WO2023055826A1 - Carbonate electrolytes, methods of making same, and uses thereof - Google Patents

Abstract

Compositions, which may be electrolyte compositions, and uses of same. A composition comprises lithium nitrate; optionally, one or more other lithium salt(s); one or more cation(s), and one or more carbonate(s). In various examples, a cation is a high charge density cation or the cations are high charge density cations. A composition can be used in a device. In various examples, a composition is an electrolyte in a device, such as, for example, a battery, such as, for example, a primary battery, a secondary/rechargeable battery, or the like, a supercapacitor, a fuel cell, an electrolyzer, an electrolytic cell, or the like. In various examples, a battery is a lithium ion-conducting battery, a lithium metal battery, or the like.

Description

CARBONATE ELECTROLYTES, METHODS OF MAKING SAME, AND USES THEREOF

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63/249,419, filed September 28, 2021, the contents of the above-identified application are hereby fully incorporated herein by reference in their entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under grant no. 1919013 awarded by the National Science Foundation. The government has certain rights in the invention.

BACKGROUND OF THE DISCLOSURE

[0003] In pursuit of high-energy-density electrical energy storage/conversion devices, rechargeable batteries that employ metals (Li, Na, etc.) as anodes have gained attention recently. Through replacing low capacity graphite anode (372mAh/g) by metal anode (3800mAh/g for Li), this technology breaks the energy bottleneck of traditional Li-ion batteries (300 Wh/Kg) and provides potential higher energy density over 500 Wh/kg.

[0004] Traditional Li-ion batteries usually apply Li salts dissolved in carbonate solvent (Ethylene carbonate-EC, Dimethyl carbonate-DMC etc.) as electrolytes. Compared with ether solvents, carbonate solvent is more thermostable and cost-effective. However, when lithium metal is used as anode, the interphase generated on lithium in traditional carbonate electrolytes is heterogenous, leading to low reversibility of Li metal stripping/plating. The inhomogeneous SEI will lead to the uneven nucleation of Li, further guide rugged growth of Li (mossy Li or even dendrite Li). This uncontrolled growth of lithium generates at least two problems, the low efficiency of Li plating/stripping (loss of energy) and the short circuit of batteries (concerns of safety).

[0005] LiNOs is known to stabilize lithium metal by various approaches such as forming passivation film on lithium metal, reducing the reactivity of electrolytes. However, LiNCF usually dissolves in ether-based solvents, which exhibit limited oxidation stability at high voltage. Meanwhile, most ether electrolytes show lower boiling temperature and flaming points than carbonate solvent.

[0006] Lithium metal batteries (LMBs) are the subject of a large and growing volume of studies and industrial research because their potential to provide large increases in energy density of rechargeable batteries. However, they are limited by multiple fundamental challenges that lie at the intersection of multiple fields (e.g., electrochemistry, materials science, mechanics, chemistry, etc.). It is known for instance that parasitic chemical and electrochemical reactions between the reactive Li metal anode and liquid electrolyte components will over time deplete electrolyte components; increase the cell resistance by thickening the interphases formed on the anode that typically protect the Li anode against parasitic interfacial reactions; and will ultimately drive Li to deposit in non-uniform, mossy, low-density, mechanically fragile structures during battery recharge, which severely limit lifetime and compromise the safety of LMBs.

[0007] Efforts on both anode (Li) and electrolyte design have been taken in recent years to overcome these challenges, including fabricating structured electrodes to relieve the volume shrinkage/expansion during discharge/charge process, building new interphase on lithium metal to regulate the ion transport and growth of Li metal, developing advanced electrolytes (highly concentrated, solid-state electrolyte etc.) to slow down the parasitic reactions and mechanically suppress the dendrite like growth of lithium metal. Among the various approaches, intentional design of liquid electrolytes to facilitate stability at the Li anode and cathode provides the most straightforward path to LMBs that live up to the promise of this chemistry and are suitable for practical application. It has recently been reported, for instance, that LMBs with cycle life over 400 cycles can be achieved under rigorous conditions (Thickness of lithium < 50 pm, areal loading of cathode > 1 mAh/cm²), through rational design of electrolytes alone. Motivated in part by early studies demonstrating the important role of LiF as an interfacial agent in stabilizing Li metal anodes, most state-of- the art for LMB electrolyte designs focus on F-rich solvent and salts that are believed to be reduced at the anode to form a LiF dominated interphases. A quiet concession in the field, however, is that conventional F-rich salts such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)amide (LiFSI) that offer the most impressive performance improvements for LMBs are far too costly to be of practical interest at the concentrations typically employed. Emerging F-rich solvents such as tris(2,2,2- trifluoroethyl)orthoformate, fluorinated 1 ,4dimethoxylbutane, which also show promise, are even more expensive — and their life cycle impacts are uncertain because there is evidence of their slow degradation in the environment with potential climate impacts. Additionally, the high salt concentrations required to achieve the greatest LMB stability poses other challenges associated with ion transport over the wide range of battery operating temperatures required in practical applications. [0008] LiNCh, is in contrast, a low-cost commodity chemical that even when added in small quantities to ether-based electrolytes is known to produce dramatic improvements in the stability & reversibility of Li metal anodes. While the mechanism for these improvements is still not fully understood, an emerging consensus is that LiNCL is effective because it fundamentally changes the intrinsic properties of electrolytes as well as the interphases they form on a Li metal anode. Unfortunately, the energies of highest occupied molecular orbital (HOMO) for most ether solvents are too high to prevent continuous oxidative degradation in LMBs based on the most mature energy-dense cathode technologies (NCM622, NCM811, etc.). Carbonate electrolytes, such as ethylene carbonate (EC) and diethyl carbonate (DEC), are in contrast electrochemically stable in the oxidizing environments of these cathodes and as a consequence are the most common electrolyte solvents employed in commercial Li-ion batteries that utilize these cathodes. These solvents nevertheless fail to form stable interphases at the highly reducing potential at the lithium metal anode, resulting in low reversibility for lithium stripping/plating (typically, < 90%).

[0009] A longstanding question in the field is whether simple, but powerful salt additives like LiNCh can be designed for use in electrochemically stable carbonates — to prepare LMBs that benefit from high reversibility at both electrodes. Previous works have reported that LiNCh exhibits limited solubility (^ 1000 ppm) in EC and DEC due to strong interaction between Li⁺ and NCh”. These results are puzzling (EC has a dielectric constant, ksc, which exceeds that of all cyclic ethers used in batteries (ksc 90; Propylene carbonate (PC), kpc ~ 65; 1,2-dimethoxy ethane (DME), koME ~ 7.2; 1,3-dioxolane (DOL), kooL ~ 8), and even that of water (kmo 80); meaning that from a strictly classical point of view, pure carbonate electrolytes based on either EC or PC would be anticipated to provide good or better solubility for LiNCh than cyclic ethers. Lewis acid salt additives based on Cu²⁺, Sn²⁺, In³⁺, etc., have been reported to facilitate dissolution of LiNCh in carbonate solvents through strong interactions of the cations with the NO3 ion. However, the studies considered the additives in mixtures of EC and lower dielectric constant linear carbonate solvents ( .g., dimethyl carbonate (DMC), koMC ~ 3.1; diethyl carbonate (DEC), koEC ~ 2.8) containing LiPFe, which means that other complicating factors are likely involved.

SUMMARY OF THE DISCLOSURE

[0010] The present disclosure provides, inter alia, compositions. In various examples, a composition (e.g., an electrolyte composition) comprises lithium nitrate; optionally, one or more other lithium salt(s); one or more cation(s) (where the cation(s) are not lithium cation(s); and one or more carbonate(s). In various examples, the lithium nitrate is present at about 0.1 M to about 1 M based on the total volume of the composition. In various examples, the other lithium salt(s) is/are chosen from bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), lithium triflate (LiOTf), lithium bis(fluorosulfonyl)imide (LiFSI), LiPFe, LiClO₄, lithium difluoro(oxalato)borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), LiBF₄, and the like, and any combination thereof. In various examples, the cation(s) is/are chosen from Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Sn⁴⁺, Sb³⁺, and the like, and any combination thereof. In various examples, the other lithium salt(s) are present at about 0.1 M to about 4 M based on the total volume of the composition. In various examples, the cation(s) are present at about 0.01 M to about 0.2 M based on the total volume of the composition. In various examples, the composition further comprises one or more anions(s) chosen from CF₃SO₃“ (triflate), N(SO₂CF₃)₂ , halides, and the like, and any combination thereof. In various examples, the cation(s) and anion(s) are provided by one or more salt(s). In various examples, the salt(s) is/are chosen from A1(CF₃SO₃)₃, A1[N(SO₂CF₃)₂]₃, A1F₃, A1C1₃, AlBr₃, A1I₃, Ga(CF₃SO₃)₃, Ga[N(SO₂CF₃)₂]₃, GaF₃, GaCl₃, GaBr₃, Gal₃, In(CF₃SO₃)₃, In[N(SO₂CF₃)₂]₃, InF₃, InCl₃, InBr₃ Inl₃, Ge(CF₃SO₃)₄, Ge[N(SO₂CF₃)₂]₄, GeF₄, GeCl₄, GeBr₄, Gel₄, In(CF₃SO₃)₄, In[N(SO₂CF₃)₂]₄, InF₄, InCl₄, InBr₄, Inl₄, and the like, and any combinations thereof. In various examples, the carbonate(s) is/are chosen from alkyl carbonates, cyclic carbonates, and the like, and combinations thereof. In various examples, the carbonate(s) is/are chosen from dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), di-2,2,2-trifluoroethyl carbonate (TFEC), and any combinations thereof. In various examples, the composition is an electrolyte in a battery.

[0011] The present disclosure provides, inter alia, devices. In various examples, a device comprising one or more composition(s) of the present disclosure, where the composition(s) is/are an electrolyte/electrolytes in a device. In various examples, the device is an electrochemical device or comprises one or more electrochemical device(s). In various examples, the device (e.g., electrochemical device) is a battery, a supercapacitor, a fuel cell, an electrolyzer, an electrolytic cell, or the like. In various examples, the battery is a lithium ion-conducting battery, a lithium metal battery, or the like. In various examples, the battery or ion-conducting battery is a rechargeable lithium-ion conducting battery, or the like. In various examples, the battery further comprises a cathode, and anode, optionally, one or more separator(s), optionally, one or more current collector(s), optionally, one or more solid-phase electrolyte(s), and, optionally, and/or one or more additional structural component(s). In various examples, the cathode comprises (or is) one or more lithium-containing cathode material(s), one or more nickel cobalt manganese oxide cathode material(s), one or more conversion type cathode material(s), or the like or any combination thereof. In various examples, the anode comprises (or is) one or more lithium-ion conducting anode material(s), lithium metal, silicon-containing materials, tin and its alloys, tin/carbon, and phosphorus, or the like, or any combination thereof. In various examples, the separator comprises an organic polymeric material, an inorganic material, or any combination thereof. In various examples, the one or more additional structural component(s) is/are chosen from bipolar plates, external packaging, electrical contacts/leads to connect wires, and the like, and combinations thereof. In various examples, the battery comprises 1 to 500 cells. In various examples, the battery comprises a plurality of cells, each cell comprising one or more anode(s) and/or one or more anode material(s), and optionally, one or more cathode(s), one or more electrolyte(s), one or more current collector(s), or any combination thereof.

BRIEF DESCRIPTION OF THE FIGURES

[0012] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures herein.

[0013] FIGS. 1A-1C show a solubility diagram for the LiNOi-EC/DMC electrolyte system with different DMC contents. (FIG. 1 A) Solubility map for LiNOs for carbonate electrolytes, with and without the Lewis acid salt, 0.06 M A1(CF3SC>3)3 (Al³⁺). The solid line is the theoretical solubility limit assuming a linear mixing rule for the EC molecule. (FIG. IB) Arrhenius plot of d.c. ionic conductivity of LiNCE/EC electrolytes at various LiNCE concentrations an as a function of temperature. (FIG. 1C) ATR-FTIR spectra of LiNCE/EC solutions.

[0014] FIG. 2 shows a solubility illustration of LiNCE in carbonate electrolytes.

[0015] FIGS. 3A-3F show improved reversibility of EC electrolytes containing LiNCE. (FIGS. 3A-3C) Performance of Li||Cu electrochemical cells. (FIG. 3A) Coulombic efficiencies (CEs). (FIG. 3B) Corresponding galvanostatic lithium stripping/plating profiles with the electrolyte of IM LiFSI +0.5M LiNCE/EC. (FIG. 3C) Average CE of different electrolytes. In each cycle, ImAh/cm² lithium is plated on Cu first and then the voltage is increased to 1 V in stripping process. The current density for lithium stripping/plating is 0.5 mA/cm². (FIGS. 3F-3F) Performance of Li||NCM622 batteries. The loading of cathode is 2mAh/cm². The thickness of lithium foil is 50 pm. (FIG. 3D) Cycling performance with CEs. Commercial (Com.) electrolyte is IM LiPFe in EC/DMC/DEC (1 :1 :1 by vol.) (FIG. 3E) Corresponding galvanostatic charge/discharge profiles, and (FIG. 3F) CEs of first cycle and average. The Li||NCM622 batteries are firstly activated at 0.1 C (2 cycles) and 0.2 C (2 cycles) (1 C= 2 mA/cm²). Then, the CC (0.5C)-CV (0.2C) charge mode and CC discharge mode (0.5 C) are applied for the following cycles. The loading for NCM622 cathode is 2 mAh/cm².

[0016] FIGS. 4A-4B show interphase characterization of anode and cathode in EC electrolytes. (FIG. 4A) Ci_s, Ni_s, Oi_s, Fi_s and S2_P spectra on anode side. (FIG. 4B) Ci_s, Ni_s, Ois, Fis and S2_P spectra on cathode side. The electrolyte is 1 M LiFSI +0.5 M LiNO₃/EC. [0017] FIGS. 5A-5I show upgrading traditional carbonate electrolytes for practical lithium metal batteries. The thickness of lithium for all the batteries is 50 pm. (FIGS. 5A-5C) Li||NCM622 (2mAh/cm²) batteries. (FIGS. 5D-5F) Li||NCM811 (2.3 mAh/cm²) batteries. (FIGS. 5G-5I), Li||NCM811 (4mAh/cm²) batteries. (FIGS. 5A, 5D, 5E) Cycling performance with CEs. . (FIGS. 5B-5C, 5E-5F, 5H-5I) Charge/discharge profiles of different cycles. (FIGS. 5A-5F) The batteries are firstly activated at 0.1 C (2 cycles) and 0.2 C (2 cycles). Then, the CC (0.5 C)-CV (0.2 C) charge mode and CC discharge mode (0.5 C) are applied for the following cycles. (FIGS. 5G-5I), The protocol for cycling at 0.5 C is the same with above batteries (FIGS. 5A-5F). Batteries cycling at 0.2 C are firstly activated at 0.1 C (2 cycles), followed by CC charge/discharge mode (0.2 C). (FIGS. 5H-5I) Charge/discharge profiles of 0.2 C. Reference electrolyte is 0.1 M LiNO₃ + 0.4 M LiBOB + 0.6 M LiTFSI + 0.4 M LiF + 0.05 M LiPF₆ + 0.03 M LiBF₄ in EC/DMC (2: 1 by volume) with 1 vol.% FEC, 2 vol.% VC, 3 v% TFEC. Upgraded carbonate E-l is 0.06 M Al(OTf)₃ +0.5 M LiNO₃ + 0.4 M LiBOB + 0.6 M LiTFSI + 0.4 M LiF + 0.05 M LiPF₆ + 0.03 M LiBF₄ in same solvent of reference electrolytes. Upgraded carbonate E-2 is 0.06 M Al(OTf)₃ +0.5 M LiNO₃+0.2 M LiDFOB+ 0.2 M LiBOB + 0.6 M LiFSI + 0.05 M LiPFe + 0.03 M LiBF₄ in same solvent of reference electrolytes.

[0018] FIG. 6 shows comparisons on cycling life of lithium metal batteries towards practical conditions through modification of electrolytes. (Lithium anode is not thicker than 60 pm). E1-E9 = electrolytes reported in literature. Com. = commercial electrolyte. Ref. = reference electrolyte. T1-T3 = upgrading electrolytes in this work. The cycling life is calculated when the capacity retention is close to 80%. The details can be found in Table 5. [0019] FIGS. 7A-7B show Li||NCM622 pouch cells with upgraded carbonate electrolytes E-2. (FIG. 7A) Cycling performance with CEs. The inset is a digital picture of 1 Ah pouch cells. (FIG. 7B) Charge/discharge profiles of different cycles. The batteries are firstly activated at 0.1 C (2 cycles) and 0.2 C (2 cycles). Then, the CC (0.5 C)-CV (0.2 C) charge mode and CC discharge mode (0.5 C) are applied for the following cycles.

[0020] FIG. 8 shows ATR-FTIR spectra of Li NO , /EC electrolytes.

[0021] FIGS. 9A-9C show the nature of high Li plating/stripping reversibility of EC based electrolytes. Coulombic efficiencies (CEs) of IM conventional electrolyte (FIG. 9A) without or (FIG. 9B) with the addition of LiNO (FIG. 9C) CE comparisons of various electrolytes. The CEs are tested in Li||Cu electrochemical cells. In each cycle, ImAh/cm² lithium is plated on Cu first and then the voltage is increased to IV in stripping process. The current density for lithium stripping/plating is 0.5 mA/cm².

[0022] FIG. 10 shows XPS survey spectra with atomic ratio analysis of the surface information of the anode side and the cathode side.

[0023] FIG. 11 shows conductivity of pure EC electrolyte with or without addition of LiNO₃

[0024] FIGS 12A-12D show electrochemical performance of EC dominant electrolyte with the mixture of other solvents. (FIGS. 12A-12B) Performance of Li||Cu electrochemical cells. (FIG. 12A) Coulombic efficiencies (CEs). (FIG. 12B) Corresponding galvanostatic lithium stripping/plating profiles (100th cycle). (FIGS. 12C-12D) Thin Li (50 gm) || NCM622 batteries. (FIG. 12C) Charge/discharge profiles and d, cycling performance with CEs at 0.5C. The electrolyte for FIGS. 12C and 12D is 1.2 M LiFSI + 0.5 M LiNO₃ in EC/THF (7:3 by vol.)

[0025] FIGS. 13A-13B show digital image of prepared electrolytes. (FIG. 13A) 0.06 M Al(OTf)₃ + 0.5 M LiNO₃ + 0.4 M LiBOB + 0.6 M LiTFSI + 0.4 M LiF + 0.05 M LiPF₆ + 0.03 M LiBF₄ in EC:DMC (2:1 by vol.) with 1 vol.% FEC + 2 vol.% VC +3 vol.% TFEC (FIG. 13B) 0.06 M Al(OTf)₃ + 0.5 M LiNO₃ + 0.2 M LiBOB+ 0.2 M LiDFOB + 0.6 M LiFSI + 0.05 M LiPF₆ + 0.03 M LiBF₄ in EC:DMC (2:1 by vol.) with 1 vol.% FEC + 2 vol. % VC +3 vol. % TFEC.

[0026] FIG. 14 shows Coulombic efficiencies of Li ||Cu batteries. The CE is tested through Aurbach method. 1) In the formation cycle, 5 mAh/cm² Li was deposited on Cu under 0.5 mA cm^-2 followed by the stripping process until the voltage reaching 1 V. 2) 5 mAh/cm² (QT= 5 mAh/cm²) Li is deposited on Cu under 0.5 mA cm^-2 and acted as Li reservoir. 3) Continuous lithium stripping/plating for 10 cycles at a capacity of 1 mAh/cm² (Qc = 1 mAh/cm²) and current density of 0.5 mAh/cm². 4) Lithium stripping process until the voltage reaches 1 V at current density of 0.5 mAh/cm². The capacity of lithium stripping is recorded as Qs. The average CE is calculated according to the following equation:

[0027] FIGS. 15A-15B show reactivation of lithium metal batteries after failure. (FIG. 15 A) Cycling performance with Coulombic efficiency of batteries through refilling electrolyte and replacing lithium metal. (FIG. 15B) Corresponding charge/discharge profiles. The current density is 0.5 C.

[0028] FIGS. 16A-16C show upgrading pure EC electrolytes for practical lithium metal batteries. The lithium used for all the batteries is 50 pm (pm = micrometer(s)). The cathode is NCM622 with areal capacity of 2 mAh/cm². (FIG. 16A) Cycling performance with CEs.

(FIGS. 16B-16C) Charge/discharge profiles of different cycles. The batteries are firstly activated at 0.1 C (2 cycles) and 0.2 C (2 cycles). Then, the CC (0.5 C)-CV (0.2 C) charge mode and CC discharge mode (0.5 C) are applied for the following cycles. (FIG. 16B) ECupdate- 1 is 0.06 M (M = molarity) Al(OTf)₃ + 0.5 M LiNO₃ + 0.2 M LiBOB+ 0.2 M LiDFOB + 0.6 M LiFSI + 0.05 M LiPF₆ + 0.03 M LiBF₄ in EC with 1 vol.% FEC + 2 vol.% VC +3 vol.% TFEC. (FIG. 16C) EC-update-2 is 0.06 M Al(OTf)₃ + 0.5 M LiNO₃ + 0.2 M LiBOB+ 0.2 M LiDFOB + 0.6 M LiTFSI + 0.4 M LiF + 0.05 M LiPF₆ + 0.03 M LiBF₄ in EC with 1 vol.% FEC + 2 vol.% VC +3 vol.% TFEC.

[0029] FIGS. 17A-17B show digital images of batteries after failure (>400 cycles). (FIG. 17A) Electrolytes with major solvent of EC and DMC mixture. (FIG 17B) Electrolytes with major solvent of EC.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0030] Although claimed subject matter will be described in terms of certain examples, other examples, including examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various compositional, structural, and logical changes may be made without departing from the scope of the disclosure.

[0031] As used herein, unless otherwise stated, "about," "approximately," “substantially,” or the like, when used in connection with a measurable variable such as, for example, a parameter, an amount, a temporal duration, or the like, are meant to encompass variations of, for example, a specified value including, for example, those within experimental error (which can be determined by for example, a given data set, an art accepted standard, and/or with a given confidence interval (e.g. 90%, 95%, or more confidence interval from the mean), such as, for example, variations of +/-10% or less, +/-5% or less, +/-!% or less, and +/-0.1% or less of and from the specified value), insofar such variations are appropriate to perform in the context of the disclosure. As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” can mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, and the like, and other factors known to those of skill in the art such that, for example, equivalent results, effects, or the like are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It is understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0032] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also, unless otherwise stated, include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0033] As used herein, unless otherwise stated, the term “group” refers to a chemical entity that is monovalent (i.e., comprises one terminus that can be covalently bonded to other chemical species), divalent, or polyvalent (i.e., comprises two or more termini that can be covalently bonded to other chemical species). The term “group” also includes radicals (e.g., monovalent and multivalent, such as, for example, divalent radicals, trivalent radicals, and the like). Illustrative, non-limiting examples of groups include:

the like.

[0034] As used herein, unless otherwise indicated, the term “alkyl group” refers to branched or unbranched hydrocarbon groups that include only single bonds between carbon atoms (not including substituent(s), if any). In various examples, an alkyl group is a Ci to G> alkyl group, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., Ci, C2, C3, C4, C5, or C6). In various examples, an alkyl group is a saturated group. Examples of alkyl groups include, but are not limited to, methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and the like. In various examples, an alkyl group is unsubstituted or substituted with one or more substituent(s). Examples of substituents include, but are not limited to, various substituents such as, for example, halide groups (-F, -Cl, -Br, and -I), and the like, and any combination thereof. In various examples, an alkyl group is a halogenated group (e.g., a perhalogenated group or the like).

[0035] As used herein, unless otherwise indicated, the term “alkenyl group” refers to branched or unbranched unsaturated hydrocarbon groups comprising at least one carboncarbon double bond. Examples of alkenyl groups include, but are not limited to, ethylene groups, propenyl groups, butenyl groups, isopropenyl groups, tert-butenyl groups, and the like. For example, the alkenyl group is Ci to Ce, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., Ci, C2, C3, C4, C5, or C6). The alkenyl group maybe unsubstituted or substituted with one or more substituent. Examples of substituents include, but are not limited to, various substituents such as, for example, halogens (-F, -Cl, -Br, and -I), and the like, and combinations thereof. [0036] The present disclosure provides compositions. The present disclosure also provides devices comprising one or more composition(s) of the disclosure.

[0037] The present disclosure provides, inter alia, an approach to increase the solubility of lithium nitrate (LiNO;) in carbonate solvents via adding cation(s) (e.g., Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Sn⁴⁺, or the like, or a combination thereof). These cations may be referred to as high charge density cations. In various examples, the carbonate solvents with more LiNO are used as electrolytes for rechargeable batteries, e.g., for the batteries with lithium (e.g., high- capacity metal lithium) as anode.

[0038] Without intending to be bound by any particular theory, it is considered cations with high charge density (Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Sn⁴⁺, etc.) strongly attract and solvate NO; from LiNCh, therefore increase the solubility of lithium nitrate in, for example, carbonate(s). For example, it was found that with the addition of aluminum tritiate (A1(CF3SO3)3, Al(OTf)3), the solvent of EC/DMC mixture can dissolve more than 0.5M LiNO;. The applications of carbonate electrolytes with addition of LiNO;- demonstrated desirable cycle stability in rechargeable lithium metal batteries with high voltage lithium nickel cobalt manganese oxide (NCM622 and NCM811) cathodes.

[0039] In an aspect, the present disclosure provides compositions. A composition may be an electrolyte composition. A composition or compositions may be used in devices (e g., as electrolytes in electrochemical devices, such as, for example, batteries or the like). Nonlimiting examples of compositions are provided herein.

[0040] In various examples, a composition (e.g., an electrolyte composition) comprises lithium nitrate (which may be referred to as a first lithium salt); one or more cation(s) (e.g., cation(s) having high charge density); and one or more carbonate(s). A composition may further comprise one or more other lithium salt(s). In various examples, the lithium nitrate is present in the composition at a greater concentration than the solubility of the lithium nitrate in the same composition that does not comprise the one or more cation(s).

[0041] A composition can comprise various cation(s). In various examples, the cation(s) is/are Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Sn⁴⁺, Sb³⁺, or any combination thereof. In various examples, at least a portion or all of the cation(s) are Lewis acid cations. In various examples, at least a portion or all of the cation(s) are high charge density cations. In various examples, at least a portion or all of the cation(s) are high charge density Lewis acid cations. None of the cation(s) is a lithium cation. In various examples, at least a portion or all of the cation(s) have high charge density. [0042] Without intending to be bound by any particular theory, it is considered the cation(s) increase lithium nitrate solubility relative to its solubility in a composition having the same components with the exception of the cation(s). In various examples, a composition has a higher concentration of lithium nitrate than a composition having the same components except for the cation(s). In various examples, a composition has a concentration of lithium nitrate that exceeds the solubility (e g., the expected solubility, such as, for example, the theoretical solubility or the like) of lithium nitrate in the carbonate(s) (e.g., the carbonate(s) alone).

[0043] In various examples, the cation(s) and, optionally, the anion(s) are provided by one or more salt(s). Non-limiting examples of salts include A1(CF3SO3)3, A1[N(SO2CF3)2]3, A1F₃, AlCh, AlBr₃, AII3, Ga(CF₃SO₃)3, Ga[N(SO₂CF₃)2]3, GaF₃, GaCl₃, GaBr₃, Gal₃, In(CF₃SO₃)3, In[N(SO₂CF₃)2]3, 111F3, InCh, InBr₃ Inl₃, Ge(CF₃SO₃)4, Ge[N(SO₂CF₃)2]4, GeF₄, GeCl₄, GeBr₄, Gel₄, In(CF₃SO₃)₄, In[N(SO₂CF₃)2]₄, InF₄, InCl₄, InBr₄, Inl₄, and the like and combinations thereof.

[0044] A composition can comprise various amounts of cation(s). In various examples, the cation(s) are present at about 0.01 M to about 0.2 M (based on the total volume of the composition ((e.g., based on the total volume of the composition (such as, for example, the volume of the carbonate(s)), including all 0.001 M values and ranges therebetween.

[0045] A composition can comprise various carbonate(s). A carbonate may be referred to, in the alternative, as a carbonate ester. The carbonate(s) may independently be a liquid carbonate or a solid carbonate. In various examples, a composition comprises one or more liquid carbonate(s). In various examples, at least one of the or the only carbonate(s) are liquid carbonate(s). In various examples, the carbonate(s) (e g., liquid carbonate(s)) makes/make up the remainder of the composition.

[0046] In various examples, a carbonate is an alkyl carbonate, a linear carbonate, or the like. Combinations of carbonates can be used. In various examples, at least a portion (e.g., at least at least 70% by volume, at least 80% by volume, at least 90% by volume, at least 95% by volume, at least 99% by volume) or substantially all or all of the carbonate(s) is/are cyclic carbonate(s). In various examples, the carbonate(s) do not comprise linear carbonate(s).

[0047] In various examples, an alkyl carbonate comprises two alkyl groups (which may be linear alkyl group(s), branched alkyl group(s), or a combination thereof). In various examples, the alkyl groups are independently chosen from Ci, C2, C3, C₄ alkyl groups, or the like, which may be linear or branched and/or fluorinated (e.g., comprising one or more fluorine group(s) or be perfluorinated). [0048] In various examples, a cyclic carbonate comprises a C2, C3, C4, C5, or Ce alkyl group or comprises a C2 alkenyl group, which may be linear or branched and/or may be fluorinated (e.g., comprising one or more fluorine group(s) or be perfluorinated). In various examples, a cyclic carbonate comprises a C2, C3, C4, C5, or Ce alkenyl group, which may be linear or branched and/or may be fluorinated (e.g., comprising one or more fluorine group(s) or be perfluorinated).

[0049] Non-limiting examples of carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), di-2,2,2- trifluoroethyl carbonate (TFEC), and the like, and combinations thereof.

[0050] A composition may further comprise one or more other lithium salt(s). An other lithium salt (which may be referred to as a second lithium salt) is not lithium nitrate. Examples of suitable other lithium salts (e.g., lithium salts used in lithium batteries to provide conductivity) are known in the art. Nonlimiting examples of other lithium salts include bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), lithium triflate (LiOTf), lithium bis(fluorosulfonyl)imide (LiFSI), LiPFe, LiCICU, lithium difluoro(oxalato)borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), LiBF4, and the like, and combinations thereof.

[0051] A composition can comprise various amounts of other lithium salt(s). In various examples, the other lithium salt(s) is/are present at about 0.1 M to about 4 M (based on the total volume of the composition ((e.g., based on the total volume of the composition (such as, for example, the volume of the carbonate(s)), including all 0.01 M values and ranges therebetween.

[0052] A composition can be made by dissolving one or more salt(s) in one or more carbonates (which may be carbonate solvent(s)). In various examples, the salt(s) include LiNCh, the cation salt(s), and, optionally, one or more lithium salt(s) (e.g., bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), lithium triflate (LiOTf), Lithium bis(fluorosulfonyl)imide (LiFSI), LiPFe, LiNOs, LiClOr, lithium difluoro(oxalato)b orate (LiDFOB), lithium bi s(oxalate)b orate (LiBOB), LiBF4, or the like, or a combination thereof. In various examples, the salts are added to the carbonate (s) together or in any order or combination.

[0053] In an aspect, the present disclosure provides devices. The devices comprise one or composition(s) of the present disclosure. Non-limiting examples of devices are provided herein. [0054] A device may be an electrochemical device. In various examples, the device is an electrochemical device or comprises one or more electrochemical device(s) comprising one or more composition(s) of the present disclosure. In various examples, the composition(s) is/are an electrolyte/electrolytes in a device. Non-limiting examples of electrochemical devices include batteries, supercapacitors, fuel cells, electrolyzers, electrolytic cells, and the like.

[0055] A device can be various batteries. Non-limiting examples of batteries include secondary/rechargeable batteries, primary batteries, and the like. A battery may be a lithium- ion conducting battery. A battery may be a lithium-metal battery, or the like. A device may be a solid-state battery or a liquid electrolyte battery.

[0056] In the case of a device, which may be a battery, comprising a composition/composition(s) of the present disclosure, the device may comprise one or more cathode(s). In various examples, a cathode comprises one or more cathode material(s). In various examples, a cathode comprises a conducting carbon material. Combinations of cathode materials may be used. Examples of suitable cathode materials are known in the art. [0057] A device can comprise various cathode material(s). Non-limiting examples of lithium-containing cathode materials include lithium nickel manganese cobalt oxides, LiCoCE, LiNii/3Coi/3Mm/3O2, LiNio.5Coo.2Mno.3O2, lithium manganese oxides (LMOs), lithium iron phosphates (LFPs), LiMnPO4, LiCoPO4, and Li2MMn30s, where M is chosen from Fe, Co, and the like (e.g., lithium nickel cobalt manganese oxides (such as, for example, NCM622, NCM811, and the like)), and combinations thereof, and the like, and combinations thereof.

[0058] In various examples, the cathode material(s) is/are conversion-type cathode materials, intercalation-type cathode materials, or the like. Non-limiting examples of conversion-type cathode materials include air (e.g., oxygen), iodine, sulfur, sulfur composite materials, polysulfides, metal (e.g., transition metal or the like) sulfides (such as, for example, M0S2, FeS2, TiS2, and the like), oxides, selenides, fluorides, nitrides, phosphides, and the like, and the like, and any combinations thereof. In various examples, the cathode material(s) is/are one or more lithium-containing cathode material(s), or the like. Examples of suitable lithium-containing cathode materials are known in the art. Non-limiting examples of lithium- containing cathode materials include lithium nickel manganese cobalt oxides, LiCoCh, LiNii/3Coi/3Mni/3O2, LiNio.5Coo.2Mno.3O2, lithium manganese oxides (LMOs), lithium iron phosphates (LFPs), LiMnPO4, LiCoPO4, and Li2MMn30s, where M is chosen from Fe, Co, and the like (e.g., lithium nickel cobalt manganese oxides (such as, for example NCM622, NCM81 1, and the like)), and combinations thereof, and the like, and combinations thereof. Any of these cathodes/cathode materials may comprise one or more conducting carbon material(s).

[0059] In the case of a device, which may be a battery, comprising a composition/composition(s) of the present disclosure, the device may comprise one or more anodes(s). An anode may independently comprise one or more anode material(s).

Combinations of anode materials may be used. Examples of suitable anode materials are known in the art.

[0060] A device can comprise various anode material(s). In various examples, the anode material(s) is/are one or more lithium-ion conducting anode material(s) (e.g., wherein the lithium ion-conducting anode material is a lithium containing material chosen from lithium carbide, LigC, lithium titanates (LTOs), and the like, and combinations thereof), and combinations thereof, lithium metal, silicon-containing materials, tin and its alloys, tin/carbon, and phosphorus, and the like, and combinations thereof.

[0061] A device, which may be a battery, may further comprise a solid electrolyte. Examples of suitable solid electrolytes are known in the art.

[0062] A device may further comprise a current collector disposed on at least a portion of the cathode and/or the anode. In various examples, the current collector is a conducting metal or metal alloy. Examples of suitable current collectors are known in the art.

[0063] A solid-state electrolyte, cathode, anode, and, optionally, the current collector may form a cell of a battery. The battery may comprise a plurality of the cells and each adjacent pair of the cells is separated by a bipolar plate. The number of cells in the battery is determined by the performance requirements (e.g., voltage output and the like) of the battery and is limited only by fabrication constraints. For example, the battery comprises 1 to 500 cells, including all integer number of cells and ranges therebetween.

[0064] The following Statements describe various examples of methods, products and systems of the present disclosure and are not intended to be in any way limiting:

Statement 1. A composition (e.g., an electrolyte composition) comprising: lithium nitrate; optionally, one or more other lithium salt(s); one or more cation(s) (e.g., cation(s) having high charge density); and one or more carbonate(s).

Statement 2. A composition according to Statement 1, wherein the lithium nitrate is present at about 0.1 M to about 1 M (e.g., based on the total volume of the composition (such as, for example, the volume of the carbonate(s)), including all 0.01 M values and ranges therebetween. Statement 3. A composition according to Statement 1 or 2, wherein the cation(s) are chosen from Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Sn⁴⁺, Sb³⁺, and the like, and combinations thereof.

Statement 4. A composition according to any one of the preceding Statements, wherein the cation(s) are present at about 0.01 M to about 0.2 M (based on the total volume of the composition ((e.g., based on the total volume of the composition (such as, for example, the volume of the carbonate(s)), including all 0.001 M values and ranges therebetween.

Statement 5. A composition according to any one of the preceding Statements, wherein the composition further comprises one or more anions(s) chosen from CFsSCh” (triflate), N(SO₂CF₃)₂“, halides (e.g., F“, Cl", Br“, I-), and the like, and combinations thereof.

Statement 6. A composition according to any one of the preceding Statements, wherein the carbonate(s) is/are chosen from alkyl carbonates, cyclic carbonates, and the like, and combinations thereof.

Statement 7. A composition according to any one of the preceding Statements, wherein the composition is an electrolyte in a battery.

Statement 8. A device comprising one or more composition(s) of any of Statements 1-7. Statement 9. A device according to Statement 8, wherein the device (or electrochemical device) is a battery (e.g., a primary battery, a secondary/rechargeable battery, or the like) a supercapacitor, a fuel cell, an electrolyzer, an electrolytic cell, or the like.

Statement 10. A device according to Statement 9, wherein the battery is a lithium ionconducting battery or a lithium metal battery.

Statement 11. A device according to Statement 9 or 10, wherein the battery or ion-conducting battery is a rechargeable lithium-ion conducting battery, or the like.

Statement 12. A device according to any of Statements 9-11, wherein the battery further comprises a cathode, and anode, optionally, one or more separator(s) (which may be disposed between the cathode and anode), optionally, one or more current collectors), optionally, one or more solid-phase electrolyte(s), and, optionally, and/or one or more additional structural component(s).

Statement 13. A device according to any of Statements 9-12, wherein the cathode comprises (or is) one or more lithium-containing cathode material(s), one or more nickel cobalt manganese oxide cathode material(s) (e.g., NCM622 and the like), one or more conversion type cathode material(s), or the like, or a combination thereof.

Statement 14. A device according to any of Statements 9-13, wherein the anode comprises (or is) one or more lithium-ion conducting anode material(s) (e.g., wherein the lithium ionconducting anode material is a lithium containing material chosen from lithium carbide, LigC, lithium titanates (LTOs), and the like, and combinations thereof), lithium metal, silicon- containing materials, tin and its alloys, tin/carbon, and phosphorus, and the like, and combinations thereof.

Statement 15. A device according to any of Statements 9-14, wherein the separator comprises (or is) an organic polymeric material (e.g., polymer(s), polymer resin(s), and the like, and combinations thereof), an inorganic material, or the like, or a combination thereof. Statement 16. A device according to Statement 12, wherein the one or more additional structural component(s) is/are chosen from bipolar plates, external packaging, electrical contacts/leads to connect wires, and the like, and combinations thereof.

Statement 17. A device according to any of Statements 9-16, wherein the battery comprises a plurality of cells, each cell comprising one or more anode(s) and/or one or more anode material(s), and optionally, one or more cathode(s), one or more electrolyte(s), one or more current collector(s), or a combination thereof.

Statement 18. A device according to Statement 17, wherein the battery comprises 1 to 500 cells

[0065] The following examples are presented to illustrate the present disclosure. They are not intended to be limiting in any manner.

EXAMPLE 1

[0066] The following is an example of compositions of the present disclosure and uses thereof.

[0067] Upgrading Carbonate Electrolytes for Ultra-stable Practical Lithium Metal Batteries. Lithium metal batteries (LMBs) have reemerged in the last decade as promising candidates for next generation electrical energy storage/conversion. A large body of work now exists that provides advanced understanding of both their failure modes and remedies, resulting in extension of the calendar life of LMBs from tens of cycles to hundreds of cycles under rigorous conditions. Liquid alkyl carbonates are typically the starting point in designing liquid electrolytes for LMBs because of their superiority in terms of their low cost, high voltage tolerance, and mature manufacturing processes. These electrolytes are unfortunately intrinsically unstable at the Li anode and are unable to maintain the long-term stability required for practical applications. LiNCh is a widely used salt-additive that markedly improves the stability of ether-based electrolytes at a Li metal anode, but for a variety of reasons are generally regarded as incompatible with alkyl carbonates. The phase diagram of alkyl carbonate-LiNCh electrolytes was studied and it was found that contrary to common wisdom, cyclic carbonate solvents such as ethylene carbonate (EC) can dissolve up to 0.7 M Li NO; at room temperature. It was further found that at these concentrations LINO; can have as large an effect on anode reversibility in carbonates as in ether-based electrolytes. The effect of these findings was demonstrated by upgrading various state-of-the art carbonate electrolytes with LiN6; and showed that this yields remarkable capacity retention in LMBs based on thin lithium (50 pm) anode and high voltage cathode (LiNio.eMno 2C002O2-NCM62 or LiNio.8Mno.iCoo.i02-NCM811), which is 90.5% after 600 cycles forNCM622 cathode (2 mAh/cm², 0.5 C), 84.7% after 400 cycles for NCM811 cathode (2.3 mAh/cm², 0.5 C), 92.5% after 200 cycles for high loading NCM811 cathode (4 mAh/cm², 0.2 C). The upgraded electrolytes were used to create 1 Ah LMBs pouch cells with an energy density of -300 Wh/kg. These cells are reported to retain more than 87.5 % of their initial capacity after 100 cycles at 0.5 C. This work illustrates that reforming traditional carbonate electrolytes provides a scalable, cost-effective approach towards practical LMBs.

[0068] Puzzled by the conflict with classical solubility theory, the solubility of Li NO; was investigated in pure cyclic (EC, PC) and linear (DMC, DEC) carbonates, as well as in EC/DMC mixtures. It was found that LiNO actually showed considerable solubility in EC solvent, but the solubility dropped markedly as the concentration of linear carbonate, DMC, increases. The idea was also tested that Lewis acid salts can promote LiNOs dissolution in carbonates by incorporating A1(CF3863)3. The results showed that A1(CF3863)3 did improve LiNO3 solubility in carbonates, but that the highest solubility of LiNO; was still determined by the EC content in the carbonate solvent. Motivated by the observation that successful ECLiNO; electrolyte systems are possible, Li||NCM batteries were created in which EC dominant-LiNO3 electrolytes with conventional salt concentrations were used. The focus was only on cells with thin lithium metal anode (50 pm) and high loading NCM622 cathode (2 mAh/cm²). It was found that the batteries demonstrated over 90% capacity retention after 600 cycles at 0.5 C, without any additional interventions (e.g., separator re-design or 3D Li anode design). 1 Ah pouch cells were created and studied with a designed energy density of 300 Wh/kg and it was found that these cells retained 87.9% of their original capacity after 100 cycles. These results therefore demonstrated L1NO3 salt additives can be as effective in stabilizing LMBs based on carbonate electrolyte solvents.

[0069] Dissolution of LiN6; in EC. The results in FIG. 1A show that pure EC solvent dissolved up to 0.7 M LiN63 with ionic conductivity of 2.2 mS/cm at 40 °C (see Table 1, showing the solubility of LiN6; in carbonate electrolyte). Another cyclic carbonate solvent of PC dissolved up to 0.2 M LiNDs with ionic conductivity of 0.72 mS/cm at room- temperature (R.T.). In comparison, LiNCE hardly dissolved in either of the linear carbonate solvents studied (DMC, DEC), and the ionic conductivity was negligible (< 10"⁴ mS/cm) in both DMC and DEC saturated with LiNC . Next, the solubility of LiNCE was investigated in EC/DMC mixtures.

[0070] Table 1.

[0071] If the solubility of LiNCE is totally determined by EC, the estimated solubility limit should be about 0.5 M for 70 vol.% EC, and 0.2 M for 30 vol.% EC. However, the actual solubility was lower than the theoretical value (FIG. 1 A), suggesting that the addition of DMC disturbed the dissociation of LiNCE. This point was considered further by introducing the Lewis acid of Al³⁺ (A1(CF3SCE)3) with high charge density, which is supposed to strongly attract NCE and thus promote dissociation of LiNCE in solution. Intriguingly, after adding 0.06 M Al³⁺, the effect of DMC on LiNCE solubility was consistent with the theoretical line (FIG. 1A). It was supposed that the addition of A1(CF3SC )3 liberated EC molecules to dissociate LiNCE in the fraction present in the electrolyte. This conjecture seemed to be confirmed by the additional observation that LiNCE was still hardly dissolved in DMC even with the assistance of A1(CF3SCE)3. It was also supported by the literature result that elevated solubility of LiNCE in EC/DEC mixtures is achieved with the assistance of CUF₂. Other works with assistance of In(OTf)3 and Sn(OTf)2 show slightly higher solubility in EC/DEC solvent than theoretical, which may be caused by the enhanced temperature (60 °C) of preparing electrolytes. Meanwhile, the color change of electrolyte from transparent to yellow indicated the formation of NCE' after heating.

[0072] In comparison with other Li salts used in LMB electrolytes (e.g., LiFSI, LiTFSI, LiPFe etc.), the ionic conductivity of the LiNC /EC electrolyte was lower under similar concentrations, suggesting less mobility of active ions in the electrolyte (FIG. IB; Table 2, showing Arrhenius fitting of LiNCE/EC electrolytes versus commercial (Com.) electrolyte). It is known that the high melting point of EC and its solid-like physical properties at room temperature could lead to sluggish ion transport and low ion mobility. As shown in FIG. IB, the ionic conductivity of the EC-LiNCE electrolytes displays Arrhenius-like transport characteristics down to approximately 40 °C; the conductivity falls more quickly at temperatures below this value due to the freezing of EC.

[0073] Table 2.

[0074] The structure of EC is indistinguishably affected by Li NO in the LiNCL/EC electrolytes, but the opposite is not the case. Attenuated total reflection-Fourier-transform infrared spectroscopy (ATR-FTIR) measurements in fact revealed that whereas all characteristic peaks of EC, such as C=O stretch, skeletal stretch, and C-FE vibrations were maintained (FIG. 8) upon addition of LiNO, consecutive changes with emerging peaks appeared in the region in or near the vibration of nitrate (NO-) (FIG. 1C). In particular, NO3- shows D3h symmetry, in which three major FTIR peaks can be assigned to the solid crystal, including the asymmetric stretch at -1330 cm’¹, symmetric bending at - 836 cm’¹, asymmetric bending at - 736 cm’¹. When LiNCh is dissolved in EC, the peak located at -1330 cm shifted to the higher wavenumber, consistent with the idea that EC promotes dissociation of LiNCL. This peak was also seen to move to lower wavenumber again when the concentration of LiNCL increases, suggesting that even in the dissolved salt, some fraction of LiNO; exists as associated ion-pairs. This hypothesis is further confirmed by the spectra below 850 cm¹, especially for the peak located at - 736 cm’¹, which firstly shifted to lower wavenumber with weak signals at low concentration and then emerged as a shoulder peak at high concentration. This variation tendency is similar to the LiNCh/EEO solution. Based on the FTIR analysis, it can be concluded that in low concentrated Li NO, /EC electrolytes, the inner shell of Li-ion is the EC molecule and most LiNCL can be fully dissociated in the solvent. At higher LiNCL concentration, the inner shell of Li-ion includes both EC and anion (NO3-), meaning that part of L1NO3 retains its ion-pair structure. These observations lead to the following proposed equilibrium dissociation reaction:

[0075] Although LiNOs can be dissolved in pure EC, the moderate to low conductivity at R.T. hinders the direct use of this electrolyte system in practical batteries. The effect was studied of adding 1 M LiFSI in EC solvent — due to the interaction between LiFSI and EC, the prepared electrolyte remained liquid at room temperature. Although the literature has reported that EC can dissolve over 4M LiFSI, due to the strong coordination between LiNCE and EC, the solubility of LiFSI is largely inhibited and only ~1 M LiFSI can be dissolved in 0.5 M LiNCE/EC solution. The R.T. conductivity nonetheless increases markedly, to 7mS/cm, proving the important contribution of LiFSI on ion transport (Table 3, showing the competition of LiNCE/EC electrolytes). In order to explore the complementary role of the Lewis acid (Al³⁺) salts in increasing the solubility of LiNCE in EC/DMC solvent blends, a few electrolytes were prepared (Table 4, showing the effect of Lewis acid on the solubility of LiNCE). With the participation of linear solvent and LiFSI, Al³⁺ is still seen to enhance the LiNCE solubility towards the theoretical values. Taken together, these findings can be used to clarify the mystery about the solubility of LiNCE (see FIG. 2): 1) Solvents with high dielectric constant (EC, PC) can dissolve A type salt (LiNCE), B type salt (LiFSI, LiPFg), and C type linear carbonate (DMC, DEC). 2) The solubility of A, B and C have competition. The easy dissociation B type salts and C solvents will occupy EC and prevent the dissociation of LiNCE, explaining why literature reports the negligible dissolving capacity of LiNCE in carbonate electrolytes. 3) Lewis acid (Al³⁺, Sn²⁺, Cu²⁺, In³⁺ et al) with high charging density has strong interaction with type B salt and type C solvent, thus liberate the EC molecule to dissolve LiNCE.

[0076] Table 3.

4ote: Different LiNCE is dissolved in EC first. Then IM LiFSI is added into the electrolyte with carefully shaking. EC itself has high solubility of LiFSI (>4M). However, due to the strong coordination between LiNCE and EC, the solubility of LiFSI into EC is largely inhibited.

[0077] Table 4.

[0078] Various types of batteries have been assembled to evaluate the effect of Li N Ch on the cycling stability of LMBs in carbonate electrolytes. Among the carbonate solvents studied, EC exhibited the highest reversibility in lithium stripping/plating process. The average Coulombic efficiency (CE) of IM LiFSI/EC electrolyte was 93.34%, much higher than PC (60.89%), DMC (32.23%), and DEC (2.59%) (FIG. 9). Note: In the electrolytes with DMC or DEC solvent, the LiNOa was hardly dissolved. After adding LiNOa, the CE was further increased to 96.65%, 97.78% and 98.5% with the addition of 0.1 M, 0.3 M and 0.5 M LiNOa, respectively (FIGS. 3A-3C).

[0079] In addition to the advantage towards lithium anode, EC based electrolytes also showed good oxidative stability towards high Ni cathode (NCM622). LiFSI is known to be oxidized on the surface of high voltage cathode and to corrode Al current collector, which is results in endless charging profiles in lithium) |NCM622 batteries (FIG. 3D). Through simple combination of LiNOa and LiFSI, the life was largely improved from 36 to over 200 cycles (FIG. 3D). For the 0.5M LiNOa + IM LiFSI in EC, the average CE for 200 cycles reached 99.45% (FIG. 3F).

[0080] X-ray photoelectron spectroscopy (XPS) spectra were employed to unveil the stability of LiNOa at the interphase of both anode and cathode (FIG. 10, FIG. 4). On the surface of anode, the solid electrolyte interphase (SEI) majorly consists of inorganic compounds with only weak signals from organic compounds (C-O-R peak). Inorganic compounds such as LiaN, LiaO, LiF, LiaS and Li_xSO_y are mainly decomposed from LiFSI (FIG. 4A). In comparison, on the cathode side, it seems both solvent and salts participated in the formation of interphase. The formation of LiaCOa was attributed to the decomposition of EC. Meanwhile, no noteworthy S signal was observed on the surface of cathode, indicating that LiFSI did not decompose completely on the cathode side (FIG. 4B). Under this consideration, the peaks of Ni_s (LiaN and LiNO_x) can be attributed to decomposition of LiNOa. The F peaks (LiF and -CF3) could have come from both LiFSI and binders (polyvinylidene difluoride (PVdF)) of the cathode. According to the analysis of XPS, it can be concluded that adding moderate LiNOa contributed to the stability of both anode and cathode side. At low voltage, due to the interaction between LiNOa and EC, LiFSI contributed the most mobility of ions and thus became the major compound to generate inorganic rich SEI. At high voltage, the decomposition of LiNOa and EC elevated the stability of LiFSI. Although pure EC-based electrolyte demonstrates promising high reversibility in LMBs, the electrolyte will still freeze below 10 °C (FIG. 11). Therefore, EC was further combined with a low melting and low viscosity solvent such as DMC, tetrahydrofuran (THF), and DOL. The results in FIG. 12 prove these electrolytes also demonstrated excellent properties for LMBs. Note: The CEs were tested in Li| |Cu electrochemical cells. In each cycle, 1 mAh/cm² lithium was plated on Cu first and then the voltage was increased to 0.5 V in stripping process. The current density for lithium stripping/plating was 0.5 mA/cm². The Li||NCM622 batteries were firstly activated at 0.1 C (2 cycles) and 0.2 C (2 cycles). Then, the CC (0.5C)-CV (0.2C) charge mode and CC discharge mode (0.5 C) were applied for the following cycles. The loading for NCM622 cathode was 2 mAh/cm².

[0081] In order to further improve the long cycle performance of carbonate electrolytes, specifically with the goal of achieving at least 500 cycles for practical LMBs, one of the state-of-the-art carbonate electrolytes reported in literature was chosen (0.1 M LiNO , + 0.4 M lithium bis(oxalato)borate (LiBOB) + 0.6 M LiTFSI + 0.4 M LiF + 0.05 M LiPF,-,+ 0.03 M LiBF4 in solvent of EC/DMC (2:1 by volume) with addition of 1 vol.% fluoroethylene carbonate (FEC), 2 vol.% vinylene carbonate (VC), 3 v% di-2,2,2-trifluoroethyl carbonate (TFEC)), which was labeled as the reference (Ref.) electrolyte in FIG. 5A. As the primary solvents were EC and DMC, and the major salts were LiTFSI, LiBOB, and LiF with total concentration less than 2 M, the electrolytes can be regarded as cost-competitive. LiNO^ upgrading of the electrolytes was considered based on two concepts. Firstly, through addition of 0.06 M Al(OTf)3 into the reference electrolyte, the concentration of LiNCF could be increased to 0.5 M. Therefore, the resultant carbonate electrolyte (El) had a composition: 0.06 M Al(OTf)₃ +0.5 M LiNO₃ + 0.4 M LiBOB + 0.6 M LiTFSI + 0.4 M LiF + 0.05 M LiPFe+ 0.03 M LiBF4 (FIG. 5A). Secondly, noticing that LiBOB was slow to dissolve in the reference carbonate solvent and LiF could only uniformly disperse into the electrolyte in the form of colloidal particles (FIG. 13), leading to a cloudy mixture, LiFSI was used to replace LiF and lithium difluoro(oxalato)borate (LiDFOB) was used to replace part of the LiBOB. These changes yielded a second upgraded electrolyte (E2) that was completely transparent (FIG. 5A) and with composition: 0.06 M Al(OTf)₃ +0.5 M LiNO₃+0.2 M LiDFOB+ 0.2 M LiBOB + 0.6 M LiFSI + 0.05 M LiPFe+ 0.03 M HBF4 based on the same solvent (FIG. 13B) as the reference.

[0082] Both electrolytes revealed high reversibility for lithium metal with CE over 98.8% (Fig.S7). Further LMBs full cells were tested with thin Li metal anode (50 pm) and high loading NCM cathodes. FIGS. 5A-5C show that for the NCM622 cathode with areal loading of 2 mAh/cm², the capacity retention was 90.5% for El electrolyte after 600 cycles, and 81.8% for E2 electrolyte after 600 cycles, largely exceeding the commercial electrolyte (1 M LiPFe in EC/DMC/DEC (1 : 1 : 1 by vol.) 77.3%, 36 cycles) and reference electrolyte (79.8%, 165 cycles). The NCM811 cathode was further studied with loading of 2.3mAh/cm². The capacity retention was 84.7% for El and 80.6% for E2 after 400 cycles (FIGS. 5D-5F). Finally, the batteries were tested at even more challenging conditions, in which the high areal loading NCM811 cathode (4mAh/cm²) was coupled with thin lithium metal, the capacity retention of El was 94.5% after 150 cycles, and 92.5% for E2 after 200 cycles (FIGS. 5G- 51). In addition, for all the batteries systems, the average CEs were over 99.7%.

[0083] In order to unveil the fading mechanism for the LMBs with upgraded carbonate electrolyte, the coin cells were disassembled after observing rapid capacity fading and replaced the lithium anode and electrolyte. The results in FIG. 15 demonstrate that even updating the electrolyte and anode, the cathode still delivered a capacity retention lower than 60% of the theoretical capacity, which means that the failure not only comes from the consumption of lithium and electrolytes, but also due to the interphase characteristics at the cathode. In addition, it was observed that even without the addition of DMC, the upgrading EC dominant electrolyte also demonstrated high stability towards NCM622 cathode, the capacity retention was higher than 80% over 400 cycles (FIG. 16). It is worth mentioned that EC electrolyte was consumed slower than EC/DMC mixture electrolyte (FIG. 17). The separator employed in the battery was still filled with electrolyte over 400 cycles, suggesting that if the low temperature shortage can be well resolved, pure EC electrolyte should be beneficial for LMBs at low electrolyte to cathode ratio.

[0084] The battery properties have been compared with the reports in literature. As shown in FIG. 6, the LMBs with electrolytes developed in this work showed the longest cycling lives and highest areal capacities (Table 5, showing the details of recent progress on lithium metal batteries through electrolyte modifications). The accumulated capacity could reach to 1.25 Ah with only 50 pm Li as primary anode. In order to demonstrate the application interest of upgrading electrolyte, pouch cells were designed and assembled with energy density of -300 Wh/kg, in which the N to P ratio was about 2.5 (Table 6, showing in formation on pouch cells). The assembled pouch cells obtained a capacity retention of 87.9 % after 100 cycles at a high current density of 0.5 C. [0085] Table 5.

MTFP = methyl 3,3,3-trifluoropropionate; FEC = fluoroethylene carbonate. E1-E9 = electrolytes reported in literature, Com. = commercial electrolyte. Ref. = reference electrolyte. T1-T3 = upgrading electrolytes in this work. [0086] Table 6

[0087] Based on the results it is considered LiNCf could be as effective a salt additive for carbonate electrolyte solvents and that the previously reported difficulty in achieving high LiNCL solubility in carbonate solvents most likely stemmed from the common practice of using cyclic/linear carbonate solvent blends as battery electrolytes. It is on the one hand tempting to go one step further to argue that the limited solubility has a straightforward classical explanation (i.e., DMC « I<EC), which lowers the dielectric constant of the blend. Based on these findings, it has been shown that EC dominant and LiNCL-rich electrolytes can dramatically enhance the stability of LMBs from 36 cycles to over 600 cycles. As this work focused on the studies of electrolytes, other strategies such as building artificial interphase on lithium metal, fabricating structured lithium metal anodes can be easily cooperated with the present disclosure to further prolong the life of batteries.

[0088] Methods. Electrolyte preparation: Electrolytes were prepared in an Ar-filled glove box (Inert Inc.) in which both the content of O2 and H2O are lower than 0.5 ppm. 50 pm Li and all NCM cathodes are kindly provided by NOHMs technologies. Solvents: vinylene carbonate (VC >98%, stabilized with BHT, TCI America), fluoroethylene carbonate (FEC >98%, TCI America), di-2,2,2-trifluoroethyl carbonate (TFEC >98%, TCI America), ethylene carbonate (EC, anhydrous, 99%, Sigma-Aldrich), diethyl Carbonate (DEC anhydrous, 99%, Sigma-Aldrich), dimethyl carbonate (DMC anhydrous, 99%, Sigma- Aldrich), propylene carbonate (PC, anhydrous, 99%, Sigma-Aldrich), 1,3-dioxolane (DOL, anhydrous; 99.8%, contains~75 ppm butylated hydroxytoluene as an inhibitor, Sigma- Aldrich), tetrahydrofuran (THF, anhydrous, >99.9%, Sigma-Aldrich). Salts: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, 99.95% trace metals basis, Sigma-Aldrich), lithium nitrate (LiNOs, 99.99% metal basis, Chem-Impex Inf 1. Inc.), lithium bis(fluorosulfonyl)amide (LiFSI, 99% purity, Oakwood Products Inc.), aluminum triflate (Al(OTf)3, 99%; Alfa Aesar ), lithium bis(oxalato)borate (LiBOB, Sigma-Aldrich), lithium difluoro(oxalato)b orate (LiDFOB, Sigma-Aldrich), lithium hexafluorophosphate (LiPFe, battery grade, Sigma-Aldrich), lithium tetrafluoroborate (LiBF4, >98%, TCI America), LiF (>99.98% trace metals basis, Sigma-Aldrich), All salts were used without further purification. Electrolyte: IM Li PE, in EC/DMC/DEC (1 :1 :1 by vol.) (Battery grade, Sigma-Aldrich). Other electrolytes were prepared in glovebox. LiNO VEC electrolytes were prepared by dissolving various amount of Li NO;; in pure EC solvent. EC was firstly melted in the temperature 60 °C and stored in 40 °C. When various amount of LiNOi was added into EC, the electrolytes were shaken with the assistance of touch mixer machine at room temperature (RT) for 10 minutes. The solution remained liquid form through the shaking process. After preparation, the electrolyte could freeze after resting over 0.5 hour. However, as soon as melting at 40 °C, the electrolyte would become transparent again without additional shaking. [0089] Materials and electrochemical characterizations. The interphase of anode and cathode was characterized by X-ray photoelectron spectroscopy SSX-100 (XPS). In order to observe the interphase generated on the anode side, Li| |Cu electrochemical batteries were assembled and discharged at current density of ImA/cm² for 20 hours, followed by a charge process at same current density until the voltage reached 0.5 V. The cells were then taken apart in the glovebox to obtain the Cu foil with new interphase on it. For the cathode side, Li||NCM622 batteries were cycled at 0.1 C for two cycles, then the NCM622 cathode at fully discharged state was taken out for characterization. Both Cu foil and NCM cathode were washed by DMC solvent and dried in glovebox first. Then an inert chamber was used to load the samples for XPS test, which could avoid exposing sensitive interphase to the air. ATR- FTIR analysis was conducted on Thermo Scientific FTIR spectra. All liquid solutions were store at 40 °C and the remained liquid phase during FTIR test. The conductivities of electrolytes were measured on Novocontrol Broad band dielectric/impedance spectrometer. [0090] Electrochemical Performance. 2032 type coin-cell batteries were assembled in a glovebox. Li| |Cu asymmetric electrochemical cells were assembled with thick lithium foil (500 pm) as anode (diameter, 3/8 inch), Cu foil as counter electrode (diameter, 3/8 inch), Celgard 3501 as separator. The amount of electrolyte was about 60-70 pl. Li||NCM batteries were assembled with thin Li foil (50 pm) as anode, NCM622 or NCM811 as cathode. For the electrolytes with solvent mixture of DMC, THF, or DOL, AI2O3 coated Celgard membranes was applied as separator. For other electrolytes, Celgard 3501 was used as separator. All electrochemical batteries were performed on Neware battery tester. lAh Pouch cell were assembled using facilities at NOHMs Technologies, Inc. Detailed information can be found in Table 6. [0091] Although the present disclosure has been described with respect to particular examples, it will be understood that other examples of the present disclosure may be made without departing from the scope of the present disclosure.

Claims

CLAIMS:

1. An electrolyte composition comprising lithium nitrate; optionally, one or more other lithium salt(s); one or more cation(s), wherein the cation(s) are not lithium cation(s); and one or more carbonate(s).

2. The composition of claim 1, wherein the lithium nitrate is present at about 0.1 M to about 1 M based on the total volume of the composition.

3. The composition of claim 1, wherein the other lithium salt(s) is/are chosen from bis(trifluoromethane)sulfonimide lithium salt (LiTFSI), lithium triflate (LiOTf), lithium bis(fluorosulfonyl)imide (LiFSI), LiPFe, LiCICU, lithium difluoro(oxalato)borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), LiBF4, and any combination thereof.

4. The composition of claim 1, wherein the cation(s) is/are chosen from Al³⁺, Ga³⁺, In³⁺, Ge⁴⁺, Sn⁴⁺, Sb³⁺, and any combination thereof.

5. The composition of claim 1, wherein the other lithium salt(s) are present at about 0.1 M to about 4 M based on the total volume of the composition.

6. The composition of claim 1, wherein the cation(s) are present at about 0.01 M to about 0.2 M based on the total volume of the composition.

7. The composition of claim 1, wherein the composition further comprises one or more anions(s) chosen from CF₃SO₃' (triflate), N(SO2CF₃)2', halides, and any combination thereof.

8. The composition of claim 1, the cation(s) and anion(s) are provided by one or more salt(s).

9. The composition of claim 8, wherein the salt(s) is/are chosen from A1(CF₃SO₃)₃, A1[N(SO₂CF₃)₂]₃, A1F₃, A1C1₃, AlBr₃, A1I₃, Ga(CF₃SO₃)₃, Ga[N(SO₂CF₃)₂]₃, GaF₃, GaCh, GaBr₃, Gal₃, In(CF₃SO₃)₃, In[N(SO2CF₃)₂]₃, InF₃, InCh, InBr₃ Inl₃, Ge(CF₃SO₃)₄,

- 29 - Ge[N(SO₂CF₃)₂]₄, GeF₄, GeCl₄, GeBr₄, Gel₄, In(CF₃SO₃)₄, In[N(SO₂CF₃)₂]₄, InF₄, InCl₄, InBr₄, Inl₄, and any combinations thereof.

10. The composition of claim 1, wherein the carbonate(s) is/are chosen from alkyl carbonates, cyclic carbonates, and combinations thereof.

11. The composition of claim 1, wherein the carbonate(s) is/are chosen from dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), di-2,2,2-trifluoroethyl carbonate (TFEC), and any combinations thereof.

12. The composition of claim 1, wherein the composition is an electrolyte in a battery.

13. A device comprising one or more composition(s) of claim 1, wherein the composition(s) is/are an electrolyte/electrolytes in a device.

14. The device of claim 13, wherein the device is an electrochemical device or comprises one or more electrochemical device(s).

15. The device of claim 13, wherein the device is a battery, a supercapacitor, a fuel cell, an electrolyzer, or an electrolytic cell.

16. A device according to claim 15, wherein the battery is a lithium ion-conducting battery or a lithium metal battery.

17. The device of claim 13, wherein the battery or ion-conducting battery is a rechargeable lithium-ion conducting battery.

18. The device of claim 13, wherein the battery further comprises a cathode, and anode, optionally, one or more separator(s), optionally, one or more current collector(s), optionally, one or more solid-phase electrolyte(s), and, optionally, and/or one or more additional structural component(s).

- 30 -

19. The device of claim 18, wherein the cathode comprises (or is) one or more lithium- containing cathode material(s), one or more nickel cobalt manganese oxide cathode material(s), one or more conversion type cathode material(s), or any combination thereof.

20. The device of claim 18, wherein the anode comprises (or is) one or more lithium-ion conducting anode material(s), lithium metal, silicon-containing materials, tin and its alloys, tin/carbon, and phosphorus, or any combination thereof.

21. The device of claim 18, wherein the separator comprises an organic polymeric material, an inorganic material, or any combination thereof.

22. The device of claim 18, wherein the one or more additional structural component(s) is/are chosen from bipolar plates, external packaging, electrical contacts/leads to connect wires, and combinations thereof.

23. The device of claim 18, wherein the battery comprises 1 to 500 cells.

24. The device of claim 18, wherein the battery comprises a plurality of cells, each cell comprising one or more anode(s) and/or one or more anode material(s), and optionally, one or more cathode(s), one or more electrolyte(s), one or more current collector(s), or any combination thereof.