Non-aqueous electrolytes for lithium batteries
An electrochemical cell includes a cathode active material, lithium metal, a separator, and an electrolyte comprising a lithium salt, an organic aprotic solvent and a fluorinated sulfone represented by Formula II:
1. An electrochemical cell comprising:
a cathode comprising a cathode active material;
an anode comprising lithium metal;
a separator; and
an electrolyte comprising a lithium salt, an organic aprotic solvent and a fluorinated sulfone represented by Formula II:
wherein:
R 3 and R 4 are individually H, F, Cl, Br, I, OR 9 , alkyl, alkenyl, alkynyl, silyl, siloxy, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, cycloalkyl, cycloalkylalkyl, —C(O)R 10 , —C(O)OR 10 , or —OC(O)R 10 ;
R 5 , R 6 , R 7 , and R 8 are individually H, F, Cl, Br, I, OR 9 , alkyl, alkenyl, alkynyl, silyl, siloxy, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, cycloalkyl, cycloalkylalkyl, —C(O)R 10 , —C(O)OR 10 , or —OC(O)R 10 ;
R 9 is H, alkyl, alkenyl, alkynyl, aryl, aralkyl, or heterocyclyl;
R 10 is H, alkyl, alkenyl, alkynyl, aryl, aralkyl, or heterocyclyl; and
q is 1 or 2;
wherein: at least one of R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is F, fluorinated alkyl, fluorinated alkenyl, fluorinated alkynyl, fluorinated silyl, fluorinated siloxy, fluorinated —C(O)R 10 , fluorinated —C(O)OR 10 , or fluorinated —OC(O)R 10 .
2. The electrochemical cell of claim 1 , wherein:
R 3 and R 4 are individually H, F, Cl, Br, I, OR 9 , fluorinated alkyl, fluorinated alkenyl, fluorinated alkynyl, fluorinated silyl, fluorinated siloxy, fluorinated —C(O)R 10 , fluorinated —C(O)O 10 , or fluorinated —OC(O)R 10 ;
R 5 , R 6 , R 7 , and R 8 are individually H, F, Cl, Br, I, OR 9 , fluorinated alkyl, fluorinated alkenyl, fluorinated alkynyl, fluorinated silyl, fluorinated siloxy, fluorinated —C(O)R 10 , fluorinated —C(O)OR 10 , or fluorinated —OC(O)R 10 ;
R 9 is H, fluorinated or non-fluorinated alkyl, fluorinated or non-fluorinated alkenyl, fluorinated or non-fluorinated alkynyl, fluorinated or non-fluorinated aryl, fluorinated or non-fluorinated aralkyl, or fluorinated or non-fluorinated heterocyclyl,
R 10 is H, fluorinated or non-fluorinated alkyl, fluorinated or non-fluorinated alkenyl, fluorinated or non-fluorinated alkynyl, fluorinated or non-fluorinated aryl, fluorinated or non-fluorinated aralkyl, or fluorinated or non-fluorinated heterocyclyl.
3. The electrochemical cell of claim 1 , wherein:
R 3 and R 4 are individually H, F, OH, OCH 3 , OCFH 2 , OCF 2 H, OCF 3 , OCHCH 2 , OCFCH 2 , OCHCFH, OCHCF 2 , OCFCF 2 , OCH 2 CHCH, OCFHCHCH, OCH 2 CFCH, OCH 2 CHCF, OCH 2 CFCF, OCF 2 CFCF, CH 2 Ph, CF 2 Ph, CF 2 (fluorinated phenyl), CH 2 (fluorinated phenyl), C n H x F y , CH 2 C n H x F y , CH 2 OC n H x F y , or CF2OC n H x F y ;
R 5 , R 6 , R 7 , and R 8 are individually H, F, OH, OCH 3 , OCFH 2 , OCF 2 H, OCF 3 , OCHCH 2 , OCFCH 2 , OCHCFH, OCHCF 2 , OCFCF 2 , OCH 2 CHCH, OCFHCHCH, OCH 2 CFCH, OCH 2 CHCF, OCH 2 CFCF, OCF 2 CFCF, CH 2 Ph, CF 2 Ph, CF 2 (fluorinated phenyl), CH 2 (fluorinated phenyl), C n H x F y , CH 2 C n H x F y , CH 2 OC n H x F y , or CF 2 OC n H x F y ;
n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;
x is 0, 1, 2, or 3; and
y is 0, 1, 2, or 3.
4. The electrochemical cell of claim 1 , wherein:
R 3 and R 4 are individually H, F, OH, OCH 3 , OCF 3 , C n H x F y , CH 2 C n H x F y , CH 2 OC n H x F y , or CF 2 OC n H x F y ;
R 5 , R 6 , R 7 , and R 8 are individually H, F, OH, OCH 3 , OCF 3 , C n H x F y , CH 2 C n H x F y , CH 2 OC n H x F y , or CF 2 OC n H x F y ;
n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;
x is 0, 1, 2, or 3; and
y is 0, 1, 2, or 3.
5. The electrochemical cell of claim 1 , wherein at least one of R 3 and R 4 and at least one of R 5 , R 6 , R 7 , and R 8 is F, fluorinated alkyl, fluorinated alkenyl, fluorinated alkynyl, fluorinated silyl, fluorinated siloxy, fluorinated —C(O)R 10 , fluorinated —C(O)OR 10 , or fluorinated —OC(O)R 10 .
6. The electrochemical cell of claim 1 , wherein the electrolyte further comprises a compound of Formula I:
wherein:
R 1 and R 2 are individually H, F, Cl, Br, I, OR 9 , alkyl, alkenyl, alkynyl, silyl, siloxy, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, cycloalkyl, cycloalkylalkyl, —C(O)R 10 , —C(O)OR 10 , or —OC(O)R 10 ; and
at least one of R 1 and R 2 is F, fluorinated alkyl, fluorinated alkenyl, fluorinated alkynyl, fluorinated silyl, fluorinated siloxy, fluorinated —C(O)R 10 , fluorinated —C(O)OR 10 , or fluorinated —OC(O)R 10 .
7. The electrochemical cell of claim 6 , wherein:
R 1 and R 2 are individually H, F, Cl, Br, I, OR 9 , fluorinated alkyl, fluorinated alkenyl, fluorinated alkynyl, fluorinated silyl, fluorinated siloxy, fluorinated —C(O)R 10 , fluorinated —C(O)OR 10 , or fluorinated —OC(O)R 10 ;
R 9 is H, fluorinated or non- fluorinated alkyl, fluorinated or non- fluorinated alkenyl, fluorinated or non- fluorinated alkynyl, fluorinated or non- fluorinated aryl, fluorinated or non- fluorinated aralkyl, or fluorinated or non- fluorinated heterocyclyl;
R 10 is H, fluorinated or non- fluorinated alkyl, fluorinated or non- fluorinated alkenyl, fluorinated or non- fluorinated alkynyl, fluorinated or non- fluorinated aryl, fluorinated or non- fluorinated aralkyl, or fluorinated or non- fluorinated heterocyclyl.
8. The electrochemical cell of claim 6 , wherein:
R 1 and R 2 are individually H, F, OH, OCH 3 , OCFH 2 , OCF 2 H, OCF 3 , OCHCH 2 , OCFCH 2 , OCHCFH, OCHCF 2 , OCFCF 2 , OCH 2 CHCH, OCFHCHCH, OCH 2 CFCH, OCH 2 CHCF, OCH 2 CFCF, OCF 2 CFCF, CH 2 Ph, CF 2 Ph, CF 2 (fluorinated phenyl), CH 2 (fluorinated phenyl), C n H x F y , CH 2 C n H x F y , CH 2 OC n H x F y , or CF 2 OC n H x F y ;
n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;
x is 0, 1, 2, or 3; and
y is 0, 1, 2, or 3.
9. The electrochemical cell of claim 6 , wherein:
R 1 and R 2 are individually H, F, OH, OCH 3 , OCF 3 , C n H x F y , CH 2 C n H x F y , CH 2 OC n H x F y , or CF 2 OC n H x F y ;
n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12;
x is 0, 1, 2, or 3; and
y is 0, 1, 2, or 3.
10. The electrochemical cell of claim 1 , wherein the lithium salt comprises lithium alkyl fluorophosphates; lithium alkyl fluoroborates; lithium 4,5-dicyano-2-(trifluoromethyl)imidazole; lithium 4,5-dicyano-2-methylimidazole; trilithium 2,2′,2″-tris(trifluoromethyl)benzotris(imidazolate); LiN(CN)2; Li(CF3CO2); Li(C2F5CO2); LiCF 3 SO 3 ; LiCH 3 SO 3 ; LiN(SO 2 CF 3 ) 2 ; LiN(SO 2 F) 2 ; LiC(CF 3 SO 2 ) 3 ; LiN(SO 2 C 2 F 5 ) 2 ; LiClO 4 ; LiBF 4 ; LiAsF 6 ; LiPF 6 ; LiBF 2 (C 2 O 4 ), LiB(C 2 O 4 ) 2 , LiPF 2 (C 2 O 4 ) 2 , LiPF 4 (C 2 O 4 ), LiAsF 6 , CsF, CsPF 6 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 F) 2 , Li 2 (B 12 X 12-p H p ); Li 2 (B 1 oX 10-p′ H p′ ); or a mixture of any two or more thereof, wherein X is independently at each occurrence a halogen, p is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and p′ is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
11. The electrochemical cell of claim 1 , wherein the organic aprotic solvent is a linear carbonate, cyclic carbonate, ester, cyclic ester, or sulfone.
12. The electrochemical cell of claim 1 , wherein the organic aprotic solvent is a compound represented by Formula III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIV, or a mixture of any two or more thereof:
Formula
R 11 OC(O)OR 12
III
IV
R 11 OC(O)R 12
V
VI
VII
R 11 —S(O) 2 —R 12
VIII
R 11 —CN
IX
NC(CH 2 ) m CN
X
R 11 —O—R 12
XI
R 11 —(OCH 2 CH 2 ) m OR 12
XII
R 11 C(O)NR 12 R 13
XIII
R 11 OC(O)NR 12 R 13
XIV
R 11 , R 12 , R 13 , and R 14 are individually H, F, Cl, Br, I, CN, oxo, OR 9 , alkyl, alkenyl, alkynyl, silyl, siloxy, —C(O)R 10 , —C(O)OR 10 , or —OC(O)R 10 ; and
m is 1, 2, 3, 4, 5, or 6.
13. The electrochemical cell of claim 12 , wherein at least one of R 11 , R 12 , R 13 , and R 14 is F or a fluorinated group.
14. The electrochemical cell of claim 13 , wherein at least one of R 11 , R 12 ,R 13 , and R 14 is F, C n H x F y , CH 2 C n H x F y , CH 2 OCnHx-yFy, or CF 2 OC n H x F y ; n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; x is 0, 1, 2, or 3; and y is 0, 1, 2, or 3.
15. The electrochemical cell of claim 1 , wherein the organic aprotic solvent in the electrolyte comprises a pyrrolidinium-based ionic liquid, a piperidinium-based ionic liquid, a imidazolium-based ionic liquid, a ammonium-based ionic liquid, phosphonium-based ionic liquid, or a cyclic phosphonium-based ionic liquid.
16. The electrochemical cell of claim 1 that is a lithium secondary battery, and the secondary battery is a lithium battery, a lithium-ion battery, a lithium-sulfur battery, or a lithium-air battery.
17. The electrochemical cell of claim 1 , wherein the polar aprotic solvent comprises one or more of ethylmethylsulfone (EMS), ethyl(trifluoromethyl)sulfone (FMES), ethylene carbonate (EC), ethylmethyl carbonate (EMC), fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC).