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US 20110281 177A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0281177 A1 Xu (43) Pub. Date: Nov. 17, 2011

(54) NONAQUEOUSELECTROLYTESOLVENTS (52) U.S. Cl...... 429/330; 429/336: 429/338; 429/340 AND ADDITIVES (75) Inventor: Kang Conrad Xu, North Potomac, (57) ABSTRACT MD (US) A series of polar and aprotic organic molecules, which, when used as solvents or additives in nonaqueous , (73) Assignee: s SENSE Rented afford improved performance for electrochemical cells that Adelphi, MD (US) operate at high Voltages. These polar and aprotic solvents or s additives may contain at least one unsaturated functionality (21) Appl. No.: 12/987,241 per molecule. The unsaturated functionality is conjugated with the polar functionality of the molecule. The unsaturated (22) Filed: Jan. 10, 2011 functionality that is either a double or triple bond could be between -carbon, or between carbon-heteroatom, or Related U.S. Application Data between hetroatom-heteroatom. Nonaqueous Solutions are provided comprising one or more salts (60) Provisional application No. 61/334.265, filed on May dissolved in the mixture solvents, which comprises, in all 13, 2010. possible ratios, at least one of the polar, aprotic and unsatur O O ated solvent or additives, one or more cyclic carbonic diesters Publication Classification Such as , and one or more acyclic carbonic (51) Int. Cl. diesters such as , diethyl carbonate, and HIM IO/02 (2006.01) ethylmethyl carbonate.

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NONAQUEOUSELECTROLYTE SOLVENTS potentials become focus of research efforts, and the passiva AND ADDITIVES tion layer formed by these solvents or additives of the con ventional solutions can no longer ensure the stable operation CROSS REFERENCE TO RELATED of the cell chemistry. APPLICATION 0001. This application claims the benefit of U.S. Provi SUMMARY sional Patent Application No. 61/334.265 filed on May 13, 2010, the complete disclosure of which, in its entirety, is 0009. In view of the foregoing, an embodiment herein herein incorporated by reference. provides an electrochemical device comprising a negative GOVERNMENT INTEREST electrode of a metal and an electrode active material that reversibly intercalates and de-intercalates cations; a positive 0002 The invention was made in a U.S. Army laboratory electrode comprising an electrode active material that revers and so the embodiments described herein may be manufac tured, used, sold, imported and/or licensed by or for the ibly intercalates and de-intercalates any of cations and United States Government without the payment of royalties anions; a barrier comprising any of a porous polyolefin sepa thereon. rator and a gellable polymer film separating the negative electrode from the positive electrode; and a nonaqueous elec BACKGROUND trolyte contacting the negative electrode and the positive elec trode, the nonaqueous electrolyte comprising at least one 0003 1. Technical Field 0004. The embodiments herein generally relate to non unsaturated molecule acting as a solvent or an additive and aqueous electrolytes that Support the operation of electro comprising any of the following structures (1) through (8): chemical devices with high cell Voltages, and more particu larly, to the solvents and additives that form the nonaqueous electrolytes and can stably support the cell chemistry of the (1) electrochemical devices with high cell Voltages. 0005 2. Description of the Related Art C X C 0006. The electrochemical devices that output high cell R1 NO O m\R2 voltages utilize nonaqueous and aprotic solvents to dissolve rt) the conducting salts, because these solvents are able to afford (2) the stability against the oxidative or reductive reactions H H incurred by electrode surfaces of extreme potentials. Because (e }-or-to-(-)-pi the electrolyte components are almost never thermodynami (O), cally stable on the strongly reductive surfaces of anode or strongly oxidative Surfaces of cathode, the electrochemical (CH2) stability is rather attained through the passivation of the elec trode surfaces. The above passivation is realized by the initial decompositions of solvents in trace amount and the concomi (3) H tant deposition of these decomposition products which deac R2 C R4 tivate the catalytic sites of the electrode surfaces. Generally, all electrochemical devices that produce cell Voltages higher than 3.0 V, and particularly in lithium-based battery chemis tries, certain solvents were developed in the conventional R Z R3 Solutions so that their decomposition products on anode and (4) cathode Surfaces are able to form dense and protective passi H vation layers. These solvents include ethylene carbonate R2 C R4 (EC), vinylene carbonate (VC), and other polar and aprotic Solvents and/or additives, and have become indispensable " components in commercial Li batteries. In other words, R Z R3 the conventional Liion batteries operate at high Voltages (3-5 (5) V), which were made possible by the passivation film formed R-Z-R2 on the surfaces of the anode and/or cathode. While providing protection, the film also presents resistance to the kinetics of (6) the cell chemistry, rendering poor power density as well as H poor low temperature performances. N =c-(-)- 0007. However, the passivation layers formed by the 2 (7) above-described solvents and/or additives in conventional R electrolytes also constitute the most resistive component in the electrochemical cells, which not only compromises the cell performances at low temperatures but also impose the R3-N=C ) kinetic restrictions on the power density of the devices at room temperature. } :)iii. 0008 Furthermore, as the battery chemistries of higher R1 energy density are being pursued, cathode materials of higher US 2011/0281 177 A1 Nov. 17, 2011

approximately 10% to 100% with respect to a total solvent -continued weight, wherein a concentration of the additive ranges from (8) approximately 0.005% to 10% with respect to the total sol vent weight, and wherein a concentration of the lithium CCEO A ranges from approximately 0.5 to 3.0 mole/liter. R2 0013 The active material of the negative electrode may comprise any of lithium metal, lithium alloys with other met wherein i, j, and k are integers independent from each other als, carbonaceous materials with various degrees of graphiti and range from 0 to 1, andl, m, and nare integers independent Zation, lithiated metal , and chalcogenides. Also, the from each other and range from 0 to 2, respectively, wherein active material of the positive electrode may comprise any of R" are saturated substituents comprising hydrogen, C1-C10 transition metal oxides, metalphosphates, chalcogenides, and normal or C3-C10 branched alkyls, halogen radicals, carbonaceous materials with various degree of graphitization. alkoxyls, thioalkoxyls, aromatic radicals, and unsaturated Substituents comprising any of the radicals in the following 0014) Another embodiment provides an electrolyte solu structures (9) through (11): tion and a method of forming the same comprising at least one lithium salt and a solvent system mixed with at least one lithium salt, the solvent system of a plurality of polar and (9) aprotic organic molecules comprising at least one unsaturated \ /R5 functionality per molecule that is conjugated with a polar CFC functionality of the molecule, wherein at least one unsatur A. V R4 R6 ated functionality comprises any of a double bond and a triple (10) bond between any of a carbon-carbon chain, a carbon-het -CEC-R eroatom chain, and a hetroatom-heteroatom chain; at least (11) one cyclic carbonic diester; and at least one acyclic carbonic \ /R5 diester. Preferably, the solvent system comprises any of the CECEC A V structures (1) through (8): R4 R6

(0010 wherein Rare selected from any of H radical, (1) C1-C10 normal or C3-C10 branched alkyls, halogen radicals, alkoxyls, thioalkoxyls, and aromatic radicals. C X C 0011. The nonaqueous electrolyte may comprise at least R1 NO rto)O m\R2 one of the R' substituents selected from the structures (9) through (11). Additionally, the nonaqueous electrolyte may (2) comprise one of the structures (1), (2), (3), (4), (5), (6), or (7). H H and wherein at least one of l, m, and n equals Zero. Further R ( }-or-to-(-)-pi more, the nonaqueous electrolyte may comprise only struc (O), ture (1), wherein X comprises sulfonyl, and wherein one of i or equals Zero. Moreover, the nonaqueous electrolyte may (CH2) comprise one of the structures (1) or (2), wherein X comprises Sulfonyl, carbonyl, thionyl orphosphoryl, whereini, j, k, l, m, (3) and n equal zero, and wherein at least one of R' is selected H from radicals comprising any of structures (9) through (11). R2 C R4 Also, the nonaqueous electrolyte may comprise a solvent containing at least one unsaturated molecule. Furthermore, the nonaqueous electrolyte may comprise a co-solvent con taining any of cyclic and acyclic carbonates and carboxylic R Z R3 esters containing any of ethylene carbonate, propylene car (4) bonate, vinyl carbonate, dimethyl carbonate, diethyl carbon H ate, ethylmethyl carbonate, Y-butyrolactone, methylbutyrate, R2 C R4 ethylbutyrate, and mixtures thereof. 0012. Alternatively, the nonaqueous electrolyte may com " prise a co-solventin mixture with at least one of the molecules R Z R3 ofstructures (1) through (8) as a co-solvent oran additive. The (5) nonaqueous electrolyte may be a lithium salt comprising any R-Z-R2 of lithium hexafluorophosphate, lithium fluoro(perfluoro (6) alkyl)phosphate, lithium tetrafluoroborate, lithium hexafluo H roarsenate, lithium perchlorate, lithium tetrahloaluminate, NEC-C-R lithium tris(trifluoromethanesulfonyl)methide, lithium per fluoroalkylsulfonate, lithium arylsulfonate, lithium bis(ox alato)borate, lithium difluoro(oxalato)borate, and mixtures thereof. Preferably, a concentration of the solvent ranges from US 2011/0281 177 A1 Nov. 17, 2011

0018 FIGS. 1A through 1K are molecular structures used -continued in accordance with the embodiments herein; 2 (7) 0019 FIG. 2 is a graphical representation illustrating a R cyclic voltametry of a Pt working electrode measured in vari ous electrolyte solvents according to the embodiments ki) herein; R3-N=C " 0020 FIG. 3 is a table summarizing selected electrolyte Solutions formulated by using the solvents and additives ; :)iii. according to the embodiments herein; R1 0021 FIG. 4A is a perspective view of an electrochemical (8) device according to the embodiments herein; R 0022 FIG.4B is a front view of the electrochemical device CECEO of FIG. 4A according to the embodiments herein; and R2 0023 FIG. 5 is a flow diagram illustrating a method according to the embodiments herein. wherein i, j, and k are integers independent from each other DETAILED DESCRIPTION OF PREFERRED and range from 0 to 1, andl, m, and nare integers independent EMBODIMENTS from each other and range from 0 to 2, respectively, wherein R" is any saturated substituents comprising hydrogen, 0024. The embodiments herein and the various features C1-C10 normal or C3-C10 branched alkyls, halogen radicals, and advantageous details thereof are explained more fully alkoxyls, thioalkoxyls, aromatic radicals, and unsaturated with reference to the non-limiting embodiments that are illus Substituents comprising any of the radicals in the following trated in the accompanying drawings and detailed in the fol structures (9) through (11): lowing description. Descriptions of well-known components and processing techniques are omitted so as to not unneces sarily obscure the embodiments herein. The examples used (9) herein are intended merely to facilitate an understanding of R5 ways in which the embodiments herein may be practiced and \CRC / to further enable those of skill in the art to practice the A V embodiments herein. Accordingly, the examples should not R4 R6 be construed as limiting the scope of the embodiments herein. CEC-R (10) 0025 Before describing the embodiments herein in detail, it is to be understood that the terminology used herein is for R5 (11) the purpose of describing particular embodiments only, and is \ / CECRC not intended to be limiting. Therefore, the following terms are A V defined in accordance with the embodiments herein: R4 R6 0026. The term “unsaturated functionality” refers to either double or triple bond that could be hydrogenated under cata wherein R'' are selected from Hradical, C1-C10 normal or lytic conditions. C3-C10 branched alkyls, halogen radicals, alkoxyls, thio (0027. The term “polar functionality” refers to either elec alkoxyls, or aromatic radicals. tron-withdrawing groups such as, but not limited to, carbonyl, 00.15 Preferably, the solvent system comprises any of (i) a nitrile, Sulfonyl and Sulfone, or electron-donating groups neat solvent with at least one additive, (ii) a neat solvent Such as, but not limited to, alkyl, alkoxy, thioalkoxy, phenyl, without an additive, (iii) a mixture of at least two solvents phenolic, and thiophenolic. with at least one additive, and (iv) a mixture of at least two 0028. The term "hetero-atom” refers to non-carbon atoms solvents without an additive. Furthermore, the mixing of the that are able to form multiple bonds with carbon or among Solvent system with at least one lithium salt may form any of themselves, which may include, but are not limited to, sulfur, methylallyl Sulfone, methylallyl Sulfonate, methylpropargyl , , and phosphorus. Sulfone, methylallenic Sulfone, methylacetylenic Sulfone, 0029. The term “solvents’ refers to molecular components methylpropargyl Sulfonate, methylacetylenic carbonate, of the electrolyte, whose concentrations are higher than 10% acetylenic butyrate, thiophene-1-, and . by weight. 0016. These and other aspects of the embodiments herein will be better appreciated and understood when considered in 0030. The term “additives' refers to the molecular com conjunction with the following description and the accompa ponents of the electrolyte, whose concentrations are lower nying drawings. It should be understood, however, that the than 10% by weight. following descriptions, while indicating preferred embodi 0031. The term “radicals' refers to atoms or molecules, ments and numerous specific details thereof, are given by way either inorganic or organic, which have unpaired electrons. of illustration and not of limitation. Many changes and modi 0032. The term “normal alkyl refers to unbranched, satu fications may be made within the scope of the embodiments rated hydrocarbon radicals, such as methyl, ethyl, n-propyl. herein without departing from the thereof, and the n-octyl and the like. embodiments herein include all Such modifications. 0033. The term “branched alkyl refers to saturated hydro carbon radicals that contain as least one secondary or tertiary BRIEF DESCRIPTION OF THE DRAWINGS carbon designated as “branch points'. Such as iso-propyl. 0017. The embodiments herein will be better understood sec-butyl, iso-pentyl, and the like. from the following detailed description with reference to the 0034. The term “skeleton refers to the main backbone of drawings, in which: a molecule that comprise either carbon or hetero-atoms. US 2011/0281 177 A1 Nov. 17, 2011

0035. The term “conjugated system” refers to a skeleton phosphoryl that possess alternating unsaturated bonds, so that the involved pi-electrons are delocalized. 0036. The term “neat solvent” refers to a solvent having the following properties: anion-solvating tendency, hydro gen-bonding acidity, and electrophilicity, and cation-solvat ing tendency, hydrogen-bonding basicity, and nucleophilic ity, respectively. Some examples of a neat Solvent include, but are not limited to, deionized or methanol. 0037. The embodiments herein provide new electrolyte solvents or additives that enable cell chemistries of high out put cell voltages. More specifically, the embodiments herein provide new solvents and additives, which, when used either as the bulk electrolyte solvents or co-solvents, or as additives in low concentrations, can form passivation layers on either or both anode and cathode surfaces, which not only are effec tively protective in wide temperature range, but also are con Y is a polar functionality selected from phosphinyl ductive and allow fast kinetics of the cell chemistry. The embodiments hereinformulate electrolyte solutions utilizing the solvents and additives, and provide electrochemical devices utilizing the electrolyte solutions. The devices that can be developed deliver Superior performances as compared 1N with the state-of-the-art technologies. 0038. The embodiments utilize one or more polar and aprotic organic compounds as either solvent or additive in the or phosphoryl nonaqueous electrolytes. More particularly, the embodiments herein utilize as either solvent or additive in the nonaqueous electrolytes one or more polar, aprotic and unsaturated organic compounds, which contain at least one unsaturated functionality per molecule. Still more particularly, the unsat urated functionality may include, but is not limited to, an unsaturated bond between carbon-carbon, or an unsaturated bond between carbon-heteroatom, or an unsaturated bond Z is a polar functionality selected from carbonyl between heteroatom-heteroatom. Still more particularly, the unsaturated functionality is located in a position that is con jugated with the polar functionality of the polar molecule. 0039 Referring now to the drawings, and more particu larly to FIGS. 1 through 5, where similar reference characters C denote corresponding features consistently throughout the figures, there are shown preferred embodiments. 0040. As a primary aspect of the embodiments herein, the thionyl new solvents or additives are constructed on the basis of the molecule structures 1 through 8, respectively shown in FIGS. 1A through 1H in which i, j, and k are integers independent O from each other and range from 0 to 1, and l, m, and n are integers independent from each other and range from 0 to 2. 1N). respectively, X is a polar functionality selected from carbonyl sulfonyl

(-S-), thionyl mercapto (-S-), or oxy (-O-), and R' are either saturated Substituents independently selected from hydrogen radicals, C1-C10 normal or C3-C10 branched alkyls, halogen radicals, alkoxyls, thioalkoxyls, or selected from the unsaturated Sub stituents in radical structures 9-11, respectively shown in FIGS. 1 I through 1 K, where R in turn are selected from US 2011/0281 177 A1 Nov. 17, 2011

hydrogen, C1-C10 normal or C3-C10 branched alkyls, halo Example 1 gen radicals, alkoxyls, thioalkoxyls, or aromatic radicals. Synthesis of Methylallyl Sulfone 0041 More preferentially but not intending to be limiting, the new solvents or additives of the embodiments herein are 0049 created from the structures of 1 through 8, in which at least one of R' is selected from the unsaturated substituents in O structures 9-11, respectively shown in FIGS. 1 I through 1K. 0042 Still more preferentially but not intending to be lim ic--,3 W n 4-ch 2 iting, in the unsaturated solvents or additives as described by O H structures 1-7, at least one of l, m, or n is 0, so that the unsaturated functionalities in radicals 9-11 are located on the 0050. To a flask containing 304.50g thiourea suspended in alpha-position to the polar groups in these molecules, and that 500 mL water, 190.36 g dimethylsulfate is added dropwise a conjugated skeleton is thus formed. under stirring. Upon completion of addition, the solution is 0043 Still more preferentially but not intending to be lim heated to reflux, and then 320 g NaOH dissolved in 500 mL water is gradually added. Under vehement stirring 484 g iting, the above described conjugated system could be either allylbromide is added dropwise. The organic phase of the electron-deficient or electron-rich. More specifically, the reactant is separated and then added dropwise to a mixture of polar functionality that conjugates with the unsaturated func 810 g 30% hydrogen peroxide and 1200 g glacier acetic tionalities could be either electron-pulling or electron-push with effective cooling and stirring. The resultant reactant, ing. The former includes, but is not limited to, carbonyl, after being concentrated to 50% of the original volume by nitrile, sulfonyl and sulfone. The latter includes, but is not evaporation, is subject to multiple extractions with chloro limited to, alkyl, alkoxy, thioalkoxy, phenyl, phenolic, and form. The combined extractions are subject to evaporation to thiophenolic. remove . Following drying the crude product over 0044 Still more particularly, the unsaturated functional activated molecular sieves, the solvent methylallyl sulfone is ities in the solvents include, but are not limited to, carbon obtained at 80% yield through distillation. carbon double bonds, carbon-carbon triple bonds, carbon Example 2 nitrogen double bonds, and carbon-nitrogen triple bonds, and other unsaturated bonds between carbon and other hetero Synthesis of Methylallyl Sulfonate atoms, wherever possible. 0051 0045. In still further aspects of the embodiments herein, the electrolyte solutions are prepared by using the solvents or additives selected from structures 1 through 8 by following O the procedures that can be readily performed by one of ordi nary skill in the art. HC-S-O HC=CH2. 0046. In yet further aspects of the embodiments herein, O| \/H electrochemical devices that operate with high cell Voltages are fabricated based on the electrolyte solutions as prepared 0.052 114.55g methylsulfonyl chloride is added dropwise above. These devices include, but are not limited to, (1) to a mixture of 58.08 gallyl alcohol and 101.2 g triethylamine lithium and lithium ion cells that use lithiated transition metal dissolved in 500 mL dichloromethane. Upon filtering, the oxides or lithiated olivine metalphosphate as cathode, and organic phase is Subject to drying and distillation, which lithium metal, lithium alloys, metal oxides or Sulfides, car yields the solvent at 80% yield. bonaceous materials as anode; (2) dual intercalation cells in which both cation and anion intercalate simultaneously into Example 3 lattices of anode and cathode materials, respectively; (3) elec trochemical double layer capacitors based on various elec Synthesis of Methylpropargyl Sulfone trode materials of high Surface area; and (4) electrolysis cells that produce chemical species at extreme potentials. 0053 0047. The above cells are assembled according to the pro cedures that can be readily performed by one of ordinary skill O | H, in the art. These electrochemical devices containing the co HC-S-C solvents or additives disclosed in the embodiments hereincan provide improved performance. J. Y. \ 0048 Having described the embodiments herein, the fol \ lowing examples are given to illustrate specific applications of the embodiments herein. They are intended to provide 0054) To a flask containing 30.45 g thiourea suspended in those of ordinary skills in the art with a complete disclosure 100 mL water, 19.036 g dimethylsulfate is added dropwise and description of how to make and use the novel solvents and under stirring. Upon completion of addition, the solution is additives of the embodiments herein. These specific examples heated to reflux, and then 32 g NaOH dissolved in 50 mL are not intended to limit the scope of the embodiments herein water is gradually added. Under vehement stirring, 95.20 g described in this application. propargyl bromide Solution in Xylene is added dropwise. The US 2011/0281 177 A1 Nov. 17, 2011 organic phase of the reactant is then separated and added to a Example 6 mixture of 81 g 30% hydrogen peroxide and 120 g glacier acetic acid with effective cooling and stirring. Following the Synthesis of Methylpropargyl Sulfonate similar purification procedure as described in Example 1, the solvent methylpropargyl sulfone is obtained in 80% yield. 0059

Example 4 O CH | A. Synthesis of Methylallenic Sulfone HC-S-O C O| \/H 0055

O H 0060 1 14.55g methylsulfonyl chloride is added dropwise | to a mixture of 56.06 g propargyl alcohol and 101.2 g triethy HC-S-C lamine dissolved in 500 mL dichloromethane. Following a | \ similar purification procedure as described in Example 2, the O VY-H, solvent is obtained at 80% yield. Example 7 0056 56.06 g dry propargyl alcohol and 101.20 g triethy lamine are dissolved in 1.0L dry dichloromethane and is then Synthesis of Methylacetylenic Carbonate cooled by liquid nitrogen. A solution of 37.10 g methylsulfe nyl chloride in 300 mL dichloromethane is added dropwise 0061 under stirring. When the temperature rises to -20°C., the salt is filtered away and then rinsed with dichloromethane. The residue is subject to vacuum evaporation. The remaining O organic phase is added to a mixture of 88 g 30% hydrogen peroxide and 110 g glacier acetic acid with effective cooling and stirring. Following the similar purification procedure as ics--" described in Example 1, the solvent methylallenic sulfone is obtained in 40% yield. 0062) 94.5g methylchloroformate is added dropwise to a mixture of 114.96 g 2.2-dichloroethanol, 79.10 g pyridine Example 5 and 200 mL chloroform at 0-5°C. under stirring. Further stirring at room temperature overnight is followed by pouring Synthesis of Methylacetylenic Sulfone the reactant over ice, the resultant mixture of which is subse quently neutralized by adding 6 M hydrogen chloride until 0057 the pH reaches 2.0. The organic phase is then separated and then subjected to dehydrobromination with dry ethoxide. After filtration, the organic phase is Subjected to distillation, which yields the solvent methylacetylenic carbonate at 50% HC-S-CECH yield. Example 8 0058 48.11g methane thiol dissolved in 100 mL dioxlane Synthesis of Acetylenic Butyrate with 20% KOH is sealed in an autoclave at -10°C. Acetylene gas is then introduced at room temperature through a valve, 0063 whose pressure is maintained at approximately 100 psi. The autoclave is heated to approximately 120° C. under stirring. During the interval, additional acetylene gas is introduced until the pressure stopped decreasing. After evaporation of the CH volatile fractions, the reactant is cooled down to -20°C. and CH7 1N O 2 then treated with excess liquid bromine under stirring. The oily phase is then subject to dehydrobromination in the pres ence of triethylamine and powdered potassium hydroxide 0064. 106.55 g butyryl chloride is added dropwise to a under vacuum. The brown oily product is added dropwise to mixture of 114.96 g 2,2-dichloroethanol, 101.2 g triethy a mixture of 200 g 30% hydrogen peroxide and 300 g glacier lamine and 500 mL dichloromethane at 0-5°C. under stirring. acetic acid. Following the similar purification procedure as Following a similar purification procedure as described in described in Example 1, the solvent methylacetylenic sulfone Example 7, the solvent acetylenic butyrate is obtained at is obtained at moderate yield. moderate yield. US 2011/0281 177 A1 Nov. 17, 2011

Example 9 the embodiments herein and are as described in structures 1 Synthesis of Thiophene-1-Oxide through 8 (FIGS. 1A through 1H). 0073. The solvent or solvent mixtures with or without the 0065 additives are weighed and mixed according to specific ratios, then the lithium salt or mixture of lithium salts are weighed and dissolved in the above solvent or solvent mixtures. HC-CH 0074. With purpose of illustration only, FIG. 2 shows the // W comparison of oxidative stability for various Sulfones as elec HCN, -CH trolytic solvents on the Surface of lithium compositions. 0075 FIG. 3 lists some typical electrolyte solutions pre O pared and tested. It should be noted that the compositions disclosed in FIG. 3 are merely examples of compositions 0066 84.14 g thiophene dissolved in 200 mL dry acetone which can be used for the respective electrochemical devices, is added dropwise to 103 g 30% hydrogen peroxide under and they are not intended to limit the scope of the embodi stirring and cooling at 0-5°C. Upon completion of addition, ments herein. the reactant is left standing at room temperature overnight. After the solvent is removed under vacuum, the solvent Example 12 thiophene-1-oxide is obtained through distillation at a yield Fabrication of a Lithium Ion Cell of 70%. 0076. This example summarizes the general procedure of the assembly of a lithium ion cell. A piece of Celgard(R) Example 10 polypropylene separator (available from Celgard, LLC, Synthesis of Carbon Suboxide North Carolina, USA) is sandwiched between an anode com posite film that is based on graphitic carbon and coated on 0067 copper foil, and a cathode composite film that is based on O-C-C-C-O either lithiated transition metal oxides, lithiated metalphos 0068. 104.1 g malonic acid and 300g phosphorus pentox phate or mixture thereof and that is coated on aluminum foil. ide are finely ground and mixed under anhydrous condition. The lithium ion cell is then activated by soaking the separator The reactant mixture is heated up to 200° C. The solvent with the electrolyte solutions as prepared in Example 11, and carbon suboxide is collected in a receiver at -10° C. sealed with appropriate means. with good yield. Example 13 Example 11 Fabrication of a Dual Ion Intercalation Cell Preparation of Novel Electrolyte Solutions 0077. This example summarizes the general procedure of the assembly of dual ion intercalation cells. A piece of Cel 0069. This example summarizes a general procedure for gard R. polypropylene separator (available from Celgard, the preparation of electrolyte Solutions comprising the novel LLC, North Carolina, USA) is sandwiched between an anode Solvents or additives, whose synthesis has been disclosed in composite film that is based on graphitic carbon coated on Examples 1 through 10. Both the concentration of the lithium copper foil, and a cathode composite film that is also based on salts and the relative ratios between the solvents or additives graphitic carbon but coated on aluminum foil. The lithium ion can be varied according to individual needs. cell is then activated by soaking the separator with the elec 0070 The electrolyte solution is prepared under a mois trolyte Solutions as prepared in Example 11, and sealed with ture-free environment to have the following composition: one appropriate means. lithium salt or the mixture of lithium salts, and a solvent system that either comprises a neat solvent with or without Example 14 one or more additives, or mixtures of two or more solvents with or without additives. Fabrication of an Electrochemical Capacitor 0071. The lithium salts selected include, but are not lim 0078. This example summarizes the general procedure of ited to, lithium hexafluorophosphate, lithium hexafluoro the assembly of electrochemical double layer capacitors. A arsenate, lithium tetrafluoroborate, lithium perfluoroalky piece of Celgard(R) polypropylene separator (available from lfluorophosphate, lithium perfluoroalkylfluoroborate, lithium Celgard, LLC, North Carolina, USA) is sandwiched between bis(trifluoromethanesulfonyl)imide, lithium bis(perfluoroet a pair of composite electrodes based on activated carbon hanesulfonyl)imide, lithium bis(oxalato)borate, and lithium materials and coated on various metal current collectors. The (difluorooxalato)borate. separator is then activated with the electrolyte solutions as 0072 The solvents or additives are selected from the sol prepared in Example 11, and sealed with appropriate means. vents or additives that are provided by the embodiments herein and the commonly-used nonaqueous electrolyte sol Example 15 vents, which include, but are not limited to, cyclic or acylic carboxylic esters, such as ethyl acetate and gamma-butyro Testing of the Electrochemical Cells lactone, cyclic or acylic diesters of carbonic , such as 0079. This example summarizes the general procedure of ethylene carbonate and dimethyl carbonate, nitriles such as testing the electrochemical devices assembled in Examples acetonitrile and 3-(2.2.2-trifluoroethoxy)propionitrile, or the 12 through 15. The half-cells of lithium ion anode and cath mixtures thereof. The resultant electrolyte solution contains ode are Subject to both Voltammetric and galvanostatic at least one of those solvents or additives that are provided by cyclings, and the full lithium ion cells, dual intercalation cells US 2011/0281 177 A1 Nov. 17, 2011

and electrochemical double layer capacitors are subject to I0085. The embodiments herein relate to new polar and galvanostatic cyclings followed by potentiostatic floating. aprotic organic molecules that, when serving as solvents in Standard potentiostat/galvanostat and battery testers are the nonaqueous electrolytes, can form desirable interfaces employed. As an example for the purpose of illustration, the with both the cathode and anode of an electrochemical cell, galvanostic cycling results of anode half-cells in a few while presenting little electrical resistance. The electro selected electrolytes are shown in FIG. 3. chemical cells based on these new electrolyte solvents and 0080 FIGS. 4A and 4B illustrate a schematic diagram of additives can afford both high stability and faster kinetics in an electrochemical device 10 having a negative electrode 12 the cell chemistry. comprising any of a metal and an electrode active material I0086 Examples of high voltage electrochemical devices that reversibly intercalates and de-intercalates cations; a posi which may utilize the embodiments herein include, but are tive electrode 14 of an electrode active material that reversibly not limited to, high energy density or high power density intercalates and de-intercalates any of cations and anions; a batteries, high power density double-layer capacitors, or elec barrier 16 comprising any of a porous polyolefin separator trolysis cells operating at extreme potentials. More particu and a gellable polymer film separating the negative electrode larly, the electrochemical devices that can benefit from utiliz 12 from the positive electrode 14; and a nonaqueous electro ing the embodiments herein include, but are not limited to, lyte 18 contacting the negative electrode 12 and the positive rechargeable batteries based on lithium metal, lithium-based electrode 14, the nonaqueous electrolyte 18 comprising at alloys or lithium ion-intercalatable materials as anode, least one unsaturated molecule acting as any of a solvent and lithium ion-intercalatable materials as cathode, and non an additive and comprising any of the structures (1) through aqueous solution of lithium salt in mixed electrolyte solvents. (8) (corresponding to FIGS. 1A through 1H, respectively). The solvents and additives provided by the embodiments I0081 FIG. 5, with reference to FIGS. 1A through 4B, is a herein can also be used in other electrochemical devices Such flow diagram illustrating a method of forming an electrolyte as ultracapacitors, electrolytic cells, and electroplating cells. solution 18, wherein the method comprises providing (25) at I0087. The solvents and additives provided by the embodi least one lithium salt; and mixing (30) a solvent system with ments herein offer enhanced performance and safety for Li the at least one lithium salt, the solvent system comprising a metal and Li ion cells, double layer capacitors, and electroly plurality of polar and aprotic organic molecules comprising at sis cells by manipulating the chemical composition of the least one unsaturated functionality per molecule that is con passivating films through the use of the new solvents/addi jugated with a polar functionality of the molecule, wherein at tives. The solvents and additive structures are configured Such least one unsaturated functionality comprises any of a double that the lowest unoccupied molecular orbital (LUMO) energy bond and a triple bond between any of a carbon-carbon chain, level is far above the rest of the electrolyte components. As a a carbon-heteroatom chain, and a hetroatom-heteroatom result, the electrode passivating film in the electrochemical chain; at least one cyclic carbonic diester; and at least one cells utilizing such solvents/additives is dictated by the poly acyclic carbonic diester. Preferably, the solvent system com merization chemistry of these solvents/additives, yielding prises any of the structures (1) through (8) corresponding to dense, protective yet conductive passivation films. Accord FIGS. 1A through 1H, respectively. ingly, these new solvents and additives are useful in a wide 0082 In FIGS. 1A through 1H, i, j, and k are integers spectrum of electrochemical devices whose operation relies independent from each other and range from 0 to 1, and l, m, on the wide stability window of the electrolytes. and n are integers independent from each other and range I0088. The solvents and additives provided by the embodi from 0 to 2, respectively, and R' have saturated substituents ments herein are configured to be oxidized or reduced prior to comprising any of hydrogen, C1-C10 normal or C3-C10 the rest of the electrolyte components, and their unsaturated branched alkyls, halogen radicals, alkoxyls, thioalkoxyls, functionalities render an electrode surface film that is of poly aromatic radicals, and unsaturated Substituents of any of the meric nature. Therefore, Li ion cells utilizing such solvents radicals in the structures (9) through (11) corresponding to and additives are better protected and also exhibit improved FIGS. 1 I through 1 K, respectively. In FIGS. 1 I through 1 K, performances. R" are selected from any of Hradical, C1-C10 normal or I0089. The structure of the solvents and additives provided C3-C10 branched alkyls, halogen radicals, alkoxyls, thio by the embodiments herein offers tailored surface chemistry alkoxyls, and aromatic radicals. on electrodes so that the operation of electrochemical cells 0083 Preferably, the solvent system comprises any of (i) a can be better controlled. In this regard, the solvents or addi neat solvent with at least one additive, (ii) a neat solvent tives provided by the embodiments herein are unsaturated so without an additive, (iii) a mixture of at least two solvents that their decomposition products are likely to be polymeric, with at least one additive, and (iv) a mixture of at least two which protect the electrode surfaces more efficiently; and solvents without an additive. Furthermore, the mixing of the their unsaturated functionalities are preferably in conjugation Solvent system with at least one lithium salt may form any of with the polar group, so that their LUMO energy level is low, methylallyl Sulfone, methylallyl Sulfonate, methylpropargyl which makes them the dominant species in passivating film Sulfone, methylallenic Sulfone, methylacetylenic Sulfone, chemistry. methylpropargyl Sulfonate, methylacetylenic carbonate, 0090 The embodiments herein provide a series of unsat acetylenic butyrate, thiophene-1-oxide, and carbon Suboxide. urated polar organic compounds that can be used as either 0084. The lithium salt may comprise any of lithium Solvents or additives in non-aqueous electrolytes. The decom hexafluorophosphate, lithium fluoro(perfluoroalkyl)phos position potentials of these compounds are controlled by the phate, lithium tetrafluoroborate, lithium hexafluoroarsenate, location of the unsaturated bonds relative to the polar group, lithium perchlorate, lithium tetrahloaluminate, lithium tris and the resultant decomposition compounds of polymeric (trifluoromethanesulfonyl)methide, lithium perfluoroalkyl nature are expected to offer better protections to the elec sulfonate, lithium arylsulfonate, lithium bis(oxalato)borate, trodes while minimizing the resistance. Such an electro lithium difluoro(oxalato)borate, and mixtures thereof. chemical device provides an optimized stabilization. US 2011/0281 177 A1 Nov. 17, 2011

0091. The foregoing description of the specific embodi ments will so fully reveal the general nature of the embodi -continued ments herein that others can, by applying current knowledge, 2 (7) readily modify and/or adapt for various applications such R specific embodiments without departing from the generic concept, and, therefore, Such adaptations and modifications (H) should and are intended to be comprehended within the R3-N=C " meaning and range of equivalents of the disclosed embodi ments. It is to be understood that the phraseology or termi } :)iii. nology employed herein is for the purpose of description and R1 not of limitation. Therefore, while the embodiments herein (8) have been described in terms of preferred embodiments, R those skilled in the art will recognize that the embodiments CECEO hereincan be practiced with modification within the spirit and Scope of the appended claims. R2 What is claimed is: whereini,j, and kare integers independent from each other 1. An electrochemical device comprising: and range from 0 to 1, and l, m, and n are integers a negative electrode comprising any of a metal and an independent from each other and range from 0 to 2, electrode active material that reversibly intercalates and respectively; de-intercalates cations; wherein R' comprise any of saturated substituents com a positive electrode comprising an electrode active mate prising any of hydrogen, C1-C10 normal or C3-C10 rial that reversibly intercalates and de-intercalates any of branched alkyls, halogen radicals, alkoxyls, thio cations and anions; alkoxyls, aromatic radicals, and unsaturated Substitu a barrier comprising any of a porous polyolefin separator ents comprising any of the radicals in the following and a gellable polymer film separating said negative structures (9) through (11): electrode from said positive electrode; and a nonaqueous electrolyte contacting said negative elec trode and said positive electrode, said nonaqueous elec (9) trolyte comprising at least one unsaturated molecule R5 acting as a solvent or an additive and comprising any of \CEC / the following structures (1) through (8): A V R4 R6 CEC-R (10) (1) R5 (11) C X C \ M RI NO O my R2 CECEC rt) A. V (2) R4 R6

R -(-)-or-to-(-)-C or to k C pi R wherein Rare selected from any of H radical, C1-C10 normal or C3-C10 branched alkyls, halogen radicals, (O), alkoxyls, thioalkoxyls, and aromatic radicals; (CH2) wherein X is selected from the group of carbonyl, thionyl, phosphoryl or Sulfonyl: (3) wherein Y is selected from the group of phosphinyl or H phosphoryl; R2 C R4 and wherein Z is selected from the group of carbonyl, thionyl, Sulfonyl, mercapto or oxy. RI Z R3 2. The electrochemical device of claim 1, wherein said (4) nonaqueous electrolyte comprises at least one of the R' H substituents selected from said structures (9) through (11). R2 C R4 3. The electrochemical device of claim 1, wherein said nonaqueous electrolyte comprises one of the structures (1), " (2), (3), (4), (5), (6), or (7), and wherein at least one of 1, m. RI Z R3 and n equals Zero. (5) 4. The electrochemical device of claim 1, wherein said R 1-Z-R2 nonaqueous electrolyte comprises structure (1), wherein X (6) comprises Sulfonyl, and wherein one of i or equals Zero. H NEC-C-R 5. The electrochemical device of claim 1, wherein said nonaqueous electrolyte comprises one of the structures (1) or (2), wherein X comprises any of Sulfonyl and phosphoryl, US 2011/0281 177 A1 Nov. 17, 2011

whereini, j, k, l, m, and nequal Zero, and wherein at least one of R' is selected from radicals comprising any of structures (9) through (11). (1) 6. The electrochemical device of claim 1, wherein said C X C nonaqueous electrolyte comprises a solvent containing at R1 O O iii. R2 least one unsaturated molecule. rto) 7. The electrochemical device of claim 1, wherein said (2) nonaqueous electrolyte comprises a co-solvent containing H H any of cyclic and acyclic carbonates and carboxylic esters of R-(-)-or-to-(-)-pi any of ethylene carbonate, , vinyl car (O), bonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, Y-butyrolactone, methylbutyrate, ethylbutyrate, (CH2) and mixtures thereof. 8. The electrochemical device of claim 1, wherein said (3) H nonaqueous electrolyte comprises a cosolvent in mixture R2 C R4 with at least one of the molecules of structures (1) through (8) as a co-solvent or an additive. 9. The electrochemical device of claim 1, wherein said R1 Z R3 nonaqueous electrolyte comprises a lithium salt containing (4) any of lithium hexafluorophosphate, lithium fluoro(perfluo H roalkyl)phosphate, lithium tetrafluoroborate, lithium R2 C R4 hexafluoroarsenate, lithium perchlorate, lithium tetrahloalu minate, lithium tris(trifluoromethanesulfonyl)methide, " lithium perfluoroalkylsulfonate, lithium arylsulfonate, R1 Z R3 (5) lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, R-Z-R2 and mixtures thereof. (6) 10. The electrochemical device of claim 9, wherein a con H centration of said solvent ranges from approximately 10% to NEC-CH-R 100% with respect to a total solvent weight, wherein a con 2 (7) centration of said additive ranges from approximately R 0.005% to 10% with respect to said total solvent weight, and wherein a concentration of said lithium salt ranges from ) approximately 0.5 to 3.0 mole/liter. R-N=C 11. The electrochemical device of claim 1, wherein the electrode active material of said negative electrode comprises } :)iii. any of lithium metal, lithium alloy with other metals, carbon R1 aceous materials with various degree of graphitization, lithi (8) ated metal oxides, and chalcogenides. R 12. The electrochemical device of claim 1, wherein the CCEO electrode active material of said positive electrode comprises R2 any of transition metal oxides, metalphosphates, chalco genides, and carbonaceous materials with various degree of graphitization. whereini,j, and kare integers independent from each other and range from 0 to 1, and l, m, and n are integers 13. An electrolyte solution comprising: independent from each other and range from 0 to 2, at least one lithium salt; and respectively; a solvent system mixed with said at least one lithium salt, wherein R' comprise any of saturated substituents com said solvent system comprising: prising any of hydrogen, C1-C10 normal or C3-C10 a plurality of polar and aprotic organic molecules com branched alkyls, halogen radicals, alkoxyls, thio prising at least one unsaturated functionality per mol alkoxyls, aromatic radicals, and unsaturated Substitu ecule conjugated with a polar functionality of said ents comprising any of the radicals in the following molecule, wherein said at least one unsaturated func structures (9) through (11): tionality comprises any of a double bond and a triple bond between any of a carbon-carbon chain, a carbon (9) heteroatom chain, and a hetroatom-heteroatom chain; R5 at least one cyclic carbonic diester; and \CEC / A V at least one acyclic carbonic diester. R4 R6 14. The electrolyte solution of claim 13, wherein said sol (10) vent system comprises any of the following structures (1) -CEC-R through (8): US 2011/0281 177 A1 Nov. 17, 2011 11

-continued -continued (11) (3) \ , CECEC A. V R4 R6 R1 Z R3 wherein Rare selected from any of H radical, C1-C10 (4) H normal or C3-C10 branched alkyls, halogen radicals, R2 CJ R4 alkoxyls, thioalkoxyls, and aromatic radicals; wherein X is selected from the group of carbonyl, thionyl, phosphoryl or Sulfonyl, R1 Z R3 wherein Y is selected from the group of phosphinyl or 5 phosphoryl; R-Z-R2 (5) and wherein Z is selected from the group of carbonyl, (6) thionyl, Sulfonyl, mercapto or oxy. N=c- H }-R 15. The electrolyte solution of claim 13, wherein said sol 2 (7) vent system comprises any of (i) a neat solvent with at least R one additive, (ii) a neat Solvent without an additive, (iii) a mixture of at least two solvents with at least one additive, and (iv) a mixture of at least two solvents without an additive. R3-N-C) ) 16. The electrolyte solution of claim 13, wherein the mix ing of said solvent system with said at least one lithium salt CH)iii. forms any of methylallyl sulfone, methylallyl sulfonate, R1 methylpropargyl Sulfone, methylallenic Sulfone, methy (8) lacetylenic Sulfone, methylpropargyl Sulfonate, methylacety R lenic carbonate, acetylenic butyrate, thiophene-1-oxide, and CECEO M carbon suboxide. R2 17. A method of forming an electrolyte solution, said method comprising: providing at least one lithium salt; and whereini,j, and kare integers independent from each other and range from 0 to 1, and l, m, and n are integers mixing a solvent system with said at least one lithium salt, independent from each other and range from 0 to 2, said solvent system comprising: respectively, a plurality of polar and aprotic organic molecules com wherein R' comprise any of saturated substituents com prising at least one unsaturated functionality per mol prising any of hydrogen, C1-C10 normal or C3-C10 ecule that is conjugated with a polar functionality of branched alkyls, halogen radicals, alkoxyls, thio said molecule, wherein said at least one unsaturated alkoxyls, aromatic radicals, and unsaturated Substitu functionality comprises any of a double bond and a ents comprising any of the radicals in the following triple bond between any of a carbon-carbon chain, a structures (9) through (11): carbon-heteroatom chain, and a hetroatom-heteroa tom chain; at least one cyclic carbonic diester; and (9) at least one acyclic carbonic diester. \ /R5 CEC 18. The method of claim 17, wherein said solvent system A. V comprises any of the following structures (1) through (8): R4 R6 CEC-R (10) (1) R5 (11) \ / CECEC A V R4 R6 (2) H H wherein Rare selected from any of H radical, C1-C10

R-C on-to CHRpi normal or C3-C10 branched alkyls, halogen radicals, (O), alkoxyls, thioalkoxyls, and aromatic radicals; wherein X is selected from the group of carbonyl, thionyl, (CH2) phosphoryl or Sulfonyl: wherein Y is selected from the group of phosphinyl or phosphoryl; US 2011/0281 177 A1 Nov. 17, 2011 12

and wherein Z is selected from the group of carbonyl, 20. The method of claim 17, wherein the mixing of said thionyl, Sulfonyl, mercapto or oxy. Solvent system with said at least one lithium salt forms any of 19. The method of claim 17, wherein said solvent Svstem methylallyl sulfone, methylallyl Sulfonate, methylpropargyl s y Sulfone, methylallenic Sulfone, methylacetylenic Sulfone, comprises any of (i) a neat solvent with at least one additive, methylpropargyl Sulfonate, methylacetylenic carbonate, (ii) a neat solvent without an additive, (iii) a mixture of at least acetylenic butyrate, thiophene-1-oxide, and carbon Suboxide. two solvents with at least one additive, and (iv) a mixture of at least two solvents without an additive. ck