Binder composition for lithium ion secondary battery electrode-use, slurry composition for lithium ion secondary battery electrode-use, electrode for lithium ion secondary battery-use, and lithium ion secondary battery
Provided is a binder composition for lithium ion secondary battery electrode-use that reduces internal resistance of a lithium ion secondary battery while also providing the lithium ion secondary battery with excellent life characteristics. The binder composition contains a copolymer X and a solvent. The copolymer X is obtained from a monomer composition X that contains at least 20.0 mass % and no greater than 75.0 mass % of an ethylenically unsaturated carboxylic acid compound (A) composed of either or both of an ethylenically unsaturated carboxylic acid and an ethylenically unsaturated carboxylic acid salt, and at least 20.0 mass % and no greater than 75.0 mass % of a copolymerizable compound (B) that has an ethylenically unsaturated bond and a solubility of at least 7 g in 100 g of water at 20° C. The copolymer X has a degree of swelling in electrolysis solution of less than 120 mass %.
1. A binder composition for lithium ion secondary battery electrode-use comprising
a copolymer X and a solvent, wherein
the copolymer X is obtained through polymerization of a monomer composition X,
the monomer composition X contains an ethylenically unsaturated carboxylic acid compound (A) a compound (B) that is copolymerizable and has an ethylenically unsaturated bond, and a multifunctional compound (C) having a polyoxyalkylene structure and at least two ethylenically unsaturated bonds,
the ethylenically unsaturated carboxylic acid compound (A) is selected from the group consisting of acrylic acid, methacrylic acid, an acrylic acid salt, and a methacrylic acid salt,
the compound (B) is either or both of acrylamide and methacrylamide,
the multifunctional compound (C) is an ethoxylated pentaerythritol tetraacrylate represented by the following general formula (V):
in the formula (V), n1, n2, n3, and n4 are integers of greater than or equal to 2 that may be the same or different,
in the monomer composition X, a percentage content of the ethylenically unsaturated carboxylic acid compound (A) among all monomers is at least 21.0 mass % and no greater than 50.0 mass %, a percentage content of the compound (B) among all monomers is at least 48.0 mass % and no greater than 75.0 mass %, and a percentage content of the multifunctional compound (C) among all monomers is at least 0.1 mass % and no greater than 20.0 mass %, and
the copolymer X has a degree of swelling in electrolysis solution of less than 120 mass %, and wherein
the degree of swelling is measured using an LiPF 6 solution having a concentration of 1.0 M as the electrolysis solution in which mixed solvent of 3/7 (volume ratio) ethylene carbonate/ethyl methyl carbonate is used as solvent, and 2 volume % of vinylene carbonate is contained as additive.
2. The binder composition for lithium ion secondary battery electrode-use of claim 1 , wherein
a value (A/B) obtained by dividing the percentage content of the ethylenically unsaturated carboxylic acid compound (A) among all monomers in the monomer composition X by the percentage content of the compound (B) among all monomers in the monomer composition X is less than 1.5.
3. The binder composition for lithium ion secondary battery electrode-use of claim 1 , wherein
the copolymer X has a lithium carboxylate group.
4. The binder composition for lithium ion secondary battery electrode-use of claim 1 , further comprising
a water-soluble polymer Y having a degree of swelling in electrolysis solution of at least 120 mass %, wherein
the degree of swelling is measured using an LiPF 6 solution having a concentration of 1.0 M as the electrolysis solution in which mixed solvent of 3/7 (volume ratio) ethylene carbonate/ethyl methyl carbonate is used as solvent, and 2 volume % of vinylene carbonate is contained as additive, and wherein
the copolymer X is water-soluble,
the water-soluble polymer Y is obtained through polymerization of a monomer composition Y,
the monomer composition Y contains methacrylic acid, ethyl acrylate, and ethylene dimethacrylate, and
in the monomer composition Y, a percentage content of the methacrylic acid among all monomers is at least 25 mass % and no greater than 40 mass %, a percentage content of the ethyl acrylate among all monomers is at least 45 mass % and no greater than 70 mass %, and a percentage content of the ethylene dimethacrylate among all monomers is at least 0.2 mass % and no greater than 2 mass %.
5. The binder composition for lithium ion secondary battery electrode-use of claim 4 , wherein
a value (Y/X) obtained by dividing an amount of mass of the water-soluble polymer Y included in the binder composition by an amount of mass of the copolymer X included in the binder composition is at least 0.01 and no greater than 0.5.
6. The binder composition for lithium ion secondary battery electrode-use of claim 4 , wherein
the monomer composition Y further contains a fluorine-containing monomer.
7. The binder composition for lithium ion secondary battery electrode-use of claim 1 , further comprising
a particulate polymer Z, wherein
the copolymer X is water-soluble.
8. The binder composition for lithium ion secondary battery electrode-use of claim 7 , wherein
a value (Z/X) obtained by dividing an amount of mass of the particulate polymer Z included in the binder composition by an amount of mass of the copolymer X included in the binder composition is at least 0.05 and no greater than 3.
9. The binder composition for lithium ion secondary battery electrode-use of claim 7 , wherein
the particulate polymer Z has a gel content of at least 85 mass % and no greater than 98 mass %.
10. The binder composition for lithium ion secondary battery electrode-use of claim 7 , wherein
the particulate polymer Z has a degree of swelling in electrolysis solution of at least 140 mass % and less than 800 mass %, and wherein
the degree of swelling is measured using an LiPF 6 solution having a concentration of 1.0 M as the electrolysis solution in which mixed solvent of 3/7 (volume ratio) ethylene carbonate/ethyl methyl carbonate is used as solvent, and 2 volume % of vinylene carbonate is contained as additive,
the particulate polymer Z is either or both of a styrene-butadiene-based polymer and an acrylic-based polymer,
the styrene-butadiene-based polymer is obtained through polymerization of a monomer composition Z1,
the monomer composition Z1 contains styrene and 1,3-butadiene,
in the monomer composition Z1, a percentage content of the styrene among all monomers is at least 55 mass % and no greater than 65 mass %, and a percentage content of the 1,3-butadiene among all monomers is at least 30 mass % and no greater than 35 mass %,
the acrylic-based polymer is obtained through polymerization of a monomer composition Z2,
the monomer composition Z2 contains n-butyl acrylate, and
in the monomer composition Z2, a percentage content of the n-butyl acrylate among all monomers is at least 58 mass % and no greater than 94 mass %.
11. The binder composition for lithium ion secondary battery electrode-use of claim 7 , wherein
the particulate polymer Z is either or both of a styrene-butadiene-based polymer and an acrylic-based polymer.
12. A slurry composition for lithium ion secondary battery electrode-use comprising:
the binder composition for lithium ion secondary battery electrode-use of claim 1 ; and
an electrode active material.
13. An electrode for lithium ion secondary battery-use comprising:
a current collector; and
an electrode mixed material layer on the current collector, wherein
the electrode mixed material layer is formed using the slurry composition for lithium ion secondary battery electrode-use of claim 12 .
14. The electrode for lithium ion secondary battery-use of claim 13 , wherein
a degree of coating of the electrode active material calculated by formula (1) shown below
degree of coating of electrode active material=(BET specific surface area of electrode active material−BET specific surface area of electrode)/BET specific surface area of electrode active material (1)
is at least 0.25 and no greater than 0.70.
15. A lithium ion secondary battery comprising
a positive electrode, a negative electrode, an electrolysis solution, and a separator, wherein
either or both of the positive electrode and the negative electrode are the electrode for lithium ion secondary battery-use of claim 13 .
16. The binder composition for lithium ion secondary battery electrode-use of claim 1 , wherein
the ethylenically unsaturated carboxylic acid compound (A) is either or both of acrylic acid and an acrylic acid salt.
17. The binder composition for lithium ion secondary battery electrode-use of claim 1 , wherein
the compound (B) is acrylamide.
18. The binder composition for lithium ion secondary battery electrode-use of claim 16 , wherein
the compound (B) is acrylamide.