CA2228985A1 - New ionically conductive material with improved conductivity and stability - Google Patents
New ionically conductive material with improved conductivity and stability Download PDFInfo
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- CA2228985A1 CA2228985A1 CA002228985A CA2228985A CA2228985A1 CA 2228985 A1 CA2228985 A1 CA 2228985A1 CA 002228985 A CA002228985 A CA 002228985A CA 2228985 A CA2228985 A CA 2228985A CA 2228985 A1 CA2228985 A1 CA 2228985A1
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- H01M10/052—Li-accumulators
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Sulfamides or mixtures thereof having the formula wherein one to three R substituents are methyl groups, the remainder being ethyl groups, or one R is a methoxyethyl, the remaining R being methyl or ethyl groups. They are useful as electrolytic composition with outstanding conductivity and aprotic solvents. An electrolyte comprising them is highly useful in a lithium battery, a supercapacity type device, an electrochomic device or as a component of a solvent.
Description
CA 0222898~ 1998-02-09 New Ionically Conductive Material with Improved Conductivity and Stability BACKGROUND OF INVENTION
5 (a) FieldoftheInvention This invention relates to an ionically conductive m~t~ri~l with improved conductivity and stability. More particularly, the present invention is concerned with sulfamide derivatives of the formula:
Rl R2 NSO2 N R3 R4 wherein Rl, R2, R3 and R4 are methyl, the rem~ining groups being ethyl groups, or one of Rl, R2, R3 and R4 is a methoxyethyl, the rem~ining groups being methyl or ethyl groups, which are used as aprotic solvents 15 which can be used as media for organic reactions and/or synthesis; as ionically conductive material when a salt is added as a solute to a sulfamide of the above formula; as solid or gel polymer electrolytes useful for electrochemical applications, such as lithium type batteries or so-called rocking chair or lithium ion batteries, the electrolytes being 20 obtained by adding a sulfamide of the above formula with a salt, to a solid or liquid polymer.
(b) Description of the Prior Art:
Sulfamides (RIR2NSO2NR3R4) wherein Rl, R2, R3 and R4 represent alkyl groups and their derivatives are used in many chemical 25 and biological applications. Richey et al (Journal of Organic Chemistry, Vol. 52, No 4, (1987) p. 479-483) report that when used as solvents they are particularly stable toward polar organometallic compounds as well as toward other strongly basic and nucleophilic reagents. It has been found by Richey et al that organomagnesium 30 compounds are indefinitely stable in tetraethylsulfamide identified as TES when Rl, R2, R3 and R4 are all ethyl groups and that the half-life of butyllithium in TES exceeds 15 minutes while in other solvent the half-lives are less than 5 mimltes.
Sulfamides are also used in the field of pesticides (U.S.
35 Patent No. 5,596,017) and in biological applications. A method for preparing sulfamide compounds is described in U.S. Patent No.
5,506,355. U.S. Patent No. 3,879,528, U.S. Patent No. 5,539,102, and CA 0222898~ 1998-02-09 U.S. Patent No. 3,923,886 describe routes and processes for producing sulfamide compounds for those applications.
Sulfamides are also well known for their capability to increase the flame resistance of polymers. U.S. Patent Nos. 3,888,819 and 3,915,931 describe sulfamide compositions and a process for that particular application.
Proton-vacancy conducting polymers based on polyethylene oxide (PEO) and sulfamide-type salts were also reported in the literature by Bermudez and al. (Electrochimica Acta, Vol. 37, No 9, 10 (1992) pp 1603-1609) as a novel basic proton conducting polymer. The presence of the sulfamide-type salt is a key issue of this concept for proton conducting polymer.
In the field of lithium battery, battery performances of PEO polymer modified with sulfonamide end groups provide better 15 conductivity than the PEO system alone. It was reported for example by Ito et al (Solid State Ionics, 86-88, (1996), p 325-328) that PEO having aLkyl-sulfonamide end groups such as PEOlooo-(NKso2Me)2 result in a higher ionic conductivity as compared to PEOlooo. The authors explain this higher conductivity by the higher dissociation constant of the ~0 termin~l sulfonamide.
The identification of new solvents having high dielectric constants, and solvatation powers (adequate high donor (DN) and acceptor (AN) numbers) as well as low viscosities is a paramount for high energy lithium cell development operating at ambient temperature.
25 Mixture of solvents intended to improve overall battery performances may also be of utility as exemplified for instance in U.S. Patent No 4,129,691. These solvents could be used in liquid lithium batteries as well as in gel electrolyte containing polymers networks (cf. U.S. Patent Nos. 4,792,504 and 5,501,920).
U.S. Patent Nos. 4,851,307 and 5,063,124 describe new ionically conductive materials which comprise a salt dissolved in a solvent or mixed therewith in variable amounts of this solvent with a polymer having solvating groups; this solvent being a sulfamide derivative of general formula:
Rl R2 NSO2 N R3 R4 CA 0222898~ 1998-02-09 wherein Rl, R2, R3 and 1~4 are each independently a C(1-10) aL~yl group or a C(1-10) oxaalkyl group. A representative example of this group is Rl = R2, = R3 = R4= ethyl, abbreviated TES, will be considered the 5 reference molecule in the description which follows.
Neither U.S. Patent No. 4,851,307 or U.S. Patent No.
5,063,124 report or claim specific chemical or electrochemical properties or benefits by selecting specific R groups nor describe their relative position on the two nitrogen atoms.
It is an object of the present invention to provide a new family of sulfamides having different Ri groups and which possess different chemical propelties, m~kin~ them useful for different applications such as in the field of lithium batteries and other organic 15 chemistry in general.
It is another object of the present invention to provide a family of sulfamide derivatives that can be used as aprotic solvents for organic reactions and/or synthesis.
It is another object of the present invention to provide 20 derivatives of the present invention to provide sulfamide derivatives which can be used to produce ionically conductive m~tçri~l~, solids or gel polymer electrolytes or solid and liquid electrolytes.
It is another object of the present invention to provide sulfamide compositions whose chemical and electrochemical properties 25 are especially advantageous for applications as solvent for chemical and electrochemical reactions.
lt is another object of the present invention to provide sulfamides whose properties are especially advantageous for applications as solvent for chemical and electrochemical reactions, and 30 especially for liquid and/or solid and/or gel lithi~lm baKeries or rocking chair batteries.
The present invention relates to sulfamides or llfi~ es for use in an electrolytic composition or as aprotic solvents, said sulfarnides having the general formula:
RIR2Nso2NR3R4 CA 0222898~ 1998-02-09 wherein one to three R substituents are methyl groups, the rem~inder being ethyl groups, or one R is a methoxyethyl, the rem~ining R being methyl or ethyl groups.
When Rl = R2 = R3 = methyl, R4 = ethyl, the sulfamide has a dielectric constant of 57, and a melting point of -33~C.
When Rl = R2 = methyl, R3 = R4 = ethyl, the sulfamide has a dielectric constant of 40.5, a melting point of -24~C and a glass transition temperature of-122~C.
When Rl = R3 = methyl, R2 = R4 = ethyl, the sulfamide has a dielectric constant of 44, a melting point of -56~C and a glass transition temperature of-130~C.
When Rl = R2 = R3 methyl, R4 = methoxy-ethyl, the sulfamide has a dielectric constant of 41.7 and a glass transition 15 temperature of-110~C.
When Rl = R2 = R3 = ethyl, R4 = methoxy-ethyl, the sulfamide has a dielectric constant of 29, a glass transition temperature of-118~C and a stability window ext~n(1ing from 0 to 5 V. vs. lithium.
The invention also relates to an electrolytic composition 20 which comprises at least one sulfamide composition defined above and at least one dissociable salt in solution therein. The sulfamide may be in a-lmixtllre with a co-solvenl, and the salt may be a lithium salt.
According to a preferred embodiment the lithinm salt is selected from the group consisting of LiBF4, LiPF6, Li(RFSO2)2N
25 Li(RFSO2)3C where RF is fluorine or a fluorinated carbon radical having 1 - 4 carbon atoms.
The co-solvent may be chosen from the group consisting of dimethyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, and/or ethylene carbonate, propylene carbonate, dimethyl 30 carbonate, diethyl carbonate r-butyrolactone.
In the electrolytic composition the sulfamide may be in ~l.";x~ e with an aprotic polymer, such as polyethers comprising at least 70% ethylene oxide units, poly(methyl methacrylate), poly(acrylonitrile), and copolymers cont~ining at least 70% vinylidene 35 fluoride units.
CA 0222898~ 1998-02-09 The sulfamide to polymer ratio is preferably less than or equal to 20% and the sulfamide acts as a plasticizer.
The solvent to polymer ratio may be greater than or equal to 50% and the resulting mixture then constitutes a gel.
The invention also relates to a lithium battery wherein the electrolyte, alone or as a component of composite electrodes comprises an electrolytic composition as defined above. In this battery the negative electrode may contain either metallic lithium, a lithium alloy, a carbon intercalation compound or a low voltage intercalation oxide or 10 nitride, and may contain a high voltage intercalation electrode derived from v~n~ m, m~ng~nese, cobalt or nickel oxides, iron or m~ng~rlese iron phosphate or pyrophosphate. The positive electrode may also contain a polydisulfide or sulfur mixed with a conductive additive such as high surface area carbon.
The invention also relates to a supercapacity type device wherein the electrolyte comprises a composition as defined above, wherein the electrodes may contain high surface area carbon.
The invention also relates to an electrochomic device wherein the electrolyte comprises a composition as defined above, and wherein one of the electrodes may be a thin film of tungsten trioxide.
The invention also relates to a solvent composition for use as media co~ lg a sulfamide as defined above alone or in ~ ixll-,es with organic solvents. Such composition may include co-solvents such as aromatic hydrocarbons, or halocarbons, and may be used as media for organic reactions comprising carbanion preparation, Friedel & Craft reactions, Diels & Alder or Michael reactions, cationic or anionic polymerizations .
It is known to the specialist in the field that:
~shortening of a alkyl groups usually results in molecules with less conformational freedom thus increased meltin~ points, viscosities or glass transition temperalules Tg for glass-forming compositions. Examples are for instance the well know propylene carbonate, turning into a glass below -40~C and ethylene carbonate (melting point Tmp= 39~C); dimethylcarbonate, Tmp= 4~C, diethylcarbonate, Tmp= -43~C; acetonitrile Tmp= -48~C, propionitrile CA 0222898~ 1998-02-09 Tmp- -93~C. Similarly, tetramethyl~-llf~mi~e abbreviated TMS melts at 73~C;
~shorter alkyl groups, especially methyl have reduced electron-releasing properties, and the donor numbers (DN) in Gl~tm~nn's 5 definition [V. G-l~n~nn Electochimica Acta 21, 661-670, (1976)] of the corresponding molecules built from these alkyl chains are lower (i.e.
acetonitrile, DN = 14.1, butyronitrile DN = 16.6). Conversely, the acceptor number (AN) is usually moderately affected by chain length (ethanol: AN = 37, n-butanol AN = 36.8);
10 ~ the oxidative stability of ether groups does not extend beyond 3.8 Volts vs. the lithium reference electrode;
~ an increase in dielectric constant is usually accompanied by in increase in reactivity, as the dipoles bear a higher charge and/or are closer to the outer part of the molecule, thus are more exposed to 15 reactants.
Properties varying progressively could be expected when going from TES to TMS with sequential replacement of ethyl by methyl groups. Surprisingly, outstanding behavior was observed on these compounds and those cont~ining the ether linkage in methoxyethyl 20 substi~nt~. The properties were not foreseen or anticipated by one skilled in the art, thus clearly establishing the novelty aspect of the present invention.
The principal properties of interest as solvent for chemical and electrochemical applications are: the liquid temperature 25 range, the dielectric constant (e), the donor (DN) and acceptor (AN) numbers, the glass transition temperature, (Tg) alone or in ~ iX~ es, especially with polar polymers. For electrochemical use, the property values of the first three parameters allow for an increase in the specific conductivity. The electrochemical stability window towards metallic 30 lithium and the potential beyond which solvent oxidation takes place is also a very important property for battery application and must be as wide as possible.
A good solvent for liquid lithium batteries must have a low viscosity, a high boiling point, a low melting point and should be 35 able to dissolve a large quantity of salt (high DN and AN). For lithillm solid polymer batteries, the solvent can be used as a plasticizer (small CA 0222898~ 1998-02-09 amount of solvent is added to the polymer, typically less than 50%
volume). In this particular application, a good plasticizer will lower the Tg of the polymer matrix and its crystallinity. For gel electrolytes (large volume fraction, 50% or higher, of the solvent immobilized by a compatible polymer matrix), all the mentioned properties are important since ion transport mech~ni~m (specific conductivity) can be dependent on both media (solvent and polymer).
DRAWINGS
The invention is illustrated but is not limited by the 10 following drawings in which:
FIGURE 1 is a graph showing the increase in conductivity of NES-I-4 as compared to TES;
FIGURE 2 illustrates the conductivity of PEO-LiTFSI
mixture, POE-LiTFST-NES-I-6 (9% weight) mixture and PEO-LiTFSI-15 TES (8% weight) mixture, all systems having a 35% weight LiTFSI;
FIGURE 3 is a graph comparing the electrochemical stability of NES-II-17 and that of TES; and FIGURE 4 is a graph comparing the capacities of cells having NES-I-3 and NES-II-65 with cells having TES under cycling.
The invention will also be illustrated by means of the following non limitin~ examples.
EXAMPLES
Example 1 The following table summarizes some of the properties of 25 the new sulfamides (Me = methyl, Et = ethyl, s is the conductivity in mS/cm, e the dielectric constant, DN the donor number and AN the acceptor number according to Glltnl~nn~s clefinition; n.m.: not measurable; n. misc.: not miscible) and show the outst~n(lin~ behavior of these compounds:
Example 1 Solvent Trn T solvent r~ mixture Max Conc. at E oxidation St biliq v~
Rl,R2,R3~i Narne~olvent (CB~ solvent and ~ DN AN ~ rnax~ (V + va Li~ (> than ~C) PEO (mSlcm) moUlCg Li/Li ) 200 l~n) (C) Tr ',' '' ' TES -38 -111 47 29.2 19.3 10.6 0.974 0.310 +4.3 Izood T ' : '' ' TMS +73 none 70t misc n m n m n m n m Me Me Me Et ES-14 ~ 0-455 ;~
Me Me,E~,Et NES-I-3 ~ .. 8~:;;i.:.. ~ ,:. :;,.i~ ~ {~" t~ 0.420 ~
Me Et,Me,Et NES-I~ ~ ~0.4 0 ~;" ~l '. ~, Me, Me, Me, EtOMeNES-11~5 ~ ' ~it~ 0-500 ~ A~
Et,Et,Et,E:OMe NES-11-17 - ~ l:~:.:::.::::~: ~:i::.. ::.. : .::~;.:.:~.:: ~ -'i~ '~ ~"~::::: 0.794 0.446 5 Example 2 In this example, the conductivity of a solution co~
0.33 moVkg of LiTFSI in the solvent NES-I-4 (which have the highest dielectric constant) is compared to the conductivity of the TES-LiTFSI
(TESA) system at the same concentration of salt. Conductivity data are 10 measured at di~erenl temperatures (from -20~C to 55~C) with a built in-house bridge similar to the Beckman model RC-15 commercial bridge.
Pl~tini~e~ pl~tinllm Orion (Boston, USA) cells are used and resistance measurements are made at 1 and 3 kHz and extrapolated to 0 kHz.
From FIGURE 1 it is noted that replacement of 3 ethyl 15 groups of TES by 3 methyl groups (NES-I-4) considerably increases the conductivity, more than three times for all temperalu,es.
Example 3 In this example, the conductivity of PEO-LiTFSI
mixtures are illustrated. Samples are prepared as follows: 1) PEO (Mw 20 = 4 x 106) and LiTFSI are dissolved in acetonitrile; 2) the solution obtained is coated on an inert support and then dried under partial vacuum (40 mm Hg) for 2-3 hours at ambient temperature and 3) the electrolyte film is dried under vacuum at 140~C for 48 hours. Samples having plasticizer or diluent NES-I-6 or TES are prepared ~imil~rly.
25 NES-I-6 or TES are added to the mixture of PEO-LiTFSI in acetonitrile and the same procedure as above is respected except that the final drying step is done under 2 mm Hg during 48h at ambient temperature. NES-I-CA 0222898~ 1998-02-09 6 or TES concentration in the final solid electrolyte film is controlled by RMN lH
The SPE films are then disposed between two stainless steel electrodes. Conductivity cells are introduced in an air-tight cell 5 holder that permit electrical contact. The conductivity measurements are performed in an Instron (Burlington, Ont., Canada) temperature chamber equipped with a con~uler-driven controller. Impedance data were collected at intervals of 10~C over the frequency range 5Hz-13MHz using a mode 4192A Hewlett-Packard impedance analyser.
The conductivity of the PEO-LiTFSI-(NES-I-6) ~ e is around 2 times higher as compared to PEO-LiTFSI-TES and close to an order of m~gnit~lde (at 0~C) higher compared to the PEO-LiTFSI system.
Example 4 In this example, the electrochemical stability of NES-II-15 17 is compared to TES for the same concentration of LiTFSI introducedin the solution (0.37 M). A conventional three-electrode cell is used for that study and the working electrode is a glassy carbon rod embedded in Kel-F. Current responses in function of voltage sc~nning (scan rate = 20 mV/sec) are recorded and t~le results are pres~nte~ in Figure 3. Massive 20 solvent oxidation occurs near 5 V for NES-II-17 which is almost 700 mV more noble than for TES. NES-II-17 is therefore a better c~n~lid~te for high voltage-energy lithium batteries.
Example 5 In this example, the effect of different sulfamides on the 25 power and cyclability of lithium polymer cells is compared. The three cells are made of a lithium anode (35 mm thick) supported on a thin sheet of nickel and a composite cathode whose composition by volume is about 40% TiS2, 10% acetylene black and 50% of an ethylene oxide copolymer. This copolymer includes about 80% ethylene oxide as 30 described in the following patents: EPO 0,013,199; U.S. 4,578,326; and U.S. 4,758,483, to which there is added the lithillm salt LiTFSI in a ratio of 30/1. The cathode of effective capacity near 3C/cm2 is placed on a thin nickel collector. The thickness of the separator of the polymer electrolyte is 15 mm and the latter is also made of an ethylene oxide 35 base polymer. The batteries with useful surface of 3.89 cm2 are assembled by hot pressing at 80~C. The sulfamide is added to the separator and the cathode just before the hot pressing step and the molecular sulfamide ratio introduced is 1:1 coll~aled to the amount of LiTFSI in the cell.
5 The batteries are cycled at 25~C at constant current (both charge and discharge) at around C/40 rate and the power performance in discharge of these cells is obtained between cycles 7 to 15. Figure 4 show that cells having NES-I-3 and NES-II-65 retain higher capacity for C/x rate where x = 20 through 4 compared to TES. The cyclability at C/40 for 10 all the cells is very good and similar.
5 (a) FieldoftheInvention This invention relates to an ionically conductive m~t~ri~l with improved conductivity and stability. More particularly, the present invention is concerned with sulfamide derivatives of the formula:
Rl R2 NSO2 N R3 R4 wherein Rl, R2, R3 and R4 are methyl, the rem~ining groups being ethyl groups, or one of Rl, R2, R3 and R4 is a methoxyethyl, the rem~ining groups being methyl or ethyl groups, which are used as aprotic solvents 15 which can be used as media for organic reactions and/or synthesis; as ionically conductive material when a salt is added as a solute to a sulfamide of the above formula; as solid or gel polymer electrolytes useful for electrochemical applications, such as lithium type batteries or so-called rocking chair or lithium ion batteries, the electrolytes being 20 obtained by adding a sulfamide of the above formula with a salt, to a solid or liquid polymer.
(b) Description of the Prior Art:
Sulfamides (RIR2NSO2NR3R4) wherein Rl, R2, R3 and R4 represent alkyl groups and their derivatives are used in many chemical 25 and biological applications. Richey et al (Journal of Organic Chemistry, Vol. 52, No 4, (1987) p. 479-483) report that when used as solvents they are particularly stable toward polar organometallic compounds as well as toward other strongly basic and nucleophilic reagents. It has been found by Richey et al that organomagnesium 30 compounds are indefinitely stable in tetraethylsulfamide identified as TES when Rl, R2, R3 and R4 are all ethyl groups and that the half-life of butyllithium in TES exceeds 15 minutes while in other solvent the half-lives are less than 5 mimltes.
Sulfamides are also used in the field of pesticides (U.S.
35 Patent No. 5,596,017) and in biological applications. A method for preparing sulfamide compounds is described in U.S. Patent No.
5,506,355. U.S. Patent No. 3,879,528, U.S. Patent No. 5,539,102, and CA 0222898~ 1998-02-09 U.S. Patent No. 3,923,886 describe routes and processes for producing sulfamide compounds for those applications.
Sulfamides are also well known for their capability to increase the flame resistance of polymers. U.S. Patent Nos. 3,888,819 and 3,915,931 describe sulfamide compositions and a process for that particular application.
Proton-vacancy conducting polymers based on polyethylene oxide (PEO) and sulfamide-type salts were also reported in the literature by Bermudez and al. (Electrochimica Acta, Vol. 37, No 9, 10 (1992) pp 1603-1609) as a novel basic proton conducting polymer. The presence of the sulfamide-type salt is a key issue of this concept for proton conducting polymer.
In the field of lithium battery, battery performances of PEO polymer modified with sulfonamide end groups provide better 15 conductivity than the PEO system alone. It was reported for example by Ito et al (Solid State Ionics, 86-88, (1996), p 325-328) that PEO having aLkyl-sulfonamide end groups such as PEOlooo-(NKso2Me)2 result in a higher ionic conductivity as compared to PEOlooo. The authors explain this higher conductivity by the higher dissociation constant of the ~0 termin~l sulfonamide.
The identification of new solvents having high dielectric constants, and solvatation powers (adequate high donor (DN) and acceptor (AN) numbers) as well as low viscosities is a paramount for high energy lithium cell development operating at ambient temperature.
25 Mixture of solvents intended to improve overall battery performances may also be of utility as exemplified for instance in U.S. Patent No 4,129,691. These solvents could be used in liquid lithium batteries as well as in gel electrolyte containing polymers networks (cf. U.S. Patent Nos. 4,792,504 and 5,501,920).
U.S. Patent Nos. 4,851,307 and 5,063,124 describe new ionically conductive materials which comprise a salt dissolved in a solvent or mixed therewith in variable amounts of this solvent with a polymer having solvating groups; this solvent being a sulfamide derivative of general formula:
Rl R2 NSO2 N R3 R4 CA 0222898~ 1998-02-09 wherein Rl, R2, R3 and 1~4 are each independently a C(1-10) aL~yl group or a C(1-10) oxaalkyl group. A representative example of this group is Rl = R2, = R3 = R4= ethyl, abbreviated TES, will be considered the 5 reference molecule in the description which follows.
Neither U.S. Patent No. 4,851,307 or U.S. Patent No.
5,063,124 report or claim specific chemical or electrochemical properties or benefits by selecting specific R groups nor describe their relative position on the two nitrogen atoms.
It is an object of the present invention to provide a new family of sulfamides having different Ri groups and which possess different chemical propelties, m~kin~ them useful for different applications such as in the field of lithium batteries and other organic 15 chemistry in general.
It is another object of the present invention to provide a family of sulfamide derivatives that can be used as aprotic solvents for organic reactions and/or synthesis.
It is another object of the present invention to provide 20 derivatives of the present invention to provide sulfamide derivatives which can be used to produce ionically conductive m~tçri~l~, solids or gel polymer electrolytes or solid and liquid electrolytes.
It is another object of the present invention to provide sulfamide compositions whose chemical and electrochemical properties 25 are especially advantageous for applications as solvent for chemical and electrochemical reactions.
lt is another object of the present invention to provide sulfamides whose properties are especially advantageous for applications as solvent for chemical and electrochemical reactions, and 30 especially for liquid and/or solid and/or gel lithi~lm baKeries or rocking chair batteries.
The present invention relates to sulfamides or llfi~ es for use in an electrolytic composition or as aprotic solvents, said sulfarnides having the general formula:
RIR2Nso2NR3R4 CA 0222898~ 1998-02-09 wherein one to three R substituents are methyl groups, the rem~inder being ethyl groups, or one R is a methoxyethyl, the rem~ining R being methyl or ethyl groups.
When Rl = R2 = R3 = methyl, R4 = ethyl, the sulfamide has a dielectric constant of 57, and a melting point of -33~C.
When Rl = R2 = methyl, R3 = R4 = ethyl, the sulfamide has a dielectric constant of 40.5, a melting point of -24~C and a glass transition temperature of-122~C.
When Rl = R3 = methyl, R2 = R4 = ethyl, the sulfamide has a dielectric constant of 44, a melting point of -56~C and a glass transition temperature of-130~C.
When Rl = R2 = R3 methyl, R4 = methoxy-ethyl, the sulfamide has a dielectric constant of 41.7 and a glass transition 15 temperature of-110~C.
When Rl = R2 = R3 = ethyl, R4 = methoxy-ethyl, the sulfamide has a dielectric constant of 29, a glass transition temperature of-118~C and a stability window ext~n(1ing from 0 to 5 V. vs. lithium.
The invention also relates to an electrolytic composition 20 which comprises at least one sulfamide composition defined above and at least one dissociable salt in solution therein. The sulfamide may be in a-lmixtllre with a co-solvenl, and the salt may be a lithium salt.
According to a preferred embodiment the lithinm salt is selected from the group consisting of LiBF4, LiPF6, Li(RFSO2)2N
25 Li(RFSO2)3C where RF is fluorine or a fluorinated carbon radical having 1 - 4 carbon atoms.
The co-solvent may be chosen from the group consisting of dimethyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, and/or ethylene carbonate, propylene carbonate, dimethyl 30 carbonate, diethyl carbonate r-butyrolactone.
In the electrolytic composition the sulfamide may be in ~l.";x~ e with an aprotic polymer, such as polyethers comprising at least 70% ethylene oxide units, poly(methyl methacrylate), poly(acrylonitrile), and copolymers cont~ining at least 70% vinylidene 35 fluoride units.
CA 0222898~ 1998-02-09 The sulfamide to polymer ratio is preferably less than or equal to 20% and the sulfamide acts as a plasticizer.
The solvent to polymer ratio may be greater than or equal to 50% and the resulting mixture then constitutes a gel.
The invention also relates to a lithium battery wherein the electrolyte, alone or as a component of composite electrodes comprises an electrolytic composition as defined above. In this battery the negative electrode may contain either metallic lithium, a lithium alloy, a carbon intercalation compound or a low voltage intercalation oxide or 10 nitride, and may contain a high voltage intercalation electrode derived from v~n~ m, m~ng~nese, cobalt or nickel oxides, iron or m~ng~rlese iron phosphate or pyrophosphate. The positive electrode may also contain a polydisulfide or sulfur mixed with a conductive additive such as high surface area carbon.
The invention also relates to a supercapacity type device wherein the electrolyte comprises a composition as defined above, wherein the electrodes may contain high surface area carbon.
The invention also relates to an electrochomic device wherein the electrolyte comprises a composition as defined above, and wherein one of the electrodes may be a thin film of tungsten trioxide.
The invention also relates to a solvent composition for use as media co~ lg a sulfamide as defined above alone or in ~ ixll-,es with organic solvents. Such composition may include co-solvents such as aromatic hydrocarbons, or halocarbons, and may be used as media for organic reactions comprising carbanion preparation, Friedel & Craft reactions, Diels & Alder or Michael reactions, cationic or anionic polymerizations .
It is known to the specialist in the field that:
~shortening of a alkyl groups usually results in molecules with less conformational freedom thus increased meltin~ points, viscosities or glass transition temperalules Tg for glass-forming compositions. Examples are for instance the well know propylene carbonate, turning into a glass below -40~C and ethylene carbonate (melting point Tmp= 39~C); dimethylcarbonate, Tmp= 4~C, diethylcarbonate, Tmp= -43~C; acetonitrile Tmp= -48~C, propionitrile CA 0222898~ 1998-02-09 Tmp- -93~C. Similarly, tetramethyl~-llf~mi~e abbreviated TMS melts at 73~C;
~shorter alkyl groups, especially methyl have reduced electron-releasing properties, and the donor numbers (DN) in Gl~tm~nn's 5 definition [V. G-l~n~nn Electochimica Acta 21, 661-670, (1976)] of the corresponding molecules built from these alkyl chains are lower (i.e.
acetonitrile, DN = 14.1, butyronitrile DN = 16.6). Conversely, the acceptor number (AN) is usually moderately affected by chain length (ethanol: AN = 37, n-butanol AN = 36.8);
10 ~ the oxidative stability of ether groups does not extend beyond 3.8 Volts vs. the lithium reference electrode;
~ an increase in dielectric constant is usually accompanied by in increase in reactivity, as the dipoles bear a higher charge and/or are closer to the outer part of the molecule, thus are more exposed to 15 reactants.
Properties varying progressively could be expected when going from TES to TMS with sequential replacement of ethyl by methyl groups. Surprisingly, outstanding behavior was observed on these compounds and those cont~ining the ether linkage in methoxyethyl 20 substi~nt~. The properties were not foreseen or anticipated by one skilled in the art, thus clearly establishing the novelty aspect of the present invention.
The principal properties of interest as solvent for chemical and electrochemical applications are: the liquid temperature 25 range, the dielectric constant (e), the donor (DN) and acceptor (AN) numbers, the glass transition temperature, (Tg) alone or in ~ iX~ es, especially with polar polymers. For electrochemical use, the property values of the first three parameters allow for an increase in the specific conductivity. The electrochemical stability window towards metallic 30 lithium and the potential beyond which solvent oxidation takes place is also a very important property for battery application and must be as wide as possible.
A good solvent for liquid lithium batteries must have a low viscosity, a high boiling point, a low melting point and should be 35 able to dissolve a large quantity of salt (high DN and AN). For lithillm solid polymer batteries, the solvent can be used as a plasticizer (small CA 0222898~ 1998-02-09 amount of solvent is added to the polymer, typically less than 50%
volume). In this particular application, a good plasticizer will lower the Tg of the polymer matrix and its crystallinity. For gel electrolytes (large volume fraction, 50% or higher, of the solvent immobilized by a compatible polymer matrix), all the mentioned properties are important since ion transport mech~ni~m (specific conductivity) can be dependent on both media (solvent and polymer).
DRAWINGS
The invention is illustrated but is not limited by the 10 following drawings in which:
FIGURE 1 is a graph showing the increase in conductivity of NES-I-4 as compared to TES;
FIGURE 2 illustrates the conductivity of PEO-LiTFSI
mixture, POE-LiTFST-NES-I-6 (9% weight) mixture and PEO-LiTFSI-15 TES (8% weight) mixture, all systems having a 35% weight LiTFSI;
FIGURE 3 is a graph comparing the electrochemical stability of NES-II-17 and that of TES; and FIGURE 4 is a graph comparing the capacities of cells having NES-I-3 and NES-II-65 with cells having TES under cycling.
The invention will also be illustrated by means of the following non limitin~ examples.
EXAMPLES
Example 1 The following table summarizes some of the properties of 25 the new sulfamides (Me = methyl, Et = ethyl, s is the conductivity in mS/cm, e the dielectric constant, DN the donor number and AN the acceptor number according to Glltnl~nn~s clefinition; n.m.: not measurable; n. misc.: not miscible) and show the outst~n(lin~ behavior of these compounds:
Example 1 Solvent Trn T solvent r~ mixture Max Conc. at E oxidation St biliq v~
Rl,R2,R3~i Narne~olvent (CB~ solvent and ~ DN AN ~ rnax~ (V + va Li~ (> than ~C) PEO (mSlcm) moUlCg Li/Li ) 200 l~n) (C) Tr ',' '' ' TES -38 -111 47 29.2 19.3 10.6 0.974 0.310 +4.3 Izood T ' : '' ' TMS +73 none 70t misc n m n m n m n m Me Me Me Et ES-14 ~ 0-455 ;~
Me Me,E~,Et NES-I-3 ~ .. 8~:;;i.:.. ~ ,:. :;,.i~ ~ {~" t~ 0.420 ~
Me Et,Me,Et NES-I~ ~ ~0.4 0 ~;" ~l '. ~, Me, Me, Me, EtOMeNES-11~5 ~ ' ~it~ 0-500 ~ A~
Et,Et,Et,E:OMe NES-11-17 - ~ l:~:.:::.::::~: ~:i::.. ::.. : .::~;.:.:~.:: ~ -'i~ '~ ~"~::::: 0.794 0.446 5 Example 2 In this example, the conductivity of a solution co~
0.33 moVkg of LiTFSI in the solvent NES-I-4 (which have the highest dielectric constant) is compared to the conductivity of the TES-LiTFSI
(TESA) system at the same concentration of salt. Conductivity data are 10 measured at di~erenl temperatures (from -20~C to 55~C) with a built in-house bridge similar to the Beckman model RC-15 commercial bridge.
Pl~tini~e~ pl~tinllm Orion (Boston, USA) cells are used and resistance measurements are made at 1 and 3 kHz and extrapolated to 0 kHz.
From FIGURE 1 it is noted that replacement of 3 ethyl 15 groups of TES by 3 methyl groups (NES-I-4) considerably increases the conductivity, more than three times for all temperalu,es.
Example 3 In this example, the conductivity of PEO-LiTFSI
mixtures are illustrated. Samples are prepared as follows: 1) PEO (Mw 20 = 4 x 106) and LiTFSI are dissolved in acetonitrile; 2) the solution obtained is coated on an inert support and then dried under partial vacuum (40 mm Hg) for 2-3 hours at ambient temperature and 3) the electrolyte film is dried under vacuum at 140~C for 48 hours. Samples having plasticizer or diluent NES-I-6 or TES are prepared ~imil~rly.
25 NES-I-6 or TES are added to the mixture of PEO-LiTFSI in acetonitrile and the same procedure as above is respected except that the final drying step is done under 2 mm Hg during 48h at ambient temperature. NES-I-CA 0222898~ 1998-02-09 6 or TES concentration in the final solid electrolyte film is controlled by RMN lH
The SPE films are then disposed between two stainless steel electrodes. Conductivity cells are introduced in an air-tight cell 5 holder that permit electrical contact. The conductivity measurements are performed in an Instron (Burlington, Ont., Canada) temperature chamber equipped with a con~uler-driven controller. Impedance data were collected at intervals of 10~C over the frequency range 5Hz-13MHz using a mode 4192A Hewlett-Packard impedance analyser.
The conductivity of the PEO-LiTFSI-(NES-I-6) ~ e is around 2 times higher as compared to PEO-LiTFSI-TES and close to an order of m~gnit~lde (at 0~C) higher compared to the PEO-LiTFSI system.
Example 4 In this example, the electrochemical stability of NES-II-15 17 is compared to TES for the same concentration of LiTFSI introducedin the solution (0.37 M). A conventional three-electrode cell is used for that study and the working electrode is a glassy carbon rod embedded in Kel-F. Current responses in function of voltage sc~nning (scan rate = 20 mV/sec) are recorded and t~le results are pres~nte~ in Figure 3. Massive 20 solvent oxidation occurs near 5 V for NES-II-17 which is almost 700 mV more noble than for TES. NES-II-17 is therefore a better c~n~lid~te for high voltage-energy lithium batteries.
Example 5 In this example, the effect of different sulfamides on the 25 power and cyclability of lithium polymer cells is compared. The three cells are made of a lithium anode (35 mm thick) supported on a thin sheet of nickel and a composite cathode whose composition by volume is about 40% TiS2, 10% acetylene black and 50% of an ethylene oxide copolymer. This copolymer includes about 80% ethylene oxide as 30 described in the following patents: EPO 0,013,199; U.S. 4,578,326; and U.S. 4,758,483, to which there is added the lithillm salt LiTFSI in a ratio of 30/1. The cathode of effective capacity near 3C/cm2 is placed on a thin nickel collector. The thickness of the separator of the polymer electrolyte is 15 mm and the latter is also made of an ethylene oxide 35 base polymer. The batteries with useful surface of 3.89 cm2 are assembled by hot pressing at 80~C. The sulfamide is added to the separator and the cathode just before the hot pressing step and the molecular sulfamide ratio introduced is 1:1 coll~aled to the amount of LiTFSI in the cell.
5 The batteries are cycled at 25~C at constant current (both charge and discharge) at around C/40 rate and the power performance in discharge of these cells is obtained between cycles 7 to 15. Figure 4 show that cells having NES-I-3 and NES-II-65 retain higher capacity for C/x rate where x = 20 through 4 compared to TES. The cyclability at C/40 for 10 all the cells is very good and similar.
Claims (27)
1. Sulfamides or mixtures for use in an electrolytic composition or as aprotic solvents, said sulfamides having the general formula:
wherein one to three R substituents are methyl groups, the remainder being ethyl groups, or one R is a methoxyethyl, the remaining R being methyl or ethyl groups.
wherein one to three R substituents are methyl groups, the remainder being ethyl groups, or one R is a methoxyethyl, the remaining R being methyl or ethyl groups.
2. Sulfamide according to claim 1, characterized in that R1 =
R2 = R3 = methyl, R4 = ethyl, having a dielectric constant of 57, and a melting point of -33°C.
R2 = R3 = methyl, R4 = ethyl, having a dielectric constant of 57, and a melting point of -33°C.
3. Sulfamide according to claim 1, characterized in that R1 =
R2 = methyl, R3 = R4 = ethyl, having a dielectric constant of 40.5, a melting point of -24°C and a glass transition temperature of -122°C.
R2 = methyl, R3 = R4 = ethyl, having a dielectric constant of 40.5, a melting point of -24°C and a glass transition temperature of -122°C.
4. Sulfamide according to claim 1, characterized in that R1 =
R3 = methyl, R2 = R4 = ethyl, having a dielectric constant of 44,. a melting point of -56°C and a glass transition temperature of -130°C.
R3 = methyl, R2 = R4 = ethyl, having a dielectric constant of 44,. a melting point of -56°C and a glass transition temperature of -130°C.
5. Sulfamide according to claim 1, characterized in that R1 =
R2 = R3 methyl, R4= methoxy-ethyl, having a dielectric constant of 41.7 and a glass transition temperature of -110°C.
R2 = R3 methyl, R4= methoxy-ethyl, having a dielectric constant of 41.7 and a glass transition temperature of -110°C.
6. Sulfamide according to claim 1, characterized in that R1 =
R2 = R3 = ethyl, R4 = methoxy-ethyl, having a dielectric constant of 29, a glass transition temperature of -118°C and a stability window extending from 0 to 5 V. vs. lithium.
R2 = R3 = ethyl, R4 = methoxy-ethyl, having a dielectric constant of 29, a glass transition temperature of -118°C and a stability window extending from 0 to 5 V. vs. lithium.
7. Electrolytic composition which comprises at least one sulfamide composition according to claim 1 and at least one dissociable salt in solution therein.
8. Electrolytic composition according to claim 7 wherein said sulfamide is in admixture with a co-solvent.
9. Electrolytic composition according to claim 7 wherein the salt is a lithium salt.
10. Electrolytic composition according to claim 8 wherein the lithium salt is selected from the group consisting of LiBF4, LiPF6, Li(RFSO2)2N Li(RFSO2)3C where RF is fluorine or a fluorinated carbon radical having 1 - 4 carbon atoms.
11. Electrolytic composition according to claim 8 wherein the co-solvent is chosen from the group consisting of dimethyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, and/or ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate g-butyrolactone.
12. Electrolytic composition according to claim 7 wherein said sulfamide is in admixture with an aprotic polymer.
13. Electrolytic composition according to claim 12 wherein the aprotic polymer is selected from polyethers comprising at least 70%
ethylene oxide units, poly(methyl methacrylate), poly(acrylonitrile), and copolymers containing at least 70% vinylidene fluoride units.
ethylene oxide units, poly(methyl methacrylate), poly(acrylonitrile), and copolymers containing at least 70% vinylidene fluoride units.
14. Electrolytic composition according to claims 11 and 13 wherein the sulfamide to polymer ratio is less than or equal to 20% and the sulfamide acts as a plasticizer.
15. Electrolytic composition according to claims 11 and 13 wherein the solvent to polymer ratio is greater than or equal to 50% and the resulting mixture constitutes a gel.
16. Electrolytic composition according to claims 11 and 13 wherein the solvent to polymer ratio is less than 50% and the resulting mixture is a highly plasticized polymer base system.
17. Lithium battery wherein the electrolyte, alone or as a component of composite electrodes comprises an electrolytic composition according to claims 7 to 16.
18. Lithium battery according to claim 17 wherein the negative electrode contains either metallic lithium, a lithium alloy, a carbon intercalation compound or a low voltage intercalation oxide or nitride.
19. Lithium battery according to claims 17 and 18 wherein the positive electrode contains a high voltage intercalation electrode derived from vanadium, manganese, cobalt or nickel oxides, iron or manganese iron phosphate or pyrophosphate.
20. Lithium battery according to claims 17 and 18 wherein the positive electrode contains a polydisulfide or sulfur mixed with a conductive additive such as high surface area carbon.
21. Supercapacity type device wherein the electrolyte comprises a composition according to claims 7 to 16.
22. Surpercapacity type device according to claim 21 wherein the electrodes contain high surface area carbon.
23. Electrochomic device wherein the electrolyte comprises a composition according to claims 7 to 16.
24. Electrochomic device to claim 23 wherein one of the electrodes is a thin film of tungsten trioxide.
25. Solvent composition for use as media containing a sulfamide according to claims 1 to 5 alone or in admixtures with organic solvents.
26. Solvent composition according to claim 25 wherein the co-solvents are like aromatic hydrocarbons, or halocarbons.
27. Solvent composition according to claims 25 and 26 for use as media for organic reactions comprising carbanion preparation, Friedel & Craft reactions, Diels & Alder or Michael reactions, cationic or anionic polymerizations.
Priority Applications (1)
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|---|---|---|---|
| CA002228985A CA2228985A1 (en) | 1997-02-07 | 1998-02-09 | New ionically conductive material with improved conductivity and stability |
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|---|---|---|---|
| CA2,197,056 | 1997-02-07 | ||
| CA002197056A CA2197056A1 (en) | 1997-02-07 | 1997-02-07 | New ionically conductive material with improved conductivity and stability |
| CA002228985A CA2228985A1 (en) | 1997-02-07 | 1998-02-09 | New ionically conductive material with improved conductivity and stability |
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| CN109563402A (en) * | 2016-08-04 | 2019-04-02 | 默克专利有限公司 | The preparation of organic functional material |
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| CN109563402A (en) * | 2016-08-04 | 2019-04-02 | 默克专利有限公司 | The preparation of organic functional material |
| CN109563402B (en) * | 2016-08-04 | 2022-07-15 | 默克专利有限公司 | Preparation of organic functional materials |
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