TWI456826B - Resins for binder for electrodes of lithium ion secondary batteries, compositions and pastes containing the same and electrodes of lithium ion secondary batteries using the same - Google Patents

Claims (11)

A resin for a lithium ion secondary battery electrode binder, wherein a main component is at least one constituent unit selected from the group consisting of any one of the following general formulae (1) to (3), and the general formula (1) The content (a) of the constituent unit shown, the content (b) of the constituent unit represented by the formula (2), and the content (c) of the constituent unit represented by the formula (3) have the relationship of the following formula (A). And the logarithmic viscosity at 30 ° C is 0.02 ~ 2.0 dl / g; 0 < a / (a + b + c) ≦ 0.55 (Mo Er ratio) (A) (in the formula (A), b > 0, c >0); (In the above formulae (1) to (3), R is represented by the following formula (4) Divalent aromatic group, Ar1 Is a divalent aromatic group represented by the following formula (5), Ar2 It is a trivalent aromatic group represented by the following general formula (6), and each of the different constituent units R and each of Ar1 And each Ar2 Independent); (In the above formula (4), X represents a direct bond, -O-, -S-, -CO-, -SO2 -, -C (CH3 )2 -or-C(CF3 )2 -, p represents an integer from 0 to 3; in the above formula (5), Y represents a direct bond, -O-, -CO-, -SO2 -, -CH2 -, -C (CH3 )2 -or-C(CF3 )2 -, q represents 0 or 1; in the above formula (6), Z represents direct bonding, -O-, -CO-, -COO-, -OCO-, -SO2 -, -CH2 -, -C (CH3 )2 -or-C(CF3 )2 -, r represents 0 or 1; in the above formulae (4), (5) and (6), each benzene ring may optionally contain a fluorocarbon selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and a carbon number of 1 to 4. At least one substituent of the group consisting of a chlorine atom, a bromine atom, a nitro group and a cyano group). For example, the lithium ion secondary battery electrode binder for the first application of the patent scope is a resin comprising R in the above formulas (1) to (3) as a constituent unit of a 4,4'-diaminodiphenyl ether residue and R as a constituent unit of an m-phenylenediamine residue, in a resin The content (x) of the 4,4'-diaminodiphenyl ether residue and the content (y) of the m-phenylenediamine residue have the following relationship: 1.5 ≦ x / y ≦ 4 (mole ratio). The resin for a lithium ion secondary battery electrode binder according to the first aspect of the invention, wherein the content of each constituent unit represented by any one of the above formulas (1) to (3) has the following formula (B) Relationship: 0.05 ≦ a / (a + b + c) ≦ 0.55 (mole ratio) (B). A resin for a lithium ion secondary battery electrode binder according to the first aspect of the invention, which has a residual carboxyl group amount of 0.05 to 0.40 mmol/g. The resin for a lithium ion secondary battery electrode binder according to the first aspect of the invention, wherein the gelation activity expressed by the following formula (7) is 3.0% by weight or less after heating in an atmosphere at 280 ° C for 2 hours. Activity (% by weight) = (N-methyl-2-pyrrolidone insoluble weight / sample weight) × 100 (7). A resin composition for a lithium ion secondary battery electrode binder, which comprises 5 to 30% by weight of a resin for a lithium ion secondary battery electrode binder according to any one of claims 1 to 5, and a polar solvent. A paste for a lithium ion secondary battery electrode material, comprising a resin for a lithium ion secondary battery electrode binder according to any one of claims 1 to 5, a polar solvent, and a lithium ion secondary battery electrode active material particle The content of the lithium ion secondary battery electrode binder resin is from 1 to 20 parts by weight based on 100 parts by weight of the lithium ion secondary battery electrode active material particle content. A paste for a lithium ion secondary battery electrode material according to claim 7, which comprises a lithium ion secondary battery negative electrode active material particle, and the particle is in lithium relative to a volume 100 before lithium ion sorption When the ions are fully charged, the volume is 130 or more and 250 or less. A lithium ion secondary battery electrode comprising a current collector and a paste for a lithium ion secondary battery electrode material coated on the current collector according to claim 7 or 8. A lithium ion secondary battery electrode according to claim 9, wherein the current collector is a metal foil. A lithium ion secondary battery electrode according to claim 9, wherein the paste is in a dry state.