Zinc-containing cathode material for sodium ion battery and preparation method and application thereof
The present invention discloses a cathode material for a sodium ion battery and a preparation method and application thereof. The general chemical formula of the cathode material is Na 1+a M y Zn x O 2+c , where −0.40≤a≤0.25, 0.1<x≤0.22, 0.78<y≤0.93, −0.3<c<0.3. M is one or a combination of two or more selected from the group consisting of Mn, Fe, Ni, Co, Al, Zr, Y, Ca, Li, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, V, Sc, Sr, B and Cu. In the powder X-ray diffraction graph, there are at least five diffraction peaks exist when 2θ is 30°-40°. A minor strong peak exist when 2θ is around 16° and a major strong peak exists when 2θ is around 41°. The sodium ion cathode material of the present invention has a low residual alkali content and avoids the occurrence of gelation phenomenon in the battery slurrying process. In addition, the capacity and rate of the sodium ion battery prepared therefrom are at a relatively high level.
1 . A cathode material for a sodium ion battery, characterized in that the cathode material has a chemical formula of Na 1+a M d Zn x O 2+c , wherein −0.40≤a≤0.25, 0.78<d≤0.93, 0.1<x≤0.22, −0.3<c<0.3; M is one or a combination of two or more selected from the group consisting of Mn, Fe, Ni, Co, Al, Zr, Y, Ca, Li, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, V, Sc, Sr, B and Cu; one diffraction peak exists when a diffraction angle 2θ is around 16°, at least five diffraction peaks exist when the diffraction angle 2θ is 30°-40°, and one diffraction peak exists when the diffraction angle 2θ is around 41°.
2 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in the cathode material Na 1+a M y Zn x O 2+c for the sodium ion battery, M contains an element A and an element B; the content of the element A is represented by b; the cathode material has a general chemical formula of Na 1+a B 1−b−x Zn x A b O 2+c , where 0.1<x≤0.22, 0.0<b≤0.06, −0.40≤a≤0.25, −0.3<c<0.3, y=1−x; A and B are both one or a combination of two or more selected from the group consisting of Mn, Fe, Ni, Co, Al, Zr, Y, Ca, Li, Rb, Cs, W, Ce, Mo, Ba, Ti, Mg, Ta, Nb, V, Sc, Sr, B and Cu, and A and B may be the same or different.
3 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the B element in the cathode material for the sodium ion battery is one or a combination of two or more selected from the group consisting of Mn, Fe, Ni and Co.
4 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the cathode material for the sodium ion battery has a general chemical formula of Na 1+a Ni y Mn z Fe 1−x−y−z−b Zn x A b O 2+c , where 0.15≤y≤0.35, 0.20≤z≤0.38, −0.40≤a≤0.25, 0.0<b≤0.06, −0.3<c<0.3, 0.1<x≤0.22.
5 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the content of zinc element in the cathode material for the sodium ion battery is 5.0%-20.0% by mass.
6 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the content of zinc element in the cathode material for the sodium ion battery is 5.0%-15.0% by mass.
7 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the cathode material powder for the sodium ion battery has an X-ray diffraction graph showing an α-NaFeO 4 layered structure.
8 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in a X-ray diffraction graph of the cathode material powder for the sodium ion battery, a full width at half maxima of the diffraction peak having a 2θ value of 30°-40° is 0.04°-0.4°.
9 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in a X-ray diffraction graph of the cathode material powder for the sodium ion battery, a minor strong peak exists when 2θ is around 16° and a major strong peak exists when 2θ is around 41°.
10 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in a X-ray diffraction graph of the cathode material powder for the sodium ion battery, a full width at half maxima of the diffraction peak having a 2θ of around 16° and around 41° is 0.05°-0.35°.
11 . The cathode material for the sodium ion battery according to claim 1 , characterized in that, in a X-ray diffraction graph of the cathode material powder for the sodium ion battery, six diffraction peaks exist when 2θ is 30°-40°, where 2θ is around 32°, around 33°, around 34°, around 35°, and around 36°, respectively.
12 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in a X-ray diffraction graph (XRD) of the cathode material powder for the sodium ion battery, a full width at half maxima FWHM of a diffraction peak around the diffraction angle 2θ of 31.8° is 0.06°-0.25°; a full width at half maxima FWHM of a diffraction peak around the diffraction angle 2θ of 34.4° is 0.07°−0.25°; a full width at half maxima FWHM of the diffraction peak around the diffraction angle 2θ of 36.3° is 0.06°-0.25°.
13 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in a X-ray diffraction graph (XRD) of the cathode material powder for the sodium ion battery, the peak intensity ratio of the diffraction peak around the diffraction angle 2θ of 31.8° to the diffraction peak around the diffraction angle 2θ of 34.4° is (1-2):1.
14 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in a X-ray diffraction graph (XRD) of the cathode material powder for the sodium ion battery, the peak intensity ratio of the diffraction peak around the diffraction angle 2θ of 36.3° to the diffraction peak around the diffraction angle 2θ of 34.4° is (2-3):1.
15 . The cathode material for the sodium ion battery according to claim 1 , characterized in that in the X-ray diffraction graph (XRD) of the cathode material powder for the sodium ion battery, a full width at half maxima FWHM of the diffraction peak around the diffraction angle satisfies one or more of the following conditions:
(a) a full width at half maxima FWHM of the diffraction peak around the diffraction angle 2θ of 16.5° is 0.08°-0.25°,
(b) a full width at half maxima FWHM of the diffraction peak around the diffraction angle 2θ of 33.4° is 0.08°-0.23°,
(c) a full width at half maxima FWHM of the diffraction peak around the diffraction angle 2θ of 35.2° is 0.07°-0.22°,
(d) a full width at half maxima FWHM of the diffraction peak around the diffraction angle 2θ of 36.6° is 0.08°-0.20°,
(e) a full width at half maxima FWHM of the diffraction peak around the diffraction angle 2θ of 41.6° is 0.06°-0.20°.
16 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the cathode material for the sodium ion battery has a specific surface area of 0.25-1.5 m 2 /g.
17 . The cathode material for the sodium ion battery according to claim 1 , characterized in that a particle size D50 of the cathode material for the sodium ion battery is 2-15 μm.
18 . The cathode material for the sodium ion battery according to claim 1 , characterized in that the cathode material for the sodium ion battery is prepared by a method comprising the following steps:
either
(i) mixing an M source and a Zn source in a certain proportion to obtain a precursor, mixing the precursor uniformly with a Na source, or
(ii) mixing the M source, the Zn source and the Na source uniformly,
and after either step (i) or step (ii), then sintering at a temperature of 750-980° C. to obtain the cathode material for the sodium battery.
19 . A positive electrode for a sodium ion battery, characterized by comprising the cathode material for the sodium ion battery according to claim 1 as a positive electrode active substance.
20 . A sodium ion battery, characterized in that the sodium ion battery comprises the positive electrode for a sodium ion battery according to claim 19 , a negative electrode, and an electrolyte containing a sodium salt.