Lithium ion secondary battery active material, lithium ion secondary battery electrode, lithium ion secondary battery, electronic device, electric power tool, electric vehicle, and power storage system
View Patent ↗A lithium ion secondary battery capable of improving the lithium ion input-output characteristics. An active material capable of storing and releasing lithium ions is a Li complex oxide or a Li complex oxoacid salt. A plurality of primary particles have a particle size distribution with 1 nm<D10<65 nm, 5 nm<D50<75 nm, and 50 nm<D90<100 nm. The maximum peak pore size A in a pore size distribution as measured by a mercury intrusion technique is 10 nm≦A≦75 nm. The ratio B/A of the maximum peak pore size A and the crystallite size B is 0.5<B/A≦1.
1. A lithium ion secondary battery comprising:
a positive electrode;
a negative electrode; and
an electrolytic solution;
at least one of the positive electrode and the negative electrode being capable of storing and releasing lithium ions, and containing an active material that satisfies the following conditions (A) to (D):
(A) the active material being a Li complex oxide or a Li complex oxoacid salt that contains lithium, oxygen, and at least one of the elements of Groups 2 to 15 of the long-form periodic table;
(B) the active material containing a plurality of primary particles having a particle size distribution (median diameter: nm) with 1 nm<D10<65 nm, 5 nm<D50<75 nm, and 50 nm<D90<100 nm;
(C) the active material having a plurality of pores between the plurality of primary particles, wherein the maximum peak pore size A (nm) in a pore size distribution as measured by a mercury intrusion technique is 10 nm≦A.≦75 nm; and
(D) the ratio B/A of the maximum peak pore size A (nm) and the crystallite size B (nm) determined from the half width of the X-ray diffraction pattern of the active material as measured by X-ray diffractometry is 0.5<B/A≦1.
2. The lithium ion secondary battery according to claim 1 , wherein the active material includes a carbon material-containing coating on at least a part of the surface of the primary particles, the coating having a Raman spectrum with an intensity ratio (I D /I G ) of 0.65 or more between a peak (intensity I D ) in a 1,250 cm −1 to 1,350 cm −1 range and a peak (intensity I G ) in a 1,500 cm −1 to 1,700 cm −1 range as measured by Raman spectroscopy.
3. The lithium ion secondary battery according to claim 2 , wherein the weight ratio of the coating with respect to the primary particles is 0.01 weight % to 10 weight %.
4. The lithium ion secondary battery according to claim 1 , wherein the active material is contained in the positive electrode, and has a direct current resistivity of 7.5 k.Ω·cm or less in a charged state with 80% charge depth.
5. The lithium ion secondary battery according to claim 1 , wherein the active material contained in the positive electrode has a laminar rock salt structure, a spinel structure, or an olivine structure, and wherein the active material contained in the negative electrode has a spinel structure.
6. The lithium ion secondary battery according to claim 5 , wherein the active material contained in the positive electrode is at least one of the compounds of the formulae (1) to (3) below, and wherein the active material contained in the negative electrode is at least one of the compounds of the formulae (4) to (6) below
Li a M1O 2 (1)
(where M1 is at least one of the elements of Groups 2 to 15 of the long-form periodic table, and a satisfies 0<a≦1.2),
Li b Mn c M2 d O 4 (2)
(where M2 is at least one of the elements of Groups 2 to 15 of the long-form periodic table (excluding Mn), and b, c, and d satisfy 0≦1, 0<c≦2, 0≦d<2, and c+d=2),
Li e M3 f PO 4 (3)
(where M3 is at least one of the elements of Groups 2 to 4 and 6 to 15 and Niobium, Tantalum, and of the long-form periodic table, and e and f satisfy 0<e≦1, and 0≦1),
Li[Li x M4 (1−3x)/2 Ti (3+x)/2 ]O 4 (4)
(where M4 is at least one of Mg, Ca, Cu, Zn, and Sr, and x satisfies 0≦x≦⅓),
Li[Li y M5 1−3y Ti 1+2y ]O 4 (5)
(where M5 is at least one of Al, Sc, Cr, Mn, Fe, Ga, and Y, and y satisfies 0≦y≦⅓), and
Li[Li 1/3 M6 z Ti (5/3)−z ]O 4 (6)
(where M6 is at least one of V, Zr, and Nb, and z satisfies 0≦z.≦⅔).
7. The lithium ion secondary battery according to claim 6 ,
wherein the M1 is at least one of Ni, Co, Mn, Cu, Fe, Zn, Y, Ti, Mo, Al, Mg, B, V, Cr, Sn, Ca, Sr, and W,
wherein the M2 is at least one of Co, Ni, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Mo, Sn, Ca, Sr, and W, and
wherein the M3 is at least one of Co, Mn, Fe, Ni, Mg, Al, B, Ti, Nb, Cu, Zn, Mo, Ca, Sr, W, and Zr.
8. An electrode for lithium ion secondary batteries, the electrode comprising an active material capable of storing and releasing lithium ions and satisfying the following conditions (A) to (D):
(A) the active material being a Li complex oxide or a Li complex oxoacid salt that contains lithium, oxygen, and at least one of the elements of Groups 2 to 15 of the long-form periodic table;
(B) the active material containing a plurality of primary particles having a particle size distribution (median diameter: nm) with 1 m<D10<65 nm, 5 nm<D50<75 nm, and 50 nm<D90<100 nm;
(C) the active material having a plurality of pores between the plurality of primary particles, wherein the maximum peak pore size A (nm) in a pore size distribution as measured by a mercury intrusion technique is 10 nm≦A≦75 nm; and
(D) the ratio B/A of the maximum peak pore size A (nm) and the crystallite size B (nm) determined from the half width of the X-ray diffraction pattern of the active material as measured by X-ray diffractometry is 0.5<B/A≦1.
9. An active material for lithium ion secondary batteries, the active material capable of storing and releasing lithium ions and satisfying the following conditions (A) to (D):
(A) the active material being a Li complex oxide or a Li complex oxoacid salt that contains lithium, oxygen, and at least one of the elements of Groups 2 to 15 of the long-form periodic table;
(B) the active material containing a plurality of primary particles having a particle size distribution (median diameter: nm) with 1 nm<D10<65 nm, 5 nm<D50<75 nm, and 50 nm<D90<100 nm;
(C) the active material having a plurality of pores between the plurality of primary particles, wherein the maximum peak pore size A (nm) in a pore size distribution as measured by a mercury intrusion technique is 10 nm≦A≦75 nm; and
(D) the ratio B/A of the maximum peak pore size A (nm) and the crystallite size B (nm) determined from the half width of the X-ray diffraction pattern of the active material as measured by X-ray diffractometry is 0.5<B/A≦1.
10. An electronic device comprising the lithium ion secondary battery of claim 1 .
11. An electric power tool comprising the lithium ion secondary battery of claim 1 .
12. An electric vehicle comprising the lithium ion secondary battery of claim 1 .
13. A power storage system comprising the lithium ion secondary battery of claim 1 .
14. The lithium ion secondary battery according to claim 1 , wherein the positive electrode contains the active material and the active material comprises a carbon material-containing coating on at least a portion of a surface of the primary particle.
15. The lithium ion secondary battery according to claim 14 , wherein the active material further comprises a plurality of secondary particles.
16. The lithium ion secondary battery according to claim 1 , wherein the active material is a Li complex oxide or a Li complex oxoacid salt that contains lithium, oxygen, and at least one of Niobium, Tantalum, and of the long-form periodic table.
17. The electrode for lithium ion secondary batteries according to claim 8 , wherein the active material is a Li complex oxide or a Li complex oxoacid salt that contains lithium, oxygen, and at least one of Niobium, Tantalum, and of the long-form periodic table.
18. The active material for lithium ion secondary batteries according to claim 9 , wherein the active material is a Li complex oxide or a Li complex oxoacid salt that contains lithium, oxygen, and at least one of Niobium, Tantalum, and of the long-form periodic table.