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1. (WO1997018595) HIGH CONDUCTIVITY ELECTROLYTE SOLUTIONS AND RECHARGEABLE CELLS INCORPORATING SUCH SOLUTIONS
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Description

High Conductivity Electrolyte Solutions And
Rechargeable Cells Incorporating Such Solutions

The present application is a nonprovisional application which claims priority rights based on U.S. Provisional Patent Application Serial No. 60/006,436, filed on November 13, 1995, and U.S. Nonprovisional Patent Application Serial No. 08/748,009, filed
November 12, 1996, which is titled "High Conductivity Electrolyte Solutions and Rechargeable Cells
Incorporating Such Solutions," has attorney identification number AP- 30365, and was transmitted to the Patent and Trademark Office under Express Mail No. EH 801506705 US.

Government License Rights
The U.S. Government has a paid-up license in this invention, and the right in limited circumstances to require the patent owner to license others on
reasonable terms.

Introduction
This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer
electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention is directed to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents.

Background of the Invention
Typical electrolyte solvents for use in liquid or polymer electrolyte solutions include alkyl ethers such as dimethyl ether, diethyl ether, dioxalane, diglyme and tetraglyme; and alkene carbonates such as ethylene carbonate (hereinafter "EC") and propylene carbonate (hereinafter "PC") . These solvents are used to
dissolve electrolyte solutes and/or rubberizing polymer additives to form electrolyte solutions which may be used in electrochemical devices.
Both alkyl ethers and alkene carbonates present significant disadvantages as electrochemical solvents . Specifically, alkyl ethers are relatively volatile, and therefore may evaporate over time. This is a
disadvantage in any electrochemical device that is meant to operate for an extended period of time because evaporation of the solvent may change the electrical behavior of the device. Furthermore, such volatile solvents present fire hazards.
Moreover, alkyl ethers typically have low
dielectric constants which discourage solvation of electrolyte salts. Therefore, alkyl ethers generally depend on cation chelation effects to dissolve
significant amounts of electrolyte salts. Such
compositions, containing limited amounts of
electrolyte, tend to have a limited number of available charge carrier ions .
Alkene carbonates have higher dielectric constants than alkyl ethers, and therefore are better electrolyte solvents for liquid or polymer electrolytes. However, PC is not a suitable solvent because it is unstable in the presence of alkali metals, and forms a passivating layer on lithium. EC is also problematic because its melting point is above room temperature, and therefore it must be mixed with compounds that lower its melting temperature to obtain a liquid or rubbery electrolyte. It has never heretofore been appreciated that the relatively involatile sulfonyl/phospho-compound
electrolyte solvents according to the invention would function as advantageous non-aqueous electrolyte solvents.

Summary of the Invention
The present invention relates to sulfonyl/phospho-compound electrolyte solvents and electrolyte solutions incorporating such solvents. The present invention further relates to rechargeable batteries and other electrochemical devices which utilize electrolyte solutions .
The sulfonyl-compound electrolyte solvents
according to the present invention include compounds having the formula (I) shown below:
O
R-S-X (I)
O
wherein X is a halide, and
R is an alkyl group, a perfluorinated alkyl group, a perchlorinated alkyl group, or -N=PX3. The phospho-compound electrolyte solvents according to the present invention further include compounds having the formula (II) shown below:
X
X-P=N-R (ID
X
wherein X is a halide, and R is -P(0)X2 or a 1-6 carbon alkyl group.
More preferable sulfonyl/phospho-compound
electrolyte solvents according to formula (I) include C13PNS02C1, CH3S02C1 and CF3 (CF2) 3S02F .
More preferable sulfonyl/phospho-compound
electrolyte solvent according to formula (II) are
C13PNP(0)C12, CI3PNCH3 or C13PNCH2CH3.
Sulfonyl/phospho-compound electrolyte solutions according to the present invention comprise an
electrolyte solute (such as an electrolyte salt) dissolved in a sulfonyl/phospho-compound electrolyte solvent. Preferable electrolyte solutes include alkali cation-containing salts. More preferable electrolyte solutes include LiAlCl4, LiN (S02CF3) 2 and their
corresponding sodium analogs. The sulfonyl/phospho-compound electrolyte solutions according to the present invention comprise less than 50 mole percent, and preferably less than 30 mole percent electrolyte solute .
The sulfonyl/phospho-compound electrolyte
solutions according to the present invention are particularly advantageous because they:
(i) exhibit high electrochemical stability;
(ii) are either involatile (boiling point
> 300 °C) or relatively involatile
(e.g. CH3S02C1, boiling point = 165 °C) ;
(iii) are capable of dissolving large mole
fractions of most electrolyte solutes,
including alkali metal salts, to provide
high room temperature conductivity
electrolyte solutions which maintain
relatively high conductivity at
temperatures below 0 °C;
(iv) do not crystallize at temperatures above
0 °C;
(v) exhibit wide electrochemical windows,
thus enabling use in cells with high
reducing potential anodes and high
oxidizing potential cathodes; and
(vi) are stable in the presence of alkali
metals .
In a further advantageous embodiment of the invention, the sulfonyl/phospho-compound electrolyte solutions may further comprise a high molecular weight polymer which imparts a rubbery consistency to the solution. Such rubbery electrolytes are commonly referred to as "gel electrolytes."
The above-mentioned sulfonyl/phospho-compound electrolyte solutions and gel electrolytes may be employed as electrolytes in most any type of
electrochemical device.

These and other features, aspects and advantages of the present invention will become better understood with reference to the following description, and accompanying drawings .

Brief Description of the Drawings
Figure 1 is an overlay plot of log conductivity (Sem"1) versus mole fraction of (LiAlCl4) dissolved in CH3S02C1 at several different temperatures.
Figure 2 is an overlay plot of log conductivity (Sem1) versus reciprocal temperature (K) for various mole fractions of LiAlCl4 dissolved in CH3S02C1.
Figure 3 is an overlay plot of log conductivity (Sem"1) versus reciprocal temperature (K) for two electrolyte solutions containing 12 mole percent
LiN(S02CF3)2 dissolved in CH3S02C1 , and 12 mole percent LiAlCl4 dissolved in CH3S02C1.
Figure 4 is a plot of log conductivity (Sem"1) versus reciprocal temperature (K) for an electrolyte solution containing 10 mole percent LiAlCl4 dissolved in C13PNP(0)C12.
Figure 5 is an overlay plot of log conductivity (Sem1) versus reciprocal temperature (K) for an
electrolyte solution containing 15 mole percent LiAlCl4 dissolved in CH3S02C1 compared to a solution further containing a high molecular weight polymer (polymethyl methacrylate ("PMMA")).
Figure 6 is a cyclic voltammogram for a solution of 10 mole percent LiN(S02CF3) 2 in CH3S02C1.
Figure 7 is a cyclic voltammogram for a solution of 12 mole percent LiAlCl4 in CH3S02C1.
Figure 8 is a plot of cell voltage versus time for several discharge/charging cycles for a Li/50 mole percent LiAlCl4 dissolved in Cl3PNS02Cl/LiMn204 battery.

Figure 9 is a plot of voltage versus time over several discharge cycles for a rechargeable Na-S battery incorporating sulfonyl/phospho-compound
electrolyte solution.

Detailed Description of the Invention
As used herein, the term "sulfonyl/phospho-compound electrolyte solvent" refers to a compound according to the above-mentioned formula (I) or
formula (II) .
As used herein, the term "electrolyte solute" refers to a conductive species, such as a salt, which behaves as an electrolyte (i.e., transports an electric current via long-range motion of ions) , and may be dissolved in the sulfonyl/phospho-compound electrolyte solvent.
As used herein, the term "sulfonyl/phospho-compound electrolyte solution" refers to a composition comprising an electrolyte solute dissolved in a
sulfonyl phospho-compound electrolyte solvent.
Sulfonyl/phospho-compound electrolyte solvents according to the present invention are preferably
C13PNS02C1, CH3S02C1, CF3 (CF2) 3S02F, C13PNP (O) Cl2 , C13PNCH3 or C13PNCH2CH3.
As shown in Examples 1 and 2 , C13PNS02C1 and
C13PNP(0)C12 were prepared by reacting NH2S03H and
(NH4)2S04, respectively, with PC1S . CF3 (CF2) 3S02F and CH3S02C1 are both commercially available from the
Aldrich Chemical Company.
Sulfonyl/phospho-compound electrolyte solutions were prepared by dissolving weighed amounts of
electrolyte solutes in sulfonyl/phospho-compounds .
These solutions are prepared in a glove box under an inert atmosphere as described in Example 5.
Sulfonyl/phospho-compound electrolyte solutions
according to the invention comprise less than 50% and preferably less than 30% electrolyte solute.

Ionic conductivities of the sulfonyl/phospho-compound electrolyte solutions were determined from complex impedance plots obtained using a HEWLETT-PACKARD Model HP4192A - Frequency Analyzer.
Measurements were automated to cover a predetermined temperature range at a sequence of temperatures
controlled by a EUROTHERM temperature controller.
The cyclic voltammograms shown in Figs . 6 and 7 were obtained using a PAR Potentiometer. All scans were performed at room temperature with a scan speed of lOmV/S. A Li/Li* reference electrode was used for all the scans.
As shown in Example 6, it may be desirable to add a small amount of high molecular weight polymer to a sulfonyl/phospho-compound electrolyte solution to impart a rubbery consistency to the electrolyte.
The sulfonyl/phospho-compound electrolyte solutions described herein are useful in all manner of electrochemical devices which require electrolytes. Some examples of electrochemical devices which require electrolytes include batteries, fuel cells,
photochromic displays, photovoltaic cells and gas sensors. This list is merely exemplary, and is not meant to limit the invention to any particular
electrochemical device. The sulfonyl/phospho-compound electrolyte solutions of the present invention are especially useful as electrolytes for rechargeable cells as shown in Example 8.
Specific embodiments of the present invention will now be described in detail. These examples are
intended to be illustrative, and the invention is not limited to the materials or amounts set forth in these embodiments .

Example 1
Preparation of C13PNS07C1
C13PNS02C1 was synthesized by the following
procedure: 546.5 grams (2.62 moles) of PC15 (purified by sublimation of commercial product obtained from the Aldrich Chemical Company) and 127.14 grams (1.31 moles) of NH2S03H (Aldrich, 99.8 percent), were ground and mixed in a 1000 ml flask equipped with a condenser, an N2-inlet and an HCl-absorbing device. Under a flowing nitrogen atmosphere, the flask was heated in a water bath to near 100° C until the above-mentioned solid reagents completely liquified. Most of the P0C13 was removed by vacuum-distillation at a maximum temperature of 110° C. Then the remaining gold-colored oil was left to crystallize at room temperature. The crystallized product was washed several times with dry n-hexanes and recrystallized at about 5° C. The
resultant product consisted of pale yellow needle crystals and had a melting point of about 35° C.

Example 2
Preparation of C1-.PNP (0) Cl,
C13PNP(0)C12 was prepared by the following
procedure. 300 grams (1.44 moles) of PC1S (Aldrich) was purified by sublimation. The PC15 was then ground together with 47.55 grams (0.36 moles) of (NH4)2S04 and mixed in a three-necked flask equipped with a gas inlet , a condenser and a drying tube . The mixture was heated up to 150 °C in an oil-bath under flowing nitrogen. Three hours later, the mixture was
completely liquified. Then most of the low-boiling side products were removed by vacuum distillation. The final product was distilled at 160 °C under 0.5 mmHg. The product was a clear viscous liquid which slowly crystallized at room temperature.

Example 3
Preparation of Cl.PNCH,
Cl3PNCH3 was prepared by the following procedure. 200 grams (0.96 moles) of PC15 (Aldrich) was purified by sublimation. The PC15 was then ground together with

64.75 grams (0.96 moles) of CH3NH2HC1 (Aldrich, 98%) and mixed in a three-necked flask equipped with a gas inlet, a condenser and a drying tube. 200 mL of chlorobenzene was then added to this mixture. The mixture was refluxed under flowing nitrogen. After five hours, the mixture was allowed to cool. A white needle crystalline product precipitated. The crystals were separated by filtration and subsequently washed in toluene. After drying under vacuum, the crystals were further purified by sublimation. The final purified product was white needle crystals with a melting point of 178 °C.

Example 4
Preparation of C1,PNCH7CH,
C13PNCH2CH3 was prepared by the following
procedure. 200 grams (0.96 moles) of PC15 (Aldrich) was purified by sublimation. The PC1S was then ground together with 173.28 grams (0.96 moles) of CH3CH2NH2HC1 (Aldrich, 98%) and mixed in a three-necked flask equipped with a gas inlet, a condenser, an acid
absorbing device and a drying tube. 200 mL of
tetrachloroethane was added to the mixture, which was then heated to reflux under a nitrogen atmosphere. The flask was allowed to cool after HCl-evolution stopped. Most of the solvent was removed by vacuum distillation until a white needle crystalline product began to precipitate. The crystalline product was washed in toluene and dried under vacuum at room temperature.

Example 5
Preparation and Characterization of
Sulfonyl/Phospho-Compound Electrolyte Solutions
Solutions comprising from 10-40 mole percent
LiAlCl4 dissolved in CH3S02C1 were prepared by weighing out appropriate amounts of LiAlCl4 in a glove box and adding it to an appropriate amount of CH3S02C1. Figs . 1 and 2 show that the room temperature conductivity of this solution approaches a maximum of 10"1 8 Sem"1 at approximately 15 mole percent LiAlCl4.
A solution comprising 12 mole percent LiN(S02CF3)2 dissolved in CH3S02C1 was prepared by weighing out the appropriate ingredients in a glove box. Fig. 3 shows that the room temperature conductivity for the
LiN(S02CF3)2 solution (10"2-8Scm_1) is lower than for an otherwise identical LiAlCl4 solution.
A solution comprising 10 mole percent LiAlCl4 dissolved in C13PNP(0)C12 was prepared in a similar manner to the above-described solutions. Fig. 4 shows that the room temperature conductivity for this
solution was 10"2 8Scm"1.

Example 6
Preparation and Characterization
of a Rubberized Gel Electrolyte Solution
A solution of 15 mole percent LiAlCl4 in CH3S02C1 was prepared according to Example 3. Eight percent by weight high molecular weight polymer "PMMA" was added to the solution to form a rubberized gel. Fig. 5 shows that the conductivity decreased to IO"2 5S/cm"1 upon adding the polymer. It is noted that the process responsible for the conductivity decrease below 0 °C in the 15 mole percent LiAlCl4 solution has been suppressed by the addition of polymer.

Example 7
Testing of Electrochemical Stability of the
Sulfonyl/Phospho-Compound Electrolyte Solutions
A solution comprising 10 mole percent LiN(S02CF3)2 in CH3S02C1 was prepared as in Example 3. Fig. 6 shows that this solution has a wide electrochemical window of approximately 5.6 volts.
A second solution comprising 12 mole percent
LiAlCl4 in CH3S02C1 was prepared as described in Example 5. Fig. 7 shows that this solution has a voltage window of about 4.8 volts. The electrochemical window is limited in the positive direction by deposition of

Cl from the A1C14" anion, rather than by the solvent. A piece of lithium foil was placed in this solution and held for several days at temperatures of 100°C. The lithium foil remained shiny, indicating that the solutions are stable in the presence of alkali metals.

Example 8
A Rechargeable Li Battery Incorporating
Sulfonyl/Phospho-Compound Electrolyte Solution
A voltaic cell was formed using a Li foil anode and a cathode made from LiMn204, carbon black, and a binder, separated by a sulfonyl/phospho-compound electrolyte solution comprising 10 mole percent LiAlCl4 dissolved in C13PNS02C1. Fig. 8 shows several
discharge/charge/discharge cycles for this cell. This cell was cycled 50 times and showed no signs of
deterioration. The cell exhibited a very high capacity of about 140 mAh per gram of LiMn?04.

Example 9
A Rechargeable Na-S Battery Incorporating A
Sulfonyl/Phospho-compound Electrolyte Solution
A sulfur cathode was prepared by mixing 80% by weight sulfur, 15% by weight carbon black and 5% gel electrolyte to serve as a binder. The gel electrolyte was made according to Example 6 , above with the exception that only 1% PMMA was used to ensure the electrolyte was a viscous liquid rather than a rubber. The resultant slurry was cast on a stainless steel substrate which served as a current collector.
A voltaic cell was formed using a Na pellet anode and the above-described cathode separated by a
sulfonyl/phospho-compound electrolyte solution
containing 12 mole % NaAlCl4 dissolved in CH3S02C1.
The cell exhibited a reversible charge-discharge behavior over more than 20 cycles. Figure 9 plots the discharge behavior of the above-described cell.