WO2025117282A1

WO2025117282A1 - Anode-less/lithium metal batteries and method to make them

Info

Publication number: WO2025117282A1
Application number: PCT/US2024/056654
Authority: WO
Inventors: Ke Chen; Jinhua Huang; Bin Li
Original assignee: Wildcat Discovery Technologies Inc
Current assignee: Wildcat Discovery Technologies Inc
Priority date: 2023-11-28
Filing date: 2024-11-20
Publication date: 2025-06-05
Anticipated expiration: 2026-05-28

Abstract

An lithium battery (anode-less or lithium metal battery) is comprised of a separator, a cathode, an anode absent a lithium intercalation material, and an electrolyte comprised of a polymerizable aromatic compound. The polymerizable aromatic compound improves the cycle life of anode-less lithium ion batteries or lithium metal batteries (LMBs) when subjected to a sufficient voltage versus lithium such as 3.5 volts. The cathode of the anode-less lithium ion battery or LMB may be an oxide, phosphate or combination thereof.

Description

ANODE-LESS/LITHIUM METAL BATTERIES AND METHOD TO MAKE THEM Field

[0001] This invention is directed to lithium ion batteries and in particular anode-less/ anode free lithium ion batteries and lithium metal batteries.

Background

[0002] Rechargeable lithium ion batteries that are anode-less (anode-less battery) or have a lithium metal anode (“lithium metal battery” or “LMB”), could dramatically increase the celllevel energy of state-of-the-art lithium ion batteries (LIBs) compared to those containing a carbon anode, due to the extremely low density, high theoretical capacity, and negative redox potential of Li metal. Unfortunately, the commercialization of LMBs is very challenging due to the high reactivity of Li metal anode, the formation of an unstable solid electrolyte interphase (SEI), the growth of Li dendrites, the evolution of inactive Li during the Li plating and stripping, and the volume change during the battery operation. These consequences eventually lead to a low coulombic efficiency (CE), shortened battery life, sluggish electrode kinetics and safety issues. Similar issues arise for so-called anode-less batteries (e.g., those using a metal current collector as the anode in which Li is deposited thereon during charging).

[0003] When cycling a battery, the stripping and plating of lithium on the anode may lead to formation of high surface area lithium and lithium dendrites. This may lead to capacity fade and catastrophic failure in batteries. To help stabilize batteries, high salt concentration electrolytes have been formulated and demonstrated to improve cycle performance for LMBs. In these types of high salt concentration electrolytes, it is believed essentially all of the solvent molecules are involved in solvating the salt cations minimizing, for example, the formation of solid electrolyte from decomposition/reaction of the solvent. This enables reduction of the salt anion for solid electrolyte (SEI) formation and may also increase the electrochemical stability of the electrolyte. The increased salt concentration also reduces ionic concentration gradients at the electrode, which may be responsible for inhomogeneous lithium deposition during cycling. A disadvantage to the superconcentrated electrolytes is the high viscosity of the formulation due to its high salt concentration, which may be detrimental, for example, to the power performance of the battery. [0004] Recently to attempt remedy some of the shortcoming of high salt concentration electrolytes, a diluent solvent has been added to the high salt concentration electrolyte to form a localized high salt concentration electrolyte (LHCE) that has desirable viscosity while retaining some of the performance improvements of high concentration electrolytes (sec, for example, US Pat Nos. 11,094,966 and 10,367,232).

[0005] Localized high concentration electrolytes (LHCE) contain a lithium salt (e.g., lithium bis(fluorosulfonyl)imide, LiFSI), solvating solvent (e.g., dimethoxy ethane, DME), as well as diluents such as 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE). In LHCEs, diluent solvents do not disrupt the solvent structure of the primary solvent(s) around the ions from the salt, but largely reduces the viscosity of the electrolyte. Due to the highly solvated structure, the Li salt is able to be reduced and form a LiF rich solid electrolyte interphase (SEI), that has improved LMBs. However, further improvements are desirable, particularly for anode-less LIBs and lithium metal batteries (LMBs).

[0006] Accordingly, it would be desirable to provide electrolytes, and electrolyte-cathode combination to realize an anode-less LIB or LMB with improved performance such as longer cycle life and desirable power delivery.

Summary

[0007] An anode-less battery has been discovered having improved cycle life without adversely affecting desirable characteristics such as power delivery. For example, certain polymerizable aromatic compounds (PACs) when present in an electrolyte such as a LHCE electrolyte improves the cycling performance of an anode-less battery or LMB battery. Generally, such improvements arise when a sufficient charge voltage is realized such as at least about 3.5 or 3.8 V (Li/Li⁺), which advantageously occurs on the first charging of the battery. Without being limiting, it is believed that the PACs undergo polymerization, which may be oxidative, reductive or both, forming a useful polymeric structure within the battery. Anode-less or anode free battery herein is a battery that has an anode that is essentially free of: (i) lithium prior to the first charge and (ii) a lithium intercalating material such as graphite or titanium oxide. The anodeless battery may contain a metal or silicon that alloys with Li at battery operating conditions, but are not preferred. An LMB is a battery that contains a lithium metal anode, which, is a lithium metal foil/sheet or lithium metal layer deposited on a transition metal current collector such as copper or nickel that essentially do not alloy with Li (less than 1 or 2% by mole) at battery operating conditions. It is understood that the anode may contain certain carbons that are clcctroconductivc, but substantially do not intercalate lithium (c.g., less than 1% by mole). [0008] An illustration is a battery comprised of a separator, a cathode, an anode absent a lithium intercalation material, and an electrolyte comprised of a polymerizable aromatic compound. In other words, an anode-less battery or LMB comprised of an electrolyte having a PAC. The anode absent a lithium intercalation material, for example, may be a metal commonly used for anode current collectors (e.g., transition metals such as copper, nickel and alloys thereof and lithium metal in the case of an LMB) as well as electroconductive carbons that essentially do not intercalate lithium (less than 1 or 2% by mole of Li being intercalated). The anode may be comprised of other metals (e.g., Sn and Al) or Si that alloy with Li at battery operating conditions, but these arc not preferred. Preferably, the electrolyte is a LHCE. An LHCE is a solution comprised of a solvating solvent, diluent and a dissolved lithium salt, the lithium salt being at least 5 times more soluble in the solvating solvent than the diluent.

[0009] Another aspect is a method of forming a battery comprising: incorporating a polymerizable aromatic compound into an electrolyte of an uncharged battery comprised of a separator, a cathode, an anode absent a lithium intercalation material, and an electrolyte; and charging the battery to a voltage sufficient to polymerize the polymerizable aromatic compound to form the battery. It has been surprisingly discovered that anode-less batteries and LMBs comprised of an electrolyte having a PAC when charged to a sufficient voltage, which is typically above 3.5 V or 3.8 V, display longer cycle life. Illustratively, an anode-less battery may have a cycle life that is 20%, 30%, 40% or 50% greater than without the PACs. This discovery is applicable regardless of the cathode chemistry such as varying oxides and phosphates.

Brief Description of the Drawings

[0010] Figure 1 displays the cycling behavior of batteries of this invention and not of this invention.

[0011] Figure 2 displays the cycling behavior of batteries of this invention and not of this invention.

[0012] Figure 3 displays the cycling behavior of batteries of this invention and not of this invention. [0013] Figure 4 displays the cycling behavior of batteries of this invention and not of this invention.

[0014] Figure 5 displays the cycling behavior of batteries of this invention and not of this invention.

[0015] Figure 6 displays the cycling behavior of batteries of this invention and not of this invention.

[0016] Figure 7 displays the cycling behavior of batteries not of this invention.

[0017] Figure 8 displays the cycling behavior of batteries not of this invention.

[0018] Figure 9 displays the cycling behavior of batteries of this invention.

Detailed Description

[0019] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75^th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March’s Advanced Organic Chemistry, 5^th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modem Methods of Organic Synthesis, 3^rd Edition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

[0020] Hydrocarbyl refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may contain one or more heteroatoms which may be comprised of a heteroatom such as: halogen; oxygen; nitrogen; sulfur; silicon; or phosphorous. Generally, the hydrocarbyl group is a Ci-36 hydrocarbyl group that may have from 1 to 5 heteroatoms. “Halo” and “halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I). Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and/or triple bonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkcnyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions. Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene.

[0021] Hydrocarbyl group may be a straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Heteroatom as used herein means any one of nitrogen, oxygen, silicon, and sulfur. The hydrocarbyl group may contain 1-36 carbon atoms, 1-20 carbon atoms, 2-20 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1- 6 carbon atoms, 1-5 carbon atoms, 1-4 carbon atoms, 1-3 carbon atoms, or 1 or 2 carbon atoms. Exemplary hydrocarbyl groups include, but are not limited to, linear or branched, alkyl and alkenyl groups, and hybrids thereof such as (cycloalkyl) alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl. The aliphatic groups may be unsubstituted or substituted. Substituted means that one or more C or H atoms is replaced with a heteroatom. Typically, one to six carbon atoms may be independently replaced by the aforementioned and in particular oxygen, sulfur or nitrogen. The hydrocarbyl group may have one or more “halo” and “halogen” atoms selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).

[0022] If not otherwise specified any characteristic or property may be determined by standard laboratory practices for determining such properties or characteristics The boiling temperature may be determined by ASTM D86 if not generally available in the literature. “Solubility” may be determined by the ‘shake flask’ method based on the guidelines provided by OECD, Paris, 1981, Test Guideline 107, Decision of the Council C(81) 30 final. “Viscosity” may be determined by ATSM D445 if not generally available in the literature.

[0023] The battery is comprised of an anode absent a lithium intercalation material. That is the battery is an anode-less battery or LMB as described above. That is the anode in an anode-less battery is essentially a metal or electrically conductive material that does not intercalate lithium ions and preferably essentially does not alloy with Li at battery operating conditions. Exemplary materials include those suitable as current collectors such as a transition metal or alloy with copper, nickel and alloys of each being illustrative. In some embodiments, the anode may be comprised of an electrically conductive carbon. Electrically conductive carbons are as defined above and an illustration of such a carbon may be carbon black such as those available from Timcal under the tradename SUPER P. Preferably, the anode is a transition metal current collector. It is recognized upon the initial charging of the battery (oxidation of the cathode), lithium ions from the oxidation of the cathode coats the anode (e.g., transition metal/electrically conductive carbon current collector/sheet with lithium). When an electrically conductive carbon is present, typically it is present as a coating on the transition metal current anode sheet or foil including a binder such as described herein and as described in U.S. Pat. No. 9,172,085 incorporated herein by reference. [0024] The battery may be a so-called lithium metal battery (LMB), wherein the anode is comprised of lithium metal or lithium metal alloy prior to the initial charging of the battery. The lithium metal may be present in any suitable amount and typically is present as a thin layer upon a transition metal current collector such as described above for the anode-less battery (1 or 5 micrometers to 50, 30 or 20 micrometers thick layer). The LMB likewise is free of an intercalation material, but may be comprised of other components as described for the anode-less battery.

[0025] The battery is comprised of a cathode. Generally, the cathode is comprised of a current collector, which may be a sheet or foil of a transition metal as described for the anode coated with a cathode material (one capable of intercalating Li). Typically the cathode material (powder) is coated on the current collector using a binder and electrically conductive materials. The binder may be any suitable such as those known in the art and may include, for example, carboxy methyl cellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), poly-tetrafluoroethylene (PTFE), or a mixture of two or more thereof. Desirably, the cathode is comprised of PVDF. The electrically conducting additive may be any suitable such as graphite, carbon black, carbon nanotubes, graphene and carbon fiber. The amount of other cathode components may be any suitable amount, but generally is at most about 20% or 10% by weight to about 0.1%, 0.5% or 1% by weight of the cathode (i.e., cathode material and other cathode components not including the current collector).

[0026] The cathode material may be any suitable for intercalating Li such as those known in the art. Illustratively, the cathode material may be a lithium transition metal oxide, a transition metal sulfide, and the like. The cathode may include any material sufficient to have desirable discharge capacity and charge retention when used with an anode. Examples of suitable cathode materials may include phosphates, fluorophosphates, fluorosulfates, fluorosilicates, spinels, lithium-rich layered oxides, and composite layered oxides. Further examples of suitable cathode materials may include spinel structure lithium metal oxides, layered structure lithium metal oxides, lithium-rich layered structured lithium metal oxides, lithium metal silicates, lithium metal phosphates, metal fluorides, metal oxides, sulfur, metal sulfides, disordered rock salt structures, or any combination thereof.

[0027] Illustratively, the positive electrode material may be at least one complex oxide of lithium and a metal selected from cobalt (Co), nickel (Ni), and a combination thereof, and 65 more particularly, a compound represented by at least one Formula of Li_aAi-bBbD2 (wherein, 0.90<1.8 and 0<b<0.5); LiaEi-bBbCh-cDc (wherein, 0.90<a<1.8, 0<b<0.5, 0<c<0.05);

LiE2-bBbO4-cD_c (wherein, 0<b<0.5, 0<c<0.05); Li_aNii-b-cCobB_cDa (wherein, 0.90<a<l .8, 0<b<0.5, 0<c<0.05, 0<a<2); Li_aNii-b-cCobB_cO2-_aFct (wherein, 0.90<a<1.8, 0<b<0.5, 0<c<0.05, 0<a<2);

LiaNii-b-cCobBcOi-aFa (wherein, 0.90<a<1.8, 0<b<0.5, 0<c<0.05, 0<a<2); Li_aNii-b-cMnbB_cDa (wherein, 0.90<a<1.8, 0<b<0.5, 0<c<0.05, 0<a<2); Li_aNii-b-cMnbB_cO2-aFa (wherein, 0.90<a<1.8, 0<b<0.5, 0<c<0.05, 0<a<2); Li_aNibE_cGdO2 (wherein, 0.90<a<1.8, 0<b<0.9, 0<c<0.5, 0.001<d<0.1); LiaNibCocMnaGeCh (wherein, 0.90<a<l .8, 0<b<0.9, 0<c<0.5, 0<d<0.5);

Li_aNiGbO2 (wherein, 0.90<a<1.8, 0.001<b<0.1.); Li_aCoGbO2(wherein, 0.90<a<1.8, 0.001<b<0.1);

Li_aMnGbO2 (wherein, 0.90<a<1.8, 0.001<b<0.1); Li_aMn2GbO4 (wherein, 0.90<a<1.8, 0.001<b<0.1); QO₂; QS₂; LiQS₂; V₂O₅; LiV₂O2; LiIO₂; LiNiVO₄; Lio-phPCLh (wherein 0<f<2); Li₍3-f)Fe₂(PO4)3 (wherein 0<f<2); and LiFcPCL.

[0028] In the Formulae above, A is Ni, Co, manganese (Mn), or a combination thereof; B is aluminum (Al), Ni, Co, Mn, chromium (Cr), iron (Fe), strontium (Sr), vanadium (V), or a combination thereof; D is oxygen (0), fluorine (F), sulfur (S), phosphorus (P), or a combination thereof; E is Co, Mn, or a combination thereof; F is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, magnesium (Mg), lanthanum (La), Cerium (Ce), Sr, V, or a combination thereof; Q is titanium (Ti), molybdenum (Mo), Mn, or a combination thereof; I is Cr, V, Fe, scandium (Sc), yttrium (Y), or a combination thereof; J is V, Cr, Mn, Co, Ni, copper (Cu), or a combination thereof.

[0029] Desirably, the cathode is a lithium metal phosphate or lithium oxide comprised of Ni, Mn, and Co (NMC). The NMC desirably is one have at least 50% by mole Ni of the total moles of the Ni, Mn and Co present in the NMC. Preferably, the NMC is a layered oxide.

[0030] The battery is comprised of an electrolyte. Any electrolyte suitable for use in lithium ion batteries may be used, but generally it is desirable for the electrolyte to be a high salt concentration electrolyte such as those known in the art. The electrolyte is a solution comprised of a lithium salt and a solvent. Desirably, the electrolyte also comprises a diluent that is soluble in the solvating solvent, but does not solubilize the salt to form a localized high concentration electrolyte (LHCE). Illustratively, the LHCE generally has solvating solvent, diluent and a dissolved lithium salt, the lithium salt typically being at least 2, 3 or 5 times more soluble in the solvating solvent than the diluent.

[0031] The LHCE may include a combination of diluents with different substitutions. For examples, a combination of diluents containing linear alkyl groups, branched alkyl groups, or both may provide for a different miscible molar ratio with the solvating solvent while achieving desirable discharge capacity and capacity retention.

[0032] The LHCE may include any number of different diluents sufficient to be miscible with the solvating solvent and/or adjust the viscosity of the electrolyte. For example, the electrolyte may include one or more, two or more, three or more, four or more, or a plurality of diluents.

[0033] The diluent may include one or more fluorinated ethers. The fluorinated ethers may be any compound that includes a combination of ether groups, fluorine atoms, and carbon atoms that are fully saturated with hydrogen.

[0034] Examples of fluorinated ethers may include one or more of 1,1,2,2-tetrafluoroethyl 2, 2,3,3- tetrafluoropropyl ether (TTE); bis(2,2,2-trifluoroethyl) ether (BTFE), hexafluoroisopropyl methyl ether (HFPME); 1,1,2,2-tetrafluoroethyl ethyl ether (TFEEE); lH,lH,5H-octafluoropentyl 1,1, 2, 2, -tetrafluoroethyl ether (OFPTFEE); 1,1,2,2-tetrafluoroethyl ether, 1,2-(1,1,2,2,- tetrafluoroethoxy) ethane (TFEE); 1,3-(1,1,2,2-Tetrafluoroethoxy)propane (TFEP), 1, 1,2, 3,3,3- hexafluoro propyl 2,2,2-trifluoroethyl ether (HFPTFEE); n -butyl 1,1,2,2-tetrafluoroethyl ether (BTFEE); lH,lH,2’H,3H-decafluoro dipropyl ether (DFDPE); 1,1,2,3,3,3-hexafluoropropyl ethyl ether (HFPEE); l,l,l-trifluoro-2-[l-(2,2,2-trifluoroethoxy)ethoxy] ethane (TTFEEE); lH,lH,2’H-perfluorodipropyl ether (PFDPE); 1,1,2,2-tetrafluoroethyl isobutyl ether (TFEBE); l,l,l,2,2,3,4,5,5,5-decafluro-2-methoxy-4-(trifluoromethyl)pentane; 1 -(ethoxy Jnonafluorobutanc having a mixture of n- and iso-butyl isomers; 2-(trifluoromethyl)-3-ethoxydodecafluorohexane; 3- methoxyperfluoro(2-methylpentane); heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether; 1,1, 2, 2- tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE); methoxynonafluorobutane (MOFB); ethoxynonafluorobutane (EOFB); tris(2,2,2-trifluroethyl)orthoformate; di(2,2,2-trifluroethyl) carbonate; or any combination thereof. [0035] The solvating solvent may be any solvent or combination of solvents that are miscible in the diluent and/or can dissolve the lithium salt with or without the presence of the diluent. The electrolyte may include any number of solvating solvents sufficient to form desirable solvation around cation and/or anion of the lithium salt. For example, the electrolyte may include one or more, two or more, three or more, four or more, or a plurality of solvating salts. The solubility of the salts in the solvating solvent and/or diluent may be essentially the same and or different. It may be desirable, for example, to have one salt that has a greater solubility (e.g., 5%, 10% or 20% more soluble than the other salts) in the diluent, which may be desirable in forming an advantageous SEI layer. In some examples, the solvating solvent may include one or more of dialkoxy alkanes, dialkyl glycol ethers, disubstituted esters, disubstituted carbonates, trisubstituted phosphates, disubstituted sulfones, tetrasubstituted silanes, or any combination thereof.

[0036] Dialkoxy alkanes may include a pair of alkyl ethers bound by a C1-12 alkane group that may be branched or linear. For example, dialkoxy alkanes may include one or more of dimethoxy ethane (DME), 1,2-Diethoxyethane (DEE), 1,2-dimethoxypropane (DMP), The dialkoxy alkane may have the following structure:

where each Ri may independently comprise a C1-12 alkyl group that may be linear or branched, or any combination thereof. where R2 may comprise a C1-12 alkyl group that may be linear or branched, or any combination thereof. where n is an integer between 1 and 5.

[0037] Dialkyl glycol ethers may include a series of three either groups separated by alkyl chains that may be linear’ or branched. Example of dialkyl glycol eithers may include one or more of 1 ,2- diethylene glycol isopropyl methyl ether (DEG1M), diethylene glycol butyl methyl ether (DEGBM), or any combination thereof. The dialkyl glycol may have the following structure:

where each Ri may independently comprise a C1-12 alkyl group that may be linear or branched, or any combination thereof. where each R2 may independently comprise a C1-12 alkyl group that may be linear or branched, or any combination thereof. where each n is an integer between 1 and 5.

[0038] Disubstituted esters may include an ester that is substituted at the carbon atom of the carbonyl or the oxygen atom of the hydroxyl group by one or more groups including hydrogen, C1-12 alkyl, C1-12 aryl, or any combination thereof. Examples of disubstituted esters may include one or more of ethyl difluoroacetate, ethyl propionate, or any combination thereof. The disubstituted ester may have the following structure:

where each Ri may independently comprise a hydrogen atom, a C1-12 alkyl group that may be linear or branched, a hetero-alkyl group that may be linear or branched, or any combination thereof. Both Ri in combination may form a cyclic alkyl ring that may optionally include one or more hetero atoms.

[0039] Disubstituted carbonates may be substituted independently at each of the carbon atoms. Disubstituted carbonates may include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate, or any combination thereof. The disubstituted carbonate may have the following structure:

[0040] Trisubstituted phosphates may be substituted at each of the single bonded oxygen atoms. Trisubstituted phosphates may include trimethyl phosphate, triethyl phosphate, or any combination thereof. The trisubstituted phosphates may have the following structure:

where each Ri may independently comprise a hydrogen atom, a C1-12 alkyl group that may be linear or branched, a hetero atom, a hetero-alkyl group, or any combination thereof. where each R2 may independently comprise a hydrogen atom, C1-12 alkyl group that may be linear or branched, or any combination thereof.

[0041] Disubstituted sulfones may be substituted at the sulfur atom by one or more groups including hydrogen, C1-12 alkyl, C1-12 aryl, or any combination thereof. Disubstituted sulfones may include sulfolane, methyl ethyl sulfone, methyl isopropyl sulfone, or any combination thereof. The disubstituted sulfones may have the following structure:

[00421 Tetrasubstituted silanes may be substituted at the silicon atom and/or each oxygen atom. Tetrasubstituted silanes may include triethyoxymethyl silane, trimethoxymethylsilane, or any combination thereof. The tetrasubstituted silanes may have the following structure:

where each R3 may independently comprise a hydrogen atom, a C1-12 alkyl group that may be linear or branched, a hetero atom, a hetero-alkyl group, C1-12 alkoxy group that may be linear or branched, a hetero atom, a hetero-alkyl group, or any combination thereof. Further illustrations of suitable solvents and diluents are described in U.S. Pat. No. 10,367,232 and copending U.S. Provisional Application 63/435,662 incorporated herein by reference. [0043] The lithium salt may be any suitable lithium salt such as those known in the art. Typically, the lithium salt may have a solubility in the solvating solvent of about 1 M or more, about 3 M or more, or about 5 M or more. The lithium salt may have a solubility in the solvating solvent of about 20 M or less, about 15 M or less, or about 10 M or less. The lithium salt may be present in a concentration of about 3.5 M or less, about 2.0 M or less, or about 1.5 M or less. The lithium salt and combination of diluent/solvating solvent may be present in a molar ratio of about 1:2 or more, 1:2.6 or more, or 1:3.2 or more. The lithium salt and combination of diluent/solvating solvent may be present in a molar ratio of about 1:6 or less, about 1:5 or less, or about 1:4.

[0044] The lithium salt may include one or more of (oxalato)borate (LiBOB), lithium bis(pentafluoroethylsulfonyl)imide (Li- BETI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium tetrafluoroborate (LiBF4), lithium trifluoromethanesulfonate (LiTriflate), lithium hexafluoroarsenate (LiAsFe), lithium bis(trifluoromethanesulfonimide) (LiTFSI), and lithium hexafluoro- phosphate (LiPFe), lithium nitrate (LiNO₃), LiNCSCFCFiJi, LiN(SO2F)2, LiCF₃SO₃, LiCICL, lithium difluoro oxalato borate anion (LiDFOB), Lil, LiBr, LiCl, LiOH, LiSCU, or any combination thereof.

[0045] In some examples, another salt may be included in the electrolyte, such as another alkali metal salt, an alkaline earth metal salt, or any combination thereof. For example, the lithium salt may include a sodium salt, a magnesium salt, a mixture of lithium and sodium salts, a mixture of lithium and magnesium salts, a mixture of lithium, magnesium, and sodium salts, a mixture of sodium and magnesium salts, or any combination thereof. For example, the lithium salt may include one or more of sodium bis(fhiorosulfonyl)imide (NaFSI), sodium bis(trifhioromethylsulfonyl)imide (NaTFSI), sodium bis(oxalato)borate (NaBOB), NaFSI, NaTFSI, any lithium salt, or any combination thereof.

[0046] Other exemplary LHCE combinations may include salt comprising lithium bis(fhiorosulfonyl)imide (LiFSI) , lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), sodium bis(fluorosulfonyl)imide (NaFSI) , sodium bis(trifhioromethylsulfonyl)imide (NaTFSI), lithium bis(oxalato)borate (LiBOB) , LiPF₆ , LiAsF₆ , LiN(SO₂CF₃)₂ ,LiN(SO₂F)₂ , LiCF₂SO₃ , LiC10₄ , lithium difluoro oxalato borate anion ( LiDFOB ), Lil, LiBr, LiCl, LiOH, LiNO₃, LiSO4 , or any combination thereof, a solvating solvent comprising dimethoxyethane (DME), 1 ,2-diethoxyethane (DEE), dimethylcarbonate (DMC) , 1 , 3 - dioxolane (DOL) , ethyl methyl carbonate (EMC), diethyl carbonate (DEC) , dimethyl sulfoxide (DMSO) , ethyl vinyl sulfone (EVS) , tetram- ethylene sulfone (TMS) , ethyl methyl sulfone (EMS), ethylene carbonate (EC) , vinylene carbonate (VC), fluorocthylcnc carbonate (FEC), 4 - vinyl- l,3-dioxolan-2-onc, dimethyl sulfone, methyl butyrate, ethyl propionate, trimethyl phosphate, triethyl phosphate, gamma-butyrolactone, 4-methylene-l,3-dioxolan-2-one, methylene ethylene carbonate (MEC) , 4,5-dimethylene-l,3- dioxolan-2-one , allyl ether , triallyl amine , triallyl cyanurate , triallyl isocyanurate or any combination thereof (the salt being present at a molar ratio of salt/solvating solvent of about 0.7 to 1.5) and a diluent comprising l,l,2,2-tetrafluoroethyl-2,2,2,3-tetrafluoropropyl ether (TTE), bis(2,2,2-trifluoroethyl) ether (BTFE), 1 , 1 ,2,2-tetrafluoroethyl ether, 1, 2-(l, 1,2,2,- - tetrafluoroethoxy) ethane (TFEE); 1,3-(1,1,2,2-Tetrafluoroethoxy)propane (TFEP), 1, 1,2,2, - tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE), methoxynonafluorobutane ( MOFB ) , ethoxynonafluorobutane ( EOFB ) , or any combination thereof.

[0047] Particular useful LHCEs are comprised of the following combinations: a lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), 1,1,2,2-tetrafluoroethyl 2, 2,3,3- tetrafluoropropyl ether (TTE) combination; LiFSI, DME, 1,2-(1,1,2,2-Tetrafluoroethoxy)ethane (TFEE) combination; LiFSI, 1 ,2-Diethoxyethane (DEE), TTE combination, and LiFSI, DEE, TFEE combination. The molar ratios of these may be (salt/solvating solvent/diluent) 110.2/1.2+0.3/312.

[0048] The electrolyte is also comprised of a polymerizable aromatic compound (PAC). Herein a PAC is an aromatic compound that may be polymerized and generally is comprised of a 5 member aromatic ring having at least one heteroatom, which is desirably nitrogen. The PAC may be a pyrrole, indole, or any combination thereof. The pyrrole and indole may be represented by:

Where each R is H or a Ci to C36 hydrocarbyl group. Desirably, R is H or has 1 or 2 to 20 or 10 carbons and may be aromatic, aliphatic or combination thereof and may be comprised of one or more heteroatoms as described herein. Desirably, if a heteroatom is present it comprises one or more oxygens forming one or more carbonyl or ether groups.

[0049] Examples of pyrroles and indoles may include lH -indole, I -methyl- 1 H -indole, 2- Methylindole, 3-Methylindole, 5-methyl-l H -indole, 1,2-Dimethylindole, 1,3-Dimethyl-1H- indole, 2-(Trifhioromethyl)indole, 1 -heptyl- 1 H -indole. 5-cholro-17/-indole, 4-fluoro-l H -indole, 5-fluoro-lH -indole, 6-fluoro-l H -indole, l/Z-indole-5-carbonitrile, 2-phenyl-l -H -indole, 5- methoxy-1 H -indole, lH -pyrrole, N -methylpyrrole, 2-methyl-l H -pyrrole, 3-methyl-lH -pyrrole, 2,5-dimethyl-lH -pyrrole, 3,4-dimethyl-lH -pyrrole, 2,3-dimethyl-l H -pyrrole, 2,4-dimethyl-lH - pyiTole, 2-ethy 1-1 H -pyrrole, methyl lH-pyrrole-2 carboxylate, tert-Butyl 1 -pyrrolecarboxylate (N- Boc pyrrole), l-ethyl-2methyl-lH-pyrrole, 2-(Trifluoroacetyl)pyrrole, N-phenylpyrrole and N- Boc-pyrrole-2-boronic acid MIDA ester.

[0050] The amount of PAC present in the electrolyte may be any useful amount, but generally is from about 0.05% or 0.1% to 2%, 1.5%, 1% or 0.75% by weight of the electrolyte.

[0051] The battery is comprised of separator, which may any suitable separator such as those known in the art. Illustratively, the separator may have one or more layers that may be bonded together. Examples of suitable separators includes a poly- imide, polyolefin (such as polypropylene), polyethylene terephthalate, ceramic-coated polyolefin, cellulose, or a mixture of two or more thereof. Such materials may be in the form of microfibers or nanofibers. The separator may include a combination of microfibers and nanofibers. In certain embodiments, the separator includes polyethylene terephthalate microfibers and cellulose nanofibers. [0052] A separator having multiple layers may be used, each of which may have differing melting points. However, one of these layers may have a melting point lower than the other layer and may serve the purpose of a shutdown separator. For example, an inner layer of a separator may have a melting point of approximately 130° C. and a layer that may have a melting point of approximately 160°C. In this illustration, the inner layer would melt at a temperature of about 130° C, preventing ion flow in the battery but maintaining physical separation between the anode and cathode to prevent shorting. An example of a useful material having a melting point of approximately 130° C is high density polyethylene or ultra high molecular weight polyethylene. Examples of useful materials that have a melting point of >200° C include polyimide, polyethylene terephthalate, cellulose, aramid fibers, ceramics, and combinations thereof. In certain embodiments, the multiple separator layers with different melting points may be laminated together to form a single multilayer composite separator. In certain embodiments, a layer of positive temperature coefficient material may be used.

Illustrations

[0053] Illustration 1 is a battery comprised of a separator, a cathode, an anode absent a lithium intercalation material, and an electrolyte comprised of a polymerizable aromatic compound.

[0054] Illustration 2 is the battery of illustration 1, wherein the polymerizable aromatic compound is present in an amount of 0.05% to 2% by weight of the electrolyte.

[0055] Illustration 3 is the battery of either illustration 1 or 2, wherein the electrolyte is a localized high salt concentration electrolyte (LHCE) being a solution comprised of a solvating solvent, diluent and a dissolved lithium salt, the lithium salt being at least 5 times more soluble in the solvating solvent than the diluent.

[0056] Illustration 4 is the battery of any one of the preceding illustrations, wherein the anode is a transition metal, non intercalating carbon or combination thereof.

[0057] Illustration 5 is the battery of any one of the preceding illustrations, wherein the polymerizable aromatic compound comprises a pyrrole.

[0058] Illustration 6 is the battery of illustration 5, wherein the pyrrole may be represented by:

where each R is independently H or a Cl to C36 hydrocarbyl group.

[0059] Illustration 7 is the battery of any one of the preceding illustrations, wherein the polymerizable aromatic compound is comprised of an indole.

[0060] Illustration 8 is the battery of illustration 7, wherein the indole is represented by:

where each R is independently H or a Cl to C36 hydrocarbyl group.

[0061] Illustration 9 is the battery of any one of the preceding illustrations, wherein the polymerizable aromatic compound is comprised of one or more of IH-indole, 1 -methyl- IH-indole, 2-Methylindole, 3-Methylindole, 5-methyl- IH-indole, 1 ,2-Dimethylindole, 1,3-Dimethyl- IH- indole, 2-(Trifluoromethyl)indole, 1 -heptyl- IH-indole, 5-cholro- IH-indole, 4-fluoro- IH-indole, 5 -fluoro- IH-indole, 6-fluoro- IH-indole, lH-indole-5-carbonitrile, 2-phenyl-l-H-indole, 5- methoxy- IH-indole, IH-pyrrole, N methylpyrrole, 2-methyl-lH-pyrrole, 3-methyl-lH-pyrrole, 2,5-dimethyl-lH-pyrrole, 3,4-dimethyl-lH-pyrrole, 2,3-dimethyl-lH-pyrrole, 2,4-dimethyl-lH- pyrrole, 2-ethyl-lH-pyrrole, methyl lH-pyrrole-2 carboxylate, tert-Butyl 1 -pyrrolecarboxylate (N- Boc pyrrole), l-ethyl-2methyl-lH-pyrrole, 2-(Trifluoroacetyl)pyrrole, N-phenylpyrrole and N- Boc-pyrrole-2-boronic acid MIDA ester. [0062] Illustration 10 is the battery of any one of the preceding illustrations, wherein the LHCE is comprised of a lithium bis(fluorosulfonyl)imidc (LiFSI), dimcthoxycthanc (DME), 1,1, 2, 2- tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) combination; LiFSI, DME, 1, 2-(l, 1,2,2- Tetrafluoroethoxy)ethane (TFEE) combination; LiFSI, DME, lH,lH,5H-octafluoropentyl 1,1, 2, 2, -tetrafluoroethyl ether (OFPTFEE) combination; LiFSI, DME, 1, 3-(l, 1,2,2- Tetrafluoroethoxy)propane (TFEP) combination; LiFSI, DEE, TTE combination; LiFSI, DEE, TFEE combination; LiFSI, DEE, OFPTFEE combination; or LiFSI, DEE, TFEP combination.

[0063] Illustration 11 is the battery of any one of the preceding illustrations, wherein the cathode is a layered oxide.

[0064] Illustration 12 is the battery of illustration 10, wherein the layered oxide is comprised of Ni, Mn, Co.

[0065] Illustration 13 is the battery of illustration 11, wherein the Ni is at least 50% by mole of the Ni, Mn and Co in the layered oxide.

[0066] Illustration 14 is the battery of any one of the preceding illustrations, wherein the polymerizable aromatic compound has polymerized.

[0067] Illustration 15 is the battery of illustration 14, wherein the anode has a coating of lithium.

[0068] Illustration 16 is a method of forming a battery comprising, incorporating a polymerizable aromatic compound into an electrolyte of an uncharged battery comprised of a separator, a cathode, an anode absent a lithium intercalation material and an electrolyte, and charging the battery to a voltage sufficient to polymerize the polymerizable aromatic compound to form the battery.

[0069] Illustration 17 is the method of illustration 16, wherein the cathode is comprised of a lithium metal phosphate.

[0070] Illustration 18 is the method of illustration 16, wherein the cathode is comprised of a lithium metal oxide.

[0071] Illustration 19 is the method of any one of illustrations 16 to 18 wherein, the voltage is at least 3.5 V.

[0072] Illustration 20 is the method of any one of illustrations 16 to 19, wherein the electrolyte is a localized high salt concentration electrolyte. [0073] Illustration 21 is the method of any one of illustrations 16 to 20, wherein the anode consists essentially of a transition metal.

[0074] Illustration 22 is the method of illustration 21, wherein the anode is comprised of copper. [0075] Illustration 23 is the method any one of illustrations 16 to 22, wherein the battery is an anode-less battery.

[0076] Illustration 24 is the method of any one of illustrations 16 to 20, wherein the battery is a lithium metal battery.

[0077] Illustration 25 is the battery of any one of illustrations 1-15, wherein the battery is an anodeless battery.

[0078] Illustration 26 is the battery of any one of illustrations 1-15, wherein the battery is a lithium metal battery.

Examples

[0079] The following examples are intended to be illustrative and do not unduly limit the scope of the disclosure.

[0080] Battery cells are made with the same materials other than different electrolytes including different PACs. Battery cells are formed in a high purity Argon filled glove box (M-Braun, 02 and humidity content < 0.1 ppm). In the case of the cathode, a commercial high Ni NMC (Ni content >80%, referred to herein as NMC811)) active material is mixed with poly vinylidene fluoride (PVDF), carbon black powder, and liquid l-methyl-2-pyrolidinone (NMP) to form a sluny. The resulting slurry is deposited on an aluminum current collector and dried to form a composite cathode film. In the case of the anode current collector, a bare copper metal foil without present of any other active anode materials was used as anode. Each battery cell includes a composite cathode film deposited on a current collector, a polypropylene separator, and anode current collector (anode-less).

[0081] A localized high salt concentration electrolyte is prepared by molar ratio. For example, the electrolyte referred to as “control” is prepared by mixing lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), and 1 , 1 ,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) in a 1/1.2/3 molar ratio, which unless otherwise stated is the electrolytes that are used in the Examples and Comparative Examples. Other electrolytes referred to as control electrolytes mixes LiFSI, DME, 1,2-(1,1,2,2-Tctrafluorocthoxy)cthanc (TFEE) in a 1/1.2/3 molar ratio, and LiFSI, 1,2- Diethoxyethane (DEE), TFEE in a 1/1.2/3 are also tested showing the applicability of the PACs in differing electrolyte formulations. The PACs are added by weight ratio (0.2, and 0.5%). The amount of electrolyte used is a lean amount to accentuate the effect of the PACs on the performance of the battery. A lean electrolyte amount is an amount of electrolyte that is about 20% greater than the amount of open porosity in the cathode and anode (noting there is no open porosity in the Examples battery cells). The amount of electrolyte in the battery may be any useful such as from lean to 20X or 10X the volume of open porosity in the cathode and anode of the battery. The battery cell is then sealed and initially cycled at ambient temperature using 0.1C charge to upper cutoff voltage 4.3V followed by constant voltage hold until the current dropped to 0.05C and then discharged to 3.5V or 3.6V using 0.1C constant current. The cycle was repeated one more time prior to being cycled at 0.2C/0.5C for subsequent cycles. All cycling was performed at about 25 °C.

[0082] Four PACs, pyrrole, N-Methylpyrrole, 1 -Phenylpyrrole and N-Boc-pyrrole (tert-butyl pyrrole- 1 -carboxylate), are selected and their chemical structures are shown in Figure 1 along with their cycling performance compared to the same battery cell without the PAC (Comparative Example 1 also referred to as control). The battery with the control electrolyte without additives exhibited a capacity retention of 80% after 92 cycles, while the addition of 0.2% or 0.5% of the pyrrole-type additives significantly improved the cycling stability, except for 0.2% of pyrrole, which showed similar performance as the control. The PACs also affected the capacity at the third cycle, as the higher concentration of additives resulted in lower capacity value. This may be attributed to a higher lithium loss or forming thicker SEI during initial charging and polymerization of the PAC.

[0083] Indole and its derivative, 1-Methylindole PACs are result in similar performance as the pyrrole PACs. The results are shown in Figure 2. As observed with the pyrrole-type PACs, the cycling performance is significantly improved by the addition of indole and 1-Methylindole. Both of these exhibit better cycling performance at a concentration of 0.2 wt%.

[0084] Two differing electrolytes, LiFSI/DME/TFEE = 1/1.2/3 and LiFSI/DEE/TFEE = 1/1.2/3 are mixed with and without a PAC (N-Boc-pyrrole). Control is a battery without the PAC added. Figure 3 shows the improvement of cycle life of a battery after adding the PAC to the LiFSI/DME/TFEE = 1/1 .2/3 electrolyte. Figure 4 shows the improvement of the cycle life of a battery after adding the PAC to the LiFSI/DEE/TFEE = 1/1.2/3 electrolyte. These results demonstrate the compatibility of PACs with various LHCEs. The initial capacity decay was significantly reduced by the addition of the PAC, indicating a lower lithium inventory loss, which may be due to the reduction of side reactions.

[0085] The effect of a PAC on the cycle life of anode-free cells was demonstrated in a single-layer pouch cell (SLP). Figure 5 compares the capacity retention of the cells with and without 0.5 wt% of N-Methylpyrrole as the PAC in an electrolyte (LiFSI/DME/TTE = 1/1.2/3). The control cell reached 80% capacity retention after 179 cycles. In contrast, the cell with N-Methylpyrrole shows improved cycling stability and achieved 80% capacity retention after 201 cycles. The result demonstrates that the PAC is compatible with a larger cell format.

[0086] The robustness of the PACs are evaluated with >2 Ah multi-layer pouch cell (MLP) with a different cathode chemistries. The cathode material of MLP was changed from NMC811 to LiNio.6Mno.2Coo.2O2 (NMC622) to evaluate the compatibility of the additives with different cathode chemistries. The electrolyte with 0.5 wt% of N-Methylpyrrole as an additive shows a remarkable improvement in the cycle life of the MLPs, reaching 80% capacity retention after 262 cycles. On the other hand, the control electrolyte without additive exhibited only 164 cycles shown in Figure 6. The result demonstrates that the polymerizable additives are versatile and can work well with different cathode materials such as (NMC811 and NMC622) and cell sizes.

[0087] To gain a further understanding of the enhancement of cycle performance in anode-free lithium metal batteries, N-Methylpyrrolidine and N-Methylpiperidine are tested (Comparative Examples). These compounds exhibit structural similarities to N-methylpyrrole but lack the capability for polymerization due to the lack of unsaturated bonds carbon bonds (as depicted in Figure 7). By using a 0.5 wt% concentration of non-polymerizable additives, the anode-free Li metal battery displayed around 35 cycles, a notably diminished performance when contrasted with the control electrolyte. This data indicates that the improvement of cycling performance may be attributed at least in part to the polymerization nature of the additive rather than the presence of the amine group without the aromatic ring. In contrast, anode-less batteries are made in the same manner as above, except that the polymerizable additive is boron allyloxide. The electrolyte is LiFSI/DME/TEE = 1/1.2/3 molar ratio, and the cathode is 811 NMC. The results of the battery cycling are shown in Figure 8, where it is readily apparent the cycling of these anode-less batteries arc not improved with such a polymerizable additive (i.c., aliphatic).

[0088] Lithium metal batteries are produced and tested in a similar fashion as described for the anode-less batteries (NMC-811), except that the anode is further comprised of a 20 micrometer thick layer on the current collector. From the results in Figure 9, the cycling is improved about 10% on average, but is more sensitive to the amount of the PAC used and is not as consistently improved as for the anode-less batteries, the anode-less batteries typically having an improvement of at least 15%, 20%, 30%, 40% or even 50% improvement in cycles prior to reaching 80% of capacity.

Claims

CLAIMS What is claimed is:

1. A battery comprised of a separator, a cathode, an anode absent a lithium intercalation material, and an electrolyte comprised of a polymerizable aromatic compound.

2. The battery of claim 1, wherein the polymerizable aromatic compound is present in an amount of 0.05% to 2% by weight of the electrolyte.

3. The battery of claim 1, wherein the electrolyte is a localized high salt concentration electrolyte (LHCE) being a solution comprised of a solvating solvent, diluent and a dissolved lithium salt, the lithium salt being at least 5 times more soluble in the solvating solvent than the diluent.

4. The battery of claim 1, wherein the anode is a transition metal, non-intercalating carbon or combination thereof.

5. The battery of claim 1, wherein the polymerizable aromatic compound comprises a pyrrole.

6. The battery of claim 5, wherein the pyrrole may be represented by:

where each R is independently H or a Ci to C36 hydrocarbyl group.

7. The battery of claim 1, wherein the polymerizable aromatic compound is comprised of an indole.

8. The battery of claim 7, wherein the indole is represented by:

where each R is independently H or a Ci to C36 hydrocarbyl group.

9. The battery of claim 1, wherein the polymerizable aromatic compound is comprised of one or more of I H -indole, 1 -methyl- 1 H -indole, 2-Methylindole, 3- Methylindole, 5-methyLl H -indole, 1 ,2-Dimethylindole, 1,3-Dimethyl-lH-indole, 2- (Trifluoromethyl)indole, 1 -heptyl- 1 H -indole, 5-cholro-l H -indole, 4-fluoro-l H -indole, 5- fluoro-1 H -indole, 6-fluoro-lH -indole, lH -indole-5-carbonitrile, 2-phenyl-l -H -indole, 5- methoxy-1 H -indole, l/Z-pyrrole, N-methylpyrrole, 2-methyl-lH -pyrrole, 3-methyl-lH - pyrrole, 2, 5-dimethy 1-1 H -pyrrole, 3,4-dimethyl-l H -pyrrole, 2, 3 -dimethyl- 1 H -pyrrole, 2,4-dimethyl- 1 H -pyrrole, 2-ethyl-l H -pyrrole, methyl lH-pyrrole-2 carboxylate, tert- Butyl 1 -pyrrolecarboxylate (N-Boc pyrrole), l-ethyl-2methyl-lH-pyrrole, 2- (Trifluoroacetyl)pyrrole, N-phenylpyrrole and N-Boc-pyrrole-2-boronic acid MIDA ester.

10. The battery of claim 3, wherein the LHCE is comprised of a lithium bis(fluorosulfonyl)imide (LiFSI), dimethoxyethane (DME), 1 , 1 ,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) combination; LiFSI, DME, 1,2-(1, 1,2,2- Tetrafluoroethoxy)ethane (TFEE) combination; LiFSI, DME, lH,lH,5H-octafluoropentyl 1,1, 2, 2, -tetrafluoroethyl ether (OFPTFEE) combination; LiFSI, DME, 1,3-(1, 1,2,2- Tctralluorocthoxyjpropanc (TFEP) combination; LiFSI, DEE, TTE combination; LiFSI, DEE, TFEE combination; LiFSI, DEE, OFPTFEE combination; or LiFSI, DEE, TFEP combination.

11. The battery of claim 1, wherein the cathode is a layered oxide.

12. The battery of claim 11 , wherein the layered oxide is comprised of Ni,

Mn, Co.

13. The battery of claim 12, wherein the Ni is at least 50% by mole of the Ni, Mn and Co in the layered oxide.

14. The battery of claim 1, wherein the polymerizable aromatic compound has polymerized.

15. The battery of claim 14, wherein the anode has a coating of lithium.

16. A method of forming a battery comprising,

(i) incorporating a polymerizable aromatic compound into an electrolyte of an uncharged battery comprised of a separator, a cathode, an anode absent a lithium intercalation material and an electrolyte, and

(ii) charging the battery to a voltage sufficient to polymerize the polymerizable aromatic compound to form the battery.

17. The method of claim 16, wherein the cathode is comprised of a lithium metal phosphate.

18. The method of claim 16, wherein the cathode is comprised of a lithium metal oxide.

19. The method of claim 16 wherein, the voltage is at least 3.5 V.

20. The method of claim 16, wherein the electrolyte is a localized high salt concentration electrolyte.

21. The method of claim 16, wherein the anode consists essentially of a transition metal.

22. The method of claim 21, wherein the anode is comprised of copper.

23. The method of claim 16, wherein the battery is an anode-less battery.

24. The method of claim 16, wherein the battery is a lithium metal battery.

25. The battery of any one of claim 1-15, wherein the battery is an anode-less battery.

26. The battery of any one of claims 1-15, wherein the battery is a lithium metal battery.