Lithium ion battery having a high performance anode comprising

Abstract

A battery anode includes a binder, a conductive additive, and an active material mixture including silicon (Si)-containing active material particles and graphite active material particles. In some embodiments, the battery anode has a reversible capacity loading in the range of about 2 mAh / cm2 to about 16 mAh / cm2, the silicon (Si)-containing active material particles have a specific capacity in the range of about 800 mAh / g to about 3000 mAh / g, and the silicon (Si)-containing active material particles contribute to about 25% to about 99% of the total capacity of the battery anode.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims the benefit of U.S. Provisional Application No. 63 / 483,680, filed on February 7, 2023, entitled “Lithium-ion Battery with High-Performance Anode Comprising Graphite and Silicon-Based Nanocomposites,” and U.S. Non-Provisional Application No. 18 / 434,744, filed on February 6, 2024, entitled “Lithium-ion Battery with High-Performance Anode Comprising Graphite and Silicon-Based Nanocomposites,” both of which are assigned to the present assignee and are expressly incorporated herein by reference in their entireties. background Technical Field

[0002] Various aspects of the present invention relate generally to energy storage devices and, more particularly, to battery technology and the like. Background Art

[0003] Advanced rechargeable batteries are attractive for consumer electronics, electric vehicles, grid storage, and other important applications, in part due to their relatively high energy density, relatively high specific energy, light weight, and potential for long life. However, despite the increasing commercialization of batteries, further development of these batteries is still needed, especially for applications in low- or zero-emission, hybrid or pure electric vehicles, consumer electronics, wearable devices, energy-efficient cargo ships and locomotives, drones, aerospace applications, and power grids. Further improvements are needed for various rechargeable battery types, such as rechargeable lithium and lithium-ion batteries, sodium and sodium-ion batteries, potassium and potassium-ion batteries, and dual-ion batteries.

[0004] In certain types of lithium metal and lithium ion rechargeable batteries, the charge storage anode may include silicon (Si)-containing anode particles having a pycnometer capacity in the range of about 800 mAh / g to about 3000 mAh / g (unit mass of the silicon-containing anode particles in the lithium-free state). A subset of such anodes includes anodes having an electrode layer capacity in the range of about 400 mAh / g to about 2800 mAh / g (unit mass of the electrode layer in the lithium-free state, excluding the mass of the current collector). This type of charge storage anode offers significant potential for increasing the gravimetric and volumetric energy of rechargeable batteries.

[0005] In certain types of rechargeable batteries, charge storage anode active materials can be produced in the form of high-capacity (nano) composite powders that exhibit moderately high volume changes (e.g., about 8-180 vol%) during the first charge-discharge cycle and moderate volume changes (e.g., about 5-50 vol% or about 5-50 vol%) during subsequent charge-discharge cycles. A subset of such charge storage anode particles includes anode particles having an average size (e.g., diameter or thickness) in the range of about 0.2 to about 40 micrometers (micrometers, or μm) as measured using laser particle size distribution analysis (LPSA), laser image analysis, electron microscopy, optical microscopy, or other suitable techniques. This type of charge storage particle offers great promise for scalable manufacturing and achieving high battery-level energy density and other performance characteristics.

[0006] One example of a high-performance anode can include a mixture of a novel silicon-based (or, more broadly, silicon-containing) anode active material and a graphite-based active material, a so-called silicon-graphite hybrid. In some examples of hybrid anodes, the silicon-containing anode active material can be a nanocomposite material containing silicon and carbon (referred to herein as a Si-C composite, Si-C nanocomposite, or Si-C composite (or nanocomposite) particles, with the carbon separated from the graphite-based active material. Even if such particles contain elements other than Si and C, the content of these elements is relatively small, less than about 10-20 at.%), with the graphite-based active material contributing approximately 20% to 99% of the capacity, with the remainder of the capacity coming from the graphite-based active material. Such anodes have higher volumetric and gravimetric energy densities than the intercalated pure graphite anodes commonly used in commercial lithium-ion batteries. Furthermore, in such hybrid anodes, the graphite-based active material can be composed of natural graphite, synthetic graphite, or a mixture of natural and synthetic graphite. Si-C nanocomposite-graphite hybrid anodes can exhibit an overall moderate volume change during the first cycle and lower volume change during subsequent charge cycles.

[0007] However, when hybrid anodes are produced using graphite and novel silicon-based (or silicon-containing in a broad sense, such as nanocomposites) anode active materials commonly used in lithium-ion batteries, the hybrid anodes generally have limitations such as insufficient stability, excessive volume change, insufficient electrical conductivity and ionic conductivity, low packing density, and insufficient volume capacity.

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

[0009] The following is a simplified description of one or more aspects disclosed herein. Therefore, the following description should not be considered an extensive overview of all contemplated aspects, nor should it be considered to identify important or critical elements related to all contemplated aspects, or to describe the scope of any particular aspect. Therefore, the sole purpose of the following summary is to present certain concepts related to one or more aspects of the mechanisms disclosed herein in a simplified form before providing the detailed description presented later.

[0010] In one aspect, the battery anode comprises a binder; a conductive additive; and an active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, wherein: the battery anode has a charge / discharge capacity of about 2 mAh / cm 2 to about 16 mAh / cm 2 The silicon-containing active material particles exhibit a specific capacity in the range of about 800 mAh / g to about 3000 mAh / g; the silicon-containing active material particles contribute about 25% to about 99% of the total capacity of the battery anode; and at least a subset of the graphite active material particles is characterized by Raman spectroscopy, in which the D band has a full-width half-maximum (FWHM) of about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5cm -1 to about 105cm -1 In the range, the FWHM of the 2D1 band is about 30 cm -1 to about 110cm -1 range, 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 aspects, the D / G peak intensity ratio is in a range from about 0.12 to about 0.30.

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

[0013] In some aspects, the at least one subset of the graphite active material particles is characterized by an X-ray diffraction (XRD) spectrum having a FWHM of a (002) reflection peak in a range from about 0.220 degrees to about 5.620 degrees.

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

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

[0016] In some aspects, the average grain size is in a range from about 15 nm to about 30 nm.

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

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

[0019] In some aspects, the at least a subset of graphite active material particles has a tap density ranging from about 0.10 g / cc to about 1.25 g / cc.

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

[0021] In some aspects, the at least a subset of graphite active material particles has a pycnometry density in a range from about 2.15 g / cc to about 2.35 g / cc.

[0022] In some aspects, the 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

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

[0024] In some aspects, the 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

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

[0026] In some aspects, the 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

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

[0028] In some aspects, the at least a subset of the graphite active material particles has a Brunauer-Emmett-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0029] In some aspects, the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0030] In some aspects, the weight fraction of the at least a subset of graphite active material particles in the battery anode is in a range from about 1 wt. % to about 50 wt. % of the active material mixture.

[0031] In some aspects, the weight fraction is in the range of about 2 wt. % to about 20 wt. % of the active material mixture.

[0032] In some aspects, the silicon-containing active material particles include about 5 wt. % or less of oxygen (O) atoms based on the total mass of the silicon-containing active material particles.

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

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

[0035] In some aspects, the at least one subset of graphite active material particles exhibits a specific capacity in a range from 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 coupling the battery anode and cathode.

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

[0038] In some aspects, the mass ratio of silicon-containing active material particles to graphite active material particles is in a range from about 75:25 to about 95:5.

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

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

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

[0042] In some aspects, at least a subset of the graphite active material particles has a tap density in a range from about 0.10 g / cc to about 1.25 g / cc.

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

[0044] In some aspects, the 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

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

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

[0047] In some aspects, the 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

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

[0049] In some respects, D90 The range is from about 19 μm to about 26 μm.

[0050] In some aspects, the 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

[0051] In some respects, D 10 The range is from about 5 μm to about 11 μm.

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

[0053] In some aspects, at least a subset of the graphite active material particles has a Bronner-Emmett-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0054] In some aspects, the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0055] In some aspects, the BET-SSA range is about 1 m 2 / g to about 3m 2 / g.

[0056] In some aspects, the silicon-containing active material particles include about 5 wt. % or less of oxygen (O) atoms based on the total mass of the silicon-containing active material particles.

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

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

[0059] In some aspects, the at least one subset of graphite active material particles exhibits a specific capacity in a range from about 320 mAh / g to about 372 mAh / g.

[0060] In some aspects, the battery anode has a current density of about 2 mAh / cm 2 to about 16 mAh / cm 2 Reversible capacity load within the range.

[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 coupling the battery anode and cathode.

[0062] In one aspect, a battery anode includes a binder; a conductive additive; and an active material mixture, the active material mixture 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.%; the 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 subset of the graphite active material particles is characterized by Raman spectroscopy, and in the Raman spectrum, the full width at half maximum (FWHM) of the D band is about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 110cm -1 and a D / G peak intensity ratio (defined as the D peak intensity divided by the G peak intensity) is in a range of about 0.02 to about 1.12; and an average pressure (Cx) required to deform the at least one subset of the graphite active material particles by 10% during a microcompression hardness test is in a range of about 20 MPa to about 30 MPa.

[0063] In some aspects, the mass ratio of silicon-containing active material particles to graphite active material particles is in a range from about 10:90 to about 30:70.

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

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

[0066] In some aspects, the at least a subset of graphite active material particles has a tap density in a range from about 0.10 g / cc to about 1.25 g / cc.

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

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

[0069] In some aspects, the 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

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

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

[0072] In some aspects, the 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

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

[0074] In some aspects, the 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

[0075] In some respects, D 10 The range is from about 5 μm to about 11 μm.

[0076] In some aspects, at least a subset of the graphite active material particles has a Bronner-Emmett-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0077] In some aspects, the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0078] In some aspects, the BET-SSA range is about 1 m 2 / g to about 3m 2 / g.

[0079] In some aspects, the silicon-containing active material particles include about 5 wt. % or less of oxygen (O) atoms based on the total mass of the silicon-containing active material particles.

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

[0081] In some aspects, the Si-containing active material particles include Si-C nanocomposite particles.

[0082] In some aspects, the at least one subset of graphite active material particles exhibits a specific capacity in a range from about 320 mAh / g to about 372 mAh / g.

[0083] In some aspects, the battery anode has a current density of about 2 mAh / cm2 to about 16 mAh / cm 2 Reversible capacity load within the range.

[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 coupling the battery anode and cathode.

[0085] In one aspect, the battery anode comprises a binder; a conductive additive; and an active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, wherein: the battery anode has a conductivity of about 2 mAh / cm 2 to about 16 mAh / cm 2 The invention relates to a method for producing a reversible capacity load within a range of about 1000 mAh / g to about 2000 mAh / g of the battery; wherein the Si-containing active material particles exhibit a specific capacity within a range of about 800 mAh / g to about 3000 mAh / g; wherein the Si-containing active material particles contribute about 25% to about 99% of the total capacity of the battery anode; and wherein at least a subset of the graphite active material particles is characterized by Raman spectroscopy, wherein the D band has a full width at half maximum (FWHM) of about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 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 aspects, the D / G peak intensity ratio is in a range from about 0.12 to about 0.30.

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

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

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

[0090] In some aspects, at least some of the graphite active material particles have an average crystallite size in a range from about 1 nm to about 40 nm, as estimated by applying the Scherrer equation to the (002) reflection.

[0091] In some aspects, the average grain size is in a range from about 15 nm to about 30 nm.

[0092] In some aspects, the average pressure (Cx) required to deform at least some 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 aspects, the average pressure ranges from about 1 MPa to about 18 MPa.

[0094] In some aspects, 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 aspects, the tap density ranges from about 0.90 g / cc to about 1.10 g / cc.

[0096] In some aspects, at least some of the graphite active material particles have a pycnometer density in the range of about 2.15 g / cc to about 2.35 g / cc.

[0097] In some aspects, at least some of the graphite active material particles have a 50th percentile volume-weighted particle size parameter D50 in a range from about 2 μm to about 22 μm.

[0098] In some aspects, D50 ranges from about 12 μm to about 17 μm.

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

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

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

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

[0103] In some aspects, at least some of the graphite active material particles have a Bronner-Emmet-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0104] In some aspects, the BET-SSA range is about 1 m 2 / g to about 5m2 / g.

[0105] In some aspects, the weight fraction of at least some of the graphite active material particles in the battery anode ranges from about 1 wt. % to about 50 wt. % of the active material mixture.

[0106] In some aspects, the weight fraction is in the range of about 2 wt. % to about 20 wt. % of the active material mixture.

[0107] In some aspects, the silicon-containing active material particles include about 5 wt. % or less of oxygen (O) atoms based on the total mass of the silicon-containing active material particles.

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

[0109] In some aspects, the Si-containing active material particles include Si-C nanocomposite particles.

[0110] In some aspects, at least some of the graphite active material particles exhibit a specific capacity in a range from 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 coupling the battery anode and cathode.

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

[0113] The following is a simplified description of one or more aspects disclosed herein. Therefore, the following description should not be considered as an extensive overview of all contemplated aspects, nor should it be considered to identify important or critical elements related to all contemplated aspects, or to describe the scope of any particular aspect. Therefore, the sole purpose of the following description is to present certain concepts related to one or more aspects of the mechanisms disclosed herein in a simplified form before providing the detailed description presented later. BRIEF DESCRIPTION OF THE DRAWINGS

[0114] The accompanying drawings are presented to assist in describing embodiments of the present invention and are provided solely for the purpose of illustrating the embodiments and not for limiting the same. Unless otherwise indicated or implied by the context, the different hatching, shading, and / or filling patterns in the drawings are intended solely for the purpose of contrasting different components, elements, features, etc. and are not intended to convey specific materials, colors, or other characteristics that may be used for the particular pattern employed and are not limited to the present invention.

[0115] Figure 1 An example lithium-ion battery is shown in which the components, materials, processes, and / or other techniques described herein may be implemented.

[0116] Figure 2 Table 1 is shown, which lists example graphite particles and / or other electrochemically active material particles and the measured pressure average required to deform each particle by 10%, which is represented as Cx and is expressed in MPa.

[0117] Figure 3 Table 2 is shown, which lists the measured values ​​of tap density of exemplary graphite particle samples and corresponding graphite particle samples.

[0118] Figure 4 Table 3 is shown, which lists example graphite particle samples and density measurements of each graphite particle sample obtained using nitrogen (N2) pycnometry.

[0119] Figure 5A 、 5B 5C, 5D, 5E, and 5F show scanning electron microscope (SEM) images of exemplary graphite samples G1, G2, G3, G4, G5, and G6, respectively.

[0120] Figure 6 Table 4 is shown, which lists exemplary graphite particle samples and the 10th percentile volume-weighted particle size parameter D of the particle size distribution (PSD) of each exemplary graphite particle sample. 10 , 50th percentile volume-weighted particle size parameter D 50 and the 90th percentile volume-weighted particle size parameter D 90 value.

[0121] Figure 7 Table 5 is shown, which lists exemplary graphite particle samples and the Bronner-Emmet-Teller (BET) specific surface area (SSA) values ​​for each exemplary graphite particle sample.

[0122] Figure 8A X-ray diffraction data patterns are shown for example graphite samples G1, G2, G3, G4, and G6.

[0123] Figure 8B Table 6 is shown, which lists exemplary graphite particle samples and selected X-ray diffraction data for individual graphite particle samples.

[0124] Figure 9A Raman spectra of example graphite samples G1, G3, G4, and G6 are shown.

[0125] Figure 9BTable 7 is shown, which lists example graphite particle samples and selected Raman data associated with the D and G spectral features of each graphite particle sample.

[0126] Figure 9C Table 8 is shown, which lists example graphite particle samples and selected Raman data associated with the 2D1 and G spectral features of each graphite particle sample.

[0127] Figure 10A A graph showing the cycle life, expressed as the estimated number of cycles to reach 80% (N80) of the charge capacity as determined by a pycnometer at the start of cycling, of a lithium-ion battery test cell in which the anode is a hybrid anode comprising Si-C nanocomposite particles and corresponding example graphite particles.

[0128] Figure 10B Capacity curves are shown for lithium-ion battery test cells ("full cells") in which each anode was one of: (1) a hybrid anode containing Si-C nanocomposite particles and a corresponding example graphite particle sample; and (2) an anode containing Si-C nanocomposite particles without added graphite particles. Capacity is normalized to anode weight.

[0129] Figure 10C Graphs showing (a) lithiated anode coating density, (b) coating and calendared coating density, (c) volumetric energy density, and (d) volumetric capacity of the anode at the start of cycling for lithium-ion battery test cells in which each anode was one of: (1) a hybrid anode comprising Si-C nanocomposite particles and a corresponding example graphite particle sample, and (2) an anode comprising Si-C nanocomposite particles but no added graphite particles.

[0130] Figure 11 is a process flow diagram for manufacturing a lithium-ion rechargeable battery cell according to certain embodiments.

[0131] Figure 12 Graphs showing the estimated cycle life (N80) as a function of cycle number for lithium-ion battery test cells: (1) containing no graphite particles (graph 1202); (2) containing 10 wt.% of the anode active material with graphite particles (graph 1204); (3) containing 20 wt.% of the anode active material with graphite particles (graph 1206); and (4) containing 30 wt.% of the anode active material with graphite particles (graph 1208).

[0132] Figure 13Table 9 is shown, listing example graphite particle samples, their selected properties (Cx, tap density, particle size distribution (PSD) properties, BET-SSA values, and D / G ratios), and certain battery performance characteristics of lithium-ion battery cells using the example graphite particle samples at low mass fractions of graphite particles in the respective anode active materials.

[0133] Figure 14 Table 10 is shown, which lists example graphite particle samples, their selected properties (Cx, tap density, particle size distribution characteristics, BET-SSA values, and D / G ratios), and certain battery performance characteristics of lithium-ion battery cells using the example graphite particle samples at higher mass fractions of graphite particles in the respective anode active materials.

[0134] Figure 15 Table 11 is shown, which lists certain anode characteristics (particle size (D 50 ) value, calendering pressure during battery anode formation, binder material used in battery anode formation), and certain battery performance characteristics of lithium-ion battery cells using graphite particles (G1) and Si-C nanocomposite particles (the mass fraction of graphite particles G1 in each anode active material is 10 wt.%).

[0135] Figure 16 The direct current resistance (DCR) curves for lithium-ion battery cells using a PAA salt copolymer-based (acrylic acid) anode binder (1602) and a CMC:SBR anode binder (1604) are shown. Both types of lithium-ion battery cells use a mixed anode containing Si-C nanocomposite particles and graphite particles (G1) (the mass fraction of the graphite particles G1 is 10 wt.% of the corresponding anode active material).

[0136] Figure 17 A graph showing the relative discharge capacity versus normalized discharge rate (C-rate) for lithium-ion battery cells using a PAA salt copolymer-based anode binder (1702) and a CMC:SBR anode binder (1704). Both types of lithium-ion battery cells use a mixed anode material of Si-C nanocomposite particles and graphite particles (G1) (the mass fraction of the graphite particles G1 is 10 wt.% of the corresponding anode active material). DETAILED DESCRIPTION

[0137] Various aspects of the present invention are disclosed in the following description of specific embodiments of the invention and the associated drawings. The term "embodiments of the invention" does not require that all embodiments of the invention include the discussed features, advantages, processes, or modes of operation, and alternative embodiments may be devised without departing from the scope of the invention. Furthermore, well-known elements of the invention may not be described in detail or may be omitted to avoid obscuring other, more relevant details.

[0138] Some aspects of the present invention provide methods for making advanced carbonaceous composite particles for use in electrodes (e.g., anode electrodes or cathode electrodes) for lithium-ion, sodium-ion, or potassium-ion rechargeable batteries and other types of batteries, electrochemical capacitors, and hybrid electrochemical energy storage devices.

[0139] Any numerical range described herein with respect to any embodiment of the present invention is intended to define not only the upper and lower limits of the relevant numerical range, but also implicitly disclose each discrete value within the range in units or increments consistent with the level of precision characterizing the upper and lower limits. For example, a numerical distance range of 7 nm to 20 nm (i.e., with a level of precision in units of 1 or increments of 1) includes the set of [7, 8, 9, 10, ..., 19, 20] (in nm), just as the intermediate numbers 8 to 19 are explicitly disclosed in units of 1 or increments of 1. In another example, a temperature range of about -120°C to about -60°C includes the set of temperature ranges (in °C): about -120°C to about -119°C, about -119°C to about -118°C, ..., about -61°C to about -60°C, just as the intermediate numbers (in °C) between -120°C and -60°C are explicitly disclosed in increments. In yet another example, a numerical percentage range from 30.92% to 47.44% (i.e., a level of precision in percents or increments) encompasses the set (in %) [30.92, 30.93, 30.94, ..., 47.43, 47.44] as if the intervening numbers between 30.92% and 47.44% in percents or increments were explicitly disclosed. Thus, it is intended that any intervening numbers included in any disclosed numerical range be interpreted as if they had been explicitly disclosed, and any such intervening numbers may therefore constitute their own upper and / or lower limits for sub-ranges within the broader range. Thus, it is intended that each sub-range (e.g., each range that includes at least one intervening number from the broader range as an upper and / or lower limit) be interpreted as implicitly disclosed by virtue of the explicit disclosure of the broader range. In another example, numerical ranges with upper and lower limits defined at different levels of precision are to be interpreted in increments corresponding to the limits with the higher levels of precision. For example, the numerical percentage range from 30.92% to 47.4% (i.e., with precision levels in units or increments of one hundredth and one tenth, respectively) encompasses the set (in %) [30.92, 30.93, 30.94, ..., 47.39, 47.40] just as if 47.4% (a precision level of one tenth) were stated as 47.40% (a precision level of one hundredth), and as if intermediate numbers between 30.92 and 47.40 were expressly disclosed in units or increments of one hundredth.

[0140] It is understood that the level of precision of any particular measurement, threshold, or other imprecise parameter may vary depending on various factors, such as the measurement instrument, environmental conditions, etc. Therefore, references to these measurements or thresholds below may be interpreted as representing the corresponding values ​​with a pseudo-precise level of precision (e.g., a threshold of 80% includes 80.0000…%). Alternatively, references to these measurements or thresholds may be described by a modifier that defines the pseudo-precise value plus a range extending above and / or below the pseudo-precise value. For example, the 80% threshold described above may be interpreted as "about," "approximately," "near," or "~" 80%, which includes "exactly" 80% (e.g., 80.0000…%) plus a range around 80%. In some designs, the range encompassed by the modifiers "about," "approximately," "near," or "~" around the measurement or threshold may include the level of precision of the corresponding measurement or threshold that can be measured using the most accurate commercially available instrument as of the priority date of this application.

[0141] In the following description, we will describe various material properties to characterize materials in various states (e.g., binders, molecules, particles, powders, slurries, electrodes, separators, electrolytes, battery cells, etc.). It is noted that a person skilled in the art is generally able to select (and it is assumed herein that a selection is made) the most appropriate measurement technique for any particular measurement. In addition, in some cases, the most appropriate measurement technique may include a combination of multiple techniques. Although the following table lists various measurement type options for specific material types and specific material properties, if necessary, certain embodiments of the present invention may be combined with specific measurement techniques and / or specific commercially available instruments for more specific characterization. It is noted that although the following table describes measurements for active material particles, similar measurements can also be made for other particle types, such as precursor particles (e.g., carbon particles, etc.). Therefore, unless otherwise stated, the following table provides an example of how a person skilled in the art can easily measure such material properties using commercially available instruments:

[0142] Material performance measurement technology and instrumentation

[0143] In some aspects, the present invention relates to batteries. Although the following description may describe certain examples in the context of lithium metal and lithium ion batteries (for simplicity and convenience, and because lithium technology is currently more prevalent), it should be understood that various aspects are applicable to other rechargeable and disposable batteries (e.g., sodium and sodium ion batteries, magnesium and magnesium ion batteries, potassium and potassium ion batteries, calcium and calcium ion batteries, as well as other metal and metal ion batteries, dual ion batteries, alkaline batteries or alkaline ion batteries, flow batteries, etc.), as well as electrochemical capacitors and hybrid energy storage devices.

[0144] Although the following description may describe certain examples in the context of composite materials comprising specific (e.g., alloying or conversion) active anode materials (e.g., Si, etc.) or specific (e.g., insertion or conversion) active cathode materials, it should be understood that various aspects can be applicable to many other types and chemistries of conversion anode and cathode active materials, insertion anode and cathode active materials, pseudocapacitive anode and cathode active materials, and materials that can exhibit hybrid electrochemical energy storage mechanisms.

[0145] Although the following description also describes certain examples of material formulations in a lithium-free state (e.g., silicon-containing nanocomposite anodes or metal fluoride cathodes or sulfur cathodes, etc.), it should be understood that various aspects can be applied to lithium-containing electrodes and active materials (e.g., partially or fully lithiated silicon-containing anodes or partially or fully lithiated silicon-containing anode particles, partially or fully lithiated metal fluoride cathodes (e.g., mixtures of LiF with metals (e.g., Cu, Fe, Ni, Bi, Zr, Ti, Mg, Nb) and various other metals and metal alloys, and mixtures of these and / or other metals, etc.) or partially or fully lithiated metal halide cathode particles, partially or fully lithiated chalcogenides (e.g., Li2S, Li2S / metal mixtures, Li2Se, Li2Se / metal mixtures, Li2S-Li2Se mixtures, and various other compositions containing lithiated chalcogenides, etc.), partially or fully lithiated metal oxides (e.g., Li2O, Li2O / metal mixtures, etc.), partially or fully lithiated insertion cathode materials, partially or fully lithiated carbon, etc.). In some designs, various material properties (e.g., at the particle level, at the interparticle level, at the electrode level, etc.) may vary depending on whether the active material particles are in a lithium-free state, a partially lithiated state, or a fully lithiated state. Such lithium-dependent material properties may include particle pore volume, electrode pore volume, etc. Unless otherwise stated or implied, references to such lithium-dependent anode material properties (e.g., at the particle level, at the interparticle level, at the electrode level, etc.) can be assumed to be in a lithium-free state for the active material particles. In addition, some examples below are characterized at the electrode level (e.g., as opposed to the particle level, interparticle level, or cell level, etc.). Hereinafter, unless otherwise stated or implied, references to such electrode-level properties (e.g., electrode porosity, areal capacity loading, gravimetric / volumetric capacity, etc.) can be assumed to refer to the electrode components (e.g., active material particles, binder, conductive additives, etc.), but not the current collector.

[0146] While the following description may describe certain examples in the context of certain specific alloy, conversion, and insertion chemistries for lithium-ion battery anode active materials and conversion and insertion chemistries for lithium-ion battery cathode active materials (e.g., silicon-containing anodes or metal fluoride-containing cathodes or lithium sulfide-containing cathodes), it should be understood that various aspects can be applied to other chemistries of lithium-ion batteries (other conversion and alloy electrodes and various insertion anodes and cathodes) and other battery chemistries. For metal ion batteries (e.g., lithium ion batteries), examples of other suitable conversion 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, and the like.

[0147] During the operation of a battery (such as a lithium-ion battery), a conversion-type material transforms from one crystal structure to another (hence the term "conversion-type"), where the structure and composition of the material may undergo chemical and structural changes, transforming into one or more structures. This process is also accompanied by the breaking of chemical bonds and the formation of new chemical bonds. During the operation of a battery (such as a lithium-ion battery), lithium ions are inserted into alloy-type materials to form lithium alloys (hence the term "alloy-type"). Sometimes, "alloy-type" electrode materials are considered a subclass of "conversion-type" electrode materials.

[0148] Although the following description may describe certain 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 which may contain other elements (e.g., nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), fluorine (F), etc.), and wherein the total mass of the Si and C atoms may comprise from about 75 wt.% to about 100 wt.% of the total mass of the composite particles), it should be understood that various aspects may be applicable to other types of high capacity silicon-containing anode active materials (including, but not limited to, for example, various silicon-containing or silicon oxide-containing or silicon nitride-containing or silicon oxynitride-containing or silicon phosphide-containing particles, or particles comprising mixtures or alloys or other combinations of such active materials, various other types of silicon-containing composite materials, including, but not limited to, core-shell or hierarchical or nanocomposite particles, etc.).

[0149] One aspect of the present invention relates to a battery anode and / or battery anode precursor composition comprising a group of silicon-containing particles (e.g., nanocomposite particles, etc.), wherein some or all of the silicon-containing particles comprise silicon (Si) and carbon (C) elements and may include other elements such as nitrogen (N), phosphorus (P), boron (B), oxygen (O), hydrogen (H), sulfur (S), fluorine (F), etc. In some embodiments, the total mass (average) of Si and C in the silicon-containing particles may be from about 75 wt.% to about 100 wt.% of the total mass of the silicon-containing particles. Such composite particles are sometimes referred to herein as Si-C composites (or nanocomposites, for example, if the Si and / or C are nanostructured).

[0150] In some embodiments, the total mass of O may (on average) comprise from about 0 wt.% to about 10 wt.% of the total mass of the Si-containing particles (in some designs, from about 0 wt.% to about 1 wt.%; in other 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, from about 5 wt.% to about 10 wt.%). In some embodiments, the total mass of O may (on average) comprise less than about 5 wt.% of the total mass of the Si-containing particles. In some embodiments, the total mass of N may (on average) comprise from about 0 wt.% to about 10 wt.% of the total mass of the Si-containing particles (in some designs, from about 0 wt.% to about 0.1 wt.%; in other designs, from about 0.1 wt.% to about 2 wt.%; in other designs, from about 2 wt.% to about 5 wt.%; in still other designs, from about 5 wt.% to about 10 wt.%). In some embodiments, the total mass of P may (on average) account for about 0 wt.% to about 10 wt.% of the total mass of the silicon-containing particles (in some designs, about 0 wt.% to about 0.1 wt.%; in other designs, about 0.1 wt.% to about 1 wt.%; in other designs, about 1 wt.% to about 5 wt.%; in still other designs, about 5 wt.% to about 10 wt.%). In some embodiments, the total mass of B may (on average) account for about 0 wt.% to about 5 wt.% of the total mass of the silicon-containing particles (in some designs, about 0 wt.% to about 0.1 wt.%; in other designs, about 0.1 wt.% to about 2.5 wt.%; in still other designs, about 2.5 wt.% to about 5 wt.%). In some embodiments, the total mass of H may (on average) account for about 0 wt.% to about 2 wt.% of the total mass of the silicon-containing particles (in some designs, about 0 wt.% to about 0.5 wt.%; in other designs, about 0.5 wt.% to about 1 wt.%; in still other designs, about 1 wt.% to about 2 wt.%). In some embodiments, the total mass of S may (on average) account for about 0 wt.% to about 2.5 wt.% of the total mass of the silicon-containing particles (in some designs, about 0 wt.% to about 0.1 wt.%; in other designs, about 0.1 wt.% to about 0.5 wt.%; in still other designs, about 0.5 wt.% to about 2.5 wt.%). In some embodiments, the total mass of F may (on average) comprise from about 0 wt.% to about 2.5 wt.% of the total mass of the Si-containing particles (in some designs, from about 0 wt.% to about 0.1 wt.%; in other designs, from about 0.1 wt.% to about 0.5 wt.%; in yet other designs, from about 0.5 wt.% to about 2.5 wt.%).

[0151] In some embodiments, the total atomic fraction of Si and C can be from about 75 at.% to about 100 at.% or from about 80 at.% to about 100 at.% of the entire composite particle. Such composite particles are sometimes referred to herein as Si-C composite materials. 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), which can be referred to as nanocomposite particles. In some embodiments, the Si or Si-containing active material present in such nanocomposite materials can be in the form of nanoparticles. In some embodiments, the average size of Si or Si-containing material nanoparticles (e.g., silicon nanoparticles or silicon nanocrystals) may range from about 1 nm to about 200 nm (in some designs, about 1.0 nm to about 10.0 nm; in other designs, about 10.0 nm to about 30.0 nm; in other designs, about 30.0 nm to about 100.0 nm; in yet other designs, about 100.0 nm to about 200.0 nm), as measured using electron microscopy (e.g., transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM)) image analysis, X-ray microscopy, X-ray diffraction, neutron scattering, and / or other suitable techniques. In some designs, Si or Si-containing material nanoparticles (e.g., silicon nanoparticles) may be doped (e.g., doped with Group V or Group III elements, such as N, P, B, etc., in some designs; or doped with Group IV elements, such as C, etc., in other designs; or various combinations thereof). The doping level can be in the range of about 10 ppm to about 50,000 ppm (e.g., in some designs, about 10 ppm to about 100 ppm; in other designs, about 100 ppm to about 1000 ppm; in other designs, about 1000 ppm to about 10,000 ppm; in other designs, about 10,000 ppm to about 50,000 ppm). In some designs, X-ray diffraction is particularly convenient and easy to determine the average size of Si nanocrystals. Silicon nanocrystals that are too small (e.g., less than about 1.0 nm in some designs, or about 2 nm in other designs) may exhibit too high a reactivity during the synthesis process, resulting in reduced activity or excessive first cycle capacity loss; while silicon crystals that are too large (e.g., greater than about 200 nm in some designs, or about 100 nm in other designs) may reduce the cycling stability of such Si-C composite materials (nanocomposites) or nanocomposite silicon in a broad sense. As used herein, "nano" materials (e.g., nanostructures, nanoparticles, or nanocomposites, etc.) may refer to any material having at least one dimension less than about 200 nm.

[0152] One aspect of the present invention relates to a battery anode and / or battery anode precursor composition comprising a plurality of silicon-containing composite particles (e.g., nanocomposite particles, etc.), wherein each silicon-containing composite particle comprises Si and C, and the silicon-containing composite particles have certain properties. In some embodiments, the mass fraction of silicon in the silicon-containing composite particles is in the range of about 3 wt.% to about 80 wt.% (in some designs, about 3 wt.% to about 20 wt.%; in other designs, about 20 wt.% to about 35 wt.%; in other designs, about 35 wt.% to about 50 wt.%; in other designs, about 50 wt.% to about 80 wt.%; in other designs, about 50 wt.% to about 60 wt.%; in other designs, about 60 to about 70 wt.%; in other designs, about 70 wt.% to about 80 wt.%; in other designs, about 20 wt.% to about 80 wt.%; in other designs, about 35 wt.% to about 60 wt.%). In some embodiments, the silicon-containing composite particles (eg, nanocomposite particles, etc.) have a Bronner-Emmett-Teller (BET) specific surface area (SSA) of about 0.5 m 2 / g to about 150m 2 / g range (in some designs, about 0.5 to about 3 m 2 / g; in other designs, about 3m 2 / g to about 12m 2 / g; in other designs, about 12m 2 / g to about 18m 2 / g; in other designs, about 18m 2 / g to about 30m 2 / g; in other designs, about 30m 2 / g to about 50m 2 / g; in other designs, about 50m 2 / g to about 150m 2 / g). In some embodiments, about 90% or more of the silicon-containing composite particles (e.g., nanocomposite particles, etc.) 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 greater, or an aspect ratio of about 1.35 or greater.

[0153] One aspect of the present invention relates to a battery electrode and / or battery electrode precursor composition comprising a group of silicon-containing active material particles (e.g., nanocomposite particles, etc.), wherein the particle population can be characterized by a particle size distribution (PSD), which can be determined by laser particle size distribution analysis (LPSA), electron microscopy image analysis, or other suitable techniques. Characterizing the particle size distribution (PSD) of a particle population can be determined, for example, by performing laser particle size distribution analysis (LPSA) on a well-dispersed particle suspension, or by electron microscopy image analysis, or other suitable techniques. Although there are many ways to measure PSD, laser particle size distribution analysis (LPSA) is very effective for certain applications. Using LPSA, particle size parameters of the population PSD can be measured, such as: the 10th percentile volume-weighted particle size parameter (e.g., abbreviated as D 10 ), the 50th percentile volume-weighted particle size parameter (e.g., abbreviated as D 50 ), the 90th percentile volume-weighted particle size parameter (e.g., abbreviated as D 90 ) and the 99th percentile volume-weighted particle size parameter (e.g., abbreviated as D 99 ). In addition, parameters related to the characteristic width of the PSD can be derived from these particle size parameters, such as D 50 –D 10 (sometimes referred to herein as left width), D 90 –D 50 (sometimes referred to herein as right width) and D 90 –D 10 (Sometimes referred to herein as full width). The cumulative volume fraction, defined as the cumulative volume of composite particles having a particle size equal to or less than a threshold value divided by the total volume of all composite particles, can be estimated by LPSA. In some embodiments, the 50th percentile volume-weighted particle size parameter (D 50 ) is preferably in the range of about 0.5 μm to about 25.0 μm, or in the range of about 0.5 μm to about 4.0 μm, or in the range of about 4.0 μm to about 6.0 μm, or in the range of about 6.0 μm to about 8.0 μm, or in the range of about 8.0 μm to about 16.0 μm, or in the range of about 16.0 μm to about 25.0 μm. The cumulative volume fraction, defined as the cumulative volume of composite particles having a particle size equal to or less than the threshold value divided by the total volume of all composite particles, can be estimated by LPSA. In some embodiments (e.g., when D 50 When the threshold particle size is between about 0.5 μm and about 4.0 μm), the cumulative volume fraction is preferably about 99 vol.% or less, or about 95 vol.% or less, or about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less when the threshold particle size is 5 μm. In other embodiments (e.g., when D 50When the threshold particle size is between about 4.0 μm and about 6.0 μm), the threshold particle size is 7 μm, and the cumulative volume fraction is preferably about 99 vol.% or less, or about 95 vol.% or less, or about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less. In other embodiments (e.g., when D 50 In the range of about 6.0 μm to about 8.0 μm), the threshold particle size is 10 μm, and the cumulative volume fraction can advantageously be about 99 vol.% or less, or about 95 vol.% or less, or about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less. In other embodiments (e.g., when D 50 In the range of about 8.0 μm to about 16.0 μm), the threshold particle size is 20 μm, and the cumulative volume fraction can advantageously be about 99 vol.% or less, or about 95 vol.% or less, or about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less. In other embodiments (e.g., when D 50 In the range of about 16.0 μm to about 25.0 μm), the threshold particle size is 30 μm, and the cumulative volume fraction can advantageously be about 99 vol.% or less, or about 95 vol.% or less, or about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less. In some embodiments, D 50 Particularly advantageous is the range of about 7.0 μm to about 13.0 μm. In such embodiments, the threshold particle size is 20 μm and the cumulative volume fraction can advantageously be about 99 vol.% or less, or about 95 vol.% or less, or about 90 vol.% or less, or about 85 vol.% or less, or about 80 vol.% or less.

[0154] It should be noted that in some designs, excessively large silicon-containing active material particles (e.g., in the form of nanocomposite particles, etc.) may reduce battery performance characteristics (e.g., reduce battery stability, increase battery impedance, reduce rate performance, reduce stacking density, reduce electrode smoothness or uniformity, reduce electrode mechanical properties, reduce volume capacity, increase (e.g., local) volume expansion, etc.). In some embodiments (e.g., when D 50 When the threshold particle size is about 10 μm, the cumulative volume fraction can be advantageously about 80 vol.% or more, or about 85 vol.% or more, or (in some designs) even about 90 vol.% or more. In some embodiments (e.g., when D 50When the threshold particle size is 12 μm, the cumulative volume fraction can be advantageously about 90 vol.% or higher, or about 95 vol.% or higher, or (in some designs) even about 98 vol.% or higher. In other embodiments (e.g., when D 50 When the threshold particle size is 15 μm, the cumulative volume fraction can be advantageously about 80 vol.% or more, or about 85 vol.% or more, or (in some designs) even about 90 vol.% or more. In other embodiments (e.g., when D 50 When the threshold particle size is in the range of about 4.0 μm to about 6.0 μm), the cumulative volume fraction can advantageously be about 90 vol.% or higher, or about 95 vol.% or higher, or (in some designs) even about 98 vol.% or higher. In other embodiments (e.g., when D 50 When the threshold particle size is about 18 μm, the cumulative volume fraction can be advantageously about 80 vol.% or more, or about 85 vol.% or more, or (in some designs) even about 90 vol.% or more. In other embodiments (e.g., when D 50 In the case of a particle size range of about 6.0 μm to about 8.0 μm or about 8.0 μm to about 12.0 μm), the threshold particle size is about 22 μm or about 25 μm, and the cumulative volume fraction can advantageously be about 80 vol.% or more, or about 85 vol.% or more, about 90 vol.% or more, or about 95 vol.% or more, or (in some designs) even about 98 vol.% or more. In other embodiments (e.g., when D 50 In other embodiments (e.g., when D 50 When the threshold particle size is in the range of about 8.0 μm to about 16.0 μm), the cumulative volume fraction can advantageously be about 90 vol.% or higher, or about 95 vol.% or higher, or (in some designs) even about 98 vol.% or higher. In other embodiments (e.g., when D 50 When the threshold particle size is in the range of about 7.0 μm to about 13.0 μm), the cumulative volume fraction can advantageously be about 90 vol.% or higher, or about 95 vol.% or higher, or (in some designs) even about 98 vol.% or higher. In other embodiments (e.g., when D50 In the range of about 7.0 μm to about 13.0 μm), with a threshold particle size of 40 μm, the cumulative volume fraction may advantageously be about 90 vol. % or higher, or about 95 vol. % or higher, or (in some designs) even about 98 vol. % or higher.

[0155] In one or more embodiments of the present disclosure, silicon-containing active material particles (e.g., silicon-containing active material composite particles) may exhibit a true density (e.g., as measured using a nitrogen pycnograph, and therefore sometimes referred to as pycnometry density or pycnometry density or pyc density in this context) in the range of about 1.1 g / cc to about 2.8 g / cc (in some designs, about 1.1 g / cc to about 1.5 g / cc; in other 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; and in still other designs, about 2.4 g / cc to about 2.8 g / cc).

[0156] In one or more embodiments of the present disclosure, the silicon-containing active material particles may include internal pores. In some designs, the open (e.g., to nitrogen at 77K) pore volume (e.g., measured by nitrogen adsorption / desorption isotherm measurement techniques and including pores in the range of about 0.4 nm to about 100 nm) may be in the range of about 0.00 cc / g to about 0.50 cc / g (assuming the theoretical density of the individual material components present in the silicon-containing active material particles)—in some designs, about 0.00 cc / g to about 0.10 cc / g; in other designs, about 0.10 cc / g to about 0.20 cc / g; in other designs, about 0.20 cc / g to about 0.30 cc / g; in other designs, about 0.30 cc / g to about 0.40 cc / g; and in other designs, about 0.40 cc / g to about 0.50 cc / g. In some designs, the closed (e.g., to nitrogen at 77 K) pore volume (e.g., as measured by analyzing the true density value measured using an argon pycnometer and comparing it to the theoretical density of the individual material components present in the silicon-containing active material particles) can range from about 0.00 cc / g to about 1.00 cc / g - in some designs, from about 0.00 cc / g to about 0.10 cc / g; in other designs, from about 0.10 cc / g to about 0.20 cc / g; and in other designs, from about 0.20 cc / g to about 0.30 cc / g. ; in other designs, from about 0.30cc / g to about 0.40cc / g; in other designs, from about 0.40cc / g to about 0.50cc / g; in other designs, from about 0.50cc / g to about 0.60cc / g; in other designs, from about 0.60cc / g to about 0.70cc / g; in other designs, from about 0.70cc / g to about 0.80cc / g; in other designs, from about 0.80cc / g to about 0.90cc / g; in other designs, from about 0.90cc / g to about 1.00cc / g). In some designs, the open (e.g., to nitrogen at 77 K) pore volume average size 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; in yet other designs, from about 50 nm to about 100 nm.In some designs, the closed (e.g., for nitrogen at 77 K) pore volume average size (e.g., as measured by image analysis of cross-sectional electron microscopy images (e.g., SEM or TEM) or by neutron scattering or other suitable technique) 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 yet other designs, from about 100 nm to about 200 nm.

[0157] In one or more embodiments of the present disclosure, the silicon-containing active material particles may exhibit a moderate (e.g., about 7-120 vol.%) or high (e.g., about 120-200 vol.%) volume change during initial lithiation (e.g., down to about 0.01 V compared to Li / Li+). In some designs, the silicon-containing active material particles may exhibit a volume change in the range of about 8 vol.% to about 180 vol.% during one or more charge and discharge cycles of the battery cell. In one or more embodiments of the present disclosure, during battery operation, the silicon-containing active material particles may exhibit a moderately small (e.g., about 3-7 vol.%) or moderate (e.g., about 7-120 vol.%) volume change during cycling of the electrochemical cell from about 0-5% state of charge (SOC) to about 90-100% state of charge (SOC) and back.

[0158] In one or more embodiments of the present disclosure, a preferred anode of a battery cell may include a mixture of silicon-containing active material particles (e.g., nanocomposite silicon-carbon particles, nanocomposite silicon particles, etc.) and graphite active material particles (or, more broadly, carbon active material particles) as anode active material particles, a so-called hybrid anode. In addition to the anode active material particles, the anode may also include inactive materials, such as a binder (e.g., a polymer binder) and / or other functional additives (e.g., a surfactant, a conductive additive, etc.). In some embodiments, the anode active material particles may be in the range of about 85 wt.% to about 89 wt.%; in other designs, about 89 wt.% to about 98 wt.% of the total weight of the anode (excluding the weight of the current collector) - in some designs, from about 89 wt.% to about 91 wt.%; in other designs, from about 91 wt.% to about 93 wt.%; in other designs, from about 93 wt.% to about 95 wt.%; in yet other designs, from about 95 wt.% to about 98 wt.%.

[0159] In some embodiments, the hybrid anode may include silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in a range of about 7 wt.% to about 98 wt.% of all anode active material particles, and graphite (e.g., particles) (e.g., about 2 wt.% to about 93 wt.%) constituting the remaining mass (weight) of the anode active material particles. In some designs, the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) constitute about 7 wt.% to about 15 wt.% of the hybrid anode active material particles; in other designs, about 15 wt.% to about 25 wt.% of the hybrid anode active material particles; in other designs, about 25 wt.% to about 40 wt.% of the hybrid anode active material particles; in other designs, about 40 wt.% to about 60 wt.% of the hybrid anode active material particles; in other designs, about 60 wt.% to about 80 wt.% of the hybrid anode active material particles; and in other designs, about 80 wt.% to about 98 wt.% of the hybrid anode active material particles.

[0160] While the following description may also describe certain examples of hybrid anode formulations expressed as the mass (wt.%) of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the anode active material or the mass (wt.%) of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the entire anode (excluding the weight of the current collector), it should be understood that various aspects of the present disclosure can be applied to hybrid anode formulations expressed as the wt.% of Si in the anode (calculating the weight of all active material particles, binders, conductive agents, and / or other additives, but excluding the weight of the current collector). In some embodiments, about 7 wt.% of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition (relative to the total weight of all active materials, binders, conductive agents, and / or other additives in the anode, but excluding the weight of the current collector) can correspond to, for example, about 3 wt.% of Si in the hybrid anode. In some embodiments, about 19 wt.% of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition can correspond to, for example, about 8 wt.% of Si in the hybrid anode. In some embodiments, about 35 wt.% of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) of the hybrid anode composition may correspond to, for example, about 15 wt.% of Si in the hybrid anode. In some embodiments, about 50 wt.% of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) of the hybrid anode composition may correspond to, for example, about 21 wt.% of Si in the hybrid anode. In some embodiments, about 70 wt.% of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) of the hybrid anode composition may correspond to, for example, about 30 wt.% of Si in the hybrid anode. In some embodiments, about 90 wt.% of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) of the hybrid anode composition may correspond to, for example, about 38 wt.% of Si in the hybrid anode. The weight percent (wt.%) of Si in the anode depends on the weight percent of Si in the silicon-containing active material particles, the weight percent of the binder and conductive additive, and the weight percent of graphite in the hybrid anode. The lower the proportion of inactive material (e.g., binder and conductive agent or other additives), the higher the proportion of Si in the silicon-containing anode material particles (e.g., Si-C composite particles), and the lower the proportion of graphite in the hybrid anode, the higher the weight percentage of Si in the anode. For example, in some embodiments, a hybrid anode composition containing about 80 wt.% silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) and about 20 wt.% of the total amount of binder, conductive agent or other additives (if present), and graphite can correspond to, for example, about 30 wt.% Si in the hybrid anode.In other embodiments, the hybrid anode composition contains about 80 wt.% silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) and about 20 wt.% of a binder, a conductive agent, or other additives (if present), and graphite in a total amount, which can correspond to, for example, about 40 wt.% Si content in the hybrid anode. In other embodiments, the hybrid anode composition contains about 80 wt.% silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) and about 20 wt.% of a binder, a conductive agent, or other additives (if present), and graphite in a total amount, which can correspond to, for example, about 50 wt.% Si content in the hybrid anode. In other embodiments, the hybrid anode composition contains about 80 wt.% silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) and about 20 wt.% of a binder, a conductive agent, or other additives (if present), and graphite in a total amount, which can correspond to, for example, about 60 wt.% Si in the hybrid anode. In various embodiments, hybrid anodes can be obtained having a silicon mass (weight) ranging from about 3 wt. % to about 60 wt. % of the total mass of the anode (excluding the weight of the current collector).

[0161] While the following description also describes certain examples of hybrid anode formulations expressed in terms of the mass (wt.%) of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the active material mixture, it should be understood that various aspects of the present disclosure are applicable to hybrid anode formulations in which the capacity of silicon-containing active material particles accounts for a certain percentage (e.g., %) of the total capacity of the hybrid anode. For example, in some embodiments, when the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) account for approximately 5-8 wt.% of the total weight of the active material particles (including silicon-containing and graphite active material particles) in the hybrid anode composition, approximately 25% of the total capacity of the hybrid anode can be obtained from the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In other embodiments, for example, when the content of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition is approximately 15-21 wt.%, approximately 50% of the total capacity of the hybrid anode can be obtained from the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In other embodiments, when the content of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition is about 30-40 wt.%, about 70% of the total capacity of the hybrid anode can be obtained from the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In other embodiments, when the content of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition is about 45-55 wt.%, about 80% of the total capacity of the hybrid anode can be obtained from the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In other embodiments, when the content of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition is about 65-75 wt.%, about 92% of the total capacity of the hybrid anode can be obtained from the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In some other embodiments, when the content of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition is about 75-85 wt.%, about 95% of the total capacity of the hybrid anode can be obtained by the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). In some other embodiments, when the content of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) in the hybrid anode composition is about 85-95 wt.%, about 98% of the total capacity of the hybrid anode can be obtained by the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.). It should be noted that in a hybrid anode having a specific weight percentage of silicon-containing active material particles, the exact percentage of capacity provided by the silicon-containing active material particles depends on the specific capacity of the plurality of silicon-containing active material particles and the specific capacity of the plurality of graphite (or more broadly, carbon) active material particles.

[0162] In some embodiments, the battery anode composition may advantageously include one, two or more carbon-containing functional additives (e.g., additives that enhance electrode conductivity or rate capability or mechanical properties). 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, exfoliated graphite (e.g., exfoliated graphite flakes), graphene oxide (e.g., graphite oxide flakes), and graphene (e.g., flakes) (including but not limited to, for example, single-layer and / or multi-layer graphene or graphene oxide). In some embodiments, the carbon additives may be purified, defective, curved, and / or contain chemical functional groups. In some embodiments, the battery electrode composition may include one or more binders (in some designs, two or more binder components).

[0163] One aspect relates to a battery anode. In some embodiments, the battery anode comprises any of the aforementioned battery anode electrode compositions, which is 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, nanowire or nanosheet current collector, etc.). In some embodiments, the battery anode comprises the battery electrode composition and a binder. In some embodiments, the coating density of the battery electrode is between about 0.8 and about 1.7 g / cm 3 In the range (in some designs, about 0.8 to about 0.9 g / cm 3 In other designs, from about 0.9 to about 1.0 g / cm 3 In other designs, from about 1.0 to about 1.2 g / cm 3 In other designs, from about 1.2 to about 1.4 g / cm 3 , in still other designs, from about 1.4 to about 1.7 g / cm 3 The higher the proportion of suitable graphite materials in the hybrid anode and the higher the anode density, the better the performance (for example, better stability, better rate performance, higher volumetric capacity, less expansion during cycling, etc.). However, too high a density may also be detrimental to these and other properties. Therefore, detailed optimization can be carried out for specific battery designs, taking into account factors such as electrode thickness, areal capacity loading, and battery cycling environment and system.

[0164] One aspect also relates to a hybrid battery anode in which silicon-containing anode active material particles (e.g., nanocomposite silicon-carbon particles, etc.) and graphite (or, more broadly, carbon-based) active anode materials can be present simultaneously. The anode preferably includes an amount of binder optimized for the properties of the silicon-containing active material particles and the graphite particles. For example, the anode can be characterized by an areal binder loading, which is defined as the mass of binder in the battery anode (e.g., in mg) divided by the surface area (e.g., in m) of the active material particles (e.g., silicon-containing (e.g., nanocomposite, etc.) anode active material particles and (if present) graphite active material particles in the same battery anode). 2 The unit is , and is defined as the mass of the active material particles (in g) multiplied by the mass in m 2 The binder loading is preferably adjusted based on the desired areal binder loading. The higher the BET-SSA of the active anode material (in m2 / g), the higher the BET-SSA of the active anode material (in m2 / g). 2 / g), the higher the mass fraction of the binder in the anode electrode is, the higher the BET-SSA is. For example, a group of active material particles (e.g., a group of active anode material particles containing silicon (e.g., nanocomposites, etc.) or a mixture of silicon active material particles and graphite active material particles) is 10 m 2 / g, generally about 20 mg to about 150 mg of binder is required for every about 1 g of active material particles (about 2-13 wt.% relative to the total weight of the binder and the active material composition, excluding the weight of the conductive agent or other additives or the weight of the current collector), while another anode electrode including another active material particle group (for example, a silicon-containing (for example, nanocomposite materials, etc.) anode active material particle group or a mixture of silicon-containing active material particles and graphite active material particles) has a BET-SSA of only about 1 m 2 / g, typically about 2 mg to about 40 mg of binder is required for every about 1 g of active material particles (about 0.2-4 wt.% of the total weight of the binder + active material composition, excluding the weight of the conductive agent or other additives or the weight of the current collector). However, in some designs, the binder area loading of the battery anode in both cases is about 2.0 mg / m 2 to about 40.0 mg / m 2 range (e.g., in some designs, approximately 2.0 mg / m 2 to about 5.0 mg / m 2 In other designs, approximately 5.0 mg / m 2 to about 9.0 mg / m 2 In other designs, approximately 9.0 mg / m 2to about 15.0 mg / m 2 In other designs, approximately 15.0 mg / m 2 to about 40.0 mg / m 2 ). In some designs, the higher the proportion of the Si-containing (e.g., nanocomposite, etc.) anode active material particle group in the anode (relative to the total weight of all active materials), the higher the binder area loading may be preferably exhibited. In some designs, the average particle size of the Si-containing (e.g., nanocomposite, etc.) anode active material particle group in the anode is larger, and a slightly smaller area binder loading may be preferably required. In some designs, the BET-SSA of the Si-containing (e.g., nanocomposite, etc.) anode active material particle group is larger, and a slightly higher binder area loading may be preferably exhibited. In some designs, the binder area loading may also depend on the components and properties of the binder (e.g., adhesion, chemical composition, hardness, elastic modulus when exposed to electrolyte, maximum elongation at break, etc.). Therefore, in some designs, the optimal binder area loading (at about 2.0 mg / m 2 to about 40.0 mg / m 2 For example, in some designs, the optimal binder area loading can be around 2.0 mg / m 2 to about 5.0 mg / m 2 range; in other designs, approximately 5.0 mg / m 2 to about 9.0 mg / m 2 ; in other designs, approximately 9.0 mg / m 2 to about 15.0 mg / m 2 ; in other designs, approximately 15.0 mg / m 2 to about 40.0 mg / m 2 ).

[0165] Although the following description describes certain examples of intercalated graphites suitable for use in combination with silicon-containing (e.g., Si-C nanocomposites, etc.) active material particles in a mixture, it should be understood that various aspects of the present disclosure are applicable to various soft synthetic graphites (or soft carbons in a broad sense), various hard synthetic graphites (or hard carbons in a broad sense), and various natural graphites (e.g., which may be pitch carbon coated, among others); including but not limited to those exhibiting a discharge capacity of about 320 to about 372 mAh / g (e.g., in some designs, about 320 to about 350 mAh / g; or in other designs, about 350 to about 362 mAh / g; or in other designs, about 362 to about 372 mAh / g); including but not limited to those exhibiting low, medium, and high expansion; including but not limited to those exhibiting good and poor compressibility, including but not limited to those exhibiting about 0.5 to about 40 mAh / g; 2 / g of BET-SSA (e.g., in some designs, about 0.5 to about 2 m 2 / g; or in other designs, from about 2 to about 4 m 2 / g; or in other designs, from about 4 to about 6 m 2 / g; or in other designs, from about 6 to about 8 m 2 / g; or in other designs, about 8 to about 10m 2 / g; or in other designs, from about 10 to about 14 m 2 / g; or in other designs, from about 14 to about 20 m 2 / g; or in other designs, from about 20 to about 40 m 2 / g); including but not limited to those exhibiting lithiation efficiencies of about 85-90% and higher; including but not limited to those exhibiting true densities ranging from about 1.5 g / cm 3 to about 2.3g / cm 3 those (e.g., in some designs, from about 1.5 to about 1.8 g / cm 3 , in other designs, from about 1.8 to about 2.3 g / cm 3 ); including but not limited to those that exhibit poor, moderate, or good cycle life when used alone as lithium ion battery anodes (e.g., do not contain silicon or other active material particles); including but not limited to those that are coated and include a coating that can significantly improve compression and elasticity during cycling with the thickness of the coating.

[0166] One aspect relates to a battery and an anode thereof, wherein the anode includes silicon-containing active material particles, the silicon-containing active material particles also including carbon (C) (e.g., Si-C nanocomposite particles, C-coated particles, etc.), wherein the average domain size of C is approximately 1000 nm as determined by synchrotron X-ray diffraction (XRD) atomic pair distribution function (PDF) analysis. to about On the one hand, the C portion of such Si-C composite particles may be inactive and separate from any C-containing active material (eg, graphite) in the anode.

[0167] One aspect relates to a battery and an anode comprising silicon-containing active material particles that also include carbon (e.g., Si-C nanocomposite particles, C-coated particles, etc.), wherein the intensity ratio of the carbon D band to the carbon G band in the Raman spectrum of most silicon-containing and carbon-containing particles (I D / I G ) (e.g., measured using a laser wavelength of about 532 nm; and, for example, at about 1000 to about 2000 wavenumbers cm -1 The spectral range was analyzed by fitting two Gaussian peaks after linear background subtraction in this range) with an I of about 0.7.D / I G to about 2.7 I D / I G (In some designs, about 0.7 to about 0.9; in other designs, about 0.9 to about 1.2; in other designs, about 1.2 to about 1.5; in other designs, about 1.5 to about 1.8; in other designs, about 1.8 to about 2.1; in other designs, about 2.1 to about 2.4; in still other designs, about 2.4 to about 2.7.) In one aspect, the C portion of such Si-C composite particles may be inactive and separate from any C-containing active material (e.g., graphite) in the anode.

[0168] One aspect also relates to a lithium-ion battery comprising: (i) a suitable hybrid battery anode (wherein silicon-containing anode active material particles (e.g., nanocomposite Si-C particles, etc.) and a suitable graphite (or broadly, carbon-based) active anode material (e.g., graphite active material particles) are present in the anode); and (ii) a suitable battery cathode, wherein, in some designs, the suitable cathode may include one or more of the following: (iia) an insertion cathode or (iib) a conversion cathode (which may include a substitutional cathode, a chemical conversion cathode, or a true conversion cathode) or (iic) a hybrid insertion / conversion cathode. Illustrative examples of suitable insertion-type cathodes for preferred battery cells may 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 (LiNiPO4), lithium vanadium fluorophosphate (LiVFPO4), lithium iron fluorosulfate (LiFeSO4F), various lithium-excess materials (e.g., lithium-excess (rock salts) transition metal oxides and oxyfluorides, such as Li 1.211 Mo 0.467 Cr 0.3 O2、Li 1.3 Mn 0.4 Nb 0.3 O2、Li 1.2 Mn 0.4 Ti 0.4 O2、Li 1.2 Ni 0.333 Ti 0.333 Mo 0.133 O2, etc.), various high-capacity lithium-ion based materials (e.g., rock salt Li2Mn 2 / 3 Nb 1 / 3 O2F、Li2Mn 1 / 2 Ti1 / 2 O2F、Li 1.5 Na 0.5 MnO 2.85 I 0.12 etc.) and many other types of lithium-containing disordered, layered, lithium feldspar, olivine or spinel type active materials or mixtures thereof, containing at least oxygen or fluorine or sulfur and at least one transition metal and / or other lithium transition metal (TM) oxide or phosphate or sulfate (or mixed) cathode active materials that rely on lithium (Li) insertion and changes in TM oxidation state (including but not limited to those that can be doped or heavily doped; including but not limited to those with compositional or core-shell morphology gradients; including but not limited to those that can be partially fluorinated or contain some meaningful fluorine fraction in their composition (e.g., about 0.001-10 at.%), etc.). It should also be understood that the various aspects are applicable to high voltage lithium transition metal oxide (or phosphate, sulfate, mixed metal or other) cathodes, wherein the transition metal and oxygen (O) are covalently bonded and both the transition metal and oxygen participate in electrochemical redox reactions during charge and discharge (including but not limited to those oxides, phosphates, sulfates or mixed cathodes that may contain at least about 0.25 at.% of Mn, Fe, Ni, Co, Nb, Mg, Cr, Mo, Zr, W, Ta, Ti, Hf, Y, La, Sb, V, Sn, Si or Ge). Illustrative examples of suitable conversion cathodes for preferred batteries may include, but are not limited to: metal fluorides, metal oxyfluorides, metal chlorides, metal sulfides, metal selenides, various mixtures thereof, composite materials and / or others. 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, various mixtures, alloys, and combinations thereof, and the like. In some designs, the production of nanocomposites and / or core-shell structures comprising metal fluorides may be advantageous for improving their performance and stability. In some designs, it may be advantageous to dope the metal fluorides with oxygen or to utilize metal oxyfluorides. In the fully lithiated state, the pure metal fluoride is converted to a composite material comprising a mixture of metal and LiF clusters (or nanoparticles). Examples of overall reversible reactions for conversion-type metal fluoride cathodes include: reaction, or FeF3-based cathode reaction. It will be understood that metal fluoride-based cathodes can be prepared in a lithium-free, partially lithiated, or fully lithiated state. In addition to fluorides, other illustrative examples of conversion-active electrode materials can include, but are not limited to, various metal oxyfluorides, sulfur fluorides, chlorofluorides, oxychlorofluorides, oxysulfur fluorides, fluorophosphates, sulfur phosphates, sulfur fluorophosphates, metal mixtures (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 NaF), metal oxyfluorides, metal oxides, metal sulfur fluorides, metal fluorophosphates, metal sulfides, metal oxysulfur fluorides, various combinations thereof, etc.) and / or other salts containing halogens or sulfur or oxygen or phosphorus or combinations of these elements, etc. In some designs, the fluorine in the metal fluoride can be completely or partially replaced by other halogens (such as chlorine, bromine or iodine, etc.) or mixtures thereof to form corresponding metal chlorides or metal fluoride-chloride and / or other metal halide complexes. Another promising and suitable example of a conversion-type cathode active material is sulfur (S) (in a lithium-free state) or lithium sulfide (Li2S, in a fully lithiated state). In some designs, selenium (Se) can also be used together with sulfur or alone to form such a cathode active material. In some designs, preparing nanocomposites and / or core-shell structures comprising S, Li2S, Se, Li2Se or various mixtures and combinations thereof may be beneficial for enhancing their performance and stability. In some designs, the conversion-type active cathode material may also advantageously comprise a metal oxide or a mixed metal oxide. In some designs, such a (nano)composite material may also advantageously comprise a metal sulfide or a mixed metal sulfide. In some examples, the mixed metal oxide or mixed metal sulfide may comprise lithium. In some examples, the mixed metal oxide may comprise titanium or vanadium or manganese or iron metal. In some examples, the lithium-containing metal oxide or metal sulfide may exhibit a layered structure. In some examples, the metal oxide or mixed metal oxide or metal sulfide or mixed metal sulfide may advantageously have both ionic and electrical conductivity (e.g., at about 10 -7 to about 10 +4 S / cm). In some examples, various other intercalation-type active materials can be used in place of or in addition to metal oxides or metal sulfides. In some designs, such intercalation-type active materials are in the potential range close to S or Li2S (e.g., relative to Li / Li +In some designs, the use of so-called lithium air cathodes (e.g., cathodes whose active material is lithiated Li2O2, Li2O, or LiOH) or similar metal air cathodes based on sodium, potassium, calcium, aluminum, iron, manganese, zinc, and / or other metals (rather than lithium) can also be beneficial due to their extremely high capacity. In some designs, such cathode active materials should ideally react reversibly with oxygen or oxygen-containing species in the electrochemical cell and disappear completely upon complete delithiation (removal of the metal). Cathode active materials with this characteristic can also be considered conversion cathodes.

[0169] In some preferred embodiments, the surface of the cathode active material (e.g., an insertion-type cathode material such as LCO, NCM, NCMA, NCA, LMO, LMNO, LFP, LMP, LMFP, etc., or a conversion-type active material containing S, Li2S, metal sulfides, metal fluorides, etc.) can be coated with a layer of ceramic material. Illustrative examples of preferred coating materials for such cathodes include, but are not limited to, titanium dioxide (e.g., TiO2), tantalum oxide (Ta2O5), aluminum oxide (e.g., Al2O3), tungsten oxide (e.g., WO), chromium oxide (e.g., Cr2O3), niobium oxide (e.g., NbO or NbO2), and zirconium oxide (e.g., ZrO2), lithium phosphate (e.g., Li3PO4), lithium oxythiophosphate (e.g., Li3P 1+x O4S 4x ) and their various mixtures, alloys and combinations. In some designs, such ceramic materials may also contain lithium (Li), such as lithium phosphate, lithium thiophosphate, lithium titanate, lithium tantalate, lithium aluminate, lithium tungstate, lithium chromate, lithium niobate, lithium zirconate and their various alloys, mixtures and combinations. In other preferred embodiments, LCO, NCM, NCMA, NCA, LFP, LMFP, LMP, LMO or LMNO may be doped with aluminum, titanium, magnesium, niobium, zirconium, chromium, hafnium, tantalum, tungsten, molybdenum or lanthanum. In some designs, the preferred cathode current collector material is aluminum or an aluminum alloy. In some designs, the preferred battery cell includes a polymer separator. In some preferred embodiments, the polymer separator is made of or contains polyethylene, polypropylene or a mixture thereof. In some preferred embodiments, the surface of the polymer separator is coated with a layer of ceramic material. Examples of preferred coating materials for polymer separators include, but are not limited to, titanium oxide (TiO2), aluminum oxide (Al2O3), aluminum hydroxide or aluminum oxide hydroxide, zirconium oxide (ZrO 2), magnesium oxide (MgO) or magnesium hydroxide or aluminum oxyhydroxide. In some designs, the preferred battery cell includes a diaphragm based on or containing ceramics (e.g., a ceramic / polymer composite). The ceramic or ceramic component of such a ceramic or diaphragm containing ceramics may include titanium oxide (TiO2), aluminum oxide (Al2O3), aluminum hydroxide or aluminum oxyhydroxide, zirconium oxide (ZrO2), magnesium oxide (MgO) or magnesium hydroxide or aluminum oxyhydroxide. In some designs, the ceramic or ceramic component of such a ceramic or diaphragm containing ceramics may include ceramic particles (e.g., elongated particles, nanofibers, flaky particles, randomly shaped particles including nanoparticles, etc.).

[0170] One aspect relates to a lithium-ion battery having a hybrid anode (e.g., including a silicon-containing active material and a graphite active material, etc.) exhibiting a relatively high areal capacity loading and a suitably matched (by areal capacity) cathode (e.g., having a slightly lower areal capacity loading, selected based on a desired negative electrode (N) to positive electrode (P) ratio, N / P ranging 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; in other designs, from about 1.25 to about 1.35; wherein 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, if the electrode areal capacity loading exceeds about 1-2 mAh / cm 2 Even if the electrode area capacity exceeds about 4-5 mAh / cm 2 , and even if the electrode area capacity exceeds about 6-8 mAh / cm 2%, then the performance characteristics and cycling stability of lithium-ion batteries containing some such hybrid anodes (particularly for hybrid anodes with high silicon content or high silicon active material particle content - for example, for hybrid anodes with about 3-60 wt.% Si; in some designs, hybrid anodes with about 10-20 wt.% Si or about 20-40 wt.% Si or about 40-60 wt.% Si, or for hybrid anodes with about 20-100% of the total hybrid anode capacity of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.); in some designs, with about 50-70% or about 70-80% or about 80-90% or about 90-95% or about 95-99% of the total hybrid anode capacity of silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.)) may become particularly unsatisfactory, especially for applications requiring long calendar life or long cycle life or low first cycle loss or other performance. However, higher loadings are beneficial for reducing the cost of energy storage devices and increasing their energy density. One or more embodiments of the present disclosure relate to the synthesis process, composition, and various physical and chemical properties of the graphite and / or binder in such a hybrid anode, which has an electrode area loading of about 2 mAh / cm 2 to about 5 mAh / cm 2 The performance is satisfactory when the load is about 5 mAh / cm 2 to about 8 mAh / cm 2 Provides better performance when the load is about 8mAh / cm 2 to about 16 mAh / cm 2 Even better performance is provided when the areal capacity loading of the electrode composition can be in the range of about 2 mAh / cm in some designs (e.g., the areal capacity loading of the electrode composition can be in the range of about 2 mAh / cm 2 to about 16 mAh / cm 2 ).

[0171] One aspect relates to a lithium-ion battery having a hybrid anode (e.g., including silicon-containing active material particles and graphite active material particles, etc.) that exhibits high energy. In some designs, for multi-layer (e.g., stacked or wound) medium-sized battery cells (e.g., battery cells with a battery capacity in the range of 0.2 Ah to about 10 Ah), if the hybrid anode of the lithium-ion battery does not contain suitable graphite or binder, the degradation of the lithium-ion battery may become particularly undesirably fast, and for large batteries (e.g., batteries with a battery capacity in the range of about 10 Ah to about 40 Ah), even for very large batteries (e.g., batteries with a battery capacity in the range of about 40 Ah to about 400 Ah) or giant batteries (e.g., batteries with a battery capacity in the range of about 400 Ah to about 4000 Ah), the degradation of the lithium-ion battery may become particularly undesirable fast. This is particularly true for batteries in the range of 50 to 60 wt. % or even larger, particularly if the hybrid anode contains a moderate to relatively high proportion of Si (e.g., about 3-60 wt. %; in some designs, about 10-20 wt. % or about 20-40 wt. % or about 40-60 wt. %), or if the silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) contribute a moderate or relatively high proportion to the total anode capacity (e.g., about 20-100%; in some designs, about 50-70% or about 70-80% or about 80-90% or about 90-95% or about 95-99%). However, multi-layer medium or large batteries may be attractive for certain electronic devices, while multi-layer large, ultra-large, or giant batteries may be particularly attractive for certain electric transportation or grid storage applications. One or more aspects of the present disclosure facilitate the use of appropriate graphite (or more broadly, carbon) and an appropriate binder with suitable microstructural, chemical, physical, and / or other properties in hybrid anodes to alleviate or overcome some or all of such limitations of hybrid anodes and significantly improve the performance of such lithium-ion batteries.

[0172] Figure 1 An exemplary metal ion (e.g., Li-ion) battery is shown in which the components, materials, methods and / or other techniques described herein, or combinations thereof, may be applied according to various embodiments. A cylindrical battery is shown for illustrative purposes, but other types of battery shapes, including diamond or pouch-shaped (laminated) batteries, may also be used as desired. The example battery 100 includes a negative electrode (positive electrode or anode) 102, a positive electrode (negative electrode or cathode) 103, a separator 104 between the anode 102 and the cathode 103, an electrolyte (impliedly shown) impregnating the separator 104, a battery housing 105, and a seal 106 that seals the battery housing 105. The electrolyte ionically couples the anode (negative electrode) and the cathode (positive electrode). The electrolyte is between the anode and the cathode. In some embodiments, the battery 100 further 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.

[0173] One aspect relates to a lithium-ion battery having a hybrid anode (e.g., comprising silicon-containing active material particles and graphite active material particles, etc.), which exhibits high energy and excellent performance characteristics. Intuitively, one skilled in the art might assume that graphite, or more broadly, carbon materials, which exhibit excellent stability or rate performance in lithium-ion battery anodes based on pure intercalated graphite (or more broadly, carbon) active materials, would provide optimal performance when used in a hybrid anode containing a silicon-based active material (e.g., Si-C nanocomposites, etc.). Unexpectedly, the present inventors have discovered that this assumption is not true in many designs. In some designs, graphites may exhibit relatively poor performance on their own (e.g., relatively low stability or rate capability when calendered / densified to the same density as a benchmark graphite anode, or low volumetric capacity with comparable stability characteristics, etc.), but can significantly improve the performance of the hybrid anode, particularly when their mass fraction or contribution to the total capacity is relatively small (e.g., when such graphite (and more broadly, carbon), which may be referred to in this disclosure as "high quality graphite for hybrid anodes (GRSBA)", contributes approximately 1% of the reversible capacity relative to the total reversible capacity of the hybrid anode). 50% or less; in some designs, when such graphite (carbon) provides a capacity contribution of about 40% or less relative to the total anode capacity; in some designs, the capacity contribution is about 30% or less relative to the total anode capacity; in some designs, the capacity contribution is about 20% or less relative to the total anode capacity; in some designs, the capacity contribution is about 15% or less relative to the total anode capacity; in some designs, the capacity contribution is about 10% or less relative to the total anode capacity; in some designs, the capacity contribution is about 8% or less relative to the total anode capacity; in some designs In some designs, the capacity contribution is about 6% or less relative to the total anode capacity; in some designs, the capacity contribution is about 4% or less relative to the total anode capacity; in some designs, the capacity contribution is about 2% or less relative to the total anode capacity; in some designs, the capacity contribution is about 1% or less relative to the total anode capacity; for example, in some designs, when such GRSBA contributes about 0.2% to about 1% of the total hybrid anode 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 In some designs, the battery contributes 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; and in still other designs, about 40% to about 50% of the total capacity - for example, when measured in a half-cell at a potential range of 0.01-1.00 V relative to Li / Li+.In some designs, the ratio of the capacity of the GRSBA to the capacity of all silicon-containing active material particles (e.g., Si-C nanocomposite particles, etc.) is preferably in the range of about 1:200 to about 1:1 (in some designs, about 1:200 to about 1:50; in other 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, about 2:3 to about 1:1). In some designs, the hybrid anode may include two or more types of silicon-containing active material particles (e.g., each type exhibiting a significantly different composition and / or significantly different specific capacity and / or significantly different size distribution and / or significantly different specific surface area and / or significantly different morphology, etc.). In some designs, the hybrid anode may include two or more types of graphite (or broadly referred to as carbon) particles. In some designs, only a portion of the graphite (or carbon, broadly speaking) particles may be of the GRSBA type (the remainder being high-performance graphite commonly used in many graphite anodes of conventional commercial lithium-ion batteries). In some designs, the total weight of the GRSBA in the hybrid anode may range from about 1 wt.% to about 80 wt.% (in some designs, from about 1 wt.% to about 10 wt.%; in other designs, from about 10 wt.% to about 20 wt.%; in other designs, from about 20 wt.% to about 50 wt.%; and in yet other designs, from about 50 wt.% to about 80 wt.%) relative to the weight of all active material particles in the hybrid anode. In some designs, the total weight of the GRSBA in the hybrid anode may advantageously range from about 1 wt.% to about 50 wt.% relative to the weight of all active material particles in the hybrid anode. In some designs, the total weight of the GRSBA in the hybrid anode may advantageously range from about 2 wt.% to about 20 wt.% relative to the weight of all active material particles in the hybrid anode.

[0174] In one or more embodiments of the present disclosure, several key physical, chemical, mechanical, structural or other properties of the GRSBA can be particularly advantageous when used in a lithium-ion battery having the hybrid anode. Various types of graphite (or carbon) are suitable for use as the GRSBA in the hybrid anode to achieve the superior lithium-ion battery performance characteristics as described herein. In some designs, the addition of a suitable graphite (GRSBA) to a silicon-containing anode composition can provide higher volumetric capacity, lower resistance, and better rate performance, even compared to a "pure" silicon-containing anode (e.g., a non-hybrid anode containing only silicon-containing active material particles without any intercalated active material particles). Thus, described herein are superior lithium-ion battery cells, superior lithium-ion batteries, and superior lithium-ion battery packs that include a suitable GRSBA in a hybrid anode.

[0175] In one or more embodiments of the present disclosure, graphite exhibits relatively low hardness, which may be one of the key characteristics that provide excellent performance as a GRSBA (one or more) in the hybrid anode (having silicon-containing active material particles). In order to test the hardness of the graphite (carbon) powder sample, the graphite (carbon) particles arranged in a dry powder are placed on a hardened steel disk and distributed as evenly as possible in the smallest possible amount, and the particles are as dispersed as possible so that individual particles can be distinguished directly on the hardened steel surface. The hardened steel disk with dispersed graphite particles is then added to the Shimadzu MCT micro-compression test tool. The hardened steel disk is placed on a platform that can be moved between an optical microscope and a compressor tip. The optical microscope of the tool is used to find individual particles from the graphite sample. Once a single graphite particle is found, the platform is switched to the compressor tip and a hardness test is performed, pressing in (crushing) a single graphite particle while measuring force and displacement to calculate the pressure (Cx, expressed in MPa) required to deform the graphite particle by 10% (linear dimension). At least ten graphite particles are measured for each sample, and the average Cx is calculated.

[0176] Figure 2Table 1 in the present invention lists examples of Cx measurements for selected graphite (carbon) samples (numbered G1 to G22), as well as examples of other suitable graphite particles, including graphite materials known as "soft graphite." Graphite particles with average Cx values ​​in the range of 1 to 10 MPa are sometimes referred to herein as "soft graphite." Graphite samples with Cx values ​​in the range of about 1 MPa to about 30 MPa have been found to be most suitable for use as the GRSBA in part or all of the hybrid anode. In some designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may preferably exhibit an average Cx value of less than about 30 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 25 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 20 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 15 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 11 MPa. values; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 10 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 9 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 8 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 7 MPa; in other designs, the GRSBA (or at least a majority, 50 wt.% or more of the GRSBA) may more preferably exhibit an average Cx value of less than about 6 MPa. In some designs, the majority of the GRSBA in the hybrid anode (e.g., about 50-60 wt.% or about 60-70 wt.% or about 70-80 wt.% or about 80-100 wt.%) may preferably 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 or about 7 MPa to about 10 MPa or about 10 MPa to about 14 MPa or about 14 MPa to about 18 MPa).In some designs, the majority of the GRSBA in the hybrid anode (e.g., about 50-60 wt.%, or about 60-70 wt.%, or about 70-80 wt.%, or about 80-100 wt.%) may preferably 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, or about 20 MPa to about 24 MPa, or about 24 MPa to about 30 MPa, or about 20 MPa to about 30 MPa). It should be noted that in some designs, too soft graphite (e.g., an average Cx value of less than 1 MPa) may result in reduced anode performance or reduced rate performance, while too hard graphite (e.g., an average Cx value exceeding about 30 MPa; in some designs, exceeding about 25 MPa) may not achieve sufficient or ideal volumetric capacity or energy density or discharge rate or even cycling stability, especially for silicon-rich hybrid anodes. Interestingly, typical measured Cx values ​​for suitable silicon-containing active material particles (e.g., Si-C particles, C-coated SiOx particles, etc.) often exceed 40 MPa (e.g., in some designs, Cx can be from about 40 MPa to about 60 MPa; in other designs, Cx is from about 60 MPa to about 80 MPa; in other designs, Cx is from about 80 MPa to about 120 MPa; in other designs, Cx is from about 120 MPa to about 160 MPa; and in other designs, Cx is from about 160 MPa to about 400 MPa), making them quite hard. Furthermore, some silicon-containing active material particles can be so brittle that they break before reaching 10% deformation, and their fracture strength can be less than 400 MPa. Therefore, the reported findings may indicate that combining such relatively hard silicon-containing active material particles (e.g., with Cx values ​​exceeding 40 MPa in some designs) with an appropriate (or ideal) amount of relatively soft GRSBA particles for use in high-quality hybrid anodes can be particularly advantageous.

[0177] In one or more embodiments of the present disclosure, the tap density of the graphite particles can be another key characteristic that provides excellent performance as a GRSBA in the hybrid anode (having silicon-containing active material particles). For the tap density measurements disclosed herein, graphite (carbon) particles arranged as a dry powder are added to a graduated cylinder, which is then loaded into the TD1 tap density tester tool and initially tapped 10 times. The initial volume [mL] is then determined and recorded. Depending on the sample size, the graduated cylinder is further "tapped" a different number of times. For example, a filled 25mL graduated cylinder (typically suitable for approximately 10g samples) is tapped 6,000 times. A filled 100mL graduated cylinder (typically suitable for approximately 50g samples) is tapped 12,000 times. After the "tapping" is completed, the final volume is measured and the tap density (mass / volume) is calculated using the added mass and the observed volume, as known in the art.

[0178] Figure 3 Table 2 shows exemplary tap density measurements for each selected graphite (carbon) sample (exemplary graphite samples G1 to G22 described in Table 1). In some designs, suitable tap density values ​​for GRSBA can generally be 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 other designs; from about 0.900 g / ml to about 1.250 g / ml in other designs; and from about 0.900 g / ml to about 1.200 g / ml in other designs). However, in some designs, too high a density (e.g., in some designs, exceeding about 1.250 g / ml; in other designs, exceeding about 1.100 g / ml; in other designs, exceeding about 1.200 g / ml) may reduce the performance of hybrid anode lithium-ion battery cells. In some designs, too low a density (e.g., in some designs, below about 0.050 g / ml; in other designs, below about 0.100 g / ml), such as certain expanded graphites, may also lead to adverse effects, including reduced volumetric capacity performance in some cases. In some designs, graphite (carbon) samples having tap density values ​​from about 0.900 g / ml to about 1.100 g / ml (e.g., in some designs, from about 0.900 g / ml to about 0.950 g / ml; in other designs, from about 0.950 g / ml to about 1.000 g / ml; in other designs, from about 0.950 g / ml to about 1.050 g / ml; and in yet other designs, from about 1.050 g / ml to about 1.100 g / ml) were generally found to perform particularly well as GRSBAs in hybrid anodes. In some designs, graphite (carbon) samples having tap density values ​​of about 0.900 g / ml to about 1.200 g / ml (e.g., in some designs, the tap density is about 0.900 g / ml to about 0.950 g / ml; in other designs, the tap density is about 0.950 g / ml to about 1.000 g / ml; in other designs, the tap density is about 0.950 g / ml to about 1.050 g / ml; in other designs, the tap density is about 1.050 g / ml to about 1.100 g / ml; in other designs, the tap density is about 1.100 g / ml to about 1.200 g / ml) are generally found to perform particularly well as GRSBAs in hybrid anodes.

[0179] In one or more embodiments of the present disclosure, the pycnometric density of the graphite particles (measured using a nitrogen (N2) pycnometer) can be another key property that provides excellent performance as a GRSBA in the hybrid anode (with suitable silicon-containing active material particles).

[0180] The pycnometer density measurements described in this article were performed using a Micromeritics AccuPycII 1340 pycnometer equipped with a 1cc container. Sample preparation: Vortex a vial of sample powder for 15 seconds and let it sit for several minutes before use. Using an electronic balance, weigh 195mg-200mg of sample powder into the designated weighing cup for the pycnometer density measurement.

[0181] Figure 4 Table 3 in shows example pycnometer density measurements made for each selected graphite (carbon) sample (exemplary graphite samples G1 to G8, G10, G13 to G16, G18 to G22). In some designs, suitable GRSBA pycnometer-measured density values ​​can generally be from about 2.150 g / ml (or g / cc) to about 2.350 g / ml (g / cc) (e.g., from about 2.150 g / ml to about 2.200 g / ml in some designs; from about 2.200 g / ml to about 2.250 g / ml in other designs; from about 2.250 g / ml to about 2.275 g / ml in other designs; from about 2.275 g / ml to about 2.300 g / ml in other designs; from about 2.300 g / ml to about 2.325 g / ml in other designs; and from about 2.325 g / ml to about 2.350 g / ml in other designs). Note that in some designs, the theoretical density of crystal-perfect graphite at room temperature and atmospheric pressure is about 2.265 g / ml (g / cc). In some designs, a pycnometer-measured density that is too low (e.g., below about 2.150 g / cc) may result in excessive losses during the first or subsequent cycles or lead to other poor battery performance characteristics. In some designs, a pycnometer-measured density that is too high may also degrade battery performance characteristics or cause challenges during slurry and electrode preparation and may indicate the presence of microporosity.

[0182] In one or more embodiments of the present disclosure, the shape of the graphite sample may also affect its performance as the GRSBA(s) in the hybrid anode (with suitable silicon-containing active material particles). In some designs, spherical (e.g., spherical, nearly spherical, or rounded, with primarily rounded edges) GRSBA samples may perform better when used in larger proportions relative to the silicon-containing active material particles. In some designs, flat GRSBA samples may perform better when used in smaller proportions relative to the silicon-containing active material particles. In some designs, it may be advantageous to combine spherical GRSBA samples with flat (more two-dimensional, 2D) GRSBA samples.

[0183] Figure 5A 、 5B 5C, 5D, 5E and 5F show SEM micrographs of each selected graphite (carbon) sample. Figure 5A An SEM micrograph 502 of a portion of a G1 example graphite sample is shown. Figure 5B An SEM micrograph 504 of a portion of a G2 example graphite sample is shown. Figure 5C An SEM micrograph 506 of a portion of a G3 example graphite sample is shown. Figure 5D An SEM micrograph 508 of a portion of a G4 example graphite sample is shown. Figure 5E An SEM micrograph 510 of a portion of a G5 example graphite sample is shown. Figure 5F An SEM micrograph 512 of a portion of an example graphite sample G6 is shown. Some graphite samples have jagged edges (e.g., G1 of 502, G2 of 504, G3 of 506), while some have rounded edges (e.g., G4 of 508, G5 of 510, G6 of 512). Some graphite samples are primarily composed of flat particles (e.g., G1 of 502, G2 of 504, G3 of 506), while some have a mixture of flat and rounded (more spherical) particles (e.g., G4 of 508, G5 of 510, G6 of 512).

[0184] To perform the particle size analysis disclosed herein, samples were prepared using a Malvern Mastersizer 3000 laser PSA (particle size distribution analysis) instrument within 1 hour before analysis. The original sample bottle was vortexed for 15 seconds to ensure that the powder was uniform. Approximately 20.0 mg (+ / - 5.0 mg) of the thoroughly mixed sample was weighed and transferred to a 20 mL glass bottle. After the sample was transferred to the glass bottle, 15-20 mL of a 20 g / L lecithin Isopar G solution (dispersant) was added to the glass bottle. In order to break down agglomerated particles that may be present in some samples, the sample was also ultrasonically treated for 30 minutes. The sample bottle containing the powder, lecithin, and Isopar G was then vortexed for 15 seconds using the maximum setting of the vortexer. After the sample was prepared, it was analyzed using a Malvern Mastersizer 3000 laser PSA instrument.

[0185] In one or more embodiments of the present disclosure, the size distribution of the graphite particles may also affect their performance as GRSBA(s) in the hybrid anode (having suitable silicon-containing active material particles). In some designs, both overly large particles and overly small particles may reduce the performance of the lithium-ion battery cell having a hybrid anode. For example, overly large particles may cause localized inhomogeneities in the distribution of the anode's mechanical properties and its areal capacity. For example, overly small particles may increase the tortuosity of the anode (e.g., for the same anode density), thereby affecting the charge rate performance and power capacity of the lithium-ion battery (e.g., for a fixed areal capacity loading), requiring the use of a larger binder fraction or reducing the anode fill rate and volumetric capacity in some designs. However, the total mass fraction (or total capacity fraction) of the GRSBA, the areal capacity loading, the size of the silicon-containing active material particles, the desired battery characteristics, and / or other factors may affect the most ideal size distribution of the GRSBA. However, in some (e.g., most) designs, the appropriate D of the GRSBA is preferably 0.05. 50 The value may be from about 2 μm to about 22 μm (in some designs, from about 2 μm to about 5 μm; in other designs, from about 5 μm to about 10 μm; in other designs, from about 10 μm to about 12 μm; in other designs, from about 12 μm to about 17 μm; in other designs, from about 11 μm to about 17 μm; in other designs, from about 17 μm to about 22 μm). In some (e.g., most) designs, a suitable D for a GRSBA is 90The values ​​may range from about 4 μm to about 30 μm (in some designs, about 4 μm to about 10 μm; in other 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, about 26 μm to about 30 μm). In some (e.g., most) designs, a suitable D for a GRSBA is 10 Values ​​may range from about 0.5 μm to about 15 μm (in some designs, about 0.5 μm to about 2.5 μm; in other 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, about 11 μm to about 15 μm).

[0186] Figure 6 Table 4 in the table lists the D values ​​of selected graphite (carbon) samples (exemplary graphite samples G1 to G10, G13 to G22). 10 、D 50 and D 90 In the examples shown, the particle size distribution (PSD) was measured using the Laser Particle Size Analyzer (LPSA) described herein.

[0187] In one or more embodiments of the present disclosure, the BET-SSA of the graphite particles may also affect their performance as a GRSBA in the hybrid anode (with suitable silicon-containing active material particles). In some designs, both too high a BET-SSA and too low a BET-SSA may reduce the performance of lithium-ion batteries using hybrid anodes. However, the optimal BET-SSA value may depend on a variety of factors, including the battery characteristics required for a particular application. However, in some (e.g., most) designs, a suitable BET-SSA value range for the GRSBA may be about 0.450 m 2 / g to about 450m 2 / g (in some designs, about 0.450m 2 / g to about 1m 2 / g; in other designs, about 1m 2 / g to about 2m 2 / g; in other designs, about 2m 2 / g to about 3m 2 / g; in other designs, about 1m 2 / g to about 3m 2 / g; in other designs, about 3m 2 / g to about 5m 2 / g; in other designs, about 5m 2 / g to about 10m 2 / g; in other designs, about 10m 2 / g to about 20m 2 / g; in other designs, about 20m 2 / g to about 100m 2 / g; in other designs, about 100m 2 / g to about 450m 2 However, in some designs (e.g., when long calendar or long cycle life is important or a lower proportion 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 to about 5-15m 2 / g; in some designs, about 1m 2 / g to about 5m 2 / g; in some other designs, about 2m 2 / g to about 3m 2 / g; in some other designs, about 1m 2 / g to about 3m 2 / g).

[0188] Figure 7 Table 5 in the accompanying drawings lists the BET-SSA values ​​for selected graphite (carbon) samples (exemplary graphite samples G1 to G22). In the examples shown, the BET-SSA of each exemplary graphite particle population (G1 to G22) was measured by nitrogen physical adsorption (approximately 77 K) on a powder sample degassed at 300° C. under vacuum conditions for 10 hours.

[0189] The microstructural characteristics of the graphite (carbon) sample may also affect its performance as a GRSBA in the hybrid anode (with suitable silicon-containing active material particles). Some of these characteristics can be revealed by X-ray diffraction (XRD) techniques, Raman spectroscopy and / or other characterization techniques.

[0190] For the microstructural characterization analysis disclosed in this article, graphite (carbon) particle powder was arranged into a powder form using standard material preparation methods for powder XRD analysis. An aluminum sample holder was used, and a 1mm glass slide was placed at the bottom of the sample hole to prevent the metal sample holder from affecting the measurement results. Approximately 100-300 mg of each powder was added to the sample holder and smoothed using a glass slide to obtain a uniform sample surface. A copper X-ray source was used. All measurements were performed using a Rigaku X-ray diffractometer (Rigaku Smartlab). The tube voltage and tube current were 40 kV and 44 mA, respectively, for the Cu anode. All measurements were performed using the Bragg-Brentano measurement geometry between 10 and 90 degrees 2θ with a continuous scan rate of 1 degree per minute. In addition to the 5.0 degree Soller slit, a 10 degree incident limiting slit was used for both the incident and detector. Copper K-β (K β The radiation was filtered directly through a nickel filter before reaching the one-dimensional silicon strip detector. The full width at half maximum (FWHM) value of the graphite (002) reflection peak was calculated by fitting the corresponding peak with a Gaussian-Lorentzian cross product function, which is defined as follows: Where y0 is defined as the function basis, x c is the peak center, A is the peak amplitude, w is the peak width, and s is the parameter that defines the peak shape. Based on the known Scherrer formula, the Scherrer grain size is directly calculated from the fitting data of each graphite (carbon) sample: where D is the calculated grain size, K is the shape factor, set to 0.7, and λ is the X-ray wavelength. β is the FWHM of the peak at the Bragg angle, and θ is the Bragg angle calculated from the 2θ position of the (002) reflection peak.

[0191] In some designs, a (002) graphite reflection peak with a full width at half maximum (FWHM) that is too narrow or too wide, and correspondingly, an average grain size of the (002) reflection peak estimated using the Scherrer equation that is too large or too small, may reduce the performance of lithium-ion battery cells using hybrid anodes. However, in some designs, the optimal value for a particular application may depend on the proportion of GRSBA in the hybrid anode, the nature of the silicon-containing anode particles, the areal capacity loading, the amount and type of binder used, the desired battery performance characteristics, and / or other factors. However, in some (e.g., most) designs, a suitable FWHM of the (002) graphite reflection peak (measured using the analytical procedure and apparatus employed) is preferably in the range of about 0.220 degrees to about 5.620 degrees (in some designs, about 0.220 degrees to about 0.250 degrees; in other designs, about 0.250 degrees to about 0.300 degrees; in other designs, about 0.300 degrees to about 0.340 degrees; in other designs, about 0.340 degrees to about 0.500 degrees; in other designs, about 0.500 degrees to about 0.600 degrees; in other designs, about 0.600 degrees to about 1.220 degrees; in other designs, about 1.220 degrees to about 5.620 degrees). Moreover, in some (e.g., most) designs, a suitable GRSBA average crystallite size for the (002) reflection peak estimated using the Scherrer equation (as measured using the analytical procedure and apparatus employed) preferably ranges from about 1 nm to about 40 nm (in some designs, from about 1 nm to about 5 nm; in other designs, from about 5 nm to about 10 nm; in other designs, from about 10 nm to about 15 nm; in other designs, from about 15 nm to about 21 nm; in other designs, from about 15 nm to about 30 nm; in other designs, from about 21 nm to about 26 nm; in other designs, from about 26 nm to about 29 nm; in other designs, from about 29 nm to about 40 nm).

[0192] Figure 8A A graphical representation 802 of the XRD spectra of each selected graphite (carbon) sample (exemplary graphite samples G1 , G2, G3, G4, and G6) is shown.

[0193] Figure 8B Table 6 shows selected results of X-ray diffraction measurements of selected graphite (carbon) samples (exemplary graphite samples G1 to G22, and some other suitable graphite examples). The X-ray analysis results shown are from left to right: (1) according to the (002) reflection angle (in (1) the interplanar spacing (also called d-spacing) of each graphite sample determined by θ; (2) the full width at half maximum (FWHM) of the (002) reflection peak of each graphite sample, expressed in degrees; (3) the angle of the (002) reflection peak of each graphite sample, expressed in degrees; (4) the average crystallite size of the (002) reflection peak of each graphite sample estimated using the Scherrer equation, expressed in nm; and (5) the intensity of the (002) reflection peak, expressed in counts.

[0194] For the Raman analysis described in this article, graphite (carbon) particles were arranged in a dry powder form using standard material preparation methods for Raman scattering experiments. A sample of graphite (carbon) powder was collected and placed on a glass slide using a spatula. The powder was then firmly pressed into a strip on the glass slide, transferring a sufficiently thick layer of powder from the spatula to the top of the strip. This process was repeated until the strip was completely covered with powder. Once the strip was completely covered with powder, any remaining powder on the strip was blown off using a handheld air pump. Once the remaining powder on the strip was blown off, the sample was ready for Raman analysis. The samples were analyzed using a Renishaw In-Via Qontor Raman microscope with a 532 nm laser diode (maximum laser power of 3 mW). A 100x 1.2 numerical aperture (NA) objective was used to focus the laser beam on the sample. Unless otherwise noted, the laser beam was intentionally aimed at the center of large particles. The spectra were recorded using a Renishaw 1800 diffraction grating with an acquisition time of 3 seconds. Ten spectra were recorded for each sample and averaged to improve the signal-to-noise ratio. The following graphite (carbon) peaks were selected in the spectra: D peak (1200-1500 cm -1 ), G peak (1500-1750cm -1 ), 2D1 peak (2600-2800cm -1 ) and 2D2 peak (2400-3700cm -1 To calculate the D / G ratio, the spectrum was taken between 1000 and 2000 cm -1 After linear background subtraction within the range, the D peak range (1200-1500 cm -1 ) divided by the G peak range (1500-1750cm -1 ) in the G peak range. When calculating the 2D1 / G ratio, the 2D1 peak range (2600-2800cm -1 ) divided by the height of the 2D1 peak within the G peak range (1500-1750cm -1 ) The height of the G peak. -1 The G peak in the range of 2000-4000cm -1The peak heights of the 2D1 peaks within the range were calculated after linear background subtraction of each peak. The FWHM value was calculated using the Scipy (Scientific Python) peak quantification function scipy.signal.peak_widths, and the peak width was measured as 0.5 times the relative height.

[0195] In some designs, the FWHM values ​​of the D, G, and 2D1 bands of graphite (carbon) samples, as well as the D / G and 2D1 / G ratios, may be correlated with the performance of hybrid anode lithium-ion batteries. However, in some designs, the optimal values ​​for a particular application may depend on the proportion of GRSBA in the hybrid anode, the nature of the silicon-containing anode particles, the areal capacity loading, the amount and type of binder, the desired battery performance characteristics, and / or other factors. However, in some (e.g., most) designs, an appropriate FWHM of the D band of the GRSBA (determined using the described method) is generally in the range of about 30 cm -1 to about 90cm -1 (In some designs, about 30cm -1 to about 40cm -1 ; in other designs, approximately 40cm -1 to about 60cm -1 ; in other designs, approximately 60cm -1 to about 70cm -1 In some designs, about 70 cm -1 to about 90cm -1 In some (e.g., most) designs, the FWHM of the G band suitable for GRSBA (determined using the described method) is typically in the range of about 5 cm -1 to about 105cm -1 (In some designs, about 5cm -1 to about 15cm -1 ; in other designs, approximately 15cm -1 to about 30cm -1 ; in other designs, approximately 15cm -1 to about 18cm -1 ; in other designs, approximately 18 cm -1 to about 22cm -1 ; in other designs, approximately 22 cm -1 to about 30cm -1 ; in other designs, approximately 30cm -1 to about 50cm -1 ; in other designs, about 50cm -1 to about 105cm -1 In some (e.g., most) designs, a suitable FWHM for the 2D1 band for GRSBA (determined using the described method) is typically in the range of about 30 cm-1 to about 110cm -1 (In some designs, about 30cm -1 to about 50cm -1 ; in other designs, about 50cm -1 to about 65cm -1 ; in other designs, approximately 65cm -1 to about 80cm -1 ; in other designs, approximately 80cm -1 to about 105cm -1 ; in other designs, approximately 105cm -1 to about 110cm -1 In some (e.g., most) designs, suitable D / G peak intensity ratios for GRSBA (determined using the described method) can generally range from about 0.02 to about 1.12 (in some designs, from about 0.02 to about 0.12; in other designs, from about 0.12 to about 0.30; in other designs, from about 0.08 to about 0.30; in other designs, from about 0.30 to about 0.50; in other designs, from about 0.50 to about 0.80; and in other designs, from about 0.80 to about 1.12). In some (e.g., most) designs, suitable 2D1 / G ratios for GRSBAs (determined using the described methods) can generally range from about 0.10 to about 0.90 (in some designs, about 0.10 to about 0.35; in other designs, about 0.35 to about 0.50; in other designs, about 0.41 to about 0.55; in other designs, about 0.41 to about 0.45; in other designs, about 0.45 to about 0.50; in other designs, about 0.50 to about 0.55; in other designs, about 0.50 to about 0.60; in other designs, about 0.30 to about 0.65; in other designs, about 0.60 to about 0.75; in other designs, about 0.75 to about 0.90).

[0196] Figure 9A Typical Raman spectra of selected graphite (carbon) samples are shown. Figure 9A Raman spectra 902 including D and G bands are shown, for example, graphite samples G1, G3, G4, and G6. Figure 9A A Raman spectrum 904 including a D band, a G band, a 2D1 band, and a 2D2 band is shown, for example, graphite samples G3 and G4.

[0197] Figure 9B Table 7 shows the processed Raman data of selected graphite (carbon) samples (exemplary graphite samples G1 to G12, G14 to G22, and other suitable graphite particle examples), with the values ​​in cm shown from left to right. -1 The FWHM of the D band peak is expressed in cm-1 The D peak position, D / G ratio, and -1 The FWHM of the G band peak is expressed in cm -1 Indicates the G band peak position.

[0198] Figure 9C Table 8 shows the Raman data of selected graphite (carbon) samples (exemplary graphite samples G2 to G5, G18, and other suitable graphite particle examples) after additional processing, showing from left to right the Raman data in cm -1 The 2D1 band peak position is expressed in cm -1 The FWHM of the 2D1 band peak and the 2D1 / G ratio are shown.

[0199] for Figure 10A 、 10B 10C, lithium-ion battery cells were produced using the following method: (i) an anode, wherein the Si-C nanocomposite active material (e.g., particles) contributed about 95%, about 98%, and about 100% of the capacity, while the GRSBA sample contributed about 5%, about 2%, and about 0% of the capacity (when normalized by the weight of the Si-C nanocomposite, the specific reversible Si-C nanocomposite capacity was about 1600 to about 1700 mAh / g, which corresponds to a silicon mass fraction of about 40 to about 44 wt.% in the Si-C composite particles), the anode being cast on a Cu current collector foil from a water-based suspension comprising the following solids: about 89.6 wt.% active material (for the anode, about 95%, about 98%, and about 100% of the capacity was contributed by the Si-C nanocomposite active material); % of anode:cathode (NP) areal capacity ratio of about 1.1:1 and an areal reversible capacity loading of about 3.6 mAh / cm 2Matched with the anode, (iii) a polymer ceramic separator, and (iv) a LiPF6-based electrolyte comprising: about 14.7 wt.% LiPF6, about 9.7 wt.% propylene carbonate (PC, cyclic carbonate), about 23.4 wt.% fluoroethylene carbonate (FEC, fluorinated cyclic carbonate), about 8.1 wt.% ethyl methyl carbonate (EMC, linear carbonate), about 7.8 wt.% diethyl carbonate (DEC, linear carbonate), about 34.1 wt.% ethyl propionate (EP, linear ester) and about 2.2 wt.% vinylene carbonate (VC, cyclic carbonate). All electrochemical (ECT) tests were performed using an Arbin Instruments LBT battery cycler running MITSXPRO software. The cycling voltage range was 2.5–4.4 V, with 1 C charge and 1 C discharge. The capacity check cycle was as follows: charge to 4.0 V at 1 C, then charge to 4.4 V at 0.5 C, then hold the voltage to 0.05 C, followed by discharge at 0.2 C. 50 The values ​​are in the range of 5 to 6 μm. In the above-mentioned lithium-ion battery cell example, the Si-C nanocomposite active material contributes approximately 95% of the capacity, wherein approximately 20 wt.% of the anode active material is GRSBA particles and approximately 80 wt.% of the anode active material is Si-C nanocomposite active material particles. In the above-mentioned lithium-ion battery example, the Si-C nanocomposite active material contributes approximately 98% of the capacity, wherein approximately 10 wt.% of the anode active material is GRSBA particles and approximately 90 wt.% of the anode active material is Si-C nanocomposite active material particles.

[0200] Figure 10AGraph 1002 is shown, showing the estimated number of cycles required to reach 80% state of health (SOH) (sometimes referred to as "N80") for each lithium-ion battery test cell containing an LCO cathode and a Si-containing anode (based on pure Si-C nanocomposite particles or Si-C nanocomposite particles mixed with appropriate GRSBA particles in these illustrative examples) by adding GRSBA. In some cases, N80 is a convenient metric for measuring the cycle life of a battery cell. N80 is obtained by estimating the number of cycles required to reach 80% of the cycle start capacity (during cycling at 25°C). The cycle start capacity is defined as the capacity at the third cycle. In graph 1002, lithium-ion battery cells have hybrid anodes using exemplary graphite particles G6, G7, and G23, respectively. The G23 graphite sample is an example of soft graphite. The plotted data for each hybrid type (exemplary graphite type) represents the average of the data for (a) a hybrid in which approximately 98% of the capacity is contributed by the Si-C nanocomposite active material and (b) a hybrid in which approximately 95% of the capacity is contributed by the Si-C nanocomposite active material. In the examples shown, using G6, G7 and G23 graphite samples, the cycling stability (cycle life) is estimated to be improved by 6-15%.

[0201] Figure 10B Graph 1012 is shown, which shows the anode capacity retention during cycling for lithium-ion battery cells containing an LCO cathode and a silicon-containing anode, where the anode active material comprises only Si-C nanocomposite particles or a mixture of Si-C nanocomposite particles as described above with appropriate GRSBA graphite particles. In this example, G6, G7, and G23 are used as GRSBAs. In graph 1012, lithium-ion battery cells with hybrid anodes use exemplary graphite particles G6, G7, and G23, respectively. The plotted data for each hybrid type (exemplary graphite type) represents the average of (a) a mixture in which approximately 98% of the capacity is contributed by the Si-C nanocomposite active material and (b) a mixture in which approximately 95% of the capacity is contributed by the Si-C nanocomposite active material. Graph 1012 plots the capacity versus cycle number for each cell type (anode containing G6, G7, G23, or no graphite), so the slope of the corresponding graph is an indicator of cycling stability. The smaller the slope (lower the gradient), the better the cycling stability. Compared to cells containing only Si-C nanocomposite particles in the anode active material, cells containing G6, G7, or G23 graphite exhibited a more gradual slope (less inclination). The addition of GRSBA improved cycling stability (decreased slope of the capacity retention curve) with only a slight decrease in pycnometer-determined anode capacity. Furthermore, cells containing G6 and G7 graphite samples exhibited a relatively small decrease in anode capacity compared to cells containing only Si-C nanocomposite particles in the anode active material.

[0202] Figure 10C Graphs (1022, 1024, 1026, 1028) are shown showing: (a) anode coating density after first lithiation, (b) anode coating density in the coated state (before calendering) and in the calendered state, (c) estimated volumetric energy density (simplified VED or VED), and (d) cycle start volumetric charge capacity (VQD) of a battery cell employing a silicon-containing anode (or coating density of the anode coating in the coated state and in the calendered state). In the examples shown, the cathode includes LCO and an anode active material comprising only Si-C nanocomposite particles or a mixture of Si-C nanocomposite particles as described above with appropriate GRSBA graphite particles. VQD is defined as the anode capacity (third cycle) (expressed in mAh) divided by the anode volume (expressed in cm 3 express ) . VED is defined as the battery energy (third cycle) (in Wh) divided by the battery external volume (in liters). In the example shown, G6, G7 and G23 were used as GRSBA (GRSBA contributed 2% and 5% of the total anode capacity, and Si-C nanocomposite particles contributed 98% and 95% of the total anode capacity). Figure 10C In each column of data plotted for each graphite-containing cell (from left to right, 1024 for G23, 1026 for G7, and 1028 for G6), the left data point represents the case where the Si-C nanocomposite particles contribute 98% of the total anode capacity, and the right data point represents the case where the Si-C nanocomposite particles contribute 95% of the total anode capacity. For example, the VQD of the cell composed of G7 is approximately 783 mAh / cm 3 , where Si-C nanocomposite particles contribute 98% of the total anode capacity; the VQD of the battery cell composed of G7 is about 757 mAh / cm 3 , where the Si-C nanocomposite particles contribute 95% of the total anode capacity (in comparison, the VQD of the battery cell containing only Si-C nanocomposite particles is about 783 mAh / cm 3For example, a cell composed of G7 had a VED of approximately 1048 Wh / l, with 98% of the total anode capacity contributed by the Si-C nanocomposite particles, while a cell composed of G7 had a VED of approximately 1038 Wh / l, with 95% of the total anode capacity contributed by the Si-C nanocomposite particles (in comparison, a cell composed solely of Si-C nanocomposite particles had a VED of approximately 1042 Wh / l). Thus, although the high capacity Si-C nanocomposite particles are diluted by the incorporation of lower cost but lower capacity graphite particles, if the graphite particles are properly selected (as described herein) and the mass fraction of graphite in the anode active material is kept at a relatively low level (e.g., from about 2 wt.% to about 5 wt.%, from about 5 wt.% to about 15 wt.%, from about 15 wt.% to about 25 wt.%, from about 5 wt.% to about 25 wt.%, or from about 5 wt.% to about 20 wt.%, or from about 2 wt.% to about 25 wt.%, or from about 2 wt.% to about 20 wt.%, or from about 2 wt.% to about 15 wt.%, or from about 2 wt.% to about 10 wt.%), then the volumetric energy density (VED) and volumetric mass density (VQD) are generally comparable to (and in some cases even higher than) those of battery cells whose anode active material is composed solely of Si-C nanocomposite particles. For example, the coating density of a battery cell containing G7 is about 783 mAh / cm 3 , where 98% of the total anode capacity is contributed by Si-C nanocomposite particles, and the VQD of the battery cell containing G7 is about 757 mAh / cm 3 , where 95% of the total anode capacity is contributed by Si-C nanocomposite particles (in comparison, the battery cell containing only Si-C nanocomposite particles exhibited approximately 783 mAh / cm 3 VQD).

[0203] Figure 10CThe anode coating density during coating (after slurry drying and before calendering) and after calendering is shown. The calendering pressure is set to about 5 tons. In the second row of data (coating density during coating and after calendering) and the columns of data drawn for each battery cell (from left to right, 1022 represents the anode active material containing only Si-C nanocomposite particles, 1024 for G23, 1026 for G7, 1028 for G6), the bottom data point (smaller value) represents the density during coating, and the top data point (larger value) represents the coating density after calendering. For example, the coating density of the anode coating containing only Si-C nanocomposite particles in the anode active material is about 0.812 g / cc, while the calendering density of the anode coating containing only Si-C nanocomposite particles in the anode active material is about 0.872 g / cc (an increase of about 0.060 g / cc compared to after calendering). For example, when the Si-C nanocomposite particles in the anode active material contribute 98% of the anode capacity, the original coating density of the anode coating comprising G7 (the mass fraction of G7 in the anode active material is about 10 wt.%) is about 0.817 g / cc; when the Si-C nanocomposite particles in the anode active material contribute 98% of the anode capacity, the rolled density of the anode coating comprising G7 is about 0.897 g / cc (an increase of about 0.080 g / cc compared to the rolled density). For example, the original coating density of the anode coating comprising G7, in which 95% of the total anode capacity is contributed by the Si-C nanocomposite particles (the mass fraction of G7 in the anode active material is about 20 wt.%), is about 0.843 g / cc; the rolled coating density of the anode coating comprising G7, in which 95% of the total anode capacity is contributed by the Si-C nanocomposite particles, is about 0.976 g / cc (an increase of about 0.133 g / cc after the rolled density). In these examples, the increase in coating density after calendering increases with increasing mass fraction of the G7 graphite particles. Coatings using other graphite samples (G23, G6) also show an increase in coating density, and this increase increases with increasing mass fraction of graphite particles in the anode active material. In these examples, the significant lubrication effect of certain graphite particles in the hybrid anode may contribute to the increased coating density. This lubrication may include improving the packing of particles in the anode coating and / or reducing fracture and other damage to the Si-C nanocomposite particles.

[0204] In the present disclosure, some lithium-ion battery embodiments comprising hybrid anodes with suitable GRSBA graphite particles may benefit from the use of certain binders in their compositions. For example, one or more properties of the GRSBA may make it suitable for use as a solid lubricant during slurry processing and calendaring, thereby facilitating the formation of smooth calendared electrodes and reducing or minimizing damage to suitable binders, even if the binder is relatively brittle. For example, in some designs, a suitable binder may be selected for its strong adhesion and good dispersion of slurry particles, rather than for its high elasticity.

[0205] Illustrative examples of such suitable (and in some designs preferred) binders include, but are not limited to, polyacrylic acid (PAA) and its derivatives including various salts of PAA (e.g., Na-PAA, Li-PAA, NH4-PAA and / or others or combinations thereof), polyacrylic acid (PAA) and its salts including PAA (e.g., Na-PAA, Li-PAA, NH4-PAA and / or others) (e.g., poly(acrylamide-co-acrylic acid) or partial or full poly(acrylamide-co-acrylic acid) salts (e.g., Na or Li or Ca or K or mixed), various copolymers of various derivatives thereof (for example, to give only illustrative examples); various derivatives thereof including various (full or partial) salts of alginic acid (for example, sodium alginate, lithium alginate, calcium alginate, aluminum alginate, etc.); various copolymers of various derivatives thereof including various (full or partial) salts of alginic acid (for example, poly(acrylamide-co-alginic acid) or partial or full poly(acrylamide-co-alginic acid) salts (for example, Na or Li or Ca or K or mixed), for example, to give only illustrative examples); various salts of carboxymethyl cellulose (CMC), such as Na-CMC and / or other salts , and its various derivatives, including various copolymers containing part or all of CMC salts; including styrene (such as styrene-butadiene rubber (SBR)), xanthan gum and including xanthan gum, polyvinyl chloride (PVC), nanocellulose, chitosan, butyrate and its various copolymers, gum arabic and its various copolymers, guar gum and its various copolymers, carrageenan and its various copolymers, gelatin and its various copolymers, polyvinyl alcohol (PVA) and its various copolymers, maleic acid and its various salts (such as Li, Na, K, etc.; in some designs, lithium salts may generally be particularly advantageous), various Various (poly)ethyleneimine (PEI) and copolymers thereof, various (poly)amideimides (PAI) and copolymers thereof, various (poly)amide-amines and copolymers thereof, various other polyamine-based polymers, various (poly)ethyleneimines and copolymers thereof, sulfonic acids and their various salts and copolymers thereof, various polymers containing catechol groups, various polymers containing lignin or derived from lignin, various epoxy resins, various cellulose-derived polymers (including but not limited to nanocellulose fibers and nanocrystals, carboxyethyl cellulose, etc.), other polymers (for example, preferably water-soluble polymers) and various copolymers and mixtures thereof.

[0206] In some designs, the water-soluble copolymer adhesive may include at least one of the following components: vinyl acetate (or butyl or methyl or propyl, etc.), vinyl acrylate (or butyl or methyl or propyl, etc.), vinyl (or butyl or methyl or propyl, etc.) alcohol, vinyl acetate (or butyl or methyl or propyl, etc.)-acrylate, vinyl acrylate (or butyl or methyl or propyl, etc.), styrene-acrylate, alginic acid (or its salts, such as Na, K, Ca, Mg, Li, Sr, Cs, Ba, La and / or other salts), acrylic acid (or its salts, such as Na, K, Ca, Mg, Li, Sr, Cs, Ba, La and / or other salts), vinyl (or butyl or methyl or propyl, etc.) siloxane (or other siloxanes), pyrrolidone, styrene, various sulfonates (such as styrene sulfonate, etc.), various amines (including quaternary amines), various dicyandiamide resins, amide-amine, ethyleneimine, diallyldimethylammonium chloride.

[0207] In some designs, the water-soluble copolymer binder may include cellulose. In some designs, this cellulose-containing binder may include nanocellulose (nanofiber). In some designs, nanocellulose may include branched or dendritic cellulose nanofibers. In some designs, the binder containing nanocellulose may include at least one binder component with strong adhesion (e.g., CMC or other) to enhance the excellent performance of the hybrid anode. In some designs, the binder containing nanocellulose may be water-soluble.

[0208] In some designs, the copolymer binder may comprise poly(acrylamide) (i.e., comprising acrylamide (-CH2CHCONH2-) 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 comprise acrylic acid, carboxylic acid, alginic acid, or metal salts thereof (e.g., Na, K, Ca, Mg, Li, Sr, Cs, Ba, La, and / or other salts of these acids). These and other additives may be used to adjust the polymer's ionic properties, solubility, and interaction with the solvent and active (electrode) particles (e.g., to achieve slurry stability, etc.).

[0209] In some designs, anion-conducting heterogeneous polymers (e.g., alkoxysilane / acrylate or epoxyalkoxysilane, etc.), various anion-conducting interpenetrating polymer networks, various anion-conducting polyionic liquids (crosslinked ionic liquids) or polyacrylonitrile, various anion-conducting polyquaternary ammonium salts, various anion-conducting copolymers containing quaternary ammonium salts (e.g., benzyltrialkylammonium, tetraalkylammonium, trimethylammonium, dimethylammonium, diallyldimethylammonium, etc.), various anion-conducting copolymers containing ammonium groups, various anion-conducting copolymers containing norbornene, various anion-conducting copolymers containing cyclic olefins (e.g., cyclooctene), methacrylate, butyl acrylate, vinylbenzyl or poly(phenylene), Various anion-conducting copolymers containing organochlorine compounds (e.g., epichlorohydrin, etc.), various anion-conducting copolymers containing ethers, bicyclic amines (e.g., quinuclidine), various anion-conducting copolymers (e.g., ionic liquids) (cross-linked ionic liquids), various anion-conducting copolymers containing other amines (e.g., diamines such as ethylenediamine, monoamines, etc.), various anion-conducting copolymers containing polyetherimides, various polysaccharides (e.g., chitosan, etc.), xylylene, guanidine and / or pyridinium groups, and other groups (repeating units) can be advantageously used as copolymer binders (or components of polymer / copolymer binder mixtures) for hybrid anodes in one or more embodiments of the present disclosure. In some designs, suitable copolymer binders can be cationic and highly charged.

[0210] In some designs, various cationically conductive polymers (including interpenetrating polymer networks) and crosslinked ionic liquids (e.g., cation conductivities greater than about 10 -10 S sm -1 ) can be advantageously used as a binder or binder component of a hybrid anode, in accordance with one or more embodiments of the present disclosure. In some designs, such polymers can advantageously exhibit moderate to high conductivity (e.g., greater than about 10 -10 S sm -1 , or more preferably above about 10 -6 S sm -1 ).

[0211] In some designs, various conductive polymers or copolymers (e.g., preferably with a conductivity greater than about 10 -2 S sm -1Polymers or copolymers of conductive materials), particularly those that are soluble in water (or at least processable in water-based electrode slurries), can be advantageously used as binders or binder components (e.g., components of a binder mixture or components of a copolymer binder) for the hybrid anodes of one or more embodiments of the present disclosure. In particular, in some designs, sulfur (S)-containing polymers / copolymers can be advantageously utilized that also contain aromatic rings. In some examples, S may be located in the aromatic ring (e.g., polythiophene (PT) or poly(3,4-ethylenedioxythiophene) (PEDOT)), while in other examples, S may be located outside the aromatic ring (e.g., poly(p-phenylene sulfide) (PPS)). In some designs, suitable conductive polymers / copolymers may also contain nitrogen (N) as a heteroatom. For example, the N atom can be located in the aromatic ring (e.g., polypyrrole (PPY), polycarbazole, polyindole, or polyazapine, etc.), or outside the aromatic ring (e.g., polyaniline (PANI)). Certain conductive polymers may not contain heteroatoms (e.g., polyfluorene, polyphenylene, polypyrene, polycyanocyclic, polynaphthalene, etc.). In some designs, the backbone may contain double bonds (e.g., polyacetylene (PAC) or polyparaphenylene vinyl (PPV), etc.). In some designs, it may be advantageous for the polymer / copolymer binder to contain an ionomer (e.g., in polyelectrolytes, the ionic groups are covalently bound to the polymer backbone; in violets, the ionic groups are part of the polymer backbone). In some designs, it may be advantageous to use a polymer mixture of two or more ionomers. In some designs, such ionomers may have opposite charges (e.g., one negatively charged and one positively charged). Examples of ionomers that may carry a negative charge include, but are not limited to, various deprotonated compounds (e.g., partial deprotonation of the sulfonyl group, such as sulfonated polystyrene). Examples of ionomers that may carry a positive charge include, but are not limited to, various conjugated polymers, such as polyethylenediaminetetraacetic acid (PEDOT), etc. An example of a suitable polymer blend of two oppositely charged ionomers is poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. In some designs, it may be advantageous to use a polymer binder comprising 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, or for enhancing adhesion to active materials or current collectors, or for enhancing solubility in water or other slurry solvents, etc.).

[0212] In some designs, for hybrid anodes, the copolymer binder may advantageously include a halogen anion (e.g., chloride, fluoride, bromide, etc.). In some designs, the copolymer binder may advantageously include an ammonium cation (e.g., in addition to a halogen anion, such as 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, and butylammonium fluoride, to name a few.

[0213] In some designs, the copolymer binder of the hybrid anode can include both poly(acrylamide) and an ammonium halide (e.g., ammonium chloride) in its structure. A suitable example is poly(acrylamide-diallyldimethylammonium chloride) (PAMAC), which can be advantageously used as a copolymer binder in the present disclosure. In some designs, such a PAMAC copolymer binder can also include a small amount (e.g., less than about 5-10 wt.%) of acrylic acid, carboxylic acid, or alginic acid or a metal salt thereof (e.g., Na, K, Ca, Mg, Li, Sr, Cs, Ba, La, and / or other salts of such acids).

[0214] It should be noted that in some designs, the slurry containing a suitable binder, conductive additives and mixed active materials may also contain a dispersant.

[0215] In some designs, elastic nanofibers or nanobelts (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., 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; with pores in some designs) can be advantageously used to replace or supplement traditional elastic nanoparticles. Suitable components of such particles include, but are not limited to, styrene-butadiene rubber (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 (e.g., polydimethylsiloxane), chlorosulfonated polyethylene, ethylene-vinyl acetate, various mixtures and copolymers thereof, and other suitable elastomers. In some designs, the suitable mass fraction of such elastic nanoparticles (or nanofibers or nanosheets) can range from about 5 wt.% to about 70 wt.% (as a proportion of the total binder content in the hybrid anode).

[0216] Some embodiments of the present disclosure regarding lithium-ion batteries comprising hybrid anodes and suitable GRSBA graphite particles may benefit from the use of certain separators in battery manufacturing. For example, anodes comprising hard silicon-containing active material particles (e.g., Si-C nanocomposites, SiOx-based particles, etc.) or a mixture of silicon-containing active material particles and hard graphite (or broadly referred to as hard carbon) may exhibit some roughness even after calendering (particularly for anodes in which the silicon-containing active material particles contribute about 20% or more, about 30% or more, about 50% or more, or about 75% or more of the capacity). In some designs, such high roughness may induce stress concentration areas within the separator, which may lead to premature failure during cycling, resulting in faster degradation, thermal runaway, and / or other adverse factors. In some designs, to reduce or minimize the probability of such adverse events to an acceptable level, the choice of separator may be limited to a relatively thick single separator (e.g., in some designs, thickness exceeding about 12 microns; in other designs, thickness exceeding about 17 microns; etc.), which can reduce the energy density of the battery and increase cost. In addition, in such batteries, the use of ceramic-based or ceramic-coated separators can be challenging due to the brittleness and / or possible crack formation of the ceramic layer. However, in some designs, ceramic-free separators (e.g., polymer separators) may exhibit insufficient safety, insufficient thermal performance, or other limitations. In contrast, in lithium-ion battery cell designs, the hybrid anode contains an appropriate amount of suitable GRSBA graphite (carbon) particles, and the rolled anode can be very smooth (e.g., because the GRSBA can act as a solid lubricant during the rolling process, thereby promoting the formation of a dense and smooth anode layer). Therefore, in some designs, relatively thin separators can be safely and effectively used with the disclosed anodes (e.g., the total separator thickness is less than about 12 microns (μm); in some designs, less than about 10 microns; in some designs, less than about 8 microns; in some designs, less than about 6 microns; in some designs, less than about 4 microns). In some designs, the thickness of the thin separator can be greater than about 0.5 μm; in certain other designs, greater than about 1 μm; in certain other designs, greater than about 2 μm; in certain other designs, greater than about 3 μm. In addition, the diaphragm (including such thin diaphragms) may comprise suitable ceramic (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, etc.) materials (e.g., ceramic nanofibers, ceramic nanowires, ceramic nanotubes, ceramic particles, ceramic flakes, ceramic surface coatings, ceramic layers, and various combinations thereof, etc.).In some designs, the total weight fraction of ceramic material in such a separator may be in the range of about 10 wt.% to about 100 wt.% (e.g., in some designs, from about 10 wt.% to about 25 wt.%; in other designs, from about 25 wt.% to about 50 wt.%; in other designs, from about 50 wt.% to about 75 wt.%; in still other designs, from about 75 wt.% to about 100 wt.%). In some designs, such a separator may include two or more layers. In some designs, at least one of the layers may contain a much higher fraction of ceramic material than one or more other layers. In some embodiments, where there are multiple layers and at least one of the layers (the "higher ceramic content layer") has a higher ceramic weight fraction than another layer (the "lower ceramic content layer"), the ceramic weight fraction of the higher ceramic content layer may be at least about 50% that of the lower ceramic content layer. In other embodiments, if a multilayer structure is present and at least one layer (a "high ceramic content layer") has a higher ceramic weight fraction than another layer (a "low ceramic content layer"), the ceramic weight fraction of the high ceramic content layer may be at least about 100% higher than the ceramic weight fraction of the low ceramic content layer. In some designs, at least a portion of the separator can be deposited directly on the surface of the hybrid anode. Alternatively, a solid electrolyte can be used as the separator between the anode and cathode, eliminating the need for a polymer or ceramic separator. In this case, the solid electrolyte needs to be thick enough to ensure safe operation, for example, in some cases, a thickness greater than about 0.5 μm.

[0217] Some embodiments of the present disclosure relate to lithium-ion batteries comprising hybrid anodes having suitable GRSBA graphite particles that can benefit from the use of certain electrolyte compositions in battery manufacturing to achieve superior properties. In some designs, suitable electrolyte compositions can include (i) one, two, three, or more lithium salts in a total concentration ranging from about 0.8 M to about 2.0 M (in some designs, about 0.8 M to about 1.0 M; in other designs, about 1 M to about 1.1 M; in other designs, about 1.1 M to about 1.2 M; in other designs, about 1.2 M to about 1.3 M; in other designs, about 1.3 M to about 1.4 M; in other designs, about 1.4 M to about 1.6 M; in other designs, about 1.6 M to about 1.7 M; in other designs, about 1.7 M to about 1.8 M; in other designs, about 1.8 M to about 2.0 M); (ii) one, two, or more cyclic carbonates (in some designs, including fluorinated cyclic carbonates, (e.g., polycarbonates, such as FEC, etc.), (iii) zero, one, two, three or more nitrogen-containing co-solvents (in some designs, at least some of the nitrogen-containing co-solvents may advantageously contain two or three or more nitrogen atoms per molecule), (iv) zero, one, two, three or more sulfur-containing co-solvents, (v) zero, one, two, three or more phosphorus-containing co-solvents (note that some co-solvents may advantageously contain both phosphorus and sulfur), (vi) zero, one, two, three or more linear or branched esters as co-solvents, (vii) zero, one, two or more linear carbonates as co-solvents, (viii) zero, one, two, three or more additional electrolyte co-solvents or additives, or (ix) any combination thereof. In some designs, the volume fraction of the linear ester (as a proportion of all co-solvents in the electrolyte) may be between about 20 vol.% and about 85 vol.% (in some designs, about 20 vol.% to about 40 vol.%; in other designs, about 40 vol.% to about 60 vol.%; in still other designs, about 60 vol.% to about 85 vol.%). In some designs, the volume fraction of the branched ester (as a proportion of all co-solvents in the electrolyte) may be between about 10 vol.% and about 80 vol.% (in some designs, about 10 vol.% to about 30 vol.%; in other designs, about 30 vol.% to about 60 vol.%; in still other designs, about 60 vol.% to about 80 vol.%). In some designs, the volume fraction of the cyclic carbonate (as a proportion of all co-solvents in the electrolyte) can be about 5 vol.% to about 40 vol.% (in some designs, about 5 vol.% to about 10 vol.%; in other designs, about 10 vol.% to about 20 vol.%; in other designs, about 20 vol.% to about 40 vol.%).In some designs, the volume fraction of the fluorinated cyclic carbonate (as a proportion of all co-solvents in the electrolyte) may be from about 1 vol.% to about 10 vol.% to about 20 vol.% (in some designs, from about 1 vol.% to about 4 vol.%; in other designs, from about 4 vol.% to about 6 vol.%; in other designs, from about 6 vol.% to about 12 vol.%; in still other designs, from about 12 vol.% to about 20 vol.%). In some designs, the volume fraction of vinylene carbonate (VC) (as a proportion of all co-solvents in the electrolyte) may be from about 0.25 vol.% to about 6 vol.% (in some designs, from about 0.25 vol.% to about 0.5 vol.%; in other designs, from about 0.5 vol.% to about 1 vol.%; in other designs, from about 1 vol.% to about 2 vol.%; in still other designs, from about 2 vol.% to about 6 vol.%). In some designs, about 50 vol.% or more of the co-solvent can advantageously exhibit a melting point below about negative (-) 60°C (in some designs, below about -70°C; in other designs, below about -80°C). In some designs using two or more salts (e.g., two salts or three salts or four salts or five salts, etc.), it may be advantageous for at least one salt to include LiPF6. In some designs, the addition of such a salt can enhance the performance of the cathode electrolyte interphase (CEI) layer or the anode solid electrolyte interface (SEI) layer (e.g., cycling stability, resistance, thermal stability, high or low temperature performance, etc.), or provide other performance advantages. In some designs, it may be more advantageous if at least one other salt is also a lithium salt. Examples of such suitable salts include, but are not limited to, LiFSI, LiTFSI, LiBETI and / or other lithium imide salts, lithium bis(oxalatoborate) (LiBOB), lithium difluorooxalatoborate (LiDFOB), 2-trifluoromethyl-4,5-dicyanoimidazole lithium (LiTDi), 4,5-dicyano-2-pentafluoroethylimidazole lithium (LiPDi), lithium difluorophosphate (LiDFP), lithium nitrate (LiNO3), and the like.

[0218] Figure 11 The invention is shown for manufacturing lithium ion batteries (e.g. Figure 1 1124, 1132, 1134, and 1140. The flowchart includes an anode branch (left branch) including operations 1122 and 1124, and a cathode branch (right branch) including operations 1132 and 1134. In operation 1122, suitable anode particles (e.g., conventional graphite (carbon) anode particles or silicon-containing particles (e.g., Si-C nanocomposites, core-shell, SiO x Base or SiNx In operation 1124, a suitable hybrid anode is formed. Similarly, in operation 1132, cathode particles (e.g., conventional intercalation cathode particles or core-shell cathode particles or composite cathode particles, including but not limited to composite particles comprising conversion cathode materials) are provided or manufactured, and in operation 1134, a cathode is formed.

[0219] Electrodes used in lithium-ion batteries are typically produced by: (i) preparing a slurry containing active material, conductive additives, binder solution, and (in some cases) surfactants or other functional additives; (ii) casting the slurry onto a metal foil current collector (e.g., most anodes use copper foil or copper alloy foil, and most cathodes use aluminum foil or aluminum alloy foil); and (iii) drying the cast electrode to allow the solvent to completely evaporate. It is important to note that in some designs, metal mesh, metal foam, or very rough metal foil (e.g., containing metal nanowires or metal nanosheets on the surface) can be used as the current collector (e.g., to increase the area capacity loading or achieve faster charging speed, etc.). It is also important to note that in some designs, metal-coated thin polymer sheets can also be used as the current collector (e.g., to improve safety or reduce the weight of the current collector, etc.). It is also important to note that in some designs, porous metal foil or composite (e.g., nanocomposite) metal foil can be used in certain designs (e.g., to improve performance, reduce weight, etc.).

[0220] Operation 1124 includes forming an anode electrode including the anode particles produced in operation 1122. For example, operation 1124 may include (1) producing an anode slurry including the anode particles (e.g., from operation 1122) and other anode slurry ingredients (e.g., binder, additives, etc.), and (2) casting the anode slurry onto and / or (in the case of a porous current collector) into an anode current collector (e.g., a copper or copper alloy foil current collector, a porous copper or copper alloy or nickel or nickel alloy foam or foil, or a nickel alloy current collector or a polymer-containing current collector, etc.). For example, other anode slurry components may include: other electrochemically active anode active materials (e.g., suitable natural or synthetic graphite, soft carbon or hard carbon (e.g., including GRSBA) mixed with silicon-containing active material particles, such as Si-C nanocomposite particles, etc.), conductive additives (e.g., carbon nanotubes or carbon black or branched carbon or carbon nanofibers or graphite flakes or exfoliated graphite or graphene or graphene oxide or soft graphite or various combinations thereof, etc.), binders (e.g., polymer binders) and solvents (e.g., water or suitable organic solvents). In some designs, a solvent-free electrode manufacturing process may be employed.

[0221] Operation 1134 includes forming a cathode electrode comprising the cathode particles prepared in operation 1132. For example, operation 1134 may include: (1) preparing a cathode slurry comprising the cathode particles (e.g., from operation 1132) and other cathode slurry ingredients; and (2) casting the cathode slurry onto a cathode current collector (e.g., an aluminum foil or aluminum alloy foil current collector) and / or within the cathode current collector (if a porous current collector). For example, the other cathode slurry ingredients may include: other electrochemically active cathode active materials, conductive additives (e.g., carbon nanotubes or carbon black or branched carbon or carbon nanofibers or graphite flakes or graphene or graphene oxide or soft graphite or various combinations thereof), a binder (e.g., a polymer binder), and a solvent (e.g., water, a suitable organic solvent, or a suitable mixture thereof). In some designs, a solvent-free ("dry") electrode manufacturing process may be employed.

[0222] In operation 1140, a lithium-ion rechargeable battery cell is assembled from at least an anode electrode (e.g., a hybrid anode comprising GRSBA and silicon-containing active material particles (e.g., Si-C nanocomposites, etc.)) and a cathode electrode, with an electrolyte inserted between the anode electrode and the cathode electrode. The electrolyte provides ionic conduction between the (e.g., hybrid) anode and cathode. The electrolyte couples the anode and cathode ions. At the battery operating temperature, the electrolyte may include a liquid electrolyte or a solid electrolyte (or a mixture of liquid and solid electrolytes) (e.g., in some designs, the solid electrolyte may be in a molten or semi-molten state during the melt infiltration process and may subsequently solidify). 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).

[0223] A battery module or battery pack may advantageously include a battery having an electrode and / or electrolyte composition provided in one or more embodiments of the present disclosure. Such a battery module or battery pack may provide better performance characteristics, a simpler design, better safety features, or lower cost.

[0224] Figure 12 Graphs showing the estimated cycle life (N80) as a function of the number of cycles for lithium-ion battery test cells: (1) containing no graphite particles (graph 1202); (2) containing 10 wt.% of the anode active material graphite particles (G1 or G23) (graph 1204); (3) containing 20 wt.% of the anode active material graphite particles (G1 or G23) (graph 1206); and (4) containing 30 wt.% of the anode active material graphite particles (G1 or G23) (graph 1208). The lithium-ion battery cells used in the measurements are Figure 10A 、 10BSimilar to the unit reported in 10C, except that the D 50The value is about 4.56 μm. In the embodiments shown, (1) the anode having 10 wt.% of the graphite particles as the anode active material (1204) has a mass ratio of Si-C nanocomposite particles to graphite active material particles of about 90:10; (2) the anode having 20 wt.% of the graphite particles as the anode active material (1206) has a mass ratio of Si-C nanocomposite particles to graphite active material particles of about 80:20; and (3) the anode having 30 wt.% of the graphite particles as the anode active material (1206) has a mass ratio of Si-C nanocomposite particles to graphite active material particles of about 70:30. Among the graphite samples considered, G1 is a relatively hard graphite among the graphite samples studied in this paper, with a Cx value of about 25.5 MPa, while G23 is considered to be a soft graphite, although its exact Cx value is unknown. The cycle life (N80) characteristics of the battery cells containing G1 and G23 are different. When G23 was used in the hybrid anode at 10 wt.% of the anode active material (1204), N80 increased by approximately 15% compared to a comparative example in which the anode active material did not contain graphite particles and only Si-C nanocomposite particles were used in the anode active material. When G23 was used in the hybrid anode at 20 wt.% of the anode active material (1206), N80 increased by approximately 5% compared to the comparative example. When G23 was used in the hybrid anode at 30 wt.% of the anode active material (1208), N80 did not increase significantly compared to the comparative example. Thus, in some embodiments, the soft graphite particles in the hybrid anode can help increase cycle life, especially when the mass fraction of the graphite particles in the anode active material is relatively low (e.g., in the range of about 2 to about 40 wt.%, in the range of about 2 to about 35 wt.%, in the range of about 2 to about 25 wt.%, in the range of about 2 to about 15 wt.%, in the range of about 5 to about 35 wt.%, in the range of about 5 to about 25 wt.%, or in the range of about 5 to about 15 wt.%). In some embodiments, the soft graphite particles in the hybrid anode can help increase cycle life, especially when the mass ratio of Si-C nanocomposite particles (which is an example of Si-containing active material particles) to graphite active material particles is relatively high (e.g., in the range of about 60:40 to about 98:2, in the range of about 65:35 to about 98:2, in the range of about 75:25 to about 98:2, in the range of about 85:15 to about 98:2, in the range of about 65:35 to about 95:5, in the range of about 75:25 to about 95:5, or in the range of about 85:15 to about 95:5). In contrast, when G1 was used in the hybrid 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 example.

[0225] Figure 13Table 9 shows exemplary graphite particle samples, their selected properties (Cx, tap density, particle size distribution (PSD) properties, BET-SSA values, and D / G ratios), and certain battery performance characteristics of lithium-ion batteries using the exemplary graphite particle samples when the mass fraction of the graphite particles in the respective anode active materials is low (e.g., compared to Figure 14 Table 10 in the table is compared). Table 9 considers the following types of lithium-ion batteries: (A) a comparative example, in which the anode active material does not contain graphite particles, and only Si-C nanocomposite particles are used in the anode active material (the mass ratio of Si-C nanocomposite particles to graphite particles is 100:0, and the graphite particles account for 0 wt.% of the anode active material); (B) an example in which the mass ratio of Si-C nanocomposite particles to graphite particles is 90:10 (graphite particles account for 10 wt.% of the anode active material) (Si-C nanocomposite particles contribute about 98% of the anode capacity), and the graphite particles are G1, G6, G7 or G23; (C) an example in which the mass ratio of Si-C nanocomposite particles to graphite particles is 80:20 (graphite particles account for 20 wt.% of the anode active material) (Si-C nanocomposite particles contribute about 95% of the anode capacity), and the graphite particles are G1, G6, G7 or G23. The lithium-ion battery cells used in the measurements are the same as Figure 10A 、 10B Similar to that reported in 10C.

[0226] In Table 9, the N80 values ​​of the battery cells using G1 (graphite content in the anode active material is 10 wt.% and 20 wt.%, respectively) are similar to the N80 values ​​of the comparative battery cells (about 650 cycles). On the other hand, the N80 values ​​of the battery cells using G6, G7 and G23 (graphite content in the anode active material is 10 wt.% and 20 wt.%, respectively) are higher, about 720 cycles, about 690 cycles and about 750 cycles, respectively. The VED and VQD values ​​measured for the battery cells using G6, G7 and G23 (graphite content in the anode active material is 10 wt.% and 20 wt.%, respectively) are roughly equivalent to the VED and VQD values ​​of the comparative battery cells. Among the graphite samples considered in Table 9, the following are some distinguishing features of G1 from the other graphite samples: G1 has a relatively large Cx value (25.5 MPa), a relatively small D 10 value (5.6μm), relatively large D 90 value (26.3 μm) (therefore, the full width D 90 -D 10 relatively large), relatively small BET-SSA value (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 is in the range of about 2 to about 40 wt.% (e.g., about 5 to about 35 wt.%, about 5 to about 25 wt.%, or about 5 to about 15 wt.%). In some embodiments, the mass ratio of the Si-C nanocomposite particles to the graphite active material particles is in the range of about 60:40 to about 98:2 (e.g., about 65:35 to about 95:5, about 75:25 to about 95:5, or 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 is in the range of about 1 MPa to about 18 MPa (e.g., about 7 MPa to about 18 MPa, about 10 MPa to about 18 MPa, or about 14 MPa to about 18 MPa). In some embodiments, at least a portion of the graphite active material particles have a D / G ratio 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 In some embodiments, the D value of at least a portion of the graphite active material particles is in the range of about 2 to about 22 μm (e.g., about 11 to about 17 μm, or about 12 to about 17 μm). 90 The value is in the range of about 4 to about 30 μm (e.g., about 19 to about 30 μm, or about 19 to about 26 μm). In some embodiments, at least a portion of the graphite active material particles have a D 10 The BET-SSA value of at least a portion of the graphite active material particles is in the range of about 0.5 to about 15 μm (e.g., about 5 to about 11 μm, or about 7 to about 11 μm). In some embodiments, the BET-SSA value of at least a portion of the graphite active material particles is in the range of about 0.450 to about 450 μm. 2 / g (e.g., about 1 to about 5 m 2 / g, or from about 1 to about 3 m 2 / g).

[0227] Figure 14 Table 10 is shown, which lists exemplary graphite particle samples, their selected properties (Cx, tap density, particle size distribution (PSD) properties, BET-SSA values ​​and D / G ratios), and certain battery performance characteristics of lithium-ion batteries using the exemplary graphite particle samples when the mass fraction of graphite particles in the respective anode active materials is high (e.g., compared to Figure 13Table 10 considers the following types of lithium-ion batteries: (A) a comparative example in which the anode active material does not contain graphite particles and only Si-C nanocomposite particles are used in the anode active material (the mass ratio of Si-C nanocomposite particles to graphite particles is 100:0, and the graphite particles account for 0 wt.% of the anode active material); (D) an example in which the mass ratio of Si-C nanocomposite particles to graphite particles is 50:50 (the graphite particles account for 50 wt.% of the anode active material) (the Si-C nanocomposite particles contribute to about 80% of the anode capacity), and the graphite particles are G1, G2, G3, or G8; and (E) an example in which the mass ratio of Si-C nanocomposite particles to graphite particles is 20:80 (the graphite particles account for 80 wt.% of the anode active material) (the Si-C nanocomposite particles contribute to about 50% of the anode capacity), and the graphite particles are G1, G2, G3, G4, G5, or G6.

[0228] The details of the battery cells used in the results reported in Table 10 are as follows. The comparative battery cells are the same as those reported in Table 9 and Figure 10A 、 10B Similar to that reported in 10C. In a D-type battery cell (50wt.% graphite), (a) the anode composition was adjusted so that the mixed anode contained Si-C nanocomposite particles and graphite particles in a mass ratio of about 50:50; (b) the cathode was an NCM-based cathode. The cathode was made of NMC811 (composition of about LiNi 0.8 Mn 0.1 Co 0.1 The battery is composed of a Lithium Nickel Manganese Cobalt Oxide (NMC) material and a Lithium Nickel Manganese Cobalt Oxide (NMC) material. The NMC811 material is a lithium nickel manganese cobalt oxide (NCM) material. The battery cell consists of a cathode, an anode, a polymer ceramic separator between the anode and cathode, and a LiPF6-based electrolyte. The LiPF6-based electrolyte composition includes: 13.92 wt.% LiPF6 (as the main 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). In the E-type battery (graphite content 80wt.%), the anode composition was adjusted so that the mixed anode contained Si-C nanocomposite particles and graphite particles in a mass ratio of about 20:80. Figure 10A 、 10B Similar to the batteries reported in 10C.

[0229] In the E-type (80 wt.% graphite) cells shown in Table 10, a wide range of N80 values ​​(cycle life) was observed, ranging from about 476 cycles (cell containing G4) to about 1207 cycles (cell containing G1). It is worth noting that G1 is the graphite sample with the lowest N80 value (about 650 cycles) among the 10 wt.% and 20 wt.% graphite cells in Table 9. The D values ​​of the considered graphite samples (G1, G2, G3, G4, G5, G6) are 50 The values ​​range from 11 μm to 17 μm. In these graphite samples, there is a positive correlation between the N80 value (cycle life) and the Cx value (representing hardness). Relatively high BET-SSA values ​​(e.g., between about 2 and about 5 μm) 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 2 / g or about 1 to about 2 m 2 There is a correlation between the BET-SSA value of the graphite particles (e.g., in the range of about 1 to about 3 m / g) and the higher N80 value. 2 / g or about 1 to about 2 m 2 / g range) can help to improve the N80 value (extend cycle life). In the examples shown, the choice of graphite particles seems to be correlated with the N80 performance of the battery cell. On the other hand, other performance characteristics (e.g., formation efficiency and VED) do not seem to be strongly correlated with graphite selection. Formation efficiency is defined as the discharge capacity at the start of the cycle (the discharge capacity at the 3rd cycle) divided by the charge capacity at the first cycle. In the D-type (50 wt.% graphite) battery cells shown in Table 10, variations in N80 values ​​(cycle life) were observed, ranging between about 933 cycles (battery cells containing G8) and about 1421 cycles (battery cells containing G1). However, the D of the G8 graphite sample 50The value is about 6.8 μm, which is smaller than some other graphite samples considered. In some embodiments, the mass fraction of the graphite active material particles in the anode active material is in the range of about 60 to about 93 wt.% (e.g., about 60 to about 70 wt.%, about 70 to about 90 wt.%, or about 90 to about 93 wt.%). In some embodiments, the mass ratio of the Si-C nanocomposite particles to the graphite active material particles is in the range of about 7:93 to about 40:60 (e.g., about 7:93 to about 10:90, about 10:90 to about 30:70, or about 30:70 to about 40:60). In some embodiments, the average Cx value of at least a portion of the graphite active material particles is in the range of about 18 MPa to about 30 MPa (e.g., about 20 MPa to about 30 MPa, about 18 MPa to about 20 MPa, about 20 MPa to about 24 MPa, or about 24 MPa to about 30 MPa). In some embodiments, at least a portion of the graphite active material particles have a D / G ratio 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 In some embodiments, the D value of at least a portion of the graphite active material particles is in the range of about 2 to about 22 μm (e.g., about 11 to about 17 μm, or about 12 to about 17 μm). 90 The value is in the range of about 4 to about 30 μm (e.g., about 19 to about 30 μm, or about 19 to about 26 μm). In some embodiments, at least a portion of the graphite active material particles have a D 10 The BET-SSA value of at least a portion of the graphite active material particles is in the range of about 0.5 to about 15 μm (e.g., about 5 to about 11 μm, or about 7 to about 11 μm). In some embodiments, the BET-SSA value of at least a portion of the graphite active material particles is in the range of about 0.450 to about 450 μm. 2 / g range (e.g., about 1 to about 5 m 2 / g, about 1 to about 2 m 2 / g, or from about 1 to about 3 m 2 / 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 (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).

[0230] Figure 15 Table 11 shows some anode characteristics (particle size (D 50) value, rolling pressure during battery anode formation, binder material used in battery anode formation) and some battery performance characteristics of lithium-ion battery cells using graphite particles (G1) and Si-C nanocomposite particles (in the example of Table 11, the mass fraction of graphite particles G1 in each anode active material is 10 wt.%). Table 11 compares different binders and different particle sizes (D 50 The figure shows the performance of the battery cell with Si-C nanocomposite particles. Figure 10A 、 10B Similar to the battery cell reported in 10C, a PAA-based copolymer binder was used in the anode and D 50 The Si-C nanocomposite particles are in the range of 5 to 6 μm. The type 3 battery is similar to the type 1 battery, but the Si-C nanocomposite particles are smaller. 50 The value is about 3μm. The anode coating of type 1 and type 3 cells was calendered under a calendering pressure of about 5 tons. Type 2 and type 4 cells use CMC:SBR binder in the anode instead of PAA-based copolymer binder. In type 2 cells, the CMC:SBR mass ratio is about 1:6, and in type 4 cells, the CMC:SBR mass ratio is about 1:9.8. The D of Si-C nanocomposite particles in type 2 cells is about 1:6. 50The values ​​are 5 to 6 μm and approximately 3 μm in the Type 4 cell. The anode coatings of the Type 2 and Type 4 cells were rolled under a rolling pressure of approximately 8 tons. Table 11 reports the following battery performance characteristics, from left to right: average discharge voltage (N80), expansion ratio (VED), VQD, DC resistance (DCR), and 2C discharge capacity retention (2C discharge retention rate). Definitions of N80, VED, and VQD are given elsewhere in this document. The average discharge voltage of a battery cell is defined as the discharge energy (Wh) divided by the discharge capacity (Ah). 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 immersion in the electrolyte. The DC resistance (DCR) is determined by applying a series of high-rate current pulses to the battery at a predetermined state of charge (e.g., 10% state of charge, 50% state of charge, etc.) and measuring the resulting voltage. The average voltage is determined by averaging the corresponding voltages measured for each current pulse. The DCR is the average voltage divided by the normalized applied current. DCR is often normalized to facilitate comparison and eliminate the effects of factors such as cell size, capacity, or energy. When DCR is normalized by capacity, its units are Ω-Ah. Normalized applied current is expressed as applied current (in A) divided by cell capacity (capacity in Ah). In the example shown in Table 11, DCR was measured at a 50% state of charge, a 2.3C discharge rate, and a total pulse time of 30 seconds. Capacity retention (sometimes also called normalized capacity or relative discharge capacity) is defined as the charge capacity (in mAh) achieved at a given discharge rate (e.g., a 2C rate in this example) normalized by the start-of-cycle capacity (capacity at the 3rd cycle) (in mAh), which is typically the low-C equilibrium state. The results in Table 11 demonstrate that CMC:SBR binders can replace PAA-based binders in hybrid anodes of Si-C nanocomposite particles and graphite particles. For performance characteristics such as average discharge voltage, DCR, and high rate capacity retention (e.g., 2C discharge or 2.8C discharge), in some cases, CMC:SBR binders may be preferred. In some cases, to improve VED (increase VED), PAA-based (copolymer) binders may be preferred. Compared with anodes using PAA salt-based (copolymer) binders, anodes using CMC:SBR exhibited larger expansion ratios but smaller expansion in the xy direction parallel to the coating. Si-C nanocomposite particle size (D 50 ) from 5–6 μm to approximately 3 μm results in an increase in VED and a decrease in N80. The DCR values ​​of the battery cells using 3 μm Si-C nanocomposite particles (types 3 and 4) are lower than those of the battery cells using 5–6 μm Si-C nanocomposite particles and a PAA-based (copolymer) binder (type 1 cell).

[0231] Figure 16Graphs showing the direct current resistance (DCR) values ​​for lithium-ion battery cells using a PAA copolymer-based binder system (1602) and a CMC:SBR binder system (1604). Both types of lithium-ion battery cells use a mixed anode comprising Si-C nanocomposite particles and graphite particles (G1), wherein the mass fraction of the graphite particles G1 is 10 wt.% of the anode active material. Graph 1602 shows the DCR for type 1 battery cell from Table 11. Graph 1604 shows the DCR for type 2 battery cell from Table 11.

[0232] Figure 17 Graphs showing the relative discharge capacity (capacity retention) of lithium-ion battery cells using a PAA copolymer-based binder (1702) and a CMC:SBR binder (1704) as a function of the normalized discharge rate (C-rate) (C-rate range of approximately 0.5 to 2). Both types of lithium-ion battery cells use a mixed anode of Si-C nanocomposite particles and graphite particles (G1), wherein the mass fraction of the graphite particles G1 is 10 wt.% of the respective anode active materials. Graph 1702 shows the relative discharge capacity (capacity retention) of type 1 battery cell from Table 11. Graph 1704 shows the relative discharge capacity (capacity retention) of type 2 battery cell from Table 11. Over the C-rate range of 0.6 to 2.2, the discharge capacity retention of type 1 battery cell is higher than that of type 2 battery cell.

[0233] In the detailed description above, it can be seen that different features are combined together in the examples. This disclosure should not be interpreted as an exemplary clause containing more features than those explicitly mentioned in each clause. On the contrary, various aspects of the present disclosure may contain fewer than all the features disclosed in a single exemplary clause. Therefore, the following clauses should be regarded as being incorporated into the specification, where each clause itself can serve as a separate example. Although each dependent clause may refer to a specific combination with one of the other clauses in the clause, the aspects of the dependent clause are not limited to that specific combination. It should be understood that other exemplary clauses may also include a combination of the dependent clause aspects with the subject matter of any other dependent clause or independent clause, or a combination of any features with other dependent clauses and independent clauses. The various aspects disclosed herein explicitly include these combinations, unless it is expressly expressed or can be easily inferred that a specific combination is not intended (for example, contradictory aspects, such as defining an element as both an electrical insulator and an electrical conductor). In addition, even if a clause does not directly refer to an independent clause, its various aspects may be included in any other independent clause.

[0234] Implementation examples are described in the following numbered clauses:

[0235] Item 1. A battery anode comprising: a binder; a conductive additive; and an active material mixture, the active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, wherein: the battery anode has a conductivity of about 2 mAh / cm 2 to about 16 mAh / cm 2 The invention relates to a battery cell having a reversible capacity loading within a range of about 100 mAh / g to about 3000 mAh / g; the Si-containing active material particles exhibit a specific capacity (i.e., lithiation capacity) within a range of about 800 mAh / g to about 3000 mAh / g (e.g., about 800-1400 mAh / g or about 1400-1750 mAh / g or about 1750-2250 mAh / g or 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 some of the graphite active material particles are characterized by Raman spectroscopy (e.g., collected using a 532 nm laser), in which the D band has a full width at half maximum (FWHM) of about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 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.

[0236] Item 2. The battery anode of Item 1, wherein the D / G peak intensity ratio is in a range from about 0.12 to about 0.30.

[0237] Item 3. A battery anode according to any one of items 1 to 2, wherein: the 2D1 / G peak intensity ratio is in the range of about 0.10 to about 0.90, which is defined as the 2D1 peak intensity divided by the G peak intensity of a Raman spectrum (e.g., collected using a 532 nm laser).

[0238] Item 4. The battery anode of any one of items 1 to 3, wherein: at least some of the graphite active material particles are characterized by X-ray diffraction (XRD) spectroscopy, wherein the FWHM of the (002) reflection in the X-ray diffraction (XRD) spectrum is in the range of about 0.220 degrees to about 5.620 degrees.

[0239] Item 5. The battery anode of Item 4, wherein the FWHM of the (002) reflection is in the range of about 0.220 degrees to about 0.620 degrees.

[0240] Item 6. The battery anode of any one of Items 4 to 5, wherein: the average crystallite size of at least some of the graphite active material particles estimated by applying the Scherrer equation to the (002) reflection is in the range of about 1 nm to about 40 nm.

[0241] Item 7. The battery anode of Item 6, wherein the average grain size is in a range from about 15 nm to about 30 nm.

[0242] Clause 8. The battery anode of any one of clauses 1 to 7, wherein: the average pressure (Cx) required to deform at least some of the graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

[0243] Clause 9. The battery anode of Clause 8, wherein: the average pressure ranges from about 1 MPa to about 18 MPa.

[0244] Clause 10. The battery anode of any one of Clauses 1 to 9, wherein: 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.

[0245] Item 11. The battery anode of Item 10, wherein: the tap density is in a range of about 0.90 g / cc to about 1.10 g / cc.

[0246] Clause 12. The battery anode of any one of Clauses 1 to 11, wherein: at least some of the graphite active material particles have a pycnometer density in the range of about 2.15 g / cc to about 2.35 g / cc.

[0247] Clause 13. A battery anode according to any one of clauses 1 to 12, wherein: at least some of the graphite active material particles have a 50th percentile volume-weighted particle size parameter D 50 The range is from about 2 μm to about 22 μm.

[0248] Clause 14. The battery anode according to clause 13, wherein: D 50 Ranges from about 12 μm to about 17 μm.

[0249] Clause 15. The battery anode of any one of clauses 1 to 14, wherein: at least some of the graphite active material particles have a 90th percentile volume-weighted particle size parameter D 90 The range is from about 4 μm to about 30 μm.

[0250] Clause 16. The battery anode according to clause 15, wherein: D 90 The range is from about 19 μm to about 26 μm.

[0251] Clause 17. A battery anode according to any one of clauses 1 to 16, wherein: the 10th percentile volume-weighted particle size parameter D of at least some of the graphite active material particles is 10 The range is from about 0.5 μm to about 15 μm.

[0252] Clause 18. The battery anode according to clause 17, wherein: D 10 The range is about 7 μm to about 11 μm.

[0253] Clause 19. The battery anode of any one of clauses 1 to 18, wherein: at least some of the graphite active material particles have a Bronner-Emmet-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0254] Item 20. The battery anode according to Item 19, wherein: the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0255] Clause 21. The battery anode of any one of clauses 1 to 20, wherein: the weight fraction of at least some of the graphite active material particles in the battery anode is in a range from about 1 wt.% to about 50 wt.% of the active material mixture.

[0256] Clause 22. The battery anode of Clause 21, wherein: the weight fraction is in the range of about 2 wt.% to about 20 wt.% of the active material mixture.

[0257] Item 23. A battery anode according to any one of items 1 to 22, wherein: the silicon-containing active material particles contain oxygen (O) atoms, the mass of which is about 5 wt.% or less (in other designs, about 2 wt.% or less; in other designs, about 1 wt.% or less) of the total mass of the silicon-containing active material particles.

[0258] Clause 24. The battery anode of any one of clauses 1 to 23, wherein the silicon-containing active material particles comprise silicon (Si) atoms and carbon (C) atoms totaling in the range of 80 wt.% to about 100 wt.% of the total mass of the silicon-containing active material particles.

[0259] Clause 25. The battery anode of Clause 24, wherein the Si-containing active material particles comprise Si—C nanocomposite particles.

[0260] Clause 26. The battery anode of Clause 25, wherein the Si-containing active material particles comprise Si nanoparticles.

[0261] Item 27. The battery anode of Item 26, wherein: at least some of the Si nanoparticles are coated with a conductive carbon layer (eg, with an average thickness of about 0.3-10 nm).

[0262] Clause 27. The battery anode of Clause 26, wherein: the Si nanoparticles have a weight average size ranging from about 2 nm to about 40 nm.

[0263] Item 28. The battery anode of Item 26, wherein: the average crystallite size of the Si nanoparticles ranges from about 1 nm to about 20 nm as estimated by X-ray diffraction using the Scherrer equation.

[0264] Item 29. A battery anode according to Item 25, wherein: the Si-containing active material particles are Si-C nanocomposite particles that exhibit a true density in the range of about 1.4 to about 1.9 g / cc (e.g., about 1.4-1.6 g / cc or about 1.6-1.75 g / cc or about 1.75-1.9 g / cc) when measured using N2 pycnometer method.

[0265] Item 30. The battery anode according to Item 25, wherein the Si-containing active material particles are Si-C nanocomposite particles, and the 50th percentile volume weighted particle size parameter (D 50 ) is in the range of about 4 to about 16 microns (e.g., about 4-7 microns or 7-10 microns or about 10-13 microns or about 13-16 microns or about 7-13 microns).

[0266] Clause 31. The battery anode of any one of Clauses 1 to 30, wherein: at least some of the graphite active material particles exhibit a specific capacity in a range from about 320 mAh / g to about 372 mAh / g.

[0267] 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 cathode; and an electrolyte ionically coupling the battery anode and cathode.

[0268] Implementation examples are described in the following numbered additional clauses:

[0269] Additional Clause 1. A battery anode comprising: a binder; a conductive additive; and an active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, wherein: the battery anode has a conductivity of about 2 mAh / cm 2 to about 16 mAh / cm 2The silicon-containing active material particles exhibit a reversible capacity loading within a range of about 800 mAh / g to about 3000 mAh / g (e.g., about 800-1400 mAh / g or about 1400-1750 mAh / g or about 1750-2250 mAh / g or about 2250-2500 mAh / g or about 2500-3000 mAh / g); the silicon-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 Raman spectroscopy (e.g., collected using a 532 nm laser), in which the D band has a full width at half maximum (FWHM) at about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 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.

[0270] Additional clause 2. The battery anode of additional clause 1, wherein the D / G peak intensity ratio is in a range from about 0.12 to about 0.30.

[0271] Additional clause 3. The battery anode of any one of additional clauses 1 to 2, wherein: the 2D1 / G peak intensity ratio is in the range of about 0.10 to about 0.90, which is defined as the intensity of the 2D1 peak divided by the intensity of the G peak in a Raman spectrum (e.g., collected using a 532 nm laser).

[0272] Additional clause 4. The battery anode of any one of additional clauses 1 to 3, wherein: at least a subset of the graphite active material particles is characterized by X-ray diffraction (XRD) spectroscopy, in which the FWHM of the (002) reflection peak is in the range of about 0.220 degrees to about 5.620 degrees.

[0273] Additional clause 5. The battery anode according to additional clause 4, wherein the FWHM of the (002) reflection peak is in the range of about 0.220 degrees to about 0.620 degrees.

[0274] Additional clause 6. A battery anode according to any one of additional clauses 4 to 5, wherein: the average grain size of at least a subset of the graphite active material particles is in the range of about 1 nm to about 40 nm, as estimated by applying the Scherrer formula to the (002) reflection peak.

[0275] Additional clause 7. The battery anode of additional clause 6, wherein the average grain size is in a range from about 15 nm to about 30 nm.

[0276] Additional clause 8. The battery anode of any one of additional clauses 1 to 7, wherein: the average pressure (Cx) required to deform at least a subset of the graphite active material particles by 10% during a microcompression hardness test ranges from about 1 MPa to about 30 MPa.

[0277] Additional clause 9. The battery anode of additional clause 8, wherein: the average pressure ranges from about 1 MPa to about 18 MPa.

[0278] Additional clause 10. The battery anode of any one of additional clauses 1 to 9, wherein: the tap density of at least a subset of the graphite active material particles is in a range from about 0.10 g / cc to about 1.25 g / cc.

[0279] Additional clause 11. The battery anode of additional clause 10, wherein: the tap density is in a range from about 0.90 g / cc to about 1.10 g / cc.

[0280] Additional clause 12. The battery anode of any one of additional clauses 1 to 11, wherein: at least a subset of the graphite active material particles has a pycnometer density in the range of about 2.15 g / cc to about 2.35 g / cc.

[0281] Additional clause 13. A battery anode according to any one of additional clauses 1 to 12, wherein: the 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

[0282] Additional clause 14. The battery anode according to additional clause 13, wherein: D 50 The range is from about 12 μm to about 17 μm.

[0283] Additional clause 15. A battery anode according to any one of additional clauses 1 to 14, wherein: the 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

[0284] Additional clause 16. The battery anode according to additional clause 15, wherein: D 90 The range is about 19 μm to about 26 μm.

[0285] Additional clause 17. A battery anode according to any one of additional clauses 1 to 16, wherein: the 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

[0286] Additional clause 18. The battery anode according to additional clause 17, wherein: D 10 The range is about 7 μm to about 11 μm.

[0287] Additional clause 19. A battery anode according to any one of additional clauses 1 to 18, wherein: at least a subset of the graphite active material particles has a Bronner-Emmett-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0288] Additional clause 20. The battery anode according to additional clause 19, wherein: the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0289] Additional clause 21. The battery anode of any one of additional clauses 1 to 20, wherein the weight fraction of at least a subset of graphite active material particles in the battery anode is in the range of about 1 wt.% to about 50 wt.% of the active material mixture.

[0290] Additional clause 22. The battery anode of additional clause 21, wherein: the weight fraction is in the range of about 2 wt.% to about 20 wt.% of the active material mixture.

[0291] Additional clause 23. A battery anode according to any one of additional clauses 1 to 22, wherein: the silicon-containing active material particles contain oxygen (O) atoms, the mass of which is about 5 wt.% or less (in other designs, about 2 wt.% or less; in other designs, about 1 wt.% or less) of the total mass of the silicon-containing active material particles.

[0292] Additional clause 24. The battery anode of any one of additional clauses 1 to 23, wherein the silicon-containing active material particles comprise silicon (Si) atoms and carbon (C) atoms totaling in the range of 80 wt.% to about 100 wt.% of the total mass of the silicon-containing active material particles.

[0293] Additional clause 25. The battery anode of additional clause 24, wherein the Si-containing active material particles comprise Si-C nanocomposite particles.

[0294] Additional clause 26. The battery anode of any one of additional clauses 1 to 25, wherein: at least a subset of the graphite active material particles exhibits a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0295] Additional clause 27. A lithium ion battery comprising: a battery anode of Additional clause 1; a cathode; a separator electrically separating the battery anode and cathode; and an electrolyte ionically coupling the battery anode and cathode.

[0296] Additional clause 28. A battery anode comprising: a binder; a conductive additive; and an active material mixture, the active material mixture comprising 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.%; 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; at least a subset of the graphite active material particles is characterized by Raman spectroscopy (e.g., collected using a 532 nm laser), and in the Raman spectrum, the full width at half maximum (FWHM) of the D band is about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 110cm -1 and a D / G peak intensity ratio (defined as the D peak intensity divided by the G peak intensity) is in a range of about 0.02 to about 1.12; and an average pressure (Cx) required to deform at least a subset of the graphite active material particles by 10% during a microcompression hardness test is in a range of about 1 MPa to about 18 MPa.

[0297] Additional clause 29. The battery anode of additional clause 28, wherein the mass ratio of silicon-containing active material particles to graphite active material particles is in the range of about 75:25 to about 95:5.

[0298] Additional clause 30. The battery anode of any one of additional clauses 28 to 29, wherein the average pressure ranges from about 7 MPa to about 18 MPa.

[0299] Additional clause 31. The battery anode of additional clause 30, wherein: the average pressure ranges from about 10 MPa to about 18 MPa.

[0300] Additional clause 32. The battery anode of any one of additional clauses 28 to 31, wherein the D / G peak intensity ratio is in a range from about 0.12 to about 0.30.

[0301] Additional clause 33. The battery anode of any one of additional clauses 28 to 32, wherein: the tap density of at least a subset of the graphite active material particles is in the range of about 0.10 g / cc to about 1.25 g / cc.

[0302] 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.

[0303] Additional clause 35. A battery anode according to any one of additional clauses 28 to 34, wherein: the 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

[0304] Additional clause 36. The battery anode according to additional clause 35, wherein: D 50 Ranges from about 11 μm to about 17 μm.

[0305] Additional clause 37. The battery anode according to additional clause 36, wherein: D 50 Ranges from about 12 μm to about 17 μm.

[0306] Additional clause 38. A battery anode according to any one of additional clauses 28 to 37, wherein: the 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

[0307] Additional clause 39. The battery anode according to additional clause 38, wherein: D 90 The range is about 19 μm to about 30 μm.

[0308] Additional clause 40. The battery anode according to additional clause 39, wherein: D 90 The range is about 19 μm to about 26 μm.

[0309] Additional clause 41. A battery anode according to any one of additional clauses 28 to 40, wherein: the 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

[0310] Additional clause 42. The battery anode according to additional clause 41, wherein: D 10 The range is about 5 μm to about 11 μm.

[0311] Additional clause 43. The battery anode according to additional clause 42, wherein: D 10 The range is about 7 μm to about 11 μm.

[0312] Additional clause 44. The battery anode of any one of additional clauses 28 to 43, wherein: at least a subset of the graphite active material particles has a Bronner-Emmett-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0313] Additional clause 45. The battery anode according to additional clause 44, wherein: the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0314] Additional clause 46. The battery anode according to additional clause 45, wherein: the BET-SSA range is about 1 m 2 / g to about 3m 2 / g.

[0315] Additional clause 47. A battery anode according to any one of additional clauses 28 to 46, wherein: the silicon-containing active material particles contain oxygen (O) atoms, the mass of which is about 5 wt.% or less (in other designs, about 2 wt.% or less; in other designs, about 1 wt.% or less) of the total mass of the silicon-containing active material particles.

[0316] Additional clause 48. The battery anode of any one of additional clauses 28 to 47, wherein the Si-containing active material particles comprise silicon (Si) atoms and carbon (C) atoms totaling from about 80 wt.% to about 100 wt.% of the total mass of the Si-containing active material particles.

[0317] Additional clause 49. The battery anode of additional clause 48, wherein the Si-containing active material particles comprise Si-C nanocomposite particles.

[0318] Additional clause 50. The battery anode of any one of additional clauses 28 to 49, wherein: at least a subset of the graphite active material particles exhibits a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0319] Additional clause 51. The battery anode of any one of additional clauses 28 to 50, wherein: the battery anode has a 2 to about 16 mAh / cm 2 Reversible capacity load within the range.

[0320] Additional clause 52. A lithium ion battery comprising: the battery anode of additional clause 28; a cathode; a separator electrically separating the battery anode and cathode; and an electrolyte ionically coupling the battery anode and cathode.

[0321] Additional clause 53. A battery anode comprising: a binder; a conductive additive; and an active material mixture, the active material mixture comprising 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.%; the 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 subset of the graphite active material particles is characterized by Raman spectroscopy (e.g., collected using a 532 nm laser), and in the Raman spectrum, the full width at half maximum (FWHM) of the D band is about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 110cm -1 and a D / G peak intensity ratio (defined as the D peak intensity divided by the G peak intensity) in a range of about 0.02 to about 1.12; and an average pressure (Cx) required to deform at least a subset of the graphite active material particles by 10% during a microcompression hardness test in a range of about 20 MPa to about 30 MPa.

[0322] Additional clause 54. The battery anode of additional clause 53, wherein the mass ratio of silicon-containing active material particles to graphite active material particles is in the range of about 10:90 to about 30:70.

[0323] Additional clause 55. The battery anode of any one of additional clauses 53 to 54, wherein the average pressure ranges from about 24 MPa to about 30 MPa.

[0324] Additional clause 56. The battery anode of any one of additional clauses 53 to 55, wherein the D / G peak intensity ratio is in a range from about 0.08 to about 0.30.

[0325] Additional clause 57. The battery anode of any one of additional clauses 53 to 56, wherein: the tap density of at least a subset of the graphite active material particles is in the range of about 0.10 g / cc to about 1.25 g / cc.

[0326] 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.

[0327] 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.

[0328] Additional clause 60. A battery anode according to any one of additional clauses 53 to 59, wherein: the 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

[0329] Additional clause 61. A battery anode according to additional clause 60, wherein: D 50 The range is from about 11 μm to about 17 μm.

[0330] Additional clause 62. A battery anode according to additional clause 61, wherein: D 50 The range is from about 12 μm to about 17 μm.

[0331] Additional clause 63. A battery anode according to any one of additional clauses 53 to 62, wherein: the 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

[0332] Additional clause 64. The battery anode according to additional clause 63, wherein: D 90 The range is from about 19 μm to about 30 μm.

[0333] Additional clause 65. A battery anode according to any one of additional clauses 53 to 64, wherein: the 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

[0334] Additional clause 66. The battery anode according to additional clause 65, wherein: D 10 The range is about 5 μm to about 11 μm.

[0335] Additional clause 67. A battery anode according to any one of additional clauses 53 to 66, wherein: at least a subset of the graphite active material particles has a Bronner-Emmett-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

[0336] Additional clause 68. The battery anode according to additional clause 67, wherein: the BET-SSA range is about 1 m 2 / g to about 5m 2 / g.

[0337] Additional clause 69. The battery anode according to additional clause 68, wherein: the BET-SSA range is about 1 m 2 / g to about 3m 2 / g.

[0338] Additional clause 70. A battery anode according to any one of additional clauses 53 to 69, wherein: the silicon-containing active material particles contain oxygen (O) atoms, the mass of which is about 5 wt.% or less (in other designs, about 2 wt.% or less; in other designs, about 1 wt.% or less) of the total mass of the silicon-containing active material particles.

[0339] Additional clause 71. A battery anode according to any one of additional clauses 53 to 70, wherein: the Si-containing active material particles include silicon (Si) atoms and carbon (C) atoms totaling in the range of about 80 wt.% to about 100 wt.% of the total mass of the Si-containing active material particles.

[0340] Additional clause 72. The battery anode of additional clause 71, wherein the Si-containing active material particles comprise Si-C nanocomposite particles.

[0341] Additional clause 73. The battery anode of any of additional clauses 53 to 72, wherein: at least a subset of the graphite active material particles exhibits a specific capacity in the range of about 320 mAh / g to about 372 mAh / g.

[0342] Additional clause 74. The battery anode of any one of additional clauses 53 to 73, wherein: the battery anode has a capacitance at about 2 mAh / cm 2 to about 16 mAh / cm 2 Reversible capacity load within the range.

[0343] Additional clause 75. A lithium ion battery comprising: a battery anode of additional clause 53; a cathode; a separator electrically separating the battery anode and cathode; and an electrolyte ionically coupling the battery anode and cathode.

[0344] 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.

[0345] Additional clause 77. The battery anode of additional clause 75, wherein: at least some of the Si nanoparticles are coated with a conductive carbon layer (e.g., with an average thickness of about 0.3-10 nm).

[0346] 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.

[0347] Additional clause 79. The battery anode of additional clause 75, wherein: the average grain size of the Si nanoparticles is in the range of about 1 nm to about 20 nm as estimated by X-ray diffraction using the Scherrer equation.

[0348] 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 that exhibit a true density in the range of about 1.4 to about 1.9 g / cc (e.g., about 1.4-1.6 g / cc or about 1.6-1.75 g / cc or about 1.75-1.9 g / cc) when measured using an N2 pycnometer method.

[0349] Additional clause 81. A battery anode according to any one of additional clauses 1 to 79, wherein the Si-containing active material particles are Si-C nanocomposite particles, and the 50th percentile volume weighted particle size parameter (D 50 ) is in the range of about 4 to about 16 microns (e.g., about 4-7 microns or 7-10 microns or about 10-13 microns or about 13-16 microns or about 7-13 microns).

[0350] This description is intended to assist those skilled in the art in making or using the embodiments of the present invention. However, it should be understood that the present invention is not limited to the specific formulations, process steps, and materials disclosed herein, as various modifications to these embodiments will be readily apparent to those skilled in the art. In other words, the general principles defined herein can be applied to other embodiments without departing from the spirit or scope of the present invention.

Claims

1. A battery anode, comprising: Adhesives; Conductive additives; and an active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, in: The battery anode has a current of about 2 mAh / cm 2 to about 16 mAh / cm 2 Reversible capacity load within the range; The silicon-containing active material particles exhibit a specific capacity in a range of about 800 mAh / g to about 3000 mAh / g; The silicon-containing active material particles contribute from about 25% to about 99% of the total capacity of the battery anode; and At least a subset of the graphite active material particles is characterized by Raman spectroscopy in which a D band has a full width at half maximum (FWHM) of about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 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.

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

30.

3. The battery anode according to claim 1, wherein: The 2D1 / G peak intensity ratio, defined as the 2D1 peak intensity divided by the G peak intensity of the Raman spectrum, is in the range of about 0.10 to about 0.

90.

4. The battery anode according to claim 1, wherein: The at least one subset of the graphite active material particles is characterized by an X-ray diffraction (XRD) spectrum in which a FWHM of a (002) reflection peak is in a range from about 0.220 degrees to about 5.620 degrees.

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

6. The battery anode according to claim 4, wherein: The average crystallite size of the at least one subset of the graphite active material particles is estimated to be in a range from about 1 nm to about 40 nm by applying the Scherrer equation to the (002) reflection peak.

7. The battery anode according to claim 6, wherein The average grain size is in a range from about 15 nm to about 30 nm.

8. The battery anode according to claim 1, wherein: An average pressure (Cx) required to deform the at least one subset of the graphite active material particles by 10% during a micro-compression hardness test ranges from about 1 MPa to about 30 MPa.

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

10. The battery anode according to claim 1, wherein: The at least a subset of the graphite active material particles has a tap density in a range from about 0.10 g / cc to about 1.25 g / cc.

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

12. The battery anode according to claim 1, wherein: The at least a subset of the graphite active material particles has a pycnometer density in a range from about 2.15 g / cc to about 2.35 g / cc.

13. The battery anode according to claim 1, wherein: The 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

14. The battery anode according to claim 13, wherein: The D 50 The range is from about 12 μm to about 17 μm.

15. The battery anode according to claim 1, wherein: The 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

16. The battery anode according to claim 15, wherein: The D 90 The range is from about 19 μm to about 26 μm.

17. The battery anode according to claim 1, wherein: The 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

18. The battery anode according to claim 17, wherein: The D 10 The range is from about 7 μm to about 11 μm.

19. The battery anode of claim 1, wherein: The at least one subset of the graphite active material particles has a Bronner-Emmet-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

20. The battery anode of claim 19, wherein: The Bronner-Emmet-Tyler specific surface area is in the range of about 1 m 2 / g to about 5m 2 / g.

21. The battery anode of claim 1, wherein: The weight fraction of the at least a subset of the graphite active material particles in the battery anode is in a range from about 1 wt. % to about 50 wt. % of the active material mixture.

22. The battery anode of claim 21, wherein: The weight fraction is in the range of about 2 wt. % to about 20 wt. % of the active material mixture.

23. The battery anode of claim 1, wherein: The silicon-containing active material particles include oxygen (O) atoms at about 5 wt. % or less based on the total mass of the silicon-containing active material particles.

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

25. The battery anode of claim 24, wherein: The silicon-containing active material particles include silicon-carbon nanocomposite particles.

26. The battery anode of claim 1, wherein: The at least one subset of the graphite active material particles exhibits a specific capacity in a range from about 320 mAh / g to about 372 mAh / g.

27. A lithium-ion battery comprising: The battery anode according to claim 1; cathode; a separator electrically isolating the battery anode from the battery cathode; as well as An electrolyte that ionically couples the battery anode and the cathode.

28. A battery anode comprising: Adhesives; Conductive additives; and an active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, in: The mass fraction of silicon in the silicon-containing active material particles is in the range of about 20 wt % to about 80 wt %; The mass ratio of the silicon-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 subset of the graphite active material particles is characterized by Raman spectroscopy, wherein the D band has a full width at half maximum (FWHM) of about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 110cm- 1 and a D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, in a range of about 0.02 to about 1.12; and An average pressure (Cx) required to deform the at least a subset of the graphite active material particles by 10% during a micro-compression hardness test ranges from about 1 MPa to about 18 MPa.

29. The battery anode of claim 28, wherein: A mass ratio of the silicon-containing active material particles to the graphite active material particles is in a range of about 75:25 to about 95:

5.

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

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

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

30.

33. The battery anode of claim 28, wherein: The at least a subset of the graphite active material particles has a tap density in a range from about 0.10 g / cc to about 1.25 g / cc.

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

35. The battery anode of claim 28, wherein: The 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

36. The battery anode of claim 35, wherein: The D 50 The range is from about 11 μm to about 17 μm.

37. The battery anode of claim 36, wherein: The D 50 The range is from about 12 μm to about 17 μm.

38. The battery anode of claim 28, wherein: The 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

39. The battery anode of claim 38, wherein: The D 90 The range is from about 19 μm to about 30 μm.

40. The battery anode of claim 39, wherein: The D 90 The range is from about 19 μm to about 26 μm.

41. The battery anode of claim 28, wherein: The 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

42. The battery anode of claim 41, wherein: The D 10 The range is from about 5 μm to about 11 μm.

43. The battery anode of claim 42, wherein: The D 10 The range is from about 7 μm to about 11 μm.

44. The battery anode of claim 28, wherein: The at least one subset of the graphite active material particles has a Bronner-Emmet-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

45. The battery anode of claim 44, wherein: The Bronner-Emmet-Tyler specific surface area is in the range of about 1 m 2 / g to about 5m 2 / g.

46. ​​The battery anode of claim 45, wherein: The Bronner-Emmet-Tyler specific surface area is in the range of about 1 m 2 / g to about 3m 2 / g.

47. The battery anode of claim 28, wherein: The silicon-containing active material particles include oxygen (O) atoms at about 5 wt. % or less based on the total mass of the silicon-containing active material particles.

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

49. The battery anode of claim 48, wherein: The silicon-containing active material particles include silicon-carbon nanocomposite particles.

50. The battery anode of claim 28, wherein: The at least one subset of the graphite active material particles exhibits a specific capacity in a range from about 320 mAh / g to about 372 mAh / g.

51. The battery anode of claim 28, wherein: The battery anode has a current of about 2 mAh / cm 2 to about 16 mAh / cm 2 Reversible capacity load within the range.

52. A lithium-ion battery comprising: The battery anode according to claim 28; cathode; a separator that electrically separates the battery anode and the cathode; as well as An electrolyte that ionically couples the battery anode and the cathode.

53. A battery anode comprising: Adhesives; Conductive additives; and an active material mixture comprising silicon (Si)-containing active material particles and graphite active material particles, in: The mass fraction of the silicon in the silicon-containing active material particles is in the range of about 20 wt % to about 80 wt %. The mass ratio of the silicon-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 subset of the graphite active material particles is characterized by Raman spectroscopy, wherein the D band has a full width at half maximum (FWHM) of about 30 cm -1 to about 90cm -1 The FWHM of the G band is about 5 cm -1 to about 105cm -1 The FWHM of the 2D1 band is about 30 cm -1 to about 110cm -1 and a D / G peak intensity ratio, defined as the D peak intensity divided by the G peak intensity, in a range of about 0.02 to about 1.12; and An average pressure (Cx) required to deform the at least one subset of the graphite active material particles by 10% during a microcompression hardness test ranges from about 20 MPa to about 30 MPa.

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

70.

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

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

30.

57. The battery anode of claim 53, wherein: The at least a subset of the graphite active material particles has a tap density in a range from about 0.10 g / cc to about 1.25 g / cc.

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

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

60. The battery anode of claim 53, wherein: The 50th percentile volume-weighted particle size parameter (D 50 ) ranges from about 2 μm to about 22 μm.

61. The battery anode of claim 60, wherein: The D 50 The range is from about 11 μm to about 17 μm.

62. The battery anode of claim 61, wherein: The D 50 The range is from about 12 μm to about 17 μm.

63. The battery anode of claim 53, wherein: The 90th percentile volume-weighted particle size parameter (D 90 ) ranges from about 4 μm to about 30 μm.

64. The battery anode of claim 63, wherein: The D 90 The range is from about 19 μm to about 30 μm.

65. The battery anode of claim 53, wherein: The 10th percentile volume-weighted particle size parameter (D 10 ) ranges from about 0.5 μm to about 15 μm.

66. The battery anode of claim 65, wherein: The D 10 The range is from about 5 μm to about 11 μm.

67. The battery anode of claim 53, wherein: The at least one subset of the graphite active material particles has a Bronner-Emmet-Teller (BET) specific surface area (SSA) in the range of about 0.450 m 2 / g to about 450m 2 / g.

68. The battery anode of claim 67, wherein: The Bronner-Emmet-Tyler specific surface area is in the range of about 1 m 2 / g to about 5m 2 / g.

69. The battery anode of claim 68, wherein: The Bronner-Emmet-Tyler specific surface area is in the range of about 1 m 2 / g to about 3m 2 / g.

70. The battery anode of claim 53, wherein: The silicon-containing active material particles include oxygen (O) atoms at about 5 wt. % or less based on the total mass of the silicon-containing active material particles.

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

72. The battery anode of claim 71, wherein: The silicon-containing active material particles include silicon-carbon nanocomposite particles.

73. The battery anode of claim 53, wherein: The at least one subset of the graphite active material particles exhibits a specific capacity in a range from about 320 mAh / g to about 372 mAh / g.

74. The battery anode of claim 53, wherein: The battery anode has a current of about 2 mAh / cm 2 to about 16 mAh / cm 2 Reversible capacity load within the range.

75. A lithium-ion battery comprising: The battery anode according to claim 53; cathode; a separator electrically separating the battery anode and the cathode; as well as An electrolyte that ionically couples the battery anode and the cathode.

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