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US 6,280,883 B1Granted
Bis (perfluoralkanesulfonyl)imide surfactant salts in electrochemical systems
Assignee3M Innovative Properties Company
InventorsWilliam M. Lamanna, Robert B. Loch, Alan D. Fanta, Steven D. Boyd, Hiroshi Shimada, Phat T. Pham, Bryan J. Johnson
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Abstract
Electrolyte compositions and electrochemical systems containing such compositions are described where the electrolyte includes in a matrix material a combination of a conductive salt and a bis(perfluoroalkanesulfonyl)imide surfactant salt. The compositions improve wettability of electrodes and separators while maintaining and improving conductivity, stability, and compatibility with other cell components.
Claims41
An electrolyte composition comprising:
- (a) a conductive salt comprising
- a cation selected from the group consisting of an alkali metal;
- an alkaline earth metal;
- a Group IIB metal;
- a Group IIIB metal;
- a transition metal;
- a rare earth metal;
- a nitrogen onium cation, and a proton;
- and
- an anion selected from the group consisting of Rf0SO3−;
- in which Rf0 is a perfluoroalkyl group having between 2 and 4 carbon atoms;
- an anion of the formula:
- in which Rf1 and Rf2 are each independently a straight or branched perfluoroalkyl group of 1 to 4 carbon atoms, with Rf1 and Rf2 having a total of up to 5 carbon atoms;
- and Rf3 is a perfluoroalkylene moiety of 2 to 4 carbon atoms optionally substituted by a straight or branched perfluoroalkyl group of 1 to 2 carbon atoms, with Rf3 having a total of up to 4 carbon atoms;
- an anion having a formula Rf4Rf5N—(CF2)n′SO2—X;
- in which X− is —O−, —N−SO2Rf4, or
- Z is —CF2—, —O—,
- or —SF4—;
- Rf4, Rf4′, and Rf5, independently, are —CmF2m+1′ or —(CF2)q—SO2—X−;
- Rf6 and Rf7, independently, are —CmF2m+1, —(CF2)4—SO2—X−,
- Rf8 is —CmF2m+1, or —(CF2)q—SO2—X−;
- Rf6′ and Rf7′, independently, are perfluoroalkylene moieties having the formula —CrF2r—;
- n′ is 1-4;
- r is 1-4;
- m is 1-4;
- and q is 1-4;
- a bis-fluoroalkylsulfonyl methide anion RfII—SO2—C−(R)—SO2—RfIII in which RfII and RfIII, independently, are perfluoroalkyl groups having between 1 and 4 carbon atoms, wherein the sum of R4II and RfIII is up to 5 carbon atoms, and R is H, CN, F, alkyl of 1 to 6 carbon atoms, phenyl or phenyl substituted by alkyl of 1 to 4 carbon atoms;
- and a tris-(perfluoroalkanesulfonyl)methide anion of the formula −C(SO2RfII)(SO2RfIII)(SO2RfIV) in which RfII, RfIII, and RfIV, independently, are perfluoroalkyl groups having between 1 and 4 carbon atoms, wherein the sum of RfII, RfIII and RfIV are up to 6 carbon atoms;
- and
- (b) a surfactant salt of the formula:
- ((RfSO2)(Rf′SO2)N−)nM+n
- wherein M+n is a cation with a valence equal to n;
- n is from 1 to 4;
- Rf is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms on the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms;
- and
- Rf′ is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms on the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms;
- wherein Rf and Rf′ have a total of at least 8 carbon atoms;
- and
- wherein the molar ratio of conductive salt to surfactant salt is between about 99.9:0.1 to about 75:25.
36 more elements
An electrochemical system comprising:
- at least one positive electrode;
- at least one negative electrode;
- and
- an electrolyte composition comprising:
- (a) a conductive salt comprising:
- a cation selected from the group consisting of an alkali metal;
- an alkaline earth metal;
- a Group IIB metal;
- a Group IIIB metal;
- a transition metal;
- a rare earth metal;
- a nitrogen onium cation, and a proton;
- and
- an anion selected from the group consisting of Rf0SO3−;
- in which Rf0 is a perfluoroalkyl group having between 2 and 4 carbon atoms;
- an anion of the formula:
- in which Rf1 and Rf2 are each independently a straight or branched perfluoroalkyl group of 1 to 4 carbon atoms, with Rf1 and Rf2 having a total of 5 carbon atoms;
- and Rf3 is a perfluoroalkylene moiety of 2 to 4 carbon atoms optionally substituted by a straight or branched perfluoroalkyl group of 1 to 2 carbon atoms, with Rf3 having a total of up to 4 carbon atoms;
- an anion having a formula Rf4Rf5N—(CH2)n′SO2—X;
- in which X− is —O−, —N−SO2Rf4′ or
- Z is —CF2—, —O—,
- or —SF4—;
- Rf4, Rf4′ and Rf5, independently, are —CmF2m+1, or —(CF2)q—SO2—X−;
- Rf6 and Rf7, independently, are —CmF2m+1′—(CF2)4—SO2—X−;
- Rf8 is —CmF2m+1, or —(CF2)q—SO2—X−;
- Rf6′, and Rf7′, independently, are perfluoroalkylene moieties having the formula —CrF2r—;
- n′ is 1-4;
- r is 1-4;
- m is 1-4;
- and q is 1-4;
- a bis-fluoroalkylsulfonyl methide anion RfII—SO2—C−(R)—SO2—RfIII in which RfII and RfIII, independently, are perfluoroalkyl groups having between 1 and 4 carbon atoms, wherein the sum of RfII and RfIII is up to 5 carbon atoms, and R is H, CN, F, alkyl of 1 to 6 carbon atoms, phenyl or phenyl substituted by alkyl of 1 to 4 carbon atoms;
- and a tris-(perfluoroalkanesulfonyl)methide anion of the formula −C(SO2RfII)(SO2RfIII)(SO2RfIV) in which RfII, RfIII, and RfIV, independently, are perfluoroalkyl groups having between 1 and 4 carbon atoms, wherein the sum of RfII, RfIII and RfIV are up to 6 carbon atoms;
- and
- (b) a surfactant salt of the formula:
- ((RfSO2)(Rf′SO2)N−)nM+n
- wherein M+n is a cation with a valence equal to n;
- n is from 1 to 4;
- Rf is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms;
- and
- Rf′ is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms, wherein Rf and Rf′ have a total of at least 8 carbon atoms;
- and
- wherein the molar ratio of conductive salt to surfactant salt is between about 99.9:0.1 to about 75:25.
39 more elements
A method of improving safety and performance of an electrochemical system which comprises using an electrolyte composition in said system comprising:
- (a) an effective amount of a surfactant salt of the formula
- ((RfSO2)(Rf′SO2)N−)nM+n
- wherein M+n is a cation with a valence equal to n;
- n is from 1 to 4;
- Rf is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms;
- and
- Rf′ is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms, wherein Rf and Rf′ have a total of at least 8 carbon atoms;
- and
- (b) a conductive salt having a cation selected from the group consisting of an alkali metal;
- an alkaline earth metal;
- a Group IIB metal;
- a Group IIIB metal;
- a transition metal;
- a rare earth metal;
- a nitrogen onium cation;
- and a proton;
- and an anion of the formula
- in which Rf1 and Rf2 are each independently a straight or branched perfluoroalkyl group of 1 to 4 carbon atoms, with Rf1 and Rf2 having a total of up to 5 carbon atoms;
- Rf3 is a perfluoroalkylene moiety of 2 to 4 carbon atoms optionally substituted by a straight or branched perfluoroalkyl group of 1 to 2 carbon atoms, with Rf3 having a total of up to 4 carbon atoms;
- and
- a matrix material.
18 more elements
An electrochemical system comprising:
- at least one positive electrode;
- at least one negative electrode;
- and
- an electrolyte composition comprising in a non-aqueous matrix material:
- (a) a conductive salt having a cation selected from the group consisting of an alkali metal;
- an alkaline earth metal;
- a Group IIB metal;
- a Group IIIB metal;
- a transition metal;
- a rare earth metal;
- a nitrogen onium cation;
- and a proton;
- and an anion of the formula
- in which Rf1 and Rf2 are each independently a straight or branched perfluoroalkyl group of 1 to 4 carbon atoms, with Rf1 and Rf2 having a total of up to 5 carbon atoms;
- Rf3 is a perfluoroalkylene moiety of 2 to 4 carbon atoms optionally substituted by a straight or branched perfluoroalkyl group of 1 to 2 carbon atoms, with Rf3 having a total of up to 4 carbon atoms;
- and
- (b) an effective amount of a surfactant salt of the formula
- ((RfSO2)(Rf′SO2)N−)nM+n
- wherein M+n is a cation with a valence equal to n;
- n is from 1 to 4;
- Rf is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms;
- and
- Rf′ is a straight or branched perfluoroalkyl group of 1 to 8 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms, wherein Rf and Rf′ have a total of at least 8 carbon atoms.
20 more elements
An electrolyte composition comprising in a matrix material:
- (a) a conductive salt having a cation selected from the group consisting of an alkali metal;
- an alkaline earth metal;
- a Group IIB metal;
- a Group IIIB metal;
- a transition metal;
- a rare earth metal;
- a nitrogen onium cation;
- and a proton;
- and an anion of the formula:
- in which Rf1 and Rf2 are each independently a straight or branched perfluoroalkyl group of 1 to 4 carbon atoms, with Rf1 and Rf2 having a total of up to 5 carbon atoms;
- Rf3 is a perfluoroalkylene moiety of 2 to 4 carbon atoms optionally substituted by a straight or branched perfluoroalkyl group of 1 to 2 carbon atoms, with Rf3 having a total of up to 4 carbon atoms;
- and
- (b) a surfactant salt of the formula ((RfSO2)(Rf′SO2)N−)nM+n
- wherein M+n is a cation with a valence equal to n;
- n is from 1 to 4;
- Rf is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms;
- and
- Rf′ is a straight or branched perfluoroalkyl group of 1 to 12 carbon atoms, a perfluorocycloalkyl group or a perfluorocycloalkyl perfluoroalkyl group of 4-7 ring carbon atoms and 1-4 carbon atoms in the alkyl chain, which perfluoroalkyl or perfluorocycloalkyl chain may optionally contain catenary heteroatoms, wherein Rf and Rf′ have a total of at least 8 carbon atoms.
15 more elements
Dependencies are inferred from the claim text.