Phosphorus containing electrolytes
The present disclosure is directed to phosphorus based thermal runaway inhibiting (TRI) materials, the synthesis thereof and an electrochemical cell electrolyte containing the phosphorus based materials.
1. An electrical energy storage device electrolyte comprising:
a) an aprotic organic solvent system;
b) an alkali metal salt; and
c) at least one of the following phosphate based compounds in an amount of from 0.01 wt. % to 60 wt. % of the electrolyte
wherein:
A is oxygen or sulfur;
Ph is a phenyl ring;
L is oxygen or sulfur;
x and y are either 1 or 2, but must sum to equal 3;
R is a phenyl ring with at least one of the hydrogen atoms on the ring is substituted with a halogen, alkyl, alkoxy, silyl, sulfoxide, perfluorinated alkyl, silane, sulfoxides, azo, amide, ether or thioether group or combination thereof.
2. The electrolyte of claim 1 , wherein the aprotic organic solvent comprises an open-chain or cyclic carbonate, carboxylic acid ester, nitrite, ether, sulfone, ketone, lactone, dioxolane, glyme, crown ether, siloxane, phosphoric acid ester, phosphite, mono- or polyphosphazene or mixtures thereof.
3. The electrolyte of claim 1 , wherein the cation of the alkali metal salt comprises lithium, sodium, aluminum or magnesium.
4. The electrolyte of claim 1 , further comprising an additive.
5. The electrolyte of claim 4 , wherein the additive comprises a sulfur-containing compound, phosphorus-containing compound, boron-containing compound, silicon-containing compound, fluorine-containing compound, nitrogen-containing compound, compound containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydride or the mixtures thereof.
6. The electrolyte of claim 1 , wherein the additive comprises a concentration in the electrolyte of from about 0.01 wt. % to about 5 wt. %.
7. The electrolyte of claim 1 , further comprising an ionic liquid.
8. The electrolyte of claim 7 , wherein the ionic liquid comprises an organic cation comprising N-alkyl-N-alkyl-pyrrolidinium, N-alkyl-N-alkyl-pyridnium, N-alkyl-N-alkyl-sulfonium, N-alkyl-N-alkyl-ammonium, or N-alkyl-N-alkyl-piperdinium.
9. The electrolyte of claim 7 , wherein the ionic liquid comprises an anion comprising tetrafluoroborate, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, bis(pentafluoroethylsulfonyl)imide, or trifluoroacetate.
10. An electrical energy storage device comprising:
a cathode;
an anode; and
an electrolyte according to claim 1 .
11. The device of claim 10 , wherein the cathode comprises a lithium metal oxide, spinel, olivine, carbon-coated olivine, LiFePO 4 , LiCoO 2 , LiNiO 2 , LiNi 1x Co y Met z O 2 , LiMn 0.5 Ni 0.5 O 2 , LiMn 0.3 Co 0.3 Ni 0.3 O 2 , LiMn 2 O 4 , LiFeO 2 , Li 1+x′ Ni α Mn β Co γ Met′ δ O 2−z′ F z′ , A n′ B 2 (XO 4 ) 3 (NASICON), vanadium oxide, lithium peroxide, sulfur, polysulfide, a lithium carbon monofluoride or mixtures of any two or more thereof, where Met is Al, Mg, Ti, B, Ga, Si, Mn or Co; Met′ is Mg, Zn, Al, Ga, B, Zr or Ti; A is Li, Ag, Cu, Na, Mn, Fe, Co, Ni, Cu or Zn; B is Ti, V, Cr, Fe or Zr; X is P, S, Si, W or Mo; and wherein 0≤x≤0.3, 0 ≤y≤0.5, 0≤z≤0.5, 0≤x′≤0.4, 0≤α≤1, 0≤β≤1, 0≤γ≤1, 0≤δ≤0.4, 0≤z′≤0.4 and 0≤h′≤3.
12. The device of claim 10 , wherein the anode comprises lithium metal, graphitic material, amorphous carbon, Li 4 Ti 5 O 12 , tin alloy, silicon alloy, intermetallic compound or mixtures thereof.
13. The device of claim 10 , wherein the device comprises a lithium battery, lithium-ion battery, lithium-sulfur battery, lithium-air battery, sodium ion battery, magnesium battery, electrochemical cell, capacitor, lithium/MnO 2 battery, Li/poly(carbon monofluoride) battery, or solar cell.
14. The device of claim 10 , further comprising a porous separator separating the anode and cathode from each other.
15. The device of claim 14 , wherein the porous separator comprises an electron beam-treated micro-porous polyolefin separator or a microporous polymer film comprising nylon, cellulose, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, polybutene, or co-polymers or blends of any two or more such polymers.
16. The device of claim 10 , wherein the aprotic organic solvent comprises an open-chain or cyclic carbonate, carboxylic acid ester, nitrite, ether, sulfone, ketone, lactone, dioxolane, glyme, crown ether, siloxane, phosphoric acid ester, phosphite, mono- or polyphosphazene or mixtures thereof.
17. The device of claim 10 , wherein the cation of the alkali metal salt comprises lithium, sodium, aluminum or magnesium.
18. The device of claim 10 , wherein the electrolyte further comprises an additive.
19. The device of claim 18 , wherein the additive comprises a sulfur-containing compound, phosphorus-containing compound, boron-containing compound, silicon-containing compound, fluorine-containing compound, nitrogen-containing compound, compound containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydride or the mixtures thereof.
20. The device of claim 10 , further comprising an ionic liquid.
21. The device of claim 20 , wherein the ionic liquid comprises an organic cation comprising N-alkyl-N-alkyl-pyrrolidinium, N-alkyl-N-alkyl-pyridnium, N-alkyl-N-alkyl-sulfonium, N-alkyl-N-alkyl-ammonium, or N-alkyl-N-alkyl-piperdinium.
22. The device of claim 20 , wherein the ionic liquid comprises an anion comprising tetrafluoroborate, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, bis(pentafluoroethylsulfonyl)imide, or trifluoroacetate.