CA2435218A1 - Plastic crystal electrolytes based on a polar, neutral matrix - Google Patents

Plastic crystal electrolytes based on a polar, neutral matrix Download PDF

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CA2435218A1
CA2435218A1 CA002435218A CA2435218A CA2435218A1 CA 2435218 A1 CA2435218 A1 CA 2435218A1 CA 002435218 A CA002435218 A CA 002435218A CA 2435218 A CA2435218 A CA 2435218A CA 2435218 A1 CA2435218 A1 CA 2435218A1
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solid
mixed conductor
conductor according
state ionic
polymer
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Michel Armand
Yaser Abu-Lebdeh
Pierre-Jean Alarco
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    • H—ELECTRICITY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • 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
    • H—ELECTRICITY
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Description

PLASTIC CRYSTAL ELECTROLYTES BASED ON A POLAR, NEUTRAL MATRIX
Co-invented by:
Yaser Abu-Lebdeh; Pierre-Jean Alarco: Michel Armand Invention owned by:
Yaser Abu-Lebdeh; Pierre-Jean Alarco; Michel Armand Addresses of Inventors/Owners of the invention:
Michel Armand : 3180 Fendall, Montreal, Quebec, Canada H3T-1N4 Yaser Abu-Lebdeh : 1206-1225 Saint-Marc, Montreal, Quebec, Canada H3H-2E7 Pierre-Jean Alarco : 940 Saint-Fran~ois-Xavier, Ville Saint-Laurent, Quebec, Canada Description of prior art:
Interest for solid ionic conductors based on plastic crystals has been raised recently when significant room temperature conductivities were reported. This was achieved by adding a lithium salt (< 10 molar %) to salts of either tetraalkylammonium or some heterocyclic canons like pyrrolidinium and pyrazolium (M D. MacFarlane et al , Nature 1999, 402, 792-794). These materials show a unique combination of excellent mechanical (high plasticity) and structural properties (high diffusivity) as compared to conventional solid electrolytes making them good candidates for electrochemical devices such as lithium batteries and photoelectrochemical devices. However, ambient temperature conductivities above 10-4 Sari ~ could not be achieved practically with this method of preparing plastic crystal electrolytes.
Description of the invention:
In the present invention, neutral organic or inorganic molecules with a high dipole moment are used as a solid matrix for inorganic salts in order to give high ionic conductivity of "ions-of interest". The plastic crystalline phase of the solid matrices covers a wide range of temperatures, which allows for the design of ionic conductors working at the required operating temperature of the devices.
One or more of the different matrices described (sections 1.1 to 1.5) may be used in combination with one or more of the salts described (section 2).
The general formulas of the materials of the invention are:
1. The plastic crystal matrices:
1.1 Cyano-containing matrices:
CN CN
R3i~ _W_ ~ R2 R4 R~
where:
W represents an intercalating group which can be but is not limited to:
A single, double or triple bond; An intercalating group, such as an atom (O, S) or groups of atoms (CH2, Si(CH3)2); A repeating unit.
Rl, R2, R3 and R4 represents organic groups chosen from but not limited to:
CN; H, alkyl or aryl group; COZR3, and/or CONR3R4 (R3, R4= H, alkyl or aryl);
A
repeating unit.
1.2 t-butyl derivative matrices:

H3C--~--R

where:
R represents organic groups chosen from but not limited to:
Cl; CN; alkyl or aryl group; C02R~; CONR~R2; S03R~; SOzR~; NHR~; NR1R2;
(R', R2= H, alkyl heteroalkyl, aryl or heteroaryl).
1.3 Metallotranes:
Ra R3 R~2 R~~
W", ' ::C Y", Rs R8 A C-W-C-Y" Z-R'3 C W' C-Y' Ri~ ~ 2 Rs' ~ ~ o where:
A represents an atom or group of atoms which can be but is not limited to:
N, P, As, P(O), P(S), As(O).
W, W', W" ,Y, Y', Y" represents a group which can be but is not limited to:
A single, double or triple bond; An intercalating group, such as an atom (O, S) or groups of atoms (CHZ, Si(CH3)z); A repeating unit.
R' to R'2 represents organic groups chosen from but not limited to:
CN; H, alkyl or aryl group; COZR, COR and/or CONRR' (R, R'= H, alkyl or aryl).
R'3 represents:
An organic group as defined for Rl to R12, a free orbital.
Z represents a metal atom, which can be but is not limited to:
Al, B, Si, Ti.
1.4 Caged inorganic molecules:
B~~ ~B
B
\A~
where:
A represents an atom which can be but is not limited to:
P, As, Sb.
B represents a group which can be but is not limited to:
An atom (O,S, As); A group such as NR, PR (R = H, alkyl or aryl).
1.4 Caged organic molecules:

H,,, ~'' H

O

where:
R1 and R2 represent organic groups chosen from but not limited to:
H, Cl; CN; alkyl or aryl group; COZR'; CONR'R2; S03R'; SOZR'; NHR'; NR'R2;
(R', RZ= H, alkyl heteroalkyl, aryl or heteroaryl or sulphonyl fluoroalkyl).
1.5 sulphonyl based molecules:

where:
R1 and R2 represent organic groups chosen from but not limited to:
Alkyl, cycloalkyl, heteroalkyl or aryl.
Z. The salts:
M+r X_9 where:
+p represents the oxidation state taken values from 1 to S.
's represents the oxidation state taken values from 1 to 5.
M represents a canon chosen from but not limited to:
Li+; Na+; K+; Cs+; Ag+; Cu+; Ca2+; Cu2+; NH4+; Eu3+; Nd3+.
X represents an anion of general formulas:
R'RZN with: R', R2= CN, COR, S02R (R= C"H2n+~, CnF2n+~, unsaturated alkyls), for instance: (F3CSOz)ZN-; (CN)ZN.
RS03~ with R defined as above, for instance: CF3S03- CH3SO3~.

AX" for instance: BF4 ; PF6 ; AsF6, SbF6.
One aspect of the invention deals with cyano containing plastic crystals like succinonitrile. The cyano groups provide the compounds with high dipole moment. This will allow the dissociation of a salt to its ionic components. The plastic range of succinonitrile extends from -30°C to 60°C. The measured conductivities at room temperature of NH4N(SOZCF3)2 (5 molar) in succinonitrile was 3.2x10-3 S.crri ~
( at room temperature). A value that is comparable to liquid electrolytes. For lithium battery applications many lithium salts were doped in the matrix and among which Li(S02CF3)2 (S molar%), in succinonitrile, showed room temperature conductivity of 2.410'3 S.crri ~.
Another aspect of the invention describes the utilisation of the plastic crystalline phase of cage molecules of either inorganic or organic nature. The ease of rotation of cage-like molecules allows a greater disorder within the crystalline lattice structure and hence higher concentration of different type of defects as compared to normal crystals. The inorganic caged molecules like P4Se3 can be n or p-doped in order to work as a semiconductor with enhanced properties as compared to normal semiconductors.
Others like metallotranes can be doped with different type of salt to give high conductivities at moderate or high temperatures.
The compounds of the invention are useful for a wide number of applications.
Particularly as electrolytes for electrochemical and photo-electrochemical devices like batteries, fuel cells, smart windows, sensors and super capacitors. In lithium batteries they are good candidates to replace polymer electrolytes as they offer the same mechanical flexibility but higher conductivities. In fuel cells the community is desperately in need for a proton conductor in the intermediate temperature range (100-600 °C). Our compounds like Metallotranes can solve this problem by doping with a proton source.
The compounds of the present invention are either commercially available or easily prepared by direct addition of two precursors. Doping with the required salt is achieved by melting the desired salt and plastic crystal mixtures.

A non-exhaustive list of properties of matrices/salts combination is given (table 1). A
non-exhaustive list of structures for these materials is presented below (see tables 2-6).

3. Examples:
All operations were handled in a He-flushed Glove box with a dew point of -95°C, and 02 <lvpm. Conductivity measurements were performed using a conductivity cell with a cell constant of 1 cm'. An HP and Gamry frequency analyzers were used to sweep the frequency from 1x10-6 to 13x106 Hz at lOmV.
Example 1 To a well-stirred glass vial, the required amount of LiN(SOZCF3)2 and Succinonitrile were added, lg in total. The mixture was heated at 55-60 °C until it turned transparent.
The plastic range extending from the transition to the melting temperature was determined by DSC (table 1). Conductivity was measured between -20 and 80 °C
(figure 2).
Example 2 A Succinonitrile-LiN(SOZCF3)2 mixture was prepared as in example 1. This was mixed with a poly(ethyleneoxide): LiN(SOZCF3)z (6:1 O:Li ratio) in acetonitrile. The solution was left to react for 24h and then was cast on a Teflon dish. The film was then dried and its conductivity was measured. between -20 and 80 °C. The ratio of the poly(ethyleneoxide): LiN(S02CF3)Z in the mixture was varied between 5 to 20%
in weight.
Example 3 The lithium dicyanamide salt, was prepared by standard methods. To a well-stirred glass vial, the required amount of LiN(CN)Z, and succinonitrile were added, 1 g in total. The mixture was heated at 60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC, (table 1, figure 1).
Conductivity was measured between -20 and 80 °C figure (2).

Example 4 The potassium dicyanamide salt, was prepared by standard methods. To a well-stirred glass vial, the required amount of KN(CN)z, and succinonitrile were added, 1 g in total.
The mixture was heated at 60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC.
Conductivity was measured between -20 and 80 °C (figure 2).
Example 5 To a well-stirred glass vial, the required amount of Ba[N(SOzCF3)z]z and Succinonitrile were added, lg in total. The mixture was heated at 55-60 °C until it turned transparent.
The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C
(figure 2).
Example 6 To a well-stirred glass vial, the required amount of Ca[N(SOZCF3)z]z and Succinonitrile were added, lg in total. The mixture was heated at 55-60 °C until it turned transparent.
The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C
(figure 2).
Example 7 To a well-stirred glass vial, the required amount of NH4N(SOZCF3)z and Succinonitrile were added, lg in total. The mixture was heated at 55-60 °C until it turned transparent.
The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C
(figure 2).

Example 8 To a well-stirred glass vial, the required amount of Cu(CF3S03) and Succinonitrile were added, lg in total. The mixture was heated at SS-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC (table 1, figure 1). Conductivity was measured between -20 and 80 °C (figure 2).
Example 9 To a well-stirred glass vial, the required amount of CuN(S02CF3) and Succinonitrile were added, lg in total. The mixture was heated at SS-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C (figure 2).
Example 10 To a well-stirred glass vial, the required amount of Li(CF3S03) and Succinonitrile were added, lg in total. The mixture was heated at SS-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C (figure 2).
Example 11 To a well-stirred glass vial, the required amount of KN(S02CF3)2 and Succinonitrile were added, lg in total. The mixture was heated at SS-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C (figure 2).

Example 12 To a well-stirred glass vial, the required amount of KN(S02F)Z and Succinonitrile were added, 1 g in total. The mixture was heated at 55-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC, (table 1, figure 1 ). Conductivity was measured between -20 and 80 °C (figure 2).
Example 13 To a well-stirred glass vial, the required amount of K(CF3S03) and Succinonitrile were added, 1 g in total. The mixture was heated at 55-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C (data not shown).
Example 14 To a well-stirred glass vial, the required amount of LiBF4 and Pivalonitrile were added, lg in total. The mixture was heated at 40 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC.
Conductivity was measured between -20 and 80 °C (figure 2).
Example 15 To a well-stirred glass vial, the required amount of LiBF4 and 1,1,3,3-Tetracynoprpane were added, 1 g in total. The mixture was heated at 140°C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C (data not shown).

Example 16 To a well-stirred glass vial, the required amount of Ag(CF3S03) and Succinonitrile were added, lg in total. The mixture was heated at 55-60 °C until it turned transparent. The plastic range extending from the transition to the melting temperature was determined by DSC, (table 1, figure 1). Conductivity was measured between -20 and 80 °C (figure 2).
Example 17 To a well-stirred glass vial, the required amount of LiN(SOZCF3)2 and Succinonitrile were added, 1 g in total. The mixture was heated at 55-60 °C until it turned transparent.
The plastic range extending from the transition to the melting temperature was determined by DSC. Conductivity was measured between -20 and 80 °C
(figure 2).
Example 18 Boratrane was prepared by adding triethanolamine (1.49g) to boric acid (0.618g) in 100 ml toluene with stirring under azeotropic conditions. The reaction mixture was left to cool to room temperature and the precipitate was filtered and dried under vacuum.
Example 19 Silatrane was prepared by adding triethanolamine (1.49g) to ethyltrimethoxysilane (l.Sg) in 100 ml toluene with stirring under azeotropic conditions. The reaction mixture was left to cool to room temperature and the precipitate was filtered and dried under vacuum.

Example 20 A solid-state battery using a 10 ~ m lithium-titanium spinet Li 1+yTi2_,~404 (0 < x, y < 1 ) as an anode and laminated on a 10 p m nickel foil, a 25 ~ m polymer electrolyte and a 45 ~, m positive electrode is constructed with a total active surface of 4 cm2. The electrolyte is 5% molar Li(CF3S02)2N-Succinonitrile. The positive electrode is obtained from a slurry of 53% by volume of HS-100 carbon source, 40 % by volume LiCo02 in acetonitrile, by coating technique on a 12 ~ m aluminum foil. 1.2 lithium per formula units can be cycled between 2.4 and 3.5 volts.
Example 21 A gel type rocking-chair ("lithium ion") battery is constructed using a 40 p m anode made from graphite flakes (4p. m) with an ethylene-propylene-dime binder (5%
by volume), and laminated on a 10 p. m copper foil, a 45 p, m electrolyte containing a vinylidene fluoride-hexafluoropropylene co-polymer (Solvay, Belgium, 30 w/w %), and fumed silica (5%w/w %) which were gelled with a liquid electrolyte consisting of 1.2 molar lithium hexafluorophosphate in a mixed solvent composed of equivolumic ethylene carbonate:ethylmethyl carbonate (65ww%). The positive electrode consists of a blend of the electrode material of example 5 (80 w/w %), Ketjen black (8 w/w %) and the vinylidene fluoride-hexafluoropropylene co-polymer used in the electrolyte (12 w/w %).
The battery is housed in a flat metal-plastic laminated container allowing for the passage of current leads. At 25°C, the battery operation allows the exchange of 1.3 lithium per manganese in the positive electrode in the voltage range 2 to 4.3 volts.

Claims (43)

1) A solid-state ionic or mixed conductor comprising at least in part one initially neutral plastic crystalline phases holding in solution a salt or a mixture of salts
2) A solid-state ionic or mixed conductor according to claim 1 characterised in that the neutral plastic crystalline phases comprises at least an organic compound
3) A solid-state ionic or mixed conductor according to claim 2 characterised in that the organic compound contains at least one polar group chosen between CN, CX1(X2R1), CX3NR2R3, R4COR5, R6SOR7, R8SOR9, SONR10R11, SO2NR12R13, R14R15R16T~NR17R18R18, R19R20R21QR22~NR23R24R25,(R26R27N=O~) where R1-24, identical or different are organic radicals, mono or multivalent, two or more R groups having the possibility to join together to form a cyclic structure or being part of a polymer, X = O, S, Se, T = B, Al, Q = Si, Ge, Sn
4) A solid-state ionic or mixed conductor according to claim 1 characterised in that the neutral plastic crystalline phase contains at least one inorganic phase
5) A solid-state ionic or mixed conductor according to claim 4 characterised in that the inorganic phase contains pnicnogens chalcogenides
6) A solid-state ionic or mixed conductor according to claim 1 comprising besides the one or several plastic crystalline phases, one or several additives, possessing or not, an electrical conductivity.
7) A solid-state ionic or mixed conductor according to claim 6 characterised in that one of the additives is at least partially under the form of dispersed particles.
8) A solid-state ionic or mixed conductor according to claim 7 characterised in that at least a fraction of the dispersed particles have sizes ranging from 2 to 500 nm.
9) A solid-state ionic or mixed conductor according to claim 6 characterised in that one of the additives is at least partially under the form of a polymer or a mixture of polymers.
10) A solid-state ionic or mixed conductor according to claim 9 characterised in that at least one polymer is under the form of fibres, or of a porous matrix.
11) A solid-state ionic or mixed conductor according to claim 9 characterised in that at least a polymer is under the form porous matrix containing the plastic crystal phase whose pore size is comprised between 2 and 80000 nm.
12) A solid-state ionic or mixed conductor according to claim 9 characterised in that the polymer is miscible with the plastic crystal phase when in the molten state.
13) A solid-state ionic or mixed conductor according to claim 9 characterised in that the polymer is processed or co-processed at a temperature above the melting point of the plastic crystal phase.
14) A solid-state ionic or mixed conductor according to claim 9 characterised in that one of the polymer is at least partially miscible or swollen melting point of the plastic crystal material above its melting point.
15) A solid-state ionic or mixed conductor according to claim 9 characterised in that the polymer and the plastic crystal phase have a common solvent which can be used for casting, painting, or as an extrusion additive.
16) A solid-state ionic or mixed conductor according to claim 6 to 15 characterised in that at least one of the additives contains ionophoretic groups.
17) A solid-state ionic or mixed conductor according to claims 6 to 16 characterised in that at least one of the additives possesses ion-solvating capabilities and that the salt partition coefficients in the two phases ensures that the concentration in the plastic crystal phase corresponds to a high conductivity value.
18) A solid-state ionic or mixed conductor according to claim 17 characterised in that at least one the additives is a solvating polymer
19) A solid-state ionic or mixed conductor according to claim 18 characterised in that the solvating polymer comprises ether units
20) A solid-state ionic or mixed conductor according to claim 19 characterised in that the ether units are oxyethylene -CH2CH2O-
21)A solid-state ionic or mixed conductor according to claims 1 to 20 characterised in that a salt or a mixture of salts are at least partly engaged as a solid solution in the plastic crystal phase.
22) A solid-state ionic or mixed conductor according to claim 18 characterised in that the salt or a mixture of salts contains at least one type of metal ion.
23) A solid-state ionic or mixed conductor according to claim 19 characterised in that the metal ion is chosen among H+, Li+, Na+, K+, Rb+, Cs+, NH4+, Cu+, Ag+, Mg2+, Ca2+, Sr2+, Ba2+, Zn2+, Cu2+, Sn2+, Pb2+, Al3+, Ga 3+, the rare earth in the +2, +3 and +4 valence states, the transition elements in the +2 , + 3 or +4 valence states
24) A solid-state ionic or mixed conductor according to claim 18 characterised in that the salt or a mixture of salts contain at least an onium ion.
25) A solid-state ionic or mixed conductor according to claim 18 characterised in that the opium ion is an ammonium, an amidimium, a guanidinium, a pyridinium, a, imidazolium, a pyrazolium, an oxonium, a sulfonium, a sulfoxonium, a phosphonium, bearing alkyl, alkenyl, arylalkyl, alkylaryl substituents, one or more substituents occasionally forming a ring structure.
26) A solid-state ionic or mixed conductor according to claims 1 to 22 characterised in that a salt or a mixture of salts contain at least one type of anion
27) A solid-state ionic or mixed conductor according to claim 26 characterised in at least one type of anion has a Gutmann Donor Number smaller than 55 in the reference solvent 1,2-dichoroethane
28) A solid-state ionic or mixed conductor according to claim 26 characterised in that least one type of anion is chosen between: Cl-, Br , I-, SCN-, NO3-, ClO4-, BF4-, PF6-, ASF6-, SbF6-, [B(CO2CO2)2]-, AlCl4-, X1COY-, X2SO3-, [X3SO2NSO2X4]-, [X5SO2N(SO2X6)SO2X7]-, the pentacycles derivatives [(CQ)5-p N p]-, where X1-7 are F, Cl, an organic radical, hydrogenated, either partially or totally halogenated, containing catenary oxygens, nitrogen, sulfurs or SO2 groups, the O an N being optionally the atoms linking the organic radical to the anionic part a defined; Y =
_ -O, -NC.ident. N, -C(C.ident. N)2; Q = X, -C.ident. N, -NO2, -SO2X.
29) A solid-state ionic or mixed conductor according to claim 28 characterised in that the halogens are Cl and F.
30) A solid-state ionic or mixed conductor according to claim 28 characterised in that the halogen is F and that more than 50% of the hydrogen atoms are substituted by fluorine.
31) An electrochemical device comprising a solid-state ionic or mixed conductor according to claims 1 to 30.
32) An electrochemical device according to claim 31 characterised in that it is an electrochemical generator comprising at least one positive electrode and one negative electrode.
33) An electrochemical generator according to claim 32 characterised in that at least one negative electrode comprises, alone or in mixtures, lithium metal, lithium dissolved (intercalated) into a hard or a soft carbon, including graphite, a lithium alloy, including those containing Al, Sn, Sb, a mixed transition metal-lithium nitride or phosphide, a lithium-titanium spinel Li1+y Ti2-x/4O4 (0 <= x, y <=1).
34) An electrochemical generator according to claim 32 characterised in that at least one positive electrode comprises, alone or in mixtures, a lithium-transition metal, mixed oxide, where the transition metal is Mn, Co, Ni having a layered or spinel structure, with optional substituents as Mg, B, Al, for the transition metals or fluorine, for oxygen in the lattice.
35) An electrochemical generator according to claim 32 characterised in that at least one positive electrode comprises lithium-transition metal phosphate of general formula Li1+z M'1-x M" x P y Si1-y O4 where M' = Fe, Mn, Co, Ni, M" = Mg, Ca, Al, V, a Nasicon structure Li3-w (M"'1-x M" x)1P y Si1-y-s S s O 4-q F q, M"' = Fe, Mn, Co, Ni, Ti, V, (0 <= x, y, s, q <= 0), z and w corresponding to the advancement of the insertion reaction so that the electro-neutrality in the structure is preserved~
36) An electrochemical device according to claims 1 to 30 characterised in that it is a super-capacitor.
37) A super-capacitor according to claims 36 characterised in that at least one of its electrode comprises high surface carbon, a conjugated polymer, a transition metal oxide or mixed oxide with lithium, on oxyhydroxide, of a transition metal.
38) An electrochemical device according to claims 1 to 30 characterised in that it is a fuel cell.
39) A fuel cell according to claim 38 characterised in that the conductivity of the compounds in claim 1 is at least partially due to H+, hydronium ions, OH-ions, protonated or deprotonated azoles.
40) A fuel cell according to claim 38 characterised in that the fuel is hydrogen, a lower alcohol or glycol of less than 5 carbons, dimethoxymethane, CO, formaldehyde, ammonia.
41) An electrochemical device according to claims 1 to 30 characterised in that it is an electrochromic device able to control the absorption or the reflection of light end near-Infra read upon application of an external electrical stimulation.
42) an electro-chromic device according to claim 41 characterised in that the active electrode comprises a transition metal oxide, a conjugated polymer, a viologen, an hexacyanometallate complex, including prussian blue.
43) An electrochromic device according to claim 41 characterised in that the counter electrode comprises Prussian blue, LiFePO4, FePO4, a Nasicon structure Li3-w (M"'1-x M"x)2P y Si1-y-s S s O4-q F q, M"' = Fe, Mn, CO, Ni, Ti, V, (0 <= x, y, s, q <= 0), z and w corresponding to the advancement of the insertion reaction so that the electro-neutrality in the structure is preserved, a mixed Lithium/ cerium /
tin or titanium oxide.
CA002435218A 2003-07-28 2003-07-28 Plastic crystal electrolytes based on a polar, neutral matrix Abandoned CA2435218A1 (en)

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WO2014153146A1 (en) * 2013-03-14 2014-09-25 Angell C Austen Inorganic plastic crystal electrolytes
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