Negative electrode material for secondary battery
A negative electrode material for a secondary battery includes a matrix containing silicon oxide, a composite oxide of one or more doping elements selected from the group consisting of an alkali metal, an alkaline earth metal, and a post-transition metal, and silicon, or a mixture thereof; and silicon nanoparticles dispersed and embedded in the matrix; wherein a hardness and a Young's modulus measured by a nanoindentation test are 4.0 GPa or more and 40 GPa or more, respectively, and in an X-ray diffraction pattern using a CuKα ray, a ratio (A 1 /A 2 ) of an area (A 1 ) of a first peak present in a region where a diffraction angle 2 θ is 10° to 27.4° to an area (A 2 ) of a second peak present in a region where the diffraction angle 2 θ is 28±0.5° is 0.8 to 6.
1. A negative electrode material for a secondary battery, comprising:
a matrix containing silicon oxide, and a composite oxide of a doping element; wherein the doping element is magnesium (Mg), and
silicon nanoparticles dispersed and embedded in the matrix;
wherein a hardness and a Young's modulus measured by a nanoindentation test are 4.0 GPa or more and 40 GPa or more, respectively, and in an X-ray diffraction pattern using a CuKα ray, a ratio (A 1 /A 2 ) is 0.8 to 6, wherein A 1 is an area of a first peak present in a region where a diffraction angle 2 θ is 10° to 27.4°, and A 2 is an area of a second peak present in a region where the diffraction angle 2 θ is 28±0.5°, and
wherein the negative electrode material satisfies the following Expression 3:
B/A≤ 0.65 (Expression 3)
wherein A is an average value (A) obtained by averaging contents (wt %) of the doping element measured at 100 random points based on a cross section crossing the center of the negative electrode material, and B is a standard deviation (B) of the contents of the doping element.
2. The negative electrode material of claim 1 , wherein in the X-ray diffraction pattern, a ratio (L 1 /L 2 ) of a full-width at half maximum (FWHM) (L 1 ) of the first peak to a full-width at half maximum (FWHM) (L 2 ) is 6 to 15.
3. The negative electrode material of claim 1 , wherein an intensity ratio (I 1 /I 2 ) of a maximum intensity (I 1 ) of the first peak to a maximum intensity (I 2 ) of the second peak is 0.05 to 1.25.
4. The negative electrode material of claim 1 , wherein the first peak is derived from amorphous silicon oxide, and the second peak is derived from crystalline silicon.
5. The negative electrode material of claim 1 , wherein an FWHM of a Raman peak of nanoparticulate silicon contained in the negative electrode material is larger than an FWHM of a Raman peak of bulk single crystal silicon.
6. The negative electrode material of claim 5 , wherein the FWHM of the Raman peak of the nanoparticulate silicon contained in the negative electrode material is 4 to 20 cm −1 .
7. The negative electrode material of claim 5 , wherein the following Expression 1 is satisfied based on a Raman signal of silicon,
1 <WN (Si)/ WN (ref) (Expression 1)
wherein WN(ref) is the center wavenumber of the Raman peak of the bulk single crystal silicon, and WN(Si) is the center wavenumber of the Raman peak of the nanoparticulate silicon contained in the negative electrode material.
8. The negative electrode material of claim 7 , wherein when the negative electrode material is subjected to two-dimensional mapping analysis based on a Raman signal of silicon, a difference between a maximum value and a minimum value of a shift defined by the following Expression 2 under the following mapping conditions is 5 cm −1 or less,
Mapping conditions: excitation laser wavelength=532 nm, laser power=0.1 mW, detector exposure time (exposure time per unit analysis area)=1 sec, focal length=30 mm, grating=1,800 grooves/mm, pixel resolution=1 cm −1 , and mapping size=14 μm×14 μm,
Shift= WN i (Si)− WN (ref) (Expression 2)
wherein WN(ref) is the same as defined in Expression 1, and WN(Si) is the center wavenumber of the Raman peak of the nanoparticulate silicon contained in the negative electrode material in one pixel that is the unit analysis area at the time of the mapping analysis.
9. The negative electrode material of claim 8 , wherein when a shift is analyzed based on a Raman signal of silicon at 20 different positions at random in a 20 mm×20 mm sample, a difference between a maximum value and a minimum value of a shift defined by the following Expression 2 is 5 cm −1 or less,
Mapping conditions: excitation laser wavelength=532 nm, laser power=0.1 mW, detector exposure time (exposure time per unit analysis area)=1 sec, focal length=30 mm, grating=1,800 grooves/mm, and pixel resolution=1 cm −1 ,
Shift= WN i (Si)− WN (ref) (Expression 2)
wherein WN(ref) is the same as defined in Expression 1, and WN(Si) is the center wavenumber of the Raman peak of the nanoparticulate silicon contained in the negative electrode material in one pixel that is the unit analysis area at the time of the mapping analysis.
10. The negative electrode material of claim 1 , wherein when a stress of the silicon nanoparticle is analyzed at 20 different positions at random in a 20 mm×20 mm sample, a compressive stress is 80% or more.
11. The negative electrode material of claim 1 , wherein the negative electrode material includes a plurality of negative electrode material particles, and the particles have a composition uniformity represented by the following Expression 3,
1.3≤ UF ( D ) (Expression 3)
wherein UF(D) is a value obtained by dividing an average doping element composition of the negative electrode material particles by a standard deviation of a doping element composition based on wt % of the composition.
12. The negative electrode material of claim 1 , wherein an average diameter of the silicon nanoparticles is 2 to 30 nm.
13. The negative electrode material of claim 1 , wherein an interface between the silicon nanoparticle and the matrix is a coherent interface.
14. The negative electrode material of claim 1 , wherein the negative electrode material is in a form of particles having an average diameter of 5 μm to 30 μm.
15. The negative electrode material of claim 1 , further comprising a coating layer that contains carbon and is coated on a surface of the negative electrode material.
16. A secondary battery comprising the negative electrode material for a secondary battery of claim 1 .