FIELD

[1] This application claims the benefit of priority to US Provisional Patent Application No. 62/723,431, filed August 27, 2018, the entire contents of which are herein incorporated by reference in their entirety for all purposes.

[2] The present disclosure concerns rechargeable (i.e., secondary) batteries as well as methods of making and using the same. In some examples, the present disclosure concerns rechargeable batteries such as, but not limited to, rechargeable batteries having a metal and metal alloy anode (i.e., Al-Li, Zn-Li-Al, Al-Zn, Zn-Li, Sn-Li, negative electrode).

BACKGROUND

[3] A battery’s energy density is related to the electrochemical potential difference for an atom (e.g., Li) in the anode relative to the corresponding ion (e.g, Li ⁺ ) in the cathode. A rechargeable battery’s energy density is therefore maximized when the anode is a single metal. The electrochemical potential for a metal atom in a metal made of identical atoms that is 0 V. Thus, metal anodes as compared to intercalation anodes (e.g. , Lir,C or lithium titanate) maximize the energy difference between the anode and any cathode. Therefore, to increase the energy density of current batteries, as well as for safety and economic reasons, metal anode rechargeable batteries are desired.

[4] Aluminum (Al) is an attractive metal for a metal anode rechargeable battery. The three-electron redox properties of Al provides a theoretical gravimetric capacity as high as 2,980 mAh/g and a volumetric capacity as high as 804 Ah cnr ³ , when paired with a carbon-containing cathode. Al is also the third most abundant element in the Earth’s crust. Al is generally less reactive than other metal anodes [e.g., lithium (Li) and sodium (Na)] and is easier to process. Al is therefore an economically viable choice for large scale battery manufacturing and, for example, grid storage applications.

[5] Key to commercializing Al-metal anode rechargeable batteries, is the development of electrolytes which are chemically compatible with Al and which are sufficiently ionically conductive. Also critical is the development of electrolytes that can be paired with lithium-intercalating cathode active materials. Some researchers have developed Al-metal anode rechargeable batteries and used ionic liquid or deep eutectic electrolytes which included, or were prepared using, electrolyte mixtures of AlCh and l-ethyl-3- methylimidazolium chloride (EMIMC) or mixtures of AlCb and urea. See, for example, US Patent Application Publication No. 2015-0249261; Lin, M-C, et al, Nature, 2015, doi: l038/naturel43040; and Angell, et al, PNAS, Early Edition, 2016, p. 1-6,

doi: 10. l073/pnas.1619795114, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes. See also Carlin, et al, Journal of Applied Electrochemistry, 26 (1996) 1147-1160; Xie, et al, Journal of The Electrochemical Society, 147 (11) 4247-4251 (2000); Cheng, et al, Chem. Commun., 2014, 50, 9644; Yoo, et al, ChemElectroChem 2017, 4, 1-8; available as https://doi.org/l0. l002/celc.20l70027l; Sun, et al, DOI: l0. l039/c5cc090l9a; Riechel, et al. , J. Electrochem. Soc., Vol. 140, No. 11, November 1993; Piersma, B, Electrochemistry of Lithium in Room Temperature Molten Salt Electrolytes, DOI: 10.1149/199413.0415PV ; and Piersma, B , J. Electrochem. Soc., Vol. 143, No. 3, March 1996, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes.

[6] The pure Al-metal batteries with ionic liquid or deep eutectic solvent electrolytes have been prepared suffer from disadvantages including low energy density, and sensitivity to water, causing instability problems. Trace amounts of water in these electrolytes are difficult to remove and can form hydrochloric acid (HC1), hydrogen gas (Eh) and carbon dioxide (CO ₂ ). If these by-products are sealed in an Al-metal or Al-alloy battery, they can result in corrosion, deformation, or destruction of the battery or its packaging. Another problem with Al-metal batteries in ionic liquid or deep eutectic solvent electrolytes is the electrolyte is highly acidic, containing AI ₂ CI ₇ species that can cause severe corrosion problems to electrodes and cell enclosures.

[7] In view of these as well as other unmet challenges, there exists a need for improved metal anode rechargeable batteries, including Al-metal and Al-alloy anode rechargeable batteries. SUMMARY

[8] In one embodiment, set forth herein is an electrochemical cell, comprising: (i) an electrolyte, wherein the electrolyte comprises: (a) AlCL ¹ : (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (d) wherein the electrolyte is free of any AI2CI7 ^{1 "} (as detected by Raman

spectroscopy); (ii) a metal anode comprising a metal or alloy selected from the group consisting of aluminum (Al), lithium (Li), Al-Li, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), Al-Zn, copper (Cu), Al-Li-Zn, Zn-Al and tin (Sn); and (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AlCL ¹ . In some examples, the metal anode comprises a metal or alloy with a metal or an alloy coating thereupon.

[9] In a second embodiment, set forth herein is an electrochemical cell, comprising: (i) an electrolyte, wherein the electrolyte comprises: (a) AlCL ¹ ; (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (d) wherein the electrolyte is free of any AI2CI7 ^{1 "} (as detected by Raman spectroscopy); (ii) a metal anode comprising a metal or alloy selected from the group consisting of aluminum (Al), lithium (Li), Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), magnesium (Mg), Al-Mg alloy, Al-Zn alloy, Al-Zn-Mg alloy, copper (Cu), Al-Li-Zn alloy, Zn-Al alloy, CuZn alloy, and tin (Sn); and (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AlCL ¹ . In some examples, the metal anode comprises a metal or alloy with a metal or an alloy coating thereupon.

[10] In a third embodiment, set forth herein is an electrochemical cell, comprising: (i) an electrolyte, wherein the electrolyte comprises: (a) AlCL ¹ ; (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (ii) a metal anode comprising a metal or alloy selected from the group consisting of aluminum (Al), lithium (Li), Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), magnesium (Mg), Al-Mg alloy, Al-Zn alloy, Al-Zn-Mg alloy, copper (Cu), Al-Li-Zn alloy, Zn-Al alloy, CuZn alloy, and tin (Sn); (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AlCL ¹ ; and (iv) at least one member selected from the group consisting of LiF, LLO, and combinations thereof. In some examples, the metal anode comprises a metal or alloy with a metal or an alloy coating thereupon.

[11] In fourth embodiment, set forth herein is an electrochemical cell, comprising: (i) an electrolyte, wherein the electrolyte comprises: (a) AlCL ¹ ; (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (ii) a metal anode comprising a metal or alloy selected from the group consisting of aluminum (Al), lithium (Li), Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), magnesium (Mg), Al-Mg alloy, Al-Zn alloy, Al-Zn-Mg alloy, copper (Cu), Al-Li-Zn alloy, Zn-Al alloy, CuZn alloy, and tin (Sn); (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and A1CL ¹ : and (iv) wherein the electrolyte has a mole ratio of ALCF : AlCL of 0.12 or less. In some examples, the metal anode comprises or metal or alloy with a metal or an alloy coating thereupon. In some examples, the ratio of AI2CI7 : AlCU that is 0 to 0.05.

[12] In a fifth embodiment, set forth herein is an electrochemical cell, comprising: an electrolyte, wherein the electrolyte comprises: (a) A1CL ¹ : (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (d) wherein the electrolyte is free of any AI2CI7 ¹ ; (e) wherein the electrolyte is further doped with an additive selected from LiF, LLO and combinations thereof.

[13] In a sixth embodiment, set forth herein is a process for making an electrolyte, wherein the electrolyte comprises: AlCU ¹ ; Li ⁺ ; at least one member selected from the group consisting of organic cations and organic-metal complex cations; wherein the electrolyte is free of any AI2CI7 ¹ ; and wherein the electrolyte is further doped with an additive selected from the group consisting of LiF, LLO, and combinations thereof; the process comprising contacting the electrolyte with aluminum metal in the presence of an additive selected from SnCL. GaCb, and combinations thereof.

[14] In a seventh embodiment, set forth herein an electrolyte, comprising: (a) AlCL ¹ ; (b) Li ⁺ ; (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (d) wherein the electrolyte is free of any AI2CI7 ¹ ; (e) an additive selected from the group consisting of LiF, LLO, and combinations thereof; and (f) wherein the electrolyte is made by contacting the electrolyte with aluminum metal in the presence of an additive selected from SnCL. GaCb, and combinations thereof.

[15] In an eighth embodiment, set forth herein is a process for making an electrolyte, comprising contacting (i) AlCb with: (ii) an organic cation or organic-metal complex cation, wherein the organic cation is selected from the group consisting of urea ions, imidazolium ions, ammonium ions, pyrrolidinium ions, pyridinium ions, phosphonium ions, and combinations thereof; and (iii) a saturated amount of a halide of a metal selected from the group consisting of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof.

BRIEF DESCRIPTIONS OF THE DRAWINGS

[16] FIG. 1 shows the electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the Al- LiFeP0 ₄ electrochemical cell described in Example 1. FIG. 1(a) show the results of the cell prepared using a saturated amount of LiCl and an AlChiEMIMC (1.3: 1 mol/mol) electrolyte. FIG. 1(b) show the results of the cell prepared using a saturated amount of LiCl and an A1CE: Et3NHCl (1.7: 1 mol/mol) electrolyte. FIG. 1(c) show the results of the cell prepared using a saturated amount of LiCl and an AlCl3:Urea (1.3:1 mol/mol) electrolyte. Et3NHCl =

Triethylamine hydrochloride.

[17] FIG. 2 shows the electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the

Al-LiNiCoMnCh electrochemical cell described in Example 2. FIG. 2(a) show the cell prepared using a saturated amount of LiCl and an A1CE:EMIMC (1.1 : 1 mol/mol) electrolyte. FIG. 2(b) show the cell prepared using a saturated amount of LiCl and an AlCl3:Urea (1.3: 1 mol/mol) electrolyte.

[18] FIG. 3 shows the electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the Al- graphite electrochemical cell described in Example 3. FIG. 3(a) show the cell with 200 pm glass separator, which was prepared using an A1CE:EMIMC (1.6: 1 mol/mol) electrolyte with Mg ²⁺ . FIG. 3(b) show the cell with 200 pm glass separator, which was prepared using an AlCl3:Et3NHCl (1.6: 1 mol/mol) electrolyte with Cu ²⁺ . TIL in FIG. 3 is an abbreviation for Et3NHCl, or Triethylamine hydrochloride.

[19] FIG. 4 shows the electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the Ni- LiFePCri electrochemical cell described in Example 4. The cell was prepared using a saturated amount of LiCl with an AlChiEtsNHCl (1.7: 1 mol/mol) electrolyte.

[20] FIG. 5 shows electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the Zn-LiFePCri electrochemical cell described in Example 5. The cell was prepared using a saturated amount of LiCl in an AlCh:EhNHCl (1.7: 1 mol/mol) electrolyte.

[21] FIG. 6 shows electrochemical performance ((Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the 7075 type Al-Zn-Mg-alloy-LiFePCri electrochemical cell described in Example 6. The 7075 type alloy included Al with 5.5 weight percent (wt%) Zn and 2.5 wt% Mg. The cell was prepared using a saturated amount of LiCl in an AlCl3:Et3NHCl (1.7: 1 mol/mol) electrolyte.

[22] FIG. 7 shows Raman spectroscopy analysis of an electrolyte having a mole ratio of AlCbiMIC of 1.1, as set forth in Example 7.

[23] FIG. 8 shows Raman spectroscopy analysis of the series of electrolytes set forth in Example 8.

[24] FIG. 9 shows a comparison plot of the results of electrochemically cycling the electrochemical cells sets forth in Example 9.

[25] FIG. 10 shows electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the first electrochemical cell described in Example 9.

[26] FIG. 11 shows electrochemical performance (Specific capacity (left y-axis) and Coulombic efficiency (right axis) as a function of cycle number (x-axis)) of the second electrochemical cell described in Example 9.

[27] FIG. 12 shows an x-ray photoelectron spectroscopy results for the anode of the electrochemical cell as described in Example 10.

[28] FIG. 13 shows an x-ray photoelectron spectroscopy results for the anode of the electrochemical cell as described in Example 10. [29] FIG. 14 shows scanning electron microscopy results for the anode of the electrochemical cell as described in Example 10.

DETAILED DESCRIPTION

[30] The following description is presented to enable one of ordinary skill in the art to make and use the invention and to incorporate it in the context of particular applications. Various modifications, as well as a variety of uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to a wide range of embodiments. Thus, the inventions herein are not intended to be limited to the embodiments presented, but are to be accorded their widest scope consistent with the principles and novel features disclosed herein.

[31] All the features disclosed in this specification, (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[32] Please note, if used, the labels left, right, front, back, top, bottom, forward, reverse, clockwise and counter clockwise have been used for convenience purposes only and are not intended to imply any particular fixed direction. Instead, they are used to reflect relative locations and/or directions between various portions of an object.

General

[33] Set forth herein are processes for making new electrolytes, e.g., mixing AlClv EMIMC in a 1.5 molar ratio while adding saturated amounts of LiCl thereto.

[34] According to Equation [1], adding LiCl converts AI2CI7 ¹ completely into AICI4 ¹ and Li ⁺ ions:

AI2CI7 ¹ - + LiCl( _s) 2A1C14 ¹ - + Li ⁺ [1]

[35] These Li ⁺ ions can then be used to perform Li-metal (e.g., Al, Zn, Ni, Sn, Cu, W, Ca, K) alloy redox on the metal anode, and Li/Li ⁺ redox in a cathode active material, e.g., LiFeP0 ₄ also known as LFP. The following equations [2]-[3] demonstrate this:

Li-metal alloy = Li ⁺ + metal + e [2]

[36] In Equation [2], Li-metal alloy in the anode oxidizes to Li ⁺ and metal, which releases an electron, i.e., e . This would occur during a discharge cycle.

[37] The lithium ions (Li ⁺ ) produced in Equations [2] can then intercalate into a redox-active cathode material, e.g., lithium iron phosphate, or iron phosphate, according to Equation [4]:

Li ⁺ + e- + FeP0 ₄ = LiFeP0 ₄ [3]

[38] By using a saturated amount of LiCl in the A1CU ¹ containing electrolyte, the instant disclosure, to the best of the inventor’s knowledge, was the first to avoid AhCfy in the electrolyte and thus set forth a Li-metal alloy batteries operating according to Equations [l]-[3], which has a comparatively increased specific capacity of up to 140 mAh/g and Coulombic efficiency up to 99.9%. The halide-saturation and ATCE ¹ free nature of the electrolyte differ from any previous ionic liquid based batteries. This type of electrolyte is unique and would not have been expected to function as electrolyte since Al would not deposit at the anode without this anion. Surprisingly, the electrolytes described herein work well with anodes which include Al.

Definitions

[39] As used herein, the singular terms“a,”“an,” and“the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object can include multiple objects unless the context clearly dictates otherwise.

[40] As used herein, the term“about,” when qualifying a number, e.g., 100 °C, refers to the number qualified and optionally the numbers included in a range about that qualified number that includes ± 10% of the number. For example, about 100 °C includes 100 °C as well as 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, and 110 °C.

[41] As used herein,“selected from the group consisting of’ refers to a single member from the group, more than one member from the group, or a combination of members from the group. A member selected from the group consisting of A, B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, as well as A, B, and C.

[42] As used herein, the phrases“electrochemical cell” or“battery cell” shall mean a single cell including an anode and a cathode, which have ionic communication between the two using an electrolyte.

[43] As used herein, the terms“cathode” and“anode” refer to the electrodes of a battery. In some examples, the anode of an Al-metal anode battery includes Al or an alloy thereof. In some examples herein, the cathode includes graphite or lithium iron phosphate. During charging, in some examples, AICI4 ¹ ions de-intercalate from the graphite and conduct through the electrolyte to eventually plate out Al at the anode. During discharging, AI2CI7 ¹ ions dissolve from the Al anode and completely convert into A1CU ¹ ions in the electrolyte due to saturated amounts of LiCl. The A1CU ¹ ions conducts through the electrolyte and eventually intercalate in the graphite in the cathode. Additional battery chemistries may be operable depending on the cathode active material employed. For example, if the graphite in the cathode is substituted for LiFePCri, then Li ⁺ ions can intercalate and de-intercalate from the cathode (instead of AICI4 ¹ ions intercalating and de-intercalating into graphite). During a charge cycle, electrons leave the cathode and move through an external circuit to the anode. During a discharge cycle, electrons leave the anode and move through an external circuit to the cathode. Unless otherwise specified, the cathode refers to the positive electrode. Unless otherwise specified, the anode refers to the negative electrode.

[44] As used here, the phrase“direct contact,” refers to the juxtaposition of two materials such that the two materials contact each other sufficiently to conduct either an ion or electron current. As used herein, direct contact refers to two materials in contact with each other and which do not have any materials positioned therebetween.

[45] As used herein, the term“separator,” refers to the physical barrier which electrically insulates the anode and the cathode from each other. The separator is often porous so it can be filled or infiltrated with an electrolyte. The separator is often mechanically robust so it can withstand the pressure applied to the electrochemical cell. Example separators include, but are not limited to, S1O2 glass fiber separators or S1O2 glass fiber mixed with a polymer fiber or mixed with a binder. [46] As used herein, the term“ electrolyte” or“electrolyte,” refers to

nonflammable electrolytes which include a mixture of a strong Lewis acid metal halide and Lewis base ligand. Examples include, but are not limited to, electrolytes prepared using AlCb and 1 -ethyl-3 -methylimidazolium chloride ([EMIm]Cl). Example Lewis base ligands include, but are not limited to, urea, acetamide, or 4-propylpyridine. In a typical electrolyte having AlCb as a metal halide, AlCb undergoes asymmetric cleavage to form a tetrachloroaluminate anion (AlCb ¹ ) and an aluminum chloride cation (AlCh ⁺ ) in which a ligand is datively bonded to (or associated through coordination via sharing of lone pair electrons) the AlCh ⁺ cation, forming ([AlChn(ligand)] ⁺ ). These mixtures are useful as electrolytes for Al-metal anode batteries. Examples include, but are not limited to, mixtures of AlCb and l-ethyl-3- methylimidazolium chloride (EMIMC), mixtures of AlCb and urea, mixtures of AlCb and acetamide, mixtures of AlCb and 4-propylpyridine, and mixtures of AlCb and

trimethylphenylammonium chloride. These electrolyte may further comprise LiCl or any oxidation species of Li, Na, Ca, Cu, K, Mg, and combinations thereof.

[47] As used herein, the term“deep eutectic solvent,”“deep eutectic solvent electrolyte,” or“DES,” refers to a mixture of a strong Lewis acid metal halide and a Lewis base ligand. See, for example, Hogg, JM, et al, Green Chem 17(3): 1831-1841; Fang, Y, et al., Electrochim Act 160:82-88; Fang, Y, et al, Chem. Commun. 51(68)13286-13289; and also Pulletikurthi, G., et al, Nature, 520(7547):325-328 for a non-limiting set of example DES mixture. The content of each of these references in herein incorporated by reference in its entirety for all purposes. Examples include, but are not limited to, AlCb and urea.

[48] As used herein, the term“chemically compatible enclosure,” refers to an enclosure which physically contains an anode, cathode, separator and electrolyte without resulting in a substantial amount of corrosion. A substantial amount of corrosion includes an amount which degrades the Coulombic efficiency of a battery by more than 10% or which reduces its capacity by more than 10 %. Chemical compatibility is considered with respect to the reactivity of a material and an electrolyte or DES. A material which reacts with an electrolyte or DES and degrades the Coulombic efficiency of a battery by more than 10% or which reduces its capacity by more than 10 %, is not chemically compatible, as the phrase is used herein. Chemically compatible enclosures herein do not include Swage-log battery cells, plastic pouches or sealed glass battery cells. A non-limiting example of a chemically compatible enclosure is a FEP pouch surrounding a cathode, anode and electrolyte or DES. Surrounding the FEP pouch is a second multilayered pouch in which the multilayered pouch walls comprise sequential layers of a polyamide polymer layer/an adhesive layer/an aluminum layer/adhesive layer/and a polypropylene polymer layer. In some examples, the polyamide polymer layer is the outer-most layer of the pouch. In some examples, the inner layer, which contacts the FEP pouch, is the polypropylene layer. When viewed from the outside the polyamide layer is visible, in some examples. In some examples, under the polyamide layer is an adhesive. In some examples, under the adhesive is an aluminum layer. In some examples, under the aluminum layer is another adhesive. In some examples, under the another adhesive is the polypropylene layer. In some examples, under the polypropylene layer is the FEP pouch. And inside the FEP pouch, in some examples, is the cathode, anode, and electrolyte (or DES).

[49] As used herein, the term“metal halide salt,” refers to a salt which includes at least one metal atom and at least one halogen atom. Examples include, but are not limited to, LiCl, NaCl, KC1, MgCh, CaCh, CuCh, CuCl, AIF3, AlCh, AlBr3, A1B, and combinations thereof.

[50] As used herein, the term“graphitized,” refers to a material which includes graphite.

[51] As used herein, the term“crystalline,” refers to a material which diffracts x- rays. Crystalline graphite is characterized by at least an XRD peak at 26.55 2Q (the (002) peak of graphite having a d-spacing of 3.35 A). Graphite is mined as either vein, flake, or microcrystalline. Herein, graphite can be vein, flake microcrystalline, or a combination thereof. In some examples, the graphite is flake graphite. In some examples, the graphite is natural flake graphite.

[52] As used herein, the term“few defects,” refers to graphite that has less than 5% defects per mole. Defects include, but are not limited to, misshaped particles, amorphous carbon, or particles having a particle size other than the average particle size. Defects in graphite can be measured using Raman spectroscopy and comparing the defect D band intensity relative to the graphite G band. In some examples, the ratio D/G is about near zero for natural graphite with few defects. In some examples, the ratio D/G is about zero for natural graphite with few defects. [53] As used herein,“pouch,” is used interchangeably with the phrase“prismatic cell.”

[54] As used herein, the term“cycling,” refers to an electrochemical process whereby an electrochemical cell having an anode and a cathode is charged and discharged.

[55] As used herein, the term“C-rate” refers to a measure of the rate at which a battery is discharged relative to its maximum capacity. A 1C rate means that the discharge current will discharge the entire battery in 1 hour. For a battery with a capacity of 100 Amp- hrs, a 1C rate equates to a discharge current of 100 Amps.

[56] As used herein, the phrase“free of any AI2CI7 ^1" ,” means that the concentration of AI2CI7 ^{1 "} in the electrolyte is less than the amount required to detect AI2CI7 ^1" empirically using either Raman spectroscopy, infrared spectroscopy, mass spectroscopy, atomic emission spectroscopy, or inductively coupled plasma spectroscopy. Unless stated otherwise or to the contrary, the phrase“free of any AI2CI7 ^1" ,” means that the concentration of AI2CI7 ^{1 "} in the electrolyte is less than the amount required to detect AI2CI7 ^{1 "} empirically using Raman spectroscopy.

[57] As used herein, the phrase“present at least at a detectable limit,” means that the species present can be detected empirically. A variety of techniques known in the art can be used to detect species, e.g., Raman spectroscopy, infrared spectroscopy, mass

spectroscopy, atomic emission spectroscopy, or inductively coupled plasma spectroscopy. Unless specified otherwise or to the contrary,“present at least at a detectable limit,” means that the species present is detected empirically as determined by Raman spectroscopy.

[58] As used herein, the phrase“ionically conductive” refers to a media or material which conducts ions (e.g., Li ⁺ or AICI4 ^{1 "} ions with a conductivity of at least 1*10 ⁴ S/cm ² or greater).

[59] As used herein, the phrase“redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AICI4 ¹ ” refers to a material, known as a cathode active material, which can intercalate and de-intercalate any one of Li ⁺ , Na ⁺ , K ⁺ , and AICI4 ¹ and also undergo a change in redox state during the intercalation or de intercalation of any one of Li ⁺ , Na ⁺ , K ⁺ , and AICU ¹ . Redox-active materials include, but are not limited to graphite, L1C0O2, LiMmCri, LiMn1.5Nio.5O4, Li(NiCoAl)02 (NCA), Li(NiCoMn)02 (NMC), lithium iron phosphate (LiFeP04), lithium nickel phosphate

(LiNiP04), lithium cobalt phosphate (LiCoPCL), lithium manganese phosphate (LiMnP04), lithium cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese cobalt oxide, lithium nickel manganese oxide and sulfur.

Chemistry

[60] In some examples, an electrochemical cell includes an Al or Al-alloy anode and a graphite-including cathode or a LiFeP0 ₄ -including cathode. In some examples, a LiFePCL (LFP) cathode can be substituted for the graphite-including cathode. During a discharging reaction, in some examples, AlCU ¹ intercalates into graphite as carbon is oxidized. Alternatively, and in some examples, during discharging, Li ⁺ intercalates into LFP. In some of the examples, herein, the mole ratio of A1CL:| EMIm|Cl is about 1.3: 1, 1.4: 1,

1.5: 1, 1.6: 1, 1.7: 1, 1.8: 1, or 1.9: 1 unless specified otherwise. When a saturated about of LiCl is introduced, the amount of AI2CI7 ^{1 "} is reduced below a detectable limit because it completely converts to AlCL ¹ . Furthermore, the Li ⁺ produced by the addition of a saturated amount of LiCl can then be used to intercalate into a cathode other than a graphite-including cathode, for example a LiFePCL cathode.

[61] In some other examples, electrolytes can be formed by slowly mixing or otherwise combining an aluminum halide ( e.g ., AlCh) and an organic compound (e.g., EMIMC, Et3NHCl, and urea). In certain examples, the aluminum halide undergoes asymmetric cleavage to form a haloaluminate anion (e.g., AlCL ¹ ) and an aluminum halide cation that is datively bonded to the organic compound serving as a ligand (e.g.,

[AlCL n(ligand)] ⁺ ). A mole ratio of the aluminum halide and the organic compound can be at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, up to about 2, or more. In some examples, the molar ratio, m _r , is l<m _r <2. For example, the mole ratio the aluminum halide and the organic compound (e.g., urea) can be in a range of about 1.1 to about 1.7 or about 1.3 to about 1.5. In some embodiments, a ligand is provided as a salt or other compound including the ligand, and a mole ratio of the aluminum halide and the ligand-containing compound can be at least or greater than about 1.1 or at least or greater than about 1.2, and is up to about 1.5, up to about 1.8, up to about 2, or more. An electrolyte can be doped, or have additives added, to increase its electrical conductivity and lower the viscosity, or can be otherwise altered to yield compositions that favor the reversible electrodeposition/electrodissolution of metals. For example, 1, 2-dichlorobenzene can be added as a co-solvent to reduce electrolyte viscosity and increase the voltage efficiency, which can result in an even higher energy density. Also, alkali chloride additives can be added to increase the discharge voltage of a battery. In some examples, l-ethyl-3- methylimidazolium tetrafluoroborate or 1 -ethyl-3 -methylimidazolium bis(trifluoromethane sulfonimide) or 1 -ethyl-3 -methylimidazolium hexafluorophosphate can be added as additives to increase the discharge voltage of a battery.

[62] After mixing the aforementioned reagents, in some examples, the electrolyte is exposed to Cu metal.

[63] After mixing the aforementioned reagents, in some examples, the electrolyte is exposed to Zn metal.

[64] After mixing the aforementioned reagents, in some examples, the electrolyte is exposed to Ca metal.

[65] After mixing the aforementioned reagents, in some examples, the electrolyte is exposed to Li metal.

[66] After mixing the aforementioned reagents, in some examples, the electrolyte is exposed to Na metal.

[67] After mixing the aforementioned reagents, in some examples, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence of an additive selected from SnC'L. GaCL. and combinations thereof. In some examples, the electrolyte is further doped with an additive selected from LiF, Li CL and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped LLO.

[68] After mixing the aforementioned reagents, in some examples, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence SnCL. In some examples, the electrolyte is further doped with an additive selected from LiF, Li CL and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped LLO.

[69] After mixing the aforementioned reagents, in some examples, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence GaCL. In some examples, the electrolyte is further doped with an additive selected from LiF, LiC and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped LhO.

[70] After mixing the aforementioned reagents, in some examples, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence of combinations of SnCh and GaCb. In some examples, the electrolyte is further doped with an additive selected from LiF, LiCL and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped LbO.

Electrochemical cells

[71] In some examples, set forth herein is an electrochemical cell, including: (i)an electrolyte (electrolyte), wherein the electrolyte includes: (a) A1CL ¹ .

(b) Li ⁺ , (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; and (d) wherein the electrolyte is free of any AhCb ¹ ; (ii) a metal anode including a metal, or alloy thereof, selected from the group consisting of aluminum (Al), lithium (Li), Al-Li, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), Al-Zn, copper (Cu), and tin (Sn); and (iii) a cathode, wherein the cathode is redox- active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AlCb ¹ .

[72] In some examples, set forth herein is an electrochemical cell, including: (i)an electrolyte (electrolyte), wherein the electrolyte includes: (a) A1CL ¹ .

(b) Li ⁺ , (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; and (d) wherein the electrolyte is free of any AhCb ¹ ; (ii) a metal anode including a metal, or alloy thereof, selected from the group consisting of aluminum (Al), lithium (Li), Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), magnesium (Mg), Al-Mg alloy, Al-Zn alloy, Al-Zn-Mg alloy, copper (Cu), Al-Li-Zn alloy, Zn-Al alloy, CuZn alloy, and tin (Sn); and (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AlCb ¹ .

[73] In some examples, set forth herein is an electrochemical cell, including: (i) an electrolyte, wherein the electrolyte comprises: (a) AlCb ¹ ; (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (ii) a metal anode including a metal or alloy selected from the group consisting of aluminum (Al), lithium (Li), Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), magnesium (Mg), Al-Mg alloy, Al-Zn alloy, Al-Zn-Mg alloy, copper (Cu), Al-Li-Zn alloy, Zn-Al alloy, CuZn alloy, and tin (Sn); (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and A1CL ¹ : and (iv) at least one member selected from the group consisting of LiF, LLO, and combinations thereof. In some examples, the metal anode comprises or metal or alloy with a metal or an alloy coating thereupon. In certain examples, the electrochemical cell includes LiF. In certain other examples, the electrochemical cell includes LLO. In yet other certain examples, the electrochemical cell includes both LiF and LLO. Without being bound by theory, the LLO and LiF may increase the buffering effect and result in a neutral state with minimal amounts of AI ₂ CI ₇ . This may also result in an increase in coulombic efficiency and longer cycle life

[74] In some examples, set forth herein is an electrochemical cell, comprising: (i) an electrolyte, wherein the electrolyte comprises: (a) A1CL ¹ : (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (ii) a metal anode comprising a metal or alloy selected from the group consisting of aluminum (Al), lithium (Li), Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), zinc (Zn), magnesium (Mg), Al-Mg alloy, Al-Zn alloy, Al-Zn-Mg alloy, copper (Cu), Al-Li-Zn alloy, Zn-Al alloy, CuZn alloy, and tin (Sn); (iii) a cathode, wherein the cathode is redox-active to at least one intercalation species selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , and AlCL ¹ ; and (iv) wherein the electrolyte has a mole ratio of ALCL ; AlCL of 0.12 or less. In some examples, the metal anode comprises or metal or alloy with a metal or an alloy coating thereupon. In some examples, the ratio of AI ₂ CI ₇ : AlCL that is 0 to 0.05.

[75] In some examples, including any of the foregoing, the electrolyte has a mole ratio of AI ₂ CI ₇ : AlCL of 0.12. In certain examples, the electrolyte has a mole ratio of ALCL :AlCL of 0.11. In certain other examples, the electrolyte has a mole ratio of ALCL : AlCL of 0.10. In other examples, the electrolyte has a mole ratio of ALCL : AlCL of 0.09. In some certain examples, the electrolyte has a mole ratio of ALCL : AlCL of 0.08. In yet other examples, the electrolyte has a mole ratio of ALCL : AlCL of 0.07. In some examples, the electrolyte has a mole ratio of ALCL : AlCL of 0.06. In other examples, the electrolyte has a mole ratio of ALCL : AlCL of 0.05. In certain examples, the electrolyte has a mole ratio of AbCb : AlCb of 0.04. In yet other examples, the electrolyte has a mole ratio of AbCb : AlCb of 0.03. In some examples, the electrolyte has a mole ratio of AbCb :AlCb of 0.02. In other examples, the electrolyte has a mole ratio of AbCb :AlCb of 0.01. In certain examples, the electrolyte has a mole ratio of AbCb : AlCb of 0.

[76] In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.05.

[77] In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.01. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.011. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCLf that is 0 to 0.012. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb :AlCb that is 0 to 0.013. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.014. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.015. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb :AlCl4 that is 0 to 0.016. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.017. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.018. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb :AlCb that is 0 to 0.019. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.02. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.021. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb :AlCb that is 0 to 0.022. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.023. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.024. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb :AlCb that is 0 to 0.025. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.026. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb : AlCb that is 0 to 0.027. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AbCb :AlCb that is 0 to 0.028. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.029. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.03. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : AICU that is 0 to 0.031. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : AICU that is 0 to 0.032. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AhCU : AICU that is 0 to 0.033. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : AICU that is 0 to 0.034. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.035. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.036. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : AICU that is 0 to 0.037. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.038. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.039. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : AICU that is 0 to 0.04. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.041. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.042. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.043. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.044. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.045. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.046. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU :AlCU that is 0 to 0.047. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.048. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.049. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCl7 :AlCU that is 0 to 0.05. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.051. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.052. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.053. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AUCU : A1CU that is 0 to 0.054. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AI2CI7 : AlCU that is 0 to 0.055. In some examples, including any of the foregoing, the electrolyte has a mole ratio of ALCL : AlCU that is 0 to 0.056. In some examples, including any of the foregoing, the electrolyte has a mole ratio of ALCL

: AlCU that is 0 to 0.057. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AI2CI7 : AlCU that is 0 to 0.058. In some examples, including any of the foregoing, the electrolyte has a mole ratio of AI2CI7 : AlCU that is 0 to 0.059.

[78] In some other examples, set forth herein is an electrochemical cell, comprising: an electrolyte, wherein the electrolyte comprises: (a) AICI4 ¹ ; (b) Li ⁺ ; and (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (d) wherein the electrolyte is free of any AI2CI7 ¹ ; (e) wherein the electrolyte is further doped with an additive selected from LiF, LLO and combinations thereof. In some examples, the electrolyte is further doped LiF. In some other examples, the electrolyte is further doped with LLO.

[79] In some other examples, set forth herein an electrochemical cell, comprising: an electrolyte, wherein the electrolyte comprises: (a) A1CL ¹ : (b) Li ⁺ ; (c) at least one member selected from the group consisting of organic cations and organic-metal complex cations; (d) wherein the electrolyte is free of any AI2CI7 ¹ ; (e) wherein the electrolyte is further doped with an additive selected from LiF, LLO and combinations thereof; and (f) wherein the electrolyte is made by contacting the electrolyte with aluminum metal in the presence of an additive selected from SnCL. GaCL. and combinations thereof. In some examples, the process includes contacting and reacting the electrolyte with aluminum metal in the presence of an additive selected from SnCL, GaCL, and combinations thereof.

[80] In some examples, including any of the foregoing, the metal anode is an Al metal anode or Al metal alloy anode.

[81] In some examples, including any of the foregoing, the metal anode is aluminum (Al).

[82] In some examples, including any of the foregoing, the metal anode is lithium (Li).

[83] In some examples, including any of the foregoing, the metal anode is Al-Li alloy. [84] In some examples, including any of the foregoing, the metal anode is nickel (Ni).

[85] In some examples, including any of the foregoing, the metal anode is tungsten (W).

[86] In some examples, including any of the foregoing, the metal anode is titanium (Ti).

[87] In some examples, including any of the foregoing, the metal anode is sodium (Na).

[88] In some examples, including any of the foregoing, the metal anode is zinc (Zn).

[89] In some examples, including any of the foregoing, the metal anode is magnesium (Mg).

[90] In some examples, including any of the foregoing, the metal anode is Al-Mg alloy.

[91] In some examples, including any of the foregoing, the metal anode is Al-Zn alloy.

[92] In some examples, including any of the foregoing, the metal anode is Al-Zn- Mg alloy.

[93] In some examples, including any of the foregoing, the metal anode is copper (Cu).

[94] In some examples, including any of the foregoing, the metal anode is Al-Li-Zn alloy.

[95] In some examples, including any of the foregoing, the metal anode is Zn-Al alloy.

[96] In some examples, including any of the foregoing, the metal anode is CuZn alloy. [97] In some examples, including any of the foregoing, the metal anode is tin (Sn).

[98] In some examples, including any of the foregoing, the electrolyte further comprises at least one species selected from the group consisting of Mg, Zn, Ca, Cu, Na, and combinations thereof, wherein the species are metal species in any of their possible oxidation states. In certain examples, the electrolyte further comprises Mg. In certain examples, the electrolyte further comprises Zn. In certain examples, the electrolyte further comprises Ca. In certain examples, the electrolyte further comprises Cu. In certain examples, the electrolyte further comprises Na. In certain examples, the electrolyte further comprises a combination of Mg, Zn, Ca, Cu, or Na.

[99] In some examples, including any of the foregoing, the species are present at concentrations from 0.1 parts-per-billion (ppb) to 500 parts-per-million (ppm).

[100] In some examples, including any of the foregoing, the species are present at concentrations from 0.1 parts-per-million (ppm) to 1% by mole

[101] In some examples, including any of the foregoing, the electrolyte includes at least one member selected from the group consisting of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ , Na ⁺ and combinations thereof. In certain examples, the electrolyte includes Mg ²⁺ . In certain examples, the electrolyte includes Zn ²⁺ . In certain examples, the electrolyte includes Ca ²⁺ . In certain examples, the electrolyte includes Cu ⁺ . In certain examples, the electrolyte includes Na ⁺ . In certain examples, the electrolyte includes K ⁺ . In certain examples, the electrolyte includes a combination of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ , or Na ⁺ .

[102] In some examples, including any of the foregoing, the electrolyte includes at least one member selected from the group consisting of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ , Na ⁺ , and combinations thereof wherein the member is present in the electrolyte at concentrations from 0.1 parts-per-billion (ppb) to 500 parts-per-million (ppm). In certain examples, the electrolyte includes Mg ²⁺ . In certain examples, the electrolyte includes Zn ²⁺ . In certain examples, the electrolyte includes Ca ²⁺ . In certain examples, the electrolyte includes Cu ⁺ . In certain examples, the electrolyte includes Na ⁺ . In certain examples, the electrolyte includes K ⁺ . In certain examples, the electrolyte includes a combination of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ , or Na ⁺ . [103] In some examples, including any of the foregoing, the electrolyte includes at least one member selected from the group consisting of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ and Na ⁺ , wherein the member is present in the electrolyte at concentrations less than 0.274 M. In certain examples, the electrolyte includes Mg ²⁺ . In certain examples, the electrolyte includes Zn ²⁺ . In certain examples, the electrolyte includes Ca ²⁺ . In certain examples, the electrolyte includes Cu ⁺ . In certain examples, the electrolyte includes Na ⁺ . In certain examples, the electrolyte includes K ⁺ . In certain examples, the electrolyte includes a combination of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ , or Na ⁺ .

[104] In some examples, including any of the foregoing, the electrolyte includes Li ⁺ and Na ⁺ , wherein the concentration of Na ⁺ is greater than the concentration of Li ⁺ .

[105] In some examples, including any of the foregoing, the electrolyte includes Li ⁺ and Na ⁺ , wherein the concentration of Na ⁺ is less than the concentration of Li ⁺ .

[106] In some examples, including any of the foregoing, the member is present at least at a detectable limit.

[107] In some examples, including any of the foregoing, the amount of AI2CI7 ^1" is below a detectable limit.

[108] In some examples, including any of the foregoing, the amount of AI2CI7 ^1" is below a detectable limit as measured by Raman spectroscopy.

[109] In some examples, including any of the foregoing, the amount of AI2CI7 ^1" is below a detectable limit as measured by mass spectroscopy.

[110] In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide of a member selected from the group consisting of Li, Na, Zn, Mg, Ca, Cu, and combinations thereof. In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide selected from Li. In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide selected from Na. In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide selected from Zn. In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide selected from Mg. In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide selected from Ca. In some examples, including any of the foregoing, the electrolyte includes a saturated amount of a halide selected from Cu.

[111] In some examples, including any of the foregoing, the electrolyte includes a saturated amount of LiCl.

[112] In some examples, including any of the foregoing, the organic cation or organic-metal complex cation comprises imidazolium ions, ammonium ions, pyrrolidinium ions, pyridinium ions, and phosphonium ions.

[113] In some examples, including any of the foregoing, the imidazolium ions include at least one of l-ethyl-3-methylimidazolium, l,2-dimethyl-3-propylimidazolium, and combinations thereof.

[114] In some examples, including any of the foregoing, the ammonium ions are selected from benzyltrimethylammonium, trimethylphenylammonium, triethylamine, and combinations thereof.

[115] In some examples, including any of the foregoing, the pyridinium ions include N-(n-butyl) pyridinium.

[116] In some examples, including any of the foregoing, the phosphonium ions include trihexyltetradecylphosphonium.

[117] In some examples, including any of the foregoing, the pyrrolidinium ions include 1 -butyl-l -methyl-pyrrolidinium.

[118] In some examples, including any of the foregoing, the organic cation or organic-metal complex cation comprises a compound, or cation derivative thereof, selected from the group consisting of acetamide, urea, methyl urea (MUrea), ethyl urea (EUrea), triethylamine hydrochloride (Et3NHCl), 1 -ethyl-3 -methylimidazolium

bis(trifluoromethylsulfonyl)imide, 1 -ethyl-3 -methylimidazolium tetrafluoroborate,

1 -ethyl-3 -methylimidazolium hexafluorophosphate, 1 -ethyl-3 -methylimidazolium chloride (EMIMC), 4-propylpyridine, N-methylacetamide, N,N-dimethylacetamide, and

trimethylphenylammonium chloride. [119] In some examples, including any of the foregoing, the electrolyte is present at a temperature from -40 °C (233.15 K) to 200 °C (473.15 K).

[120] In some examples, including any of the foregoing, the electrolyte is present at a temperature from -40 °C (233.15 K) to 120 °C (393.15 K).

[121] In some examples, including any of the foregoing, the electrolyte is molten and ionically conductive.

[122] In some examples, including any of the foregoing, the electrolyte comprises less than 100 ppm H ₂ 0.

[123] In some examples, including any of the foregoing, the electrolyte comprises less than 10 ppm H2O.

[124] In some examples, including any of the foregoing, the electrolyte comprises less than 1 ppm H2O.

[125] In some examples, including any of the foregoing, the electrolyte comprises less than 100 ppm O2.

[126] In some examples, including any of the foregoing, the amount of H2O or the amount of O2, or both, is below a detectable limit.

[127] In some examples, including any of the foregoing, the electrolyte comprises urea, Murea, Eurea, Et3NHCl, EMIMC, combinations, and cations thereof.

[128] In some examples, including any of the foregoing, the electrolyte comprises urea or a cation thereof.

[129] In some examples, including any of the foregoing, the electrolyte comprises EMIMC or a cation thereof.

[130] In some examples, including any of the foregoing, the electrolyte comprise AlCh: EMIMC in a mole ratio from 1.0 to 2.0.

[131] In some examples, including any of the foregoing, the mole ratio of

AlCh: EMIMC is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl. [132] In some examples, including any of the foregoing, the electrolyte comprises AlCL:urea in a mole ratio from 1.0 to 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[133] In some examples, including any of the foregoing, the mole ratio of

AlCb:urea is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[134] In some examples, including any of the foregoing, the electrolyte comprise AlCb :Murea in a mole ratio from 1.0 to 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[135] In some examples, including any of the foregoing, the mole ratio of

AlCb :Murea is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[136] In some examples, including any of the foregoing, the electrolyte comprises AlCL :Eurea in a mole ratio from 1.0 to 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[137] In some examples, including any of the foregoing, the mole ratio of

AlCb :Eurea is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[138] In some examples, including any of the foregoing, the electrolyte comprises AlCLiEtsNHCl in a mole ratio from 1.0 to 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[139] In some examples, including any of the foregoing, the mole ratio of

AlCL ⁱ EtsNHCl is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, the electrolyte comprises a saturated amount of LiCl.

[140] In some examples, including any of the foregoing, the electrolyte comprises: (a) 1.1 to 2.0 molar equivalents A1CL ¹ , (b) 1.0 molar equivalents l-ethyl-3-methyl imidazolium; and (c) 0.1 to 0.5 molar equivalents l-ethyl-3-methylimidazolium

bis(trifluoromethylsulfonyl)imide, 1 -ethyl-3 -methylimidazolium tetrafluoroborate, l-ethyl-3- methylimidazolium hexafluorophosphate, or a combination thereof. [141] In some examples, including any of the foregoing, the electrolyte comprises:

(a) an organic cation selected from the group consisting of l-ethyl-3-methyl imidazolium, N- (n-butyl) pyridinium, benzyltrimethylammonium, l,2-dimethyl-3-propylimidazolium, trihexyltetradecylphosphonium, and 1 -butyl- l-methyl-pyrrolidinium, and (b) an anion selected from the group consisting of chloride, tetrafluoroborate, tri-fluoromethanesulfonate, hexafluorophosphate and bis(trifluoromethanesulfonyl)imide.

[142] In some examples, including any of the foregoing, the electrochemical cell comprises a positive electrode, wherein the positive electrode comprises an active material selected from the group consisting of: LiCoCh, LiM Cfi. LiMn1 _. 5Nio _. 5O4, Li(NiCoAl)02 (NCA), Li(NiCoMn)0 ₂ (NMC), lithium iron phosphate (LiFeP0 ₄ ), lithium nickel phosphate (LiNiP04), lithium cobalt phosphate (L1C0PO4), lithium manganese phosphate (LiMnP04), a lithium cobalt oxide, a lithium manganese cobalt oxide, a lithium nickel manganese cobalt oxide, a lithium nickel manganese oxide and sulfur.

[143] In some examples, including any of the foregoing, the electrochemical cell is in a chemically compatible enclosure.

[144] In some examples, including any of the foregoing, the chemically compatible enclosure comprises a material selected from the group consisting of a hydrophobic polymer, a fluorinated polymer, an aluminum metal, a polymer coated aluminum pouch, and a polymer coated metal container.

[145] In some examples, including any of the foregoing, the electrochemical cell further comprises a positive electrode current collector selected from the group consisting of a glassy carbon, carbon fiber paper, carbon fiber cloth, graphite fiber paper, and graphite fiber cloth.

[146] In some examples, including any of the foregoing, the electrochemical cell further comprises a positive electrode current collector selected from the group consisting of a metal substrate.

[147] In some examples, including any of the foregoing, the metal substrate is a mesh or a foil or a foam. [148] In some examples, including any of the foregoing, the metal substrate comprises a metal selected from nickel (Ni) or tungsten (W).

[149] In some examples, including any of the foregoing, the metal substrate comprises a metal or alloy coated with a Ni and W thin film.

[150] In some examples, including any of the foregoing, the metal substrate is a Ni foil, a Ni mesh, a W foil, or a W mesh.

[151] In some examples, including any of the foregoing, the metal substrate includes a metal selected from nickel (Ni), stainless steel (SS), iron (Fe) or tungsten (W).

[152] In some examples, including any of the foregoing, the metal substrate includes a metal or alloy coated with a Ni, SS or W thin film.

[153] In some examples, including any of the foregoing, the metal substrate is a Ni foil, a Ni mesh, or a Ni foam, a metal foil with Ni coating, metal mesh with Ni coating, or a metal foam with Ni coating, a W foil, a W foam or a W mesh, a SS foil, a SS foam or a SS mesh.

[154] In some examples, including any of the foregoing, the SS is 304 SS or 304L SS or 316 SS or 316L SS or 201SS.

[155] In some examples, including any of the foregoing, the electrochemical cell further includes a positive electrode, wherein the positive electrode includes a polymer binder and a positive electrode active material, wherein the active material is blended with the polymer binder. In some examples, the polymer binder is a hydrophilic polymer or hydrophobic polymer binder. In some examples, the polymer binder is a hydrophilic polymer and wherein the hydrophilic polymer binder is selected from the group consisting of poly acrylate, poly acrylic acid (PAA), polyvinyl alcohol (PVA), PAA-PVA, poly acrylic latex, cellulose, cellulose derivatives, alginate, acrylonitrile, polyethylene glycol, styrene-butadiene rubber, poly(styrene-co-butadiene), styrene-butadiene rubber, poly(3,4- ethylenedioxythiophene), and combinations thereof.

[156] In some examples, including any of the foregoing, the electrochemical cell includes a separator selected from inorganics such as SiC glass fiber, polymers or inorganic- polymer composites. [157] In some examples, including any of the foregoing, the electrochemical cell includes a separator, wherein the thickness of the separator is about 20 pm, 50 pm, 100 pm, 150 pm, 200 pm or 400 pm.

[158] In some examples, including any of the foregoing, the electrochemical cell includes AlCl ₃ :Et ₃ NHCl in a mole ratio of about 1.7.

[159] In some examples, including any of the foregoing, the molar ratio, m _r , of AlCl ₃ :Et ₃ NHCl is Km _r <2.

[160] In some examples, including any of the foregoing, the electrochemical cell includes AlCl ₃ ; Et ₃ NHCl; a saturated amount of LiCl; 1.0 mol equivalent of Et ₃ NH ⁺ ; 1.7 mol equivalent of AICU : and 0.7 mol equivalent of Li ⁺ .

[161] In some examples, including any of the foregoing, the electrochemical cell includes AlCl ₃ : EMIMC in a mole ratio of about 1.7.

[162] In some examples, including any of the foregoing, the molar ratio, m _r , of A1CU: EMIMC is Km _r <2.

[163] In some examples, including any of the foregoing, the electrochemical cell includes AlCl ₃ ; EMIMC; a saturated amount of LiCl; 1.0 mol equivalent of EMIMC; 1.7 mol equivalent of AICU : and 0.7 mol equivalent of Li ⁺ .

[164] In some examples, including any of the foregoing, the cathode has an active material loading of about 8 to 16 mg/cm ² .

[165] In some examples, including any of the foregoing, the thickness of the metal anode is about 30 pm.

[166] In some examples, including any of the foregoing, the electrochemical cell includes an Al current negative electrode collector having an Al tab; a SiCh glass fiber separator; and aNi, Ni coated metal, W, SS or C positive electrode current collector having a Ni, Ni coated metal, W, SS, or C tab.

[167] In some examples, including any of the foregoing, the electrochemical cell includes AlCl ₃ :Et ₃ NHCl in a mole ratio of about 1.7; a saturated amount of LiCl; 1.0 mol equivalent of Et ₃ NH ⁺ ; 1.7 mol equivalent of A1CU ¹ ; and 0.7 mol equivalent of Li ⁺ . [168] In some examples, including any of the foregoing, the cathode has an active material loading of about 16 mg/cm ² .

[169] In some examples, including any of the foregoing, the thickness of the metal anode is about 30 pm.

[170] In some examples, including any of the foregoing, the electrochemical cell includes aluminum metal or aluminum-lithium alloy negative electrode; an Al current negative electrode collector having an Al tab; a SiC glass fiber separator; a positive electrode comprising an active material selected from the group consisting of: LiCoC , LiM Cri. LiMn1 _. 5Nio _. 5O4, Li(NiCoAl)02 (NCA), Li(NiCoMn)02 (NMC), lithium iron phosphate (LiFeP0 ₄ ), lithium nickel phosphate (LiNiP0 ₄ ), lithium cobalt phosphate (L1C0PO4), lithium manganese phosphate (LiMnP0 ₄ ), a lithium cobalt oxide, a lithium manganese cobalt oxide, a lithium nickel manganese cobalt oxide, a lithium nickel manganese oxide and sulfur; and aNi, Ni coated metal, W, SS, or C positive electrode current collector having a Ni, Ni coated metal, W, SS, or C tab.

[171] In some examples, including any of the foregoing, the thickness of the separator is about 20 pm, 100 pm, 150 pm, or 200 pm.

Batteries

[172] In some examples, the electrochemical cells or batteries, described herein, are enclosed in a chemically compatible enclosure that includes a material selected from a fluorinated polymer, aluminum metal, and combinations thereof. In some examples, the chemically compatible enclosure includes a fluorinated polymer. In some other examples, the chemically compatible enclosure includes aluminum metal. In certain other examples, the chemically compatible enclosure includes, in addition to a fluorinated polymer, a polyethylene polymer which is not in direct contact with the electrolyte. In some examples, the chemically compatible enclosure includes, in addition to a fluorinated polymer, a polypropylene polymer which is not in direct contact with the electrolyte. In some examples, the chemically compatible enclosure includes combinations of a fluorinated polymer, aluminum metal, polyethylene, and polypropylene, but wherein the polyethylene and polypropylene polymers, when present, are not in direct contact with the electrolyte. In some examples, including any of the foregoing, the fluorinated polymer layer is in contact with the electrolyte. In some examples, including any of the foregoing, the aluminum metal is between the fluorinated polymer layer and another polymer layer, such as a polypropylene layer. Batteries, electrochemical cells, and chemically compatible enclosures as set forth in

International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, are herein incorporated by reference in its entirety for all purposes.

Processes of Making

[173] In some examples, set forth herein is a process for making an electrolyte, comprising contacting (i) AlCh with (ii) organic cation or organic-metal complex cation, wherein the organic cations are selected from the group consisting of urea ions, imidazolium ions, ammonium ions, pyrrolidinium ions, pyridinium ions, and phosphonium ions; and (iii) a saturated amount of a halide of a member selected from the group consisting of Li, Na, K,

Ca, Mg, Zn, Cu, and combinations thereof. Example halides include, but are not limited to, LiCl, NaCl, KC1, Ca ₂ Cl, Mg ₂ Cl, Zn ₂ Cl, CuCl, and Cu ₂ Cl.

[174] In some other examples, set forth herein is a process for making an electrolyte, wherein the electrolyte comprises: AlCU ¹ ; Li ⁺ ; at least one member selected from the group consisting of organic cations and organic-metal complex cations; wherein the electrolyte is free of any ALCF ¹ ; and wherein the electrolyte is further doped with an additive of LiF,

Li ₂ 0 and combinations thereof; the process comprising contacting the electrolyte with aluminum metal in the presence of an additive selected from SnCl ₂ , GaCb, and combinations thereof.

[175] In some examples, including any of the foregoing, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence of an additive selected from SnCl ₂ , GaCT. and combinations thereof. In some examples, the electrolyte is further doped with an additive selected from LiF, Li0 ₂ and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped Li ₂ 0.

[176] In some examples, including any of the foregoing, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence SnCl ₂ . In some examples, the electrolyte is further doped with an additive selected from LiF, Li0 ₂ and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped Li ₂ 0. [177] In some examples, including any of the foregoing, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence GaCk In some examples, the electrolyte is further doped with an additive selected from LiF, L1O2 and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped LLO.

[178] In some examples, including any of the foregoing, the electrolyte is treated by contacting and reacting the electrolyte with aluminum metal in the presence of combinations of SnCL and GaCk In some examples, the electrolyte is further doped with an additive selected from LiF, L1O2 and combinations thereof. In some examples, the electrolyte is further doped LiF. In some examples, the electrolyte is further doped LLO.

[179] In some other examples, set forth herein is a process for making an electrolyte, comprising contacting (i) AlCh with: (ii) an organic cation or organic-metal complex cation, wherein the organic cation is selected from the group consisting of urea ions, imidazolium ions, ammonium ions, pyrrolidinium ions, pyridinium ions, phosphonium ions, and combinations thereof; and (iii) a saturated amount of a halide of a metal selected from the group consisting of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof.

[180] In some examples, including any of the foregoing, the electrolyte is free of any AI2CI7 ^{1 "} , as detected by Raman spectroscopy.

[181] In some examples, including any of the foregoing, the electrolyte is free of any AI2CI7 ^{1 "} , which differs from any previous batteries using Al metal as anode.

[182] In some examples, including any of the foregoing, the process includes reducing the pressure around the electrolyte by drawing a vacuum while cycling the electrolyte at least two or more times in an electrochemical cell.

[183] In some examples, including any of the foregoing, the process includes mixing AlCL and urea, wherein the molar ratio, m _r , of AICkurea is l<m _r <2.

[184] In some examples, including any of the foregoing, the process includes contacting AlCb and urea, wherein the molar ratio, m _r , of AlC urea is l<m _r <2.

[185] In some examples, including any of the foregoing, m _r is l.x, wherein 0<x<9. [186] In some examples, including any of the foregoing, the process includes adding x equivalent moles of a halide of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof with (i) AlCL with (ii) organic cation or organic-metal complex cation.

[187] In some examples, including any of the foregoing, the process includes adding to a mixture of AlCL and urea x equivalent moles of a halide of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof.

[188] In some examples, including any of the foregoing, the process includes adding x equivalent moles of a halide of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof.

[189] In some examples, including any of the foregoing, the process includes contacting x equivalent moles of a LiCl with AlCL and an organic cation or organic-metal complex cation.

[190] In some examples, including any of the foregoing, the process includes contacting AlCL and EMIMC, wherein the molar ratio, m _r , of AlCL:EMIMC is l<m _r <2.

[191] In some examples, including any of the foregoing, m _r is Lx, wherein 0<x<9.

[192] In some examples, including any of the foregoing, the process includes contacting x equivalent moles of a halide of a member selected from the group consisting of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof with AlCL and an organic cation or organic-metal complex cation.

[193] In some examples, including any of the foregoing, the process includes contacting x equivalent moles of a LiCl with AlCL and an organic cation or organic-metal complex cation.

[194] In some examples, including any of the foregoing, the process includes contacting AlCL and triethylamine hydrochloride (EbNElCl), wherein the molar ratio, m _r , of AlCb:EbNHCl is Km _r <2.

[195] In some examples, including any of the foregoing, m _r is Lx, wherein 0<x<9.

[196] In some examples, including any of the foregoing, the process includes contacting x equivalent moles of a metal or a metal halide of a member selected from the group consisting of Li, Na, K, Ca, Mg, Zn, Cu, and combinations thereof with AlCb and an organic cation or organic-metal complex cation.

[197] In some examples, including any of the foregoing, the process includes contacting x equivalent moles of a LiCl with AlCb and an organic cation or organic-metal complex cation. In some examples, x that is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[198] In some examples, including any of the foregoing, the process includes contacting the electrolyte with an additive selected from SnCh, GaCb, and combinations thereof. In some examples, including any of the foregoing, the process includes contacting the electrolyte with SnCh. In some examples, including any of the foregoing, the process includes contacting the electrolyte GaCb. In some examples, including any of the foregoing, the process includes contacting the electrolyte with a combination of SnCh and GaCb. In certain examples, neither SnCh, GaCb, nor combinations thereof remain in the electrolyte at the end of the process set forth herein. Without being bound by theory, this purification step produces strong color reduction. After this step, the electrochemical cell having this electrolyte demonstrates higher coulombic efficiency.

[199] In some examples, including any of the foregoing, the process includes contacting the electrolyte with SnCh.

[200] In some examples, including any of the foregoing, the process includes contacting the electrolyte with GaCb.

[201] In some examples, including any of the foregoing, the electrolyte is free of any AhCb ¹ .

[202] In some examples, including any of the foregoing, the halide is a chloride.

[203] In some examples, including any of the foregoing, the halide is LiCl.

[204] In some examples, including any of the foregoing, the electrolyte further includes at least one species selected from the group consisting of Mg, Zn, Ca, Cu, Na, K and combinations thereof, wherein the species are ions in any of their possible oxidation states. [205] In some examples, including any of the foregoing, the species are present at concentrations from 0.1 parts-per-million (ppm) to 1% by mole.

[206] In some examples, including any of the foregoing, the electrolyte includes at least one species selected from the group consisting of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ and Na ⁺ and combinations thereof.

[207] In some examples, including any of the foregoing, the electrolyte includes at least one species selected from the group consisting of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ and Na ⁺ , wherein the species is present in the electrolyte at concentrations from 0.1 parts-per- million (ppm) to 1% by mole.

[208] In some examples, including any of the foregoing, the electrolyte includes at least one cation selected from the group consisting of Mg ²⁺ , Zn ²⁺ , Ca ²⁺ , Cu ⁺ , Cu ²⁺ , K ⁺ , Na ⁺ , and combinations thereof, wherein the cation is present in the electrolyte at concentrations less than 1 M.

[209] In some examples, including any of the foregoing, the electrolyte includes Li ⁺ and Na ⁺ , wherein the concentration of Na ⁺ is greater than the concentration of Li ⁺ .

[210] In some examples, including any of the foregoing, the electrolyte includes Li ⁺ and Na ⁺ , wherein the concentration of Na ⁺ is less than the concentration of Li ⁺ .

[211] In some examples, including any of the foregoing, the cation(s) is present at least at a detectable limit.

[212] In some examples, including any of the foregoing, the amount of AI2CI7 ¹ is below a detectable limit.

[213] In some examples, including any of the foregoing, the amount of AI2CI7 ¹ is below a detectable limit as measured by Raman spectroscopy.

[214] In some examples, including any of the foregoing, the amount of AI2CI7 ¹ is below a detectable limit as measured by mass spectroscopy.

[215] In some examples, including any of the foregoing, the organic cation or organic-metal complex cation comprises a compound, or cation derivative thereof, selected from the group consisting of acetamide, urea, methyl urea (MUrea), ethyl urea (EUrea), triethylamine hydrochloride (Et3NHCl), 1 -ethyl-3 -methylimidazolium

bis(trifluoromethylsulfonyl)imide, 1 -ethyl-3 -methylimidazolium tetrafluoroborate, l-ethyl-3- methylimidazolium hexafluorophosphate, l-ethyl-3-methylimidazolium chloride (EMIMC), 4-propylpyridine, N-methylacetamide, N,N-dimethylacetamide, and

trimethylphenylammonium chloride.

[216] In some examples, including any of the foregoing, the electrochemical cell comprises a metal anode comprising a metal, or alloy thereof, selected from the group consisting of aluminum (Al), lithium (Li), zinc (Zn), Al-Li alloy, Zn-Al-Li alloy, nickel (Ni), tungsten (W), titanium (Ti), sodium (Na), ), tin (Sn). In some examples, including any of the foregoing, the electrochemical cell comprises a metal anode, a cathode, and a separator between the metal anode and the cathode.

[217] In some examples, including any of the foregoing, the electrolyte is present at a temperature from -40 °C (233.15 K) to 200 °C (473.15 K).

[218] In some examples, including any of the foregoing, the electrolyte is present at a temperature from -40 °C (233.15 K) to 120 °C (393.15 K).

[219] In some examples, including any of the foregoing, the process comprises reducing the pressure around the electrolyte by drawing a vacuum while cycling the electrolyte until the electrolyte comprises less than 100 ppm EbO.

[220] In some examples, including any of the foregoing, the process comprises reducing the pressure around the electrolyte by drawing a vacuum while cycling the electrolyte until the electrolyte comprises less than 10 ppm EbO.

[221] In some examples, including any of the foregoing, the process comprises reducing the pressure around the electrolyte by drawing a vacuum while cycling the electrolyte until the electrolyte comprises less than 1 ppm EbO.

[222] In some examples, including any of the foregoing, the process comprises reducing the pressure around the electrolyte by drawing a vacuum while cycling the electrolyte until the electrolyte comprises less than 100 ppm O2. [223] In some examples, including any of the foregoing, the organic cation or organic-metal complex cation comprises imidazolium ions, ammonium ions, pyrrolidinium ions, pyridinium ions, and phosphonium ions.

[224] In some examples, including any of the foregoing, the imidazolium ions include at least one of l-ethyl-3-methylimidazolium, l,2-dimethyl-3-propylimidazolium, and combinations thereof.

[225] In some examples, including any of the foregoing, the ammonium ions are selected from benzyltrimethylammonium, trimethylphenylammonium, triethylamine, and combinations thereof.

[226] In some examples, including any of the foregoing, the pyridinium ions include N-(n-butyl) pyridinium.

[227] In some examples, including any of the foregoing, the phosphonium ions include trihexyltetradecylphosphonium.

[228] In some examples, including any of the foregoing, the pyrrolidinium ions include 1 -butyl-l -methyl-pyrrolidinium.

[229] In some examples, including any of the foregoing, the process comprises cycling the battery for several cycles and reducing the pressure around the electrolyte by drawing a vacuum.

[230] In some examples, including any of the foregoing, the electrolyte is batched with urea, Murea, Eurea, Et3NHCl, EMIMC, combinations, and cations thereof.

[231] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising urea or a cation thereof.

[232] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising EMIMC or a cation thereof.

[233] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising AlCh: EMIMC in a mole ratio from 1.0 to 2.0. [234] In some examples, including any of the foregoing, the mole ratio of

AlCl ₃ :EMIMC is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.0. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.1. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.2. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.3. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.4. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.5. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.6. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.7. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.8. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 1.9. In some examples, including any of the foregoing, the mole ratio of AlCb:EMIMC is 2.0.

[235] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising AlCb:urea in a mole ratio from 1.0 to 2.0. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.0. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.1. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.2. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.3. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.4. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.5. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.6. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.7. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.8. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.9. In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 2.0.

[236] In some examples, including any of the foregoing, the mole ratio of

AlCb:EbNHCl is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.0. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.1. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.2. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.3. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.4. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.5. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.6. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.7. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.8. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 1.9. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNElCl is 2.0.

[237] In some examples, including any of the foregoing, the mole ratio of AlCb:urea is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0.

[238] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising AlCb:MUrea in a mole ratio from 1.0 to 2.0.

[239] In some examples, including any of the foregoing, the mole ratio of

AlCb:MUrea is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising

AlCb:Murea in a mole ratio from 1.0 to 2.0. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.0. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.1. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.2. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.3. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.4. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.5. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.6. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.7. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.8. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 1.9. In some examples, including any of the foregoing, the mole ratio of AlCb:Murea is 2.0.

[240] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising AlCb:EUrea in a mole ratio from 1.0 to 2.0.

[241] In some examples, including any of the foregoing, the mole ratio of

AlCb:Eurea is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising AlCb:Eurea in a mole ratio from 1.0 to 2.0. In some examples, including any of the foregoing, the mole ratio of AlClyEurea is 1.0. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.1. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.2. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.3. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.4. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.5. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.6. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.7. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.8. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 1.9. In some examples, including any of the foregoing, the mole ratio of AlCb:Eurea is 2.0.

[242] In some examples, including any of the foregoing, the electrolyte is batched with a mixture comprising AlCb:EbNHCl in a mole ratio from 1.0 to 2.0.

[243] In some examples, including any of the foregoing, the mole ratio of

AlCb:EbNHCl is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNHCl is 1.0. In some examples, including any of the foregoing, the mole ratio of AlCb : EbNHCl is 1.1. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNHCl is 1.2. In some examples, including any of the foregoing, the mole ratio of AlCb: EbNHCl is 1.3. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNHCl is 1.4. In some examples, including any of the foregoing, the mole ratio of AlCb: EbNHCl is 1.5. In some examples, including any of the foregoing, the mole ratio of AlCb: EbNHCl is 1.6. In some examples, including any of the foregoing, the mole ratio of AlCb:EbNHCl is 1.7. In some examples, including any of the foregoing, the mole ratio of AlCb: EbNHCl is 1.8. In some examples, including any of the foregoing, the mole ratio of AlCb: EbNHCl is 1.9. In some examples, including any of the foregoing, the mole ratio of AlCb: EbNHCl is 2.0.

[244] In some examples, set forth herein is an electrolyte made by a process herein.

[245] In some examples, set forth herein is an electrochemical cell that includes an electrolyte made herein. EXAMPLES

[246] The Examples herein show how to make and use batteries having a metal anode and the aforementioned electrolyte.

[247] Electrochemical cells in this example included, in separate instances, an Al, Al-Li, Ni, W, Zn, Mg, AlMg, Al-Zn-Mg, Cu, or CuZn metal anode. The AlMg metal anode was an alloy of Al and Mg. The Al-Zn-Mg metal anode was an alloy of Al, Zn, and Mg. The CuZn metal anode was an alloy of Cu and Zn. The Al-Li metal anode was an alloy of Li and Al. The metal anode was washed by ethanol to remove contaminants before use. A 3-mm- wide and 0.09-mm-thick nickel tab was bonded to the cathode which was comprised of lithium iron phosphate (LFP) mixed with conductive carbon and a binder pasted on a nickel foil. Loading of LFP was approximately 10-15 mg/cm ² . SiCh glass fiber filter paper was used as a separator. All of the electrode components were assembled in a pouch. The pouch was made from an aluminum-laminated film. Before filling the electrolyte in the battery pouch, the battery pouch was dried at 80°C to remove residual moisture.

[248] All electrolytes were made and electrochemical cells assembled in an Argon- filled glovebox with less than about 5 parts-per-million (ppm) water and oxygen in the glovebox. Aluminum Chloride (A1CT) (Alfa Aesar, anhydrous 99.9%) was used as received and opened inside the glovebox. 1 -ethyl-3 -methylimidazolium chloride, urea, and methylurea were vacuum dried at 60-90 °C for 24 hours.

[249] Unless specified to the contrary, all electrochemical cell components inside a pouch were fixed in place using carbon tape, which was exposed to the electrolyte. The carbon tape was used to secure certain parts of the electrochemical cell. However, the carbon tapes is not a necessary component and does not need to be present. A partially assembled cell was dried overnight at 80°C under vacuum and transferred to the glovebox. In the glovebox, two layers of glass fiber filter paper separator (previously dried at 250°C) and

1.5 g a 1.3: 1 mole ratio of an AlCUurea electrolyte were combined for use as the electrochemical cell separator.

[250] Instruments for electrochemical analysis were CHI 760D (CH Instruments), VMP3 (Bio-Logic) and Battery testing instrument (Neware). Physical Analysis

[251] Raman spectra measurement was performed to measure the defect band D band intensity relative to the graphite band G band. The data acquisition time was normally 10 s and accumulated for 10 times. The wavelength of laser excitation source was normalized by a silicon wafer at 520 cnT ¹ . A thermoelectrically cooled charge-coupled device with 1,024 x 256 pixels operating at 60 °C was used as the detector with 1 cnT ¹ resolution. The laser line was focused onto the sample using an Olympus ^c 50 objective, and the laser spot size was estimated to be 0.8-1 pm.

[252] Instruments for physical analysis were Bruker D8-advanced (X-ray diffraction measurements) and UniRAM micro-Raman spectrometer with a laser wavelength of 532 nm.

EXAMPLE 1 - ELECTROCHEMICAL CELLS WITH ALUMINUM ANODES AND

LITHIUM IRON PHOSPHATE CATHODES

[253] This Example shows some of the advantages of using an ionic liquid based electrolyte with Cu ²⁺ or Mg ²⁺ ion species in an electrochemical cell with a cathode having LiFeP04 cathode active materials. These advantages should extend to any electrochemical cell with a Li-intercalating positive electrode active material and a negative electrode suitable for use with LiAl-alloy redox active materials, and an electrolyte comprising AICU ¹ . Li ⁺ and optionally Mg ²⁺ but wherein the electrolyte is also free of Al ₂ Cl ₇ .

[254] Three aluminum-ion batteries (AIB) were prepared. The AIBs each included Al foil as the negative electrode, a 200 pm-thick glass separator with an electrolyte, and LiFePCE on Ni foil as positive electrode. The slurry used to deposit the cathode included

85 wt% LiFePCri, 10 wt% conductive carbon and 5 wt% binder, which was pasted on Ni foil and then dried at l20°C for 12 hours. The amount of LiFePCri in the cathode was approximately 10 mg/cm ² .

[255] The first electrolyte was prepared by mixing AlCh and EMIMC in a

AlCb/EMIMC molar ratio of 1.3. EMIMC is l-ethyl-3-methylimidazolium chloride. Then the electrolyte was exposed to a saturated amount of LiCl. The LiCl was added in an amount to fully neutralize the electrolyte by adding an amount higher than 0.3 equivalent moles, relative to the amount of EMIMC. The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An battery with this electrolyte was electrochemically cycled. The results are shown in FIG. 1(a).

[256] The second electrolyte was prepared by mixing AlCl ₃ and Et ₃ NHCl in a AlCl ₃ :Et ₃ NHCl molar ratio of 1.7. Then the electrolyte was exposed a saturated amount of LiCl. The LiCl was added in amount to fully neutralize the electrolyte by adding an amount higher than 0.7 equivalent moles, relative to the amount of AlCl ₃ . The electrolyte was then purified under vacuum according to the methods set forth in International

PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 1(b).

[257] The third electrolyte was prepared by mixing AlCl ₃ and Urea in a AlCl ₃ /Urea molar ratio of 1.3. Then the electrolyte was exposed a saturated amount of LiCl. LiCl was added in an amount to fully neutralize the electrolyte by adding an amount higher than 0.3 equivalent moles, relative to the amount of AlCl ₃ . The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 1(c).

EXAMPLE 2 - ELECTROCHEMICAL CELLS WITH ALUMINUM ANODES AND LITHIUM MANGANESE NICKEL COBALT OXIDE CATHODES

[258] The battery composed of aluminum anode and lithium manganese nickel cobalt oxide cathode was prepared. The electrochemical cells included Al foil as the negative electrode, a 200 pm-thick glass separator with an electrolyte, and LiNi _z Mn _y Co _z 02 (x, y, z range from 0.05-0.95; LiNii _/3 Mm _/3 Coi _/3 0 ₂ used in this example) pasted on Ni foil as positive electrode. The slurry used to prepare the cathode included 85 wt% LiNii _/3 Mni _/3 Coi _/3 0 ₂ ,

10 wt% conductive carbon and 5 wt% binder, which was pasted on Ni foil and then dried at l20°C for 12 hours. The mass loading of LiNii _/3 Mm _/3 Coi _/3 02 in the cathode was

approximately 10 mg/cm ² .

[259] The first electrolyte was prepared by mixing AlCb and EMIMC in a

AlCb/EMIMC mole ratio of 1.1. Then the electrolyte was exposed to a saturated amount of LiCl. LiCl was added in an amount higher than 0.1 mol equivalents, relative to the amount of AlCb, to fully neutralize the electrolyte. The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 2(a).

[260] The second electrolyte was prepared by mixing AlCb and Urea in a

AlCb/Urea mole ratio of 1.3. Then the electrolyte was exposed to a saturated amount of LiCl. LiCl was added in an amount higher than 0.3 mol equivalents, relative to the amount of AlCb, to fully neutralize the electrolyte. The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 2(b).

EXAMPLE 3 - ELECTROCHEMICAL CELLS WITH ALUMINUM ANODES AND

GRAPHITE CATHODES

[261] Two aluminum-ion batteries (AIB) were prepared. The AIBs each included Al foil as the negative electrode, a 200 pm-thick glass separator with an ionic liquid electrolyte, and graphite-coated Ni foil as positive electrode. The slurry used to prepare the cathode included 95 wt% graphite and 5 wt% binder, which was pasted on Ni foil and then dried at l20°C for 12 hours. The AIBs each had a different ionic liquid electrolyte (ILE).

[262] The first electrolyte was prepared by mixing AlCb and EMIC in a

AlCb/EMIC mole ratio of 1.6. This electrolyte was referred to as an ionic liquid electrolyte (ILE). Then the ILE was exposed to Mg metal which formed Mg ²⁺ ions in the ILE in parts- per-million amounts Mg ²⁺ . The ILE was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. The results are shown in FIG. 3(a).

[263] The second electrolyte was prepared by mixing AlCb and triethylamine hydrochloride (Et3NHCl) in a AlCL/EhNHCl mole ratio of 1.6. This electrolyte was referred to as an ionic liquid electrolyte (ILE). Then the ILE was exposed to Cu metal which formed Cu ²⁺ ions in the ILE in parts-per-million amounts Cu ²⁺ . The ILE was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. The results are shown in FIG. 3(b).

EXAMPLE 4 - ELECTROCHEMICAL CELLS WITH NICKEL ANODES AND

LITHIUM IRON PHOSPHATE CATHODES

[264] The electrochemical cells in this example included a nickel (Ni) anode and a lithium iron phosphate (LiFeP04) cathode. The electrochemical cells included Ni foil with a thickness of approximately 20 pm as the negative electrode, a 200 pm-thick glass separator with an electrolyte, and LiFeP0 ₄ on Ni foil as positive electrode. The slurry used to prepare the cathode included 85 wt% LiFeP04, 10 wt% conductive carbon and 5wt% binder, which was pasted on Ni foil and then dried at l20°C for 12 hours. The amount of LiFePCL in the cathode was approximately 10 mg/cm ² .

[265] The electrolyte was prepared by mixing A1CL and Et3NHCl in a

AlCL/EtsNHCl mole ratio of 1.7. Then the electrolyte was exposed a saturated amount of LiCl. LiCl in an amount higher than 0.7 mol equivalents, relative to the amount of AICL. was added to fully neutralize the 1.7 AlCL/EtiNHCl electrolyte. The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 4. EXAMPLE 5 - ELECTROCHEMICAL CELLS WITH ZINC ANODES AND LITHIUM IRON PHOSPHATE CATHODES

[266] The electrochemical cells in this example included a zinc (Zn) anode and lithium iron phosphate (LiFeP0 ₄ ) cathode. The electrochemical cells included a Zn foil with thickness of 50 pm as the negative electrode, a 200 pm-thick glass separator with an electrolyte, and LiFeP0 ₄ on Ni foil as positive electrode. The slurry used to prepare the cathode included 85 wt% LiFeP0 ₄ , 10 wt% conductive carbon and 5 wt% binder, which was pasted on Ni foil and then dried at l20°C for 12 hours. The amount of LiFePCb in the cathode was approximately 10 mg/cm ² .

[267] The electrolyte for electrochemical cells with zinc anodes and lithium iron phosphate cathodes was prepared by mixing AlCh and EbNHCl in a AlCb/EhNHCl mole ratio of 1.7. Then the electrolyte was exposed to a saturated amount of LiCl. LiCl in an amount higher than 0.7 mol equivalents, relative to the amount of AlCh. was added to fully neutralize the 1.7 AlCb/EbNHCl electrolyte. The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 5

EXAMPLE 6 - ELECTROCHEMICAL CELLS WITH METAL ALLOY ANODES

AND LITHIUM IRON PHOSPHATE CATHODES

[268] The electrochemical cells in this example included an alloy anode and lithium iron phosphate (LiFeP0 ₄ ) cathode. The electrochemical cells in this example used a metal alloy as anode as demonstrated by Al-Zn-Mg alloy. The 7075 type Al-Zn-Mg alloy

(approximately 2.5 wt% Mg, approximately 5.5 wt% Zn, and approximately 92 wt% Al) was used. The electrochemical cells included 7075 type Al-Zn-Mg alloy with thickness of 1.0 mm as the negative electrode, a 200 pm-thick glass separator with an electrolyte, and LiFePCb on Ni foil as positive electrode. The amount of LiFePCb in the cathode was approximately 10 mg/cm ² .

[269] The electrolyte for electrochemical cells with an 7075 type Al-Zn-Mg alloy anode and lithium iron phosphate cathodes was prepared by mixing AlCb and EbNHCl in a AlCb/Et3NHCl mole ratio of 1.7. Then the electrolyte was exposed to a saturated amount of LiCl. LiCl in an amount higher than 0.7 mol equivalents, relative to the amount of AlCb, was added to fully neutralize the 1.7 AlCh/EtiNHCl electrolyte. The electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. An AIB with this electrolyte was electrochemically cycled. The results are shown in FIG. 6.

EXAMPLE 7 - RAMAN SPECTROSCOPY ANALYSIS OF ELECTROLYTE

[270] An electrolyte was prepared having a mole ratio of AlCUEMIC of 1.1 according to the procedures in Sun, et al. , A HIGH PERFORMANCE HYBRID BATTERY BASED ON ALUMINUM ANODE AND LIFEPO4 CATHODE, Chem. Commun., 2015, DOI: 10. l039/c5cc090l9a. The electrolyte included 1M LiAlCU. The electrolyte was analyzed by Raman spectroscopy, the results of which are shown in FIG. 7.

[271] The results in FIG. 7 show that the electrolyte was not fully neutralized. AI2CI7 ^" species was observed at 316 cm based on Raman spectroscopy. Analysis of this electrolyte showed a mole ratio of AbCE iAlCU of approximately 0.122.

EXAMPLE 8 - RAMAN SPECTROSCOPY ANALYSIS OF ELECTROLYTE

[272] A series of electrolytes were prepared by mixing AlCh and EMIMC in AlCb/EMIMC molar ratios of 1.6, 1.7, 1.8, 1.9, and 2.0. EMIMC is l-ethyl-3- methylimidazolium chloride. Each electrolyte was exposed to a saturated amount of LiCl. Each electrolyte was then purified under vacuum according to the methods set forth in International PCT/US2018/026968, entitled BATTERY WITH LONG CYCLE LIFE, filed April 14, 2018, the entire contents of which are herein incorporated by reference in its entirety for all purposes. The series of electrolytes was analyzed by Raman spectroscopy, the results of which are shown in FIG. 8.

[273] The results in FIG. 8 show that the electrolyte was fully neutralized. No amount of AI2CI7 ^" species were observed. EXAMPLE 9 - COMPARISON OF ELECTROCHEMICAL CELLS HAVING NEUTRALIZED AND NOT NEUTRALIZED ELECTROLYTES

[274] The electrolyte from Example 7 was used in a first electrochemical cell. The first electrochemical cell included an aluminum anode that was 400 pm thick, and a cathode that included LiFeP04 (1-2 mg/cm ² loading) with LA133 binder.

[275] The electrolyte from Example 8 having a mole ratio of AlCb/EMIMC of 1.6 was used in a second electrochemical cell. The second electrochemical cell included an aluminum anode that was 400 pm thick, and a cathode that included LiFeP0 ₄ (8 mg/cm ² loading) with LA133 binder.

[276] The first electrochemical cell was electrochemically cycled. The results are shown in the bottom plot in FIG. 9.

[277] The second electrochemical cell was electrochemically cycled. The results are shown in the top plot in FIG. 9.

[278] The second electrochemical cell demonstrated a higher discharge plateau of 1.7. The first electrochemical cell demonstrated a lower discharge plateau of 1.3 V. These results demonstrate that the second electrochemical cell operated according a different anode than the first electrolyte. This is due, in part, because the electrolyte in the second electrochemical cell did not include any AI2CI7 species, whereas the electrolyte in the first electrochemical cell did include AI2CI7 species. Without being bound by theory, the second electrochemical cell operated by a Li-Al alloy redox reaction. Without being bound by theory, the first electrochemical cell operated by an Al redox reaction.

[279] The first electrochemical cell was electrochemically cycled for about one hundred sixty (160) cycles. After about ninety (90) cycles, the coulombic efficiency noticeably decays. The results are shown in FIG. 10.

[280] The second electrochemical cell was electrochemically cycled for about one hundred sixty (160) cycles. After about ninety (90) cycles, the coulombic efficiency remained greater than 99%. The results are shown in FIG. 11.

EXAMPLE 10 - X-RAY PHOTOELECTRON SPECTROSCOPY (XPS) AND SCANNING ELECTRON MICROSCOPY (SEM) ANALYSIS OF LI-AL ANODE

[281] The electrolyte from Example 8 having a mole ratio of AlCb/EMIMC of 1.6 was used in an electrochemical cell. The electrolyte included a mole ratio of AlCb/EMIC equal to 1.6, and the electrolyte was neutralized with 0.6 molar ratio LiCl. The

electrochemical cell included an aluminum anode that was 400 mhi thick, and a cathode that included LiFePCri (8 mg/cm ² loading) with LA133 binder.

[282] The electrochemical cell was de-assembled from its charged state after 10 charge-discharge cycles.

[283] XPS analysis of the anode after 10 charge-discharge cycles is shown in FIGs. 12 and 13.

[284] FIG. 12 shows an XPS signature characteristic of 81.7 % Al.

[285] FIG. 13 shows an XPS signature characteristic of 18.3 % Li.

[286] FIGs. 12 and 13 demonstrate that the electrochemical cell operated by a Li-Al alloy redox reaction, as also described in Example 9.

[287] SEM analysis also shows a morphology characteristic of the products of a Li- Al alloy redox reaction. The results are shown in FIG. 14.

[288] The embodiments and examples described above are intended to be merely illustrative and non-limiting. Those skilled in the art will recognize or will be able to ascertain using no more than routine experimentation, numerous equivalents of specific compounds, materials and procedures. All such equivalents are considered to be within the scope and are encompassed by the appended claims.