Binder resin composition for electrode, electrode mixture paste, and electrode
View Patent ↗The present invention relates to a binder resin composition for an electrode, including a polyamic acid and a solvent, wherein the polyamic acid is (i) a polyamic acid which includes a tetracarboxylic acid component including 10 to 100 mol % of 4,4′-oxydiphthalic acid and 90 to 0 mol % of 3,3′,4,4′-biphenyltetracarboxylic acid and/or pyromellitic acid and a diamine component including an aromatic diamine having 1 to 4 aromatic rings, (ii) a polyamic acid which includes a tetracarboxylic acid component including 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride and a diamine component including 10 to 90 mol % of p-phenylene diamine and 90 to 10 mol % of 4,4′-diaminodiphenyl ether, or (iii) a polyamic acid which includes a tetracarboxylic acid component including 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride and a diamine component including 40 mol % or more of a bis[4-(4-aminophenoxy)phenyl] compound.
1. A binder resin composition for an electrode, comprising:
a polyamic acid having a repeating unit represented by chemical formula (1);
pyridine compounds; and
a solvent,
wherein A and B in chemical formula (1) are as defined below in (i), (ii), or (iii):
(i) 10 to 90 mol % of A in the repeating unit is a tetravalent group represented by chemical formula (2), and
90 to 10 mol % of A in the repeating unit is a tetravalent group represented by chemical formula (3) and/or chemical formula (4), and
10 to 90 mol % of B in the repeating unit is a divalent group represented by chemical formula (5), and
90 to 10 mol % of B in the repeating unit is a divalent group represented by chemical formula (6); or
(ii) A is a tetravalent group represented by chemical formula (3),
10 to 90 mol % of B in the repeating unit is a divalent group represented by chemical formula (6), and
90 to 10 mol % of B in the repeating unit is a divalent group represented by chemical formula (5); or
(iii) A is a tetravalent group represented by chemical formula (3) and
40 mol % or more of B in the repeating unit is a divalent group represented by chemical formula (7),
with the proviso that, in the chemical formula (7), X represents any one of a direct bond, an oxygen atom, a sulfur atom, a methylene group, a carbonyl group, a sulfoxyl group, a sulfone group, a 1,1′-ethylidene group, a 1,2-ethylidene group, a 2,2′-isopropylidene group, a 2,2′-hexafluoroisopropylidene group, a cyclohexylidene group, a phenylene group, a 1,3-phenylenedimethylene group, a 1,4-phenylenedimethylene group, a 1,3-phenylenediethylidene group, a 1,4-phenylenediethylidene group, a 1,3-phenylenedipropylidene group, a 1,4-phenylenedipropylidene group, a 1,3-phenylenedioxy group, a 1,4-phenylenedioxy group, a biphenylenedioxy group, a methylenediphenoxy group, an ethylidenediphenoxy group, a propylidenediphenoxy group, a hexafluoropropylidenediphenoxy group, an oxydiphenoxy group, a thiodiphenoxy group, and a sulfone diphenoxy group.
2. The binder resin composition according to claim 1 , wherein
A and B are as defined in (iii),
50 to 90 mol % of B in the repeating unit is a divalent group represented by the chemical formula (7), and
50 to 10 mol % of B in the repeating unit is a divalent group represented by the chemical formula (5) and/or chemical formula (8)
3. An electrode mixture paste comprising an electrode active material and the binder resin composition for an electrode according to claim 2 .
4. The binder resin composition according to claim 1 , wherein
A and B are as defined in (i), and
the binder resin obtained by heating exhibits weight increase of 2% by mass or less when being impregnated in dimethyl carbonate at 25° C. for 24 hours.
5. An electrode mixture paste comprising an electrode active material and the binder resin composition for an electrode according to claim 4 .
6. The binder resin composition according to claim 1 , wherein
A and B are as defined in (ii) and
the binder resin obtained by heating exhibits weight increase of 3% by mass or less when being impregnated in dimethyl carbonate at 25° C. for 24 hours.
7. The binder resin composition according to claim 1 , wherein
A and B are as defined in (i), and
the binder resin obtained by heating exhibits tensile energy to break of 70 MJ/m 3 or more, retention ratio of the tensile energy to break of 70% or more after it is impregnated in dimethyl carbonate at 25° C. for 24 hours, and retention ratio of the tensile energy to break of 70% or more after being impregnated in a lithium alkoxides solution.
8. The binder resin composition according to claim 1 , wherein
A and B are as defined in (ii), and
the binder resin obtained by heating exhibits tensile energy to break of 100 MJ/m 3 or more and retention ratio of the tensile energy to break of 70% or more after being impregnated in dimethyl carbonate at 25° C. for 24 hours.
9. The binder resin composition according to claim 1 , wherein
A and B are as defined in (iii), and
the binder resin obtained by heating exhibits tensile energy to break of 50 MJ/m 3 or more, retention ratio of the tensile energy to break of 70% or more after it is impregnated in dimethyl carbonate at 25° C. for 24 hours, and retention ratio of the tensile energy to break of 60% or more after being impregnated in a lithium alkoxides solution.
10. An electrode mixture paste comprising an electrode active material and the binder resin composition for an electrode according to claim 1 .
11. The electrode mixture paste according to claim 10 , wherein the electrode active material is carbon powder, silicon powder, tin powder, or powder of an alloy comprising silicon or tin.
12. An electrode obtained by coating the electrode mixture paste according to claim 10 on a current collector and carrying out an imidization reaction while simultaneously removing the solvent by heating.
13. The electrode according to claim 12 , wherein the heating is performed at a temperature of 250° C. or less.
14. The electrode according to claim 12 , wherein the electrode is a negative electrode for a lithium ion secondary battery.
15. The binder resin composition according to claim 1 , wherein
A and B are as defined in (iii), and
the binder resin obtained by heating exhibits weight increase of 3% by mass or less when being impregnated in dimethyl carbonate at 25° C. for 24 hours.