Electrodes, batteries including the electrodes, and methods of making batteries

Abstract

The present disclosure provides for electrodes, batteries that include the electrodes, method of making electrodes and the like. The present disclosure provides for electrodes that are thicker than typical electrodes that have a higher energy density at the cell level, regardless of the specific cell chemistry. The electrodes are all active material (AAM) electrodes (e.g., AAM anodes and AAM cathodes). In an aspect, the electrodes of the present disclosure have improved ion transport in the electrode microstructure and the concomitant reduced tortuosity and improved retention of electrochemical capacity at increased cycling rates.

Description

[0001] ELECTRODES, BATTERIES INCLUDING THE ELECTRODES, AND METHODS OF MAKING BATTERIES

[0002] CROSS-REFERENCE TO RELATED APPLICATION

[0003] This application claims priority to U.S. provisional application entitled “Combining Ester Solvent Containing Electrolytes with All Active Material Electrodes for High Current Density Lithium-Ion Batteries” having serial number 63 / 543,211 filed on October 9, 2023, which is entirely incorporated herein by reference.

[0004] STATEMENT ON FUNDING PROVIDED BY THE U.S. GOVERNMENT

[0005] This invention was made with government support under Grant No. 1652488, awarded by the National Science Foundation. The government has certain rights in the invention.

[0006] BACKGROUND

[0007] Lithium-ion batteries, due to their high energy density, are used in many devices such as electric vehicles, portable electronics, wearable devices, and implantable products. The energy density of the electrodes can be improved by manufacturing thicker electrodes that have higher areal loading. However, there are challenges to fabricating thick composite electrodes, such as mechanical instability originating from slurry drying and ion transport limitations. Thus, there is a need to address these challenges.

[0008] SUMMARY

[0009] The present disclosure provides for electrodes, batteries that include the electrodes (e.g., lithium batteries), method of making electrodes and the like

[0010] In an aspect, the present disclosure provides for a battery comprising: an all active material anode that includes a high conductivity ester-based electrolyte; and an all active material cathode that includes a high conductivity ester-based electrolyte.

[0011] In an aspect, the present disclosure provides for a method for making an electrode, comprising: compressing a first mixture to form a compressed material, wherein the first mixture includes an electroactive material; sintering the compressed material to form an electrode; and impregnating the electrode with a high conductivity ester-based electrolyte to form an all active material electrode. BRIEF DESCRIPTION OF DRAWINGS

[0012] Further aspects of the present disclosure will be more readily appreciated upon review of the detailed description of its various embodiments, described below, when taken in conjunction with the accompanying drawings.

[0013] Figure 1 illustrates a schematic of all active material (AAM) electrode manufacturing process.

[0014] Figures 2A-2C are graphs that illustrate physical properties for a variety of ester and carbonate solvents: methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), ethylene carbonate (EC), and propylene carbonate (PC). Relevant properties are (Figure 2A) temperature range for liquid phase at atmospheric pressure, (Figure 2B) dielectric constant, and (Figure 2C) viscosity. All values are taken from literature (literature reference numbers are in reference to Example -] ) 30,31 ,41-47,32-39

[0015] Figure 3 is a graph that illustrates ionic conductivity of MA (pink), EA (blue), PA (grey), and Gen2 (black)48, as a function of LiPFe concentration. Lines added between measured data points (circles) to guide the eye.

[0016] Figure 4 is a graph that illustrates charge / discharge cycling evaluation of thick AAM LTO / LCO cells using MA (pink), EA (blue), PA (grey), and Gen2 (black) electrolytes. Cells were cycled between 1 .0-2.6 V (cell). The first 30 cycles had the same charge and discharge rate, with rates indicated on the plot. Cycles 31 through 50 all had the same relatively slow charge rate (C / 20), and the indicated increasing rates of discharge. Cycles 51-70 had charge and discharge at C / 20. C / 20 corresponded to 1 .07 mA cm2.

[0017] Figure 5 is a graph that illustrates ionic conductivity of Gen2 (black)48, 20%EA (purple), 40%EA (red), 60%EA (orange), 80%EA (green), and EA (blue), as a function LiPF6concentration.

[0018] Figure 6 is a graph that illustrates charge / discharge cycling evaluation of thick AAM LTO / LCO cells using Gen2 (black), 20%EA (purple), 40%EA (red), 60%EA (orange), 80%EA (green), and EA (blue) electrolytes. Cells were cycled between 1.0-2.6 V (cell). The first 30 cycles had the same charge and discharge rate, with rates indicated on the plot. Cycles 31 through 50 all had the same relatively slow charge rate (C / 20), and the indicated increasing rates of discharge. Cycles 51-70 had charge and discharge at C / 20. C / 20 corresponded to 1.07 mA cm2.

[0019] Figure 7 is a graph that illustrates the discharge capacity as a function of charge / discharge cycle number Gen2 (black), 20%EA (purple), 40%EA (red), 60%EA (orange), 80%EA (green), and EA (blue) cells. Cells were both charged and discharged at 1C (2.5 mA cm2) using a voltage window of 1.0-3.0 (cell). Figure 8 is a graph that illustrates a ragone plot comparing LTO / LCO cells in this work with electrolytes that had MA (pink) and 80%EA (cyan) and other works.184052-55

[0020] Figures 9A-9D illustrates graphs of representative discharge voltage profiles for LTO / LCO AAM electrode full cells at increasing rates of discharge where the electrolyte was (Figure 9A) Gen2, (Figure 9B) MA, (Figure 9C) EA, and (Figure 9D) PA. The charge rate was C / 20 for all cycles and the discharge rate was C / 20 (black), C / 10 (purple), C / 5 (red), C / 2.5 (orange), and 1C (green).

[0021] Figures 10A-10F illustrate graphs of representative discharge voltage profiles for LTO / LCO AAM electrode full cells at increasing rates of discharge where the electrolyte was (Figure 10A) Gen2, (Figure 10B) 20%EA, (Figure 10C) 40%EA, (Figure 10D) 60%EA, (Figure 10D) 80%EA, and (Figure 10F) EA electrolyte. The charge rate was C / 20 for all cycles and the discharge rate was C / 20 (black), C / 10 (purple), C / 5 (red), C / 2.5 (orange), and 1C (green).

[0022] Figures 11A-11F illustrate graphs of charge and discharge profiles from cycle life evaluation of LTO / LCO AAM cells with electrolytes of (Figure 11A) Gen2, (Figure 11B) 20%EA, (Figure 11 C) 40%EA, (Figure 11 D) 60%EA, (Figure 11 E) 80%EA, and (Figure 11 F) EA electrolyte. The cycles corresponding to the data for each cell were the 1st (black), 100th(purple), 200th(red), 300th(orange), and 400th(green), and 500th(blue) cycle.

[0023] Figures 12A and 12B illustrate Nyquist plots from EIS conducted on thin LTO / LCO AAM electrode cells (Figure 12A) before cycling and (Figure 12B) after 500 cycles cells with electrolytes of Gen2 (black), 20%EA (purple), 40%EA (red), 60%EA (orange), 80%EA (green), and EA (blue).

[0024] DETAILED DESCRIPTION

[0025] In general, the present disclosure provides for electrolyte and electrode materials, methods of making electrolyte and electrode materials, batteries, methods of making batteries, methods of using batteries, and the like. Additional details are provided herein and in the Examples.

[0026] This disclosure is not limited to particular embodiments described, and as such may, of course, vary. The terminology used herein serves the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

[0027] Where a range of values is provided, each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure.

[0028] Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of chemistry, material science, electrochemistry and the like, which are within the skill of the art. Such techniques are explained fully in the literature.

[0029] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C, and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20 °C and 1 atmosphere.

[0030] Before the embodiments of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, dimensions, frequency ranges, applications, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence, where this is logically possible. It is also possible that the embodiments of the present disclosure can be applied to additional embodiments involving measurements beyond the examples described herein, which are not intended to be limiting. It is furthermore possible that the embodiments of the present disclosure can be combined or integrated with other measurement techniques beyond the examples described herein, which are not intended to be limiting.

[0031] It should be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a support” includes a plurality of supports. In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings unless a contrary intention is apparent.

[0032] Prior to describing the various embodiments, the following definitions are provided and should be used unless otherwise indicated.

[0033] Discussion

[0034] The present disclosure provides for electrodes, batteries that include the electrodes (e.g., lithium batteries), method of making electrodes and the like. The present disclosure provides for electrodes (e.g., anodes and cathodes) that are thicker than typical electrodes that have a higher energy density at the battery cell level, regardless of the specific battery cell chemistry. The electrodes are all active material (AAM) electrodes (e.g., AAM anodes and AAM cathodes). AAM electrodes are those that are comprised of only electroactive material and pores, where the pores are filled with electrolyte during battery cell fabrication. In an aspect, the electrodes of the present disclosure have improved ion transport in the electrode microstructure and the concomitant reduced tortuosity and improved retention of electrochemical capacity at increased cycling rates. In general, the AAM electrodes (e.g., which include little to no inactive additives such as binders) can be made by compression (e.g., hydraulic compression) of the material and then the compressed material is mildly sintered. Additional details are provided in Example 1.

[0035] In general, lithium batteries include an anode, a cathode, an electrolyte material, and a separator(s). Conventional rechargeable lithium-ion batteries operate by reversibly passing lithium-ions back and forth between the negative electrode and the positive electrode. A separator and an electrolyte may be disposed between the anode and the cathode. The electrolyte is suitable for conducting lithium-ions and may be in solid (e.g., solid state diffusion) or liquid form. Lithium-ions move from a cathode to an anode during charging of the battery, and in the opposite direction when discharging the battery.

[0036] The lithium-ion battery can be charged (for example a power supply or power source) by applying a voltage between the anode and cathode, which causes lithium ions and electrons to be withdrawn from the battery's cathode. Lithium ions flow from cathode to anode through electrolyte, where they insert into the anode during the reduction process occurring at that electrode. During discharge, the reverse occurs; lithium ions and electrons enter at cathode while the anode is oxidized and lithium ions leave the anode, which is typically an energetically favorable process that drives electrons through an external circuit, thereby supplying electrical power to a device to which the battery is connected. If sodium (Na) or potassium (K) metal is used instead Lithium (Li) metal, then the cation charge carrier in the electrolyte would change to Na or K (rather than Li as the cation charge carrier used with the Li metal and / or lithium-ion electrodes).

[0037] The present disclosure provides for anodes (also referred to as “AAM anode”) and cathodes (also referred to as “AAM cathode”). The AAM anode and / or AAM electrode can be used in lithium batteries. In an aspect, the battery can include an anode, where the anode is an AAM anode that includes a high conductivity ester-based electrolyte. In an aspect, the battery can include a cathode, where the cathode is an AAM cathode that includes a high conductivity ester-based electrolyte. In another aspect, the battery includes both the AAM anode and AAM cathode, where the high conductivity ester-based electrolyte in each can be the same or different. In another aspect, the AAM anode and / or AAM cathode can include a carbonate. In an aspect, the volume percentage of the high conductivity ester-based electrolyte within the electrode region of the battery cell for an AAM electrode is about 15 vol% to 70 vol%.

[0038] In an aspect, the volume percentage of the high conductivity ester-based electrolyte and carbonate within the electrode region of the battery cell for an AAM electrode (e.g., AAM anode and / or AAM cathode) is about 15 vol% to 70 vol%.

[0039] In an embodiment, the high conductivity ester-based electrolyte is an alkyl (e.g., C1 to C6 or C1 to C4) acetate or fluorinated organic additives. In an aspect, the alkyl acetate is a methyl-acetate, an ethyl-acetate, a propyl-acetate, or a mixture two or more of these. In an aspect, the alkyl acetate an ethyl-acetate.

[0040] In an aspect, the carbonate is a linear carbonate, a cyclic carbonate, or a combination of a linear carbonate and a cyclic carbonate. In an aspect, the linear carbonate can include ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, or a combination thereof. In an aspect, the cyclic carbonate can include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate, fluoroethylene carbonate, or a combination thereof.

[0041] In an aspect, the AAM anode can be made of electroactive materials such as lithium insertion materials or alloy host materials (e.g., carbon-based materials), lithium-graphite intercalation compounds, lithium-silicon compounds, lithium-tin alloys, and lithium titanate Li4+xTi50i2, where 0<x<3, such as Li4Ti50i2(LTO). In an aspect, the AAM cathode can be made of electroactive materials such as metal oxides: lithium cobalt oxide (LiCoO2) (LCO), lithium manganese oxide (LiMn2O4) (LMO), lithium nickel manganese spinel (LiNi05Mni5O4) (LMNO), lithium nickel cobalt aluminum oxide (LiNiCoAI02) (NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO2) (NMC), lithium iron phosphate (LiFePO4) (LFP), and combinations thereof.

[0042] In some aspects, the AAM anode and AAM cathode can include electroactive materials as provided in the following: a. Li metal anode and Li TisOi2cathode; b. Li metal anode and LiN2O4cathode, where N can be: a transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals; c. Li4Ti5Oi2anode and LiMO2cathode, where M can be: a transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals; d. Li4Ti50i2anode and LiM2O4cathode, where M can be: a transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals; e. IJN2O4 anode and LiM2O4cathode, where N can be: an transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals, and where M can be: an transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals; f. Li4Ti50i2 anode and LiNixMnyC0zO2 cathode, where x+y+z=1 ; g. LiN2O4anode and LiNixMnyC0zO2 cathode; where N can be: an transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals, and where x+y+z=1 ; h. Li metal anode and LiMO2cathode, where M can be: a transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals; or i. Li metal anode and LiM2O4cathode, where M can be: a transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or an alkali metal in isolation or combination of multiple alkali metals.

[0043] In an embodiment, some transition metals that may be used include, for example one or more of any combination of the following: iron (Fe), titanium (Ti), cobalt (Co), manganese (Mn), vanadium (V), nickel (Ni), chromium (Cr), aluminum (Al), or the like.

[0044] In some aspects, the AAM anode and AAM cathode can include electroactive materials as provided in the following: a. Li metal anode and LiCo02(LCO) cathode, b. Li metal anode and LiMn2O4(LMO) cathode, c. Li4TisOi2 (LTO) anode and LiCoO2(LCO) cathode, d. Li4TisOi2 (LTO) anode and LiMn2O4(LMO) cathode, or e. Li metal anode and LiNii / 3Mni / 3C0i / 3O2 (NMC or NCM) cathode.

[0045] In some aspects, the AAM anode and AAM cathode can include materials as provided in the following: a. Na metal anode and Na4Ti50i2 cathode; b. K metal anode and K4Ti50i2cathode; c. Na metal anode and NaMO2cathode, where M can be: any transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or any alkali metal in isolation or combination of multiple alkali metals; d. K metal anode and KMO2cathode, where M can be: any transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or any alkali metal in isolation or combination of multiple alkali metals; e. Na metal anode and NaM2O4cathode, where M can be: any transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or any alkali metal in isolation or combination of multiple alkali metals; or f. K metal anode and KM2O4cathode, where M can be: any transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or any alkali metal in isolation or combination of multiple alkali metals; g. Na4Ti50i2anode and NaMO2or NaM2O4cathode, where M can be: any transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or any alkali metal in isolation or combination of multiple alkali metals; or h. K4Ti5Oi2anode and KMO2or KM2O4cathode, where M can be: any transition metal in isolation or combination of multiple transition metals, Al in isolation or in combination of one or more transition metals, or any alkali metal in isolation or combination of multiple alkali metals.

[0046] If sodium (Na) or potassium (K) metal is used instead Lithium (Li) metal then the cation charge carrier in the electrolyte would change to Na or K (rather than Li as the cation charge carrier used with the Li metal).

[0047] In an aspect, the AAM anode electrode and / or AAM cathode electrode can include: about 100% of the electroactive material (by mass before electrolyte addition), the ester- based electrolyte, and / or the carbonate on a weight basis; about 98-100% the electroactive material (by mass before electrolyte addition), the ester-based electrolyte, and / or the carbonate on a weight basis; about 90 to 100% the electroactive material (by mass before electrolyte addition), the ester-based electrolyte, and / or the carbonate on a weight basis; about 95 to about 100% the electroactive material (by mass before electrolyte addition), the ester-based electrolyte, and / or the carbonate on a weight basis; about 92 to about 98% the electroactive material (by mass before electrolyte addition), the ester-based electrolyte, and / or the carbonate on a weight basis; about 94 to about 96% the electroactive material (by mass before electrolyte addition), the ester-based electrolyte, and / or the carbonate on a weight basis; or about 90, 91 , 92, 93, 94, 95, 96, 97, 98, or 99% (or any fractions there between) the electroactive material (by mass before electrolyte addition), the ester-based electrolyte, and / or the carbonate on a weight basis. In an aspect, the AAM anode and / or AAM cathode can free of or at least substantially free of: battery binder material, conductive additive material, or battery binder material and conductive additive material. The term “at least substantially free” is defined as one of: about 100% free, about 98% free, about 90% to 100% free, about 95% to about 100% free, about 92% to about 98% free, about 94% to about 96% free, or about 98% percent to about 100% free.

[0048] In an embodiment, the AAM anode and / or AAM cathode do not include (e.g., include about 1% (by weight) or less, about 2% or less, about 4% or less, about 6% or less, or about 10% or less) inactive additives such as conductive additives and polymer binders. In an aspect, conductive additives include carbon-based materials such as acetylene black. In an aspect, binders include polyvinylidiene fluoride, carboxymethyl cellulose, polytetrafluoroethylene, styrene butadiene rubber, and / or polyvinyl pyrrolidone.

[0049] In an embodiment the AAM anode and AAM cathode consist essentially of the electroactive material, the ester-based electrolyte, and / or the carbonate, where “consist essentially of’ means that the AAM anode and AAM cathode include the electroactive material, the ester-based electrolyte, and / or the carbonate and no other inactive additives (other than trace amounts such as less than about 1% (by weight) or less or 2% or less, about 4% or less), but may include trace amounts of other materials.

[0050] The electrolyte of the battery (e.g., lithium-ion battery) can include a solution that can conduct lithium ions between the cathode and anode. A non-aqueous electrolyte solution can be an ether-based electrolyte (that is stabilized with lithium nitrite), a lithium salt dissolved in an organic solvent or a mixture of organic solvents. In an aspect, the lithium salts can include: LiCIO4, LiAICk, Lil, LiBr, LiB(C2O4)2(LiBOB), LiBF2(C2O4) (LiODFB), LiSCN, LiBF4, LiB(C6H5)4, LiAsFe, LiCF3SO3, LiN(FSO2)2(LIFSI), LiN(CF3SO2)2(LITFSI), LiPF6, LiPF4(C2O4) (LiFOP), LiNO3, and mixtures thereof. In an aspect, the ether-based solvents can include: cyclic ethers (e.g., 1 ,3-dioxolane, tetrahydrofuran, 2- methyltetrahydrofuran) and chain structure ethers (e.g., 1 ,2-dimethoxyethane, 1-2- diethoxyethane, ethoxymethoxyethane, tetraethylene glycol dimethyl ether (TEGDME), polyethylene glycol dimethyl ether (PEGDME), and mixtures thereof).

[0051] In an aspect, the AMM anode and / or AAM cathode can have a thickness of about 50 pm to 3000 pm; about 50 pm to 2000 pm; about 50 pm to 1000 pm; about 100 pm to 1 ,000 pm; about 150 pm to 400 pm; about 250 pm to 800 pm; about 270 pm to 800 pm; about 680 to 760 pm; about 350 pm to 500 pm; about 300 pm to 800 pm; about 350 pm to 400 pm; about 400 pm to 800 pm; about 450 pm to 600 pm; about 400 pm to 500 pm; about 500 pm to 800 pm; or about 800 pm to 1 ,000 pm. In an aspect, the AAM anode has a thickness of about 680 to 760 pm or about 700 to 740 pm, or about 710 to 730 pm. In an aspect, the AAM cathode has a thickness of about 400 to 500 pm or about 440 to 470 pm, or about 450 to 460 m.

[0052] In an aspect, the AAM anode has a porosity (pore volume fraction) of about 0.2 to 0.7, about 0.2 to 0.4, about 0.3 to 0.4, about 0.32 to 0.35 or about 0.33 to 0.34. In an aspect, the AAM cathode has a porosity of about 0.2 to 0.7, about 0.2 to 0.5, about 0.3 to 0.5, about 0.40 to 0.43 or about 0.41 to 0.42.

[0053] In an aspect, the AAM anode has a loading of about 20 to 1000 mg cm2, about 20 to 200 mg cm2, about 50 to 200 mg crrr2, about 100 to 200 mg cm2, about 140 to 152 mg cnr2, 142 to 150 mg cm2, 145 to 148 mg cm2. In an aspect, the AAM cathode has a loading of about 20 to 1000 mg cnr2, about 20 to 200 mg cm2, about 50 to 200 mg cm2, about 100 to 200 mg cm2, about 140 to 152 mg cm2, 142 to 148 mg cm2, 144 to 146 mg cm2.

[0054] In an aspect, the AAM anode can have an electrode areal capacity of about 2 mAh / cm2to 300 mAh / cm2or about 5 mAh / cm2to 100 mAh / cm2. In an aspect, the AAM cathode can have an electrode areal capacity of about 2 mAh / cm2to 300 mAh / cm2or about 5 mAh / cm2to 100 mAh / cm2.

[0055] In an aspect, the AAM anode can have a current density of about 105mA / cm2to 100 mA / cm2or about 105mA / cm2to 75 mA / cm2. In an aspect, the AAM cathode can have a current density of about 105mA / cm2to 100 mA / cm2or about 105mA / cm2to 75 mA / cm2.

[0056] The present disclosure provides for methods of making electrodes (e.g., AAM anode and AAM cathodes). In an aspect, the method includes compressing (e.g., hydraulic press) a first material to form a compressed material. In an aspect, the first material includes an electroactive material (e.g., powder or pellets of the materials can be made into AAM anodes and AAM cathodes as described herein). The first mixture can also include a binder. In an aspect, the compression applies a force of about 40 to 4,000 MPa (for a 1 cm2electrode) upon the first mixture for a time frame of about 1 second to 2 minutes. After compression, the compressed material can be sintered (e.g., a light sintering) to form an electrode. In an aspect, sintering includes exposing the compressed material to a temperature of about 300 to 1500° C (e.g., in an oven or furnace) for a time period of about 1 second to 30 hours. Sintered can remove (e.g., burn off) the binder or other residual material. In cases where “light sintering” is targeted, light sintering is meant to refer to a thermal processing condition where the change of the electrode dimension in any direction after sintering is less than 5% compared to the same dimension after hydraulic compression. After sintering, that electrode (e.g., AAM cathode and / or AAM electrode depending upon the electroactive material used in the first mixture) can be impregnated with the high conductivity ester-based electrolyte. For example, the high conductivity ester-based electrolyte can be impregnated in the electrode during battery cell fabrication. The electrode can consist essentially of the high conductivity ester-based electrolyte, the electroactive material, and / or the carbonate. The phrase “consist essentially of’ is intended to exclude or substantially (e.g., about 95%, about 97%, about 98%, about 99%, or about 100%) exclude polymer binders or conductive additives that are typically used in lithium battery cathodes and / or anodes.

[0057] While embodiments of the present disclosure are described in connection with the Examples and the corresponding text and figures, there is no intent to limit the disclosure to the embodiments in these descriptions. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure.

[0058] EXAMPLE 1 1. Initial Introduction

[0059] Lithium-ion batteries (LIBs) have propelled human society via enabling electric vehicles, portable electronics, wearable devices, and implantable products due to their high energy density.1 2A method to further improve energy density is to manufacture thicker electrodes with higher areal loading, which will increase energy density of the cell level regardless of electroactive material chemistry.34However, there are challenges to fabricating thick composite electrodes, such as mechanical instability originating from slurry drying and ion transport limitations.5Recently, an emerging electrode architecture composed of only electroactive material without polymer binders or conductive additives has been investigated.67These “all active material” electrodes will be referred to as “AAM” electrodes in this paper, and have also been called “sintered” electrodes in some prior works.78 17 9-16AAM electrodes are fabricated via hydraulic compression of the electroactive material powder into a porous pellet, and mildly sintered to aid inter-particle connections while maintaining moderate porosity. A schematic of AAM electrode processing can be found in Figure 1 . The direct compression and lack of slurry casting circumvents the mechanical limitations of composite electrodes, where during slurry drying at high thickness the electrode can inhomogenously sediment resulting in cracks and / or delamination.5 18For AAM electrodes, well over 500 pm thickness and loadings exceeding 100 mg cnr2has been reported with excellent cycle stability.68-14 19In addition, AAM electrode architecture has relatively lower tortuosity to facilitate ion transport, mitigating ionic overpotentials and electrolyte ion depletion. This is because of the removal of inactive conductive additives and polymer binders, which exacerbate ion transport limitations in composite electrodes.2021

[0060] When making thick Li-ion electrodes, ion transport through the electrode microstructure for most cases becomes the rate limiting process. Previous studies on AAM electrode cells suggested relatively low rate of ~C / 20 was necessary to achieve reasonable capacity delivered on a gravimetric basis. At higher rates of even C / 10 the capacity retention would drop to less than 70% relative to low rate cycling of the same materials in thin electrodes.6 12 19Various strategies have been investigated to overcome cycling rate limitations for thick electrodes, including electrode microstructure modification using methods such as ice-templating,89 22laser patterning,2324and creating porosity gradients.25-27Another option to improve ion transport in electrode microstructures is to use electrolytes with improved transport properties. Conventional carbonate-based electrolytes use blends of linear and cyclic carbonates.2829For Li-ion battery electrolyte solvents, common linear carbonates include ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC); common cyclic carbonates include ethylene carbonate (EC) and propylene carbonate (PC). With graphite being a common Li-ion anode material, cyclic carbonates with high dielectric constant are often used to facilitate formation of a stable passivating solid electrolyte interphase (SEI). A drawback of the cyclic carbonates is relatively high viscosity. Thus, in many cases linear carbonates with relatively lower viscosity (but lower dielectric constants) are blended with the cyclic carbonate when making an electrolyte solution. An additional consideration and limitation for many carbonate electrolytes is a relatively high freezing point, and low temperature electrolyte transport properties are one contributor to range reduction for electric vehicles during winter. Ester-based solvents have also been investigated for use as Li-ion battery electrolytes. The solvents investigated herein include methyl, ethyl, and propyl acetate (MA, EA, and PA), which all have freezing points below -80 °C. Figure 2a30-39displays the liquid temperature range at atmospheric pressure for range of esters and carbonates, implying low temperature operation should be suitable for ester solvents. These esters also have relatively low viscosities, and intermediate values for dielectric constants. The ester MA was previously evaluated as an electrolyte component for Li-ion cells with AAM electrodes, and the result was significantly improved rate capability compared to a carbonate electrolyte baseline.40Figures 2b and 2c41-47show the viscosity and dielectric constant of representative esters and carbonates at room temperature from literature. Herein, AAM full cells with AAM LiCoO2(LCO) cathodes and AAM Li4Ti5Oi2(LTO) anodes were fabricated, and their electrochemical outcomes were assessed for different ester-based electrolytes. These electrolytes significantly improved cell rate capabilities.

[0061] 2. Materials and Methods

[0062] 2.1 Electrolyte Preparation and Characterization

[0063] A baseline carbonate electrolyte, referred to as “Gen2”, was used for comparison to the prepared electrolytes containing esters. Gen2 was 1.2 M LiPF6in 1 :3 ethylene carbonate (EC):ethyl methyl carbonate (EMC) by volume (Gotion). Electrolytes containing only single solvents of MA (Acros Organics), EA (Acros Organics), and PA (Spectrum Chemical MFG Corp) were prepared. The as received ester solvents were equilibrated with molecular sieves for a minimum time scale of overnight to remove trace water. In addition to the pure ester solvent electrolytes, blends of electrolytes were also prepared where EA was blended with Gen2. For these carbonate / ester blends, additional LiPF6salt (Gotion) was added to adjust the salt molarity. All electrolyte compositions used LiPF6as solute, with summary composition information listed in Table 1.

[0064] Table 1. Electrolyte compositions used in this study.

[0065] Ionic conductivity of the solvents as a function of LiPFe concentration was measured using a Mettler Toledo conductivity probe. Each electrolyte concentration was achieved by adding the necessary LiPF6amount and mixing was aided through the use of a vortex mixer (Fisher).

[0066] 2.2 Electroactive material preparation

[0067] The anode material was LTO (Nanomyte from NEI), which was purchased from a commercial supplier and not modified prior to AAM electrode fabrication. Cathode material used in all battery cells in this work was LCO, which was synthesized via coprecipitation followed by solid state reaction. LCO material was not purchased from commercial vendors because commercial LCO particle size was usually much greater than the materials used, and very large particles have negatively impacted AAM electrode mechanical properties. For LCO synthesis, briefly, sodium oxalate (Na2C2O4, Fisher) and cobalt sulfate heptahydrate (COS04*7H20, Acros Organics), each of 0.2 M were separately dissolved into deionized (DI) water volumes of 400 mL. Both solutions were heated to 60 °C, followed by adding cobalt solution to the oxalate solution all at once. The combined solution was stirred at 300 RPM and maintained at 60 °C using a heater / stirrer, and the reaction was allowed to proceed for 30 min. COC2O4*2H2O powder was then collected via vacuum filtration, and the powder from the filter cake was dried at 80°C overnight in air. The dried powder was then blended with lithium carbonate (Li2CC>3, Fisher) with Li:Co molar ratio of 1 .05:1 using a mortar and pestle by hand for 10 min. The powder mixture was heated in air with a ramp rate of 1 °C min1to 800 °C without a hold, and allowed to cool down to room temperature without cooling rate controlled. Detailed characterization of the LCO materials synthesized using this method can be found in previous reports.6’11 14

[0068] 2.3 AAM Electrode Fabrication

[0069] LCO of 1 .0 g was coated with 2 mL of 1 wt% polyvinyl butyral (PVB, Pfaltz & Bauer) in ethanol. LTO of 1 .0 g was coated with 4 mL of same binder solution. The PVB solution was added to the powder, and the resulting slurry was blended in a mortar using a pestle by hand until dried in air at room temperature. The coated powder was loaded into a circular pellet die (Carver), and hydraulically compressed at 400 MPa for 2 min. Resulting pellets were sintered in air at 700 °C for 1 h, with ramp up and down rates of 2 °C min1. Thick (for assessing electrolyte conductivity impacts) and thin (for cycle life evaluation) AAM electrode cells with two loadings and thicknesses were fabricated, and detailed dimensions are listed in Table 2.

[0070] The as-prepared AAM electrode pellets were attached to coin cell stainless steel spacer discs with 15 mm diameter and 0.25 mm thickness (serving as the current collectors) using a custom carbon paste. The paste was fabricated by blending acetylene black (CB), polyvinyl pyrrolidone (PVP, Sigma Aldrich, 360 kDa molecular weight), and ethanol with mass ratio of 1 :1 :19 for CB:PVP:ethanol. After attachment the pellets were dried under vacuum at 80 °C for 30 min.

[0071] Table 2. AAM electrode parameters in this study.

[0072] 2.4 Electrochemical Evaluation

[0073] Glass fiber (G6 from Fisher) was punched into circles with an area of 2 cm2and used as separators. The pellets (adhered to the spacer discs with the buffer layer) and separators were transferred into an argon-filled glove box before cell assembly. 2032-type coin cells were fabricated using the electrolytes listed in Table 1. Thick cells, with LCO being the capacity-limiting electrode, were cycled between 1 .0-2.6 V (cell) at rates from C / 20 (1 .07 mA cm2) to 1C (21.5 mA cm2). Thin cells, with LTO being the limiting electrode, were cycled between 1 .0-3.0 V at 1C (2.54 mA cm2). For thin cells, before and after cycling, electrochemical impedance spectroscopy (EIS) was conducted using a Gamry Reference 600.

[0074] 3. Results and Discussion

[0075] 3.1 Single Solvent Ester and Gen2 Electrolytes

[0076] Ionic conductivity of MA, EA, PA, and Gen2 as a function of LiPFs concentration is shown in Figure 3. The peak ionic conductivity for MA was greatest, followed by EA, PA and Gen2. The molar concentrations where peak ionic conductivity was observed for the esters was at a higher concentration than the Gen2 carbonate electrolyte, where the esters were near 2 M while the carbonate blend was near 1 M. The higher conductivity for the esters was consistent with the lower viscosity for the ester-based solvents.

[0077] The thick AAM electrode cells were electrochemically cycled using the three single solvent ester-based electrolytes and Gen2 (salt concentrations in Table 1), and the rate capabilities (retention of capacity at increasing charge / discharge rate) for these cells can be found in Figure 4. Discharge voltage profiles can also be found in Supporting Information, Figure 9. Before cycle 30, the cells were charged and discharged at the same rate. For cycles 31-50, the charge rate was C / 20 and the discharge rate was sequentially increased every 5 cycles up to 1C. The charge rate was kept at a relatively low rate for the later cycles to remove the contribution of charging capacity limitations to the delivered discharge capacity (i.e. , a discharge rate capability test). After cycle 50, the cells were charged and discharged at a rate of C / 20 and allowed to continue to cycle to provide indications of cycle life. At C / 20, Gen2 electrolyte only achieved 94 mAh g1LCO, which was attributed to the high electrode loading coupled with high ionic overpotentials.13 19Cells with ester-based electrolytes delivered much higher capacities, where PA, EA, and MA cells reached 108, 117, and 118 mAh g-1LCO at C / 20, respectively. The ionic conductivity of the MA electrolyte was higher than the EA electrolyte, however, the first cycle capacity was similar, suggesting that at the relatively low rate of C / 20 the EA electrolyte had sufficient transport properties where the observed cell voltage mainly reflected thermodynamic potentials of the two electrode materials as a function of lithiation. At higher rates, for example at the 42ndcycle which was discharged at 8.62 mA cm2(C / 2.5), Gen2 only achieved around 30 mAh g1while the MA electrolyte cell achieved over 80 mAh g1. It is important to note that, at such high loading and thickness, ionic transport though the electrode microstructure was expected to be the cause of the relatively low rate capabilities compared to other literature reports for the same electroactive materials at much lower loadings (less than 10 mg cm2).13 19The rate capability outcomes were consistent with prior thick electrode cycling studies where ion transport within the electrode microstructure was the limiting factor in the battery cell.3Prior works with AAM electrodes have experimentally and computationally suggested the ionic transport limitations are further exacerbated by tortuosity and electrolyte depletion at increasing charge / discharge rates.6 12 13 19On an areal capacity basis, the cells in this work surpassed most in the literature, and the results will be benchmarked relative to other high loading reports later in this paper.

[0078] Although the MA electrolyte exhibited the highest ionic conductivity, the low boiling point of MA (56.9 °C)30is a concern for many applications. A prior literature report assessing 18650 cylindrical cells measured a cell temperature rise of 30 °C under some cycling conditions. A cell temperature over 60 °C could readily be encountered when considering ambient temperature in the summer coupled with 30+ °C temperature rise during cycling, and would present a significant safety concern for such a volatile solvent. As the ester molecular weight increases the boiling point also increases (i.e., MA to EA to PA, Figure 2a), but is still well below carbonates such as EC. Thus, the blending of Gen2 with an ester was investigated to attempt to improve the conductivity relative to Gen2 while still maintaining high boiling solvents such as EC. EA was the ester chosen to blend with Gen2 because the peak conductivity of PA was not as substantively higher relative to Gen2 and the higher boiling point relative to MA was considered desirable.

[0079] 3.2 EA and Gen2 Blend Electrolyte

[0080] The ester solvents have the advantage of relatively lower viscosity; however, their dielectric constants are lower than the cyclic carbonates. Thus, the net impact on overall conductivity of the EA / Gen2 blends was not expected to be a straightforward volume weighted average. Thus, the ionic conductivity of the blended solvent electrolytes as a function of LiPF6composition were measured and can be found in Figure 5. A general trend was observed, where as the EA content increased, the ionic conductivity increased.

[0081] Figure 6 contains charge / discharge cycling outcomes for Gen2, EA, and the Gen2 / EA blended electrolytes using the same cycling procedure as was conducted with the Gen2 and single component ester electrolytes (Figure 4). Discharge voltage profiles can also be found in Supporting Information, Figure 10. As the EA content increased, the first cycle capacity increased, as well as the rate capabilities. Such trend could be explained by the increase in ionic conductivity and decrease in viscosity from EA addition, with the capacity sensitivity consistent with ionic overpotentials being a major contributor in the cells which was improved with the electrolyte modifications.

[0082] Thin AAM LTO / LCO cells were also fabricated and cycled at 1C for both charge and discharge to provide insights into cycle life after more extended cycling for cells with Gen2 and the EA-containing electrolytes. The thinner electrodes reduce ion transport polarization, which enables cycling at faster rates / current density while still achieving relatively high electrode utilization (i.e. , extents of lithiation / delithiation). Higher rate cycling was needed to achieve high total cycle numbers in a reasonable time period. The results of these cycle life experiments are shown in Figure 7. Voltage profiles for the corresponding cells can also be found in Supporting Information, Figure 1 1 . Gen2 had the lowest capacity retention after 500 charge / discharge cycles at 1C, retaining 72% of initial capacity. One possible cause of the highest fade for the Gen2 electrolyte cell may have been the oxidative stability, as it has been reported that the oxidation onset of carbonate-based electrolyte can be below 4 V.49If this speculation was correct, that would suggest the cycling stability limitation was more a consequence of processes at the cathode. The cycle life improved in the sequence of 40%EA, 80%EA, EA, 20%EA, and 60%EA. The pure EA cell did not have the highest cycle life of the group, and prior studies have suggested SEI limitations for EA electrolytes.5051

[0083] EIS measurements were conducted on the thin AAM LTO / LCO cells before and after cycling, and the resulting Nyquist plots can be found in Supporting Information, Figure 12. Before cycling, the high frequency intercept (Rcen) decreased as the EA content increased, which was consistent with the increased ionic conductivity with increasing EA content. All cells exhibited a single semi-circle before activation. After cycling, two semi-circles appeared, and the total magnitude of the 60%EA was the lowest, which meant that the cell with the best retention of capacity with cycling also had the lowest resistance in the regions associated with interfacial electrode processes.

[0084] 3.3 Benchmarking performance

[0085] Figure 7 contains a Ragone plot including the outcomes for the AAM LTO / LCO electrode cells containing MA and 80%EA electrolytes. The figure also includes data pulled from selected reports from the literature where cell areal capacities exceeded 10 mAh cm2. The data in red was a previous report from our group with AAM electrodes (LTO and LiFePO4, or LFP) and an electrolyte which was a blend of acetonitrile and Gen2.40The data in orange was a three-dimensional (3D) printed electrode of LTO and LFP with thickness of 1 mm.52The data in black was a 3D architected carbon electrode cell with loading over 40 mg cm2via post pyrolysis.53The data in grey was a SnPs nanosheet anode with loading over 225 mg cm2.54The data in green was a templated electrode with thickness up to 1 .2 mm and loading up to 100 mg LFP cm2.18The data in blue was another porous thick LFP (>1 mm) electrode fabricated via spark-plasma-sintering.55In the report herein, the processing method was generally much less complex than these other prior reports, and the highest capacity was achieved relative to these prior reports for higher current densities (>5 mA cm-2). For the two previous cases where the capacity at low current densities was higher, the cathode thicknesses were much greater than in this work, suggesting there may be opportunities to achieve higher capacity for comparable cell design if needed for a low current application.

[0086] Increasing electrode thickness can generally improve energy density at the cell level, though in many cases compromises must be reached with regards to rate capability due to increased ionic transport limitations. Assuming in a multilayered electrode structure within a conventional battery, a thin composite electrode often has electrode thickness of 50 m (other relevant parameters listed in Table 3).56The electrode volume fraction for the relevant cell components (foils, composite electrodes, separators) was 72%. After accounting for inactive components within the composite electrodes by assuming porosity of 35% and polymer binder / conductive additives taking 15%, the volume fraction of electroactive material within the battery cell can be as low as 36%. However in the AAM thick electrode case, the volume fraction dedicated to the electrode is much higher, and thus the volume fraction of electroactive material for the cell components considered will be much higher at 62%. To address the power and rate capability challenges faced by thick electrode cells, in addition to electrolyte modification in this work, engineering the electrode microstructure to reduce tortuosity can significantly improve rate capability. Methods to achieve tortuosity reductions have included ice-templating,8922laser patterning,23’24and porosity grading.25-27e

[0087] Table 3. Thickness and Volume Distribution of Cell Components in Thin Composite Electrode Cells and Thick AAM Electrode Cells.

[0088] Cell Component Thin Composite Thick AAM

[0089] Electrode Cell Electrode Cell

[0090] Cu foil 15 pm 15 pm

[0091] Cathode x 2 100 pm 900 pm

[0092] Al foil 10 pm 10 pm

[0093] Anode x 2 100 pm 1100 pm

[0094] Separator x 2 50 pm 50 pm

[0095] Electrode Volume 72% 96% .

[0096] 4.

[0097] Electroactive Material Volume 36% 62%

[0098] Conclusion

[0099] In this report, lithium-ion full cells were fabricated and evaluated where the cathode was AAM LCO and anode was AAM LTO, which enabled high areal capacity cells. The electrochemical outcomes for LTO / LCO AAM electrode cells were evaluated using a common baseline carbonate solvent-based lithium-ion electrolyte (Gen2) and comparing to custom electrolytes containing pure ester-based solvents (MA, EA, and PA), and blends between EA and Gen2. The low viscosity and moderate permittivity of esters drastically improved the rate capabilities for these high areal capacity cells. EA and Gen2 blends also substantially enhanced the cycle life stability compared to the carbonate electrolyte. In comparing the cells herein to existing literature for relatively high rate cycling of high areal capacity cells, this work offers a relatively simple processing method and improved capacity retention at high charge / discharge rates.

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[0159] SUPPORTING INFORMATION SECTION (For Example 1)

[0160] Supporting Information

[0161] Combining Ester Solvent Containing Electrolytes with All Active Material Electrodes for High Current Density Lithium-Ion Batteries (Figure 8-12)

[0162] It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1 percent to about 5 percent” should be interpreted to include not only the explicitly recited concentration of about 0.1 weight percent to about 5 weight percent but also include individual concentrations (e.g., 1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges (e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4 percent) within the indicated range. The term “about” can include traditional rounding according to significant figures of the numerical value. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y

[0163] Many variations and modifications may be made to the above-described aspects. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

Claims

CLAIMSWhat is claimed:

1. A battery comprising: an all active material anode that includes a high conductivity ester-based electrolyte; and an all active material cathode that includes a high conductivity ester-based electrolyte.

2. The battery of claim 1 , wherein a volume percentage of the high conductivity ester- based electrolyte within the electrode region for an all active material anode is about 15 vol% to 70 vol%, wherein a volume percentage of the high conductivity ester-based electrolyte within the electrode region for an all active material anode is about 15 vol% to 70 vol%.

3. The battery of claim 1 , wherein the high conductivity ester-based electrolyte is an alkyl acetate.

4. The battery of claim 3, wherein the alkyl acetate is a methyl-acetate, an ethylacetate, a propyl-acetate, or a mixture two or more of these.

5. The battery of claim 3, wherein the alkyl acetate is an ethyl-acetate.

6. The battery of claim 1-5, wherein the all active material anode further comprises a carbonate, wherein the all active material cathode further comprises a carbonate.

7. The battery of claim 6, wherein in reference to the anode the carbonate is a linear carbonate, a cyclic carbonate, or a mixture of the linear carbonate and the cyclic carbonate; wherein in reference to the cathode the carbonate is a linear carbonate, a cyclic carbonate, or a mixture of the linear carbonate and the cyclic carbonate.

8. The battery of claim 6, wherein a volume percentage of the high conductivity ester- based electrolyte and carbonate within the electrode region for an all active material anode is about 15 vol% to 70 vol%, wherein a volume percentage of the high conductivity ester- based electrolyte and carbonate within the electrode region for an all active material anode is about 15 vol% to 70 vol%.

9. The battery of claim 7, wherein reference to the anode the linear carbonate isselected from ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC), and the cyclic carbonate is selected from ethylene carbonate (EC) and propylene carbonate (PC); wherein reference to the cathode the linear carbonate is selected from EMC and DMC, and the cyclic carbonate is selected from EC and PC.

10. The battery of claim 1 , wherein the anode has a thickness of about 50 to 3000 pm.11 . The battery of claim 10, wherein the anode has a porosity of about 0.2 to 0.7.

12. The battery of claims 10 or 11 , wherein the anode has a loading of about 20 to 1000 mg cm2.

13. The battery of claim 1 , wherein the cathode has a thickness of about 50 to 3000 pm.

14. The battery of claim 13, wherein the cathode has a porosity of about 0.2 to 0.7.

15. The battery of claims 13 or 14, wherein the anode has a loading of about 20 to 1000 mg cm2.

16. The battery of claim 1 , wherein the all active material anode includes Li4Ti5Oi2(LTO) and the all active material cathode includes LiCoO2(LCO).

17. A method for making an electrode, comprising: compressing a first mixture to form a compressed material, wherein the first mixture includes an electroactive material; and sintering the compressed material to form an electrode; and impregnating the electrode with a high conductivity ester-based electrolyte to form an all active material electrode.

18. The method of claim 17, wherein the compression applies a force of about 40 to 4,000 MPa upon the first mixture for a time frame of about 1 second to 2 minutes.

19. The method of claim 17, wherein the sintering includes exposing the compressed material to a temperature of about 300 to 1500° C for a time period of about 1 second to 30 hours.

20. The method of claim 17, wherein the high conductivity ester-based electrolyte is analkyl acetate.21 . The method of claim 17, wherein the all active material is all active material anode or all active material cathode of any one of claims 1 to 16.

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