Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same
To provide a negative electrode for a non-aqueous electrolyte secondary battery that can be produced even without performing a heat treatment at a high temperature such as 2,000° C. or higher and can have the discharge capacity and the cycle characteristics (capacity retention) further increased. The negative electrode for a non-aqueous electrolyte secondary battery according to the invention has a configuration in which a negative electrode active material layer containing a negative electrode material and a binder is formed on the surface of a current collector. Further, the negative electrode material has a core portion including carbonaceous negative electrode active material particles; and a shell portion including a polyimide and silicon-based negative electrode active material particles and/or tin-based negative electrode active material particles. Here, there is a feature that the content of the silicon-based negative electrode active material particles and/or tin-based negative electrode active material particles with respect to 100% by mass of the content of the carbonaceous negative electrode active material particles is 2% to 20% by mass. Furthermore, there is a feature that the binder is formed of a hydrophilic unit and a hydrophobic unit bonded together.
1. A negative electrode for a non-aqueous electrolyte secondary battery, comprising:
a current collector; and
a negative electrode active material layer formed on a surface of the current collector, the negative electrode active material containing:
a negative electrode material that includes:
a core portion including carbonaceous negative electrode active material particles, and
a shell portion including (i) a polyimide, and (ii) silicon-based negative electrode active material particles and/or tin-based negative electrode active material particles, and
a binder formed of (i) poly(meth)acrylic acid, and (ii) butadiene rubber or hydrogenated butadiene rubber, which are covalently bonded together;
wherein a content of the silicon-based negative electrode active material particles and/or tin-based negative electrode active material particles with respect to 100% by mass of a content of the carbonaceous negative electrode active material particles is 2% to 20% by mass; and
wherein, in the binder, mass proportions of the poly(meth)acrylic acid and the butadiene rubber or hydrogenated butadiene rubber are in a range of 98:2 to 85:15.
2. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein a value of a ratio of a volume average particle size (D50) of the silicon-based negative electrode active material particles and/or tin-based negative electrode active material particles with respect to a volume average particle size (D50) of the carbonaceous negative electrode active material particles is 0.001 to 0.1.
3. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the shell portion further includes a conductive aid.
4. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the carbonaceous negative electrode active material particles contain hard carbon.
5. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the silicon-based negative electrode active material particles and/or tin-based negative electrode active material particles contain simple substance of silicon or a silicon oxide.
6. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the polyimide includes an aromatic polyimide.
7. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein a content of the binder in the negative electrode active material layer is 0.5% to 10% by mass with respect to 100% by mass of the total solid content.
8. A non-aqueous electrolyte secondary battery, comprising a power generation element including:
the negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 ;
a positive electrode comprising a positive electrode active material layer containing a positive electrode active material on a surface of a current collector; and
an electrolyte layer disposed between the negative electrode and the positive electrode.
9. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the binder is formed of the poly(meth)acrylic acid unit and the butadiene rubber or hydrogenated butadiene rubber covalently bonded together in a block polymer structure.
10. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein, in the binder, mass proportions of the poly(meth)acrylic acid and the butadiene rubber or hydrogenated butadiene rubber are in a range of 97:3 to 87:13.