Modified ionic liquids containing phosphorus
The present disclosure is directed to a phosphorus-modified ionic liquid compound, the synthesis thereof and an electrochemical cell electrolyte containing the phosphorus-modified ionic liquid compound.
1. An ionic liquid compound, comprising: an anion comprising an aluminate, arsenide, cyanide, thiocyanate, nitrite, chlorate, chlorite, chromate, sulfate, sulfite, silicate, thiosulfate, oxalate, acetate, formate, hydroxide, nitrate, phosphate, imide, or borate; and a cation attached to a phosphorus moiety according to the formula:
wherein:
A is CAT + or R 1
B is CAT + or R 2
CAT + is a pyrrolidinium, piperdinium, azepanium, onium, sulfonium, phosphonium, imidazolium, pyridinium or a 5- or 6-membered heterocyclic ring having 1 to 3 heteroatoms as ring members comprising nitrogen, oxygen, silicon or sulfur;
R 1 and R 2 are independently a methyl or C 2 -C 8 alkyl, alkenyl, alkoxy, aryl, alkynyl, alkylsiloxy, silyl, thioether, sulfoxide, azo, amino or silane group or a phenyl or benzyl, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide, alkyl, alkenyl, alkoxy, aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl, thioether, sulfoxide, azo, amino or silane;
Y is O or S, with the proviso that when Y is O, CAT + is not an imidazolium or a pyridinium and R 1 and R 2 are not methyl or C 2 -C 8 alkyl; and
X is O, S, or N; or O, S, or N attached to a methylene, C 2 -C 8 alkylene, alkenylene, alkynylene, alkoxy, ester, carbonylene, phenylene, thioether, sulfoxide, azo or aryl group, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide.
2. An electrical energy storage device electrolyte comprising:
a) an aprotic organic solvent system;
b) an alkali metal salt;
c) an additive; and
d) an ionic liquid compound, comprising: an anion comprising an aluminate, arsenide, cyanide, thiocyanate, nitrite, chlorate, chlorite, chromate, sulfate, sulfite, thiosulfate, oxalate, acetate, formate, hydroxide, nitrate, phosphate, imide, or borate; and
a cation attached to a phosphorus moiety according to the formula:
wherein:
A is CAT + or R 1
B is CAT + or R 2
CAT + is a pyrrolidinium, piperdinium, azepanium, onium, sulfonium, phosphonium, imidazolium, pyridinium or a 5- or 6-membered heterocyclic ring having 1 to 3 heteroatoms as ring members comprising nitrogen, oxygen, silicon or sulfur;
R 1 and R 2 are independently a methyl or C 2 -C 8 alkyl, alkenyl, alkoxy, aryl, alkynyl, alkylsiloxy, silyl, thioether, sulfoxide, azo, amino or sane group or a phenyl or benzyl, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide, alkyl, alkenyl, alkoxy, aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl, thioether, sulfoxide, azo, amino or silane;
Y is O or S, with the proviso that when Y is O, CAT + is not an imidazolium or a pyridinium and R 1 and R 2 are not methyl or C 2 -C 8 alkyl; and
X is O, S, or N; or O, S, N attached to a methylene, C 2 -C 8 alkylene, alkenylene, alkynylene, alkoxy, ester, carbonylene, phenylene, thioether, sulfoxide, azo or aryl group, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide.
3. The electrolyte of claim 2 , wherein the aprotic organic solvent comprises open-chain or cyclic carbonates, carboxylic acid esters, nitrites, ethers, sulfones, ketones, lactones, dioxolanes, glymes, crown ethers, siloxanes, phosphoric acid esters, phosphates, phosphites, mono- or polyphosphazenes or mixtures thereof.
4. The electrolyte of claim 2 , wherein the cation of the alkali metal salt comprises lithium, sodium, aluminum or magnesium.
5. The electrolyte of claim 2 , wherein the additive comprises sulfur-containing compounds, phosphorus-containing compounds, boron-containing compounds, silicon-containing compounds, fluorine-containing compounds, nitrogen-containing compounds, compounds containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydrides or the mixtures thereof.
6. The compound of claim 1 , wherein either or both of A and B is CAT+.
7. The compound of claim 1 , wherein either or both of R 1 and R 2 is phenyl, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide, alkyl, alkenyl, alkoxy, aryl, alkynyl, alkylsiloxy, phenyl, benzyl, silyl, thioether, sulfoxide, azo, amino or silane.
8. The compound of claim 1 , wherein Y is S.