COMPOSITION

Abstract

Use of a compound of Formula (I) in a nonaqueous battery electrolyte formulation (1) wherein R is a fluorinated alkyl group and X is selected from the group consisting of F, Cl, H, CF.sub.3, and C.sub.1 to C.sub.6 alkyl which may be at least partially fluorinated and —OR group can be cis- or trans- to any other group X.

##STR00001##

Claims

1. A nonaqueous battery electrolyte formulation, comprising a compound of Formula 1: ##STR00009## wherein R is a fluorinated alkyl group; and X is selected from the group consisting of F, Cl, H, CF.sub.3, and C.sub.1 to C.sub.6 alkyl which is at least partially fluorinated; and OR is cis- or trans- to any vicinal group.

2. A battery, comprising the battery electrolyte formulation according to claim 1.

3. The formulation according to claim 1, further comprising a metal electrolyte salt, present in an amount of 0.1 to 20 wt % relative to the total mass of the battery electrolyte formulation, and wherein the metal electrolyte salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

4. (canceled)

5. The formulation according to claim 3, wherein the metal salt is a salt of lithium selected from the group consisting of lithium hexafluorophosphate (LiPF.sub.6), lithium hexafluoroarsenate monohydrate (LiAsF.sub.6), lithium perchlorate (LiClO.sub.4), lithium tetrafluoroborate (LiBF.sub.4), lithium triflate (LiSO.sub.3CF.sub.3), lithium bis(fluorosulfonyl)imide (Li(FSO.sub.2).sub.2N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CF.sub.3SO.sub.2).sub.2N).

6. The formulation according to claim 1, further comprising an additional solvent in an amount of from 0.1 wt % to 99.9 wt % of the liquid component of the formulation, wherein the additional solvent is selected from the group consisting of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC).

7-8. (canceled)

9. A formulation comprising a metal ion and a compound of Formula 2, optionally in combination with a solvent: ##STR00010## wherein R.sup.1, R.sup.2, and R.sup.3 are each independently selected from the group consisting of F, Cl, H, CF.sub.3, and C.sub.1 to C.sub.6 alkyl which is at least partially fluorinated; and R.sup.4 is selected from the group consisting of C.sub.1 to C.sub.12 alkyl which may be at least partially fluorinated; and OR.sup.4 is cis- or trans- to R.sup.1 or R.sup.2.

10. A battery comprising the formulation according to claim 9.

11. The formulation according to claim 9, further comprising a metal electrolyte salt, present in an amount of 0.1 to 20 wt % relative to the total mass of the formulation, wherein the metal electrolyte salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

12. (canceled)

13. The formulation according to claim 11, wherein the metal electrolyte salt is a salt of lithium selected from the group consisting of lithium hexafluorophosphate (LiPF.sub.6), lithium hexafluoroarsenate monohydrate (LiAsF.sub.6), lithium perchlorate (LiClO.sub.4), lithium tetrafluoroborate (LiBF.sub.4), lithium triflate (LiSO.sub.3CF.sub.3), lithium bis(fluorosulfonyl)imide (Li(FSO.sub.2).sub.2N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CF.sub.3SO.sub.2).sub.2N).

14. The formulation according to claim 9, further comprising an additional solvent in an amount of from 0.1 wt % to 99.9 wt % of the liquid component of the formulation, wherein the additional solvent is selected from the group consisting of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC).

15. (canceled)

16. A method of reducing the flammability of a battery and/or a battery electrolyte comprising adding to the battery and/or the battery electrolyte the battery electrolyte formulation according to claim 1.

17. A method of powering an article comprising a battery, the method comprising adding to the battery the battery electrolyte formulation according to claim 1.

18. A method of retrofitting a battery electrolyte comprising (a) at least partially replacing the battery electrolyte with the battery electrolyte formulation according to claim 1 and/or (b) supplementing the battery electrolyte with the battery electrolyte formulation.

19. A method of preparing a compound of Formula 1 ##STR00011## wherein R is a fluorinated alkyl group; X is selected from the group consisting of F, Cl, H, CF.sub.3, and C.sub.1 and C.sub.6 alkyl which is at least partially fluorinated; and —OR is cis- or trans- to any vicinal group; the method comprising reacting a compound of Formula 2a and/or Formula 2b: ##STR00012## with an alcohol of formula ROH under basic conditions at elevated temperature and pressure so as to produce the compound of Formula 1.

20. A method of preparing the battery electrolyte formulation according to claim 5 comprising mixing a compound of Formula 1 with ethylene, propylene, or fluoroethylene carbonate and with the salt of lithium so as to produce the formulation.

21. The method according to claim 17, wherein a capacity of the battery and/or charge transfer within the battery is improved relative to a battery without the formulation.

22. The method according to claim 16, wherein the formulation comprises a metal electrolyte salt, present in an amount of 0.1 to 20 wt % relative to the total mass of the nonaqueous electrolyte formulation, wherein the metal electrolyte salt is a salt of lithium, sodium, magnesium, calcium, lead, zinc, or nickel.

23. (canceled)

24. A The method according to claim 22, wherein the metal electrolyte salt is a salt of lithium selected from the group consisting of lithium hexafluorophosphate (LiPF.sub.6), lithium hexafluoroarsenate monohydrate (LiAsF.sub.6), lithium perchlorate (LiClO.sub.4), lithium tetrafluoroborate (LiBF.sub.4), lithium triflate (LiSO.sub.3CF.sub.3), lithium bis(fluorosulfonyl)imide (Li(FSO.sub.2).sub.2N), and lithium bis(trifluoromethanesulfonyl)imide (Li(CF.sub.3SO.sub.2).sub.2N).

25. A The method according to claim 16, wherein the formulation comprises an additional solvent in an amount of from 0.1 wt % to 99.9 wt % of a liquid component of the formulation, wherein the additional solvent is selected from the group consisting of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), fluoroethylene carbonate (FEC), propylene carbonate (PC), and ethylene carbonate (EC).

26. (canceled)

27. A method of powering an article comprising a battery, the method comprising adding to the battery the formulation according to claim 7.

Description

EXAMPLES

Example 1—Ether Preparation

[0099] The following steps were followed. [0100] Potassium hydroxide (17.0 g, 250 mmol) was added slowly and with stirring to a solution of water (4.0 g) and alcohol (40 g) in a 100 ml Hastelloy C pressure vessel which was equipped with an inlet port for gases or liquids, pressure and temperature indicators and a cruciform gas entraining stirrer assembly. [0101] The vessel was sealed, purged with nitrogen and pressure tested. The contents were then heated to 20-60° C. (depending on the reaction) with stirring at 1000 rpm [0102] Once equilibrated, the unsaturated organofluorine feed component was added and the reaction conditions maintained until no further change was indicated by the pressure or temperature indicators. [0103] The contents were recovered, washed with water and the organic fraction recovered. [0104] The organic fraction was dried over anhydrous sodium sulphate and subjected to a simple “top and tail” distillation to remove lights and heavies. [0105] The reaction products were then analysed by GC-MS.

TABLE-US-00001 Expt. E1 E2 E3 Organofluorine feed TFMA TFMA TFMA water (g) 4 4 4 Alcohol (40 g) CHF.sub.2CCF.sub.2CH.sub.2OH CF.sub.3CH.sub.2OH (CF.sub.3).sub.2CHOH Product Z—CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 Z—CF.sub.3CH═CHOCH.sub.2CF.sub.3 Z—CF.sub.3CH═CHOCH(CF.sub.3).sub.2 Yield and Comments 99.7%, reaction fast but 90.3%, reaction very KOH solubility in alcohol phase separation difficult fast, easy separation, very poor: care needed to with an emulsion phase possibly some E- avoid dehydration/ and signs of oligomers, isomer, very clean charring. KOH only to possibly some E-isomer product with only 11.7 g and water 9 g. along with some minor minor impurities Reaction very slow, (72 impurities hours). Difficult phase separation, significant emulsion phase with signs of oligomers. Crude product contained only traces of expected hexafluoroisopropyl ether Mass Spectrum m/z: 51(CHF.sub.2), 69(CF.sub.3), 75, 77, m/z: 69(CF.sub.3), 75, 77, m/z: 69(CF.sub.3), 75, 91, 91, 93, 95(CF.sub.3CH═CH), 83(CF.sub.3CH.sub.2), 91, 93, 95(CF.sub.3CH═CH), 99, 113, 125(CF.sub.3CH═CHOCH.sub.2), 207(M- 95(CF.sub.3CH═CH), 125((M- 145, 193(M-69), 243(M-F), 19), 226(M) 69, CF.sub.3CH═CHOCH.sub.2), 262(M) 175(M-19), 194(M) Expt. E4 E5 Organofluorine feed TFMA TFMA water (g) 4 4 Alcohol (40 g) (CF.sub.3).sub.2CHOH CF.sub.3CH.sub.2CH.sub.2OH Product Z—CF.sub.3CH═CHOCH(CF.sub.3).sub.2 Z—CF.sub.3CH═CHO(CH.sub.2).sub.2CF.sub.3 Yield and Comments Procedure adjusted: water 77%, phase 2.5 g, HFIP 25 g, KOH 2.6 separation very slow, g, Aliquat 336 0.1 g. emulsion phase with Reaction still slow and left signs of oligomers overnight. Phase separation impossible so volatiles recovered by vacuum distillation. 9 g of a free running clear organic liquid recovered that contained approximately 30 area % of the desired product Mass Spectrum m/z: 69(CF.sub.3), 75, 91, m/z: 51(CHF.sub.2), 69(CF.sub.3) 95(CF.sub.3CH═CH), 99, 113, 77, 91, 92, 93, 112, 18 145, 193(M-69), 243(M-F), 19), 208(M) 262(M) TFMA is trifluoromethyl acetylene indicates data missing or illegible when filed

Example 2—Large Scale Ether Preparation

[0106] The basic procedure outlined in Example 1 was followed with larger batches (300-500 g) of the organofluorine feed component and the crude products were analysed by NMR spectroscopy.

TABLE-US-00002 Expt. E6 E7 Organofluorine 1-Chloro-3,3,3- 1-Chloro-3,3,3- feed trifluoropropene trifluoropropene component (g) Product [00007] [00008] Purity ≥99.5 ≥99.5 .sup.19F NMR(56 δ −59.78 (CF.sub.3CH═, dd, δ −59.88 (CF.sub.3CH═, d, MHz) (CDCl.sub.3 vs J = 8.1, 2.1 Hz), −77.15 J = 7.9), −127.55 (CF.sub.2, tq, PFB) (CF.sub.3CH.sub.2, t, J = 8.1 Hz) J = 11.9, 3.8 Hz), −141.13 (CHF.sub.2, (dt, J = 53.1, 3.6 Hz.)

Example 3—Electrochemical Compatibility Testing

[0107] Electrochemical compatibility was assessed by cyclic voltammetry (CV) using a Gamry Instruments Potentiometer and a standard three electrode test cell. The working and counter electrodes were made of glassy carbon (area 0.071 cm.sup.2) with a platinum wire reference electrode. The basic electrolyte solution was 0.25 M tetrabutyl ammonium fluoroborate (TBAF) in acetonitrile (ACN) and the cell was referenced to ferrocene/ferrocenium (Fc/Fc.sup.+) couple at 0 V.

[0108] FIG. 1 shows three CV traces which serve to demonstrate the electrochemical compatibility of trifluoropropenyl ethers such as Product E6: [0109] CV 1 0.25 M TBAF in ACN [0110] CV 2 0.25 M TBAF in ACN+Product E6 [0111] CV 3 0.25 M TBAF in ACN+Propylene carbonate

Example 4—Preparation of Electrolyte Compositions

[0112] 1 M solutions of lithium hexafluorophosphate (LiPF.sub.6)/lithium bis(fluorosulfonyl) ( ) in solvents comprising the products of E6 or E7 and various common electrolyte solvents were prepared and analysed by .sup.19F NMR spectroscopy.

[0113] The compositions are shown in Tables 1 to 4 below. Tables 1 to 4 also contain a reference to the .sup.19F NMR spectrum (see also page 21).

[0114] In Tables 1 to 4 the following abbreviations are used. [0115] PC=propylene carbonate [0116] FEC=fluoroethylene carbonate [0117] EC=ethylene carbonate [0118] EMC=ethyl methyl carbonate

[0119] All percentages are by weight.

TABLE-US-00003 TABLE 1 % Additive Composition Base (CF.sub.3CH═CHOCH.sub.2CF.sub.3) FIG. 1 95% 1M LiPF.sub.6 in PC  5% 12a 2 85% 1M LiPF.sub.6 in PC 15% 12b 3 75% 1M LiPF.sub.6 in PC 25% 12c 4 25% 1M LiPF.sub.6 in PC 75% 12d 5 95% 1M LiPF.sub.6 in PC (90%) and  5% 13a FEC (10%) 6 85% 1M LiPF.sub.6 in PC (90%) and 15% 13b FEC (10%) 7 25% 1M LiPF.sub.6 in PC (90%) and 75% 13c FEC (10%) 8 95% 1M LiPF.sub.6 in EC (30%) and  5% 14a EMC (70%) 9 85% 1M LiPF.sub.6 in EC (30%) and 15% 14b EMC (70%) 10 25% 1M LiPF.sub.6 in EC (30%) and 75% 14c EMC (70%)

TABLE-US-00004 TABLE 2 % Additive Composition Base (CF.sub.3CH═CHOCH.sub.2CF.sub.3) FIG. 11 95% 1M LiFSI in PC  5% 15a 12 85% 1M LiFSI in PC 15% 15b 13 25% 1M LiFSI in PC 75% 15c 14 95% 1M LiFSI in PC (90%) and  5% 16a FEC (10%) 15 85% 1M LiFSI in PC (90%) and 15% 16b FEC (10%) 16 25% 1M LiFSI in PC (90%) and 75% 16c FEC (10%) 17 85% 1M LiFSI in EC (30%) and 15% 17a EMC (70%) 18 25% 1M LiFSI in EC (30%) and 75% 17b EMC (70%)

TABLE-US-00005 TABLE 3 % Additive Composition Base (CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2) FIG. 19 95% 1M LiPF.sub.6 in PC  5% 18a 20 85% 1M LiPF.sub.6 in PC 15% 18b 21 25% 1M LiPF.sub.6 in PC 75% 18c 22 95% 1M LiPF.sub.6 in PC (90%) and  5% 19a FEC (10%) 23 85% 1M LiPF.sub.6 in PC (90%) and 15% 19b FEC (10%) 24 25% 1M LiPF.sub.6 in PC (90%) and 75% 19c FEC (10%) 25 95% 1M LiPF.sub.6 in EC (30%) and  5% 20a EMC (70%) 26 85% 1M LiPF.sub.6 in EC (30%) and 15% 20b EMC (70%) 27 25% 1M LiPF.sub.6 in EC (30%) and 75% 20c EMC (70%)

TABLE-US-00006 TABLE 4 % Additive Composition Base (CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2) FIG. 28 95% 1M LiFSI in PC  5% 21a 29 85% 1M LiFSI in PC 15% 21b 30 25% 1M LiFSI in PC 75% 21c 31 95% 1M LiFSI in PC (90%) and  5% 22a FEC (10%) 32 85% 1M LiFSI in PC (90%) and 15% 22b FEC (10%) 33 25% 1M LiFSI in PC (90%) and 75% 22c FEC (10%) 34 95% 1M LiFSI in EC (30%) and  5% 23a EMC(70%) 35 85% 1M LiFSI in EC (30%) and 15% 23b EMC(70%) 36 25% 1M LiFSI in EC (30%) and 75% 23c EMC(70%)

Flammability and Safety Testing

Flash Point

[0120] Flashpoints were determined using a Miniflash FLP/H device from Grabner Instruments following the ASTM D6450 standard method:

TABLE-US-00007 Concentration (% wt) in standard electrolyte 1M LiPF.sub.6 in (30% Ethylenecarbonate & 70% ethyl methyl carbonate) 0 2 5 10 30 100 Component Flashpoint (° C.) CF.sub.3CH═CHOCH.sub.2CF.sub.3 32 ± 2 36 ± 2 35 ± 2 36 ± 1 43 ± 1 not (MEXI-1) detectable CF.sub.3CH═CHOCH.sub.2CF.sub.2CF.sub.2H 32 ± 2 35 ± 2 37 ± 1 38 ± 1 47 ± 2 61 ± 2 (MEXI-2)

[0121] These measurements demonstrate that the addition of the additives designated MEXI-1 and MEXI-2 significantly raised the flashpoint of the standard electrolyte solution.

Self-Extinguishing Time

[0122] Self-extinguishing time was measured with a custom-built device that contained an automatically controlled stopwatch connected to an ultraviolet light detector: [0123] The electrolyte to be examined (500 μL) was applied to a Whatman GF/D (ø=24 mm) glass microfiber filter [0124] The ignition source was transferred under the sample and held in this its position for a preset time (1, 5 or 10 seconds) to ignite the sample. Ignition and burning of the sample were detected using a UV light detector. [0125] Evaluation is carried out by plotting the burning time/weight of electrolyte [s g.sup.−1] over ignition time [s] and extrapolation by linear regression line to ignition time=0 s Self-extinguishing time (s.Math.g.sup.−1) is the time that is needed until the sample stops burning once inflamed.

TABLE-US-00008 Concentration (% wt) in standard electrolyte 1M LiPF.sub.6 in (30% Ethylene carbonate & 70% ethyl methyl carbonate) 0 2 5 10 30 100 Component Self-extinguishing time (s .Math. g.sup.−1) CF.sub.3CH═CHOCH.sub.2CF.sub.3 39 ± 2 36 ± 5 38 ± 3 40 ± 3 37 ± 3 14 ± 2 (MEXI-1) CF.sub.3CH═CHOCH.sub.2CF.sub.2CF.sub.2H 39 ± 2 47 ± 3 45 ± 2 43 ± 2 43 ± 2 25 ± 2 (MEXI-2)

[0126] These measurements demonstrate that the compounds MEXI-1 and MEXI-2 have flame retarding properties.

Electrochemical Testing

Drying

[0127] Before testing MEXI-1 and MEXI-2 were dried by treatment with a pre-activated type 4A molecular sieve. Water levels in the pre- and post-treated samples were determined by the Karl Fischer method:

TABLE-US-00009 Water level pre-treatment Water level post-treatment Compound (ppm w/v) (ppm w/v) MEXI-1 76 <10 MEXI-2 103 <10

Electrolyte Formulation

[0128] Electrolyte preparation and storage was carried out in an argon filled glove box (H.sub.2O and O.sub.2<0.1 ppm). The base electrolyte was 1M LiPF.sub.6 in ethylene carbonate:ethyl methyl carbonate (3:7 wt. %) with MEXI-1 or MEXI-2 additive at concentrations of 2, 5, 10 and 30 wt. %.

Cell Chemistry and Construction

[0129] The performance of each electrolyte formulation was tested in multi-layer pouch cells over 50 cycles (2 cells per electrolyte):

[0130] Chemistry 1: Lithium-Nickel-Cobalt-Manganese-Oxide (NCM622) positive electrode and artificial graphite (specific capacity: 350 mAh g.sup.−1) negative electrode. The area capacity of NMC622 and graphite amounted to 3.5 mAh cm.sup.−2 and 4.0 mAh cm.sup.−2, respectively. The N/P ratio amounted to 115%.

[0131] Chemistry 2: Lithium-Nickel-Cobalt-Manganese-Oxide (NCM622) positive electrode and SiO.sub.x/graphite (specific capacity: 550 mAh g.sup.−1) negative electrode. The area capacity of NMC622 and SiO.sub.x/graphite amount to 3.5 mAh/cm.sup.−2 and 4.0 mAh cm.sup.−2, respectively. The N/P ratio amounted to 115%.

[0132] The test pouch cells had the following characteristics: [0133] Nominal capacity 240 mAh+/−2% [0134] Standard deviations:

[0135] Capacity: ±0.6 mAh

[0136] Coulombic Efficiency (CE) 1st cycle: ±0.13%

[0137] Coulombic Efficiency (CE) subsequent cycles: ±0.1%

[0138] Positive electrode: NMC-622 [0139] Active material content: 96.4% [0140] Mass loading: 16.7 mg cm.sup.−2

[0141] Negative electrode: Artificial Graphite [0142] Active material content: 94.8% [0143] Mass loading: 10 mg cm.sup.−2 [0144] Separator: PE (16 μm)+4 μm Al.sub.2O.sub.3 [0145] Balanced at cut-off voltage of 4.2 V

[0146] Negative electrode: Artificial graphite+SiO [0147] Active material content: 94.6% [0148] Mass loading: 6.28 mg cm.sup.−2 [0149] Separator: PE (16 μm)+4 μm Al.sub.2O.sub.3 [0150] Balanced at cut-off voltage of 4.2 V

[0151] After assembly the following formation protocol was used: [0152] 1. Step charge to 1.5 V followed by 5 h rest step (wetting step @ 40° C.) [0153] 2. CCCV (C/10, 3.7 V (I.sub.limit: 1 h)) (preformation step) [0154] 3. Rest step (6 h) [0155] 4. CCCV (C/10, 4.2 V (I.sub.limit: 0.05 C)) rest step (20 min) [0156] 5. CC discharge (C/10, 3.8 V), (degassing of the cell) [0157] 6. CC discharge (C/10, 2.8 V)

[0158] Following this formation step, the cells were tested as follows: [0159] Rest step (1.5 V, 5 h), CCCV (C/10, 3.7 V (1 h)) [0160] Rest step (6 h), CCCV (C/10, 4.2 V (I.sub.limit: 0.05 C)) [0161] Rest step (20 min), CC discharge (C/10, 3.8 V) [0162] Degassing step [0163] Discharge (C/10, 2.8 V), rest step (5 h) [0164] CCCV (C/3, 4.2 V (I.sub.limit: 0.05 C)), rest step (20 min) [0165] CC discharge (C/3, 2.8 V) [0166] 50 cycles or until 50% SOH is reached at 40° C.:

[0167] CCCV (C/3, 4.2 V (I.sub.limit: 0.02 C)), rest step (20 min)

[0168] CC discharge (C/3, 3.0 V), rest step (20 min)

Test Results

[0169] The test results for both additives in each cell chemistry are summarised in Tables 5-8 and FIGS. 24-27. From this data it can be seen that both additives in both cell chemistries had a positive influence on cell performance improving both Coulombic efficiency and cycling stability. These results combined with the safety related studies demonstrate that the compounds of this invention simultaneously improved both the safety and performance of energy storage devices containing them.

TABLE-US-00010 TABLE 5 Electrochemical performance of MEXI-1 - Cell Chemistry 1 Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte 2 wt. % MEXI-1 5 wt. % MEXI-1 10 wt. % MEXI-1 30 wt. % MEXI-1 Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Cycle capacity efficiency capacity efficiency capacity efficiency capacity efficiency capacity efficiency No. (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) 1.sup.st 232.2 90.6 239.6 90.6 241.1 90.9 237.8 90.1 238.7 90.9 (0.1 C) 3.sup.rd 224.4 99.6 233.3 99.5 233.1 99.5 231.4 99.5 231.9 99.6 (0.3 C) 50.sup.th 218.1 99.8 227.0 99.8 226.8 99.8 224.8 99.8 226.8 99.9 (0.3 C)

TABLE-US-00011 TABLE 6 Electrochemical performance of MEXI-1 - Cell Chemistry 2 Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte 2 wt. % MEXI-1 5 wt. % MEXI-1 10 wt. % MEXI-1 30 wt. % MEXI-1 Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Cycle capacity efficiency capacity efficiency capacity efficiency capacity efficiency capacity efficiency No. (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) 1.sup.st 199.6 74.5 199.0 74.6 199.2 74.7 200.1 74.6 201.8 75.3 (0.1 C) 3.sup.rd 176.3 97.0 176.3 97.1 175.4 96.9 177.3 97.2 181.4 97.6 (0.3 C) 50.sup.th 125.7 99.6 125.9 99.6 125.8 99.6 127.8 99.6 134.3 99.6 (0.3 C)

TABLE-US-00012 TABLE 7 Electrochemical performance of MEXI-2 - Cell Chemistry 1 Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte 2 wt. % MEXI-1 5 wt. % MEXI-1 10 wt. % MEXI-1 30 wt. % MEXI-1 Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Cycle capacity efficiency capacity efficiency capacity efficiency capacity efficiency capacity efficiency No. (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) 1.sup.st 232.2 90.6 239.5 90.8 239.8 90.6 239.1 90.5 240.5 91.1 (0.1 C) 3.sup.rd 224.4 99.6 231.5 99.6 232.0 99.5 232.3 99.6 233.0 99.6 (0.3 C) 50.sup.th 218.1 99.8 225.6 99.8 225.6 99.8 226.2 99.8 227.9 99.9 (0.3 C)

TABLE-US-00013 TABLE 8 Electrochemical performance of MEXI-2 - Cell Chemistry 2 Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte + Base electrolyte 2 wt. % MEXI-1 5 wt. % MEXI-1 10 wt. % MEXI-1 30 wt. % MEXI-1 Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Discharge Coulombic Cycle capacity efficiency capacity efficiency capacity efficiency capacity efficiency capacity efficiency No. (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) (mAh) (%) 1.sup.st 199.6 74.5 201.6 74.8 201.1 74.8 198.0 74.4 200.8 75.3 (0.1 C) 3.sup.rd 176.3 97.0 177.9 97.0 178.3 97.0 176.7 97.3 179.8 97.5 (0.3 C) 50.sup.th 125.7 99.6 126.8 99.7 127.6 99.6 126.9 99.6 132.6 99.7 (0.3 C)

FIGURES

[0170] FIG. 1 shows three CV traces which serve to demonstrate the electrochemical compatibility of trifluoropropenyl ethers such as product E6.

[0171] FIGS. 2-11 illustrate the results of various spectroscopic analytical techniques carried out on compositions comprising some of the reaction products from the Examples and some reference products.

[0172] FIG. 2 shows a .sup.19F NMR spectrum of LiPF.sub.6 in ethylene carbonate.

[0173] FIG. 3 shows a .sup.19F NMR spectrum of LiPF.sub.6 in propylene carbonate.

[0174] FIG. 4 shows a .sup.19F NMR spectrum of LiPF.sub.6 in ethylene carbonate/propylene carbonate/dimethyl carbonate.

[0175] FIG. 5 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 30% E6/70% ethylene carbonate.

[0176] FIG. 6 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 30% E6/70% propylene carbonate.

[0177] FIG. 7 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 80% E6/20% ethylene carbonate.

[0178] FIG. 8 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 80% E6/20% propylene carbonate.

[0179] FIG. 9 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 30% E7/70% propylene carbonate.

[0180] FIG. 10 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 50% E7/50% ethylene carbonate.

[0181] FIG. 11 shows a .sup.19F NMR spectrum of LiPF.sub.6 in 80% E7/20% ethylene carbonate.

[0182] FIGS. 12a to 12d show .sup.19F NMR spectra of LiPF.sub.6 and CF.sub.3CH═CHOCH.sub.2CF.sub.3 in propylene carbonate.

[0183] FIGS. 13a to 13c show .sup.19F NMR spectra of LiPF.sub.6 and CF.sub.3CH═CHOCH.sub.2CF.sub.3 in propylene carbonate (90%) and fluoroethylene carbonate (10%).

[0184] FIGS. 14a to 14c show .sup.19F NMR spectra of LiPF.sub.6 and CF.sub.3CH═CHOCH.sub.2CF.sub.3 in ethylene carbonate (30%) and ethyl methyl carbonate (70%).

[0185] FIGS. 15a to 15c show .sup.19F NMR spectra of LiFSI and CF.sub.3CH═CHOCH.sub.2CF.sub.3 in propylene carbonate.

[0186] FIGS. 16a to 16c show .sup.19F NMR spectra of LiFSI and CF.sub.3CH═CHOCH.sub.2CF.sub.3 in propylene carbonate (90%) and fluoroethylene carbonate (10%).

[0187] FIGS. 17a to 17b show .sup.19F NMR spectra of LiFSI and CF.sub.3CH═CHOCH.sub.2CF.sub.3 in ethylene carbonate (30%) and ethyl methyl carbonate (70%).

[0188] FIGS. 18a to 18c show .sup.19F NMR spectra of LiPF.sub.6 and CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 in propylene carbonate.

[0189] FIGS. 19a to 19c show .sup.19F NMR spectra of LiPF.sub.6 and CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 in propylene carbonate (90%) and fluoroethylene carbonate (10%).

[0190] FIGS. 20a to 20c show .sup.19F NMR spectra of LiPF.sub.6 and CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 in ethylene carbonate (30%) and ethyl methyl carbonate (70%).

[0191] FIGS. 21a to 21c show .sup.19F NMR spectra of LiFSI and CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 in propylene carbonate.

[0192] FIGS. 22a to 22c show .sup.19F NMR spectra of LiFSI and CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 in propylene carbonate (90%) and fluoroethylene carbonate (10%).

[0193] FIGS. 23a to 23c show .sup.19F NMR spectra of LiFSI and CF.sub.3CH═CHOCH.sub.2CF.sub.2CHF.sub.2 in ethylene carbonate (30%) and ethyl methyl carbonate (70%).

[0194] FIG. 24 shows the electrochemical performance of MEXI-1—cell chemistry 1

[0195] FIG. 25 shows the electrochemical performance of MEXI-1—cell chemistry 2

[0196] FIG. 26 shows the electrochemical performance of MEXI-2—cell chemistry 1

[0197] FIG. 27 shows the electrochemical performance of MEXI-2—cell chemistry 2 (% in composition by weight)