Fluoroalkyl containing salts combined with fluorinated solvents for electrolytes
Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte may include a fluoroalkyl-substituted LiPF 6 salt or a fluoroalkyl-substituted LiBF 4 salt. In some embodiments, at least one fluorinated alkyl of the salt has a chain length of from 1 to 8 or, more specifically, between about 2 and 8. These fluorinated alkyl groups, in particular, relatively large fluorinated alkyl groups improve solubility of these salts in fluorinated solvents that are less flammable than, for example, conventional carbonate solvents. At the same time, the size of fluoroalkyl-substituted salts should be limited to ensure adequate concentration of the salt in an electrolyte and low viscosity of the electrolyte. In some embodiments, the concentration of a fluoroalkyl-substituted salt is at least about 0.5M. Examples of fluorinated solvents include various fluorinated esters, fluorinated ethers, and fluorinated carbonates, such a 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.
1. An electrolyte for use in an electrochemical cell, the electrolyte comprising:
an electrolyte salt having a concentration of at least about 0.5M,
the electrolyte salt selected from the group consisting of:
i) a fluoroalkyl-substituted lithium hexafluorophosphate having a general structure LiPF X R 6-X , where x is from 1 to 5 and at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group;
ii) a fluoroalkyl-substituted lithium tetrafluoroborate having a general structure LiBF x R 4-x , where x is from 1 to 3 and at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group;
iii) a fluoroalkyl-substituted lithium oxalatoborate having a general structure of LiBC 2 O 4 R 2 , where at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group,
iv) a salt represented by one of general formulas
where at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group; and
a fluorinated solvent being present at between 30% and 80% by weight excluding the electrolyte salt, and
one or more non-fluorinated esters, the electrolyte including a non-fluorinated cyclic carbonate ester, wherein the non-fluorinated cyclic carbonate ester is present at no more than 10% by weight, excluding the electrolyte salt,
wherein the electrolyte is a one-phase solution at a temperature of about −30° C.
2. The electrolyte according to claim 1 , wherein the fluorinated solvent is selected from a group consisting of 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.
3. The electrolyte according to claim 1 , wherein the fluorinated solvent comprises methyl nonafluorobutyl ether.
4. The electrolyte according to claim 1 , wherein the fluorinated alkyl of the electrolyte salt has the chain length of at least 2 carbon atoms.
5. The electrolyte according to claim 1 , wherein the electrolyte salt comprises one of LiPF 5 C 2 F 5 , LiPF 5 C 4 F 9 , LiPF 5 C 3 F 7 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (C 3 F 7 ) 3 , LiPF 3 (C 4 F 9 ) 3 , LiPF 2 (C 2 F 5 ) 4 , or LiPF(C 2 F 5 ) 5 .
6. The electrolyte according to claim 1 , wherein the electrolyte salt comprises one of LiBF 3 CF 3 , LiBF 3 C 2 F 5 , LiBF 3 C 3 F 7 , LiBF 3 C 4 F 9 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (C 3 F 7 ) 2 , or LiBF 2 (C 4 F 9 ) 2 .
7. The electrolyte according to claim 1 , further comprising a secondary electrolyte salt,
the secondary electrolyte salt being different from the electrolyte salt and having a lower concentration than the electrolyte salt,
the secondary electrolyte salt comprising at least one carbon atom and at least two fluoride atoms and selected from the group consisting of:
v) a linear imide salt having a general structure LiN(—SO 2 —R) 2 , where at least one R is a fluorinated alkyl of 1 to 8 carbon atoms;
vi) a cyclic imide salt having a general structure LiN(—SO 2 —R—), where R is fluorinated alkyl of 1 to 8 carbon atoms; and
vii) a methide salt having a general structure LiC(—SO 2 —R) 3 , where at least one R is fluorinated alkyl of 1 to 8 carbon atoms.
8. The electrolyte according to claim 7 , wherein the secondary electrolyte salt comprises one of LiN(SO 2 CF 2 CF 3 ) 2 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , LiC(SO 2 CF 3 ) 3 , or LiC(SO 2 CF 2 CF 3 ) 3 .
9. The electrolyte according to claim 1 , wherein the electrolyte salt comprises the fluoroalkyl-substituted lithium hexafluorophosphate salt having the general structure LiPF x R 6-x , wherein x is from 1 to 5 and at least one R comprises the fluorinated alkyl of 1 to 8 carbon atoms or the combination of the fluorinated alkyl of 1 to 8 carbon atoms and the sulfonyl group.
10. The electrolyte according to claim 1 , wherein the electrolyte salt comprises the fluoroalkyl-substituted lithium tetrafluoroborate salt having the general structure LiPF x R 4-x , where x is from 1 to 3 and at least one R comprises the combination of the fluorinated alkyl of 1 to 8 carbon atoms and the sulfonyl group.
11. The electrolyte according to claim 1 , wherein the electrolyte salt comprises the fluoroalkyl-substituted lithium oxalatoborate salt having the general structure of LiBC 2 O 4 R 2 , where at least one R is the fluorinated alkyl of 1 to 8 carbon atoms or the combination of the fluorinated alkyl of 1 to 8 carbon atoms and the sulfonyl group.
12. The electrolyte according to claim 1 , wherein the electrolyte salt comprises the fluoroalkyl-substituted lithium oxalatoborate salt having the general structure of LiBC 2 O 4 R 2 , where at least one R is the combination of the fluorinated alkyl of 1 to 8 carbon atoms and the sulfonyl group.
13. The electrolyte according to claim 1 , wherein the electrolyte salt comprises the salt represented by the general formula
where at least one R is the fluorinated alkyl of 1 to 8 carbon atoms or the combination of the fluorinated alkyl of 1 to 8 carbon atoms and the sulfonyl group.
14. The electrolyte according to claim 1 , wherein the electrolyte salt comprises the salt represented by the general formula
where at least one R is the combination of the fluorinated alkyl of 1 to 8 carbon atoms and the sulfonyl group.
15. The electrolyte according to claim 1 , further comprising a flame-retardant additive, the flame-retardant additive comprising a cyclic phosphazene.
16. The electrolyte according to claim 1 , further comprising an ionic liquid, wherein the ionic liquid is present at a concentration ranging from about 1% to about 25% by weight of the electrolyte, excluding the electrolyte salt.
17. The electrolyte according to claim 16 , wherein the ionic liquid comprises one or more of pyridinium, piperidinium, imidazolium, and/or phosphonium cations.
18. The electrolyte according to claim 1 , wherein the fluorinated solvent has a dynamic viscosity ranging from about 0.3 cP to about 5.0 cP.
19. An electrolyte for use in an electrochemical cell, the electrolyte comprising:
an electrolyte salt having a concentration of at least about 0.5M,
the electrolyte salt selected from the group consisting of LiPF 5 C 2 F 5 , LiPF 5 C 4 F 9 , LiPF 5 C 3 F 7 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (C 3 F 7 ) 3 , LiPF 3 (C 4 F 9 ) 3 , LiPF 2 (C 2 F 5 ) 4 , LiPF(C 2 F 5 ) 5 , LiBF 3 CF 3 , LiBF 3 C 2 F 5 , LiBF 3 C 3 F 7 , LiBF 3 C 4 F 9 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (C 3 F 7 ) 2 , and LiBF 2 (C 4 F 9 ) 2 ;
a fluorinated solvent selected from the group consisting of 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane; and
one or more non-fluorinated esters, the electrolyte including a non-fluorinated cyclic carbonate ester, wherein the non-fluorinated cyclic carbonate ester is present at no more than 10% by weight, excluding the electrolyte salt,
wherein the electrolyte is a one-phase solution at a temperature of about −30° C.
20. An electrochemical cell comprising:
a positive electrode;
a negative electrode;
an electrolyte providing ionic exchange between the positive electrode and negative electrode and comprising:
an electrolyte salt having a concentration of at least about 0.5M,
the electrolyte salt is selected from the group consisting of:
i) a fluoroalkyl-substituted lithium hexafluorophosphate having a general structure LiPF X R 6-X , where x is from 1 to 5 and at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group;
ii) a fluoroalkyl-substituted lithium tetrafluoroborate having a general structure LiBF x R 4-x , where x is from 1 to 3 and at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group;
iii) a fluoroalkyl-substituted lithium oxalatoborate having a general structure of LiBC 2 O 4 R 2 , where at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group,
iv) a salt represented by one of general formulas
where at least one R is a fluorinated alkyl of 1 to 8 carbon atoms or a combination of a fluorinated alkyl of 1 to 8 carbon atoms and a sulfonyl group; and
a fluorinated solvent being present at between 30% and 80% by weight excluding the electrolyte salt, and
one or more non-fluorinated esters, the electrolyte including a non-fluorinated cyclic carbonate ester selected from the group consisting of ethylene carbonate or propylene carbonate, wherein the non-fluorinated cyclic carbonate ester is present at no more than 10% by weight, excluding the electrolyte salt,
wherein the electrolyte is a one-phase solution at a temperature of about −30° C.