of the following: (1) a blend anode containing Si-C nanocomposite particles and each exemplary graphite particle sample, and (2) an anode containing Si-C nanocomposite particles without added graphite particles. The capacity is normalized by the weight of the anode. [Figure 10C] 1 shows graphical plots of (a) lithiated anode coating density, (b) coating density after coating and calendering, (c) volumetric energy density, and (d) volumetric capacity of the anode at the beginning of cycling for lithium ion battery test cells, each of which was one of the following anodes: (1) a blend anode comprising Si-C nanocomposite particles and each exemplary graphite particle sample, and (2) an anode comprising Si-C nanocomposite particles without added graphite particles. [Figure 11] FIG. 1 is a flow diagram of a process for manufacturing a Li-ion rechargeable battery cell according to an embodiment. [Figure 12] 12 shows graphical plots of the dependence of estimated cycle life (N80) on cycle number for (1) a lithium ion battery test cell containing no graphite particles (graphic plot 1202), (2) a lithium ion battery test cell containing graphite particles at 10% by weight of the anode active material (graphic plot 1204), (3) a lithium ion battery test cell containing graphite particles at 20% by weight of the anode active material (graphic plot 1206), and (4) a lithium ion battery test cell containing graphite particles at 30% by weight of the anode active material (graphic plot 1208). [Figure 13]Table 9 lists exemplary graphite particle samples, their selected properties (Cx, tap density, particle size distribution (PSD) properties, BET-SSA values, and D / G ratio values), and certain battery performance properties of lithium-ion battery cells employing the exemplary graphite particle samples at low mass fractions of the graphite particles in their respective anode active materials. The top row is shown in FIG. 13(a), and the bottom row is shown in FIG. 13(b). [Figure 14(a)] Table 10 is provided, which lists exemplary graphite particle samples, their selected properties (Cx, tap density, particle size distribution properties, BET-SSA values, and D / G ratio values) and certain battery performance properties of lithium-ion battery cells employing the exemplary graphite particle samples at high mass fractions of graphite particles in their respective anode active materials. [Figure 14(b)] Table 10 continues, listing exemplary graphite particle samples, their selected properties (Cx, tap density, particle size distribution properties, BET-SSA values, and D / G ratio values) and specific battery performance properties of lithium-ion battery cells employing the exemplary graphite particle samples at high mass fractions of graphite particles in their respective anode active materials. [Figure 15] Table 11 lists specific anode characteristics (particle size (D50) values ​​of each Si-C nanocomposite particle population, calendaring pressure during battery anode formation, binder material used in battery anode formation) and specific battery performance characteristics of lithium-ion battery cells employing graphite particles (G1) and Si-C nanocomposite particles (graphite particles G1 having a mass fraction of 10 wt % in each anode active material). [Figure 16] Figure 16 shows a graphical plot of DC resistance (DCR) for lithium-ion battery cells employing a PAA salt copolymer-based (acrylic) anode binder (1602) and a CMC:SBR anode binder (1604). Both types of lithium-ion battery cells employed a blend anode of Si-C nanocomposite particles and graphite particles (G1), with the mass fraction of graphite particles G1 being 10 wt% of the respective anode active materials. [Figure 17]Figure 17 shows a graphical plot of the dependence of relative discharge capacity on normalized discharge rate (C-rate) for lithium-ion battery cells employing a PAA salt copolymer-based anode binder (1702) and a CMC:SBR anode binder (1704). Both types of lithium-ion battery cells employed a blend anode of Si-C nanocomposite particles and graphite particles (G1), with the mass fraction of graphite particles G1 being 10 wt% of the respective anode active materials. DETAILED DESCRIPTION OF THE INVENTION

[0116] Aspects of the invention are disclosed in the following description and related drawings directed to specific embodiments of the invention. The term "embodiments of the invention" does not require that all embodiments of the invention include the described features, advantages, processes, or modes of operation, and alternative embodiments may be devised without departing from the scope of the invention. Additionally, well-known elements of the invention may not be described in detail or may be omitted so as not to obscure other more relevant details.

[0117] Aspects of the present disclosure provide for processes for making advanced carbon-containing composite particles for use in electrodes (e.g., anode or cathode electrodes) in Li-ion, Na-ion, or K-ion rechargeable batteries, electrochemical capacitors, and hybrid electrochemical energy storage devices, among other battery types.

[0118] Any numerical ranges described herein with respect to any embodiment of the present invention not only define the upper and lower limits of the associated numerical range, but are also intended as an implicit disclosure of each discrete value within that range in units or increments consistent with the level of precision by which the upper and lower limits are characterized. For example, a numerical distance range (i.e., a level of precision in units or increments of 1) of 7 nm to 20 nm encompasses the set (in nm) of [7, 8, 9, 10, . . . , 19, 20], as if the intervening numbers 8 to 19 in units or increments of 1 were explicitly disclosed. As another example, a temperature range of about -120°C to about -60°C encompasses the set (in °C) of temperature ranges of about -120°C to about -119°C, about -119°C to about -118°C, . . . , about -61°C to about -60°C, as if the intervening numbers (in °C) of -120°C to -60°C were explicitly disclosed in the incremental range. In yet another example, a numerical percentage range (i.e., a level of precision in hundredths or increments) of 30.92% to 47.44% encompasses (in %) the set [30.92, 30.93, 30.94, . . . , 47.43, 47.44], as if the intervening numbers between 30.92 and 47.44 in hundredths or increments were expressly disclosed. Accordingly, any intervening numbers encompassed by any disclosed numerical range are intended to be construed as if those intervening numbers were explicitly disclosed, whereby any such intervening numbers may constitute their own upper and / or lower limits of subranges falling within broader ranges. Each subrange (e.g., each range that includes at least one intervening number of the broader range as an upper and / or lower limit) is thereby intended to be construed as implicitly disclosed by the explicit disclosure of the broader range. In yet another example, numerical ranges having upper and lower limits defined with different levels of precision should be interpreted in increments corresponding to the limit values ​​having the higher level of precision.For example, a numerical percentage range of 30.92% to 47.4% (i.e., levels of precision in hundredths and tenths of a percent, respectively) encompasses the set [30.92, 30.93, 30.94, . . . , 47.39, 47.40] (in %) as if 47.4% (tenths) were stated as 47.40% (hundredths), and as if the intervening numbers between 30.92 and 47.40 in hundredths of a percent or increments were explicitly disclosed.

[0119] It should be understood that the level of precision of any particular measurement, threshold, or other imprecise parameter may vary based on various factors, such as the measurement equipment, environmental conditions, etc. Accordingly, hereinafter, references to such measurements or thresholds may be interpreted as the respective values ​​assuming a pseudo-precise level of precision (e.g., an 80% threshold would consist of 80.0000...%). Alternatively, references to such measurements or thresholds may be described via modifiers that capture the pseudo-precise value as well as a range extending above and / or below the pseudo-precise value. For example, the 80% threshold noted above may be described as "about," "approximately," "around," "approximately ...

number

[0120] In the following description, various material properties are described to characterize materials in various states (e.g., binders, molecules, particles, powders, slurries, electrodes, separators, electrolytes, battery cells, etc.). It should be noted that one skilled in the art can generally select (and is assumed herein to select) the optimal measurement technique for any particular measurement. Furthermore, in some cases, the optimal measurement technique may include a combination of techniques. While the following tables characterize various measurement type options for particular material types and particular material properties, where appropriate, particular embodiments of the present disclosure may be characterized more specifically in the context of particular measurement techniques and / or particular commercially available equipment. It should be noted that while the following tables characterize measurements on active material particles, similar measurements may also be performed on other particle types, such as precursor particles (e.g., carbon particles, etc.). Therefore, unless otherwise noted, the following tables provide examples of how such material properties may be readily measured by one skilled in the art using commercially available equipment. Table of techniques and equipment for measuring material properties [Table 1] JPEG2026508748000004.jpg231162 JPEG2026508748000005.jpg223162 JPEG2026508748000006.jpg228162 JPEG2026508748000007.jpg229162 JPEG2026508748000008.jpg218162 JPEG2026508748000009.jpg223162 JPEG2026508748000010.jpg176162

[0121] In one aspect, the present disclosure relates to batteries. While the following description may describe specific examples in the context of Li metal and Li-ion batteries (for brevity and convenience, and due to the current prevalence of Li technology), it should be understood that various aspects may be applicable to other rechargeable and primary batteries (such as Na and Na-ion, Mg and Mg-ion, K and K-ion, Ca and Ca-ion and other metal and metal-ion batteries, dual-ion batteries, alkaline or alkali-ion batteries, flow batteries, etc.), as well as electrochemical capacitors and hybrid energy storage devices.

[0122] Although the following description may describe particular examples in the context of composites including specific (e.g., alloy-type or conversion-type) anode active materials (e.g., Si, among others) or particular (e.g., intercalation-type or conversion-type) cathode active materials, it should be understood that various embodiments may be applicable to many other types and chemistries of conversion-type anode and cathode active materials, intercalation-type anode and cathode active materials, pseudocapacitive anode and cathode active materials, and materials that may exhibit combined electrochemical energy storage mechanisms.

[0123] While the following description may describe specific examples of material formulations without Li (e.g., as in silicon-containing nanocomposite anodes, metal fluoride cathodes, or sulfur cathodes), various embodiments may also include lithium-containing electrodes and active materials (e.g., partially or fully lithiated Si-containing anodes or partially or fully lithiated Si-containing anode particles, partially or fully lithiated Si-containing anode particles, mixtures of LiF with metals such as Cu, Fe, Ni, Bi, Zr, Ti, Mg, Nb, and various other metals and metal alloys, and mixtures of these and / or other metals, among others). It should be appreciated that the present invention may be applicable to metal fluoride-containing cathodes or partially or fully lithiated metal halide-containing cathode particles, partially or fully lithiated chalcogenides (such as LiS, LiS / metal mixtures, LiSe, LiSe / metal mixtures, LiS-LiSe mixtures, various other compositions containing lithiated chalcogenides, etc.), partially or fully lithiated metal oxides (such as LiO, LiO / metal mixtures, etc.), partially or fully lithiated intercalation cathode materials, partially or fully lithiated carbons, etc. In some designs, various material properties (e.g., at the particle level, interparticle level, electrode level, etc.) may change based on whether the active material particles are in a Li-free, partially lithiated, or fully lithiated state. Such Li-dependent material properties may include particle pore volume, electrode pore volume, etc. Unless otherwise stated or implied, references to such Li-dependent material properties (e.g., at the particle level, interparticle level, electrode level, etc.) may be considered to be given as if the active material particles were in a Li-free state. Also, some examples below are characterized at the electrode level (as opposed to, e.g., the particle level, interparticle level, cell level, etc.). Hereinafter, unless otherwise stated or implied, references to such electrode-level properties (e.g., electrode porosity, areal capacity loading, or gravimetric / volume capacity, etc.) may be considered to refer to the electrode components (e.g., active material particles, binder, conductive additives, etc.), excluding the current collector.

[0124] Although the following description may describe specific examples for Li-ion batteries (such as silicon-containing anodes or metal fluoride-containing or lithium sulfide-containing cathodes) in the context of some particular alloy-type, conversion-type, and insertion-type chemistries for anode active materials, and conversion-type and insertion-type chemistries for cathode active materials, it should be understood that various embodiments may be applicable to other chemistries for Li-ion batteries (such as other conversion-type and alloy-type electrodes and various insertion-type anodes and insertion-type cathodes) and other battery chemistries. In the case of metal-ion batteries (such as Li-ion batteries), examples of other suitable conversion-type electrodes include, but are not limited to, metal fluorides, metal oxyfluorides, 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.

[0125] During operation of a battery (such as a Li-ion battery), a conversion material changes (transforms) from one crystalline structure to another (hence the term "conversion"), and the material structure and composition may change chemically and structurally to one or more structures. This process also involves the breaking of chemical bonds and the formation of new chemical bonds. During operation of a battery (e.g., a Li-ion battery), Li ions are inserted into alloy-type materials to form lithium alloys (hence the term "alloy"). "Alloy"-type electrode materials are sometimes considered a subclass of "conversion"-type electrode materials.

[0126] Although the following description describes specific examples in the context of Si-C composite (e.g., nanocomposite) anode active materials (e.g., nanocomposite particles comprising silicon (Si) and carbon (C), and optionally comprising other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), and fluorine (F), to name a few, wherein the combined mass of the Si and C atoms may contribute from about 75% to about 100% by weight of the total mass of the composite particle), it should be understood that various embodiments may be applicable to other types of high capacity silicon-containing anode active materials (including, but not limited to, various silicon-containing particles, silicon oxide-containing particles, silicon nitride-containing particles, silicon oxynitride-containing particles, silicon phosphide-containing particles, or particles comprising mixtures, alloys, or other combinations of such active materials, various other types of Si-containing composites, including, but not limited to, core-shell particles, hierarchical particles, or nanocomposite particles).

[0127] Aspects are directed to battery anodes and / or battery anode precursor compositions comprising a population of Si-containing particles (e.g., nanocomposite particles, among others), some or all of which comprise the elements silicon (Si) and carbon (C), and may also include other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), and fluorine (F), to name a few. In some embodiments, the combined mass of Si and C in the Si-containing particles may contribute (on average) from about 75% to about 100% by weight of the total mass of the Si-containing particles. Such composite particles are sometimes referred to herein as Si-C composites (or nanocomposites, e.g., when Si and / or C are nanostructured).

[0128] In some embodiments, the total mass of O can contribute (on average) from about 0 wt % to about 10 wt % of the total mass of the Si-containing particle (from about 0 wt % to about 1 wt % in some designs, from about 1 wt % to about 2.5 wt % in other designs, from about 2.5 wt % to about 5 wt % in other designs, and from about 5 wt % to about 10 wt % in other designs). In some embodiments, the total mass of O can contribute (on average) less than about 5 wt % of the total mass of the Si-containing particle. In some embodiments, the total mass of N can contribute (on average) from about 0 wt % to about 10 wt % of the total mass of the Si-containing particle (from about 0 wt % to about 0.1 wt % in some designs, from about 0.1 wt % to about 2 wt % in other designs, from about 2 wt % to about 5 wt % in other designs, and from about 5 wt % to about 10 wt % in still other designs). In some embodiments, the total mass of P can contribute (on average) about 0 wt % to about 10 wt % (about 0 wt % to about 0.1 wt % in some designs, about 0.1 wt % to about 1 wt % in other designs, about 1 wt % to about 5 wt % in other designs, and about 5 wt % to about 10 wt % in still other designs) of the total mass of the Si-containing particle. In some embodiments, the total mass of B can contribute (on average) about 0 wt % to about 5 wt % (about 0 wt % to about 0.1 wt % in some designs, about 0.1 wt % to about 2.5 wt % in other designs, and about 2.5 wt % to about 5 wt % in still other designs) of the total mass of the Si-containing particle. In some embodiments, the total mass of H can contribute (on average) about 0 wt % to about 2 wt % (about 0 wt % to about 0.5 wt % in some designs, about 0.5 wt % to about 1 wt % in other designs, and about 1 wt % to about 2 wt % in still other designs) of the total mass of the Si-containing particle. In some embodiments, the total mass of S can contribute (on average) from about 0 wt. % to about 2.5 wt. % (about 0 wt. % to about 0.1 wt. % in some designs, about 0.1 wt. % to about 0.5 wt. % in other designs, and about 0.5 wt. % to about 2.5 wt. % in still other designs) of the total mass of the Si-containing particle. In some embodiments, the total mass of F can contribute (on average) from about 0 wt. % to about 2.5 wt. % (about 0 wt. % to about 0.1 wt. % in some designs, about 0.1 wt. % to about 0.5 wt. % in other designs, and about 0.5 wt. % to about 2.5 wt. % in still other designs) of the total mass of the Si-containing particle.

[0129] In some embodiments, the total atomic fraction of Si and C may contribute about 75 atomic %, or about 80 atomic % to about 100 atomic % of the overall composite particle. Such composite particles may be referred to herein as Si-C composites. In some embodiments, such composite particles include nanosized or nanostructured elements (e.g., nanosized or nanostructured Si, Si nanoparticles, nanoporous Si nanoparticles, nanosized, nanoporous, or nanostructured C, or both), and may be referred to herein as nanocomposite particles. In some examples, the Si or Si-containing active material present in these nanocomposites may be in the form of nanoparticles. In some examples, the mass average size of the Si or Si-containing material nanoparticles (e.g., silicon nanoparticles or nanocrystals) can range from about 1 nm to about 200 nm (about 1.0 nm to about 10.0 nm in some designs, about 10.0 nm to about 30.0 nm in other designs, about 30.0 nm to about 100.0 nm in still other designs, and about 100.0 nm to about 200.0 nm in still other designs), 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 / or other suitable techniques. In some designs, the Si or Si-containing material nanoparticles (e.g., silicon nanoparticles) can be doped (e.g., with a Group V or Group III element such as N, P, B, etc. in some designs, with a Group IV element such as C, etc. in other designs, or various combinations thereof). The degree of doping can range from about 10 ppm to about 50,000 ppm in some designs (e.g., about 10 ppm to about 100 ppm in some designs, about 100 ppm to about 1,000 ppm in other designs, about 1,000 ppm to about 10,000 ppm in other designs, and about 10,000 ppm to about 50,000 ppm in still other designs). X-ray diffraction can be particularly useful and easy to identify the average size of the Si nanocrystals. Si nanocrystals that are too small (e.g., smaller than about 1.0 nm in some designs, or, e.g., smaller than about 2 nm in other designs) can be too reactive during synthesis, leading to reduced activity or excessive first-cycle capacity loss.On the other hand, excessively large Si crystallites (e.g., larger than about 200 nm in some designs or, e.g., larger than about 100 nm in other designs) can reduce the cycling stability of the Si-C composite (nanocomposite) or, more broadly, nanocomposite silicon. As used herein, a "nano" material (e.g., nanostructure, nanoparticle, or nanocomposite) refers to any material exhibiting at least one dimension less than about 200 nm.

[0130] Aspects are directed to battery anodes and / or battery anode precursor compositions comprising a population of Si-containing composite particles (e.g., nanocomposite particles, among others), each of the Si-containing composite particles comprising Si and C, the Si-containing composite particles having particular properties. In some embodiments, the mass fraction of silicon in the Si-containing composite particles ranges from about 3 wt% to about 80 wt% (about 3 wt% to about 20 wt% in some designs, about 20 wt% to about 35 wt% in other designs, about 35 wt% to about 50 wt% in still other designs, about 50 wt% to about 80 wt% in still other designs, about 50 wt% to about 60 wt% in still other designs, about 60 wt% to about 70 wt% in still other designs, about 70 wt% to about 80 wt% in still other designs, about 20 wt% to about 80 wt% in still other designs, and about 35 wt% to about 60 wt% in still other designs). In some embodiments, the Brunauer-Emmett-Teller (BET) specific surface area (SSA) of the Si-containing composite particles (e.g., particularly nanocomposite particles) is about 0.5 m 2 / g~about 150m 2 / g (approx. 0.5 to approx. 3 m in some designs) 2 / g, and approximately 3m for other designs 2 / g ~ approx. 12m 2 / g, and in other designs, approximately 12 m 2 / g ~ approx. 18m 2 / g, and in other designs, approximately 18m 2 / g ~ approx. 30m 2 / g, and in other designs, approximately 30m 2 / g~about 50m 2 / g, and about 50m for other designs 2 / g~about 150m 2 / g). In some embodiments, about 90% or more of the Si-containing composite particles (e.g., especially nanocomposite particles) in the population are characterized by an aspect ratio of about 2.3 or less, or an aspect ratio of about 2.1 or less. In some embodiments, about 50% or more of the composite particles in the population are characterized by an aspect ratio of about 1.25 or more, or an aspect ratio of about 1.35 or more.

[0131] Embodiments are directed to battery electrodes and / or battery electrode precursor compositions comprising a population of Si-containing active material particles (e.g., nanocomposite particles, among others), which particle populations can be characterized by a particle size distribution (PSD) determined by laser particle size distribution analysis (LPSA), image analysis of electron microscope images, or other suitable techniques. The particle size distribution (PSD) characterizing a particle population can be determined, in one example, by laser particle size distribution analysis (LPSA) on a well-dispersed particle suspension, by image analysis of electron microscope images, or other suitable techniques. While there are various processes for measuring PSD, for some applications, laser particle size distribution analysis (LPSA) is highly efficient. Using LPSA, the 10th percentile volume-weighted particle size parameter (e.g., D 10 ), the 50th percentile volume-weighted particle size parameter (e.g., D 50 ), 90th percentile volume-weighted particle size parameters (e.g., D 90 ), and the 99th percentile volume-weighted particle size parameter (e.g., D 99 The particle size parameter of the PSD of a group of particles such as spheres (abbreviated as spheres) can be measured. Furthermore, the parameter related to the characteristic width of the PSD is D 50 -D 10 (Here it is sometimes called left width), D 90 -D 50 (Here it is sometimes called the right width) and D 90 -D 10(sometimes referred to herein as total width) can be derived from these particle size parameters. The cumulative volume fraction, defined as the cumulative volume of composite particles having particle sizes equal to or less than a threshold particle size divided by the total volume of all of the composite particles, can be estimated by LPSA. In some embodiments, the 50th percentile volume-weighted particle size parameter (D) of the PSD of the Si-containing active material particles can be calculated using the LPSA. 50 ) can advantageously be in the range of about 0.5 μm to about 25.0 μm, about 0.5 to about 4.0 μm, about 4.0 to about 6.0 μm, about 6.0 to about 8.0 μm, about 8.0 to about 16.0 μm, or about 16.0 to about 25.0 μm. The cumulative volume fraction, defined as the cumulative volume of composite particles having particle sizes equal to or less than a threshold particle size divided by the total volume of all composite particles, can be estimated by LPSA. In some embodiments (e.g., D 50 In other embodiments (e.g., when D is in the range of about 0.5 μm to about 4.0 μm), the cumulative volume fraction at the 5 μm threshold particle size can advantageously be about 99 vol. % or less, about 95 vol. % or less, about 90 vol. % or less, about 85 vol. % or less, or about 80 vol. % or less. 50 In other embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction at the 7 μm threshold particle size can advantageously be about 99 vol. % or less, about 95 vol. % or less, about 90 vol. % or less, about 85 vol. % or less, or about 80 vol. % or less. 50 In other embodiments (e.g., when D is in the range of about 6.0 μm to about 8.0 μm), the cumulative volume fraction at the 10 μm threshold particle size can advantageously be about 99 vol. % or less, about 95 vol. % or less, about 90 vol. % or less, about 85 vol. % or less, or about 80 vol. % or less. 50 In still other embodiments (e.g., when D is in the range of about 8.0 μm to about 16.0 μm), the cumulative volume fraction at the 20 μm threshold particle size can advantageously be about 99 vol.% or less, about 95 vol.% or less, about 90 vol.% or less, about 85 vol.% or less, or about 80 vol.% or less. 50In some embodiments, when D is in the range of about 16 μm to about 25 μm, the cumulative volume fraction at a 30 μm threshold particle size can be about 99 vol.% or less, about 95 vol.% or less, about 90 vol.% or less, about 85 vol.% or less, or about 80 vol.% or less. In some embodiments, D is in the range of about 7.0 μm to about 13.0 μm. 50 In such embodiments, the cumulative volume fraction at a threshold particle size of 20 μm may advantageously be about 99% by volume or less, about 95% by volume or less, about 90% by volume or less, about 85% by volume or less, or about 80% by volume or less.

[0132] It should be noted that in some designs, the presence of excessively large Si-containing active material particles (e.g., especially in the form of nanocomposite particles) can degrade cell performance characteristics (e.g., reduce cell stability, increase its impedance, reduce rate capability, reduce packing density, reduce electrode smoothness or uniformity, reduce electrode mechanical properties, reduce volumetric capacity, increase (e.g., localized) volumetric expansion, etc.). In some embodiments (e.g., D 50 In some embodiments (e.g., when D is in the range of about 0.5 μm to about 4.0 μm), the cumulative volume fraction at a threshold particle size of about 10 μm can advantageously be about 80 vol. % or more, about 85 vol. % or more, or even (in some designs) about 90 vol. % or more. 50 In other embodiments (e.g., when D is in the range of about 0.5 μm to about 4.0 μm), the cumulative volume fraction at the 12 μm threshold particle size can advantageously be about 90 vol. % or more, about 95 vol. % or more, or even (in some designs) about 98 vol. % or more. 50 In some embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction at the 15 μm threshold particle size can advantageously be about 80 vol. % or more, about 85 vol. % or more, or (in some designs) even about 90 vol. % or more. 50 In some embodiments (e.g., when D is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction at the 25 μm threshold particle size can advantageously be about 90 vol. % or more, about 95 vol. % or more, or even (in some designs) about 98 vol. % or more. 50In other embodiments (e.g., when D is in the range of about 6.0 μm to about 8.0 μm), the cumulative volume fraction at a threshold particle size of about 18 μm can advantageously be about 80 vol. % or more, about 85 vol. % or more, or even (in some designs) about 90 vol. % or more. 50 In some embodiments (e.g., when D is in the range of about 6.0 μm to about 8.0 μm or about 8.0 μm to about 12.0 μm), the cumulative volume fraction at a threshold particle size of about 22 μm or about 25 μm can advantageously be about 80 vol.% or more, about 85 vol.% or more, about 90 vol.% or more, about 95 vol.% or more, or (in some designs) even about 98 vol.% or more. 50 In some embodiments (e.g., when D is in the range of about 8.0 μm to about 16.0 μm or about 12.0 μm to about 16.0 μm), the cumulative volume fraction at a threshold particle size of about 30 μm or about 40 μm can advantageously be about 80 vol.% or more, about 85 vol.% or more, or (in some designs) even about 90 vol.% or more. 50 In some embodiments (e.g., when D is in the range of about 8.0 μm to about 16.0 μm), the cumulative volume fraction at the 50 μm threshold particle size can advantageously be about 90 vol. % or more, about 95 vol. % or more, or even (in some designs) about 98 vol. % or more. 50 In other embodiments (e.g., when D is in the range of about 7.0 μm to about 13.0 μm), the cumulative volume fraction at the 30 μm threshold particle size can advantageously be about 90 vol. % or more, about 95 vol. % or more, or even (in some designs) about 98 vol. % or more. 50 is in the range of about 7.0 μm to about 13.0 μm), the cumulative volume fraction at the 40 μm threshold particle size can advantageously be about 90 vol. % or more, about 95 vol. % or more, or (in some designs) even about 98 vol. % or more.

[0133] In one or more embodiments of the present disclosure, the Si-containing active material particles (e.g., Si-containing active material composite particles) may exhibit a true density (e.g., measured using a nitrogen gas pycnometer, and thus sometimes referred to in this case as pycnometer-measured density, pycnometer density, or pycnodensity) in the range of about 1.1 g / cc to about 2.8 g / cc (about 1.1 g / cc to about 1.5 g / cc in some designs, about 1.5 g / cc to about 1.8 g / cc in other designs, about 1.8 g / cc to about 2.1 g / cc in other designs, about 2.1 g / cc to about 2.4 g / cc in other designs, and about 2.4 g / cc to about 2.8 g / cc in still other designs).

[0134] In one or more embodiments of the present disclosure, the Si-containing active material particles may include internal pores. In some designs, the open pore volume (e.g., measured by nitrogen adsorption / desorption isotherm measurement techniques, including pores ranging from about 0.4 nm to about 100 nm, relative to nitrogen gas at 77 K) may range from about 0.00 cc / g to about 0.50 cc / g (assuming the theoretical density of the individual material components present in the Si-containing active material particles), from about 0.00 cc / g to about 0.10 cc / g in some designs, from about 0.10 cc / g to about 0.20 cc / g in other designs, from about 0.20 cc / g to about 0.30 cc / g in other designs, from about 0.30 cc / g to about 0.40 cc / g in other designs, and from about 0.40 cc / g to about 0.50 cc / g in other designs. In some designs, the occluded pore volume (e.g., relative to nitrogen gas at 77 K) (measured, for example, by analyzing true density values ​​measured using an argon gas pycnometer and comparing them to the theoretical density of the individual material components present in the Si-containing active material particles) is about 0.00 cc / g to about 1.00 cc / g (about 0.00 cc / g to about 0.10 cc / g in some designs, about 0.10 cc / g to about 0.20 cc / g in other designs, and about 0.20 cc / g in other designs). cc / g to about 0.30 cc / g in other designs, from about 0.30 cc / g to about 0.40 cc / g in other designs, from about 0.40 cc / g to about 0.50 cc / g in other designs, from about 0.50 cc / g to about 0.60 cc / g in other designs, from about 0.60 cc / g to about 0.70 cc / g in other designs, from about 0.70 cc / g to about 0.80 cc / g in other designs, from about 0.80 cc / g to about 0.90 cc / g in other designs, and from about 0.90 cc / g to about 1.00 cc / g in other designs). In some designs, the volume average size of the open pores (e.g., for nitrogen gas at 77 K) can range from about 0.5 nm to about 100 nm, in some designs from about 0.5 nm to about 5 nm, in other designs from about 5 nm to about 20 nm, in other designs from about 20 nm to about 50 nm, and in still other designs from about 50 nm to about 100 nm.In some designs, the volume average size of the closed pores (e.g., for nitrogen gas at 77 K) (e.g., as measured by image analysis of cross-sectional electron microscopy images such as SEM or TEM, or by neutron scattering or other suitable techniques) can range from about 0.5 nm to about 200 nm, in some designs from about 0.5 nm to about 5 nm, in other designs from about 5 nm to about 20 nm, in other designs from about 20 nm to about 50 nm, in other designs from about 50 nm to about 100 nm, and in still other designs from about 100 nm to about 200 nm.

[0135] In one or more embodiments of the present disclosure, the Si-containing active material particles may exhibit a moderate (e.g., about 7-120 vol%) or a high (e.g., about 120-200 vol%) volume change during initial lithiation (e.g., Li / Li + (This decreases to about 0.01 V vs. V). In some designs, the Si-containing active material particles may exhibit a volume change ranging from about 8% to about 180% by volume during one or more charge / discharge cycles of the battery cell. In one or more embodiments of the present disclosure, the Si-containing active material particles may exhibit a reasonably small (e.g., about 3-7% by volume) or moderate (e.g., about 7-120% by volume) volume change during electrochemical cell cycling from about 0-5% state of charge (SOC) to about 90-100% SOC and vice versa during battery operation.

[0136] In one or more embodiments of the present disclosure, anodes suitable for battery cells can include a mixture of Si-containing active material particles (e.g., nanocomposite Si-C particles, nanocomposite Si particles, among others) and graphite active material particles (or, more broadly, carbon active material particles) as anode active material particles, a so-called blended anode. In addition to the anode active material particles, the anode can include inactive materials such as binders (e.g., polymer binders) and / or other functional additives (e.g., surfactants, conductive additives, etc.). In some examples, the anode active material particles can range from about 85% to about 89% by weight of the total anode weight (excluding the weight of the current collector), from about 89% to about 98% by weight in other designs, from about 89% to about 91% by weight in other designs, from about 91% to about 93% by weight in other designs, from about 93% to about 95% by weight in other designs, and from about 95% to about 98% by weight in still other designs.

[0137] In some embodiments, the blended anode may comprise Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) ranging from about 7% to about 98% by weight of all anode active material particles and graphite (e.g., particles), with the remainder (about 2% to about 93% by weight) of the mass (weight) of the anode active material particles. In some designs, the Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) comprise about 7% to about 15% by weight of the blended anode active material particles, about 15% to about 25% by weight of the blended anode active material particles in other designs, about 25% to about 40% by weight of the blended anode active material particles in other designs, about 40% to about 60% by weight of the blended anode active material particles in other designs, about 60% to about 80% by weight of the blended anode active material particles in other designs, and about 80% to about 98% by weight of the blended anode active material particles in still other designs.

[0138] While the following description may describe specific examples of blended anode formulations expressed as the mass (wt%) of Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) in the anode active material or the mass (wt%) of Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) of the total anode (excluding the weight of the current collector), it should be understood that various aspects of the present disclosure may be applicable to blended anode formulations expressed as the mass (wt%) of Si in the anode (including the weight of all active material particles, binders, conductive and / or other additives, but excluding the weight of the current collector). In some examples, a blended anode composition of about 7 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) (based on the total weight of all active materials, binders, conductive and / or other additives in the anode, but excluding the weight of the current collector) may correspond to, for example, about 3 wt% Si in the blended anode. In some examples, a blended anode composition of about 19 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) can correspond to, for example, about 8 wt% Si in the blended anode. In some examples, a blended anode composition of about 35 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) can correspond to, for example, about 15 wt% Si in the blended anode. In some examples, a blended anode composition of about 50 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) can correspond to, for example, about 21 wt% Si in the blended anode. In some examples, a blended anode composition of about 70 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) can correspond to, for example, about 30 wt% Si in the blended anode. In some examples, a blended anode composition of about 90 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) can correspond to, for example, about 38 wt% Si in the blended anode, where the wt% Si in the anode depends on the wt% Si of the Si-containing active material particles, the wt% of the binder and conductive additive, and the wt% graphite in the blended anode.The lower the fraction of inactive materials (e.g., binders and conductive or other additives), the higher the fraction of Si in the Si-containing anode material particles (e.g., Si-C composite particles), and the lower the fraction of graphite in the blend anode, the higher the weight percent Si in the anode. For example, in some examples, a blend anode composition of about 80 weight percent Si-containing active material particles (e.g., particularly Si-C nanocomposite particles) and about 20 weight percent total binder, conductive or other additives (if present), and graphite can correspond to, for example, about 30 weight percent Si in the blend anode. In other examples, a blend anode composition of about 80 weight percent Si-containing active material particles (e.g., particularly Si-C nanocomposite particles) and about 20 weight percent total binder, conductive or other additives (if present), and graphite can correspond to, for example, about 40 weight percent Si in the blend anode. In another example, a blended anode composition of about 80 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) and about 20 wt% total of binder, conductive or other additives (if present), and graphite may correspond to, for example, about 50 wt% Si in the blended anode. In another example, a blended anode composition of about 80 wt% Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) and about 20 wt% total of binder, conductive or other additives (if present), and graphite may correspond to, for example, about 60 wt% Si in the blended anode. In each example, a blended anode may be obtained in which the mass (weight) of silicon is in the range of about 3 wt% to about 60 wt% of the total mass of the anode (excluding the weight of the current collector).

[0139] While the following description may describe specific examples of blend anode formulations expressed as the mass (wt%) of Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the active material blend, it should be understood that various aspects of the present disclosure may be applicable to blend anode formulations in which the Si-containing active material particles contribute a fraction (e.g., %) of capacity to the total capacity of the blend anode. In some examples, for example, about 25% of the total capacity of the blend anode may be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in a blend anode composition of about 5-8 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) relative to the total weight of the active material particles (both the Si-containing active material particles and the graphite active material particles). In some other examples, about 50% of the total capacity of the blended anode can be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in a blended anode composition of about 15-21 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In some other examples, about 70% of the total capacity of the blended anode can be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in a blended anode composition of about 30-40 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In some other examples, about 80% of the total capacity of the blended anode can be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in a blended anode composition of about 45-55 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In some other examples, about 92% of the total capacity of the blended anode can be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles) in a blended anode composition of about 65-75 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles). In some other examples, about 95% of the total capacity of the blended anode can be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles) in a blended anode composition of about 75-85 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles).In some other examples, about 98% of the total capacity of the blended anode can be obtained from Si-containing active material particles (e.g., Si-C nanocomposite particles) in a blended anode composition of about 85-95 wt% of the Si-containing active material particles (e.g., Si-C nanocomposite particles). Note that the exact % capacity provided by the Si-containing active material particles in a blended anode having a particular wt% of Si-containing active material particles depends on the specific capacity of the plurality of Si-containing active material particles and the specific capacity of the plurality of graphite (or broadly carbon) active material particles.

[0140] In some embodiments, battery anode compositions may advantageously include one, two, 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 additives are selected from carbon nanotubes (CNTs) (e.g., single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), multi-walled carbon nanotubes (MWCNTs)), carbon nanofibers, carbon black, graphite, graphite ribbons, expanded graphite (e.g., expanded graphite flakes), graphene oxide (e.g., graphene oxide flakes), and graphene (e.g., flakes) (including, but not limited to, single-layer and / or multi-layer graphene or graphene oxide). In some embodiments, the carbon additives may be refined, defective, curved, and / or include chemical functionality. In some embodiments, battery electrode compositions may include one or more binders (in some designs, two or more binder components).

[0141] Aspects are directed to battery anodes. In some embodiments, the battery anode comprises any of the above-described battery anode electrode compositions disposed on or within a current collector (e.g., a Cu-based or Cu-containing current collector, such as a dense or porous foil, mesh, foam, or nanowire- or nanoflake-containing current collector). In some embodiments, the battery anode comprises a battery electrode composition and a binder. In some embodiments, the battery electrode has a coating density of about 0.8 to about 1.7 g / cm. 3(Some designs are approximately 0.8 to 0.9 g / cm 3 , and about 0.9 to about 1.0 g / cm for other designs. 3 , and about 1.0 to about 1.2 g / cm for other designs. 3 , and about 1.2 to about 1.4 g / cm for other designs. 3 , and about 1.4 to about 1.7 g / cm in other designs. 3 ) range. Higher fractions of suitable graphite material in the blend anode can benefit from higher anode density in better performance (better stability, better rate capability, higher volumetric capacity, lower expansion rate during cycling, etc.), although excess density may be detrimental to the same or other properties. Thus, detailed optimization can be performed for a particular battery design with respect to factors such as electrode thickness, areal capacity loading, and battery cycling environment and regime, among others.

[0142] Embodiments are also directed to blended battery anodes in which both Si-containing anode active material particles (e.g., nanocomposite Si-C particles, among others) and graphite (or broadly carbon-based) anode active material may be present. The anode may preferably include a binder amount optimized for the properties of both the Si-containing active material particles and the graphite particles. For example, the anode may include a binder amount optimized for the properties of both the Si-containing (e.g., nanocomposite) anode active material particles and (if present) the graphite active material particles (e.g., in units of m 2 It is measured in m 2 The anode active material may be characterized by an areal binder loading, defined as the mass of binder (e.g., measured in mg) in the battery anode normalized by the surface area (defined by the mass of the active material particles (in g) multiplied by the Brunauer-Emmett-Teller (BET) specific surface area (SSA) in m / g. Because the BET-SSA of both the Si-containing active material particle population and the graphite active material particle population can vary between slurries, the binder loading can preferably be adjusted based on the desired areal binder loading. The BET-SSA (in m 2A higher mass fraction of binder in the anode electrode is generally required, as measured in terms of 10 m / g. 2 An active material particle population (e.g., a Si-containing (e.g., nanocomposite) anode active material particle population or a blend of Si-containing active material particles and graphite active material particles) having a BET-SSA of 1 / g typically requires about 20 mg to about 150 mg of binder (about 2 to 13 wt % based on the total weight of the binder and active material composition, excluding the weight of conductive or other additives or the weight of the current collector) per about 1 g of active material particles. 2 Other anode electrodes containing other active material particle populations (e.g., Si-containing (e.g., nanocomposite) anode active material particle populations or blends of Si-containing and graphite active material particles) having a BET-SSA of only 1.0 mg / m² typically require about 2 mg to about 40 mg of binder per about 1 g of active material particles (about 0.2 to 4 wt. % based on the total weight of the binder and active material composition, excluding the weight of conductive or other additives or the weight of the current collector). However, in some designs, the areal binder loading of the battery anode is about 2.0 mg / m² in any case. 2 ~about 40.0mg / m 2 (e.g., about 2.0 mg / m in some designs) 2 ~about 5.0mg / m 2 , and about 5.0 mg / m for other designs. 2 ~about 9.0mg / m 2 , and about 9.0 mg / m for other designs. 2 ~Approx. 15.0mg / m 2 , and about 15.0 mg / m for other designs. 2 ~about 40.0mg / m 2) range. In some designs, a higher areal binder loading may be desirable with a higher fraction of the Si-containing (e.g., nanocomposite, etc.) anode active material particle population in the anode (relative to the total weight of all active materials). In some designs, a slightly lower areal binder loading may be desirable with a larger average particle size of the Si-containing (e.g., nanocomposite, etc.) anode active material particle population in the anode. In some designs, a slightly higher areal binder loading may be desirable with a larger BET-SSA of the Si-containing (e.g., nanocomposite, etc.) anode active material particle population in the anode. In some designs, the areal binder loading may also depend on the binder composition and properties (e.g., adhesion, chemical composition, hardness, modulus when exposed to electrolyte, and ultimate elongation at break, among others). Thus, in some designs, a binder loading of about 2.0 mg / m 2 ~about 40.0mg / m 2 The optimum areal binder loading range depends on the anode composition. For example, the optimum areal binder loading is about 2.0 mg / m for some designs. 2 ~about 5.0mg / m 2 , and about 5.0 mg / m for other designs. 2 ~about 9.0mg / m 2 , and about 9.0 mg / m for other designs. 2 ~Approx. 15.0mg / m 2 , and about 15.0 mg / m for other designs. 2 ~about 40.0mg / m 2 The range may be:

[0143] While the following description may describe specific examples of intercalated graphites suitable for use in combination with Si-containing (e.g., Si-C nanocomposite, etc.) active material particles in a blend, various embodiments of the present disclosure are directed to intercalated graphites, including, but not limited to, those exhibiting discharge capacities of about 320 to about 372 mAh / g (e.g., about 320 to about 350 mAh / g in some designs, about 350 to about 362 mAh / g in other designs, or about 362 to about 372 mAh / g in other designs), including, but not limited to, those exhibiting low swelling, medium swelling, and high swelling, including, but not limited to, those exhibiting good and poor compressibility, including, but not limited to, those exhibiting a compressibility of about 0.5 to about 40 m 2 / g (e.g., about 0.5 to about 2 m in some designs) 2 / g, and about 2 to 4 m for other designs 2 / g, and about 4 to 6 m for other designs 2 / g, and about 6 to 8 m for other designs 2 / g, and about 8 to 10 m for other designs 2 / g, and about 10 to 14 m for other designs 2 / g, and about 14 to about 20 m for other designs 2 / g or about 20 to about 40 m for other designs 2 / g), including, but not limited to, those exhibiting a lithiation efficiency of about 85-90% or greater, including, but not limited to, those exhibiting a BET-SSA of about 1.5 g / cm 3 ~Approx. 2.3g / cm 3 (For example, some designs have a value of about 1.5 to about 1.8 g / cm 3 , and about 1.8 to about 2.3 g / cm for other designs. 3), including, but not limited to, those that exhibit poor, fair, or good cycle life when used by itself (e.g., without Si-containing or other active material particles) in anodes of Li-ion batteries, and including, but not limited to, those that are coated and have a coating thickness to significantly improve compressibility and springiness during cycling, various soft-type synthetic graphites (i.e., soft carbons in the broad sense), various hard-type synthetic graphites (i.e., hard carbons in the broad sense), and various natural graphites (e.g., that may be coated with pitch carbon, among others).

[0144] One embodiment is directed to batteries and anodes including Si-containing active material particles (e.g., Si-C nanocomposite particles, C-coated particles, etc.) that also contain C, wherein the average domain size of the C ranges from about 10 Å (1 nm) to about 60 Å (6 nm) as determined by synchrotron X-ray diffraction (XRD) atomic pair distribution function (PDF) analysis. In one embodiment, the C portion of such Si-C composite particles may be inert and separate from any C-containing active material (e.g., graphite) in the anode.

[0145] One embodiment is directed to a battery and anode including Si-containing material particles that also contain C (e.g., Si-C nanocomposite particles, C-coated particles, etc.), and is (e.g., measured using a laser wavelength of about 532 nm, e.g., about 1000 to about 2000 wavenumber cm -1 The ratio of the intensities of the carbon D band and the carbon G band in the Raman spectrum of the majority of Si- and C-containing particles (I = 1 / 2 ) is analyzed by fitting two Gaussian peaks after linear background subtraction in this range. D / I G ) is approximately 0.7 I D / I G ~ Approximately 2.7 I D / I G(In some designs, it ranges from about 0.7 to about 0.9, in other designs it ranges from about 0.9 to about 1.2, in other designs it ranges from about 1.2 to about 1.5, in other designs it ranges from about 1.5 to about 1.8, in other designs it ranges from about 1.8 to about 2.1, in other designs it ranges from about 2.1 to about 2.4, and in still other designs it ranges from about 2.4 to about 2.7). In one embodiment, the C portion of such Si-C composite particles may be inactive and may be separate from any C-containing active material (e.g., graphite) in the anode.

[0146] One embodiment is also directed to a Li-ion battery comprising: (i) a suitable blended battery anode in which both Si-containing anode active material particles (e.g., nanocomposite Si—C particles, among others) and a suitable graphite (or broadly carbon-based) anode active material (e.g., graphite active material particles) are present; and (ii) a suitable battery cathode, which in some designs may comprise one or more of the following: (iia) an insertion cathode, (iib) a conversion cathode (which may include a substitutional cathode, a chemical conversion cathode, or a true conversion cathode), or (iic) a mixed insertion / conversion cathode. Illustrative examples of insertion cathodes suitable for use in a preferred cell include, but are not limited to, 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 (LiNiPO), lithium vanadium fluorophosphate (LiVFPO), lithium iron fluorosulfate (LiFeSOF), various Li-rich materials (e.g., Li 1.211 Mo 0.467 Cr 0.3 O2, Li 1.3 Mn 0.4 Nb 0.3 O2, Li 1.2 Mn 0.4 Ti0.4 O2, Li 1.2 Ni 0.333 Ti 0.333 Mo 0.133 Lithium-rich (rock salt) transition metal oxides and oxyfluorides such as LiMnO and many others), various high capacity Li-ion based materials with partial substitution of oxygen for fluorine or iodine (e.g., rock salt LiMn, among others). 2 / 3 Nb 1 / 3 O2F, Li2Mn 1 / 2 Ti 1 / 2 O2F, Li 1.5 Na 0.5 MnO 2.85 I 0.12), as well as numerous other types of Li-containing disordered, layered, tavorite-type, olivine-type, or spinel-type active materials, or mixtures thereof, including at least oxygen, fluorine, or sulfur that rely on lithium (Li) insertion and transition metal (TM) oxidation state changes, and at least one transition metal and / or other lithium TM oxide, phosphate, or sulfate (or mixed) cathode active materials, including, but not limited to, those that may be doped or heavily doped, including, but not limited to, those with compositional gradients or core-shell morphologies, including, but not limited to, those that may be partially fluorinated or contain some significant fraction (e.g., about 0.001-10 atomic %) of fluorine in their composition. It should also be appreciated that various embodiments may be applicable to high voltage lithium transition metal oxide (or phosphate, sulfate, mixed, or other) cathodes (including, but not limited to, oxides, phosphates, sulfates, or mixed cathodes thereof that may contain at least about 0.25 atomic % Mn, Fe, Ni, Co, Nb, Mg, Cr, Mo, Zr, W, Ta, Ti, Hf, Y, La, Sb, V, Sn, Si, or Ge) in which TM and oxygen (O) are covalently bonded and both TM and O participate in electrochemical oxidation-reduction (redox) reactions during charge and discharge. Illustrative examples of conversion-type cathodes suitable for use in preferred cells may include, but are not limited to, metal fluorides, metal oxyfluorides, metal chlorides, metal sulfides, metal selenides, various mixtures, composites, and / or others thereof. Illustrative examples of metal fluorides in a lithium-free state include, but are not limited to, FeF3, FeF2, MnF3, CuF2, NiF2, BiF3, BiF5, SnF2, SnF4, SbF3, SbF5, CdF2, ZnF2, TiF3, TiF4, AgF, AgF2, and various mixtures, alloys, and combinations thereof. In some designs, it may be advantageous to create nanocomposites and / or core-shell structures containing metal fluorides to enhance their performance and stability. In some designs, it may be advantageous to dope metal fluorides with oxygen or utilize metal oxyfluorides.In the fully lithiated state, the pure metal fluoride converts to a composite containing a mixture of metal and LiF clusters (or nanoparticles). Examples of globally reversible reactions for conversion-type metal fluoride cathodes may include 2Li + CuF2 ←→ 2LiF + Cu for a CuF2-based cathode or 3Li + FeF3 ←→ 3LiF + Fe for an FeF3-based cathode. It should be appreciated that metal fluoride-based cathodes can be prepared in lithium-free, partially lithiated, or fully lithiated states. In addition to fluorides, other illustrative examples of conversion-type electrode active materials may include, but are not limited to, various metal oxyfluorides, sulfofluorides, chlorofluorides, oxychlorofluorides, oxysulfofluorides, fluorophosphates, sulfophosphates, sulfofluorophosphates, mixtures of metals (e.g., Fe, Cu, Ni, Co, Bi, Cr, Zn, Ti, other metals, various mixtures and alloys thereof, partially oxidized metals and metal alloys, etc.) and salts (metal fluorides (including LiF or NaF), metal chlorides (including LiCl or NaCl), metal oxyfluorides, metal oxides, metal sulfofluorides, metal fluorophosphates, metal sulfides, metal oxysulfofluorides, various combinations thereof, etc.), among others, and / or other salts containing halogens, sulfur, oxygen, phosphorus, or combinations of these elements. In some designs, the F in the metal fluoride may be fully or partially substituted with other halogens (e.g., Cl, Br, or I) or mixtures thereof to form the corresponding metal chloride, metal fluoride-chloride, and / or other metal halide compositions. Further examples of promising and suitable conversion-type cathode active materials are sulfur (S) (in a lithium-free state) or lithium sulfate (LiS in a fully lithiated state). In some designs, selenium (Se), either together with S or by itself, may be used to form such cathode active materials. In some designs, it may be advantageous to create nanocomposites and / or core-shell structures containing S, LiS, Se, LiSe, or various mixtures and combinations thereof to enhance their performance and stability. In some designs, the conversion-type cathode active material may also advantageously include a metal oxide or mixed metal oxide.In some designs, such (nano)composites may advantageously comprise metal sulfides or mixed metal sulfides. In some examples, the mixed metal oxides or mixed metal sulfides may comprise lithium. In some examples, the mixed metal oxides may comprise titanium, vanadium, manganese, or iron metals. In some examples, the lithium-containing metal oxides or metal sulfides may exhibit a layered structure. In some examples, the metal oxides or mixed metal oxides or metal sulfides or mixed metal sulfides advantageously (e.g., about 10 -7 ~about 10 +4 S / cm range). In some instances, various other intercalation active materials may be utilized in place of, or in addition to, metal oxides or metal sulfides. In some designs, such intercalation active materials may be utilized in a potential range close to that of S or LiS (e.g., Li / Li + They exhibit charge storage (e.g., Li insertion / extraction capacity) within approximately 1.5 to 3.8 V vs. . In some designs, the use of so-called lithium-air cathodes (e.g., cathodes having active materials in the form of Li2O2, Li2O, LiOH in their lithiated states) or similar metal-air cathodes based on Na, K, Ca, Al, Fe, Mn, Zn, and / or other metals (instead of Li) can be similarly beneficial due to their very high capacity. In some designs, such cathode active materials ideally react reversibly with oxygen or oxygen-containing species in the electrochemical cell and can be completely lost upon complete delithiation (metal removal). Cathode active materials exhibiting such properties may also be considered to belong to the conversion-type cathodes.

[0147] In some suitable examples, the surface of the cathode active material (e.g., an intercalation-type cathode material such as LCO, NCM, NCMA, NCA, LMO, LMNO, LFP, LMP, LMFP, etc., or a conversion-type active material including S, LiS, metal sulfides, metal fluorides, etc.) may be coated with a layer of ceramic material. Illustrative examples of coating materials suitable for such cathodes include, but are not limited to, titanium oxide (e.g., TiO), tantalum oxide (TaO), aluminum oxide (e.g., AlO), tungsten oxide (e.g., WO), chromium oxide (e.g., CrO), niobium oxide (e.g., NbO or NbO), and zirconium oxide (e.g., ZrO), lithium phosphate (e.g., LiPO), lithium oxythiophosphate (e.g., LiP), and the like. 1+x O4S 4x) and various mixtures, alloys, and combinations thereof. In some designs, such ceramic materials may additionally contain lithium (Li), for example, as lithium phosphate, lithium oxythiophosphate, titanium lithium oxide, tantalum lithium oxide, aluminum lithium oxide, tungsten lithium oxide, chromium lithium oxide, niobium lithium oxide, zirconium lithium oxide, and various alloys, mixtures, and combinations thereof. In other suitable examples, the LCO, NCM, NCMA, NCA, LFP, 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 suitable cathode current collector material is aluminum or an aluminum alloy. In some designs, the suitable battery cell includes a polymer separator. In some suitable examples, the polymer separator is made of or includes polyethylene, polypropylene, or a mixture thereof. In some suitable examples, the surface of the polymer separator is coated with a layer of ceramic material. Examples of suitable coating materials for polymer separators may include, but are not limited to, titanium oxide (TiO), aluminum oxide (AlO), hydroxide or aluminum oxyhydroxide, zirconium oxide (ZrO), magnesium oxide (MgO), or hydroxide or magnesium oxyhydroxide. In some designs, suitable battery cells include ceramic-based or ceramic-containing (e.g., ceramic / polymer composite) separators. The ceramic or ceramic component of such ceramic or ceramic-containing separators may include titanium oxide (TiO), aluminum oxide (AlO), hydroxide or aluminum oxyhydroxide, zirconium oxide (ZrO), magnesium oxide (MgO), or hydroxide or magnesium oxyhydroxide. In some designs, the ceramic or ceramic component of such ceramic or ceramic-containing separators may include ceramic particles (e.g., elongated particles, nanofibers, flake-shaped particles, irregularly shaped particles including nanoparticles, etc.).

[0148] One embodiment is directed to a Li-ion battery having a blend anode (e.g., including a Si-containing active material and a graphite active material) exhibiting a relatively high areal capacity loading and a properly matched (by areal capacity) cathode (e.g., having a slightly lower areal capacity loading and selected according to the desired anode (N) to cathode (P) ratio, where N / P ranges from about 1.01 to about 1.35, in some designs from about 1.01 to about 1.05, in other designs from about 1.05 to about 1.10, in other designs from about 1.10 to about 1.15, in other designs from about 1.15 to about 1.20, in other designs from about 1.20 to about 1.25, and in still other designs from about 1.25 to about 1.35, where the N / P ratio corresponds to the ratio of the reversible areal capacities of the anode to the cathode). It is noted that in some designs, both the performance characteristics and cycling stability of Li-ion battery cells comprising portions of such blend anodes (particularly for blend anodes having a high fraction of Si or a high fraction of Si-containing active material particles, e.g., about 3-60 wt. % Si, and in some designs about 10-20 wt. % Si, about 20-40 wt. % Si, or about 40-60 wt. % Si, or for blend anodes having Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) that contribute about 20-100% of the total blend anode capacity, and in some designs about 50-70%, about 70-80%, about 80-90%, about 90-95%, or about 95-99% of the total blend anode capacity) may be affected by electrode areal capacity loadings of about 1-2 mAh / cm. 2 When the area capacity load of the electrode exceeds 4-5 mAh / cm 2 When the area capacity load of the electrode exceeds 6 to 8 mAh / cm 2 Above about 2 mAh / cm, this can be particularly unsatisfactory for applications requiring long calendar life, long cycle life, low first cycle loss, or other properties. On the other hand, higher loads are advantageous for reducing the cost of energy storage devices and increasing their energy density. One or more embodiments of the present disclosure may achieve a load of about 2 mAh / cm. 2 ~about 5mAh / cm 2 For electrode area loadings in the range of approximately 5 mAh / cm 2 ~about 8mAh / cm 2For loads in the range of approximately 8mAh / cm 2 ~about 16mAh / cm 2 The synthesis process, composition, and various physical and chemical properties of the graphite and / or binder in the blend anode are directed to providing sufficient performance for loads in the range of 0.1 mAh / cm2 (e.g., in some designs, the areal capacity loading of the electrode composition is about 2 mAh / cm2). 2 ~about 16mAh / cm 2 (The range may be

[0149] One aspect is directed to Li-ion batteries having blend anodes (e.g., including Si-containing active material particles and graphite active material particles) that exhibit high energy. In some designs, degradation of Li-ion batteries having blend anodes without suitable graphite or binder can be observed, particularly when the blend anodes contain a moderate to relatively high fraction of Si (e.g., about 3-60 wt%, in some designs about 10-20 wt%, about 20-40 wt%, or about 40-60 wt%), or when the Si-containing active material particles (e.g., Si-C nanocomposite particles, among others) account for a moderate or relatively high fraction (e.g., about 20-100%, in some designs about 50-70%, about 70-80%, about 80-90%, or about 90-100%) of the total capacity of the anode. Contributions of 0-90%, about 90-95%, or about 95-99% may be faster for multi-layer (e.g., stacked or wound) medium-sized cells (e.g., cells having a cell capacity in the range of 0.2 Ah to about 10 Ah), for large cells (e.g., cells having a cell capacity in the range of about 10 Ah to about 40 Ah), and even faster for extra-large cells (e.g., cells having a cell capacity in the range of about 40 Ah to about 400 Ah), or for giant cells (e.g., cells having a cell capacity in the range of about 400 Ah to about 4000 Ah or more). On the other hand, multi-layer medium- or large-sized cells may be promising for some electronic devices, and multi-layer large, extra-large, or giant cells may be particularly promising for use in some electrical transportation or grid storage applications. One or more aspects of the present disclosure facilitate the use of the right graphite (or carbon, more broadly) in a blend anode having suitable microstructural, chemical, physical and / or other properties, and a suitable binder, that mitigates or overcomes some or all of such limitations of the blend anode and substantially enhances the performance of such Li-ion cells.

[0150] FIG. 1 illustrates an exemplary metal-ion (e.g., Li-ion) battery, to which the electrode particles, components, materials, processes, and / or other techniques described herein, or combinations thereof, may be applied according to various embodiments. While a cylindrical battery is shown here for illustrative purposes, other types of configurations, including prismatic or pouch-type (laminated) batteries, may also be used as desired. The exemplary battery 100 includes a negative electrode (anode electrode or anode) 102, a positive electrode (cathode electrode or cathode) 103, a separator 104 interposed between the anode 102 and the cathode 103, an electrolyte (implied) impregnating the separator 104, a battery case 105, and a sealing member 106 sealing the battery case 105. The electrolyte ionically bonds the anode (negative electrode) and the cathode (positive electrode). The electrolyte is interposed between the anode electrode and the cathode electrode. In some embodiments, the battery 100 also includes an anode current collector and a cathode current collector. The anode is disposed on or within the anode current collector, and the cathode is disposed on or within the cathode current collector.

[0151] One aspect is directed to a Li-ion battery having a blend anode (e.g., including Si-containing active material particles and graphite active material particles) that exhibits high energy and excellent performance characteristics. Intuitively, one skilled in the art might surmise that graphite or broadly carbon materials that exhibit excellent stability or rate capability in Li-ion battery anodes based on purely intercalation-type graphite (or more broadly carbon) active materials should provide the best performance when used in a blend anode that includes a Si-based active material (e.g., Si-C nanocomposite, among others). Unexpectedly, the inventors have found that this assumption is not true in many designs.In some designs, graphites that may exhibit relatively poor performance by themselves (e.g., relatively poor stability or rate capability when calendered / densified to the same density as a benchmark graphite anode, or low volumetric capacity for comparable stability characteristics), particularly when their mass fraction or total capacity contribution is small (e.g., sometimes referred to herein as "graphite for superior blend anodes (GRSBA)"), where such graphite (broadly speaking, carbon) contributes about 50% or less reversible capacity to the total blend anode capacity; in some designs, such graphite (carbon) contributes about 40% or less capacity to the total anode capacity; in some designs, about 30% or less capacity to the total anode capacity; in some designs, about 20% or less capacity to the total anode capacity; in some designs, about 15% or less capacity to the total anode capacity; in some designs, about 16% or less capacity to the total anode capacity; in some designs, about 20% or less capacity to the total anode capacity; in some designs, about 25% or less capacity to the total anode capacity; in some designs, about 30 ... For example, in some designs, such GRSBAs may contribute less than about 10% capacity to the total anode capacity, in some designs less than about 8% capacity to the total anode capacity, in some designs less than about 6% capacity to the total anode capacity, in some designs less than about 4% capacity to the total anode capacity, in some designs less than about 2% capacity to the total anode capacity, and in some designs less than about 1% capacity to the total anode capacity. for example, Li / Li, when contributing about 0.2% to about 1% of the total capacity in other designs, about 1% to about 2% of the total capacity in other designs, about 2% to about 4% of the total capacity in other designs, about 4% to about 6% of the total capacity in other designs, about 6% to about 8% of the total capacity in other designs, about 8% to about 10% of the total capacity in other designs, about 10% to about 20% of the total capacity in other designs, about 20% to about 30% of the total capacity in other designs, about 30% to about 40% of the total capacity in other designs, and about 40% to about 50% of the total capacity in still other designs. +This can significantly enhance the performance of the blend anode (as measured using half cells in the potential range of 0.01 to 1.00 V vs. Cr). In some designs, it can be advantageous to have a ratio of GRSBA capacity to total Si-containing active material particles (e.g., especially Si-C nanocomposite particles) ranging from about 1:200 to about 1:1 (about 1:200 to about 1:50 in some designs, about 1:50 to about 1:20 in other designs, about 1:20 to about 1:9 in other designs, about 1:9 to about 2:8 or 1:4 in other designs, about 1:4 to about 3:7 in other designs, about 3:7 to about 4:6 or 2:3 in other designs, and about 2:3 to about 1:1 in still other designs). In some designs, the blend anode can include two or more types of Si-containing active material particles (e.g., each type exhibiting a distinct composition, a distinct specific capacity, a distinct size distribution, a distinct specific surface area, and / or a distinct morphology, etc.). In some designs, the blend anode may contain two or more types of graphite (or, more broadly, carbon) particles. In some designs, only a portion of the graphite (or, more broadly, carbon) particles may be of the GRSBA type (the remainder being high-performance graphite commonly used in many graphite anodes in conventional commercial Li-ion batteries). In some designs, the total weight of GRSBA in the blend anode may range from about 1 wt. % to about 80 wt. % (about 1 wt. % to about 10 wt. % in some designs, about 10 wt. % to about 20 wt. % in other designs, about 20 wt. % to about 50 wt. % in other designs, and about 50 wt. % to about 80 wt. % in still other designs) based on the weight of all active material particles in the blend anode. In some designs, the total weight of GRSBA in the blend anode may advantageously range from about 1 wt. % to about 50 wt. % based on the weight of all active material particles in the blend anode. In some designs, the total weight of GRSBA in the blend anode can advantageously range from about 2% to about 20% by weight, based on the weight of all active material particles in the blend anode.

[0152] In one or more embodiments of the present disclosure, several important physical, chemical, mechanical, structural, or other properties of GRSBAs can be particularly advantageously utilized in Li-ion batteries having the blend anodes described above. Various graphites (or carbons) may be suitable for use as GRSBAs in blend anodes to achieve the superior Li-ion battery performance characteristics described herein. In some designs, the addition of a suitable graphite (GRSBA) to a Si-containing anode composition can provide higher volumetric capacity, lower resistance, and better rate performance than a "pure" Si-containing anode (e.g., an unblended anode containing only Si-containing active material particles without any intercalation-type active material particles). Thus, superior Li-ion battery cells, superior Li-ion batteries, and superior Li-ion battery packs containing a suitable GRSBA in a blend anode are described herein.

[0153] In one or more embodiments of the present disclosure, graphite exhibiting relatively low hardness may be one of the key characteristics imparting superior performance as a GRSBA in the blended anode (with Si-containing active material particles) described above. To test the hardness of graphite (carbon) powder samples, graphite (carbon) particles arranged as a dry powder were placed on a hardened steel disk and distributed as uniformly and as evenly as possible in small amounts, with the particles spread as far as possible so that individual particles were directly visible on the hardened steel surface. The hardened steel disk with the spread graphite particles was then attached to a Shimadzu MCT microcompression tester. The hardened steel disk was placed on a movable platform between the optical microscope and the compression head. Individual particles of the graphite sample were identified using the optical microscope of the tester. Once individual graphite particles were identified, the platform was switched to the compactor tip and hardness testing was performed by crushing (crushing) the individual graphite particles while measuring both force and displacement to calculate the pressure (Cx in MPa) required to deform the graphite particle by 10% (linear dimension). At least 10 graphite particles were measured for each sample and an average Cx was calculated.

[0154] Table 1 in Figure 2 shows example Cx measurements for each of selected graphite (carbon) samples numbered G1 through G22, as well as other examples of suitable graphite particles, including the graphite material referred to as "soft graphite." Graphite particles exhibiting average Cx values ​​in the range of 1 to 10 MPa are sometimes referred to as "soft graphite." It was determined that Cx values ​​in the range of about 1 MPa to about 30 MPa made the graphite samples optimal for use as GRSBAs in some or all of the blend anodes described above. In some designs, it is more preferred that the GRSBAs (or at least a majority, 50% by weight or more of the GRSBA) exhibit an average Cx value of less than about 30 MPa; in other designs, it is more preferred that the GRSBAs (or at least a majority, 50% by weight or more of the GRSBA) exhibit an average Cx value of less than about 25 MPa; in other designs, it is more preferred that the GRSBAs (or at least a majority, 50% by weight or more of the GRSBA) exhibit an average Cx value of less than about 20 MPa; in other designs, it is more preferred that the GRSBAs (or at least a majority, 50% by weight or more of the GRSBA) exhibit an average Cx value of less than about 15 MPa; and in other designs, it is more preferred that the GRSBAs (or at least a majority, 50% by weight or more of the GRSBA) exhibit an average Cx value of less than about 11 MPa. In other designs, it may be more preferred that the GRSBAs (or at least the majority, 50% by weight or more) exhibit an average Cx value of less than about 10 MPa; in other designs, it may be more preferred that the GRSBAs (or at least the majority, 50% by weight or more) exhibit an average Cx value of less than about 9 MPa; in other designs, it may be more preferred that the GRSBAs (or at least the majority, 50% by weight or more) exhibit an average Cx value of less than about 8 MPa; in other designs, it may be more preferred that the GRSBAs (or at least the majority, 50% by weight or more) exhibit an average Cx value of less than about 7 MPa; and in other designs, it may be more preferred that the GRSBAs (or at least the majority, 50% by weight or more) exhibit an average Cx value of less than about 6 MPa.In some designs, it may be preferred that a majority (e.g., about 50-60 wt%, about 60-70 wt%, about 70-80 wt%, or about 80-100 wt%) of the GRSBA in the blend anode exhibit an average Cx value in the range of about 1 MPa to about 18 MPa (e.g., about 1 MPa to about 7 MPa, about 7 MPa to about 10 MPa, about 10 MPa to about 14 MPa, or about 14 MPa to about 18 MPa). In some designs, it may be preferred that a majority (e.g., about 50-60 wt%, about 60-70 wt%, about 70-80 wt%, or about 80-100 wt%) of the GRSBA in the blend anode exhibit an average Cx value in the range of about 18 MPa to about 30 MPa (e.g., about 18 MPa to about 20 MPa, about 20 MPa to about 24 MPa, about 24 MPa to about 30 MPa, or about 20 MPa to about 30 MPa). It should be noted that in some designs, excessively soft graphite (e.g., average Cx values ​​less than 1 MPa) may result in anode degradation or poor rate performance, while excessively hard graphite (e.g., average Cx values ​​greater than about 30 MPa, and in some designs greater than about 25 MPa) may not achieve sufficient or even desirable volumetric capacity, energy density, discharge rate, or cycling stability, particularly for Si-rich blend anodes. Interestingly, the typical measured Cx values ​​of suitable Si-containing active material particles (e.g., Si—C particles, C-coated SiOx particles, etc.) generally exceed 40 MPa (e.g., Cx may be about 40 MPa to about 60 MPa in some designs, about 60 MPa to about 80 MPa in other designs, about 80 MPa to about 120 MPa in other designs, about 120 MPa to about 160 MPa in other designs, and about 160 MPa to about 400 MPa in other designs), making these Si-containing active material particles very hard. Furthermore, some of the Si-containing active material particles may be so brittle that they fracture before 10% deformation is achieved, and their fracture strength may be 400 MPa or less. Thus, the reported findings may indicate that it may be particularly advantageous to combine such very hard (e.g., Cx values ​​greater than 40 MPa in some designs) Si-containing active material particles with an appropriate (or desired) amount of relatively soft GRSBA particles for use in superior blend anodes.

[0155] In one or more embodiments of the present disclosure, the tap density of graphite particles can be another important characteristic that contributes to the superior performance of GRSBA in the blended anode (with Si-containing active material particles) described above. For the tap density measurements disclosed herein, graphite (carbon) particles arranged as a dry powder were added to a graduated cylinder, which was then loaded into a TD1 tap density tester and initially tapped 10 times. The initial volume (mL) was then identified and recorded. Depending on the sample size, the cylinder was further "tapped" a different number of times. For example, a filled 25 mL cylinder, generally suitable for a sample of approximately 10 g, was tapped 6,000 times. A filled 100 mL cylinder (generally suitable for a sample of approximately 50 g) was tapped 12,000 times. After the "tapping process" was completed, the final volume was measured, and the added mass and the identified volume were used in the tap density calculation (mass / volume) as known in the art.

[0156] Table 2 in FIG. 3 shows example tap density measurements for each of the selected graphite (carbon) samples (example graphite samples G1-G22 introduced in Table 1). In some designs, suitable tap density values ​​for GRSBAs can typically range from about 0.100 g / ml (or g / cc) to about 1.250 g / ml (or g / cc) (e.g., from about 0.100 g / ml to about 0.250 g / ml in some designs, from about 0.250 g / ml to about 0.600 g / ml in other designs, from about 0.600 g / ml to about 0.900 g / ml in other designs, from about 0.900 g / ml to about 1.100 g / ml in other designs, from about 1.100 g / ml to about 1.250 g / ml in still other designs, from about 0.900 g / ml to about 1.250 g / ml in still other designs, and from about 0.900 g / ml to about 1.200 g / ml in still other designs). On the other hand, in some designs, excessively high densities (e.g., greater than about 1.250 g / ml in some designs, greater than about 1.100 g / ml in other designs, and greater than about 1.200 g / ml in still other designs) can degrade the performance of Li-ion battery cells having blend anodes. In some designs, for example, excessively low densities in some expanded graphites (e.g., less than about 0.050 g / ml in some designs, less than about 0.100 g / ml in other designs) can also induce undesirable effects, including potentially lower volumetric capacity performance. It has often been found that graphite (carbon) samples having tap density values ​​of about 0.900 g / ml to about 1.100 g / ml in some designs (e.g., about 0.900 g / ml to about 0.950 g / ml in some designs, about 0.950 g / ml to about 1.000 g / ml in other designs, about 0.950 g / ml to about 1.050 g / ml in other designs, and about 1.050 g / ml to about 1.100 g / ml in still other designs) work particularly well as GRSBAs in blend anodes.It has been found in many cases that graphite (carbon) samples having tap density values ​​of about 0.900 g / ml to about 1.200 g / ml in some designs (e.g., about 0.900 g / ml to about 0.950 g / ml in some designs, about 0.950 g / ml to about 1.000 g / ml in other designs, about 0.950 g / ml to about 1.050 g / ml in other designs, about 1.050 g / ml to about 1.100 g / ml in still other designs, and about 1.100 g / ml to about 1.200 g / ml in still other designs) work particularly well as GRSBAs in blend anodes.

[0157] In one or more embodiments of the present disclosure, the pycnometric density (measured using a nitrogen gas (N) pycnometer) of the graphite particles can be another important characteristic that provides superior performance as GRSBA in the blend anodes described above (with suitable Si-containing active material particles).

[0158] For the pycnometric density measurements described here, a Micrometritics AccuPyc II 1340 pycnometer with a 1 cc chamber was used. To prepare the sample, a vial of sample powder was vortexed for 15 seconds and allowed to sit for several minutes before use. Using an electronic balance, 195 mg to 200 mg of sample powder was weighed from the instrument into the designated cup for pycnometric density measurements.

[0159] Table 3 in FIG. 4 shows example pycnometry density measurements for each of the selected graphite (carbon) samples (example graphite samples G1-G8, G10, G13-G16, G18-G22). In some designs, suitable pycnometrically measured density values ​​for GRSBAs may typically range from about 2.150 g / ml (or g / cc) to about 2.350 g / ml (g / cc) (e.g., about 2.150 g / ml to about 2.200 g / ml in some designs, about 2.200 g / ml to about 2.250 g / ml in other designs, about 2.250 g / ml to about 2.275 g / ml in other designs, about 2.275 g / ml to about 2.300 g / ml in other designs, about 2.300 g / ml to about 2.325 g / ml in other designs, and about 2.325 g / ml to about 2.350 g / ml in other designs). Note that in some designs, the theoretical density of crystallographically perfect graphite at room temperature and atmospheric pressure is about 2.265 g / ml (g / cc). An excessively low pycnometric density (e.g., below about 2.150 g / ml or g / cc) may result in excessive losses during the first or subsequent cycles or other undesirable cell performance characteristics in some designs. An excessively high pycnometric density may also degrade cell performance characteristics in some designs or cause problems during slurry and electrode preparation and may indicate the presence of small micropores.

[0160] In one or more embodiments of the present disclosure, the shape of a graphite sample may also affect the performance of the graphite sample for use as a GRSBA in a blended anode (with suitable Si-containing active material particles) as described above. In some designs, a more spheroidal (spherical, nearly spherical, or circular in shape with mostly rounded edges) GRSBA sample may work better when used at a high fraction relative to the Si-containing active material particles. In some designs, a flatter GRSBA sample may work better when used at a low fraction relative to the Si-containing active material particles. In some designs, it may be advantageous to combine a more spheroidal GRSBA sample with a flatter (more two-dimensional, approaching a 2D shape) GRSBA sample.

[0161] Figures 5A, 5B, 5C, 5D, 5E, and 5F show SEM micrographs of selected graphite (carbon) samples. Figure 5A shows an SEM micrograph 502 of a portion of a G1 example graphite sample. Figure 5B shows an SEM micrograph 504 of a portion of a G2 example graphite sample. Figure 5C shows an SEM micrograph 506 of a portion of a G3 example graphite sample. Figure 5D shows an SEM micrograph 508 of a portion of a G4 example graphite sample. Figure 5E shows an SEM micrograph 510 of a portion of a G5 example graphite sample. Figure 5F shows an SEM micrograph 512 of a portion of a G6 example graphite sample. Some of the graphite samples have grains with serrated edges (e.g., G1 at 502, G2 at 504, G3 at 506), some have grains with rounded edges (e.g., G4 at 508, G5 at 510, G6 at 512), some of the graphite samples contain primarily flatter grains (e.g., G1 at 502, G2 at 504, G3 at 506), and some of the graphite samples appear to be a mixture of flatter and rounder (more spheroidal) grains (e.g., G4 at 508, G5 at 510, G6 at 512).

[0162] For the particle size analysis described herein, samples were prepared within 1 hour of analysis on a Malvern Mastersizer 3000 laser PSA (particle size distribution analysis) instrument. The original sample vial was vortexed for 15 seconds to ensure powder uniformity. Approximately 20.0 mg (±5.0 mg) of the thoroughly mixed sample was weighed and transferred to a 20 mL glass vial. Once the sample was transferred to the vial, 15–20 mL of a 20 g / L lecithin in Isopar G solution (dispersant) was added to the glass vial. The sample was sonicated for an additional 30 minutes to break up any agglomerated particles that may have been present in some samples. The sample vial containing the powder, lecithin, and Isopar G was then vortexed for 15 seconds using the maximum setting. Once the sample was prepared, it was analyzed using a Malvern Mastersizer 3000 laser PSA instrument.

[0163] In one or more embodiments of the present disclosure, the size distribution of graphite particles can also affect the performance of the graphite particles for use as GRSBA in the blend anodes described above (with appropriate Si-containing active material particles). In some designs, both oversized and undersized particles can degrade the performance of Li-ion battery cells having the blend anodes. Oversized particles can, for example, induce local non-uniformities in both the distribution of anode mechanical properties and their areal capacity. Undersized particles can, for example, affect the charge rate performance and power capacity of Li-ion batteries (e.g., for a fixed areal capacity loading) by increasing anode tortuosity (e.g., for the same anode density), necessitating the use of a larger binder fraction, or reducing anode packing and volumetric capacity. Meanwhile, the total mass fraction (or total capacity fraction of GRSBA), areal capacity loading, size of the Si-containing active material particles, desired cell characteristics, and / or other factors can influence the most desirable size distribution of GRSBA. On the other hand, for some (e.g., most) designs, the appropriate D 50 The value can range from about 2 μm to about 22 μm (about 2 μm to about 5 μm in some designs, about 5 μm to about 10 μm in other designs, about 10 μm to about 12 μm in other designs, about 12 μm to about 17 μm in other designs, about 11 μm to about 17 μm in other designs, and about 17 μm to about 22 μm in still other designs). In some (e.g., most) designs, the appropriate D of the GRSBA 90 The value can range from about 4 μm to about 30 μm (about 4 μm to about 10 μm in some designs, about 10 μm to about 15 μm in other designs, about 15 μm to about 19 μm in other designs, about 19 μm to about 26 μm in other designs, about 19 μm to about 30 μm in other designs, and about 26 μm to about 30 μm in still other designs). In some (e.g., most) designs, the appropriate D of the GRSBA 10 Values ​​can range from about 0.5 μm to about 15 μm (about 0.5 μm to about 2.5 μm in some designs, about 2.5 μm to about 5 μm in other designs, about 5 μm to about 7 μm in other designs, about 7 μm to about 11 μm in other designs, about 5 μm to about 11 μm in other designs, and about 11 μm to about 15 μm in other designs).

[0164] Table 4 in FIG. 6 shows the D of selected graphite (carbon) samples (graphite samples G1 to G10, G13 to G22). 10 , D 50 and D 90 In the illustrated example, the particle size distribution (PSD) was measured using laser particle size distribution analysis (LPSA) as described herein.

[0165] In one or more embodiments of the present disclosure, the BET-SSA of the graphite particles can also affect the performance of the graphite particles for use as GRSBA in the blended anodes described above (with suitable Si-containing active material particles). In some designs, both an excessively high BET-SSA and an excessively low BET-SSA can degrade the performance of a Li-ion battery cell having the blended anode. On the other hand, the optimal BET-SSA value can depend on various factors, including the desired cell characteristics for a particular application. On the other hand, in some (e.g., most) designs, a suitable BET-SSA value for GRSBA is about 0.450 m 2 / g~about 450m 2 / g (approximately 0.450m in some designs) 2 / g ~ approx. 1m 2 / g, and approximately 1 m for other designs 2 / g ~ approx. 2m 2 / g, and approximately 2m for other designs 2 / g ~ approx. 3m 2 / g, and approximately 1 m for other designs 2 / g ~ approx. 3m 2 / g, and approximately 3m for other designs 2 / g~about 5m 2 / g, and approximately 5m for other designs 2 / g~about 10m 2 / g, and about 10m for other designs 2 / g~about 20m 2 / g, and about 20m for other designs 2 / g~about 100m 2 / g, and in other designs, approximately 100m 2 / g ~ approx. 450 2 / g). On the other hand, in some designs (e.g., when long calendar life or long cycle life is important or when a lower fraction of polymer binder may be advantageous), lower BET-SSA values ​​and a narrower range of BET-SSA values ​​may be advantageous (e.g., about 0.450 m 2 / g~about 5~15m 2 / g, approximately 1 m for some designs 2 / g~about 5m 2 / g, and in some other designs, approximately 2m 2 / g ~ approx. 3m 2 / g, and in some other designs, approximately 1 m 2 / g ~ approx. 3m 2 / g).

[0166] Table 5 in Figure 7 shows the BET-SSA values ​​for each of the selected graphite (carbon) samples (example graphite samples G1-G22). In the illustrated example, the BET-SSA for each example population of graphite particles (G1-G22) was measured by nitrogen gas physisorption (approximately 77 K) on powder samples that had been degassed under vacuum at 300°C for 10 hours.

[0167] The microstructural characteristics of a graphite (carbon) sample can also affect its performance for use as a GRSBA in the blended anodes described above (with suitable Si-containing active material particles). Some of these characteristics can be revealed by X-ray diffraction (XRD) techniques, Raman spectroscopy, and / or other characterization techniques.

[0168] For the microstructural characterization analyses disclosed herein, graphite (carbon) particles arranged as a powder were prepared for powder XRD using standard material preparation practices. An aluminum sample holder was used with a 1 mm glass slide placed at the bottom of the sample well to prevent contributions to the measurement from the metal sample holder. Approximately 100-300 mg of each powder was added to the sample holder and smoothed with the glass slide to result in a uniform sample surface. A Rigaku Smartlab was used for all measurements utilizing a copper X-ray source (λ = 1.5406 Å). The Cu anode was operated at a tube voltage and current of 40 kV and 44 mA, respectively. All measurements were performed using a Bragg-Brentano measurement geometry from 10 to 90 degrees 2θ at a continuous scan rate of 1 degree per minute. A 10-degree entrance limiting slit was used in addition to 5.0-degree Soller slits for both the entrance and detector. Copper K-beta (K β The ) radiation was directly filtered through the use of a Ni filter before reaching the 1D silicon strip detector. The full width at half maximum (FWHM) values ​​for the graphite (002) reflection peaks were calculated by fitting each peak with a Gauss-Lorentzian cross product function defined as follows:

number

number

[0169] An excessively narrow or broad FWHM of the (002) graphite reflection peak and a correspondingly large or small average crystallite size estimated using Scherrer's formula for the (002) reflection peak may degrade the performance of a Li-ion battery cell having a blend anode, while in some designs, the optimum value for a particular application may depend on the fraction of GRSBA in the blend anode, the properties of the Si-containing anode particles, the areal capacity loading, the amount and type of binder, the desired cell performance characteristics, and / or other factors. On the other hand, for some (e.g., most) designs, the FWHM appropriate for the (002) graphite reflection peak (as measured using the analytical procedures and settings employed) may preferably range from about 0.220 degrees to about 5.620 degrees (about 0.220 degrees to about 0.250 degrees for some designs, about 0.250 degrees to about 0.300 degrees for other designs, about 0.300 degrees to about 0.340 degrees for other designs, about 0.340 degrees to about 0.500 degrees for other designs, about 0.500 degrees to about 0.600 degrees for other designs, about 0.600 degrees to about 1.220 degrees for other designs, and about 1.220 degrees to about 5.620 degrees for other designs). Also, in some (e.g., most) designs, the appropriate GRSBA average crystallite size, estimated using Scherrer's formula for the (002) reflection peak (measured using the analytical procedures and settings employed), may preferably be in the range of about 1 nm to about 40 nm (about 1 nm to about 5 nm in some designs, about 5 nm to about 10 nm in other designs, about 10 nm to about 15 nm in other designs, about 15 nm to about 21 nm in other designs, about 15 nm to about 30 nm in other designs, about 21 nm to about 26 nm in other designs, about 26 nm to about 29 nm in other designs, and about 29 nm to about 40 nm in other designs).

[0170] FIG. 8A shows a graphical plot 802 of the XRD spectra of each of the selected graphite (carbon) samples (example graphite samples G1, G2, G3, G4, and G6).

[0171] 8B shows Table 6, which lists selected results obtained from X-ray diffraction measurements of selected graphite (carbon) samples (example graphite samples G1-G22 and some other examples of suitable graphite). The X-ray diffraction results shown, from left to right, are: (1) the interplanar spacing (also called d-spacing) (expressed in Å) of each graphite sample determined from the (002) reflection angle; (2) the FWHM (expressed in degrees) of the (002) reflection peak of each graphite sample; (3) the angle (expressed in degrees) of the (002) reflection peak of each graphite sample; (4) the average crystallite size (expressed in nm) of each graphite sample estimated using Scherrer's rule for the (002) reflection peak; and (5) the intensity (expressed in counts) of the (002) reflection peak.

[0172] For the Raman analysis described here, graphite (carbon) particles, arranged as a dry powder, were prepared for Raman scattering experiments using standard material preparation practices. A graphite (carbon) powder sample was collected with a spatula and placed on a microscope slide. The powder was then firmly pressed onto the tape on the slide to transfer a sufficiently thick layer of powder from the spatula onto the top of the tape. This process was repeated until the powder completely covered the tape. Once the tape was completely covered with powder, a handheld air pump was used to blow the remaining powder off the tape. Once the remaining powder was blown off the tape, the sample was ready for Raman analysis. Samples were analyzed using a Renishaw In-Via Qontor Raman microscope with a 532 nm laser diode with a maximum laser power of 3 mW. The laser beam was focused on the sample using a 100x 1.2 numerical aperture (NA) objective. The laser beam was intentionally aimed at the center of the larger particle, unless otherwise noted. Spectra were recorded using a Renishaw 1800 diffraction grating with an acquisition time of 3 seconds, and 10 spectra were averaged (per sample) to increase the signal-to-noise ratio. The following graphite (carbon) peaks were identified in the spectra: the D peak (1200–1500 cm); -1 ), G peak (1500-1750 cm -1 ), 2D1 peak (2600-2800 cm -1) and 2D2 peak (2400-3700 cm -1 ) was selected in the D peak range (1200–1500 cm ) to calculate the D / G ratio. -1 ) the height of the D peak in the range of 1000 to 2000 cm -1 After linear background subtraction in the spectrum within the G peak range (1500-1700 cm -1 To calculate the 2D1 / G ratio, the height of the G peak within the 2D1 peak range (2600–2800 cm) was divided by the height of the G peak within the 2D1 peak range (2600–2800 cm). -1 ) and the height of the 2D1 peak within the G peak range (1500–1700 cm -1 The peak height was divided by the height of the G peak in the range of 1000 to 2000 cm relative to the G peak. -1 Range and 2000-4000 cm for the 2D1 peak -1 The FWHM values ​​were calculated after linear background subtraction for each peak in the range. The FWHM values ​​were calculated by the Scipy (scientific Python) peak quantification function scipy.signal.peak_widths, where the peak width was measured at a relative height of 0.5.

[0173] The values ​​of the FWHM of the D, G, and 2D1 bands of a graphite (carbon) sample and the values ​​of the D / G and 2D1 / G ratios can be correlated to the performance of a Li-ion battery cell having a blend anode in some designs. On the other hand, in some designs, the optimal values ​​for a particular application may depend on the fraction of GRSBA in the blend anode described above, the properties of the Si-containing anode particles, the areal capacity loading, the amount and type of binder, the desired cell performance characteristics, and / or other factors. On the other hand, in some (e.g., most) designs, the appropriate FWHM of the D band for GRSBA (as determined using the methodology described above) is typically about 30 cm. -1 ~about 90cm -1 (Some designs are approximately 30cm -1 ~about 40cm -1 , and about 40cm for other designs -1 ~about 60cm -1 , and about 60cm for other designs -1 ~about 70cm -1 , and in other designs, approximately 70 cm-1 ~about 90cm -1 For some (e.g., most) designs, the appropriate FWHM in the G-band for the GRSBA (as determined using the methodology described above) is typically about 5 cm. -1 ~Approx. 105cm -1 (Approx. 5cm for some designs -1 ~Approx. 15cm -1 , and about 15cm for other designs -1 ~about 30cm -1 , and about 15cm for other designs -1 ~Approx. 18cm -1 , and about 18cm for other designs -1 ~Approx. 22cm -1 , and about 22cm for other designs -1 ~about 30cm -1 , and about 30 cm for other designs -1 ~about 50cm -1 , and in other designs, approximately 50 cm -1 ~Approx. 105cm -1 ) In some (e.g., most) designs, the appropriate FWHM of the 2D1 band for the GRSBA (as determined using the methodology described above) is typically about 30 cm -1 ~Approx. 110cm -1 (Some designs are approximately 30cm -1 ~about 50cm -1 , and about 50 cm for other designs -1 ~approx. 65cm -1 , and about 65cm for other designs -1 ~about 80cm -1 , and in other designs, approximately 80 cm -1 ~Approx. 105cm -1 , and other designs are approximately 105 cm -1 ~Approx. 110cm -1For some (e.g., most) designs, a suitable D / G peak intensity ratio for GRSBA (as determined using the methodology described above) can typically range from about 0.02 to about 1.12 (for some designs, from about 0.02 to about 0.12; for other designs, from about 0.12 to about 0.30; for other designs, from about 0.08 to about 0.30; for other designs, from about 0.30 to about 0.50; for other designs, from about 0.50 to about 0.80; and for still other designs, from about 0.80 to about 1.12). For some (e.g., most) designs, the appropriate 2D1 / G ratio for the GRSBA (as determined using the methodology described above) can typically range from about 0.10 to about 0.90 (for some designs, from about 0.10 to about 0.35; for other designs, from about 0.35 to about 0.50; for other designs, from about 0.41 to about 0.55; for other designs, from about 0.41 to about 0.45; for other designs, from about 0.45 to about 0.50; for other designs, from about 0.50 to about 0.55; for other designs, from about 0.50 to about 0.60; for other designs, from about 0.30 to about 0.65; for other designs, from about 0.60 to about 0.75; and for still other designs, from about 0.75 to about 0.90).

[0174] Figure 9A shows standard Raman spectra of selected graphite (carbon) samples. Figure 9A shows Raman spectra 902 including the D and G bands for example graphite samples G1, G3, G4, and G6. Figure 9A shows Raman spectra 904 including the D, G, 2D1, and 2D2 bands for example graphite samples G3 and G4.

[0175] Table 7 in FIG. 9B shows the processed Raman data for selected graphite (carbon) samples (example graphite samples G1-G12, G14-G22 and other examples of suitable graphite particles), from left to right: -1 FWHM of the D-band peak, expressed in cm -1 D peak position, D / G ratio, cm -1 FWHM of the G-band peak in cm -1 The G-band peak position is shown.

[0176] Table 8 in FIG. 9C shows the processed Raman data for selected graphite (carbon) samples (example graphite samples G2-G5, G18 and other examples of suitable graphite particles), from left to right: -1 2D1 band peak position, cm -1 The FWHM of the 2D1 peak, denoted by ≈ 2D1, and the 2D1 / G ratio are shown.

[0177] For the examples shown in FIGS. 10A, 10B, and 10C, Li-ion battery cells were constructed with the following: (i) an anode in which the Si-C nanocomposite active material (e.g., particles) contributed about 95%, about 98%, and about 100% of the capacity, and the GRSBA sample (having a specific reversible Si-C nanocomposite capacity of about 1600 to about 1700 mAh / g when normalized by the weight of the Si-C nanocomposite, corresponding to a silicon mass fraction of about 40 to about 44 wt% in the Si-C composite particles) contributed about 5%, about 2%, and about 0% of the capacity, respectively, and the following solids: (i) an anode in which the Si-C nanocomposite active material (e.g., particles) contributed about 95%, about 98%, and about 100% of the capacity, and the GRSBA sample (having a specific reversible Si-C nanocomposite capacity of about 1600 to about 1700 mAh / g when normalized by the weight of the Si-C nanocomposite, corresponding to a silicon mass fraction of about 40 to about 44 wt% in the Si-C composite particles) contributed about 5%, about 2%, and about 0% of the capacity, respectively; (ii) an anode comprising about 93 wt. % high-voltage lithium cobalt oxide (LCO) active material, cast on a Cu current collector foil from an aqueous suspension containing about 89.6 wt. % active material (for the anode with the remaining portion contributing), a polyacrylic acid (PAA)-based copolymer binder (about 9.6 wt. %), and about 0.79 wt. % Denka acetylene black conductive additive powder; and (iii) a cathode comprising about 93 wt. % high-voltage lithium cobalt oxide (LCO) active material, cast on an Al current collector foil from an organic solvent suspension containing a PVDF-based binder (about 3 wt. %), artificial graphite (about 2 wt. %), and pure black (about 2 wt. %) conductive additive, and having an anode:cathode (negative electrode to positive electrode, NP) areal capacity ratio of about 1.1:1 and a capacity of about 3.6 mAh / cm. 2The cells were fabricated using (iii) a cathode matching the anode at an area-reversible capacity loading of 1000 kJ / cm2, (iv) a polymer ceramic separator, and (v) a LiPF6-based electrolyte containing approximately 14.7 wt% LiPF6, approximately 9.7 wt% propylene carbonate (PC, cyclic carbonate), approximately 23.4 wt% fluoroethylene carbonate (FEC, fluorinated cyclic carbonate), approximately 8.1 wt% ethyl methyl carbonate (EMC, linear carbonate), approximately 7.8 wt% diethyl carbonate (DEC, linear carbonate), approximately 34.1 wt% ethyl propionate (EP, linear ester), and approximately 2.2 wt% vinylene carbonate (VC, cyclic carbonate). All electrochemical tests (ECT) were performed using an Arbin Instruments LBT cell cycler running MITS X PRO software. Cycling behavior was obtained using a voltage range of 2.5 to 4.4 V with 1 C charge and 1 C discharge, followed by a capacity check cycle of 1 C charge to 4.0 V, followed by 0.5 C charge to 4.4 V, then hold the voltage at 0.05 C, followed by 0.2 C discharge. 50 In the Li-ion battery cell of the aforementioned example, in which the Si-C nanocomposite active material contributed approximately 95% of the capacity, approximately 20% by weight of the anode active material was GRSBA particles, and approximately 80% by weight of the anode active material was Si-C nanocomposite active material particles. In the Li-ion battery cell of the aforementioned example, in which the Si-C nanocomposite active material contributed approximately 98% of the capacity, approximately 10% by weight of the anode active material was GRSBA particles, and approximately 90% by weight of the anode active material was Si-C nanocomposite active material particles.

[0178] FIG. 10A shows a graphical plot 1002 illustrating the estimated number of cycles to reach 80% state of health (SOH) (sometimes referred to herein as “N80”) for each respective lithium-ion battery test cell with a LCO cathode and a Si-containing anode (based on either pure Si-C nanocomposite particles or Si-C nanocomposite particles blended with optional GRSBA particles in these illustrative examples) with the addition of GRSBA. In some cases, N80 is a convenient metric of the cycle life of a battery cell. N80 is obtained by estimating the number of cycles to reach 80% of the cycling start capacity (when cycling at 25° C.). The cycling start capacity is defined as the capacity at the third cycle. In the graphical plot 1002, the lithium-ion battery cells with blended anodes employed example graphite particles G6, G7, and G23, respectively. The G23 graphite sample is an example of a soft graphite. The plotted data for each blend type (graphite type in the examples) represents the average of data for (a) blends with approximately 98% of the capacity from the Si-C nanocomposite active material, and (b) blends with approximately 95% of the capacity from the Si-C nanocomposite active material. In the examples shown, an estimated 6-15% improvement in cycling stability (cycle life) was achieved using the G6, G7, and G23 graphite samples.

[0179] FIG. 10B shows a graphical plot 1012 illustrating anode capacity retention during cycling of a Li-ion battery cell with an LCO cathode and a Si-containing anode, where the anode active material includes either Si-C nanocomposite particles alone or a blend of Si-C nanocomposite particles with optional GRSBA graphite particles, as detailed above. In this example, Examples G6, G7, and G23 were used as the GRSBA. In graphical plot 1012, the lithium-ion battery cells with blend anodes employed Example graphite particles G6, G7, and G23, respectively. The plotted data for each blend type (Example graphite type) represents an average of data for (a) blends in which the Si-C nanocomposite active material contributed approximately 98% of the capacity and (b) blends in which the Si-C nanocomposite active material contributed approximately 95% of the capacity. Graphical plot 1012 shows the dependence of capacity on cycle number for each battery type (anodes containing G6, G7, G23, or no graphite), and the slope of each plot is an indicator of cycling stability. A less steep slope (smaller gradient) is an indicator of better cycling stability. Compared to battery cells containing only Si-C nanocomposite particles in the anode active material, battery cells containing G6, G7, or G23 graphite exhibited a less steep slope (smaller gradient). Improved cycling stability (smaller gradient in the capacity retention curve) was obtained with the addition of GRSBA, with only a slight decrease in gravimetric anode capacity. Furthermore, battery cells containing the G6 and G7 graphite samples exhibited a relatively small decrease in anode capacity compared to battery cells containing only Si-C nanocomposite particles in the anode active material.

[0180] FIG. 10C shows graphical plots (1022, 1024, 1026, 1028) illustrating (a) anode coating density after initial lithiation, (b) as-coated (before calendaring) and as-calendered anode coating density, (c) estimated volumetric energy density (abbreviated VED or VED), and (d) the volumetric charge capacity (VQD) at the beginning of cycling for battery cells employing Si-containing anodes (or anode coatings in the case of as-coated and as-calendered coating densities). In the illustrated example, the cathode is comprised of LCO, and the anode active material includes either Si-C nanocomposite particles alone or a blend of Si-C nanocomposite particles with optional GRSBA graphite particles, as detailed above. VQD is the ratio of anode capacity (in mAh) (at the third cycle) to anode volume (cm 3 VED is defined as the cell energy (at the third cycle) (expressed in Wh) divided by the external volume of the cell (expressed in liters). In the illustrated example, G6, G7, and G23 were used as GRSBAs (GRSBA contributed 2% and 5% of the total anode capacity, respectively, and Si-C nanocomposite particles contributed 98% and 95% of the total anode capacity). In FIG. 10C, for each column of plotted data for each graphite-containing battery cell (from left to right: 1024 for G23, 1026 for G7, and 1028 for G6), the data point on the left represents the data for when the Si-C nanocomposite particles contributed 98% of the total anode capacity, and the data point on the right represents the data for when the Si-C nanocomposite particles contributed 95% of the total anode capacity. For example, the VQD of a battery cell containing G7, in which Si-C nanocomposite particles contribute 98% of the total anode capacity, is approximately 783 mAh / cm. 3 The VQD of the battery cell containing G7, in which the Si-C nanocomposite particles contribute 95% of the total anode capacity, is approximately 757 mAh / cm. 3 (For comparison, a battery cell with only Si-C nanocomposite particles has a capacity of about 783 mAh / cm 3For example, a battery cell containing G7, in which the Si-C nanocomposite particles contribute 98% of the total anode capacity, had a VED of approximately 1048 Wh / l, while a battery cell containing G7, in which the Si-C nanocomposite particles contribute 95% of the total anode capacity, had a VED of approximately 1038 Wh / l (for comparison, a battery cell containing only Si-C nanocomposite particles showed a VED of approximately 1042 Wh / l). Thus, despite the dilution of the higher capacity Si-C nanocomposite particles with the lower cost, lower capacity graphite particles, if the graphite particles are judiciously selected (as detailed herein) and the mass fraction of graphite in the anode active material is kept relatively low (e.g., between about 2 wt. % and about 5 wt. %, between about 5 wt. % and about 15 wt. %, between about 15 wt. % and about 25 wt. %, between about 5 wt. % and about 20 wt. %, between about 2 wt. % and about 25 wt. %, between about 2 wt. % and about 20 wt. %, between about 2 wt. % and about 15 wt. %, or between about 2 wt. % and about 10 wt. %), the VED and VQD values ​​will generally be comparable to (or in some cases greater than) those of a battery cell containing only Si-C nanocomposite particles in the anode active material. For example, the coating density of a battery cell containing G7, in which Si-C nanocomposite particles contribute 98% of the total anode capacity, is approximately 783 mAh / cm. 3 The VQD of the battery cell containing G7, in which the Si-C nanocomposite particles contribute 95% of the total anode capacity, is approximately 757 mAh / cm. 3 (For comparison, a battery cell with only Si-C nanocomposite particles has a capacity of about 783 mAh / cm 3 (shown VQD).

[0181] FIG. 10C shows the anode coating densities as-coated (after the slurry dried but before calendering) and after calendering. The calendering pressure was set at approximately 5 tons. In the second row of data (for coating densities as-coated and after calendering), and in each column of plotted data for each battery cell (from left to right: 1022 for only Si-C nanocomposite particles in the anode active material, 1024 for G23, 1026 for G7, and 1028 for G6), the lower data point (smaller value) represents the as-coated density, and the upper data point (larger value) represents the coating density after calendering. For example, the as-coated coating density of the anode coating containing only Si-C nanocomposite particles in the anode active material is approximately 0.812 g / cc, and the post-calendered coating density of the anode coating containing only Si-C nanocomposite particles in the anode active material is approximately 0.872 g / cc (an increase of approximately 0.060 g / cc due to calendering). For example, the as-coated anode coating containing G7 (the mass fraction of G7 in the anode active material is about 10 wt %), whose Si-C nanocomposite particles contribute 98% of the total anode capacity, has a coating density of about 0.817 g / cc, and the as-coated anode coating containing G7 (the mass fraction of G7 in the anode active material is about 10 wt %), whose Si-C nanocomposite particles contribute 98% of the total anode capacity, has a coating density of about 0.897 g / cc after calendering (an increase of about 0.080 g / cc due to calendering). For example, the as-coated anode coating containing G7 (the mass fraction of G7 in the anode active material is about 20 wt %), whose Si-C nanocomposite particles contribute 95% of the total anode capacity, has a coating density of about 0.843 g / cc, and the as-coated anode coating containing G7 (the mass fraction of G7 in the anode active material is about 20 wt %), whose Si-C nanocomposite particles contribute 95% of the total anode capacity, has a coating density of about 0.976 g / cc after calendering (an increase of about 0.133 g / cc due to calendering). In these examples, the increase in coating density due to calendaring increases with increasing mass fraction of G7 graphite particles. Coatings employing other graphite samples (G23, G6) also show an increase in coating density that increases with increasing mass fraction of graphite particles in the anode active material.In these instances, the pronounced lubricating effect of certain graphite particles in the blend anode may advantageously contribute to higher coating densities, which may include improved particle packing in the anode coating and / or reduced incidence of spallation and other damage to the Si-C nanocomposite particles.

[0182] Some embodiments of the present disclosure for Li-ion batteries comprising blend anodes with suitable GRSBA-graphite particles may benefit from the use of specific binders in their compositions. For example, one or more properties of GRSBA may be suitable for acting as a solid lubricant during slurry processing and calendering, thus facilitating the formation of smooth calendered electrodes and reducing or minimizing damage to suitable binders, even when the binders are relatively brittle. In some designs, for example, a suitable binder may be selected to exhibit strong adhesion and good dispersion of slurry particles rather than promoting high elasticity.

[0183] Illustrative examples of such suitable (and in some designs preferred) binders include, but are not limited to, polyacrylic acid (PAA) and its various derivatives, including various salts of PAA (such as Na-PAA, Li-PAA, NH-PAA, and / or others, or combinations thereof); various copolymers, including polyacrylic acid (PAA) and its various derivatives, including various salts of PAA (such as Na-PAA, Li-PAA, NH-PAA, and / or others) (e.g., salts (e.g., Na, Li, Ca, K, or mixed) of poly(acrylamide-co-acrylic acid) or partial or complete poly(acrylamide-co-acrylic acid), to name just a few); alginic acid and its various derivatives, including various salts (full or partial) of alginic acid (e.g., Na-alginate, Li-alginate, Ca-alginate, Al-alginate, etc.); alginic acid and its various derivatives, including various salts (full or partial) of alginic acid Copolymers (e.g., salts (e.g., Na, Li, Ca, K, or mixed) of poly(acrylamide-co-alginic acid) or partial or complete poly(acrylamide-co-alginic acid), to name just a few illustrative examples); salts of carboxymethylcellulose (CMC), such as Na-CMC and / or others, and derivatives thereof, including copolymers containing partial or complete CMC salts; copolymers containing styrene (e.g., styrene-butadiene rubber (SBR)), xanthan gum and copolymers containing xanthan gum, polyvinyl chloride (PVC), nanocellulose, chitosan, butyl acrylate and copolymers thereof, gum arabic and copolymers thereof, guar gum and copolymers thereof, carrageenan and copolymers thereof, gelatin and copolymers thereof, polyvinyl alcohol (PVA) and copolymers thereof, maleic acid and salts thereof (e.g., Li, Na, K, etc.);Li salts may be particularly suitable in some designs) and copolymers, various (poly)acrylates (including but not limited to dimethylaminoethyl acrylate and many others) and copolymers thereof, various (poly)acrylamides and copolymers thereof, various polyesters and copolymers thereof, (poly)ethylene oxide (PEO), cyclodextrin, maleic anhydride, methacrylic acid and its various salts (Li, Na, K, etc.; Li salts are often particularly suitable in some designs), various (poly)ethyleneimines (PEI) and copolymers thereof, various (poly)amideimides (PAIs) and their copolymers, various (poly)amidoamines and their copolymers, various other polyamine-based polymers, various (poly)ethyleneimines and their copolymers, sulfonic acids and their various salts and their copolymers, various catechol group-containing polymers, various lignin-containing or lignin-derived polymers, various epoxies, various cellulose-derived polymers (including, but not limited to, nanocellulose fibers and nanocrystals, carboxyethyl cellulose, etc.), other polymers (e.g., preferably water-soluble polymers), and various copolymers and mixtures thereof;

[0184] In some designs, the water-soluble copolymer binder may include at least one of the following components: vinyl (or butyl, methyl, or propyl, etc.) acetate, vinyl (or butyl, methyl, or propyl, etc.) acrylic, vinyl (or butyl, methyl, or propyl, etc.) alcohol, vinyl (or butyl, methyl, or propyl, etc.) acetate-acrylic, vinyl (or butyl, methyl, or propyl, etc.) acrylate, styrene-acrylic, alginic acid (or salts thereof, such as Na, K, Ca, Mg, Li, Sr, Cs, Ba, La, and / or other salts), acrylic acid (or salts thereof, such as Na, K, Ca, Mg, Li, Sr, Cs, Ba, La, and / or other salts), vinyl (or butyl, methyl, or propyl, etc.) siloxane (or other siloxane), pyrrolidone, styrene, various sulfonates (e.g., styrene sulfonate, among others), various amines (including quaternary amines), various dicyandiamide resins, amido-amine, ethyleneimine, and diallyldimethylammonium chloride.

[0185] In some designs, the water-soluble copolymer binder may include cellulose. In some designs, such cellulose-containing binders may include nanocellulose (nanofibers). In some designs, the nanocellulose may include branched or dendritic cellulose nanofibers. In some designs, the nanocellulose-containing binder may include at least one binder component (e.g., CMC or other) with strong adhesive properties to contribute to superior performance in the blend anode. In some designs, the nanocellulose-containing binder may be water-soluble.

[0186] In some designs, the copolymer binder may include poly(acrylamide) (i.e., may include acrylamide (—CHCHCONH—) subunits). In some designs, such poly(acrylamide)-containing copolymer binders may be water-soluble. In some designs, such poly(acrylamide)-containing copolymer binders may also include acrylic acid, carboxylic acid, alginic acid, or their metal salt(s) (e.g., Na, K, Ca, Mg, Li, Sr, Cs, Ba, La, and / or other salts of such acids). Such or other additions may be utilized to tailor the ionic properties of the polymer, its solubility and interaction with both the solvent and the active (electrode) particles (e.g., to achieve slurry stability, etc.).

[0187] Some designs include anion-conducting heterogeneous polymers (such as alkoxysilane / acrylates or epoxyalkoxysilanes), various anion-conducting interpenetrating polymer networks, various anion-conducting poly(ionic liquids) (crosslinked ionic liquids) or poly(acrylonitrile), various anion-conducting polyquaterniums, various anion conductors including quaternary ammonium salts (e.g., benzyltrialkylammonium, tetraalkylammonium, trimethylammonium, dimethylammonium, diallyldimethylammonium, etc.), various anion-conducting copolymers containing ammonium groups, various anion-conducting copolymers containing norbornene, cycloalkenes (e.g., cyclooctene), methacrylates, butylacrylates, vinylbenzyl, or poly(phenylene). Various anion-conducting copolymers containing, for example, various anion-conducting copolymers containing organic chlorine compounds (e.g., epichlorohydrin, etc.), various anion-conducting copolymers containing ethers, bicyclic amines (e.g., quinuclidine), various anion-conducting poly(ionic liquids) (crosslinked ionic liquids), various anion-conducting copolymers containing other amines (e.g., diamines such as ethylenediamine, monoamines, etc.), poly(etherimides), various polysaccharides (e.g., chitosan, etc.), xylene, various anion-conducting copolymers containing guanidine and / or pyridinium groups, among other groups (repeating units), may be advantageously used as copolymer binders (or components of polymer / copolymer binder mixtures) for blend anodes in the context of one or more embodiments of the present disclosure. In some designs, suitable copolymer binders may be cationic and highly chargeable.

[0188] In some designs, various cation-conducting polymers (including interpenetrating polymer networks) and -10 Ssm -1Crosslinked ionic liquids (having a cation conductivity of about 10 or more) can be advantageously used as binders or binder components for blend anodes in the context of one or more embodiments of the present disclosure. In some designs, such polymers have a cation conductivity of about 10 or more with respect to Li ions (for Li or Li-ion batteries). -10 Ssm -1 or more, or more preferably about 10 -6 Ssm -1 Advantageously, they may exhibit moderate to high conductivity (above).

[0189] In some designs, (e.g., preferably about 10 -2 Ssm -1Various conductive polymers or copolymers (having conductivities equal to or greater than 1000 keV), particularly those that are soluble in water (or at least processable in an aqueous electrode slurry), can be advantageously used as binders or binder components (e.g., components of binder mixtures or components of copolymer binders) for blend anodes in the context of one or more embodiments of the present disclosure. In particular, sulfur (S)-containing polymers / copolymers that also contain aromatic rings can be advantageously utilized in some designs. In some examples, S can be in the aromatic ring (e.g., as in poly(thiophene) (PT) or poly(3,4-ethylenedioxythiophene) (PEDOT)), while in other examples, S can be outside the aromatic ring (e.g., as in poly(p-phenylene sulfide) (PPS)). In some designs, suitable conductive polymers / copolymers can also contain nitrogen (N) as a heteroatom. The N atom may be, for example, in an aromatic ring (such as in poly(pyrrole) (PPY), polycarbazole, polyindole, or polyazepine), or may be outside the aromatic ring (such as in polyaniline (PANI)). Some conductive polymers may have no heteroatoms (such as in poly(fluorene), polyphenylene, propylene, polyazulene, polynaphthalene, etc.). In some designs, the backbone may contain double bonds (such as in poly(acetylene) (PAC) or poly(p-phenylenevinylene) (PPV)). In some designs, it may be advantageous for the polymer / copolymer binder to contain an ionomer (such as in polyelectrolytes, where ionic groups are covalently attached to the polymer backbone, or in ionenes, where the ionic groups are part of the actual polymer backbone). In some designs, it may be advantageous to use a polymer blend of two or more ionomers. In some designs, such ionomers may carry opposite charges (e.g., one negative and one positive). Examples of ionomers that may carry negative charges include, but are not limited to, various deprotonated compounds (e.g., when some of the sulfonyl groups are deprotonated, as in sulfonated polystyrene).Examples of ionomers that can carry a positive charge include, but are not limited to, various conjugated polymers such as PEDOT. An example of a suitable polymer mixture of two ionomers with opposite charges is poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. In some designs, it may be advantageous to use a polymer binder that includes both a conductive polymer and another polymer that provides other functionality (e.g., acting as an elastomer to significantly increase the maximum elongation of the binder, acting to improve bonding to the active material or current collector, or acting to increase solubility in water or other slurry solvents).

[0190] In some designs, the copolymer binder may advantageously include a halide anion (e.g., chloride anion, fluoride anion, bromide anion, etc.) for the blend anode. In some designs, the copolymer binder may advantageously include an ammonium cation (e.g., in addition to a halide anion, as in ammonium chloride). In some designs, the copolymer binder may advantageously include sulfur (S). In some designs, the copolymer binder may advantageously include an allyl group (e.g., in addition to an ammonium cation). For example, such a copolymer binder may advantageously include diallyldimethylammonium chloride (DADMAC) or diallyldiethylammonium chloride (DADEAC). Other suitable examples of such copolymer binder components may include (but are not limited to) methylammonium chloride, N,N-diallyl-N-propylammonium chloride, methylammonium bromide, ethylammonium bromide, propylammonium bromide, butylammonium bromide, methylammonium fluoride, ethylammonium fluoride, propylammonium fluoride, butylammonium fluoride, to name a few.

[0191] In some designs, copolymer binders for blend anodes may include both poly(acrylamide) and ammonium halide (e.g., ammonium chloride) in their structure. As one suitable example, poly(acrylamide-co-diallyldimethylammonium chloride) (PAMAC) may be advantageously used as the copolymer binder in the context of the present disclosure. In some designs, such PAMAC copolymer binders may additionally include small amounts (e.g., less than about 5-10 wt %) of acrylic acid, carboxylic acid, or alginic acid or metal salts thereof (e.g., Na, K, Ca, Mg, Li, Sr, Cs, Ba, La, and / or other salts of such acids).

[0192] It should be noted that in some designs, the above-described slurry containing a suitable binder, conductive additives, and blended active materials may also contain a dispersant.

[0193] In some designs, elastic nanofibers or nanoribbons (e.g., having an average diameter in the range of about 2 nm to about 500 nm, an average length in the range of about 10.0 nm to about 500,000.0 nm, and an average aspect ratio in the range of about 3:1 to about 10,000:1) or elastic flakes (e.g., in some designs with holes, having an average thickness in the range of about 1 nm to about 500 nm, an average length in the range of about 10.0 nm to about 500,000.0 nm, and an average aspect ratio in the range of about 3:1 to about 10,000:1) may be advantageously used in place of or in addition to conventional elastic nanoparticles. Suitable examples of such particle compositions include, but are not limited to, SBR, polybutadiene, polyethylene, polyethylene propylene, styrene ethylene butylene, ethylene vinyl acetate, polytetrafluoroethylene, perfluoroalkoxyethylene, isoprene, butyl rubber, nitrile rubber, ethylene propylene rubber, polyacrylic rubber, silicone rubber, fluorosilicone rubber, polyether block amide, polysiloxane and its various copolymers (such as polydimethylsiloxane), chlorosulfonated polyethylene, ethylene vinyl acetate, and various mixtures and copolymers thereof, among other suitable elastomers. In some designs, suitable mass fractions of such elastic nanoparticles (or nanofibers or nanoflakes) may range from about 5% to about 70% by weight (as a fraction of the total binder content in the blend anode).

[0194] Some embodiments of the present disclosure for Li-ion batteries with blended anodes having suitable GRSBA graphite particles may benefit from the use of certain separators in the manufacture of the battery cells, such as hard Si-containing active material particles (e.g., Si-C nanocomposites, SiO xAnodes containing Si-based particles or blends of Si-containing active material particles and hard graphite (or hard carbon in the broad sense) may exhibit some roughness even after calendering (particularly for anodes having about 20% or more, about 30% or more, about 50% or more, or about 75% or more of their capacity contributed by the Si-containing active material particles). Such high roughness may, in some designs, induce stress concentration areas in the separator, which may lead to premature failure of the separator during cycling, which in turn may lead to faster degradation, thermal runaway, and / or other undesirable factors. In some designs, to reduce or minimize the possibility of such undesirable events to an acceptable level, the separator selection may be limited to a single separator that is relatively thick (e.g., greater than about 12 microns in some designs, greater than about 17 microns in other designs), which reduces the energy density of the battery and increases cost. Furthermore, in such cells, the brittle nature of the ceramic layer and / or the potential for crack formation may make the use of ceramic-based or ceramic-coated separators difficult in some designs. Meanwhile, in some designs, ceramic-free separators (e.g., polymer separators) may exhibit poor safety, poor thermal properties, or other limitations. In contrast, in Li-ion battery cell designs in which the blend anode contains an adequate amount of suitable GRSBA-graphite (carbon) particles, the calendered anode can be very smooth (e.g., because the GRSBA can act as a solid lubricant during calendering, facilitating the formation of a densely packed and smooth anode layer). Therefore, in some designs, relatively thin separators (e.g., having an overall separator thickness of about 12 microns (μm) or less, in some designs about 10 microns or less, in some designs about 8 microns or less, in some designs about 6 microns or less, and even in some designs about 4 microns or less) may be safely and effectively used with the disclosed anodes. In some designs, the thin separator may have a thickness greater than about 0.5 μm, in some other designs greater than about 1 μm, in some other designs greater than about 2 μm, and in some other designs greater than about 3 μm.Additionally, separators (including such thin separators) can include suitable ceramic materials (e.g., aluminum oxide, aluminum hydroxide, aluminum oxyhydroxide, magnesium oxide, magnesium hydroxide, magnesium oxyhydroxide, lithium oxide, lithium hydroxide, other oxides, hydroxides, oxyhydroxides, and various combinations thereof) (e.g., in the form of ceramic nanofibers, ceramic nanowires, ceramic nanotubes, ceramic particles, ceramic flakes, ceramic surface coatings, ceramic layers, various combinations thereof, etc.). In some designs, the total weight fraction of ceramic material in such separators can range from about 10 wt% to about 100 wt% (e.g., from about 10 wt% to about 25 wt% in some designs, from about 25 wt% to about 50 wt% in other designs, from about 50 wt% to about 75 wt% in other designs, and from about 75 wt% to about 100 wt% in still other designs). In some designs, such separators can include two or more layers. In some designs, at least one of the layers may contain a significantly higher fraction of ceramic material than one or more of the other layers. In some examples where multiple layers are present and at least one of the layers (the "high ceramic content layer") has a higher ceramic weight fraction than another of the layers (the "low ceramic content layer"), the high ceramic content layer may have a ceramic weight fraction that is at least about 50% higher than the low ceramic content layer. In other examples where multiple layers are present and at least one of the layers (the "high ceramic content layer") has a higher ceramic weight fraction than another of the layers (the "low ceramic content layer"), the high ceramic content layer may have a ceramic weight fraction that is at least about 100% higher than the low ceramic content layer. In some designs, at least a portion of the separator may be deposited directly on the surface of the blend anode. Alternatively, a solid electrolyte interposed between the anode and cathode may be employed to function as the separator, thereby eliminating the need for a polymeric or ceramic separator. In such cases, the solid electrolyte must be thick enough to ensure safe operation, in some embodiments greater than about 0.5 μm.

[0195] Some embodiments of the present disclosure for Li-ion batteries with blend anodes having suitable GRSBA graphite particles may benefit from the use of specific electrolyte compositions in the manufacture of the battery cells to achieve superior performance. In some designs, a suitable electrolyte composition may include (i) one, two, three, or more Li salts having a total concentration ranging from about 0.8M to about 2.0M (about 0.8M to about 1.0M in some designs, about 1M to about 1.1M in other designs, about 1.1M to about 1.2M in other designs, about 1.2M to about 1.3M in other designs, about 1.3M to about 1.4M in other designs, about 1.4M to about 1.6M in other designs, about 1.6M to about 1.7M in other designs, about 1.7M to about 1.8M in other designs, and about 1.8M to about 2.0M in other designs); (ii) one, two, or more cyclic carbonates (in some designs, particularly fluorinated cyclic carbonates such as FEC); (iii) zero, one, two, three, or more Li salts having a total concentration ranging from about 0.8M to about 2.0M (about 0.8M to about 1.0M in some designs, about 1M to about 1.1M in other designs, about 1.1M to about 1.2M in other designs, about 1.2M to about 1.3M in other designs, about 1.3M to about 1.4M in other designs, about 1.4M to about 1.6M in other designs, about 1.6M to about 1.7M in other designs, about 1.7M to about 1.8M in other designs, and about 1.8M to about 2.0M in other designs). (in some designs, at least some of the nitrogen-containing cosolvents may advantageously contain two, three, or more nitrogen atoms per molecule); (iv) zero, one, two, three, or more sulfur-containing solvents; (v) zero, one, two, three, or more phosphorus-containing cosolvents (although some cosolvents may advantageously contain both phosphorus and sulfur); (vi) zero, one, two, three, or more linear or branched esters as cosolvents; (vii) zero, one, two, or more linear carbonates as cosolvents; (viii) zero, one, two, three, or more additional electrolyte cosolvents or additives; or (ix) any combination thereof. In some designs, the volume fraction of the linear ester (as a fraction of all co-solvents in the electrolyte) can range from about 20% to about 85% by volume (about 20% to about 40% by volume in some designs, about 40% to about 60% by volume in other designs, and about 60% to about 85% by volume in still other designs). In some designs, the volume fraction of the branched ester (as a fraction of all co-solvents in the electrolyte) can range from about 10% to about 80% by volume (about 10% to about 30% by volume in some designs, about 30% to about 60% by volume in other designs, and about 60% to about 80% by volume in still other designs).In some designs, the volume fraction of the cyclic carbonate (as a fraction of all co-solvents in the electrolyte) may range from about 5% to about 40% by volume (about 5% to about 10% by volume in some designs, about 10% to about 20% by volume in other designs, and about 20% to about 40% by volume in still other designs). In some designs, the volume fraction of the fluorinated cyclic carbonate (as a fraction of all co-solvents in the electrolyte) may range from about 1% to about 20% by volume (about 1% to about 4% by volume in some designs, about 4% to about 6% by volume in other designs, about 6% to about 12% by volume in other designs, and about 12% to about 20% by volume in still other designs). In some designs, the volume fraction of vinylene carbonate (VC) (as a fraction of all cosolvents in the electrolyte) can range from about 0.25% to about 6% by volume (about 0.25% to about 0.5% by volume in some designs, about 0.5% to about 1% by volume in other designs, about 1% to about 2% by volume in other designs, and about 2% to about 6% by volume in still other designs). In some designs, about 50% or more by volume of the cosolvent can advantageously exhibit a melting point of about minus (-)60°C or less (about -70°C or less in some designs, about -80°C or less in other designs). In some designs utilizing two or more salts (e.g., two salts, three salts, four salts, or five salts), it can be advantageous for at least one of the salts to comprise LiPF. In some designs, the incorporation of such salts may enhance the properties of the cathode-electrolyte interface (CEI) layer or anode-solid-electrolyte interface (SEI) layer (e.g., cycling stability, durability, thermal stability, high- or low-temperature performance, etc.) or may provide other performance advantages. In some designs, it may be further advantageous for at least one other salt to be a salt of Li. Some examples of such suitable salts include, but are not limited to, LiFSI, LiTFSI, LiBETI and / or other Li imide salts, Li bis(oxalato)borate (LiBOB), Li difluoro(oxalato)borate (LiDFOB), Li 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDi), Li 4,5-dicyano-2-(pentafluoroethyl)imidazolide (LiPDi), Li difluorophosphate (LiDFP), Li nitrate (LiNO3), and the like.

[0196] 11 shows a flow diagram of a suitable process 1120 for manufacturing a Li-ion battery, such as the example battery 100 of FIG. 1. In the illustrated example, process 1120 includes operations 1122, 1124, 1132, 1134, and 1140. The flow diagram includes an anode branch (left branch) that includes operations 1122 and 1124 and a cathode branch (right branch) that includes operations 1132 and 1134. In operation 1122, suitable anode particles (e.g., conventional graphite (carbon) anode particles or Si-containing (e.g., Si-C nanocomposite, core-shell, SiO x system or SiN x Particles (e.g., a composite cathode material, such as a conventional intercalation cathode particle, a core-shell cathode particle, or a composite cathode particle, including, but not limited to, a conversion cathode material, including composite particles) are provided or fabricated in process 1132, and a cathode is formed in process 1134.

[0197] Electrodes used in Li-ion batteries are generally fabricated by (i) forming a slurry containing active material, conductive additives, a binder solution, and optionally surfactants or other functional additives, (ii) casting the slurry onto a metal foil current collector (e.g., Cu or Cu alloy foil for most anodes and Al or Al alloy foil for most cathodes), and (iii) drying the cast electrode to completely evaporate the solvent. Metal mesh, metal foam, or highly rough metal foil (e.g., with metal nanowires or metal nanosheets on its surface) may be used as the current collector in some designs (e.g., for higher areal capacity loading or to achieve faster charging). Metal-coated thin polymer sheets may also be used as the current collector in some designs (e.g., to achieve improved safety or reduced current collector weight). Porous metal foils or composite (e.g., nanocomposite) metal foils may also be used in some designs (e.g., for improved performance, reduced weight, etc.).

[0198] Process 1124 includes forming an anode electrode, the anode electrode including the anode particles produced in process 1122. For example, process 1124 can include (1) producing an anode slurry including anode particles (e.g., from process 1122) and other anode slurry components (e.g., binder, additives, etc.), and (2) casting the anode slurry onto and / or within (in the case of a porous current collector) an anode current collector (e.g., a copper or copper alloy foil current collector, a porous copper, copper alloy, nickel, or nickel alloy foam or foil, a nickel alloy current collector, or a polymer-containing current collector, etc.). For example, other anode slurry components can include other electrochemically active anode materials (e.g., suitable natural or synthetic graphite, soft or hard carbons (e.g., including GRSBA) blended with Si-containing active material particles such as Si-C nanocomposite particles, among others), conductive additives (e.g., carbon nanotubes, carbon black, branched carbon, carbon nanofibers, graphite flakes, expanded graphite, graphene, graphene oxide, soft graphite, or various combinations thereof, to name a few), binders (e.g., polymeric binders), and solvents (e.g., water or suitable organic solvents). In some designs, solvent-free electrode fabrication can be utilized.

[0199] Process 1134 includes forming a cathode electrode, the cathode electrode including the cathode particles produced in process 1132. For example, process 1134 can include (1) producing a cathode slurry including the cathode particles (e.g., from process 1132) and other cathode slurry components, and (2) casting the cathode slurry onto and / or within (in the case of a porous current collector) a cathode current collector (e.g., an aluminum foil or aluminum alloy foil current collector). For example, the other cathode slurry components can include other electrochemically active cathode materials, conductive additives (e.g., carbon nanotubes, carbon black, branched carbon, carbon nanofibers, graphite flakes, graphene, graphene oxide, soft graphite, or various combinations thereof, to name a few), binders (e.g., polymeric binders), and solvents (e.g., water or a suitable organic solvent or a suitable mixture thereof). Some designs may utilize solvent-free ("dry") electrode fabrication.

[0200] In process 1140, a Li-ion rechargeable battery cell is assembled from at least an anode electrode (e.g., a blend anode including Si-containing active material particles such as GRSBA and Si-C nanocomposite, among others) and a cathode electrode, with an electrolyte interposed between the anode and cathode electrodes. The electrolyte (e.g., blend) provides ionic conductivity between the anode and cathode. The electrolyte ionically bonds the anode and cathode. The electrolyte may include a liquid electrolyte or a solid electrolyte (or a mixture of liquid and solid electrolytes) at the battery's operating temperature (e.g., in some designs, the solid electrolyte may be molten or semi-molten during melt infiltration and subsequently solidified). In some embodiments (e.g., embodiments using a liquid electrolyte), a separator may be used to maintain a space between the anode and cathode electrodes (e.g., to avoid short circuits).

[0201] A battery cell module or battery cell pack may advantageously include cells having electrode and / or electrolyte compositions provided in accordance with one or more embodiments of the present disclosure. Such cell modules or packs may offer improved performance characteristics, simplified design, better safety features, or lower cost.

[0202] FIG. 12 shows graphical plots of the dependence of estimated cycle life (N80) on cycle number for lithium-ion battery test cells: (1) without graphite particles (graphic plot 120), (2) with graphite particles (G1 or G23) at 10 wt. % of the anode active material (graphic plot 1204), (3) with graphite particles (G1 or G23) at 20 wt. % of the anode active material (graphic plot 1206), and (4) with graphite particles (G1 or G23) at 30 wt. % of the anode active material (graphic plot 1208). The lithium-ion battery cells used in the measurements were prepared using Si-C nanocomposite particles D 5010A, 10B, and 10C, except that the value was about 4.56 μm. In the examples shown, (1) anode (1204) in which the graphite particles were 10% by weight of the anode active material had a mass ratio of Si-C nanocomposite particles to graphite active material particles of about 90:10, (2) anode (1206) in which the graphite particles were 20% by weight of the anode active material had a mass ratio of Si-C nanocomposite particles to graphite active material particles of about 80:20, and (3) anode (1208) in which the graphite particles were 30% by weight of the anode active material had a mass ratio of Si-C nanocomposite particles to graphite active material particles of about 70:30. Among the graphite samples investigated, G1 is a relatively hard graphite, exhibiting a Cx value of approximately 25.5 MPa. Meanwhile, G23 is considered a soft graphite, although its exact Cx value is unknown. The cycle life (N80) characteristics differ between battery cells containing G1 and G23. When G23 is incorporated into the blend anode at 10 wt% of the anode active material (1204), the N80 increases by approximately 15% compared to the comparative example, in which the anode active material does not contain graphite particles and only Si-C nanocomposite particles are incorporated in the anode active material. When G23 is incorporated into the blend anode at 20 wt% of the anode active material (1206), the N80 increases by approximately 5% compared to the comparative example. When G23 is incorporated into the blend anode at 30 wt% of the anode active material (1208), the N80 does not increase significantly compared to the comparative example. Thus, in some embodiments, the soft graphite particles in the blend anode can contribute to increased cycle life, especially at relatively low mass fractions of graphite particles in the anode active material (e.g., in the range of about 2 to about 40 wt %, about 2 to about 35 wt %, about 2 to about 25 wt %, about 2 to about 15 wt %, about 5 to about 35 wt %, about 5 to about 25 wt %, or about 5 to about 15 wt %).In some examples, the soft graphite particles in the blend anode can contribute to increased cycle life, especially at relatively high mass ratios of Si-C nanocomposite particles (examples of Si-containing active material particles) to graphite active material particles (e.g., in the range of about 60:40 to about 98:2, about 65:35 to about 98:2, about 75:25 to about 98:2, about 85:15 to about 98:2, about 65:35 to about 95:5, about 75:25 to about 95:5, or about 85:15 to about 95:5). In contrast, when G1 was employed in the blend anode at 10 wt % or 20 wt % of the anode active material (1204, 1206), no significant increase in cycle life (N80) was observed compared to the comparative examples.

[0203] FIG. 13 shows Table 9, which lists example graphite particle samples, their selected properties (Cx, tap density, particle size distribution (PSD) properties, BET-SSA values, and D / G ratio values), and certain battery performance properties of lithium-ion battery cells employing the example graphite particle samples at a low mass fraction of graphite particles in each anode active material (e.g., compared to Table 10 of FIG. 14). Table 9 lists the following types of Li-ion battery cells: (A) a comparative example in which the anode active material does not contain graphite particles and only Si-C nanocomposite particles are employed in the anode active material (the mass ratio of Si-C nanocomposite particles:graphite particles is 100:0, and the graphite particles are 0 wt. % of the anode active material); (B) an example in which the mass ratio of Si-C nanocomposite particles:graphite particles is 90:10 (the graphite particles are 10 wt. % of the anode active material); % by weight) (the Si-C nanocomposite particles contributed approximately 98% of the anode capacity) and the graphite particles were G1, G6, G7, or G23; and (C) examples were studied in which the mass ratio of Si-C nanocomposite particles to graphite particles was 80:20 (the graphite particles were 20 wt% of the anode active material) (the Si-C nanocomposite particles contributed approximately 95% of the anode capacity) and the graphite particles were G1, G6, G7, or G23. The lithium-ion battery cells used for the measurements were similar to those reported for Figures 10A, 10B, and 10C.

[0204] In Table 9, the G1-containing battery cells (10 wt. % and 20 wt. % G1 in the anode active material) exhibited N80 values ​​comparable to that of the comparative battery cells (approximately 650 cycles). Meanwhile, the G6-, G7-, and G23-containing battery cells (each containing 10 wt. % of their respective graphite in their respective anode active materials) exhibited higher N80 values ​​of approximately 720, approximately 690, and approximately 750 cycles, respectively. The VED and VQD values ​​measured for the G6-, G7-, and G23-containing battery cells (each containing 10 wt. % and 20 wt. % of their respective graphite in their respective anode active materials) were generally comparable to those of the comparative battery cells. Among the graphite samples discussed in Table 9, the following are some of the characteristics that distinguish G1 from the other graphite samples: G1 exhibited a relatively large Cx value (25.5 MPa), a relatively small D 10 value (5.6 μm), relatively large D 90 value (26.3 μm) (therefore, the total width D 90 -D 10 is relatively large), and the BET-SSA value is relatively small (1.35m 2 / g) and a relatively small D / G ratio (0.09). In some embodiments, the mass fraction of the graphite active material particles in the anode active material ranges from about 2 to about 40 wt % (e.g., from about 5 to about 35 wt %, from about 5 to about 25 wt %, or from about 5 to about 15 wt %). In some embodiments, the mass ratio of the Si—C nanocomposite particles to the graphite active material particles ranges from about 60:40 to about 98:2 (e.g., from about 65:35 to about 95:5, from about 75:25 to about 95:5, or from about 85:15 to about 95:5). In some embodiments, the average Cx value of at least a portion of the graphite active material particles ranges from about 1 MPa to about 18 MPa (e.g., from about 7 MPa to about 18 MPa, from about 10 MPa to about 18 MPa, or from about 14 MPa to about 18 MPa). In some embodiments, the D / G ratio of at least some of the graphite active material particles is in the range of about 0.02 to about 1.12 (e.g., about 0.08 to about 0.30 or about 0.12 to about 0.30). 50The value ranges from about 2 to about 22 μm (e.g., from about 11 to about 17 μm or from about 12 to about 17 μm). In some embodiments, the D of at least some of the graphite active material particles 90 The value ranges from about 4 to about 30 μm (e.g., from about 19 to about 30 μm or from about 19 to about 26 μm). In some embodiments, the D of at least some of the graphite active material particles 10 In some embodiments, the BET-SSA value of at least some of the graphite active material particles ranges from about 0.450 to about 450 μm. 2 / g (e.g., about 1 to about 5 m 2 / g or about 1 to about 3m 2 / g).

[0205] FIG. 14 shows Table 10, which lists example graphite particle samples, their selected properties (Cx, tap density, particle size distribution (PSD) properties, BET-SSA values, and D / G ratio values), and certain battery performance properties of lithium-ion battery cells employing the example graphite particle samples at a high mass fraction of graphite particles in each anode active material (e.g., compared to Table 9 of FIG. 13). Table 10 lists the following types of Li-ion battery cells: (A) Comparative Examples in which the anode active material does not contain graphite particles, and only Si-C nanocomposite particles are employed in the anode active material (the mass ratio of Si-C nanocomposite particles:graphite particles is 100:0, and the graphite particles are 0 wt. % of the anode active material); (B) Examples in which the mass ratio of Si-C nanocomposite particles:graphite particles is 50:50 (the graphite particles are 0 wt. % of the anode active material); (E) Examples were considered in which the mass ratio of Si-C nanocomposite particles to graphite particles was 20:80 (the graphite particles were 80 wt% of the anode active material) (the Si-C nanocomposite particles contributed approximately 50% of the anode capacity) and the graphite particles were G1, G2, G3, G4, G5, or G6.

[0206] The details of the battery cells used in the results reported in Table 10 are as follows. The comparative battery cells were identical to those reported in Table 9 and similar to those reported for Figures 10A, 10B, and 10C. For Type D battery cells (50 wt % graphite), (a) the anode composition was adjusted so that the blend anode contained Si-C nanocomposite particles and graphite particles in a mass ratio of approximately 50:50, and (b) the cathode was an NCM-based cathode. The cathode was made of NCM811 (approximately LiNi) (having a specific reversible capacity of approximately 200 mAh / g when normalized to the weight of the active material particles in the cathode) cast onto an Al current collector foil from an organic solvent suspension containing a PVDF-based binder and carbon black conductive additive. 0.8 Mn 0.1 Co 0.1 The active material contained a 02 (composition: 02). NCM811 is an example of a lithium nickel manganese cobalt oxide (NCM) material. Battery cells were assembled using an anode, a cathode, a polymer ceramic separator between the anode and cathode, and a LiPF6-based electrolyte containing 13.92 wt% LiPF6 (as the primary lithium salt), 13.33 wt% fluoroethylene carbonate (FEC), 5.04 wt% ethylene carbonate (EC), 3.85 wt% ethyl methyl carbonate (EMC), 62.49 wt% dimethyl carbonate (DMC), 0.52 wt% vinylene carbonate (VC), and 0.85 wt% lithium difluorophosphate (LFO). For Type E battery cells (80 wt% graphite), the anode composition was adjusted so that the blend anode contained Si-C nanocomposite particles and graphite particles in a mass ratio of approximately 20:80. Except for the blend anode composition, the Type E battery cells were similar to those reported for Figures 10A, 10B, and 10C.

[0207] A large variation in N80 values ​​(cycle life) was observed among the Type E (80 wt% graphite) battery cells shown in Table 10, ranging from approximately 476 cycles (cells containing G4) to approximately 1207 cycles (cells containing G1). In particular, G1 is the graphite sample that exhibited the lowest N80 value (approximately 650 cycles) among the 10 wt% and 20 wt% graphite battery cells in Table 9. The graphite samples studied (G1, G2, G3, G4, G5, and G6) exhibited a D value ranging from 11 μm to 17 μm. 50 Among these graphite samples, there is a positive correlation between the N80 value (cycle life) and the Cx value (hardness). 2 / g or about 3 to about 5m 2 There is also a correlation between moderate BET-SSA values ​​(e.g., in the range of about 1 to about 3 m / g) and low N80 values. 2 / g or about 1 to about 2m 2 / g) and a high N80 value. Therefore, in some embodiments, the BET-SSA value of the graphite particles is determined to be in the optimal range (e.g., about 1 to about 3 m / g). 2 / g or about 1 to about 2m 2 / g) can contribute to increased N80 values ​​(better cycle life). In the examples shown, the choice of graphite particles appears to correlate with the N80 performance of the battery cells. Meanwhile, other performance characteristics (e.g., formation efficiency and VED) do not appear to correlate as strongly with the graphite selection. Formation efficiency is defined as the discharge capacity at the beginning of cycling (discharge capacity at cycle 3) divided by the first cycle charge capacity. Variations in N80 values ​​(cycle life) were observed among Type D (50 wt. % graphite) battery cells shown in Table 10, ranging from about 933 cycles (cells containing G8) to about 1421 cycles (cells containing G1). However, the G8 graphite sample had a D of about 6.8 μm. 50values, which are lower than some of the other graphite samples examined. In some examples, the mass fraction of graphite active material particles in the anode active material ranges from about 60 to about 93 wt% (e.g., from about 60 to about 70 wt%, from about 70 to about 90 wt%, or from about 90 to about 93 wt%). In some examples, the mass ratio of Si-C nanocomposite particles to graphite active material particles ranges from about 7:93 to about 40:60 (e.g., from about 7:93 to about 10:90, from about 10:90 to about 30:70, or from about 30:70 to about 40:60). In some examples, the average Cx value of at least some of the graphite active material particles ranges from about 18 MPa to about 30 MPa (e.g., from about 20 MPa to about 30 MPa, from about 18 MPa to about 20 MPa, from about 20 MPa to about 24 MPa, or from about 24 MPa to about 30 MPa). In some embodiments, the D / G ratio of at least some of the graphite active material particles is in the range of about 0.02 to about 1.12 (e.g., about 0.08 to about 0.30 or about 0.12 to about 0.30). 50 The value ranges from about 2 to about 22 μm (e.g., from about 11 to about 17 μm or from about 12 to about 17 μm). In some embodiments, the D of at least some of the graphite active material particles 90 The value ranges from about 4 to about 30 μm (e.g., from about 19 to about 30 μm or from about 19 to about 26 μm). In some embodiments, the D of at least some of the graphite active material particles 10 In some embodiments, the BET-SSA value of at least some of the graphite active material particles ranges from about 0.450 to about 450 μm. 2 / g (e.g., about 1 to about 5 m 2 / g, about 1~2m 2 / g, or about 1 to about 3 m 2 / g). In some embodiments, at least some of the graphite active material particles have a tap density in the range of about 0.01 g / cc to about 1.25 g / cc (e.g., about 0.90 g / cc to about 1.20 g / cc or about 0.90 g / cc to about 1.10 g / cc).

[0208] FIG. 15 shows Table 11, which shows the specific anode characteristics (particle size (D) of each Si-C nanocomposite particle population) of lithium ion battery cells employing graphite particles (G1) and Si-C nanocomposite particles (having graphite particles G1 at a mass fraction of 10 wt. % in each anode active material in the examples of Table 11) 50 ) values, calendering pressure during battery anode formation, binder material used in battery anode formation, and specific battery performance characteristics. Table 11 lists the D values ​​of Si-C nanocomposite particles with different binders and different particle sizes (D 50 The performance of the battery cells is compared for different electrode thicknesses (values). Four different types of battery cells are shown. Type 1 battery cells are similar to those reported in Figures 10A, 10B, and 10C, and contain a PAA salt-based copolymer binder in the anode and a D in the range of 5-6 μm. 50 The Type 3 battery cell uses Si-C nanocomposite particles with a D value of approximately 3 μm. 50 The anode coatings in Type 1 and Type 3 cells were calendered at a calendering pressure of about 5 tons. Type 2 and Type 4 cells employed a CMC:SBR binder in the anode instead of the PAA salt-based copolymer binder. The CMC:SBR mass ratio in Type 2 cells was about 1:6, and the CMC:SBR mass ratio in Type 4 cells was about 1:9.8. The D of the Si-C nanocomposite particles 50The values ​​are 5-6 μm for Type 2 battery cells and about 3 μm for Type 4 battery cells. The anode coatings in Type 2 and Type 4 battery cells were calendered at a calendering pressure of about 8 tons. Table 11 reports the following battery performance characteristics, from left to right: average discharge voltage, N80, expansion ratio, VED, VQD, direct current resistance (DCR), and capacity retention at 2C discharge (2C discharge retention). N80, VED, and VQD are defined elsewhere in this disclosure. The average discharge voltage of a battery cell is defined as the discharge energy (Wh) divided by the discharge capacity (Ah). The expansion ratio is a unitless metric expressed as the average thickness of the lithiated electrode divided by the average thickness of the treated electrode before electrolyte immersion. The DC resistance (DCR) is determined as follows: A series of high-rate current pulses are applied to the cell at a predetermined state of charge (e.g., 10% state of charge, 50% state of charge, etc.), and the resulting voltage is measured. The average voltage is determined by averaging the respective voltages measured for each current pulse. The DCR is the average voltage divided by the normalized conduction current value. DCR is usually normalized to allow comparisons that eliminate factors such as cell size, capacity, or energy. When DCR is normalized by capacity, it is expressed in Ω·Ah. The normalized conduction current is expressed as the conduction current (expressed in A) divided by the cell's capacity (capacity expressed in Ah). In the example shown in Table 11, DCR was measured at a 50% state of charge at a 2.3C discharge rate for a total pulse time of 30 seconds. Capacity retention (sometimes referred to as normalized capacity or relative discharge capacity) is defined as the charge capacity obtained for a given discharge rate (e.g., a 2C rate in this case) normalized to (divided by) the cycling start capacity (capacity at cycle 3) (expressed in mAh), which is usually the low C equilibrium state. The results in Table 11 show that CMC:SBR binder can be substituted for PAA-based binder in the blend anode of Si-C nanocomposite particles and graphite particles.For performance characteristics such as average discharge voltage (e.g., at 2C or 2.8C discharge), DCR, and high-rate capacity retention, CMC:SBR binders may be preferred in some embodiments. PAA-based (copolymer) binders may be preferred in some embodiments for improved VED (larger VED). Anodes employing CMC:SBR exhibit larger expansion ratio values ​​compared to anodes employing PAA salt-based (copolymer) binders, but exhibit smaller expansion in the x- and y-directions parallel to the coating. Si-C nanocomposite particle size (D) from 5-6 μm to approximately 3 μm. 50 ) results in an increase in VED and a decrease in N80. The DCR of the battery cells employing 3 μm Si-C nanocomposite particles (Type 3 and Type 4) shows lower DCR values ​​than the battery cells employing 5-6 μm Si-C nanocomposite particles and PAA-based (copolymer) binder (Type 1 battery cell).

[0209] FIG. 16 shows graphical plots of DC resistance (DCR) values ​​for lithium-ion battery cells employing a PAA copolymer-based binder series (1602) and a CMC:SBR binder series (1604). Both types of lithium-ion battery cells employed a blend anode of Si-C nanocomposite particles and graphite particles (G1), with the mass fraction of graphite particles G1 being 10 wt % of the respective anode active materials. Graphical plot 1602 shows the DCR for the Type 1 battery cells from Table 11. Graphical plot 1604 shows the DCR for the Type 2 battery cells from Table 11.

[0210] FIG. 17 shows a graphical plot of the dependence of relative discharge capacity (capacity retention) on normalized discharge rate (C-rate) (C-rates ranging from about 0.5 to about 2) for lithium-ion battery cells employing a PAA copolymer-based binder (1702) and a CMC:SBR binder (1704). Both types of lithium-ion battery cells employed a blend anode of Si-C nanocomposite particles and graphite particles (G1), with the mass fraction of graphite particles G1 being 10 wt % of the respective anode active materials. Graphical plot 1702 shows the relative discharge capacity (capacity retention) for the Type 1 battery cells in Table 11. Graphical plot 1704 shows the relative discharge capacity (capacity retention) for the Type 2 battery cells in Table 11. The discharge capacity retention of the Type 1 battery cells is higher than that of the Type 2 battery cells over a C-rate range of 0.6 to 2.2.

[0211] In the above detailed description, it can be seen that various features are grouped together in each example. Aspects of this disclosure should not be understood as intending that an example clause have more features than are expressly set forth in each clause. Rather, various aspects of the present disclosure may include fewer than all features of each example clause disclosed. Accordingly, the following clauses are hereby considered to be incorporated into the detailed description, with each clause standing on its own as a separate example. Although each dependent clause may refer to a specific combination with one of the other clauses in that clause, the aspects of that dependent clause are not limited to that specific combination. It should be understood that other example clauses may also include combinations of the dependent clause aspects with the subject matter of any other dependent or independent clause, or combinations of any features with other dependent and independent clauses. The various aspects disclosed herein explicitly include combinations unless it is expressly stated or readily inferable that a particular combination is not intended (e.g., contradictory aspects such as defining an element as both an electrical insulator and an electrical conductor). It is further contemplated that aspects of a clause may be included in any other dependent clause even if the clause is not directly dependent on the independent clause.

[0212] Examples are described in the following numbered clauses.

[0213] Clause 1. A battery anode, comprising: a binder; a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, wherein the battery anode has a capacity of about 2 mAh / cm 2 ~about 16mAh / cm 2 the Si-containing active material particles exhibit a specific (i.e., lithiation) capacity in the range of about 800 mAh / g to about 3000 mAh / g (e.g., about 800-1400 mAh / g, about 1400-1750 mAh / g, about 1750-2250 mAh / g, about 2250-2500 mAh / g, or about 2500-3000 mAh / g), the Si-containing active material particles contribute about 25% to about 99% of the total capacity of the battery anode, and at least a portion of the graphite active material particles are characterized by a Raman spectrum (e.g., collected using a 532 nm laser), in which the full width at half maximum (FWHM) of the D band is about 30 cm -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1 and a D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, is in the range of about 0.02 to about 1.12.

[0214] Clause 2. The battery anode of clause 1, wherein the D / G peak intensity ratio is in the range of about 0.12 to about 0.30.

[0215] Clause 3. The battery anode of clause 1 or 2, wherein the 2D1 / G peak intensity ratio, defined as the intensity of the 2D1 peak divided by the intensity of the G peak in the Raman spectrum (e.g., collected using a 532 nm laser), is in the range of about 0.10 to about 0.90.

[0216] Clause 4. The battery anode of any one of clauses 1 to 3, wherein the at least some of the graphite active material particles are characterized by an X-ray diffraction (XRD) spectrum with a FWHM of the (002) reflection in the range of about 0.220 degrees to about 5.620 degrees.

[0217] Clause 5. The battery anode of clause 4, wherein the FWHM of the (002) reflection is within the range of about 0.220 degrees to about 0.620 degrees.

[0218] Clause 6. The battery anode of clause 4 or 5, wherein the average crystallite size of at least a portion of the graphite active material particles, as estimated by applying Scherrer's rule to the (002) reflection, is in the range of about 1 nm to about 40 nm.

[0219] Clause 7. The battery anode of clause 6, wherein the average crystallite size is in the range of about 15 nm to about 30 nm.

[0220] Clause 8. The battery anode of any one of clauses 1 to 7, wherein the average pressure (Cx) required to deform said at least a portion of said graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

[0221] Clause 9. The battery anode of clause 8, wherein the average pressure ranges from about 1 MPa to about 18 MPa.

[0222] Clause 10. The battery anode of any one of clauses 1 to 9, wherein the tap density of said at least some of said graphite active material particles ranges from about 0.10 g / cc to about 1.25 g / cc.

[0223] Clause 11. The battery anode of clause 10, wherein the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0224] Clause 12. The battery anode of any one of clauses 1-11, wherein the pycnometric density of said at least some of said graphite active material particles ranges from about 2.15 g / cc to about 2.35 g / cc.

[0225] Clause 13. A 50th percentile volume-weighted particle size parameter D of said at least some of said graphite active material particles. 50 13. The battery anode of any one of clauses 1 to 12, wherein the thickness of the first electrode is in the range of about 2 μm to about 22 μm.

[0226] Article 14. Paragraph D 50 14. The battery anode of clause 13, wherein the thickness ranges from about 12 µm to about 17 µm.

[0227] Clause 15. A 90th percentile volume-weighted particle size parameter D of said at least some of said graphite active material particles. 90 15. The battery anode of any one of clauses 1 to 14, wherein the thickness of the first electrode is in the range of about 4 μm to about 30 μm.

[0228] Article 16. Paragraph D 90 16. The battery anode of clause 15, wherein the thickness ranges from about 19 µm to about 26 µm.

[0229] Clause 17. A 10th percentile volume-weighted particle size parameter D of said at least some of said graphite active material particles. 10 17. The battery anode of any one of clauses 1 to 16, wherein the thickness ranges from about 0.5 μm to about 15 μm.

[0230] Article 18. Paragraph D 10 18. The battery anode of clause 17, wherein the thickness ranges from about 7 µm to about 11 µm.

[0231] Clause 19. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of said at least some of said graphite active material particles is about 0.450 m 2 / g~about 450m 2 19. The battery anode of any one of clauses 1 to 18, in the range of 1 / g.

[0232] Article 20. The BET-SSA is approximately 1 m 2 / g~about 5m 2 20. The battery anode of clause 19, wherein the anode has a Cr content in the range of 0.1% to 0.1% by mass.

[0233] Clause 21. The battery anode of any one of clauses 1 to 20, wherein a weight fraction of the at least some of the graphite active material particles in the battery anode is in the range of about 1% to about 50% by weight of the active material blend.

[0234] Clause 22. The battery anode of clause 21, wherein the weight fraction is in the range of about 2% to about 20% by weight of the active material blend.

[0235] Clause 23. The battery anode of any one of clauses 1 to 22, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt. % or less (in other designs about 2 wt. % or less, and in still other designs about 1 wt. % or less) of the total mass of the Si-containing active material particles.

[0236] Clause 24. The battery anode of any one of clauses 1 to 23, wherein the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a combined amount in the range of 80% by weight to about 100% by weight of the total mass of the Si-containing active material particles.

[0237] Clause 25. The battery anode of clause 24, wherein the Si-containing active material particles comprise Si-C nanocomposite particles.

[0238] Clause 26. The battery anode of clause 25, wherein the Si-containing active material particles comprise Si nanoparticles.

[0239] Clause 27. The battery anode of clause 26, wherein at least a portion of the Si nanoparticles are coated with a conductive carbon layer (eg, having an average thickness of about 0.3 to 10 nm).

[0240] Clause 27. The battery anode of clause 26, wherein the weight average size of the Si nanoparticles ranges from about 2 nm to about 40 nm.

[0241] Clause 28. The battery anode of clause 26, wherein the average grain size of the Si nanoparticles ranges from about 1 nm to about 20 nm as estimated by X-ray diffraction using the Scherrer equation.

[0242] Clause 29. The battery anode of clause 25, wherein the Si-containing active material particles are Si-C nanocomposite particles exhibiting a true density, measured using N2 pycnometry, in the range of about 1.4 to about 1.9 g / cc (e.g., about 1.4 to 1.6 g / cc, about 1.6 to 1.75 g / cc, or about 1.75 to 1.9 g / cc).

[0243] Clause 30. The Si-containing active material particles have a 50th percentile volume-weighted particle size parameter (D 50 26. The battery anode of clause 25, wherein the Si—C nanocomposite particles have a particle size of about 4 to about 16 microns (e.g., about 4 to 7 microns, 7 to 10 microns, about 10 to 13 microns, about 13 to 16 microns, or about 7 to 13 microns).

[0244] Clause 31. The battery anode of any one of clauses 1 to 30, wherein said at least a portion of said graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0245] Clause 32. A lithium ion battery comprising: a battery anode according to any one of clauses 1 to 31; a cathode; a separator electrically separating the battery anode and the cathode; and an electrolyte ionically bonding the battery anode and the cathode.

[0246] Examples are set forth in the following numbered appendices:

[0247] Addendum 1. A battery anode comprising: a binder; a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, said battery anode having a capacity of about 2 mAh / cm 2 ~about 16mAh / cm 2 the Si-containing active material particles exhibit a specific capacity in the range of about 800 mAh / g to about 3000 mAh / g (e.g., about 800 to 1400 mAh / g, about 1400 to 1750 mAh / g, about 1750 to 2250 mAh / g, about 2250 to 2500 mAh / g, or about 2500 to 3000 mAh / g), the Si-containing active material particles contribute about 25% to about 99% of the total capacity of the battery anode, and at least a portion of the graphite active material particles are characterized by a Raman spectrum (e.g., collected using a 532 nm laser), in which the full width at half maximum (FWHM) of the D band is about 30 cm -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1 and a D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, is in the range of about 0.02 to about 1.12.

[0248] Additional Clause 2. The battery anode of Additional Clause 1, wherein the D / G peak intensity ratio is in the range of about 0.12 to about 0.30.

[0249] Additional Clause 3. The battery anode of Additional Clause 1 or 2, wherein the 2D1 / G peak intensity ratio, defined as the intensity of the 2D1 peak divided by the intensity of the G peak in the Raman spectrum (e.g., collected using a 532 nm laser), is in the range of about 0.10 to about 0.90.

[0250] Additional Clause 4. The battery anode of any one of Additional Clauses 1 to 3, wherein the at least a portion of the graphite active material particles are characterized by an X-ray diffraction (XRD) spectrum having a FWHM of a (002) reflection peak within a range of about 0.220 degrees to about 5.620 degrees.

[0251] Additional Clause 5. The battery anode of Additional Clause 4, wherein the FWHM of the (002) reflection peak is within the range of about 0.220 degrees to about 0.620 degrees.

[0252] Additional Clause 6. The battery anode of Additional Clause 4 or 5, wherein the average crystallite size of the at least a portion of the graphite active material particles, as estimated by applying Scherrer's formula to the (002) reflection peak, is in the range of about 1 nm to about 40 nm.

[0253] Additional Clause 7. The battery anode of Additional Clause 6, wherein the average crystallite size is within the range of about 15 nm to about 30 nm.

[0254] Additional Clause 8. The battery anode of any one of Additional Clauses 1 to 7, wherein the average pressure (Cx) required to deform the at least a portion of the graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

[0255] Additional Clause 9. The battery anode of Additional Clause 8, wherein the average pressure ranges from about 1 MPa to about 18 MPa.

[0256] Additional Clause 10. The battery anode of any one of Additional Clauses 1 to 9, wherein the tap density of said at least a portion of said graphite active material particles ranges from about 0.10 g / cc to about 1.25 g / cc.

[0257] Additional Clause 11. The battery anode of Additional Clause 10, wherein the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0258] Additional Clause 12. The battery anode of any one of Additional Clauses 1 to 11, wherein the pycnometric density of said at least a portion of said graphite active material particles ranges from about 2.15 g / cc to about 2.35 g / cc.

[0259] Addendum 13. A 50th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 50 13. The battery anode of any one of Additional Clauses 1 to 12, wherein the average particle diameter (μm) of the first and second electrodes is in the range of about 2 μm to about 22 μm.

[0260] Additional Clause 14. Paragraph D 50 The battery anode of Addendum 13, wherein the thickness of the first electrode is in the range of about 12 μm to about 17 μm.

[0261] Addendum 15. The 90th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 90 15. The battery anode of any one of Addendum 1 to 14, wherein the thickness of the first electrode is in the range of about 4 μm to about 30 μm.

[0262] Additional Clause 16. Paragraph D 90 The battery anode of Addendum 15, wherein the thickness ranges from about 19 μm to about 26 μm.

[0263] Addendum 17. A 10th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 10 17. The battery anode of any one of Addendum 1 to 16, wherein the thickness of the first electrode is in the range of about 0.5 μm to about 15 μm.

[0264] Additional Clause 18. Paragraph D 10 The battery anode of Addendum 17, wherein the thickness of the first electrode is in the range of about 7 μm to about 11 μm.

[0265] Addendum 19. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of said at least a portion of said graphite active material particles is about 0.450 m 2 / g~about 450m 219. The battery anode of any one of Addenda 1 to 18, wherein the anode has a Cr content in the range of 0.15 to 0.15 wt %, and ...

[0266] Additional Article 20. The BET-SSA is approximately 1 m 2 / g~about 5m 2 / g of the battery anode of Addendum 19.

[0267] Addendum 21. The battery anode of any one of Addendums 1 to 20, wherein a weight fraction of the at least a portion of the graphite active material particles in the battery anode is in the range of about 1% to about 50% by weight of the active material blend.

[0268] Additional Clause 22. The battery anode of Additional Clause 21, wherein the weight fraction is in the range of about 2% to about 20% by weight of the active material blend.

[0269] Addendum 23. The battery anode of any one of Addendums 1 to 22, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt. % or less (about 2 wt. % or less in other designs, and about 1 wt. % or less in still other designs) of the total mass of the Si-containing active material particles.

[0270] Additional Clause 24. The battery anode of any one of Additional Clauses 1 to 23, wherein the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a combined amount in the range of 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0271] Additional Clause 25. The battery anode of Additional Clause 24, wherein the Si-containing active material particles comprise Si—C nanocomposite particles.

[0272] Additional Clause 26. The battery anode of any one of Additional Clauses 1 to 25, wherein the at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0273] Addendum 27. A lithium ion battery comprising: a battery anode according to Addendum 1; a cathode; a separator electrically separating the battery anode and the cathode; and an electrolyte ionically bonding the battery anode and the cathode.

[0274] Addendum 28. A battery anode, comprising: a binder; a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, wherein a mass fraction of Si in the Si-containing active material particles is in the range of about 20% by weight to about 80% by weight; a mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 60:40 to about 98:2; and wherein at least a portion of the graphite active material particles are characterized by a Raman spectrum (e.g., collected using a 532 nm laser), wherein the Raman spectrum has a D band with a full width at half maximum (FWHM) of about 30 cm. -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1 a D / G peak intensity ratio, defined as the intensity of the D peak divided by the intensity of the G peak, in the range of about 0.02 to about 1.12, and an average pressure (Cx) required to deform said at least a portion of said graphite active material particles by 10% during a microcompression hardness test in the range of about 1 MPa to about 18 MPa.

[0275] Additional Clause 29. The battery anode of Additional Clause 28, wherein a mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 75:25 to about 95:5.

[0276] Additional Clause 30. The battery anode of Additional Clause 28 or 29, wherein the average pressure ranges from about 7 MPa to about 18 MPa.

[0277] Additional Clause 31. The battery anode of Additional Clause 30, wherein the average pressure ranges from about 10 MPa to about 18 MPa.

[0278] Additional Clause 32. The battery anode of any one of Additional Clauses 28 to 31, wherein the D / G peak intensity ratio is in the range of about 0.12 to about 0.30.

[0279] Additional Clause 33. The battery anode of any one of Additional Clauses 28-32, wherein the tap density of said at least a portion of said graphite active material particles ranges from about 0.10 g / cc to about 1.25 g / cc.

[0280] Additional Clause 34. The battery anode of Additional Clause 33, wherein the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0281] Addendum 35. A 50th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 50 35. The battery anode of any one of Addendum 28-34, wherein the thickness of the first and second electrodes is in the range of about 2 μm to about 22 μm.

[0282] Additional Clause 36. Paragraph D 50 The battery anode of Addendum 35, wherein the thickness ranges from about 11 μm to about 17 μm.

[0283] Additional Clause 37. Paragraph D 50 The battery anode of Addendum 36, wherein the thickness of the first electrode is in the range of about 12 μm to about 17 μm.

[0284] Addendum 38. The 90th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 90 38. The battery anode of claim 28, wherein the thickness of the first electrode is in the range of about 4 μm to about 30 μm.

[0285] Additional Clause 39. Paragraph D 90 The battery anode of Addendum 38, wherein the thickness ranges from about 19 μm to about 30 μm.

[0286] Additional Clause 40. Paragraph D 90 The battery anode of Addendum 39, wherein the thickness ranges from about 19 μm to about 26 μm.

[0287] Addendum 41. A 10th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 10 41. The battery anode of any one of Addendum 28-40, wherein the thickness of the first and second electrodes is in the range of about 0.5 μm to about 15 μm.

[0288] Additional Clause 42. Paragraph D 10 The battery anode of Addendum 41, wherein the thickness ranges from about 5 μm to about 11 μm.

[0289] Additional Clause 43. Paragraph D 10 The battery anode of Addendum 42, wherein the thickness of the first electrode is in the range of about 7 μm to about 11 μm.

[0290] Addendum 44. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of said at least a portion of said graphite active material particles is about 0.450 m 2 / g~about 450m 2 44. The battery anode of any one of Addendum 28 to 43, wherein the anode has a Cr content in the range of 0.15 to 0.15 wt %, and ...

[0291] Additional Article 45. The BET-SSA is approximately 1 m 2 / g~about 5m 2 / g of the battery anode of Addendum 44.

[0292] Additional Article 46. The BET-SSA is approximately 1 m 2 / g ~ approx. 3m 2 / g of the battery anode of Addendum 45.

[0293] Addendum 47. The battery anode of any one of Addendums 28 to 46, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt. % or less (about 2 wt. % or less in other designs, and about 1 wt. % or less in still other designs) of the total mass of the Si-containing active material particles.

[0294] Additional Clause 48. The battery anode of any one of Additional Clauses 28 to 47, wherein the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a combined amount in the range of about 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0295] Additional Clause 49. The battery anode of claim 48, wherein the Si-containing active material particles comprise Si-C nanocomposite particles.

[0296] Additional Clause 50. The battery anode of any one of Additional Clauses 28 to 49, wherein the at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0297] Additional clause 51. Approximately 2mAh / cm 2 ~about 16mAh / cm 2 51. The battery anode of any one of Addendum 28 to 50, having a reversible capacity loading in the range of

[0298] Addendum 52. A lithium ion battery comprising: a battery anode according to Addendum 28; a cathode; a separator electrically separating the battery anode and the cathode; and an electrolyte ionically bonding the battery anode and the cathode.

[0299] Additional Clause 53. A battery anode, comprising: a binder; a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles, wherein a mass fraction of Si in the Si-containing active material particles is in the range of about 20% by weight to about 80% by weight; a mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 7:93 to about 40:60; and wherein at least a portion of the graphite active material particles are characterized by a Raman spectrum (e.g., collected using a 532 nm laser), wherein the Raman spectrum has a D band with a full width at half maximum (FWHM) of about 30 cm. -1 ~about 90cm -1 The FWHM of the G band is approximately 5 cm. -1 ~Approx. 105cm -1 The FWHM of the 2D1 band is approximately 30 cm -1 ~Approx. 110cm -1 a D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, in the range of about 0.02 to about 1.12, and an average pressure (Cx) required to deform said at least a portion of said graphite active material particles by 10% during a microcompression hardness test in the range of about 20 MPa to about 30 MPa.

[0300] Additional Clause 54. The battery anode of Additional Clause 53, wherein the mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 10:90 to about 30:70.

[0301] Additional Clause 55. The battery anode of Additional Clause 53 or 54, wherein the average pressure ranges from about 24 MPa to about 30 MPa.

[0302] Additional Clause 56. The battery anode of any one of Additional Clauses 53 to 55, wherein the D / G peak intensity ratio is in the range of about 0.08 to about 0.30.

[0303] Additional Clause 57. The battery anode of any one of Additional Clauses 53 to 56, wherein the tap density of said at least a portion of said graphite active material particles ranges from about 0.10 g / cc to about 1.25 g / cc.

[0304] Additional Clause 58. The battery anode of Additional Clause 57, wherein the tap density ranges from about 0.90 g / cc to about 1.20 g / cc.

[0305] Additional Clause 59. The battery anode of Additional Clause 58, wherein the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0306] Addendum 60. A 50th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 50 60. The battery anode of any one of Addendum 53 to 59, wherein the thickness of the first and second electrodes is in the range of about 2 μm to about 22 μm.

[0307] Additional Clause 61. Paragraph D 50 The battery anode of Addendum 60, wherein the thickness ranges from about 11 μm to about 17 μm.

[0308] Additional Clause 62. Paragraph D 50 The battery anode of Addendum 61, wherein the thickness ranges from about 12 μm to about 17 μm.

[0309] Addendum 63. A 90th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles. 90 63. The battery anode of any one of Addendum 53 to 62, wherein the thickness of the first and second electrodes is in the range of about 4 μm to about 30 μm.

[0310] Additional Clause 64. Paragraph D 90 The battery anode of Addendum 63, wherein the thickness ranges from about 19 μm to about 30 μm.

[0311] Addendum 65. A 10th percentile volume-weighted particle size parameter (D) of said at least a portion of said graphite active material particles.10 65. The battery anode of any one of Addendum 53 to 64, wherein the thickness of the first and second electrodes is in the range of about 0.5 μm to about 15 μm.

[0312] Additional Clause 66. Paragraph D 10 The battery anode of Addendum 65, wherein the thickness of the first electrode is in the range of about 5 μm to about 11 μm.

[0313] Addendum 67. The Brunauer-Emmett-Teller (BET) specific surface area (SSA) of said at least a portion of said graphite active material particles is about 0.450 m 2 / g~about 450m 2 57. The battery anode of any one of Addendum 53 to 56, wherein the anode has a Cr content in the range of 0.15 to 0.15 wt %, and ...

[0314] Additional Article 68. The BET-SSA is approximately 1 m 2 / g~about 5m 2 / g of the battery anode of Addendum 67.

[0315] Additional Article 69. The BET-SSA is approximately 1 m 2 / g ~ approx. 3m 2 / g of the battery anode of Addendum 68.

[0316] Addendum 70. The battery anode of any one of Addendums 53 to 69, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5 wt. % or less (about 2 wt. % or less in other designs, and about 1 wt. % or less in still other designs) of the total mass of the Si-containing active material particles.

[0317] Additional Clause 71. The battery anode of any one of Additional Clauses 53 to 70, wherein the Si-containing active material particles contain silicon (Si) atoms and carbon (C) atoms in a combined amount in the range of about 80 wt % to about 100 wt % of the total mass of the Si-containing active material particles.

[0318] Additional Clause 72. The battery anode of Additional Clause 71, wherein the Si-containing active material particles comprise Si—C nanocomposite particles.

[0319] Additional Clause 73. The battery anode of any one of Additional Clauses 53 to 72, wherein the at least a portion of the graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0320] Additional clause 74. Approximately 2mAh / cm 2 ~about 16mAh / cm 2 74. The battery anode of any one of Addendum 53 to 73, having a reversible capacity loading in the range of

[0321] Addendum 75. A lithium ion battery comprising: a battery anode according to Addendum 53; a cathode; a separator electrically separating the battery anode and the cathode; and an electrolyte ionically bonding the battery anode and the cathode.

[0322] Additional Clause 76. The battery anode of any one of Additional Clauses 1 to 75, wherein the Si-containing active material particles comprise Si nanoparticles.

[0323] Additional Clause 77. The battery anode of Additional Clause 75, wherein at least a portion of the Si nanoparticles are coated with a conductive carbon layer (e.g., having an average thickness of about 0.3 to 10 nm).

[0324] Additional Clause 78. The battery anode of Additional Clause 75, wherein the weight average size of the Si nanoparticles ranges from about 2 nm to about 40 nm.

[0325] Additional Clause 79. The battery anode of Additional Clause 75, wherein the average grain size of the Si nanoparticles ranges from about 1 nm to about 20 nm as estimated by X-ray diffraction using the Scherrer equation.

[0326] Additional Clause 80. The battery anode of any one of Additional Clauses 1 to 79, wherein the Si-containing active material particles are Si-C nanocomposite particles exhibiting a true density, measured using N2 pycnometry, in the range of about 1.4 to about 1.9 g / cc (e.g., about 1.4 to 1.6 g / cc, about 1.6 to 1.75 g / cc, or about 1.75 to 1.9 g / cc).

[0327] Additional Clause 81. The Si-containing active material particles have a 50th percentile volume-weighted particle size parameter (D 50 80. The battery anode of any one of the preceding clauses, wherein the Si—C nanocomposite particles have a mean particle size (μm) of about 4 to about 16 microns (e.g., about 4 to 7 microns, 7 to 10 microns, about 10 to 13 microns, about 13 to 16 microns, or about 7 to 13 microns).

[0328] This description is provided to enable any person skilled in the art to make or use embodiments of the invention. However, since various modifications to these embodiments will be readily apparent to those skilled in the art, it should be understood that the invention is not limited to the particular formulations, process steps, and substances / materials disclosed herein. Indeed, the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.

Claims

1. 1. A battery anode comprising: Binder and a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles; Equipped with The battery anode has a capacity of about 2 mAh / cm ２ ~Approx. 16mAh / cm ２ and has a reversible capacity load in the range of the Si-containing active material particles exhibit a specific capacity in the range of about 800 mAh / g to about 3000 mAh / g; the Si-containing active material particles contribute from about 25% to about 99% of the total capacity of the battery anode; At least a portion of the graphite active material particles are characterized by a Raman spectrum, in which the full width at half maximum (FWHM) of the D band is about 30 cm －１ ~Approx. 90cm －１ The FWHM of the G band is in the range of about 5 cm. －１ ~Approx. 105cm －１ In the range of 2D １ The band FWHM is approximately 30 cm. －１ ~Approx. 110cm －１ and a D / G peak intensity ratio, defined as the intensity of the D peak divided by the intensity of the G peak, in the range of about 0.02 to about 1.

12.

2. 10. The battery anode of claim 1, wherein the D / G peak intensity ratio is in the range of about 0.12 to about 0.

30.

3. 2D of the Raman spectrum １ 2D, which is defined as the intensity of the peak divided by the intensity of the G peak. １ 10. The battery anode of claim 1, wherein the / G peak intensity ratio is in the range of about 0.10 to about 0.

90.

4. 10. The battery anode of claim 1, wherein said at least a portion of said graphite active material particles are characterized by an X-ray diffraction (XRD) spectrum with a FWHM of a (002) reflection peak in the range of about 0.220 degrees to about 5.620 degrees.

5. 5. The battery anode of claim 4, wherein the FWHM of said (002) reflection peak is within the range of about 0.220 degrees to about 0.620 degrees.

6. 5. The battery anode of claim 4, wherein the average crystallite size of said at least a portion of said graphite active material particles, as estimated by applying Scherrer's rule to said (002) reflection peak, is in the range of about 1 nm to about 40 nm.

7. 7. The battery anode of claim 6, wherein the average crystallite size is in the range of about 15 nm to about 30 nm.

8. 10. The battery anode of claim 1, wherein the average pressure (Cx) required to deform said at least a portion of said graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

9. 9. The battery anode of claim 8, wherein said average pressure ranges from about 1 MPa to about 18 MPa.

10. 10. The battery anode of claim 1, wherein said at least a portion of said graphite active material particles have a tap density ranging from about 0.10 g / cc to about 1.25 g / cc.

11. 11. The battery anode of claim 10, wherein said tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

12. 10. The battery anode of claim 1, wherein said at least a portion of said graphite active material particles have a pycnometric density ranging from about 2.15 g / cc to about 2.35 g / cc.

13. the 50th percentile volume-weighted particle size parameter (D ５０ 10. The battery anode of claim 1, wherein the thickness of the first electrode is in the range of about 2 μm to about 22 μm.

14. The above D ５０ 14. The battery anode of claim 13, wherein the thickness of the first electrode is in the range of about 12 μm to about 17 μm.

15. the 90th percentile volume-weighted particle size parameter (D ９０ 10. The battery anode of claim 1, wherein the thickness of the first electrode is in the range of about 4 μm to about 30 μm.

16. The above D ９０ 16. The battery anode of claim 15, wherein the thickness ranges from about 19 μm to about 26 μm.

17. the 10th percentile volume-weighted particle size parameter (D １０ 10. The battery anode of claim 1, wherein the thickness of the first electrode is in the range of about 0.5 μm to about 15 μm.

18. The above D １０ 18. The battery anode of claim 17, wherein the thickness of the first electrode is in the range of about 7 μm to about 11 μm.

19. The at least a portion of the graphite active material particles has a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m ２ / g ~ approx. 450m ２ 10. The battery anode of claim 1, wherein the anode has a surface area in the range of 0.15 to 0.5 μm.

20. The BET-SSA is approximately 1 m ２ / g ~ approx. 5m ２ 20. The battery anode of claim 19, wherein the anode has a Cr content in the range of 0.15 to 0.5% by mass.

21. 10. The battery anode of claim 1, wherein the weight fraction of said at least a portion of said graphite active material particles in said battery anode ranges from about 1% to about 50% by weight of said active material blend.

22. 22. The battery anode of claim 21, wherein said weight fraction is in the range of about 2% to about 20% by weight of said active material blend.

23. 10. The battery anode of claim 1, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5% or less by weight of the total mass of the Si-containing active material particles.

24. 10. The battery anode of claim 1, wherein the Si-containing active material particles comprise silicon (Si) atoms and carbon (C) atoms collectively in the range of 80 wt. % to about 100 wt. % of the total mass of the Si-containing active material particles.

25. 25. The battery anode of claim 24, wherein the Si-containing active material particles comprise Si—C nanocomposite particles.

26. 10. The battery anode of claim 1, wherein said at least a portion of said graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

27. The battery anode of claim 1; a cathode; a separator electrically separating the battery anode and the cathode; an electrolyte ionically bonding the battery anode and the cathode; A lithium-ion battery comprising:

28. 1. A battery anode comprising: Binder and a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles; Equipped with the mass fraction of Si in the Si-containing active material particles is in the range of about 20% by weight to about 80% by weight; a mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 60:40 to about 98:2; At least a portion of the graphite active material particles are characterized by a Raman spectrum, in which the full width at half maximum (FWHM) of the D band is about 30 cm －１ ~Approx. 90cm －１ The FWHM of the G band is in the range of about 5 cm. －１ ~Approx. 105cm －１ In the range of 2D １ The band FWHM is approximately 30 cm. －１ ~Approx. 110cm －１ and a D / G peak intensity ratio, defined as the intensity of the D peak divided by the intensity of the G peak, is in the range of about 0.02 to about 1.12; a battery anode, wherein the average pressure (Cx) required to deform said at least a portion of said graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 18 MPa.

29. 30. The battery anode of claim 28, wherein a mass ratio of said Si-containing active material particles to said graphite active material particles ranges from about 75:25 to about 95:

5.

30. 30. The battery anode of claim 28, wherein said average pressure ranges from about 7 MPa to about 18 MPa.

31. 31. The battery anode of claim 30, wherein said average pressure ranges from about 10 MPa to about 18 MPa.

32. 30. The battery anode of claim 28, wherein the D / G peak intensity ratio is in the range of about 0.12 to about 0.

30.

33. 30. The battery anode of claim 28, wherein said at least a portion of said graphite active material particles have a tap density ranging from about 0.10 g / cc to about 1.25 g / cc.

34. 34. The battery anode of claim 33, wherein said tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

35. the 50th percentile volume-weighted particle size parameter (D ５０ 29. The battery anode of claim 28, wherein the thickness of the first electrode is in the range of about 2 μm to about 22 μm.

36. The above D ５０ 36. The battery anode of claim 35, wherein the thickness ranges from about 11 μm to about 17 μm.

37. The above D ５０ 37. The battery anode of claim 36, wherein the thickness ranges from about 12 μm to about 17 μm.

38. the 90th percentile volume-weighted particle size parameter (D ９０ 29. The battery anode of claim 28, wherein the thickness of the first electrode is in the range of about 4 μm to about 30 μm.

39. The above D ９０ 39. The battery anode of claim 38, wherein the thickness ranges from about 19 μm to about 30 μm.

40. The above D ９０ 40. The battery anode of claim 39, wherein the thickness ranges from about 19 μm to about 26 μm.

41. the 10th percentile volume-weighted particle size parameter (D １０ 29. The battery anode of claim 28, wherein the thickness of the first electrode is in the range of about 0.5 μm to about 15 μm.

42. The above D １０ 42. The battery anode of claim 41, wherein the thickness ranges from about 5 μm to about 11 μm.

43. The above D １０ 43. The battery anode of claim 42, wherein the thickness ranges from about 7 μm to about 11 μm.

44. The at least a portion of the graphite active material particles has a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m ２ / g ~ approx. 450m ２ 30. The battery anode of claim 28, wherein the anode has a Cr content in the range of 0.15 to 0.5% by mass.

45. The BET-SSA is approximately 1 m ２ / g ~ approx. 5m ２ 45. The battery anode of claim 44, wherein the anode has a Mo content in the range of 0.15 wt. / g.

46. The BET-SSA is approximately 1 m ２ / g ~ approx. 3m ２ 46. ​​The battery anode of claim 45, wherein the anode has a Mo content in the range of 0.15 wt. / g.

47. 30. The battery anode of claim 28, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5% or less by weight of the total mass of the Si-containing active material particles.

48. 30. The battery anode of claim 28, wherein the Si-containing active material particles comprise silicon (Si) atoms and carbon (C) atoms collectively in the range of 80 wt% to about 100 wt% of the total mass of the Si-containing active material particles.

49. 49. The battery anode of claim 48, wherein the Si-containing active material particles comprise Si—C nanocomposite particles.

50. 30. The battery anode of claim 28, wherein said at least a portion of said graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

51. Approximately 2mAh / cm ２ ~Approx. 16mAh / cm ２ 30. The battery anode of claim 28, having a reversible capacity loading in the range of

52. 29. The battery anode of claim 28; a cathode; a separator electrically separating the battery anode and the cathode; an electrolyte ionically bonding the battery anode and the cathode; A lithium-ion battery comprising:

53. 1. A battery anode comprising: Binder and a conductive additive; and an active material blend including silicon (Si)-containing active material particles and graphite active material particles; Equipped with the mass fraction of Si in the Si-containing active material particles is in the range of about 20% by weight to about 80% by weight; a mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 7:93 to about 40:60; At least a portion of the graphite active material particles are characterized by a Raman spectrum, in which the full width at half maximum (FWHM) of the D band is about 30 cm －１ ~Approx. 90cm －１ The FWHM of the G band is in the range of about 5 cm. －１ ~Approx. 105cm －１ In the range of 2D １ The band FWHM is approximately 30 cm. －１ ~Approx. 110cm －１ and a D / G peak intensity ratio, defined as the intensity of the D peak divided by the intensity of the G peak, is in the range of about 0.02 to about 1.12; a battery anode, wherein the average pressure (Cx) required to deform said at least a portion of said graphite active material particles by 10% during a microcompression hardness test ranges from about 20 MPa to about 30 MPa.

54. 54. The battery anode of claim 53, wherein the mass ratio of the Si-containing active material particles to the graphite active material particles is in the range of about 10:90 to about 30:

70.

55. 54. The battery anode of claim 53, wherein said average pressure ranges from about 24 MPa to about 30 MPa.

56. 54. The battery anode of claim 53, wherein the D / G peak intensity ratio is in the range of about 0.08 to about 0.

30.

57. 54. The battery anode of claim 53, wherein said at least a portion of said graphite active material particles have a tap density ranging from about 0.10 g / cc to about 1.25 g / cc.

58. 58. The battery anode of claim 57, wherein said tap density ranges from about 0.90 g / cc to about 1.20 g / cc.

59. 59. The battery anode of claim 58, wherein said tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

60. the 50th percentile volume-weighted particle size parameter (D ５０ 54. The battery anode of claim 53, wherein the thickness of the first electrode is in the range of about 2 μm to about 22 μm.

61. The above D ５０ 61. The battery anode of claim 60, wherein the thickness ranges from about 11 μm to about 17 μm.

62. The above D ５０ 62. The battery anode of claim 61, wherein the thickness of the first electrode is in the range of about 12 μm to about 17 μm.

63. the 90th percentile volume-weighted particle size parameter (D ９０ 54. The battery anode of claim 53, wherein the thickness of the first electrode is in the range of about 4 μm to about 30 μm.

64. The above D ９０ 64. The battery anode of claim 63, wherein the thickness ranges from about 19 μm to about 30 μm.

65. the 10th percentile volume-weighted particle size parameter (D １０ 54. The battery anode of claim 53, wherein the thickness of the first electrode is in the range of about 0.5 μm to about 15 μm.

66. The above D １０ 66. The battery anode of claim 65, wherein the thickness ranges from about 5 μm to about 11 μm.

67. The at least a portion of the graphite active material particles has a Brunauer-Emmett-Teller (BET) specific surface area (SSA) of about 0.450 m ２ / g ~ approx. 450m ２ 54. The battery anode of claim 53, wherein the anode has a Mo content in the range of 0.15 wt. / g.

68. The BET-SSA is approximately 1 m ２ / g ~ approx. 5m ２ 68. The battery anode of claim 67, wherein the anode has a Mo content in the range of 0.15 wt. / g.

69. The BET-SSA is approximately 1 m ２ / g ~ approx. 3m ２ 69. The battery anode of claim 68, wherein the anode has a Mo content in the range of 0.15 wt. / g.

70. 54. The battery anode of claim 53, wherein the Si-containing active material particles comprise oxygen (O) atoms at about 5% or less by weight of the total mass of the Si-containing active material particles.

71. 54. The battery anode of claim 53, wherein the Si-containing active material particles comprise silicon (Si) atoms and carbon (C) atoms collectively in the range of 80 wt% to about 100 wt% of the total mass of the Si-containing active material particles.

72. 72. The battery anode of claim 71, wherein the Si-containing active material particles comprise Si—C nanocomposite particles.

73. 54. The battery anode of claim 53, wherein said at least a portion of said graphite active material particles exhibit a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

74. Approximately 2mAh / cm ２ ~Approx. 16mAh / cm ２ 54. The battery anode of claim 53, having a reversible capacity loading in the range of

75. 54. The battery anode of claim 53; a cathode; a separator electrically separating the battery anode and the cathode; an electrolyte ionically bonding the battery anode and the cathode; A lithium-ion battery comprising:

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