JP2019175829A - Positive electrode active material composite for lithium ion secondary battery or positive electrode active material composite for sodium ion secondary battery, secondary battery including the same, and method of manufacturing the same - Google Patents

Abstract

To provide a positive electrode active material composite for a lithium ion secondary battery or a positive electrode active material composite for a sodium ion secondary battery, capable of effectively improving high-temperature cycle characteristics when being used as a positive electrode active material for a lithium ion secondary battery or a sodium ion secondary battery.SOLUTION: In a positive electrode active material composite for a lithium ion secondary battery, a specific lithium-based polyanion particle (B) and a lithium composite oxide particle are compounded only on a surface of a lithium composite oxide secondary particle (A) that comprises one or more kinds of lithium composite oxide particles represented by the following formula (I): LiNiCoMnMO...(I), or the following formula (II): LiNiCoAlMO...(II). Under a specific condition, the mass ratio ((A):(B)) of the content of the lithium composite oxide secondary particle (A) and the content of the lithium-based polyanion particle (B) is 95:5-55:45.SELECTED DRAWING: None

Description

  The present invention provides a positive electrode active material composite for a lithium ion secondary battery or a positive electrode active material composite for a sodium ion secondary battery having a layered rock salt structure, which can effectively enhance the high-temperature cycle characteristics in a secondary battery, The present invention relates to a lithium ion secondary battery or a sodium ion secondary battery included as a positive electrode material, and a method for producing these positive electrode active material composites for lithium ion secondary batteries or positive electrode active material composites for sodium ion secondary batteries.

  Conventionally, lithium composite oxide has been used as a positive electrode active material capable of constituting a high-output and high-capacity lithium ion secondary battery. Such a lithium composite oxide has a layered crystal structure in which a lithium atomic layer and a transition metal atomic layer are alternately stacked via an oxygen atomic layer, and one lithium atom is included per one atom of the transition metal. It is also known to have a so-called layered rock salt structure.

  In a lithium ion secondary battery using such a lithium composite oxide as a positive electrode active material, charging / discharging is performed as lithium ions are desorbed and inserted into the lithium composite oxide, but usually the charge / discharge cycle is repeated. When the battery is used for a long time, the battery capacity may be significantly reduced. This is considered to be caused by the fact that the transition metal component of the lithium composite oxide is eluted into the electrolytic solution during charging, so that the crystal structure is easily collapsed. In particular, the higher the temperature, the greater the amount of transition metal elution and the greater the effect on cycle characteristics. In addition, when the crystal structure of the lithium composite oxide collapses, the transition metal component of the lithium composite oxide may elute into the surrounding electrolyte, which may reduce the thermal stability and impair safety.

However, for example, battery materials used in in-vehicle batteries are required to have excellent durability performance that can maintain a certain capacity or more even after a large number of charge / discharge cycles of 1000 cycles or more. Various developments have been made to meet this demand. For example, in Patent Document 1, primary particles having an average particle diameter of 1 μm to 8 μm are aggregated to form secondary particles having an average particle diameter of 5 μm to 30 μm, and the porosity of the secondary particles is 30% or less. A lithium composite oxide is disclosed. Patent Document 2 discloses a lithium composite oxide having a true density of 4.40 to 4.80 g / cm ³ and having a high volumetric energy density and having appropriate voids in the positive electrode active material. In addition, a specific example of an electrode active material having a lithium composite oxide of a core part and a lithium composite oxide of a shell part having a composition different from that of the core part is also described.

  On the other hand, since lithium is a rare valuable substance, a sodium composite oxide that has a layered rock salt structure similar to that of lithium composite oxide and that can be charged and discharged with sodium ions instead of lithium ions has been developed. Yes. For example, Patent Document 3 discloses a sodium composite oxide having excellent cycle characteristics, including Fe, Mn, Ni, Co, or Ti.

JP 2001-85006 A International Publication No. 2014/133069 Pamphlet JP 2010-80424 A

  However, in any of the techniques described in any of these documents, it is difficult to sufficiently improve the cycle characteristics of the lithium composite oxide or the sodium composite oxide, and further improvement is required.

  Therefore, the subject of this invention is the positive electrode active material composite for lithium ion secondary batteries which can improve a high temperature cycling characteristic effectively, when it uses as a positive electrode active material of a lithium ion secondary battery or a sodium ion secondary battery. Or it is providing the positive electrode active material composite_body | complex for sodium ion secondary batteries.

  Therefore, as a result of intensive investigations, the present inventors have found that the lithium composite oxide particles and the lithium composite oxide secondary particles only on the surface of the lithium composite oxide secondary particles made of specific composite oxide particles. By combining with a specific lithium-based polyanion particle having a specific mass ratio, when used as a positive electrode material of a lithium ion secondary battery, the reaction with the electrolytic solution is effectively suppressed and applied many times. It has been found that a positive electrode active material composite for a lithium ion secondary battery that does not cause a decrease in output even after a charge / discharge cycle is obtained.

  Further, only on the surface of the sodium composite oxide secondary particles composed of specific sodium composite oxide particles, the sodium composite oxide particles and the specific sodium system having a specific mass ratio with respect to the sodium composite oxide secondary particles By combining with polyanion particles, when used as a positive electrode material for sodium ion secondary batteries, the reaction with the electrolyte is effectively suppressed, resulting in a decrease in output even after many charge / discharge cycles. It was also found that a positive electrode active material composite for a sodium ion secondary battery can be obtained.

That is, the present invention provides the following formula (I):
LiNi _a Co _b Mn _c M ¹ _x O ₂ (I)
(In the formula (I), ^{M 1} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge are shown, a, b, c, and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, (0 ≦ x ≦ 0.3 and 3a + 3b + 3c + (valence of M ¹ ) × x = 3)
Or the following formula (II):
LiNi _d Co _e Al _f M ² _y O ₂ (II)
(In the formula (II), ^{M 2} is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and One or more elements selected from Ge are shown, d, e, f, and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦. (Y ≦ 0.3 and 3d + 3e + 3f + (valence of M ² ) × y = 3)
On the surface of the lithium composite oxide secondary particles (A) composed of one or more lithium composite oxide particles represented by the following formula (V):
^{_{Li s Co g Ni h M 5}} i PO 4 ··· (V)
(In the formula (V), M ⁵ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. S, g, h, and i are 0 <s ≦ 1.2, 0 ≦ g ≦ 1.2, 0 ≦ h ≦ 1.2, 0 ≦ i ≦ 0.3, and g + h ≠ 0, and s + (Co valence) × g + ( The valence of Ni) × h + (the valence of M ⁵ ) × i = a number satisfying i = 3).
Following formula (VI):
^{_{Li t Co j Ni k M 6}} l SiO 4 ··· (VI)
(In the formula (VI), M ⁶ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. T, j, k, and l are 0 <t ≦ 2.4, 0 ≦ j ≦ 1.2, 0 ≦ k ≦ 1.2, 0 ≦ l ≦ 1.2, and j + k ≠ 0, and t + (Co valence) × j + ( Ni valence) × k + (M ⁶ valence) × 1 = the number satisfying 4).
Or the following formula (VIII):
^{_{Li v Fe p Mn q M 8}} r SiO 4 ··· (VIII)
(In the formula (VIII), M ⁸ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, V, or Gd. V, p, q and r satisfy 0 <v ≦ 2.4, 0 ≦ p ≦ 1.2, 0 ≦ q ≦ 1.2, 0 ≦ r ≦ 1.2, and p + q ≠ 0, and v + (Fe Valence) × p + (valence of Mn) × q + (valence of M ⁸ ) × r = 4 is satisfied.)
And one or more lithium-based polyanion particles (B) having carbon (c) supported on the surface and lithium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the lithium-based polyanion particles (B) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the lithium-based polyanion particles (B),
The average particle diameter of the lithium-based polyanion particles (B) is 20 nm to 200 nm,
Lithium whose mass ratio ((A) :( B)) of the content of the lithium composite oxide secondary particles (A) and the content of the lithium-based polyanion particles (B) is 95: 5 to 55:45 A positive electrode active material composite for an ion secondary battery is provided.

Furthermore, the present invention provides the following formula (I):
LiNi _a Co _b Mn _c M ¹ _x O ₂ (I)
(In the formula (I), ^{M 1} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge are shown, a, b, c, and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, (0 ≦ x ≦ 0.3 and 3a + 3b + 3c + (valence of M ¹ ) × x = 3)
Or the following formula (II):
LiNi _d Co _e Al _f M ² _y O ₂ (II)
(In the formula (II), ^{M 2} is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and One or more elements selected from Ge are shown, d, e, f, and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦. (Y ≦ 0.3 and 3d + 3e + 3f + (valence of M ² ) × y = 3)
On the surface of the lithium composite oxide secondary particles (A) composed of one or more lithium composite oxide particles represented by the following formula (VII):
^{_{Li u Fe m Mn n M 7}} o PO 4 ··· (VII)
(In the formula (VII), M ⁷ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. U, m, n, and o are 0 <u ≦ 1.2, 0 ≦ m ≦ 1.2, 0 ≦ n ≦ 1.2, 0 ≦ o ≦ 0.3, and m + n ≠ 0, and u + (Fe valence) × m + ( valence of Mn) × n + (valence of ^{M 7)} shows a number satisfying × o = 3.)
Lithium-based polyanion particles (B) represented by the above and having carbon (c) supported on the surface and lithium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the lithium-based polyanion particle (B) is 0.1% by mass or more and less than 10% by mass in 100% by mass of the lithium-based polyanion particle (B),
The average particle size of the lithium-based polyanion particles (B) is 50 nm to 200 nm,
The mass ratio ((A) :( B)) between the content of the lithium composite oxide secondary particles (A) and the content of the lithium-based polyanion particles (B) is 65:35 to 55:45 (provided that 63:35)). The present invention provides a positive electrode active material composite for a lithium ion secondary battery.

The present invention also provides the following formula (III):
NaNi _{a ′} Co _{b ′} Mn _{c ′} M ³ _{x ′} O ₂ (III)
(In the formula (III), ^{M 3} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge, a ′, b ′, c ′ and x ′ are 0.3 ≦ a ′ <1, 0 <b ′ ≦ 0.7, 0 < (c ′ ≦ 0.7, 0 ≦ x ′ ≦ 0.3, and 3a ′ + 3b ′ + 3c ′ + (valence of M ³ ) × x ′ = 3).
Or the following formula (IV):
NaNi _{d ′} Co _{e ′} Al _{f ′} M ⁴ _{y ′} O ₂ (IV)
(In the formula (IV), M ⁴ is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and 1 or 2 or more elements selected from Ge, d ′, e ′, f ′, and y ′ are 0.4 ≦ d ′ <1, 0 <e ′ ≦ 0.6, and 0 <f ′. ≦ 0.3,0 ≦ y '≦ 0.3, and 3d' + 3e '+ 3f' + ( valence of ^{M 4)} shows a number satisfying × y '= 3.)
On the surface of the sodium composite oxide secondary particles (D) composed of one or more kinds of sodium composite oxide particles represented by the following formula (IX):
Na _w Cog _′ Ni _{h ′} M ⁹ _{i ′} PO ₄ (IX)
(In the formula (IX), M ⁹ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. W, g ′, h ′, and i 'Satisfies 0 <w ≦ 1.2, 0 ≦ g ′ ≦ 1.2, 0 ≦ h ′ ≦ 1.2, 0 ≦ i ′ ≦ 0.3, and g ′ + h ′ ≠ 0, and w + (The valence of Co) × g ′ + (the valence of Ni) × h ′ + (the valence of M ⁹ ) × i ′ = 3.
Formula (X) below:
Na _x Co _{j ′} Ni _{k ′} M ¹⁰ _{l ′} SiO ₄ ... (X)
(.X shown in the formula ^{(X), M 10} is Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, j ', k', and l 'Satisfies 0 <x ≦ 2.4, 0 ≦ j ′ ≦ 1.2, 0 ≦ k ′ ≦ 1.2, 0 ≦ l ′ ≦ 1.2, and j ′ + k ′ ≠ 0, and x + (Co valence) × j ′ + (Ni valence) × k ′ + (M ¹⁰ valence) × l ′ = 4).
Formula (XI):
Na _y Fem _′ Mn _{n ′} M ¹¹ _{o ′} PO ₄ (XI)
(.Y shown in the formula ^{(XI), M 11} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, m ', n', and o 'Satisfies 0 <y ≦ 1.2, 0 ≦ m ′ ≦ 1.2, 0 ≦ n ′ ≦ 1.2, 0 ≦ o ′ ≦ 0.3, and m ′ + n ′ ≠ 0, and y + (valence of Fe) × m '+ (valence of Mn) × n' + ^(valence of ^{M 11)} × o '= 3 indicates a number satisfying.)
Or the following formula (XII):
Na _z Fe _{p ′} Mn _{q ′} M ¹² _{r ′} SiO ₄ ... (XII)
(In the formula ^{(XII), M 12} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, .z showing a V or Gd, p ' , Q ′, and r ′ are 0 <z ≦ 2.4, 0 ≦ p ′ ≦ 1.2, 0 ≦ q ′ ≦ 1.2, 0 ≦ r ′ ≦ 1.2, and p ′ + q ′ ≠. 0 is satisfied, and z + (Fe valence) × p ′ + (Mn valence) × q ′ + (M ¹² valence) × r ′ = 4).
And one or more kinds of sodium-based polyanion particles (E) formed by supporting carbon (c) on the surface and sodium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the sodium-based polyanion particles (E) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the sodium-based polyanion particles (E),
The average particle size of the sodium-based polyanion particles (E) is 50 nm to 200 nm,
Sodium whose mass ratio ((D) :( E)) of the content of the sodium composite oxide secondary particles (D) and the content of the sodium-based polyanion particles (E) is 95: 5 to 55:45 A positive electrode active material composite for an ion secondary battery is provided.

  Furthermore, the present invention provides a lithium composite oxide secondary particle (A), a lithium-based polyanion particle (B) in which carbon (c) is supported on the surface, or a lithium composite oxide secondary particle (A), a surface Lithium polyanion particles (B) formed by supporting carbon (c) on the surface and water-insoluble carbon particles (c3) are mixed while applying compressive force and shearing force to form a composite. The present invention relates to a method for producing a positive electrode active material composite for a secondary battery.

  In addition, the present invention provides sodium composite oxide secondary particles (D) and sodium-based polyanion particles (E), or sodium composite oxide secondary particles (D), sodium-based polyanion particles (E), and water-insoluble carbon particles ( It is related with the manufacturing method of the said positive electrode active material composite_body | complex for sodium ion secondary batteries provided with the process of mixing and adding c3), adding compressive force and shear force.

  According to the positive electrode active material composite for a lithium ion secondary battery or the positive electrode active material composite for a sodium ion secondary battery according to the present invention, the crystal structure is prevented from collapsing while having a layered rock salt structure. In a lithium ion secondary battery or a sodium ion secondary battery obtained by using as a high temperature cycle characteristic can be effectively enhanced.

Hereinafter, the present invention will be described in detail.
The positive electrode active material composite for a lithium ion secondary battery of the present invention has the following formula (I):
LiNi _a Co _b Mn _c M ¹ _x O ₂ (I)
(In the formula (I), ^{M 1} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge are shown, a, b, c, and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, (0 ≦ x ≦ 0.3 and 3a + 3b + 3c + (valence of M ¹ ) × x = 3)
Or the following formula (II):
LiNi _d Co _e Al _f M ² _y O ₂ (II)
(In the formula (II), ^{M 2} is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and One or more elements selected from Ge are shown, d, e, f, and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦. (Y ≦ 0.3 and 3d + 3e + 3f + (valence of M ² ) × y = 3)
On the surface of the lithium composite oxide secondary particles (A) composed of one or more lithium composite oxide particles represented by the following formula (V):
^{_{Li s Co g Ni h M 5}} i PO 4 ··· (V)
(In the formula (V), M ⁵ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. S, g, h, and i are 0 <s ≦ 1.2, 0 ≦ g ≦ 1.2, 0 ≦ h ≦ 1.2, 0 ≦ i ≦ 0.3, and g + h ≠ 0, and s + (Co valence) × g + ( The valence of Ni) × h + (the valence of M ⁵ ) × i = a number satisfying i = 3).
Following formula (VI):
^{_{Li t Co j Ni k M 6}} l SiO 4 ··· (VI)
(In the formula (VI), M ⁶ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. T, j, k, and l are 0 <t ≦ 2.4, 0 ≦ j ≦ 1.2, 0 ≦ k ≦ 1.2, 0 ≦ l ≦ 1.2, and j + k ≠ 0, and t + (Co valence) × j + ( Ni valence) × k + (M ⁶ valence) × 1 = the number satisfying 4).
Or the following formula (VIII):
^{_{Li v Fe p Mn q M 8}} r SiO 4 ··· (VIII)
(In the formula (VIII), M ⁸ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, V, or Gd. V, p, q and r satisfy 0 <v ≦ 2.4, 0 ≦ p ≦ 1.2, 0 ≦ q ≦ 1.2, 0 ≦ r ≦ 1.2, and p + q ≠ 0, and v + (Fe Valence) × p + (valence of Mn) × q + (valence of M ⁸ ) × r = 4 is satisfied.)
And one or more lithium-based polyanion particles (B) having carbon (c) supported on the surface and lithium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the lithium-based polyanion particles (B) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the lithium-based polyanion particles (B),
The average particle diameter of the lithium-based polyanion particles (B) is 20 nm to 200 nm,
The mass ratio ((A) :( B)) between the content of the lithium composite oxide secondary particles (A) and the content of the lithium-based polyanion particles (B) is 95: 5 to 55:45.

Furthermore, the positive electrode active material composite for a lithium ion secondary battery of the present invention has the following formula (I):
LiNi _a Co _b Mn _c M ¹ _x O ₂ (I)
(In the formula (I), ^{M 1} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge are shown, a, b, c, and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, (0 ≦ x ≦ 0.3 and 3a + 3b + 3c + (valence of M ¹ ) × x = 3)
Or the following formula (II):
LiNi _d Co _e Al _f M ² _y O ₂ (II)
(In the formula (II), ^{M 2} is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and One or more elements selected from Ge are shown, d, e, f, and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦. (Y ≦ 0.3 and 3d + 3e + 3f + (valence of M ² ) × y = 3)
On the surface of the lithium composite oxide secondary particles (A) composed of one or more lithium composite oxide particles represented by the following formula (VII):
^{_{Li u Fe m Mn n M 7}} o PO 4 ··· (VII)
(In the formula (VII), M ⁷ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. U, m, n, and o are 0 <u ≦ 1.2, 0 ≦ m ≦ 1.2, 0 ≦ n ≦ 1.2, 0 ≦ o ≦ 0.3, and m + n ≠ 0, and u + (Fe valence) × m + ( valence of Mn) × n + (valence of ^{M 7)} shows a number satisfying × o = 3.)
Lithium-based polyanion particles (B) represented by the above and having carbon (c) supported on the surface and lithium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the lithium-based polyanion particle (B) is 0.1% by mass or more and less than 10% by mass in 100% by mass of the lithium-based polyanion particle (B),
The average particle size of the lithium-based polyanion particles (B) is 50 nm to 200 nm,
The mass ratio ((A) :( B)) between the content of the lithium composite oxide secondary particles (A) and the content of the lithium-based polyanion particles (B) is 65:35 to 55:45 (provided that 65:35 is excluded).

Moreover, the positive electrode active material composite for a sodium ion secondary battery of the present invention has the following formula (III):
NaNi _{a ′} Co _{b ′} Mn _{c ′} M ³ _{x ′} O ₂ (III)
(In the formula (III), ^{M 3} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge, a ′, b ′, c ′ and x ′ are 0.3 ≦ a ′ <1, 0 <b ′ ≦ 0.7, 0 < (c ′ ≦ 0.7, 0 ≦ x ′ ≦ 0.3, and 3a ′ + 3b ′ + 3c ′ + (valence of M ³ ) × x ′ = 3).
Or the following formula (IV):
NaNi _{d ′} Co _{e ′} Al _{f ′} M ⁴ _{y ′} O ₂ (IV)
(In the formula (IV), M ⁴ is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and 1 or 2 or more elements selected from Ge, d ′, e ′, f ′, and y ′ are 0.4 ≦ d ′ <1, 0 <e ′ ≦ 0.6, and 0 <f ′. ≦ 0.3,0 ≦ y '≦ 0.3, and 3d' + 3e '+ 3f' + ( valence of ^{M 4)} shows a number satisfying × y '= 3.)
On the surface of the sodium composite oxide secondary particles (D) composed of one or more kinds of sodium composite oxide particles represented by the following formula (IX):
Na _w Cog _′ Ni _{h ′} M ⁹ _{i ′} PO ₄ (IX)
(In the formula (IX), M ⁹ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. W, g ′, h ′, and i 'Satisfies 0 <w ≦ 1.2, 0 ≦ g ′ ≦ 1.2, 0 ≦ h ′ ≦ 1.2, 0 ≦ i ′ ≦ 0.3, and g ′ + h ′ ≠ 0, and w + (The valence of Co) × g ′ + (the valence of Ni) × h ′ + (the valence of M ⁹ ) × i ′ = 3.
Formula (X) below:
Na _x Co _{j ′} Ni _{k ′} M ¹⁰ _{l ′} SiO ₄ ... (X)
(.X shown in the formula ^{(X), M 10} is Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, j ', k', and l 'Satisfies 0 <x ≦ 2.4, 0 ≦ j ′ ≦ 1.2, 0 ≦ k ′ ≦ 1.2, 0 ≦ l ′ ≦ 1.2, and j ′ + k ′ ≠ 0, and x + (Co valence) × j ′ + (Ni valence) × k ′ + (M ¹⁰ valence) × l ′ = 4).
Formula (XI):
Na _y Fem _′ Mn _{n ′} M ¹¹ _{o ′} PO ₄ (XI)
(.Y shown in the formula ^{(XI), M 11} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, m ', n', and o 'Satisfies 0 <y ≦ 1.2, 0 ≦ m ′ ≦ 1.2, 0 ≦ n ′ ≦ 1.2, 0 ≦ o ′ ≦ 0.3, and m ′ + n ′ ≠ 0, and y + (valence of Fe) × m '+ (valence of Mn) × n' + ^(valence of ^{M 11)} × o '= 3 indicates a number satisfying.)
Or the following formula (XII):
Na _z Fe _{p ′} Mn _{q ′} M ¹² _{r ′} SiO ₄ ... (XII)
(In the formula ^{(XII), M 12} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, .z showing a V or Gd, p ' , Q ′, and r ′ are 0 <z ≦ 2.4, 0 ≦ p ′ ≦ 1.2, 0 ≦ q ′ ≦ 1.2, 0 ≦ r ′ ≦ 1.2, and p ′ + q ′ ≠. 0 is satisfied, and z + (Fe valence) × p ′ + (Mn valence) × q ′ + (M ¹² valence) × r ′ = 4).
And one or more kinds of sodium-based polyanion particles (E) formed by supporting carbon (c) on the surface and sodium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the sodium-based polyanion particles (E) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the sodium-based polyanion particles (E),
The average particle size of the sodium-based polyanion particles (E) is 50 nm to 200 nm,
The mass ratio ((D) :( E)) of the content of the sodium composite oxide secondary particles (D) and the content of the sodium-based polyanion particles (E) is 95: 5 to 55:45.

Lithium nickel composite oxide (so-called Li-Ni-Co-Mn oxide, hereinafter referred to as "Li-NCM composite oxide") particles represented by the above formula (I), and the above formula (III) Sodium-nickel composite oxide (so-called Na-Ni-Co-Mn oxide, hereinafter referred to as "Na-NCM composite oxide"). Li-NCM composite oxide and Na-NCM system Composite oxides are collectively referred to as “NCM-based composite oxides”) particles, and lithium nickel composite oxides (so-called Li—Ni—Co—Al oxides) represented by the above formula (II). -NCA-based composite oxide.) Particles, and sodium nickel composite oxide represented by the above formula (IV) (so-called Na-Ni-Co-Al oxide, hereinafter referred to as "Na-NCA-based composite oxide"). object Referred to. Further, the Li-NCA based composite oxide and Na-NCA based composite oxide are collectively referred to as "NCA based composite oxide".) Particles are both particles having a layered rock salt structure.
These particles aggregate to form lithium nickel composite oxide secondary particles (A) or sodium nickel composite oxide secondary particles (D). Therefore, these secondary particles are also referred to as “NCM-based composite oxide secondary particles”, “NCA-based composite oxide secondary particles”, and the like.

M ¹ in the above formula (I) or M ³ in the above formula (III) is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, One or more elements selected from Sn, Ta, W, La, Ce, Pb, Bi and Ge are shown.
In the above formula (I), a, b, c and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, 0 ≦ x ≦ 0.3, And 3a + 3b + 3c + (valence of M ¹ ) × x = 3, and a ′, b ′, c ′, x ′ in the above formula (III) are 0.3 ≦ a ′ <1, 0 < b ′ ≦ 0.7, 0 <c ′ ≦ 0.7, 0 ≦ x ′ ≦ 0.3, and 3a ′ + 3b ′ + 3c ′ + (valence of M ³ ) × x ′ = 3 .

In the NCM composite oxide particles represented by the above formula (I) or formula (III), it is known that Ni, Co and Mn are excellent in electronic conductivity and contribute to battery capacity and output characteristics. Further, from the viewpoint of cycle characteristics, it is preferable that a part of the transition element is substituted with another metal element M ¹ or M ³ . By substituting with these metal elements M ¹ or M ³ , the crystal structure of the NCM composite oxide particles represented by the formula (I) or the formula (III) is stabilized. It is considered that the collapse of the crystal structure can be suppressed and excellent cycle characteristics can be realized.
Specific examples of the Li-NCM composite oxide particles represented by the above formula (I) include LiNi _0.33 Co _0.33 Mn _0.34 O ₂ , LiNi _0.8 Co _0.1 Mn _0.1 O ₂ , LiNi _0.6 Co _0.2 Mn _0.2. Examples thereof include O ₂ , LiNi _0.2 Co _0.4 Mn _0.4 O ₂ , LiNi _0.33 Co _0.31 Mn _0.33 Mg _0.03 O ₂ , and LiNi _0.33 Co _0.31 Mn _0.33 Zn _0.03 O ₂ . Among them, when importance is attached to the discharge capacity, particles having a composition with a large amount of Ni, such as LiNi _0.8 Co _0.1 Mn _0.1 O ₂ and LiNi _0.6 Co _0.2 Mn _0.2 O ₂ , are preferable. Particles having a composition with a small amount of Ni, such as LiNi _0.33 Co _0.33 Mn _0.34 O ₂ and LiNi _0.33 Co _0.31 Mn _0.33 Mg _0.03 O _2, are preferable.
Specific examples of the Na-NCM composite oxide particles represented by the above formula (III) include NaNi _0.33 Co _0.33 Mn _0.34 O ₂ , NaNi _0.8 Co _0.1 Mn _0.1 O ₂ , NaNi _0.6 Co _0.2. Examples thereof include Mn _0.2 O ₂ , NaNi _0.2 Co _0.4 Mn _0.4 O ₂ , NaNi _0.33 Co _0.31 Mn _0.33 Mg _0.03 O ₂ , and NaNi _0.33 Co _0.31 Mn _0.33 Zn _0.03 O ₂ . In particular, when the discharge capacity is important, particles having a composition with a large amount of Ni, such as NaNi _0.8 Co _0.1 Mn _0.1 O ₂ , NaNi _0.6 Co _0.2 Mn _0.2 O ₂ , are preferable, and when the cycle characteristics are important. Particles having a composition with a small amount of Ni, such as NaNi _0.33 Co _0.33 Mn _0.34 O ₂ and NaNi _0.33 Co _0.31 Mn _0.33 Mg _0.03 O ₂ are preferred.

Further, two or more types of Li-NCM composite oxide particles represented by the above formula (I) having different compositions are lithium having a core-shell structure having a core part (inside) and a shell part (surface layer part). The composite oxide secondary particle (A) (Li-NCM composite oxide secondary particle (A)) may be formed.
Further, two or more kinds of Na—NCM composite oxide particles represented by the above formula (III) having different compositions from each other also have a core-shell structure lithium having a core part (inside) and a shell part (surface layer part). Complex oxide secondary particles (D) (Na-NCM complex oxide secondary particles (D)) may be formed.

By using the NCM composite oxide secondary particles (A) or (D) formed with this core-shell structure, NCM composite oxide particles having a high Ni concentration that easily elutes into the electrolyte solution are formed in the core portion. Since the NCM-based composite oxide particles having a low Ni concentration can be disposed in the shell portion that is disposed and is in contact with the electrolytic solution, it is possible to further improve the suppression of deterioration in cycle characteristics and the securing of safety. At this time, the core part may be a single phase or may be composed of two or more phases having different compositions. As a mode in which the core part is composed of two or more phases, a structure in which a plurality of phases are concentrically stacked and laminated may be used, or a structure in which the composition changes transitionally from the surface of the core part toward the center part. Good.
Furthermore, the shell part should just be formed in the outer side of a core part, may be 1 phase like a core part, and may be comprised by 2 or more phases from which a composition differs.

Specifically, as the Li-NCM composite oxide secondary particles (A) formed by forming a core-shell structure with two or more kinds of Li-NCM composite oxide particles having different compositions, (core part) )-(Shell part) is, for example, (LiNi _0.8 Co _0.1 Mn _0.1 O ₂ )-(LiNi _0.2 Co _0.4 Mn _0.4 O ₂ ), (LiNi _0.8 Co _0.1 Mn _0.1 O ₂ )-(LiNi _0.33 Co _0.33 Mn _0.34 O _2), or _{(LiNi 0.8 Co 0.1 Mn 0.1 O} 2) - (LiNi 0.33 Co 0.31 Mn 0.33 Mg 0.03 O 2) consisting of such particles.

As the Na-NCM composite oxide secondary particles (D) formed by forming a core-shell structure with two or more kinds of Na-NCM composite oxide particles having different compositions, specifically (core part) -(Shell part) is, for example, (NaNi _0.8 Co _0.1 Mn _0.1 O ₂ )-(NaNi _0.2 Co _0.4 Mn _0.4 O ₂ ), (NaNi _0.8 Co _0.1 Mn _0.1 O ₂ )-(NaNi _0.33 Co _0.33 Mn _0.34 O ₂ ), Or (NaNi _0.8 Co _0.1 Mn _0.1 O ₂ ) — (NaNi _0.33 Co _0.31 Mn _0.33 Mg _0.03 O ₂ ) or the like.

Furthermore, the Li—NCM composite oxide particles represented by the above formula (I) and the Na—NCM composite oxide particles represented by the above formula (III) are both metal oxide, metal fluoride or metal You may coat | cover with the phosphate. By coating Li-NCM composite oxide particles or Na-NCM composite oxide particles with these metal oxides, metal fluorides or metal phosphates, these Li-NCM composite oxide particles to the electrolyte solution Or elution of the metal component (Ni, Mn, Co, M ¹ or M ³ ) from the Na—NCM composite oxide particles can be suppressed. Such _{coatings, CeO 2, SiO 2, MgO} , Al 2 O 3, ZrO 2, TiO 2, ZnO, RuO 2, SnO 2, CoO, Nb 2 O 5, CuO, V 2 O 5, MoO 3, In addition to La ₂ O ₃ , WO ₃ , AlF ₃ , NiF ₂ , and MgF ₂ , in Li-NCM composite oxide particles, Li ₃ PO ₄ , Li ₄ P ₂ O ₇ , LiPO ₃ , Li ₂ PO ₃ F , And one or more selected from LiPO ₂ F ₂ , or a composite of these, and Na—NCM based composite oxide particles, Na ₃ PO ₄ , Na ₄ P ₂ O ₇ , One type or two or more types selected from NaPO ₃ , Na ₂ PO ₃ F, and NaPO ₂ F ₂ , or a complex thereof can be used.

The average particle size as the primary particles of the NCM composite oxide particles represented by the above formula (I) or formula (III) is preferably 500 nm or less, and more preferably 300 nm or less. As described above, the average particle size as the primary particles of the NCM-based composite oxide particles is at least 500 nm or less, thereby suppressing the expansion and contraction amount of the primary particles accompanying the insertion and desorption of lithium ions or sodium ions. And particle cracking can be effectively prevented. The lower limit of the average particle size of the primary particles is not particularly limited, but is preferably 50 nm or more from the viewpoint of handling.
Here, the average particle diameter means an average value of the measured values of the particle diameter (length of major axis) of several tens of particles in observation with an electron microscope of SEM or TEM, and is synonymous in the following description. It is.

The average particle diameter of the NCM composite oxide secondary particles (A) or (D) formed by aggregation of the primary particles is preferably 25 μm or less, more preferably 20 μm or less. When the average particle diameter of the secondary particles is 25 μm or less, a battery having excellent high-temperature cycle characteristics can be obtained. The lower limit of the average particle size of the secondary particles is not particularly limited, but is preferably 1 μm or more and more preferably 5 μm or more from the viewpoint of handling.
In the present specification, the NCM-based composite oxide secondary particles (A) or (D) include only primary particles formed from the respective secondary particles, and are lithium-based polyanion particles (B) or sodium-based particles. It does not contain other components such as polyanion particles (E), carbon derived from cellulose nanofibers (c1), or carbon derived from water-soluble carbon materials (c2).

Li-NCM composite oxide particles represented by the above formula (I), or Na-NCM composite oxide particles represented by the above formula (III) are NCM composite oxide secondary particles (A) or When the core-shell structure is formed in (D), the average particle size as the primary particles forming the core part is preferably 50 nm to 500 nm, more preferably 50 nm to 300 nm. And the average particle diameter of the core part which aggregates and forms the said primary particle becomes like this. Preferably they are 1 micrometer-25 micrometers, More preferably, they are 1 micrometer-20 micrometers.
Further, the average particle size as the primary particles of the Li-NCM composite oxide particles constituting the shell portion covering the surface of the core portion, or the average particle size as the primary particles of the Na-NCM composite oxide particles is The thickness of the shell part formed by aggregation of the primary particles is preferably 0.1 μm to 5 μm, more preferably 0. 5 nm to 500 nm, and more preferably 50 nm to 300 nm. 1 μm to 2.5 μm.

The internal porosity of the secondary particles (A) or (D) comprising the NCM-based composite oxide particles represented by the above formula (I) or formula (III) is determined by the Li-NCM accompanying the insertion of lithium ions or sodium ions. From the viewpoint of allowing expansion of the Ni-based composite oxide or Na-NCM-based composite oxide within the internal voids of each secondary particle, 4 volume% to 12 volume in 100 volume% of the NCM based composite oxide secondary particles % Is preferable, and 5% by volume to 10% by volume is more preferable.
By having such an average particle size and internal porosity, on the surface of the secondary particles (A) or (D) composed of the NCM-based composite oxide particles represented by the above formula (I) or formula (III), Li -NCM composite oxide particles and lithium polyanion particles (B) or Na-NCM composite oxide particles and sodium polyanion particles (E) are combined to form lithium polyanion particles (B) or sodium polyanion particles. Since (E) exists so as to cover the surface of such secondary particles, the elution of the metal component (Ni, Co, Mn, M ¹ or M ³ ) contained in the NCM composite oxide particles is effective. Can be suppressed.

Next, the Li—NCA composite oxide particles represented by the formula (II) and the Na—NCA composite oxide particles represented by the formula (IV) will be described.
M ² in the above formula (II) or M ⁴ in the above formula (IV) is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, One or more elements selected from Ta, W, La, Ce, Pb, Bi and Ge are shown.
In the above formula (II), d, e, f and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦ y ≦ 0.3, And 3d + 3e + 3f + (M ² valence) × y = 3, and d ′, e ′, f ′, and y ′ in the above formula (IV) are 0.4 ≦ d ′ <1, 0 < e ′ ≦ 0.6, 0 <f ′ ≦ 0.3, 0 ≦ y ′ ≦ 0.3, and 3d ′ + 3e ′ + 3f ′ + (valence of M ⁴ ) × y ′ = 3 .

The NCA-based composite oxide particles represented by the above formula (II) or formula (IV) are more battery capacity and output characteristics than the NCM-based composite oxide particles represented by the formula (I) or formula (III). Is excellent. In addition, due to the inclusion of Al, alteration due to moisture in the atmosphere hardly occurs, and the safety is excellent.
Specific examples of the Li-NCA composite oxide particles represented by the above formula (II) include LiNi _0.33 Co _0.33 Al _0.34 O ₂ , LiNi _0.8 Co _0.1 Al _0.1 O ₂ , LiNi _0.8 Co _0.15 Al _0.03. Examples thereof include particles made of Mg _0.03 O ₂ , LiNi _0.8 Co _0.15 Al _0.03 Zn _0.03 O _{2, and the} like. Among these, particles made of LiNi _0.8 Co _0.15 Al _0.03 Mg _0.03 O ₂ are preferable.
Specific examples of the Na-NCA composite oxide particles represented by the above formula (IV) include, for example, NaNi _0.33 Co _0.33 Al _0.34 O ₂ , NaNi _0.8 Co _0.1 Al _0.1 O ₂ , NaNi _0.8 Co _0.15 Examples thereof include particles made of Al _0.03 Mg _0.03 O ₂ , NaNi _0.8 Co _0.15 Al _0.03 Zn _0.03 O _{2, and the} like. Among these, particles made of NaNi _0.8 Co _0.15 Al _0.03 Mg _0.03 O ₂ are preferable.

Furthermore, the Li—NCA composite oxide particles represented by the above formula (II) and the Na—NCA composite oxide particles represented by the formula (IV) are both metal oxide, metal fluoride, or metal phosphoric acid. It may be coated with a salt. By coating the Li-NCA composite oxide particles or Na-NCA composite oxide particles with these metal oxides, metal fluorides or metal phosphates, these Li-NCA composite oxide particles to the electrolyte solution Or elution of the metal component (Ni, Al, Co, M ² or M ⁴ ) from the Na—NCA composite oxide particles can be suppressed. Such _{coatings, CeO 2, SiO 2, MgO} , Al 2 O 3, ZrO 2, TiO 2, ZnO, RuO 2, SnO 2, CoO, Nb 2 O 5, CuO, V 2 O 5, MoO 3, In addition to La ₂ O ₃ , WO ₃ , AlF ₃ , NiF ₂ , and MgF ₂ , Li—NCA based composite oxide particles include Li ₃ PO ₄ , Li ₄ P ₂ O ₇ , LiPO ₃ , Li ₂ PO ₃ F. , And one or more selected from LiPO ₂ F ₂ , or composites thereof, and Na—NCA-based composite oxide particles, Na ₃ PO ₄ , Na ₄ P ₂ O ₇ , One or two or more selected from NaPO ₃ , Na ₂ PO ₃ F, and NaPO ₂ F ₂ , or a complex thereof can be used.

The average particle diameter as the primary particles of the NCA-based composite oxide represented by the above formula (II) or formula (IV), and the composite oxide secondary particles (A) formed by agglomeration of the primary particles (A) or ( The average particle diameter of D) and the internal porosity of the secondary particles are the same as those of the NCM composite oxide particles. That is, the average particle size as primary particles of the NCA-based composite oxide particles represented by the above formula (II) or formula (IV) is preferably 500 nm or less, more preferably 300 nm or less. The average particle diameter of the NCA-based composite oxide secondary particles (A) or (D) is preferably 25 μm or less, more preferably 20 μm or less. Further, the internal porosity of the NCA-based composite oxide secondary particles (A) or (D) composed of the NCA-based composite oxide particles represented by the above formula (II) or formula (IV) is determined by the secondary particles. Among the volume of 100%, 4% to 12% by volume is preferable, and 5% to 10% by volume is more preferable.
By having such an average particle size and internal porosity, on the surface of the secondary particles (A) or (D) composed of the NCA-based composite oxide particles represented by the above formula (II) or formula (IV), Li -NCA-based composite oxide particles and lithium-based polyanion particles (B) or Na-NCA-based composite oxide particles and sodium-based polyanion particles (E) are combined to form lithium-based polyanion particles (B) or sodium-based polyanion particles Since (E) exists so as to cover the surface of such secondary particles, the elution of metal components (Ni, Co, Al, M ² or M ⁴ ) contained in the NCA-based composite oxide particles is effective. Can be suppressed.

  The lithium composite oxide secondary particles (A) of the present invention include Li-NCM composite oxide particles represented by the above formula (I) and Li-NCA composite oxide particles represented by the above formula (II). May be mixed. The mixed state is that primary particles that are Li-NCM composite oxide particles represented by the above formula (I) and primary particles that are Li-NCA composite oxide particles represented by the above formula (II) coexist. Secondary particles comprising only Li-NCM composite oxide particles represented by the above formula (I) and Li-NCA represented by the above formula (II). Secondary particles consisting only of the composite oxide particles may be mixed, and further, the primary particles that are Li-NCM composite oxide particles represented by the above formula (I) and the above formula (II). Secondary particles formed by the coexistence of primary particles that are Li-NCA composite oxide particles, secondary particles composed only of Li-NCM composite oxide particles represented by the above formula (I), and the above formula ( II) and secondary particles consisting only of Li-NCA composite oxide particles represented by It may be the one. And when it is a secondary particle which consists only of Li-NCA type complex oxide particles represented by the above formula (I), two or more kinds of Li-NCA type complex oxide particles having different compositions are used to form a core-shell. A structure may be formed.

  Further, the sodium composite oxide secondary particle (D) of the present invention comprises Na-NCM composite oxide particles represented by the above formula (III) and Na-NCA composite oxide represented by the above formula (IV). Object particles may be mixed. The mixed state is such that primary particles that are Na—NCM composite oxide particles represented by the above formula (III) and primary particles that are Na—NCA composite oxide particles represented by the above formula (IV) coexist. Secondary particles composed only of Na—NCM composite oxide particles represented by the above formula (III) and Na—NCA represented by the above formula (IV). Secondary particles consisting only of the composite oxide particles may be mixed, and further, the primary particles which are Na-NCM composite oxide particles represented by the above formula (III) and the above formula (IV). Secondary particles formed by the coexistence of primary particles that are Na-NCA composite oxide particles, secondary particles composed only of Na-NCM composite oxide particles represented by the above formula (III), and the above formula ( IV) secondary particles consisting only of Na-NCA composite oxide particles represented by It may be the one. And when it is a secondary particle which consists only of Na-NCM system complex oxide particles denoted by the above-mentioned formula (III), two or more kinds of Na-NCM system complex oxide particles from which composition differs mutually make core-shell A structure may be formed.

  NCM in the case where the NCM composite oxide particles represented by the above formula (I) or the above formula (III) and the NCA composite oxide particles represented by the above formula (II) or the above formula (IV) are mixed. The ratio (mass%) of the system composite oxide particles and the NCA system composite oxide particles may be appropriately adjusted depending on the battery characteristics to be obtained. For example, when importance is attached to rate characteristics, it is preferable to increase the proportion of the NCM composite oxide particles represented by the above formula (I) or the above formula (III). The mass ratio of the oxide particles to the NCA-based composite oxide particles (NCM-based composite oxide: NCA-based composite oxide) is preferably 99.9: 0.1 to 60:40. Further, for example, when importance is attached to battery capacity, it is preferable to increase the proportion of the NCA-based composite oxide particles represented by the above formula (II) or the above formula (IV). The mass ratio of the NCM composite oxide particles to the NCA composite oxide particles (NCM composite oxide: NCA composite oxide) is preferably 40:60 to 0.1: 99.9.

Next, the lithium polyanion particles (B) and the sodium polyanion particles (E) will be described.
The lithium-based polyanion particles (B), which are combined with the lithium composite oxide particles only on the surface of the lithium composite oxide secondary particles (A), have the following formula (V):
^{_{Li s Co g Ni h M 5}} i PO 4 ··· (V)
(.S shown in the formula (V), ^{M 5} is Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, g, h, and i, 0 <s ≦ 1.2, 0 ≦ g ≦ 1.2, 0 ≦ h ≦ 1.2, 0 ≦ i ≦ 0.3, and g + h ≠ 0, and s + (Co valence) × g + ( (The valence of Ni) × h + (the valence of M ⁵ ) × i = the number satisfying i = 3.)
Or the following formula (VI):
^{_{Li t Co j Ni k M 6}} l SiO 4 ··· (VI)
(In the formula (VI), M ⁶ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. T, j, k, and l are 0 <t ≦ 2.4, 0 ≦ j ≦ 1.2, 0 ≦ k ≦ 1.2, 0 ≦ l ≦ 1.2, and j + k ≠ 0, and t + (Co valence) × j + ( (The valence of Ni) × k + (the valence of M ⁶ ) × 1 = the number satisfying 1 = 4.)
A lithium compound containing at least either cobalt or nickel and capable of providing good lithium ion conductivity.

Specific examples of the lithium-based polyanion particles (B) represented by the above formula (V) include LiCoPO ₄ , LiCo _0.25 Ni _0.25 PO ₄ , LiCo _0.2 Ni _0.2 Mn _0.1 PO ₄ , and LiCo _0.2 Ni _0.2 Fe _{0.1. PO 4, Li 1.2 Co 0.9 PO} 4 , and the like. Among these, LiCoPO ₄ , LiCo _0.2 Ni _0.2 Mn _0.1 PO ₄ , or Li _1.2 Co _0.9 PO ₄ is preferable.
Specific examples of the lithium-based polyanion particles (B) represented by the above formula (VI) include Li ₂ CoSiO ₄ , Li ₂ Co _0.5 Ni _0.5 SiO ₄ , and Li ₂ Co _0.4 Ni _0.4 Mn _0.2 SiO. ₄ , Li ₂ Co _0.4 Ni _0.4 Fe _0.2 SiO ₄ , Li _2.2 Co _0.9 SiO _{4 and the} like. Among these, Li ₂ CoSiO ₄ , Li ₂ Co _0.4 Ni _0.4 Mn _0.2 SiO ₄ , or Li _2.2 Co _0.9 SiO ₄ is preferable.

Furthermore, lithium-based polyanion particles (B) that are combined with lithium composite oxide particles on the surface of the lithium composite oxide secondary particles (A) are represented by the following formula (VII):
^{_{Li u Fe m Mn n M 7}} o PO 4 ··· (VII)
(In the formula (VII), M ⁷ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. U, m, n, and o are 0 <u ≦ 1.2, 0 ≦ m ≦ 1.2, 0 ≦ n ≦ 1.2, 0 ≦ o ≦ 0.3, and m + n ≠ 0, and u + (Fe valence) × m + ( valence of Mn) × n + (valence of ^{M 7)} shows a number satisfying × o = 3.)
Or the following formula (VIII):
^{_{Li v Fe p Mn q M 8}} r SiO 4 ··· (VIII)
(In the formula (VIII), M ⁸ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, V, or Gd. V, p, q and r satisfy 0 <v ≦ 2.4, 0 ≦ p ≦ 1.2, 0 ≦ q ≦ 1.2, 0 ≦ r ≦ 1.2, and p + q ≠ 0, and v + (Fe Valence) × p + (valence of Mn) × q + (valence of M ⁸ ) × r = 4 is satisfied.)
And a lithium compound containing at least either iron or manganese.

As the lithium-based polyanion particles (B) represented by the above formula (VII), 0.5 ≦ n ≦ 1.2 is preferable from the viewpoint of the average discharge voltage of the positive electrode active material composite for a lithium ion secondary battery, 0.6 ≦ n ≦ 1.1 is more preferable, and 0.65 ≦ n ≦ 1.05 is more preferable. Specifically, for example, LiMnPO ₄ , LiMn _0.9 Fe _0.1 PO ₄ , LiMn _0.8 Fe _0.2 PO ₄ , LiMn _0.75 Fe _0.15 Mg _0.1 PO ₄ , LiMn _0.75 Fe _0.19 Zr _0.03 PO ₄ , LiMn _0.7 Fe _0.3 PO ₄ , LiMn _0.6 Fe _0.4 PO ₄ , LiMn _0.5 Fe _0.5 PO ₄ , Li _1.2 Mn _0.63 Fe _0.27 PO ₄ , Li _0.6 Mn _0.84 Fe _0.36 PO _{4 and the} like, among others, LiMn _0.8 Fe _0.2 PO ₄ , Li _1.2 Mn _0.63 Fe _0.27 PO ₄ or Li _0.6 Mn _0.84 Fe _0.36 PO ₄ is preferred.
As the lithium-based polyanion particles (B) represented by the above formula (VIII), specifically, for example, Li ₂ Fe _0.45 Mn _0.45 Co _0.1 SiO ₄ , Li ₂ Fe _0.36 Mn _0.54 Al _0.066 SiO ₄ , Li ₂ Fe _0.45 Mn _0.45 Zn _0.1 SiO ₄ , Li ₂ Fe _0.36 Mn _0.54 V _0.066 SiO ₄ , Li ₂ Fe _0.282 Mn _0.658 Zr _0.02 SiO ₄ , Li _2.2 Fe _0.252 Mn _0.594 Zr _0.027 SiO ₄ , Li _1.2 Fe _0.392 Mn _0.924 Zr _Examples include _0.042 SiO ₄ , and Li ₂ Fe _0.282 Mn _0.658 Zr _0.02 SiO ₄ , Li _2.2 Fe _0.252 Mn _0.594 Zr _0.027 SiO ₄ , or Li _1.2 Fe _0.392 Mn _0.924 Zr _0.042 SiO ₄ is preferable.

  Further, the lithium-based polyanion particles (B) include a core portion (inside) and a shell portion (surface layer portion) composed of lithium-based polyanion particles represented by the above formula (V), (VI), (VII) or (VIII). It is also possible to form a core-shell structure having carbon and to carry carbon (c) on the surface.

Due to the core-shell structure of this lithium-based polyanion particle (B), a lithium-based polyanion having a high Mn content that easily elutes from the lithium-based polyanion particle (B) into the electrolyte is disposed in the core, and the shell is in contact with the electrolyte A lithium-based polyanion having a low Mn content is arranged, or a lithium-based polyanion having a high Co content that is highly toxic to the human body and the environment is arranged in the core portion. The shell portion in contact with the electrolyte solution has a low Co content. By arranging the lithium-based polyanion, it is possible to further improve the suppression of cycle characteristics due to the lithium-based polyanion particles and the securing of safety. At this time, the core part may be a single phase or may be composed of two or more phases having different compositions. As a mode in which the core part is composed of two or more phases, a structure in which a plurality of phases are concentrically stacked and laminated may be used, or a structure in which the composition changes transitionally from the surface of the core part toward the center part. Good.
Furthermore, the shell part should just be formed in the outer side of a core part, may be 1 phase like a core part, and may be comprised by 2 or more phases from which a composition differs.

As lithium-based polyanion particles (B) formed by forming a core-shell structure with two or more kinds of lithium-based polyanion particles having different compositions, specifically, (core portion)-(shell portion) is, for example, ( _{LiMnPO 4) - (LiFePO 4)} , (LiCoPO 4) - (LiNiPO 4), (LiMnPO 4) - (LiNiPO 4), (LiCoPO 4) - (LiFePO 4), (LiMn 0.5 Co 0.5 PO 4 )-(LiFePO ₄ ), (Li ₂ MnSiO ₄ ) — (LiFePO ₄ ), or (Li ₂ MnSiO ₄ ) — (Li ₂ FeSiO ₄ ) or the like.

The average particle diameter of the lithium-based polyanion particles (B) represented by the above formulas (V) to (VIII) is close to that of the lithium composite oxide particles only on the surface of the lithium composite oxide secondary particles (A). From the viewpoint of compositing, when the lithium-based polyanion particle (B) is represented by the formula (V), (VI) or (VIII), it is 20 nm to 200 nm, preferably 25 nm to 180 nm, and more Preferably it is 30 nm-170 nm. Moreover, when lithium type polyanion particle | grains (B) are represented by Formula (VII), they are 50 nm-200 nm, Preferably they are 70 nm-150 nm.
In addition, the average particle diameter of the lithium-based polyanion particles (B) formed by forming the core-shell structure includes the lithium-based polyanion represented by the formula (VII) in the lithium-based polyanion particles (B). When the lithium-based polyanion represented by the formula (VII) is not included, the thickness is 20 nm to 200 nm, and preferably 25 nm to 180 nm.

The lithium ion conductivity of the lithium-based polyanion particles (B) represented by the above formulas (V) to (VIII) at a pressure of 20 MPa at 25 ° C. is 1 × 10 ⁻⁷ S / cm or more. It is preferably 1 × 10 ⁻⁶ S / cm or more. The upper limit value of the lithium ion conductivity of the lithium-based polyanion particle (B) is not particularly limited.

  The lithium polyanion particles (B) represented by the above formulas (V) to (VIII) may be combined with primary particles that are lithium composite oxide particles, or primary composite lithium particle particles. The lithium composite oxide secondary particles (A) obtained by agglomerating the particles may be directly composited.

  The lithium-based polyanion particle (B) has carbon (c) supported on its surface. The amount of carbon (c) supported is such that when the lithium polyanion particles (B) are represented by the formula (V), (VI) or (VIII), the lithium polyanion on which carbon (c) is supported. In the total amount of particles (B) of 100% by mass, it is 0.1% by mass or more and less than 20% by mass, preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass. is there. When the lithium-based polyanion particle (B) is represented by the formula (VII), 0.1% by mass in 100% by mass of the total amount of the lithium-based polyanion particle (B) on which carbon (c) is supported. It is less than 10 mass%, Preferably it is 0.1 mass%-7 mass%, More preferably, it is 0.1 mass%-5 mass%.

  Mass of lithium composite oxide secondary particle (A) content and lithium polyanion particle (B) content (including carbon (c) loading) with carbon (c) supported on the surface The ratio ((A) :( B)) is 95: 5 to 55:45 when the lithium-based polyanion particles (B) are represented by the formula (V), (VI) or (VIII). , Preferably 90:10 to 55:45. When the lithium-based polyanion particle (B) is represented by the formula (VII), it is 65:35 to 55:45 (excluding 65:35), preferably 63:37 to 57: 43.

Further, sodium-based polyanion particles (E) that are complexed with sodium complex oxide only on the surface of the sodium complex oxide secondary particles (D) are represented by the following formula (IX):
Na _w Cog _′ Ni _{h ′} M ⁹ _{i ′} PO ₄ (IX)
(In the formula (IX), M ⁹ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. W, g ′, h ′, and i 'Satisfies 0 <w ≦ 1.2, 0 ≦ g ′ ≦ 1.2, 0 ≦ h ′ ≦ 1.2, 0 ≦ i ′ ≦ 0.3, and g ′ + h ′ ≠ 0, and w + (The valence of Co) × g ′ + (the valence of Ni) × h ′ + (the valence of M ⁹ ) × i ′ = 3.
Or the following formula (X):
Na _x Co _{j ′} Ni _{k ′} M ¹⁰ _{l ′} SiO ₄ ... (X)
(.X shown in the formula ^{(X), M 10} is Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, j ', k', and l 'Satisfies 0 <x ≦ 2.4, 0 ≦ j ′ ≦ 1.2, 0 ≦ k ′ ≦ 1.2, 0 ≦ l ′ ≦ 1.2, and j ′ + k ′ ≠ 0, and x + (The valence of Co) × j ′ + (the valence of Ni) × k ′ + (the valence of M ¹⁰ ) × l ′ = 4.
And is a sodium compound containing at least either cobalt or nickel.

Specific examples of the sodium-based polyanion particles (E) represented by the above formula (IX) include NaCoPO ₄ , NaCo _0.25 Ni _0.25 PO ₄ , NaCo _0.2 Ni _0.2 Mn _0.1 PO ₄ , NaCo _0.2 Ni _0.2 Fe _0.1. PO ₄ , Na _1.2 Co _0.9 PO _{4 and the} like. Among these, NaCoPO ₄ , NaCo _0.2 Ni _0.2 Mn _0.1 PO ₄ , or Na _1.2 Co _0.9 PO ₄ is preferable.
Furthermore, specific examples of the sodium-based polyanion particles (E) represented by the above formula (X) include Na ₂ CoSiO ₄ , Na ₂ Co _0.5 Ni _0.5 SiO ₄ , and Na ₂ Co _0.4 Ni _0.4 Mn _0.2 SiO. ₄ , Na ₂ Co _0.4 Ni _0.4 Fe _0.2 SiO ₄ , Na _2.2 Co _0.9 SiO _4, etc., among which Na ₂ CoSiO ₄ , Na ₂ Co _0.4 Ni _0.4 Mn _0.2 SiO ₄ , or Na _2.2 Co _0.9 SiO ₄ is preferable. .

Furthermore, sodium-based polyanion particles (E) that are combined with sodium composite oxide particles only on the surface of the sodium composite oxide secondary particles (D) are represented by the following formula (XI):
Na _y Fem _′ Mn _{n ′} M ¹¹ _{o ′} PO ₄ (XI)
(.Y shown in the formula ^{(XI), M 11} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, m ', n', and o 'Satisfies 0 <y ≦ 1.2, 0 ≦ m ′ ≦ 1.2, 0 ≦ n ′ ≦ 1.2, 0 ≦ o ′ ≦ 0.3, and m ′ + n ′ ≠ 0, and y + (valence of Fe) × m '+ (valence of Mn) × n' + ^(valence of ^{M 11)} × o '= 3 indicates a number satisfying.)
Or the following formula (XII):
Na _z Fe _{p ′} Mn _{q ′} M ¹² _{r ′} SiO ₄ ... (XII)
(In the formula ^{(XII), M 12} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, .z showing a V or Gd, p ' , Q ′, and r ′ are 0 <z ≦ 2.4, 0 ≦ p ′ ≦ 1.2, 0 ≦ q ′ ≦ 1.2, 0 ≦ r ′ ≦ 1.2, and p ′ + q ′ ≠. 0 is satisfied, and z + (Fe valence) × p ′ + (Mn valence) × q ′ + (M ¹² valence) × r ′ = 4).
It may be a sodium compound containing at least either iron or manganese.

Specific examples of the sodium-based polyanion particles (E) represented by the above formula (XI) include NaFe _0.2 Mn _0.8 PO ₄ , NaFe _0.9 Mn _0.1 PO ₄ , NaFe _0.15 Mn _0.75 Mg _0.1 PO ₄ , and NaFe _0.19. Mn _0.75 Zr _0.03 PO ₄ , Na _1.2 Fe _0.27 Mn _0.63 PO ₄ , Na _0.6 Fe _0.36 Mn _0.84 PO _{4 and the} like are mentioned. Among them, NaFe _0.2 Mn _0.8 PO ₄ , Na _1.2 Fe _0.27 Mn _0.63 PO ₄ , or Na _0.6 Fe _0.36 Mn _0.84 PO ₄ is preferred.
Specific examples of the sodium-based polyanion particles (E) represented by the above formula (XII) include Na ₂ Fe _0.45 Mn _0.45 Co _0.1 SiO ₄ , Na ₂ Fe _0.36 Mn _0.54 Al _0.066 SiO ₄ , Na ₂ Fe _0.45 Mn _0.45 Zn _0.1 SiO ₄ , Na ₂ Fe _0.36 Mn _0.54 V _0.066 SiO ₄ , Na ₂ Fe _0.282 Mn _0.658 Zr _0.02 SiO ₄ , Na _2.2 Fe _0.252 Mn _0.594 Zr _0.027 SiO ₄ , Na _1.2 Fe _0.392 Mn _0.924 Zr _Examples include _0.042 SiO ₄ , among which Na ₂ Fe _0.282 Mn _0.658 Zr _0.02 SiO ₄ , Na _2.2 Fe _0.252 Mn _0.594 Zr _0.027 SiO ₄ , or Na _1.2 Fe _0.392 Mn _0.924 Zr _0.042 SiO ₄ is preferable.

  Furthermore, the sodium-based polyanion particles (E) are composed of a core portion (inside) and a shell portion (surface layer portion) composed of sodium-based polyanion particles represented by the above formula (IX), (X), (XI) or (XII). It may include a sodium-based polyanion particle (E) formed by forming a core-shell structure having carbon and having carbon (c) supported on the surface thereof.

Due to the core-shell structure of the sodium-based polyanion particles (E), a sodium-based polyanion having a high Mn content that is easily eluted from the sodium-based polyanion particles (E) into the electrolyte is disposed in the core, and the shell is in contact with the electrolyte A sodium-based polyanion having a low Mn content or a sodium-based polyanion having a high Co content, which is highly toxic to the human body or the environment, is placed in the core portion, and the Co portion has a low Co content. By disposing a sodium-based polyanion or the like, it is possible to further improve the suppression of cycle characteristics due to the sodium-based polyanion particles and the securing of safety. At this time, the core part may be a single phase or may be composed of two or more phases having different compositions. As a mode in which the core part is composed of two or more phases, a structure in which a plurality of phases are concentrically stacked and laminated may be used, or a structure in which the composition changes transitionally from the surface of the core part toward the center part. Good.
Furthermore, the shell part should just be formed in the outer side of a core part, may be 1 phase like a core part, and may be comprised by 2 or more phases from which a composition differs.

As sodium-based polyanion particles (E) formed by forming a core-shell structure with two or more kinds of sodium-based polyanion particles having different compositions, specifically, (core portion)-(shell portion) is, for example, ( _{NaMnPO 4) - (NaFePO 4)} , (NaCoPO 4) - (NaNiPO 4), (NaMnPO 4) - (NaNiPO 4), (NaCoPO 4) - (NaFePO 4), (NaMn 0.5 Co 0.5 PO 4 )-(NaFePO ₄ ), (Na ₂ MnSiO ₄ )-(NaFePO ₄ ), (Na ₂ MnSiO ₄ )-(Na ₂ FeSiO ₄ ), or the like.

The average particle diameter of the sodium-based polyanion particles (E) represented by the above formulas (IX) to (XII) is close to the sodium composite oxide particles only on the surface of the sodium composite oxide secondary particles (D). From the viewpoint of compounding, it is 50 nm to 200 nm, preferably 70 nm to 150 nm.
The average particle size of the sodium-based polyanion particles (E) formed with the core-shell structure is also 50 nm to 200 nm, preferably 70 nm to 150 nm.

The sodium-based polyanion particles (E) represented by the above formulas (IX) to (XII) have a sodium ion conductivity of 1 × 10 ⁻⁷ S / cm or more when pressurized at 20 MPa at 25 ° C. It is preferably 1 × 10 ⁻⁶ S / cm or more. The upper limit value of the lithium ion conductivity of the sodium-based polyanion particle (E) is not particularly limited.

  The sodium-based polyanion particles (E) represented by the above formulas (IX) to (XII) may be complexed with primary particles that are sodium composite oxide particles, or primary particles that are sodium composite oxide particles. It may be directly composited with a part of the sodium composite oxide secondary particles (D) formed by aggregation of the particles.

  The sodium-based polyanion particle (E) has carbon (c) supported on its surface. The supported amount of carbon (c) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the total amount of sodium polyanion particles (E) on which carbon (c) is supported, and preferably 0 0.5 mass% to 15 mass%, more preferably 1 mass% to 10 mass%.

  Mass of content of sodium composite oxide secondary particles (D) and content of sodium-based polyanion particles (E) having carbon (c) supported on the surface (including the supported amount of carbon (c)) The ratio ((D) :( E)) is preferably 95: 5 to 55:45, and more preferably 90:10 to 55:45.

  The cellulose nanofiber as the carbon source (c1), which may be supported on the surface of the lithium-based polyanion particle (B) or sodium-based polyanion particle (E), is about 50% of all plant cell walls. Is a lightweight high-strength fiber that can be obtained by defibrating plant fibers constituting such cell walls to nano-size, and carbon derived from cellulose nanofibers has a periodic structure. The fiber diameter of the cellulose nanofiber is 1 nm to 100 nm, and has good dispersibility in water. In addition, since the cellulose molecular chain constituting the cellulose nanofiber has a periodic structure formed of carbon, the lithium-based polyanion particle (B) or the sodium-based polyanion particle (B) is combined with the polyanion particle while being carbonized. E) is firmly supported on the surface of the polyanion particles, thereby imparting electronic conductivity to the polyanion particles, and a useful positive electrode active material composite for lithium ion secondary batteries or a positive electrode active for sodium ion secondary batteries having excellent cycle characteristics. A substance complex can be obtained.

  The water-soluble carbon material as the carbon source (c2), which is said to be supported on the surface of the lithium-based polyanion particle (B) or the sodium-based polyanion particle (E), is 100 g of water at 25 ° C. It means a carbon material that dissolves 0.4 g or more, preferably 1.0 g or more in terms of carbon atom of the water-soluble carbon material, and is carbonized to form the above lithium-based polyanion particles (B) or sodium-based polyanion particles (carbon). E) is present on the surface. Examples of the water-soluble carbon material include one or more selected from saccharides, polyols, polyethers, and organic acids. More specifically, for example, monosaccharides such as glucose, fructose, galactose and mannose; disaccharides such as maltose, sucrose and cellobiose; polysaccharides such as starch and dextrin; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol and butane Examples include polyols and polyethers such as diol, propanediol, polyvinyl alcohol, and glycerin; and organic acids such as citric acid, tartaric acid, and ascorbic acid. Among these, glucose, fructose, sucrose, and dextrin are preferable, and glucose is more preferable from the viewpoint of improving the solubility and dispersibility in a solvent and effectively functioning as a carbon material.

  In addition, the atomic conversion amount of carbon (c1) derived from cellulose nanofibers or carbon (c2) derived from a water-soluble carbon material existing on the surface of lithium-based polyanion particles (B) or sodium-based polyanion particles (E) (carbon The loading amount) can be confirmed as the carbon amount measured using a carbon / sulfur analyzer for the lithium-based polyanion particles (B) or the sodium-based polyanion particles (E).

  The method for producing a positive electrode active material composite for a lithium ion secondary battery according to the present invention comprises a lithium composite oxide secondary particle (A) and a lithium-based polyanion particle (B) formed by supporting carbon (c) on the surface. It is only necessary to provide a step of mixing and adding them while applying compressive force and shearing force. Moreover, the manufacturing method of the positive electrode active material composite for sodium ion secondary batteries of the present invention includes sodium composite oxide secondary particles (D), and sodium-based polyanion particles (E) having carbon (c) supported on the surface. ) May be mixed and combined while applying a compressive force and a shearing force.

  In the present invention, the composite treatment of the lithium composite oxide secondary particles (A) and the lithium polyanion particles (B), or the sodium composite oxide secondary particles (D) and the sodium polyanion particles (E). In the composite treatment, water-insoluble carbon powder (c3) other than cellulose nanofiber-derived carbon (c1) is simultaneously mixed as a carbon source, so that lithium composite oxide secondary particles (A) and lithium-based polyanion particles (B ), Or sodium composite oxide secondary particles (D) and sodium-based polyanion particles (E). The water-insoluble carbon powder (c3) is a carbon material different from the carbon (c2) derived from the water-soluble carbon material, and is water-insoluble (water at 25 ° C.) other than the carbon (c1) derived from cellulose nanofibers. The amount dissolved in 100 g is a carbon powder having conductivity of less than 0.4 g in terms of carbon atom of the water-insoluble carbon powder (c3). By combining this water-insoluble carbon powder (c3), the battery characteristics when the positive electrode active material composite for lithium ion secondary battery or the positive electrode active material composite for sodium ion secondary battery of the present invention is used as a secondary battery are obtained. Without reducing, the water-insoluble carbon powder (c3) intervenes in the gap between the lithium composite oxide secondary particles (A) and the lithium-based polyanion particles (B) in the positive electrode active material composite for a lithium ion secondary battery, or It exists so as to cover a plurality of lithium-based polyanion particles (B) on the surface of the positive electrode active material composite for a lithium ion secondary battery, or sodium composite oxide secondary particles in a positive electrode active material composite for a sodium ion secondary battery ( D) and sodium-based polyanion particles (E), or a plurality of sodium-based materials on the surface of the positive electrode active material composite for sodium ion secondary battery While existing so as to cover the dianion particles (E), the degree of complexation is further strengthened, and the lithium-based polyanion particles (B) are peeled off from the lithium composite oxide secondary particles (A). Or it can suppress effectively that a sodium system polyanion particle (E) peels from a sodium complex oxide secondary particle (D).

  Examples of the water-insoluble carbon powder (c3) include graphite, amorphous carbon (Ketjen black, acetylene black, etc.), nanocarbon (graphene, fullerene, etc.), conductive polymer powder (polyaniline powder, polyacetylene powder, polythiophene powder). , Polypyrrole powder, etc.) and the like. Among these, from the viewpoint of reinforcing the composite degree of the sodium-based polyanion particles (E) from the lithium-based composite oxide secondary particles (A) and the lithium-based polyanion particles (B) or the sodium-based composite oxide secondary particles (D). Graphite, acetylene black, graphene and polyaniline powder are preferable, and graphite is more preferable. The graphite may be any of artificial graphite (scaly, massive, earthy, graphene) or natural graphite.

  The average particle size of the water-insoluble carbon powder (c3) is preferably 0.5 μm to 20 μm, more preferably 1.0 μm to 15 μm, from the viewpoint of compositing.

  In the positive electrode active material composite for a lithium ion secondary battery of the present invention, water that is mixed and combined at the same time when the lithium composite oxide secondary particles (A) and the lithium-based polyanion particles (B) are combined. The content of the insoluble carbon powder (c3) is preferably 0.5 parts by mass to 24 parts by mass with respect to 100 parts by mass of the total amount of the lithium composite oxide secondary particles (A) and the lithium-based polyanion particles (B). Yes, more preferably 1 to 16 parts by mass, and even more preferably 1 to 10 parts by mass.

  Furthermore, the total amount of the lithium-based polyanion particles (B) on which the lithium composite oxide secondary particles (A) and carbon (c) are supported, and the carbon (c) supported on the lithium-based polyanion particles (B). ) And the total content of the water-insoluble carbon powder (c3) (((A) + (B)): ((c) + (c3))) is preferably 99.5: 0.5- 80:20, more preferably 99: 1 to 90:10, and still more preferably 99: 1 to 93: 7.

  Further, in the positive electrode active material composite for the sodium ion secondary battery of the present invention, the sodium composite oxide secondary particles (D) and the sodium-based polyanion particles (E) are simultaneously mixed and composited. The content of the water-insoluble carbon powder (c3) is preferably 0.5 parts by mass to 24 parts by mass with respect to 100 parts by mass of the total amount of the sodium composite oxide secondary particles (D) and the sodium-based polyanion particles (E). Part, more preferably 1 part by mass to 16 parts by mass, still more preferably 1 part by mass to 10 parts by mass, and the sodium composite oxide secondary particles (D) and carbon (c) are supported. Mass ratio of the total amount of sodium polyanion particles (E) and the total content of carbon (c) and water-insoluble carbon powder (c3) supported on the sodium polyanion particles (E) ((D) + (E)): ((c) + (c3))) is preferably 99.5: 0.5-80: 20, more preferably 99: 1-90: 10. More preferably, it is 99: 1 to 93: 7.

  Next, the manufacturing method of the positive electrode active material composite for lithium ion secondary batteries or the positive electrode active material composite for sodium ion secondary batteries will be described more specifically.

The method for producing a positive electrode active material composite for a lithium ion secondary battery or a positive electrode active material composite for a sodium ion secondary battery includes the following steps (X) to (Z):
(X) A mixed powder containing a lithium compound or a sodium compound, a nickel compound, a cobalt compound, and a manganese compound is fired, and the composite oxide secondary particles (A) or (A) or ( D) or calcining a mixed powder containing a lithium compound or a sodium compound, a nickel compound, a cobalt compound, and an aluminum compound to obtain composite oxide secondary particles of formula (II) or formula (IV) ( Obtaining A) or (D);
(Y) Lithium compound or sodium compound, and phosphoric acid compound or silicic acid compound, and at least one of cobalt compound or nickel compound is subjected to a wet reaction, or phosphoric acid compound or silicic acid compound, and cobalt compound or At least one of the nickel compounds is subjected to a solid phase reaction to form lithium polyanion particles (B) of the formula (V) or formula (VI) or sodium polyanion particles of the formula (IX) or formula (X) (E )
(Z) Formula (V) obtained in step (Y) to NCM-based composite oxide secondary particles or NCA-based composite oxide secondary particles (A) or (D) obtained in step (X). Alternatively, a lithium-based polyanion particle (B) of the formula (VI) or a sodium-based polyanion particle (E) of the formula (IX) or (X) is added and mixed while adding compressive force and shearing force to form a composite Or the NCM-based composite oxide secondary particles or NCA-based composite oxide secondary particles (A) or (D) obtained in the step (X) are added to the formula (Y) V) or lithium polyanion particles (B) of formula (VI) or sodium polyanion particles (E) of formula (IX) or formula (X) and water-insoluble carbon powder (c3) A step of mixing while applying a shearing force to form a composite;

Alternatively, the following steps (X ′) to (Z ′):
(X ′) A mixed powder containing a lithium compound or a sodium compound, a nickel compound, a cobalt compound, and a manganese compound is fired, and the composite oxide secondary particle (A) or the formula (I) or the formula (III) or (D) is obtained, or a mixed powder containing a lithium compound or a sodium compound, a nickel compound, a cobalt compound, and an aluminum compound is fired to obtain a composite oxide secondary particle of formula (II) or formula (IV) Obtaining (A) or (D);
(Y ′) Lithium compound or sodium compound, and phosphoric acid compound or silicic acid compound, or at least one of iron compound or manganese compound is subjected to a wet reaction, or phosphoric acid compound or silicic acid compound, and iron compound Alternatively, at least one of the manganese compounds is subjected to a solid phase reaction to form a lithium-based polyanion particle (B) of formula (VII) or formula (VIII) or a sodium-based polyanion particle of formula (XI) or formula (XII) ( E)
(Z ′) The NCM composite oxide secondary particles or NCA composite oxide secondary particles (A) or (D) obtained in the step (X) are added to the formula (VII) obtained in the step (Y). ) Or lithium polyanion particles (B) of formula (VIII) or sodium polyanion particles (E) of formula (XI) or formula (XII) and mixed while adding compressive force and shearing force to form a composite Or the NCM composite oxide secondary particles or NCA composite oxide secondary particles (A) or (D) obtained in the step (X), the formula obtained in the step (Y). (VII) or lithium polyanion particles (B) of formula (VIII) or sodium polyanion particles (E) of formula (XI) or formula (XII) and water-insoluble carbon powder (c3) And a step of mixing while applying a shearing force to form a composite.

In the step (X) or the step (X ′), a mixed powder containing a lithium compound or a sodium compound, a nickel compound, a cobalt compound, and a manganese compound is baked, and the composite oxidation of the formula (I) or the formula (III) Secondary particles (A) or (D) are obtained, or a mixed powder containing a lithium compound or a sodium compound, a nickel compound, a cobalt compound, and an aluminum compound is fired to obtain the formula (II) or the formula (IV ) Composite oxide secondary particles (A) or (D).
In the description of the step (X) and the step (X ′), the positive electrode active material composite for a lithium ion secondary battery represented by the above formula (I) or the formula (II) is used in order to avoid complicated notation. This will be specifically described. Regarding the method for producing a positive electrode active material composite for a sodium ion secondary battery represented by the above formula (III) or formula (IV), “lithium” in the following method for producing a positive electrode active material composite for a lithium ion secondary battery "Can be replaced with" sodium ". The lithium-based polyanion particles (B) or sodium-based polyanion particles (E) are also simply referred to as “polyanion particles”.

In order to obtain the composite oxide secondary particles (A) of the formula (I), a raw material compound such as a nickel compound, a cobalt compound, and a manganese compound is dissolved in water so as to have a desired composite oxide composition. To obtain an aqueous solution A. Examples of the nickel compound, cobalt compound, and manganese compound include sulfates, nitrates, carbonates, acetates, oxalates, oxides, hydroxides, and halides of the metal elements. Specific examples include nickel sulfate, cobalt sulfate, manganese sulfate, nickel acetate, cobalt acetate, and manganese acetate, but are not limited thereto.
In this process, if necessary, Mg may be used as a metal element (M ¹ ) for substituting a part of the layered lithium metal composite oxide constituting the active material so as to have a desired composite oxide composition. , Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and Ge The above elements may be mixed.

  Next, an alkaline agent is added to the aqueous solution A to form an aqueous solution B, and the dissolved metal component is coprecipitated by a neutralization reaction to obtain a metal composite hydroxide. The alkaline agent acts as a pH adjuster for maintaining the pH of the aqueous solution B at 10 to 14, and is dripped in an amount sufficient to bring about the effect. As the alkali agent, for example, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or the like can be used, but sodium hydroxide, sodium carbonate or a mixed solution thereof is preferably used.

  The aqueous solution B is stirred to produce a metal composite hydroxide, and the temperature of the aqueous solution B during the reaction is preferably 30 ° C. or higher, more preferably 30 ° C. to 60 ° C. Further, the stirring time of the aqueous solution B is preferably 30 minutes to 120 minutes, and more preferably 30 minutes to 60 minutes.

  After stirring, the aqueous solution B is filtered to recover the metal composite hydroxide. The recovered metal composite hydroxide is preferably washed with water and then dried.

  Next, the NCM composite oxide can be obtained by dry-mixing the metal composite hydroxide and the lithium compound so as to have a desired composite oxide composition and firing in an oxygen atmosphere. As the lithium compound, for example, lithium hydroxide or a hydrate thereof, lithium peroxide, lithium nitrate, lithium carbonate and the like can be preferably used. For the dry mixing of the metal composite hydroxide and the lithium compound, a normal dry mixer or a mixing granulator such as a ball mill or a V blender can be used, and it is more preferable to use a planetary ball mill capable of revolving.

  The firing of the mixture of the metal composite hydroxide and the lithium compound is preferably performed in two stages (temporary firing and main firing). By removing the thermal decomposition components such as water molecules and carbon dioxide from the hydroxide and carbonate in the mixture by preliminary calcination and then performing the main calcination, an NCM composite oxide can be obtained efficiently. The pre-baking conditions are not particularly limited, but the rate of temperature rise is preferably from room temperature to 1 ° C./min to 20 ° C./min. The atmosphere is preferably an air atmosphere or an oxygen atmosphere. Moreover, it is preferable that a calcination temperature is 700 to 1000 degreeC, and it is more preferable that it is 650 to 750 degreeC. Furthermore, the firing time is preferably 3 hours to 20 hours, and more preferably 4 hours to 6 hours.

The conditions for the next main firing are not particularly limited, but after the preliminary firing, the temporary fired product crushed in a mortar or the like is again heated from room temperature to a heating rate of 1 ° C./min to 20 ° C. / Min. The atmosphere at this time is preferably an air atmosphere or an oxygen atmosphere. Moreover, it is preferable that it is 700 to 1200 degreeC, and, as for baking temperature, it is more preferable that it is 750 to 900 degreeC. Furthermore, the firing time is preferably 3 hours to 20 hours, and more preferably 8 hours to 10 hours.
For this two-stage firing, an electric furnace, a rotary kiln, a tubular furnace, a pusher furnace, etc., adjusted to a gas atmosphere having an oxygen concentration of 20% by mass or more such as an oxygen atmosphere, a dehumidified and decarboxylated dry air atmosphere, etc. be able to.

  The average particle size of the primary particles that are NCM-based composite oxide particles can be controlled by adjusting the firing temperature of the main firing. In order to set the average particle size of the primary particles that are the NCM-based composite oxide particles to 50 nm to 500 nm, the firing temperature is preferably 700 ° C. to 1000 ° C., more preferably 750 ° C. to 900 ° C.

  Furthermore, the internal porosity of the composite oxide secondary particles (A) can be controlled by adjusting the firing time of the main firing. In order to set the internal porosity of the composite oxide secondary particles (A) composed of the primary particles of the NCM-based composite oxide to 4 vol% to 12 vol%, the firing time is preferably 6 hours to 12 hours, more preferably May be 8 hours to 10 hours.

  Finally, the obtained fired product is washed with water, filtered and dried to obtain composite oxide secondary particles (A) of the formula (I). Here, the drying is performed in two stages, and the first stage of drying is performed until the water content in the composite oxide secondary particles (A) (water content measured at a vaporization temperature of 300 ° C.) is 1% by mass or less. It is preferable to dry at 90 ° C. or lower and then perform the second stage drying at 120 ° C. or higher. The moisture content may be measured using, for example, a Karl Fischer moisture meter.

  When producing a Li-NCM composite oxide having a core-shell structure, the Li-NCM composite oxide secondary particles obtained by the main firing in the above step (X) or step (X ′) are used as the core part. If the step (X) or the step (X ′) is repeated so that Li—NCM composite oxides having different compositions are formed on the surfaces of the Li—NCM composite oxide secondary particles constituting the core part. Good. The process for generating the shell portion is referred to as process (x) or process (x ′).

  In the step (x) and the step (x ′), in order to obtain the Li—NCM composite oxide particles serving as the shell portion, the same method as the method for producing the aqueous solution A in the step (X) or the step (X ′) is used. Then, after obtaining the aqueous solution a corresponding to the composition of the desired Li-NCM composite oxide, the metal composite hydroxide is prepared in the same manner as in the method for producing the aqueous solution B in the step (X) or the step (X ′). An aqueous solution b containing is obtained.

  Next, the aqueous solution b is mixed and stirred with the Li—NCM composite oxide secondary particles constituting the core part obtained by the main calcination in the step (X) or the step (X ′), and the mixture is stirred at room temperature to 1 ° C. The mixture is heated to 100 ° C. to 110 ° C. at a temperature rising rate of 20 ° C./min to 20 ° C./min. Thereby, the raw material of the Li-NCM complex oxide particles constituting the shell portion can be co-precipitated on the surface of the Li-NCM complex oxide secondary particles constituting the core portion. In addition, the thickness of a shell part is controllable by adjusting heating temperature.

  The particles obtained through the above steps are subjected to two-step firing and two-step drying in the same manner as in step (X) or step (X ′), then washed with water, then filtered and dried, -The lithium composite oxide secondary particle (A) which has a shell structure is obtained.

Next, the case where the composite oxide secondary particles (A) of the formula (II) are obtained in the step (X) or the step (X ′) will be specifically described.
In order to obtain the composite oxide secondary particles (A) of the formula (II), a raw material compound such as a nickel compound, a cobalt compound, and an aluminum compound is dissolved in water so as to have a desired composite oxide composition. To obtain an aqueous solution A ′. Examples of such nickel compounds, cobalt compounds, and aluminum compounds include sulfates, nitrates, carbonates, acetates, oxalates, oxides, hydroxides, and halides of the metal elements. Specific examples include, but are not limited to, nickel sulfate, cobalt sulfate, aluminum sulfate, nickel acetate, cobalt acetate, and aluminum acetate. In this process, if necessary, Mg may be used as a metal element (M ₂ ) for substituting a part of the layered lithium metal composite oxide constituting the active material so as to have a desired composite oxide composition. , Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi, and Ge Elements may be mixed.

  Next, an alkaline agent is added to the aqueous solution A ′ to obtain an aqueous solution B ′, and the dissolved metal water is coprecipitated by a neutralization reaction to obtain a metal composite hydroxide. The alkaline agent is dropped in an amount sufficient to maintain the pH of the aqueous solution B ′ at 10-14. As the alkaline agent, for example, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or the like can be used, but it is preferable to use ammonia, sodium hydroxide, sodium carbonate or a mixed solution thereof.

  The aqueous solution B ′ is stirred to produce a metal composite hydroxide. The temperature of the aqueous solution B ′ during this reaction is preferably 40 ° C. or higher, more preferably 40 ° C. to 60 ° C. Further, the stirring time of the aqueous solution B ′ is preferably 30 minutes to 120 minutes, and more preferably 30 minutes to 60 minutes.

  In order to obtain a metal composite hydroxide having a high bulk density, an oxidizing agent such as sodium hypochlorite or hydrogen peroxide may be further added to the aqueous solution B ′ after the reaction.

After stirring, the aqueous solution B ′ is filtered to recover the metal composite hydroxide. The recovered metal composite hydroxide is preferably fired to form a metal composite oxide. By reacting with the lithium compound as the metal composite oxide, the quality of the obtained NCA-based composite oxide can be stabilized and can be reacted uniformly and sufficiently with lithium.
The firing conditions for obtaining the metal composite oxide are not particularly limited. For example, the firing may be performed in an air atmosphere at a temperature of preferably 500 ° C to 1100 ° C, more preferably 600 ° C to 900 ° C.

  Next, an NCA-based composite oxide can be obtained by dry-mixing the metal composite oxide and the lithium compound so as to obtain a desired composite oxide composition and firing in an oxygen atmosphere. The lithium compound is not particularly limited, and for example, lithium hydroxide or a hydrate thereof, lithium peroxide, lithium nitrate, lithium carbonate and the like can be preferably used. For the dry mixing of the metal composite oxide and the lithium compound, an ordinary dry mixer or a mixing granulator such as a ball mill or a V blender can be used. For firing, an oxygen atmosphere, dehumidification and decarboxylation are performed. An electric furnace, a rotary kiln, a tubular furnace, a pusher furnace, or the like adjusted to a gas atmosphere having an oxygen concentration of 20% by mass or more such as a dry air atmosphere can be used.

In the firing of the mixture of the metal composite oxide and the lithium compound, the firing temperature is preferably 650 ° C to 850 ° C, and more preferably 700 ° C to 800 ° C. At a firing temperature of less than 650 ° C., the resulting NCA-based complex oxide crystals are undeveloped and structurally unstable, and the structure is easily destroyed by charge and discharge. On the other hand, when the firing temperature exceeds 850 ° C., the layered structure of the NCA-based composite oxide is destroyed, and it becomes difficult to insert and desorb lithium ions. The firing time is preferably 5 hours to 20 hours, and more preferably 6 hours to 10 hours.
Furthermore, in order to remove the crystal water or carbonic acid of the lithium compound, it is preferable to perform two-stage calcination as in the case of the NCM-based composite oxide. Subsequently, the second stage main firing may be performed at 650 ° C. to 850 ° C. for 5 hours or more.

Finally, the obtained fired product is washed with water, filtered and dried to obtain composite oxide secondary particles (A) of the formula (II). The slurry concentration when washing the fired product with water is preferably 200 g / L to 4000 g / L, and more preferably 500 g / L to 2000 g / L. When the slurry concentration is less than 200 g / L, lithium is desorbed from the secondary particles of the NCA-based composite oxide.
In addition, when the water used for washing contains a large amount of carbon dioxide, lithium carbonate precipitates on the composite oxide secondary particles (A), so the electrical conductivity of the water used for washing is less than 10 μS / cm. Preferably, water of 1 μS / cm or less is more preferable.

  In the present invention, in this step (X) or step (X ′), the drying performed after washing with water and filtering needs to be performed in two stages. The first stage drying is performed at 90 ° C. or less until the moisture in the secondary particles (moisture ratio measured at a vaporization temperature of 300 ° C.) is 1% by mass or less, and then the second stage drying is performed at 120 ° C. This is done.

In the step (Y) following the step (X), a lithium compound or a sodium compound, a phosphoric acid compound or a silicic acid compound, and a cobalt compound or a nickel compound are subjected to a wet reaction, or a lithium compound. Alternatively, a sodium compound, a phosphoric acid compound or a silicic acid compound, and at least one of a cobalt compound or a nickel compound is subjected to a solid-phase reaction to form a lithium-based polyanion particle of formula (V) or formula (VI) (B ) Or a sodium polyanion particle (E) of formula (IX) or formula (X),
In addition, the step (Y ′) subsequent to the step (X ′) involves subjecting at least one of a lithium compound or a sodium compound, a phosphoric acid compound or a silicic acid compound, and further an iron compound or a manganese compound to a wet reaction, Or a lithium-based polyanion represented by the formula (VII) or the formula (VIII) by subjecting at least one of a lithium compound or a sodium compound, a phosphoric acid compound or a silicic acid compound, and further an iron compound or a manganese compound to a solid phase reaction. This is a step of obtaining particles (B) or sodium-based polyanion particles (E) of formula (XI) or formula (XII).
Hereinafter, in order to avoid complicated description, lithium represented by the above formula (VII) or formula (VIII) using an iron compound and a manganese compound as an example of the step (Y) or the step (Y ′). The case of the step (Y ′) for obtaining the polyanion particles (B) will be specifically described.
When obtaining the lithium-based polyanion particles (B) represented by the above formula (V) or formula (VI), the term “iron compound and / or manganese compound” in the step (Y ′) is changed to “cobalt compound and / Or nickel compound ”, and when obtaining the sodium-based polyanion particles (E) of the above formulas (IX) to (XII), the word“ lithium ”in the step (Y ′) is“ sodium ”. In addition, the term “iron compound and / or manganese compound” may be replaced with “cobalt compound and / or nickel compound” as necessary.

In the production by the wet reaction, in the case of phosphate-based polyanion particles represented by the above formula (VII), the coefficient relating to Li, for example, the range that u can take in the formula (VII) is 0.8 ≦ In the case of silicate-based polyanion particles represented by the above formula (VIII), u ≦ 1.2, and the coefficient relating to Li, for example, in the formula (VIII), the range that v can take is 1.6 ≦ v ≦ 2.4. On the other hand, in the production by the above solid phase reaction, the chemical composition of the resulting polyanion particles is not limited.
Below, after explaining the manufacturing method by a wet reaction first, the manufacturing method by a solid-phase reaction is demonstrated.

The step (Y ′) in the wet reaction will be described.
More specifically, the step (Y ′) includes the following (i) to (iii):
(I) a step of obtaining a composite (a-2) by mixing a phosphoric acid compound or a silicic acid compound with a mixture (a-1) containing a lithium compound;
(Ii) The composite (a-4) obtained by subjecting the obtained composite (a-2) and slurry water (a-3) containing a metal salt containing at least an iron compound or a manganese compound to a hydrothermal reaction And (iii) a step of firing the obtained composite (a-4) in a reducing atmosphere or an inert atmosphere.

Step (i) is a step of obtaining a composite (a-2) by mixing a phosphoric acid compound or a silicic acid compound with a mixture (a-1) containing a lithium compound.
Examples of the lithium compound that can be used include lithium hydroxide (for example, LiOH, LiOH.H ₂ O), lithium carbonate, lithium sulfate, and lithium acetate. Of these, lithium hydroxide is preferable.
The content of the lithium compound in the mixture (a-1) is preferably 5 to 50 parts by mass, more preferably 7 to 45 parts by mass with respect to 100 parts by mass of water. More specifically, when a phosphoric acid compound is used in step (i), the lithium compound content in the mixture (a-1) is preferably 5 to 50 parts by mass with respect to 100 parts by mass of water. More preferably, it is 10 mass parts-45 mass parts. Moreover, when using a silicate compound, content of the lithium compound in a mixture (a-1) becomes like this. Preferably it is 5 mass parts-40 mass parts with respect to 100 mass parts of water, More preferably, it is 7 mass parts- 35 parts by mass.

  In order to obtain lithium-based polyanion particles in which carbon (c1) derived from cellulose nanofibers is supported, in the step (i), a lithium compound is contained instead of the mixture (a-1) and cellulose nanofibers are contained. A mixture (a-1) ′ containing may be used. The content of cellulose nanofibers in the mixture (a-1) ′ is preferably 0.5 part by mass to 60 parts by mass, for example, more preferably 100 parts by mass of water in the mixture (a-1) ′. Is 0.8 to 40 parts by mass. More specifically, when a phosphoric acid compound is used in step (i), the content of cellulose nanofibers in the mixture (a-1) ′ is preferably 0.5 parts by mass to 20 parts by mass, and more Preferably it is 0.8 mass part-15 mass parts. Moreover, when a silicic acid compound is used, content of the cellulose nanofiber in mixture (a-1) 'becomes like this. Preferably it is 0.5 mass part-60 mass parts, More preferably, it is 1 mass part-40 mass parts It is.

  Here, when the carbon supported by the lithium-based polyanion particles is carbon (c2) derived from a water-soluble carbon material, both carbon (c1) derived from cellulose nanofibers and carbon (c2) derived from a water-soluble carbon material are combined. In order to obtain supported lithium-based polyanion particles, the term “cellulose nanofiber” in steps (i) to (iii) is replaced with “water-soluble carbon material” or “cellulose nanofiber and water-soluble carbon material”. ".

  It is preferable to stir the mixture (a-1) in advance before mixing the phosphoric acid compound or the silicic acid compound with the mixture (a-1). The stirring time of the mixture (a-1) is preferably 1 minute to 15 minutes, more preferably 3 minutes to 10 minutes. Moreover, the temperature of mixture (a-1) becomes like this. Preferably it is 20 to 90 degreeC, More preferably, it is 20 to 70 degreeC.

Examples of the phosphoric acid compound used in the step (i) include orthophosphoric acid (H ₃ PO ₄ , phosphoric acid), metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, ammonium phosphate, and ammonium hydrogen phosphate. . Of these, phosphoric acid is preferably used, and is preferably used as an aqueous solution having a concentration of 70% by mass to 90% by mass. In this process (i), when mixing phosphoric acid with the mixture (a-1), it is preferable to add phosphoric acid dropwise while stirring the mixture (a-1). By adding dropwise phosphoric acid dropwise to the mixture (a-1), the reaction proceeds well in the mixture (a-1), and the composite (a-2) is uniformly dispersed in the slurry. It is also possible to effectively prevent the complex (a-2) from being aggregated unnecessarily.

The dropping rate of phosphoric acid into the mixture (a-1) is preferably 15 mL / min to 50 mL / min, more preferably 20 mL / min to 45 mL / min, and further preferably 28 mL / min to 40 mL / min. Minutes. Moreover, the stirring time of the mixture (a-1) while dropping phosphoric acid is preferably 0.5 hours to 24 hours, and more preferably 3 hours to 12 hours. Furthermore, the stirring speed of the mixture (a-1) while dropping phosphoric acid is preferably 200 rpm to 700 rpm, more preferably 250 rpm to 600 rpm, and further preferably 300 rpm to 500 rpm.
In addition, when stirring a mixture (a-1), it is preferable to cool below the boiling point temperature of a mixture (a-1). Specifically, cooling to 80 ° C. or lower is preferable, and cooling to 20 ° C. to 60 ° C. is more preferable.

The silicic acid compound used in the step (i) is not particularly limited as long as it is a reactive silica compound, and examples thereof include amorphous silica, Na ₄ SiO ₄ (for example, Na ₄ SiO ₄ .H ₂ O), and the like. .

  The mixture (a-1) after mixing the phosphoric acid compound or the silicic acid compound preferably contains 2.0 mol to 4.0 mol of lithium with respect to 1 mol of phosphoric acid or silicic acid. More preferably, the content is from mol to 3.1 mol, and the lithium compound and the phosphoric acid compound or the silicic acid compound may be used so as to obtain such an amount. More specifically, when a phosphoric acid compound is used in the step (i), the mixture (a-1) after mixing the phosphoric acid compound is 2.7 mol to 3 mol of lithium with respect to 1 mol of phosphoric acid. 3 mol is preferable, and 2.8 mol to 3.1 mol is more preferable. When the silicate compound is used in step (i), the mixture (a- 1) preferably contains 2.0 mol to 4.0 mol of lithium, more preferably 2.0 mol to 3.0 mol, per mol of silicic acid.

By purging the mixture (a-1) after mixing the phosphoric acid compound or the silicate compound with nitrogen, the reaction in the mixture is completed, and the composite (a -2) is formed in the mixture. When nitrogen is purged, the reaction can proceed in a state where the dissolved oxygen concentration in the mixture (a-1) is reduced, and the dissolved oxygen in the mixture containing the resulting complex (a-2) Since the concentration is also effectively reduced, oxidation of iron compounds, manganese compounds, etc. added in the next step can be suppressed. In the mixture containing the complex (a-2), the precursor of the polyanion particles exists as fine dispersed particles. Such a composite (a-2) is obtained, for example, as a composite of trilithium phosphate (Li ₃ PO ₄ ) and cellulose nanofibers when a phosphate compound is used in step (i).

The pressure when purging nitrogen is preferably 0.1 MPa to 0.2 MPa, more preferably 0.1 MPa to 0.15 MPa. Moreover, the temperature of the mixture (a-1) after mixing a phosphoric acid compound or a silicic acid compound becomes like this. Preferably it is 20 to 80 degreeC, More preferably, it is 20 to 60 degreeC. For example, when a phosphate compound is used in step (i), the reaction time is preferably 5 minutes to 60 minutes, more preferably 15 minutes to 45 minutes.
Moreover, when purging nitrogen, it is preferable to stir the mixture (a-1) after mixing a phosphoric acid compound or a silicic acid compound from a viewpoint of making reaction progress favorable. The stirring speed at this time is preferably 200 rpm to 700 rpm, more preferably 250 rpm to 600 rpm.

  Moreover, the mixture (a-1) after mixing a phosphoric acid compound or a silicic acid compound from a viewpoint which suppresses the oxidation in the dispersed particle surface of a composite_body | complex (a-2) more effectively, and aims at refinement | miniaturization of a dispersed particle. ) Is preferably 0.5 mg / L or less, more preferably 0.2 mg / L or less.

  In step (ii), the composite (a-2) obtained in step (i) and slurry water (a-3) containing a metal salt containing at least an iron compound or a manganese compound are subjected to a hydrothermal reaction. And obtaining the composite (a-4). The composite (a-2) obtained by the above step (i) is used as a precursor of polyanion particles in the form of a mixture, and a metal salt containing at least an iron compound or a manganese compound is added thereto, and slurry water ( It is preferable to use as a-3). As a result, the target polyanion particles become very fine particles while simplifying the process. Further, when the above mixture (a-1) ′ containing cellulose nanofibers is used in step (i), it becomes possible to efficiently carry carbon derived from cellulose nanofibers on such polyanion particles in the subsequent step, Useful polyanion particles can be obtained.

  Examples of iron compounds that can be used include iron acetate, iron nitrate, and iron sulfate. These may be used alone or in combination of two or more. Among these, iron sulfate is preferable from the viewpoint of improving the battery characteristics of the polyanion particles.

  Examples of manganese compounds that can be used include manganese acetate, manganese nitrate, and manganese sulfate. These may be used alone or in combination of two or more. Among these, manganese sulfate is preferable from the viewpoint of improving the battery characteristics of the polyanion particles.

When both an iron compound and a manganese compound are used as the metal salt, the use molar ratio of these manganese compound and iron compound (manganese compound: iron compound) is preferably 99: 1 to 1:99, more preferably 90. : 10 to 10:90. Moreover, the total addition amount of these iron compounds and manganese compounds is preferably 0.99 mol to 1.01 mol with respect to 1 mol of Li ₃ PO ₄ contained in the slurry water (a-3), and more Preferably it is 0.995 mol-1.005 mol.

Further, if necessary, as a metal salt, a metal other than iron compound and manganese compound (M ⁷ or M ⁸⁾ may be used salts. M ⁷ or M ⁸ in the metal salt has the same meaning as M ⁷ or M ⁸ in formula (VII) ~ (VIII), as such a metal salt, sulfate, halide, organic acid salts, and their water A Japanese thing etc. can be used. These may be used alone or in combination of two or more. Especially, it is more preferable to use a sulfate from a viewpoint of improving battery physical properties.
When these metal (M ⁷ or M ⁸ ) salts are used, the total addition amount of the iron compound, manganese compound, and metal (M ⁷ or M ⁸ ) salt is determined according to the complex (a- Preferably it is 0.99 mol-1.01 mol with respect to 1 mol of phosphoric acid or silicic acid in 2), More preferably, it is 0.995 mol-1.005 mol.

  The amount of water used in the hydrothermal reaction is phosphoric acid contained in the slurry water (a-3) from the viewpoints of the solubility of the metal salt used, the ease of stirring, the efficiency of synthesis, and the like. Or it is 10 mol-50 mol with respect to 1 mol of silicate ions, More preferably, it is 12.5 mol-45 mol. More specifically, when the ions contained in the slurry water (a-3) are phosphate ions, the amount of water used for the hydrothermal reaction is preferably 10 to 30 mol. More preferably, it is 12.5 mol-25 mol. Moreover, when the ion contained in slurry water (a-3) is a silicate ion, the usage-amount of the water used when attaching | subjecting to a hydrothermal reaction becomes like this. Preferably it is 10-50 mol, More preferably 12.5 mol to 45 mol.

In step (ii), the order of addition of the iron compound, manganese compound, and metal (M ⁷ or M ⁸ ) salt is not particularly limited. Moreover, while adding these metal salts, you may add antioxidant as needed. As such an antioxidant, sodium sulfite (Na ₂ SO ₃ ), sodium hydrosulfite (Na ₂ S ₂ O ₄ ), aqueous ammonia and the like can be used. The addition amount of the antioxidant is an iron compound, a manganese compound, and a metal (M ⁷ or M ⁸ ) salt used as necessary from the viewpoint of preventing the formation of polyanion particles by being excessively added. The total amount is preferably 0.01 mol to 1 mol, more preferably 0.03 mol to 0.5 mol.

The content of the composite (a-4) in the slurry (a-3) obtained by adding an iron compound, a manganese compound, and a metal (M ⁷ or M ⁸ ) salt or an antioxidant used as necessary is as follows: , Preferably, it is 10 mass%-50 mass%, More preferably, it is 15 mass%-45 mass%, More preferably, it is 20 mass%-40 mass%.

The hydrothermal reaction in process (ii) should just be 100 degreeC or more, and 130 to 180 degreeC is preferable. The hydrothermal reaction is preferably performed in a pressure vessel. When the reaction is performed at 130 ° C. to 180 ° C., the pressure at this time is preferably 0.3 MPa to 0.9 MPa, and the reaction is performed at 140 ° C. to 160 ° C. The pressure in carrying out is preferably 0.3 MPa to 0.6 MPa. The hydrothermal reaction time is preferably 0.1 to 48 hours, more preferably 0.2 to 24 hours.
The obtained composite (a-4) is a composite containing polyanion particles represented by the above formulas (VII) to (VIII). When cellulose nanofibers are used, such polyanion grains and cellulose are used. It is a composite containing nanofibers, which can be isolated as composite particles (primary particles) containing cellulose nanofibers by filtration, washing with water, and drying. As the drying means, freeze drying or vacuum drying is used.

BET specific surface area of the resulting composite (a-4), from the viewpoint of effectively reducing the amount of adsorbed water is preferably ^{5m 2} / ^g~40m 2 / g, more preferably ^5m 2 / ^{g~20m 2} / g. If the BET specific surface area of the composite (a-4) is less than 5 m ² / g, the polyanion particles may become too large. On the other hand, if the BET specific surface area exceeds 40 m ² / g, the amount of adsorbed moisture of the positive electrode active material composite for a secondary battery may increase and affect battery characteristics.

  In the next step (iii), the complex (a-4) obtained in step (ii) is baked in a reducing atmosphere or an inert atmosphere, and a lithium-based polyanion containing carbon (c1) derived from cellulose nanofibers. This is a step of obtaining particles (B). Further, when the cellulose nanofiber is used, the lithium-based polyanion particle (B) in which the carbon (c1) derived from the cellulose nanofiber is firmly supported on the surface is obtained through this step (III). Obtainable.

  The firing temperature is preferably 500 ° C. to 800 ° C., more preferably 600 ° C. to 770 ° C., and further preferably 650 ° C. to 750 ° C. from the viewpoint of effectively carbonizing the cellulose nanofibers. . The firing time is preferably 10 minutes to 3 hours, more preferably 30 minutes to 1.5 hours.

Next, the step (Y ′) in the solid phase reaction will be described.
More specifically, the step (Y ′) includes the following (i ′) to (iii):
(I ′) A metal compound-containing slurry (b-1) is precipitated and precipitated by using a neutralization reaction of a hydroxide or oxide of iron, manganese and / or other metal components (M ⁷ or M ⁸ ). Obtaining step,
(Ii ′) The obtained metal compound-containing slurry (b-1) is filtered, washed, and then subjected to firing at 400 ° C. to 600 ° C. in the air, and then pulverized to obtain a metal oxide (b-2). And (iii ′) a step of weighing and mixing the obtained metal oxide (b-2) with a phosphoric acid compound and a lithium compound and then firing the mixture in a reducing atmosphere or an inert atmosphere. Is preferred.

In the step (i ′), a hydroxide or oxide of iron, manganese and / or other metal components (M ⁷ or M ⁸ ) is precipitated and precipitated using a neutralization reaction, and a metal compound-containing slurry (b- This is a step of obtaining 1).
When a composite metal oxide is obtained in the next step (ii ′) by using the composite metal hydroxide or the like obtained in this step (i ′), the composite metal oxide is used in the subsequent step (iii). The reactivity in firing in ') is good, and uniform lithium-based polyanion particles (B) of formula (VII) or formula (VIII) can be obtained.

  Examples of the iron compound that can be used include divalent iron compounds and hydrates thereof. For example, halides such as iron halides; sulfates such as iron sulfate; organics such as iron oxalate and iron acetate. Acid salts; and hydrates thereof. These may be used alone or in combination of two or more. Among these, iron sulfate is preferable from the viewpoint of improving the battery characteristics of the polyanion particles.

  As the manganese compound that can be used, the manganese compound may be a divalent manganese compound and hydrates thereof, for example, a halide such as manganese halide; a sulfate such as manganese sulfate; manganese oxalate, Organic acid salts such as manganese acetate; and hydrates thereof. These may be used alone or in combination of two or more. Among these, manganese sulfate is preferable from the viewpoint of improving the battery characteristics of the polyanion particles.

Furthermore, if a metal (M ⁷ or M ⁸ ) salt other than the iron compound and the manganese compound is used as the metal salt, if necessary, as the metal salt, a sulfate, a halogen compound, an organic acid salt, and water thereof. A Japanese thing etc. can be used. These may be used alone or in combination of two or more. Especially, it is more preferable to use a sulfate from a viewpoint of improving battery physical properties.

In the step (i ′), each compound of iron, manganese and / or other metal component (M ⁷ or M ⁸ ) is dissolved in water to obtain a solution b. In such a solution b, the molar ratio of water to the total amount of the above metal compounds (water: (Mn + Fe + (M ⁷ or M ⁸ ))) may be 13: 1 to 100: 1, and the subsequent alkaline agent From the viewpoint of obtaining a highly uniform slurry (b-1) by avoiding unnecessary agglomeration at the time of addition of lithium, the viewpoint of ensuring excellent battery characteristics by the obtained lithium-based polyanion particles (B), and the viewpoint of productivity Therefore, these molar ratios (water: (Fe + Mn + (M ⁷ or M ⁸ ))) are preferably 14: 1 to 80: 1, and more preferably 15: 1 to 60: 1.

In preparing the solution b, the order of addition of iron compound, manganese compound, other metal (M ⁷ or M ⁸ ) compound, and water is not particularly limited, but iron compound, manganese compound, other metal (M ⁷ or M ⁸ ) From the viewpoint of efficiently dissolving the compound, it is preferable to add an iron compound, a manganese compound, or another metal (M ⁷ or M ⁸ ) compound to water. Moreover, after adding these, it is preferable to stir the solution b, the stirring time is preferably 5 minutes to 120 minutes, more preferably 5 minutes to 90 minutes, and the temperature of the solution b during stirring is The temperature is preferably 5 ° C to 50 ° C, more preferably 10 ° C to 40 ° C.

Next, an alkali agent is added to the solution b, and a molar ratio of the alkali agent to the total amount of iron, manganese, and other metals (M ⁷ or M ⁸ ) (alkali agent: (Fe + Mn + (M ⁷ or M ⁸ )) ) Is obtained from 3: 2 to 4: 1.
Examples of the alkaline agent added to the solution b include sodium hydroxide, potassium hydroxide, or aqueous ammonia. Especially, it is preferable to use sodium hydroxide from a viewpoint of improving the battery characteristic by the viewpoint which improves the recovery rate of solid content in the process (ii ') mentioned later, and the lithium-type polyanion particle (B) obtained. As such sodium hydroxide, either solid (granular or flaky) or aqueous solution may be used.

The amount of the alkali agent added is such that the molar ratio of the alkali agent to the total amount of iron, manganese, and other metals (M ⁷ or M ⁸ ) (alkali agent: (Fe + Mn + (M ⁷ or M ⁸ ))) is 3: 2. The molar ratio (alkali agent: (Fe + Mn + (M ⁷ or M ⁸ ))) is preferably 3: 2 to 4: 1, from the viewpoint of promoting the formation of the precursor in the solution b. 3: 1, more preferably 2: 1 to 5: 2. Further, the addition rate of the alkaline agent is preferably 10 mL / min to 100 mL / min, more preferably 20 mL / min to 80 mL / min, from the viewpoint of increasing the uniformity of the resulting slurry (b-1).

  When adding the alkaline agent, it is preferable to stir, the stirring time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 90 minutes, and the temperature of the slurry (b-1) during stirring is The temperature is preferably 5 ° C to 50 ° C, more preferably 10 ° C to 40 ° C.

  The resulting slurry (b-1) is a liquid material in which the precursor of the lithium-based polyanion particles (B) is uniformly dispersed as a solid content. The pH of the slurry (b-1) is preferably 7 to 11, and more preferably 8 to 10.

  In the step (ii ′), the slurry (b-1) obtained in the step (i ′) is separated and the solid content is fired. In order to obtain the solid content by separating the slurry (b-1), an apparatus usually used for solid-liquid separation may be used. Examples of such apparatuses include a filter press machine, a centrifugal filter, a vacuum filter, a Buchner funnel, and the like. Is mentioned. The obtained solid content is a precursor of the lithium-based polyanion particles (B), and can be obtained as a powder by subsequent washing and drying.

  It is preferable to use water for washing the solid content. Specifically, it is preferable to use 3 to 10 times the amount of water, more preferably 5 to 10 times the amount of water relative to the solid content. . As a means for drying the solid content, freeze drying or vacuum drying is preferable.

  The obtained solid content is fired at a temperature of 400 ° C. to 600 ° C. in the atmosphere to obtain a metal oxide. The firing time is preferably 0.1 hour to 12 hours, more preferably 0.3 hour to 6 hours.

Next, the metal oxide obtained by firing is pulverized to form a metal oxide (b-2). The average particle size of the metal oxide (b-2) is in the D ₅₀ value in the particle size distribution based on the laser diffraction scattering method, preferably not 100μm or less, more preferably 75μm or less, particularly preferably at 50μm or less is there. Here, the put D ₅₀ value in the particle size distribution measurement, a value obtained by volume-based particle size distribution based on the laser diffraction scattering method, D ₅₀ value means a particle diameter at cumulative 50% (median diameter) To do.

  There is no restriction | limiting in particular as an apparatus used for the grinding | pulverization method, A general purpose fine grinder, such as a rolling ball mill, a vibration mill, a planetary mill, or a medium stirring mill, can be used.

  Step (iii ′) is a step in which the obtained metal oxide (b-2) is weighed and mixed with a phosphoric acid compound and a lithium compound and then baked in a reducing atmosphere or an inert atmosphere.

  As the phosphoric acid compound that can be used, ammonium dihydrogen phosphate is preferred.

  Examples of lithium compounds that can be used include lithium hydroxide, lithium carbonate, lithium sulfate, lithium acetate, and hydrates thereof. Of these, lithium carbonate is preferable from the viewpoint of reducing manufacturing costs.

  The mixture before firing obtained after mixing may be fired as it is, or may be granulated in advance and fired. The granulation method may be wet or dry, and includes extrusion granulation method, rolling granulation method, fluidized granulation method, mixed granulation method, spray drying granulation method, pressure molding granulation method, roll, etc. Any of the flake granulation methods used may be used.

In order to fire the mixture before firing, it is preferable to fire it in an inert atmosphere or a reducing atmosphere after being put in a firing furnace. Here, argon gas, nitrogen gas, helium gas, or the like can be used as the inert atmosphere, and as the reducing atmosphere, a gas containing several percent of carbon monoxide, hydrogen gas, or the like is used as the reducing atmosphere. be able to.
If such firing is performed only once, impurities are likely to be generated and the discharge capacity will be reduced. Therefore, the first firing is performed at 160 ° C. to 350 ° C. to produce a precursor of lithium-based polyanion particles (B). Then, it is preferable to sinter at 480 ° C. to 750 ° C. for the second time to synthesize lithium-based polyanion particles (B). If the temperature in the first firing is 160 ° C. or lower, the reaction to the precursor may not proceed. On the other hand, if the first firing temperature is 350 ° C. or higher, impurities that are difficult to remove by subsequent firing are present. Since it will produce | generate, it will cause the discharge capacity fall of lithium type polyanion particle | grains (B), and is not preferable. On the other hand, the temperature in the second firing needs to be 480 ° C. or higher in order to obtain single-phase lithium-based polyanion particles (B). In addition, when the firing temperature exceeds 750 ° C., single-phase lithium-based polyanion particles (B) can be obtained, but the discharge capacity may be lowered, which is not preferable.

When producing lithium-based polyanion particles (B) formed with a core-shell structure, the lithium-based polyanion particles a obtained by firing in the above step (iii) are used as the core portion, and the lithium-based material constituting the core portion In the slurry water (a-3) of step (ii) adjusted to produce a lithium-based polyanion composition b in order to produce a lithium-based polyanion composition b having a different composition on the surface of the polyanion particle a, Steps (ii) to (iii) may be performed after mixing the lithium-based polyanion particles a produced in advance.
By repeating this step, lithium-based polyanion particles (B) having a concentric layer structure composed of two or more layers of different lithium-based polyanion compositions can be obtained.

  At this time, the particle size of the lithium-based polyanion particles a can be controlled by adjusting the temperature, pressure, and time of the hydrothermal reaction in the step (ii) when the lithium-based polyanion particles a are generated. The coating thickness of the lithium-based polyanion composition b can be controlled by adjusting the temperature, pressure and time of the hydrothermal reaction in the step (ii) when the lithium-based polyanion composition b is generated.

  In the production of the lithium-based polyanion particles (B) formed with the core-shell structure, the lithium-based polyanion composition b is produced in the slurry water (a-3) when the number of repetitions is the second or later. The content of the raw material compound for the purpose is preferably 0.5% by mass to 10% by mass in 100% by mass of the slurry water (a-3) from the viewpoint of uniformly forming the coating layer of the lithium-based polyanion particles a.

  Furthermore, in the production of the lithium-based polyanion particles (B) having the core-shell structure, a carbon source such as cellulose nanofiber is used during the production of the outermost lithium-based polyanion composition b, as in the step (Y). Thus, carbon (c) can be supported on lithium-based polyanion particles (B) formed with a core-shell structure.

  In the step (Z), the NCM composite oxide secondary particles or the NCA composite oxide secondary particles (A) or (D) obtained in the step (X) are added to the step (Y) or the step (Y ′ The lithium-based polyanion particles (B) or sodium-based polyanion particles (E) obtained in (1) above and, if necessary, the water-insoluble carbon powder (c3) are added and mixed while adding compressive force and shearing force. This is a process of making a composite.

  In the step (Z), before the composite treatment, the composite oxide secondary particles (A) or (D), the lithium-based polyanion particles (B) or the sodium-based polyanion particles (E), and further if necessary. The mixture of the water-insoluble carbon powder (c3) to be added is preferably thoroughly dry-mixed. As a dry mixing method, mixing by a normal dry mixer such as a ball mill or a V blender is preferable, and mixing by a planetary ball mill capable of revolving is more preferable.

Next, the dry-mixed composite oxide secondary particles (A) or (D), the lithium-based polyanion particles (B) or the sodium-based polyanion particles (E), and water-insoluble added as necessary. A mixture of carbon powder (c3) is obtained by dispersing polyanion particles and further water-insoluble carbon powder (c3) densely and uniformly on the surface of the composite oxide secondary particles (A) or (D). From the viewpoint of obtaining a composite that is effectively combined, it is preferable to mix while applying compressive force and shearing force. The process of mixing while applying a compressive force and a shearing force is preferably performed in a closed container equipped with an impeller. The impeller has a peripheral speed of positive electrode active material obtained as a composite of the composite oxide secondary particles (A) or (D), the polyanion particles (B) or (E), and water-insoluble carbon powder (c3). From the viewpoint of increasing the tap density, it is preferably 15 m / s to 45 m / s, more preferably 15 m / s to 40 m / s. The mixing time is preferably 5 minutes to 90 minutes, more preferably 10 minutes to 80 minutes.
The peripheral speed of the impeller means the speed of the outermost end of the rotary stirring blade (impeller), which can be expressed by the following formula (1), and is mixed while applying compressive force and shearing force. The processing time may vary depending on the peripheral speed of the impeller so that it becomes longer as the peripheral speed of the impeller is slower.
Impeller peripheral speed (m / s) =
Impeller radius (m) × 2 × π × rotational speed (rpm) ÷ 60 (1)

In the step (Z), the processing time and / or the peripheral speed of the impeller at the time of performing the mixing process while applying the compressive force and shearing force are the composite oxide secondary particles (A) or (D ) And the polyanion particles (B) or (E), and further the water-insoluble carbon powder (c3), it is necessary to adjust appropriately. Then, by operating the container, it is possible to perform a process of compounding the mixture while applying a compressive force and a shearing force to the mixture between the impeller and the container inner wall. A negative electrode active material composite for a lithium ion secondary battery or a negative electrode active material composite for a sodium ion secondary battery, wherein the polyanion particles and the water-insoluble carbon powder (c3) are densely and uniformly dispersed and combined on the surface. Can be obtained.
For example, when the complexing process is performed for 5 minutes to 90 minutes in an airtight container having an impeller rotating at a peripheral speed of 15 m / s to 45 m / s, the amount of the mixture to be charged into the container is an effective container (impeller Among the sealed containers provided, a container corresponding to a part capable of accommodating the mixture) per cm ³ , preferably 0.1 g to 0.7 g, more preferably 0.15 g to 0.4 g.

Examples of the apparatus including a sealed container that can easily perform the compounding process while applying such compressive force and shear force include a high-speed shear mill, a blade-type kneader, and the like. Particle design equipment COMPOSI, mechanohybrid, high-performance fluidity mixer FM mixer (manufactured by Nihon Coke Kogyo Co., Ltd.) fine particle composite device mechanofusion, nobilta (manufactured by Hosokawa Micron), surface reformer miraro, hybridization system (Nara Machinery Co., Ltd.) Can be suitably used.
As processing conditions for the above complexing treatment, the treatment temperature is preferably 5 ° C. to 80 ° C., more preferably 10 ° C. to 50 ° C. The treatment atmosphere is not particularly limited, but is preferably an inert gas atmosphere or a reducing gas atmosphere.

The lithium-based polyanion particle (B) or the sodium-based polyanion particle (E) on the surface of the composite oxide secondary particle (A) or (D), and a water-insoluble carbon powder (c3) added as necessary. The degree of finely and uniformly dispersed and compounded can be evaluated by X-ray photoelectron spectroscopy (XPS). Specifically, when the obtained positive electrode active material composite for a lithium ion secondary battery or the positive electrode active material composite for a sodium ion secondary battery is irradiated with soft X-rays of several keV, the soft X-rays are irradiated. Since the photoelectron having an energy value specific to the element constituting the part is emitted from the part, the peak of Ni2p _3/2 emitted from the composite oxide secondary particle (A) or (D) is analyzed. By comparing the peak intensity corresponding to trivalent Ni obtained in this way with the total peak intensity of P2p or Si2P and C1s released from the polyanion particles (B) or (E). The area ratio of the material which is the surface of the active material composite or the positive electrode active material composite for sodium ion secondary battery, that is, such polyanion particles (B) or (E) and further water-insoluble carbon powder It can be seen that the powder (c3) covers the composite oxide secondary particles (A) or (D). However, since the polyanion particle (B) or (E) may contain trivalent Ni, the composite oxide secondary particle (A) or the peak intensity of Ni2p _3/2 of the (D) composite oxide The composite oxide 2 in the differential XPS profile obtained by subtracting the peak of Ni2p _3/2 derived from the polyanion particle (B) or (E) normalized to the P2p or Si2P peak of the secondary particle (A) or (D). The peak intensity of Ni2p _3/2 derived from the next particle (A) or (D) is used. This peak intensity ratio (Ni2p _3/2 trivalent Ni peak intensity) / ((P2p peak intensity) + (C1s peak intensity)) or (Ni2p _3/2 trivalent Ni peak intensity) / ((Si2p peak intensity) + (C1s peak intensity)) is preferably 0.1 or less, more preferably 0.01 or less. With such a peak intensity ratio, the surface of the obtained positive electrode active material composite for a lithium ion secondary battery or the positive electrode active material composite for a sodium ion secondary battery is a composite oxide secondary particle surface. It is densely covered with the polyanion particles and water-insoluble carbon particles that are combined with the particles.

  The positive electrode active material composite for a secondary battery of the present invention is applied as a positive electrode material, and as a secondary battery that is a lithium ion secondary battery or a sodium ion secondary battery containing the same, a positive electrode, a negative electrode, an electrolytic solution, a separator, Or it will not specifically limit if a positive electrode, a negative electrode, and a solid electrolyte are made into an essential structure.

Here, as for the negative electrode, as long as lithium ions or sodium ions can be occluded during charging and released during discharging, the material configuration is not particularly limited, and those having a known material configuration can be used. . For example, lithium metal, sodium metal, graphite, silicon-based (Si, SiO _x ), carbon materials such as lithium titanate or amorphous carbon can be used. It is preferable to use an electrode formed of an intercalating material capable of electrochemically inserting and extracting lithium ions or sodium ions, particularly a carbon material. Furthermore, two or more types of the above negative electrode materials may be used in combination, and for example, a combination of graphite and silicon can be used.

  The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that is usually used for an electrolyte solution of a lithium ion secondary battery or a sodium ion secondary battery. For example, carbonates, halogenated hydrocarbons, ethers, ketones Nitriles, lactones, oxolane compounds and the like can be used.

The type of the supporting salt is not particularly limited, but in the case of a lithium ion secondary battery, an inorganic salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ and LiAsF ₆ , a derivative of the inorganic salt, LiSO ₃ CF ₃ , an organic material selected from LiC (SO ₃ CF ₃ ) ₂ and LiN (SO ₃ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ and LiN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ) It is preferably at least one of a salt and a derivative of the organic salt. In the case of a sodium ion secondary battery, an inorganic salt selected from NaPF ₆ , NaBF ₄ , NaClO ₄ and NaAsF ₆ , a derivative of the inorganic salt, NaSO ₃ CF ₃ , NaC (SO ₃ CF ₃ ) ₂ and NaN (SO ₃ CF ₃ ) ₂ , NaN (SO ₂ C ₂ F ₅ ) ₂ and NaN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), and at least one of derivatives of the organic salt It is preferable.

  The separator plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used.

The solid electrolyte electrically insulates the positive electrode and the negative electrode and exhibits high lithium ion conductivity. For example, La _0.51 Li _0.34 TiO _2.94 , Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , Li ₇ La ₃ Zr ₂ O ₁₂ , 50Li ₄ SiO ₄ .50Li ₃ BO ₃ , Li _2.9 PO _3.3 N _0.46 , Li _3.6 Si _0.6 P _0.4 O ₄ , Li _1.07 Al _0.69 Ti _1.46 (PO ₄ ) ₃ , Li _{1 .5 Al 0.5 Ge 1.5 (PO 4} ) 3, Li 10 GeP 2 S 12, Li 3.25 Ge 0.25 P 0.75 S 4, 30Li 2 S · 26B 2 S 3 · 44LiI, 63Li _{2 S · 36SiS 2 · 1Li 3} PO 4, 57Li 2 S · 38SiS 2 · 5Li 4 SiO 4, 70Li 2 S · 30P 2 S 5, 50Li 2 S · 50GeS 2, Li 7 P 3 S 11, Li _3.25 P _0.95 S ₄ may be used.

  The shape of the lithium ion secondary battery or sodium ion secondary battery having the above configuration is not particularly limited, and various shapes such as a coin shape, a cylindrical shape, and a square shape, and an indeterminate sealed in a laminate outer package. It may be a shape.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Production Example A: Production of Secondary Particles of Li-NCM Complex Oxide (Li-NCM-A)]
After mixing 263 g of nickel sulfate hexahydrate, 281 g of cobalt sulfate heptahydrate, 241 g of manganese sulfate pentahydrate, and 3 L of water so that the molar ratio of Ni: Co: Mn is 1: 1: 1 Then, 25% aqueous ammonia was added dropwise to the mixture at a dropping rate of 300 mL / min to obtain a slurry A1 containing a metal composite hydroxide having a pH of 11.
Next, the slurry A1 was filtered and dried to obtain a metal composite hydroxide mixture B1, and then 37 g of lithium carbonate was mixed with the mixture B1 by a ball mill to obtain a powder mixture C1.
The obtained powder mixture C1 was calcined at 800 ° C. for 5 hours in an air atmosphere and pulverized, and then calcined at 800 ° C. for 10 hours in an air atmosphere as main firing, to obtain a Li-NCM composite oxide (LiNi Secondary particles A of _0.33 Co _0.33 Mn _0.34 O ₂ ) were obtained. (Average particle size of secondary particles: 10 μm)
Hereinafter, the Li-NCM composite oxide A is referred to as Li-NCM-A.

[Production Example B: Production of Secondary Particles of Li-NCM Complex Oxide (Li-NCM-B)]
In the production of Li-NCM composite oxide (1) of Production Example A, the amount of nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate pentahydrate nickel sulfate hexahydrate, 473 g, 169 g, 145 g (Ni: Co: Mn molar ratio = 6: 2: 2), except that lithium hydroxide monohydrate 22 g was mixed instead of lithium carbonate mixed in the metal composite hydroxide mixture In the same manner as in Production Example A, secondary particles B of Li-NCM composite oxide (LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ) were obtained. (Average particle size of secondary particles: 10 μm)
Hereinafter, the Li-NCM composite oxide B is referred to as Li-NCM-B.

[Production Example C: Production of secondary particles of Li—NCA-based composite oxide (Li—NCA-A)]
370 g of lithium carbonate, 950 g of nickel carbonate, 150 g of cobalt carbonate, 58 g of aluminum carbonate, and 3 L of water were mixed so that the molar ratio of Li: Ni: Co: Al was 1: 0.8: 0.15: 0.05. After that, it was mixed with a ball mill to obtain a powder mixture A3. The obtained powder mixture A3 was calcined by calcination at 800 ° C. for 5 hours in an air atmosphere, and then baked as 800 ° C. for 24 hours in an air atmosphere as main calcination _{. 8} Co _0.15 Al _0.05 O ₂ ) secondary particles C were obtained. (Average particle size of secondary particles: 10 μm)
Hereinafter, the secondary particles C of the Li-NCA composite oxide are referred to as Li-NCA-A.

[Production Example 001: Production of lithium-based polyanion particles (LMP-A)]
1272 g of LiOH.H ₂ O and 4 L of water were mixed to obtain slurry A001. Subsequently, 1153 g of 85% phosphoric acid aqueous solution was dropped at 35 mL / min while stirring the obtained slurry A001 at a temperature of 25 ° C. for 3 minutes, followed by cellulose nanofiber (Wma-1202, Sugino Machine Co., Ltd.). Manufactured, fiber diameter: 4 to 20 nm) was added and stirred at a speed of 400 rpm for 12 hours to obtain a slurry B001 containing Li ₃ PO ₄ .
The obtained slurry B001 was purged with nitrogen so that the dissolved oxygen concentration of the slurry B001 was 0.5 mg / L, and then 1688 g of MnSO ₄ · 5H ₂ O and 834 g of FeSO ₄ · 7H ₂ O were added to the total amount of the slurry B001. As a result, slurry C001 was obtained. The molar ratio of MnSO ₄ and FeSO ₄ added (manganese compound: iron compound) was 70:30.
Next, the obtained slurry C001 was put into an autoclave and subjected to a hydrothermal reaction at 170 ° C. for 1 hour. The pressure in the autoclave was 0.8 MPa. After the hydrothermal reaction, the produced crystal was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. The washed crystal was lyophilized at −50 ° C. for 12 hours to obtain a complex D001.
1000 g of the obtained composite D001 was collected, and 1 L of water was added thereto to obtain a slurry E001. The obtained slurry E001 was subjected to a dispersion treatment for 1 minute with an ultrasonic stirrer (T25, manufactured by IKA) to uniformly color the whole, and then a spray drying apparatus (MDL-050M, manufactured by Fujisaki Electric Co., Ltd.) was used. Then, it was subjected to spray drying to obtain a granulated body F001.
The obtained granule F001 was calcined at 700 ° C. for 1 hour in an argon hydrogen atmosphere (hydrogen concentration: 3%), and lithium manganese phosphate containing 2.0% by mass of cellulose nanofiber-derived carbon was supported. A (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle size: 100 nm) was obtained.
Hereinafter, the lithium iron manganese phosphate A is referred to as LMP-A.

[Production Example 002: Production of lithium-based polyanion particles (LMP-C)]
In the production of the lithium-based polyanion particles of Production Example 001, 20.0% by mass of cellulose nanofiber-derived carbon was produced in the same manner as in Production Example 001, except that the amount of cellulose nanofiber added to slurry A001 was changed from 5892 g to 58920 g. Was obtained. Lithium manganese iron phosphate C (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 20.0% by mass, average particle size: 100 nm) was obtained.
Hereinafter, the lithium iron manganese phosphate C is referred to as LMP-C.

[Production Example 003: Production of lithium-based polyanion particles (LMP-F)]
In the production of the lithium-based polyanion particles of Production Example 001, 0.1 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 001 except that the amount of cellulose nanofiber added to slurry A001 was changed to 294 g. Was obtained. Lithium manganese iron phosphate F (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 0.1% by mass, average particle size: 100 nm) was obtained.
Hereinafter, the lithium iron manganese phosphate F is referred to as LMP-F.

[Production Example 004: Production of lithium-based polyanion particles (LMP-G)]
In the production of lithium-based polyanion particles in Production Example 001, 0.05 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 001, except that the amount of cellulose nanofiber added to slurry A001 was changed from 5892 g to 147 g. Was obtained. Lithium manganese iron phosphate G (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 0.05 mass%, average particle size: 100 nm) was obtained.
Hereinafter, the lithium manganese iron phosphate G is referred to as LMP-G.

[Production Example 005: Production of lithium-based polyanion particles (LMP-H)]
In the production of the lithium-based polyanion particles of Production Example 001, 2.0 mass% cellulose was produced in the same manner as in Production Example 001, except that the hydrothermal reaction condition of slurry C001 was changed from 170 ° C. × 1 hour to 200 ° C. × 48 hours. Lithium iron manganese phosphate H (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle diameter: 500 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the lithium iron manganese phosphate H is referred to as LMP-H.

[Production Example 006: Production of lithium-based polyanion particles (LMP-K)]
In the production of the lithium-based polyanion particles of Production Example 001, 2.0% by mass of cellulose was produced in the same manner as in Production Example 001, except that the hydrothermal reaction condition of slurry C001 was changed from 170 ° C. × 1 hour to 140 ° C. × 10 minutes. Lithium iron manganese phosphate K (LiMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle size: 10 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the lithium iron manganese phosphate K is referred to as LMP-K.

[Production Example 007: Production of lithium-based polyanion particles (LMP-L)]
In the production of the lithium-based polyanion particles of Production Example 001, lithium manganese iron phosphate L (LiMn _0.7 Fe _0.3 PO ₄₎ on which carbon is not supported is the same as Production Example 001 except that cellulose nanofibers are not added to the slurry A001. , Amount of carbon = 0.0 mass%, average particle size: 10 nm).
Hereinafter, the lithium iron manganese phosphate L is referred to as LMP-L.

[Production Example 008: Production of lithium-based polyanion particles (LMP-M)]
In the production of the lithium-based polyanion particles of Production Example 001, lithium manganese iron phosphate L (LiMn _0.7 Fe _0.3 PO ₄₎ on which carbon is not supported is the same as Production Example 001 except that cellulose nanofibers are not added to the slurry A001. , Amount of carbon = 0.0 mass%, average particle size: 10 nm).
Hereinafter, the lithium iron manganese phosphate L is referred to as LMP-M.

[Example 001: (Li-NCM-A 60% + LMP-A 40%) complex A-1]
300 minutes of Li-NCM-A obtained in Production Example A and 200 g of LMP-A obtained in Production Example 001 were used at 20 m / s (2600 rpm) for 10 minutes using Mechanofusion (AMS-Lab, manufactured by Hosokawa Micron Corporation). The positive electrode active material composite A-1 for lithium ion secondary batteries formed by combining Li-NCM-A and LMP-A was obtained.

[Example 002: (Li-NCM-A 60% + LMP-F 40%) 99% + graphite 1% complex A-2]
Example 001 except that LMP-A was changed to LMP-F obtained in Production Example 003, and 5 g of graphite (manufactured by Nippon Graphite Co., Ltd., CGB10, average particle size 10 μm) was added to perform the composite treatment. Similarly, the positive electrode active material composite A-2 for lithium ion secondary batteries was obtained.

[Example 003: (Li-NCM-A 60% + LMP-F 40%) 90% + graphite 10% composite A-3]
Example 1 Similarly, the positive electrode active material composite A-3 for lithium ion secondary batteries was obtained.

[Example 004: (Li-NCM-B 60% + LMP-A 40%) complex A-4]
A positive electrode active material composite A-4 for a lithium ion secondary battery was obtained in the same manner as in Example 001 except that Li-NCM-A was changed to Li-NCM-B obtained in Production Example B.

[Example 005: (Li-NCA-A 60% + LMP-A 40%) complex B-1]
A positive electrode active material composite B-1 for a lithium ion secondary battery was obtained in the same manner as in Example 001 except that Li-NCM-A was changed to Li-NCA-A obtained in Production Example C.

[Example 006: (Li-NCA-A 60% + LMP-F 40%) 99% + graphite 1% complex B-2]
Li-NCM-A was changed to Li-NCA-A obtained in Production Example C, LMP-A was changed to LMP-F obtained in Production Example 003, and graphite (manufactured by Nippon Graphite Co., CGB10, A positive electrode active material composite B-2 for a lithium ion secondary battery was obtained in the same manner as in Example 001, except that 5 g (average particle size 10 μm) was added and composite treatment was performed.

[Example 007: (Li-NCA-A 60% + LMP-F 40%) 90% + graphite 10% composite B-3]
Li-NCM-A was changed to Li-NCA-A obtained in Production Example C, LMP-A was changed to LMP-F obtained in Production Example 003, and graphite (manufactured by Nippon Graphite Co., CGB10, A positive electrode active material composite B-3 for a lithium ion secondary battery was obtained in the same manner as in Example 001 except that 55 g was added and the composite treatment was performed.

[Example 008: (Li-NCM-A 30% + Li-NCA-A 30% + LMP-A 40%) 90% + graphite 10% composite AB-1]
A positive electrode active material composite for a lithium ion secondary battery in the same manner as in Example 001, except that Li-NCM-A 300 g was changed to a mixture of Li-NCM-A 150 g and Li-NCA-A 150 g obtained in Production Example C. The body AB-1 was obtained.

[Comparative Example 001: (Li-NCM-A 70% + LMP-A 30%) Mixture A-5]
350 g of Li-NCM-A obtained in Production Example A and 150 g of LMP-A obtained in Production Example 001 were mixed for 5 minutes using a mortar, and Li-NCM-A and LMP-A were mixed. Thus, a positive electrode active material mixture A-5 for a lithium ion secondary battery, which was simply mixed without being combined, was obtained.

[Comparative Example 002: (Li-NCM-A 70% + LMP-L 30%) Complex A-6]
Cathode active material composite A for lithium ion secondary battery in the same manner as in Example 001 except that Li-NCM-A was changed to 350 g and LMP-A 200 g was changed to LMP-L 150 g obtained in Production Example 007. -6 was obtained.

[Comparative Example 003: (Li-NCM-A 99.5% + LMP-A 0.5%) Complex A-7]
A positive electrode active material composite A-7 for a lithium ion secondary battery was obtained in the same manner as in Example 001 except that Li-NCM-A was changed to 497.5 g and LMP-A was changed to 2.5 g.

[Comparative Example 004: (Li-NCM-A 50% + LMP-A 50%) Complex A-8]
A positive electrode active material composite A-8 for a lithium ion secondary battery was obtained in the same manner as in Example 001, except that Li-NCM-A was changed to 250 g and LMP-A was changed to 250 g.

[Comparative Example 005: (Li-NCM-A 70% + LMP-G 30%) Complex A-9]
Cathode active material composite A for lithium ion secondary battery in the same manner as in Example 001 except that Li-NCM-A was changed to 350 g, and LMP-A 200 g was changed to LMP-G 150 g obtained in Production Example 004. -9 was obtained.

[Comparative Example 006: (Li-NCM-A 70% + LMP-C 30%) Complex A-10]
Cathode active material composite A for lithium ion secondary battery in the same manner as in Example 001 except that Li-NCM-A was changed to 350 g, and LMP-A 200 g was changed to LMP-C 150 g obtained in Production Example 002. -10 was obtained.

[Comparative Example 007: (Li-NCM-A 70% + LMP-K 30%) Complex A-11]
Cathode active material composite A for lithium ion secondary battery in the same manner as in Example 001 except that Li-NCM-A was changed to 350 g and LMP-A 200 g was changed to LMP-K 150 g obtained in Production Example 006. -11 was obtained.

[Comparative Example 008: (Li-NCM-A 70% + LMP-H 30%) Complex A-12]
Cathode active material composite A for lithium ion secondary battery in the same manner as in Example 001 except that Li-NCM-A was changed to 350 g and LMP-A 200 g was changed to LMP-H 150 g obtained in Production Example 005. -12 was obtained.

[Comparative Example 009: (Li-NCM-B 70% + LMP-A 30%) Mixture A-13]
A positive electrode active material mixture A-13 for a lithium ion secondary battery was obtained in the same manner as in Comparative Example 001 except that Li-NCM-A was changed to Li-NCM-B obtained in Production Example B.

[Comparative Example 010: (Li-NCA-A 70% + LMP-A 30%) Mixture B-4]
350 g of Li-NCA-A obtained in Production Example C and 150 g of LMP-A obtained in Production Example 001 were mixed for 5 minutes using a mortar, and Li-NCA-A and LMP-A Thus, a positive electrode active material mixture B-4 for a lithium ion secondary battery obtained by simply mixing without obtaining a composite was obtained.

[Comparative Example 011: (Li-NCA-A 70% + LMP-L 30%) Complex B-5]
The same as Example 001 except that Li-NCM-A 300 g was changed to Li-NCA-A 350 g obtained in Production Example C, and LMP-A 200 g was changed to LMP-L 150 g obtained in Production Example 007. Thus, a positive electrode active material composite B-5 for a lithium ion secondary battery was obtained.

[Comparative Example 012: (Li-NCA-A 99.5% + LMP-A 0.5%) Complex B-6]
For lithium ion secondary battery, in the same manner as in Example 001, except that Li-NCM-A 300g was changed to Li-NCA-A 497.5g obtained in Production Example C and LMP-A was changed to 2.5g. A positive electrode active material composite B-6 was obtained.

[Comparative Example 013: (Li-NCA-A 50% + LMP-A 50%) Complex B-7]
Lithium ion secondary battery positive electrode active material composite, except that Li-NCM-A 300 g was changed to Li-NCA-A 250 g obtained in Production Example C and LMP-A was changed to 250 g. Body B-7 was obtained.

[Comparative Example 014: (Li-NCA-A 70% + LMP-G 30%) Complex B-8]
Same as Example 001, except that Li-NCM-A 300 g was changed to Li-NCA-A 350 g obtained in Production Example C, and LMP-A 200 g was changed to LMP-G 150 g obtained in Production Example 004. Thus, a positive electrode active material composite B-8 for a lithium ion secondary battery was obtained.

[Comparative Example 015: (Li-NCA-A 70% + LMP-C 30%) Complex B-9]
The same as Example 001 except that Li-NCM-A 300 g was changed to Li-NCA-A 350 g obtained in Production Example C, and LMP-A 200 g was changed to LMP-C 150 g obtained in Production Example 002. Thus, a positive electrode active material composite B-9 for lithium ion secondary battery was obtained.

[Comparative Example 016: (Li-NCA-A 70% + LMP-K 30%) Complex B-10]
Same as Example 001, except that Li-NCM-A 300 g was changed to Li-NCA-A 350 g obtained in Production Example C, and LMP-A 200 g was changed to LMP-K 150 g obtained in Production Example 006. Thus, a positive electrode active material composite B-10 for a lithium ion secondary battery was obtained.

[Comparative Example 017: (Li-NCA-A 70% + LMP-H 30%) Complex B-11]
The same as Example 001, except that Li-NCM-A 300 g was changed to Li-NCA-A 350 g obtained in Production Example C, and LMP-A 200 g was changed to LMP-H 150 g obtained in Production Example 005. Thus, a positive electrode active material composite B-11 for a lithium ion secondary battery was obtained.

[Production Example 101: Production of lithium-based polyanion particles (LMS-A)]
LiOH · H ₂ O 428g, was obtained _{Na 4 SiO 4 · nH 2 O} 1397g, cellulose nanofibers (Wma-10002, Sugino Machine Ltd.) slurry A101 by mixing ultrapure water 3.75L to 2946G. To this slurry A101, 392 g of FeSO ₄ .7H ₂ O, 793 g of MnSO ₄ .5H ₂ O, and 53 g of Zr (SO ₄ ) ₂ .4H ₂ O were added and mixed to obtain slurry B101. At this time, the molar ratio (iron compound: manganese compound: zirconium compound) of FeSO ₄ , MnSO ₄ and Zr (SO ₄ ) ₂ added was 28: 66: 3. Next, the obtained slurry B101 was put into an autoclave and subjected to a hydrothermal reaction at 170 ° C. for 3 hours. The pressure in the autoclave was 0.4 MPa. The produced crystal was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. The washed crystal was lyophilized at −50 ° C. for 12 hours to obtain Complex C101. 500 g of the obtained composite C101 was collected, and 500 mL of water was added thereto to obtain a slurry D101. Next, the obtained slurry D101 was subjected to dispersion treatment with an ultrasonic stirrer (T25, manufactured by IKA) for 1 minute to obtain a slurry E101 that was uniformly colored as a whole. The obtained slurry E101 was spray dried using a spray drying apparatus (MDL-050M, manufactured by Fujisaki Electric Co., Ltd.), and then fired at 650 ° C. for 1 hour in an argon hydrogen atmosphere (hydrogen concentration: 3%). Lithium iron manganese silicate A (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , carbon content = 2.0 mass%, average particle size: 50 nm )
Hereinafter, the lithium iron manganese silicate A is referred to as LMS-A.

[Production Example 102: Production of lithium-based polyanion particles (LMS-B)]
In the production of lithium-based polyanion particles in Production Example 101, 4.0 mass% glucose-derived carbon was supported in the same manner as Production Example 101 except that 2946 g of cellulose nanofiber added to slurry A101 was changed to 50 g of glucose. Lithium iron manganese silicate B (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 2.0 mass%, average particle size: 50 nm) was obtained.
Hereinafter, the lithium iron manganese silicate B is referred to as LMS-B.

[Production Example 103: Production of lithium-based polyanion particles (LMS-C)]
In the production of the lithium-based polyanion particles of Production Example 101, 18.0% by mass of cellulose nanofiber-derived carbon was produced in the same manner as in Production Example 101, except that the amount of cellulose nanofiber added to slurry A101 was changed to 2946 g to 29460 g. Lithium iron silicate lithium C (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 20.0 mass%, average particle diameter: 50 nm) was obtained.
Hereinafter, the lithium iron silicate manganese C is referred to as LMS-C.

[Production Example 104: Production of lithium-based polyanion particles (LMS-D)]
In the production of lithium-based polyanion particles in Production Example 101, 12.0% by mass of cellulose nanofiber-derived carbon was produced in the same manner as in Production Example 101, except that the amount of cellulose nanofiber added to slurry A101 was changed to 2946 g to 17676 g. Lithium iron silicate lithium D (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 12.0 mass%, average particle diameter: 50 nm) was obtained.
Hereinafter, the lithium iron silicate manganese D is referred to as LMS-D.

[Production Example 105: Production of lithium-based polyanion particles (LMS-E)]
In the production of lithium-based polyanion particles in Production Example 101, 1.0 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 101, except that the addition amount of 2946 g of cellulose nanofibers to Slurry A101 was changed to 1473 g. Lithium iron silicate lithium E (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 1.0 mass%, average particle size: 50 nm) was obtained.
Hereinafter, the lithium iron silicate manganese E is referred to as LMS-E.

[Production Example 106: Production of lithium-based polyanion particles (LMS-F)]
In the production of lithium-based polyanion particles in Production Example 101, 0.1 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 101, except that the addition amount of 2946 g of cellulose nanofibers to slurry A101 was changed to 147 g. Lithium iron silicate lithium F (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 0.1 mass%, average particle diameter: 50 nm) was obtained.
Hereinafter, the lithium iron manganese silicate F is referred to as LMS-F.

[Production Example 107: Production of lithium-based polyanion particles (LMS-G)]
In the production of lithium-based polyanion particles in Production Example 101, 0.05 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 101, except that the amount of cellulose nanofiber added to slurry A101 was changed to 2946 g to 74 g. Lithium iron silicate lithium G (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 0.05 mass%, average particle size: 50 nm) was obtained.
Hereinafter, the lithium iron silicate manganese G is referred to as LMS-G.

[Production Example 108: Production of lithium-based polyanion particles (LMS-H)]
In the production of the lithium-based polyanion particles of Production Example 101, 2.0% by mass of cellulose was produced in the same manner as Production Example 101, except that the hydrothermal reaction condition of slurry B101 was changed from 170 ° C. × 3 hours to 200 ° C. × 48 hours. Lithium iron manganese silicate H (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 2.0 mass%, average particle size: 500 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the lithium iron manganese silicate H is referred to as LMS-H.

[Production Example 109: Production of lithium-based polyanion particles (LMS-I)]
In the production of the lithium-based polyanion particles of Production Example 101, 2.0% by mass of cellulose was produced in the same manner as in Production Example 101, except that the hydrothermal reaction condition of slurry B101 was changed from 170 ° C. × 3 hours to 200 ° C. × 3 hours. Lithium iron silicate lithium I (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 2.0 mass%, average particle diameter: 100 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the lithium iron manganese silicate I is referred to as LMS-I.

[Production Example 110: Production of lithium-based polyanion particles (LMS-J)]
In the production of the lithium-based polyanion particles of Production Example 101, 2.0% by mass of cellulose was produced in the same manner as in Production Example 101, except that the hydrothermal reaction condition of slurry B101 was changed from 170 ° C. × 3 hours to 140 ° C. × 1 hour. Lithium iron silicate lithium J (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 2.0 mass%, average particle size: 30 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the lithium iron manganese silicate J is referred to as LMS-J.

[Production Example 111: Production of lithium-based polyanion particles (LMS-K)]
In the production of the lithium-based polyanion particles of Production Example 101, 2.0% by mass of cellulose was produced in the same manner as in Production Example 101, except that the hydrothermal reaction condition of the slurry B101 was changed from 170 ° C. × 3 hours to 120 ° C. × 10 minutes. Lithium iron silicate lithium K (Li ₂ Fe _0.28 Mn _0.66 Zr _0.03 SiO ₄ , amount of carbon = 2.0 mass%, average particle size: 10 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the lithium iron manganese silicate K is referred to as LMS-K.

[Production Example 112: Production of lithium-based polyanion particles (LMS-L)]
In the production of the lithium-based polyanion particles of Production Example 101, except that cellulose nanofibers are not added to the slurry A101, in the same manner as in Production Example 101, lithium iron manganese silicate L (Li ₂ Fe _0.28 Mn _0.66 on which carbon is not supported). Zr _0.03 SiO ₄ , amount of carbon = 0.0 mass%, average particle diameter: 50 nm).
Hereinafter, the lithium iron manganese silicate L is referred to as LMS-L.

[Example 101: (Li-NCM-A 70% + LMS-A 30%) complex C-1]
350 g of Li-NCM-A obtained in Production Example A and 150 g of LMS-A obtained in Production Example 101 were used at 20 m / s (2600 rpm) for 10 minutes using Mechanofusion (AMS-Lab, manufactured by Hosokawa Micron Corporation). The positive electrode active material composite C-1 for lithium ion secondary batteries was obtained by performing the composite treatment.

[Example 102: (Li-NCM-A 70% + LMS-B 30%) complex C-2]
A positive electrode active material composite C-2 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that LMS-A was changed to LMS-B obtained in Production Example 102.

[Example 103: (Li-NCM-A 90% + LMS-A 10%) complex C-3]
A positive electrode active material composite C-3 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to 450 g and LMS-A was changed to 50 g.

[Example 104: (Li-NCM-A 90% + LMS-D 10%) complex C-4]
Lithium ion secondary was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to 450 g, LMS-A was changed to LMS-D obtained in Production Example 104, and the composite treatment amount was changed to 50 g. A positive electrode active material composite C-4 for a battery was obtained.

[Example 105: (Li-NCM-A 60% + LMS-A 40%) complex C-5]
A positive electrode active material composite C-5 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to 300 g and LMS-A was changed to 200 g.

[Example 106: (Li-NCM-A 70% + LMS-E 30%) complex C-6]
Except having changed LMS-A into LMS-E obtained by manufacture example 105, it carried out similarly to Example 101, and obtained the positive electrode active material composite C-6 for lithium ion secondary batteries.

[Example 107: (Li-NCM-A 70% + LMS-I 30%) complex C-7]
A positive electrode active material composite C-7 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that LMS-A was changed to LMS-I obtained in Production Example 109.

[Example 108: (Li-NCM-A 70% + LMS-J 30%) complex C-8]
Except having changed LMS-A into LMS-J obtained by manufacture example 110, it carried out similarly to Example 101, and obtained the positive electrode active material composite C-8 for lithium ion secondary batteries.

[Example 109: (NCM-A 70% + LMS-F 30%) complex C-9]
Except having changed LMS-A into LMS-F obtained by manufacture example 106, it carried out similarly to Example 101, and obtained the positive electrode active material composite C-9 for lithium ion secondary batteries.

[Example 110: (Li-NCM-A 60% + LMS-F 40%) 99% + graphite 1% composite C-10]
Li-NCM-A 350 g was changed to 300 g, LMS-A 150 g was changed to LMS-F 200 g obtained in Production Example 106, and 5 g of graphite (Nippon Graphite Co., Ltd., CGB10, average particle size 10 μm) was added. A positive electrode active material composite C-10 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that the composite treatment was performed.

[Example 111: (Li-NCM-A 60% + LMS-F 40%) 90% + graphite 10% composite C-11]
350 g of Li-NCM-A was changed to 300 g, 150 g of LMS-A was changed to 200 g of LMS-F obtained in Production Example 106, and 55 g of graphite (manufactured by Nippon Graphite Co., Ltd., CGB10, average particle size 10 μm) was added. A positive electrode active material composite C-11 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that the composite treatment was performed.

[Example 112: (Li-NCM-A 70% + LMS-F 30%) 99% + graphene 1% complex C-12]
Except that LMS-A was changed to LMS-F obtained in Production Example 106, and graphene (XG sciences, xGNP, average particle size 30 μm) 5 g was added and subjected to a composite treatment, and Example 101 was performed. Similarly, the positive electrode active material composite C-12 for lithium ion secondary batteries was obtained.

[Example 113: (Li-NCM-A 70% + LMP-F 30%) 99% + acetylene black 1% complex C-13]
Example except that LMS-A was changed to LMS-F obtained in Production Example 106, and further 5 g of acetylene black (DEN-100, LI-100, average particle size 50 nm) was added and subjected to a composite treatment. In the same manner as in 101, a positive electrode active material composite C-13 for a lithium ion secondary battery was obtained.

[Example 114: (Li-NCM-A 70% + LMS-F 30%) 99% + polyaniline 1% complex C-14]
In the same manner as in Example 101 except that LMS-A was changed to LMS-F obtained in Production Example 106, and 5 g of polyaniline (manufactured by Sigma-Aldrich) was added to perform the composite treatment, lithium ion A positive electrode active material composite C-14 for secondary battery was obtained.

[Example 115: (Li-NCM-B 70% + LMP-A 30%) complex C-15]
A positive electrode active material composite C-15 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to Li-NCM-B obtained in Production Example B.

[Example 116: (Li-NCA-A 70% + LMS-A 30%) complex D-1]
A positive electrode active material composite D-1 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to Li-NCA-A obtained in Production Example C.

[Example 117: (Li-NCA-A 70% + LMS-B 30%) complex D-2]
Li-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-B obtained in Production Example 102. A positive electrode active material composite D-2 for an ion secondary battery was obtained.

[Example 118: (Li-NCA-A 90% + LMS-A 10%) complex D-3]
Lithium ion secondary battery positive electrode active in the same manner as in Example 101 except that Li-NCM-A 350 g was changed to Li-NCA-A 450 g obtained in Production Example C and LMS-A was changed to 50 g. A substance complex D-3 was obtained.

[Example 119: (Li-NCA-A 90% + LMS-D 10%) complex D-4]
Same as Example 101 except that 350 g of Li-NCM-A was changed to 450 g of Li-NCA-A obtained in Production Example C, and 150 g of LMS-A was changed to 50 g of LMS-D obtained in Production Example 104. Thus, a positive electrode active material composite D-4 for a lithium ion secondary battery was obtained.

[Example 120: (Li-NCA-A 60% + LMS-A 40%) complex D-5]
Lithium ion secondary battery positive electrode active in the same manner as in Example 101, except that Li-NCM-A 350 g was changed to Li-NCA-A 300 g obtained in Production Example C, and LMS-A was changed to 200 g. A substance complex D-5 was obtained.

[Example 121: (Li-NCA-A 70% + LMS-E 30%) complex D-6]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-E obtained in Production Example 105. A positive electrode active material composite D-6 for ion secondary battery was obtained.

[Example 122: (Li-NCA-A 70% + LMS-I 30%) complex D-7]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-I obtained in Production Example 109. A positive electrode active material composite D-7 for ion secondary battery was obtained.

[Example 123: (Li-NCA-A 70% + LMS-J 30%) complex D-8]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-J obtained in Production Example 110. A positive electrode active material composite D-8 for ion secondary battery was obtained.

[Example 124: (Li-NCA-A 70% + LMS-F 30%) complex D-9]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-F obtained in Production Example 106. A positive electrode active material composite D-9 for ion secondary battery was obtained.

[Example 125: (Li-NCA-A 60% + LMS-F 40%) 99% + graphite 1% complex D-10]
350 g of Li-NCM-A was changed to 300 g of Li-NCA-A obtained in Production Example C, 150 g of LMS-A was changed to 200 g of LMS-F obtained in Production Example 106, and graphite (Nippon Graphite Co., Ltd.) Manufactured, CGB10, average particle size 10 μm) was added in the same manner as in Example 101, except that 5 g was added to obtain a positive electrode active material composite D-10 for a lithium ion secondary battery.

[Example 126: (Li-NCA-A 60% + LMS-F 40%) 90% + graphite 10% composite D-11]
350 g of Li-NCM-A was changed to 300 g of Li-NCA-A obtained in Production Example C, 150 g of LMS-A was changed to 200 g of LMS-F obtained in Production Example 106, and graphite (Nippon Graphite Co., Ltd.) Manufactured, CGB10, average particle size 10 μm) was added in the same manner as in Example 101 except that the composite treatment was performed to obtain a positive electrode active material composite D-11 for a lithium ion secondary battery.

[Example 127: (Li-NCA-A 70% + LMS-F 30%) 99% + graphene 1% complex D-12]
Li-NCM-A was changed to Li-NCA-A obtained in Production Example C, LMS-A was changed to LMS-F obtained in Production Example 106, and graphene (XGsciences, xGNP, average A positive electrode active material composite D-12 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that 5 g (particle diameter 30 μm) was added and the composite treatment was performed.

[Example 128: (Li-NCA-A 70% + LMP-F 30%) 99% + acetylene black 1% complex D-13]
Li-NCM-A was changed to Li-NCA-A obtained in Production Example C, LMS-A was changed to LMS-F obtained in Production Example 106, and acetylene black (manufactured by Denka, LI- 100, average particle size 50 nm) A positive electrode active material composite D-13 for a lithium ion secondary battery was obtained in the same manner as in Example 101, except that 5 g was added and the composite treatment was performed.

[Example 129: (Li-NCM-A 70% + LMS-F 30%) 99% + polyaniline 1% complex D-14]
Li-NCM-A was changed to Li-NCA-A obtained in Production Example C, LMS-A was changed to LMS-F obtained in Production Example 106, and 5 g of polyaniline (manufactured by Sigma-Aldrich) was added. A positive electrode active material composite D-14 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that the composite treatment was performed by adding.

[Example 130: (Li-NCM-A35% + Li-NCA-A35% + LMS-A30%) complex CD-1]
A positive electrode active material composite for a lithium ion secondary battery in the same manner as in Example 101 except that 350 g of Li-NCM-A was changed to a mixture of Li-NCM-A175 g and Li-NCA-A175 g obtained in Production Example C. The body CD-1 was obtained.

[Comparative Example 101: (Li-NCM-A 70% + LMS-A 30%) Mixture C-16]
The Li-NCM-A 350 g obtained in Production Example A and the LMS-A 150 g obtained in Production Example 101 were mixed to obtain a positive electrode active material mixture C-16 for a lithium ion secondary battery.

[Comparative Example 102: (Li-NCM-A 70% + LMS-L 30%) Complex C-17]
Except having changed LMS-A into LMS-L obtained by manufacture example 112, it carried out similarly to Example 101, and obtained the positive electrode active material composite C-17 for lithium ion secondary batteries.

[Comparative Example 103: (Li-NCM-A 99.5% + LMS-A 0.5%) Complex C-18]
A positive electrode active material composite C-18 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to 497.5 g and LMS-A was changed to 2.5 g.

[Comparative Example 104: (Li-NCM-A 50% + LMS-A 50%) Complex C-19]
A positive electrode active material composite C-19 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that Li-NCM-A was changed to 250.0 g and LMS-A was changed to 250.0 g.

[Comparative Example 105: (Li-NCM-A 70% + LMS-G 30%) Complex C-20]
A positive electrode active material composite C-20 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that LMS-A was changed to LMS-G obtained in Production Example 107.

[Comparative Example 106: (Li-NCM-A 70% + LMS-C 30%) Complex C-21]
A positive electrode active material composite C-21 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that LMS-A was changed to LMS-C obtained in Production Example 103.

[Comparative Example 107: (Li-NCM-A 70% + LMS-K 30%) Complex C-22]
A positive electrode active material composite C-22 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that LMS-A was changed to LMS-K obtained in Production Example 111.

[Comparative Example 108: (Li-NCM-A 70% + LMS-H 30%) Complex C-23]
A positive electrode active material composite C-23 for a lithium ion secondary battery was obtained in the same manner as in Example 101 except that LMS-A was changed to LMS-H obtained in Production Example 108.

[Comparative Example 109: (Li-NCM-B 70% + LMS-A 30%) Mixture C-24]
A positive electrode active material mixture C-24 for a lithium ion secondary battery was obtained in the same manner as in Comparative Example 101 except that Li-NCM-A was changed to Li-NCM-B obtained in Production Example B.

[Comparative Example 110: (Li-NCA-A 70% + LMS-A 30%) Mixture D-15]
Li-NCA-A 350 g obtained in Production Example C and LMS-A 150 g obtained in Production Example 101 were mixed to obtain a positive electrode active material mixture D-15 for a lithium ion secondary battery.

[Comparative Example 111: (Li-NCA-A 70% + LMS-L 30%) Complex D-16]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-L obtained in Production Example 112. A positive electrode active material composite D-16 for ion secondary battery was obtained.

[Comparative Example 112: (Li-NCA-A 99.5% + LMS-A 0.5%) Complex D-17]
Lithium ion secondary was performed in the same manner as in Example 101 except that 350 g of Li-NCM-A was changed to 497.5 g of Li-NCA-A obtained in Production Example C, and LMS-A was changed to 2.5 g. A positive electrode active material composite D-17 for batteries was obtained.

[Comparative Example 113: (Li-NCA-A 50% + LMS-A 50%) Complex D-18]
Lithium ion secondary battery was performed in the same manner as in Example 101 except that 350 g of Li-NCM-A was changed to 250.0 g of Li-NCA-A obtained in Production Example C, and LMS-A was changed to 250.0 g. Positive electrode active material composite D-18 was obtained.

[Comparative Example 114: (Li-NCA-A 70% + LMS-G 30%) Complex D-19]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-G obtained in Production Example 107. A positive electrode active material composite D-19 for ion secondary battery was obtained.

[Comparative Example 115: (Li-NCA-A 70% + LMS-C 30%) Complex D-20]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-C obtained in Production Example 103. A positive electrode active material composite D-20 for ion secondary battery was obtained.

[Comparative Example 116: (Li-NCA-A 70% + LMS-K 30%) Complex D-21]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-K obtained in Production Example 111. A positive electrode active material composite D-21 for ion secondary battery was obtained.

[Comparative Example 117: (Li-NCA-A 70% + LMS-H 30%) Complex D-22]
Lithium-NCM-A was changed to Li-NCA-A obtained in Production Example C, and LMS-A was changed to LMS-H obtained in Production Example 108. A positive electrode active material composite D-22 for ion secondary battery was obtained.

[Production Example D: Production of secondary particles of Na-NCM composite oxide (Na-NCM-A)]
After mixing 263 g of nickel sulfate hexahydrate, 281 g of cobalt sulfate heptahydrate, 241 g of manganese sulfate pentahydrate, and 3 L of water so that the molar ratio of Ni: Co: Mn is 1: 1: 1 Then, 25% aqueous ammonia was added dropwise to the mixed solution at a dropping rate of 300 mL / min to obtain a slurry A4 containing a metal composite hydroxide having a pH of 11.
Next, the slurry A4 was filtered and dried to obtain a metal composite hydroxide mixture B4. Then, 53 g of sodium carbonate was mixed with the mixture B4 with a ball mill to obtain a powder mixture C4.
The obtained powder mixture C4 was calcined by calcination at 800 ° C. for 5 hours in an air atmosphere, and then baked in the air atmosphere at 800 ° C. for 10 hours as the main calcination to obtain a Na—NCM composite oxide (NaNi _1/3 Co _1/3 Mn _1/3 O ₂ ) secondary particles D were obtained. (Average particle size of secondary particles: 10 μm)
Hereinafter, the Na-NCM composite oxide D is referred to as Na-NCM-A.

[Production Example E: Production of secondary particles of Na—NCM composite oxide (Na—NCM-B)]
In the production of the Na-NCM composite oxide (1) of Production Example D, the amount of nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate pentahydrate nickel sulfate hexahydrate, 473 g, 169 g, 145 g (Ni: Co: Mn molar ratio = 6: 2: 2), except that lithium hydroxide monohydrate 22 g was mixed instead of lithium carbonate mixed in the metal composite hydroxide mixture In the same manner as in Production Example D, secondary particles E of Na-NCM composite oxide (NaNi _1/3 Co _1/3 Mn _1/3 O ₂ ) were obtained. (Average particle size of secondary particles: 10 μm)
Hereinafter, the Na-NCM composite oxide E is referred to as Na-NCM-B.

[Production Example F: Production of secondary particles of Na—NCA-based composite oxide (Na—NCA-A)]
530 g of sodium carbonate, 950 g of nickel carbonate, 150 g of cobalt carbonate, 58 g of aluminum carbonate, and 3 L of water were mixed so that the molar ratio of Na: Ni: Co: Al was 1: 0.8: 0.15: 0.05. Then, it was mixed with a ball mill to obtain a powder mixture A6. The obtained powder mixture A6 was calcined by calcination at 800 ° C. for 5 hours in an air atmosphere and then pulverized, followed by calcination at 800 ° C. for 24 hours in an air atmosphere as the main calcination, and an NCA-based composite oxide (NaNi _{0. 8} Co _0.15 Al _0.05 O ₂ ) secondary particles E were obtained. (Average particle size of secondary particles: 10 μm)
Hereinafter, the secondary particles E of the Na-NCA composite oxide are referred to as Na-NCA-A.

[Production Example 201: Production of sodium-based polyanion particles (NMP-A)]
A slurry A201 was obtained by mixing 600 g of NaOH, 9 L of water, and 2946 g of cellulose nanofiber (Wma-1202, manufactured by Sugino Machine Co., Ltd.). Next, 577 g of 85% phosphoric acid aqueous solution was dropped at 35 mL / min while stirring the obtained slurry A201 at a temperature of 25 ° C. for 5 minutes, followed by stirring at a speed of 400 rpm for 12 hours. A slurry B201 was obtained. This slurry B201 contained 3.00 mol of sodium per mol of phosphorus. The obtained slurry B201 is purged with nitrogen gas to adjust the dissolved oxygen concentration to 0.5 mg / L. Then, 819 g of MnSO ₄ .5H ₂ O and 417 g of FeSO ₄ .7H ₂ O are added to obtain slurry C201. Obtained. Next, the obtained slurry C201 was put into an autoclave purged with nitrogen gas, and a hydrothermal reaction was performed at 170 ° C. for 3 hours. The pressure in the autoclave was 1.4 MPa. The produced crystal was filtered, and then washed with 12 parts by mass of water with respect to 1 part by mass of the crystal. The washed crystal was lyophilized at −50 ° C. for 12 hours to obtain a complex D201. 500 g of the obtained composite D201 was collected, and 0.5 L of water was added thereto to obtain a slurry E201. Next, the obtained slurry E201 was subjected to dispersion treatment with an ultrasonic stirrer (T25, manufactured by IKA) for 1 minute to obtain slurry F201 having a uniform color throughout. The obtained slurry F201 was spray dried using a spray drying apparatus (MDL-050M, manufactured by Fujisaki Electric Co., Ltd.), and then fired at 700 ° C. for 1 hour in an argon hydrogen atmosphere (hydrogen concentration: 3%). , 2.0 wt% of the cellulose nanofiber is carbon supported from iron phosphate, manganese, sodium _{a (NaMn 0.7 Fe 0.3 PO 4} , the amount of carbon = 2.0% by weight, average particle diameter: 100 nm) to give the .
Hereinafter, the sodium iron manganese phosphate A is referred to as NMP-A.

[Production Example 202: Production of sodium-based polyanion particles (NMP-B)]
In the production of sodium-based polyanion particles in Production Example 201, 2.0 mass% of carbon derived from glucose was supported in the same manner as in Production Example 201 except that 2946 g of cellulose nanofiber added to slurry A201 was changed to 63 g of glucose. In addition, sodium manganese iron phosphate B (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle size: 100 nm) was obtained.
Hereinafter, the sodium manganese iron phosphate B is referred to as NMP-B.

[Production Example 203: Production of sodium-based polyanion particles (NMP-C)]
In the production of sodium-based polyanion particles in Production Example 201, 18.0% by mass of cellulose nanofiber-derived carbon was produced in the same manner as in Production Example 201, except that the amount of cellulose nanofiber added to slurry A201 was changed from 2946 g to 29460 g. Was obtained, and thus iron manganese manganese phosphate C (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 20.0 mass%, average particle size: 100 nm) was obtained.
Hereinafter, the sodium manganese iron phosphate C is referred to as NMP-C.

[Production Example 204: Production of sodium-based polyanion particles (NMP-D)]
In the production of sodium-based polyanion particles of Production Example 201, 12.0% by mass of cellulose nanofiber-derived carbon was produced in the same manner as Production Example 201, except that the addition amount of 2946 g of cellulose nanofibers to slurry A201 was changed to 17676 g. Was obtained. Thus, manganese iron phosphate D (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 12.0% by mass, average particle size: 100 nm) was obtained.
Hereinafter, the sodium manganese iron phosphate D is referred to as NMP-D.

[Production Example 205: Production of sodium-based polyanion particles (NMP-E)]
In the production of sodium-based polyanion particles in Production Example 201, 1.0 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 201, except that the amount of cellulose nanofiber added to slurry A201 was changed to 2946 g. Was obtained. Thus, manganese iron phosphate sodium E (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 1.0% by mass, average particle size: 100 nm) was obtained.
Hereinafter, the sodium manganese iron phosphate E is referred to as NMP-E.

[Production Example 206: Production of sodium-based polyanion particles (NMP-F)]
In the production of sodium-based polyanion particles in Production Example 201, 0.1 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 201, except that the amount of cellulose nanofiber added to slurry A201 was changed to 2946 g. Was obtained, and thus manganese iron phosphate sodium F (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 0.1 mass%, average particle size: 100 nm) was obtained.
Hereinafter, the sodium manganese iron phosphate F is referred to as NMP-F.

[Production Example 207: Production of sodium-based polyanion particles (NMP-G)]
In the production of sodium-based polyanion particles in Production Example 201, 0.05 mass% of carbon derived from cellulose nanofibers was produced in the same manner as in Production Example 201 except that the amount of cellulose nanofiber added to slurry A201 was changed to 2946 g to 74 g. Was obtained, and thus, manganese iron phosphate sodium G (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 0.05 mass%, average particle size: 100 nm) was obtained.
Hereinafter, the sodium manganese iron phosphate G is referred to as NMP-G.

[Production Example 208: Production of sodium-based polyanion particles (NMP-H)]
In the production of sodium-based polyanion particles in Production Example 201, 2.0 mass% cellulose was produced in the same manner as in Production Example 201, except that the hydrothermal reaction conditions of slurry C201 were changed from 170 ° C. × 3 hours to 200 ° C. × 48 hours. Sodium manganese iron phosphate H (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle size: 500 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the sodium manganese iron phosphate H is referred to as NMP-H.

[Production Example 209: Production of sodium-based polyanion particles (NMP-I)]
In the production of sodium-based polyanion particles of Production Example 201, 2.0 mass% cellulose was produced in the same manner as Production Example 201, except that the hydrothermal reaction conditions of slurry C201 were changed from 170 ° C. × 3 hours to 200 ° C. × 3 hours. Sodium manganese iron phosphate I (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle size: 150 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the sodium manganese iron phosphate I is referred to as NMP-I.

[Production Example 210: Production of sodium-based polyanion particles (NMP-J)]
In the production of sodium-based polyanion particles in Production Example 201, 2.0 mass% cellulose was produced in the same manner as in Production Example 201, except that the hydrothermal reaction conditions of slurry C201 were changed from 170 ° C. × 3 hours to 140 ° C. × 3 hours. Sodium manganese iron phosphate J (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle size: 70 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the sodium manganese iron phosphate J is referred to as NMP-J.

[Production Example 211: Production of sodium-based polyanion particles (NMP-K)]
In the production of sodium-based polyanion particles of Production Example 201, 2.0 mass% cellulose was produced in the same manner as Production Example 201, except that the hydrothermal reaction conditions of the slurry C201 were changed from 170 ° C. × 3 hours to 140 ° C. × 10 minutes. Sodium manganese iron phosphate K (NaMn _0.7 Fe _0.3 PO ₄ , amount of carbon = 2.0 mass%, average particle diameter: 10 nm) on which carbon derived from nanofibers was supported was obtained.
Hereinafter, the sodium manganese iron phosphate K is referred to as NMP-K.

[Production Example 212: Production of sodium-based polyanion particles (NMP-L)]
In the production of sodium-based polyanion particles in Production Example 201, sodium manganese iron phosphate L (NaMn _0.7 Fe _0.3 PO ₄₎ on which carbon is not supported is the same as Production Example 201 except that cellulose nanofibers are not added to slurry A201. , Amount of carbon = 0.0 mass%, average particle size: 10 nm).
Hereinafter, the sodium manganese iron phosphate L is referred to as NMP-L.

[Example 201: (Na-NCM-A 70% + NMP-A 30%) complex E-1]
350 minutes of Na-NCM-A obtained in Production Example D and 150 g of NMP-A obtained in Production Example 201 were used at 20 m / s (2600 rpm) for 10 minutes using Mechanofusion (AMS-Lab, manufactured by Hosokawa Micron Corporation). The positive electrode active material composite body E-1 for sodium ion secondary batteries was obtained.

[Example 202: (Na-NCM-A 70% + NMP-B 30%) complex E-2]
A positive electrode active material composite E-2 for sodium ion secondary batteries was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-B obtained in Production Example 202.

[Example 203: (Na-NCM-A 90% + NMP-A 10%) complex E-3]
A positive electrode active material composite E-3 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that Na-NCM-A was changed to 450 g and NMP-A was changed to 50 g.

[Example 204: (Na-NCM-A 90% + NMP-D 10%) complex E-4]
Sodium ion secondary in the same manner as in Example 201 except that Na-NCM-A was changed to 450 g, NMP-A was changed to NMP-D obtained in Production Example 204, and the combined treatment amount was changed to 50 g. A positive electrode active material composite E-4 for a battery was obtained.

[Example 205: (Na-NCM-A 60% + NMP-A 40%) complex E-5]
A positive electrode active material composite E-5 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that Na-NCM-A was changed to 300 g and NMP-A was changed to 200 g.

[Example 206: (Na-NCM-A 70% + NMP-E 30%) complex E-6]
A positive electrode active material composite E-6 for a sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-E obtained in Production Example 205.

[Example 207: (Na-NCM-A 70% + NMP-I 30%) complex E-7]
A positive electrode active material composite E-7 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-I obtained in Production Example 209.

[Example 208: (Na-NCM-A 70% + NMP-J 30%) complex E-8]
A positive electrode active material composite E-8 for sodium ion secondary batteries was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-J obtained in Production Example 210.

[Example 209: (Na-NCM-A 70% + NMP-F 30%) complex E-9]
A positive electrode active material composite E-9 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-F obtained in Production Example 206.

[Example 210: (Na-NCM-A 60% + NMP-F 40%) 99% + graphite 1% complex E-10]
350 g of Na-NCM-A was changed to 300 g, 150 g of NMP-A was changed to 200 g of NMP-F obtained in Production Example 206, and 5 g of graphite (manufactured by Nippon Graphite Co., Ltd., CGB10, average particle size 10 μm) was added. A positive electrode active material composite E-10 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that the composite treatment was performed.

[Example 211: (Na-NCM-A 60% + NMP-F 40%) 90% + graphite 10% complex E-11]
350 g of Na-NCM-A was changed to 300 g, 150 g of NMP-A was changed to 200 g of NMP-F obtained in Production Example 206, and 55 g of graphite (manufactured by Nippon Graphite Co., Ltd., CGB10, average particle size 10 μm) was added. A positive electrode active material composite E-11 for sodium ion secondary batteries was obtained in the same manner as in Example 201 except that the composite treatment was performed.

[Example 212: (Na-NCM-A 70% + NMP-F 30%) 99% + graphene 1% complex E-12]
Except that NMP-A was changed to NMP-F obtained in Production Example 206, and graphene (XG sciences, xGNP, average particle size 30 μm) 5 g was added and subjected to a composite treatment, and Example 201 was performed. Similarly, the positive electrode active material composite E-12 for sodium ion secondary batteries was obtained.

[Example 213: (Na-NCM-A 70% + NMP-F 30%) 99% + acetylene black 1% complex E-13]
Example except that NMP-A was changed to NMP-F obtained in Production Example 206, and 5 g of acetylene black (DEN-100, LI-100, average particle size: 50 nm) was added to carry out the composite treatment. In the same manner as in 201, a positive electrode active material composite E-13 for sodium ion secondary battery was obtained.

[Example 214: (Na-NCM-A 70% + NMP-F 30%) 99% + polyaniline 1% complex E-14]
In the same manner as in Example 201 except that NMP-A was changed to NMP-F obtained in Production Example 206, and 5 g of polyaniline (manufactured by Sigma-Aldrich) was added to perform the complexing treatment, A positive electrode active material composite E-14 for a secondary battery was obtained.

[Example 215: (Na-NCM-B 70% + NMP-A 30%) complex E-15]
A positive electrode active material composite E-15 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that Na-NCM-A was changed to Na-NCM-B obtained in Production Example E.

[Example 216: (Na-NCA-A 70% + NMP-A 30%) complex F-1]
A positive electrode active material composite F-1 for a sodium ion secondary battery was obtained in the same manner as in Example 201 except that Na-NCM-A was changed to Na-NCA-A obtained in Production Example F.

[Example 217: (Na-NCA-A 70% + NMP-B 30%) complex F-2]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-B obtained in Production Example 202. A positive electrode active material composite F-2 for an ion secondary battery was obtained.

[Example 218: (Na-NCA-A 90% + NMP-A 10%) complex F-3]
In the same manner as in Example 201, except that 350 g of Na-NCM-A was changed to 450 g of Na-NCA-A obtained in Production Example F and NMP-A was changed to 50 g, the positive electrode active for sodium ion secondary battery A substance complex F-3 was obtained.

[Example 219: (Na-NCA-A 90% + NMP-D 10%) complex F-4]
Same as Example 201 except that 350 g of Na-NCM-A was changed to 450 g of Na-NCA-A obtained in Production Example F, and 150 g of NMP-A was changed to 50 g of NMP-D obtained in Production Example 204. Thus, a positive electrode active material composite F-4 for sodium ion secondary battery was obtained.

[Example 220: (Na-NCA-A 60% + NMP-A 40%) complex F-5]
In the same manner as in Example 201, except that 350 g of Na-NCM-A was changed to 300 g of Na-NCA-A obtained in Production Example F and NMP-A was changed to 200 g, the positive electrode active for sodium ion secondary battery A substance complex F-5 was obtained.

[Example 221: (Na-NCA-A 70% + NMP-E 30%) complex F-6]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-E obtained in Production Example 205. A positive electrode active material composite F-6 for ion secondary battery was obtained.

[Example 222: (Na-NCA-A 70% + NMP-I 30%) complex F-7]
In the same manner as in Example 201 except that Na-NCM-A was changed to Na-NCA-A obtained in Production Example F and NMP-A was changed to NMP-I obtained in Production Example 209, sodium A positive electrode active material composite F-7 for ion secondary battery was obtained.

[Example 223: (Na-NCA-A 70% + NMP-J 30%) complex F-8]
In the same manner as in Example 201 except that Na-NCM-A was changed to Na-NCA-A obtained in Production Example F and NMP-A was changed to NMP-J obtained in Production Example 210, sodium A positive electrode active material composite F-8 for ion secondary battery was obtained.

[Example 224: (Na-NCA-A 70% + NMP-F 30%) complex F-9]
In the same manner as in Example 201 except that Na-NCM-A was changed to Na-NCA-A obtained in Production Example F and NMP-A was changed to NMP-F obtained in Production Example 206, sodium A positive electrode active material composite F-9 for ion secondary battery was obtained.

[Example 225: (Na-NCA-A 60% + NMP-F 40%) 99% + graphite 1% complex F-10]
350 g of Na-NCM-A was changed to 300 g of Na-NCA-A obtained in Production Example F, 150 g of NMP-A was changed to 200 g of NMP-F obtained in Production Example 206, and graphite (Nippon Graphite Co., Ltd.) Manufactured, CGB10, average particle size 10 μm) was added in the same manner as in Example 201, except that 5 g was added to obtain a positive electrode active material composite F-10 for sodium ion secondary batteries.

[Example 226: (Na-NCA-A 60% + NMP-F 40%) 90% + graphite 10% complex F-11]
350 g of Na-NCM-A was changed to 300 g of Na-NCA-A obtained in Production Example F, 150 g of NMP-A was changed to 200 g of NMP-F obtained in Production Example 206, and graphite (Nippon Graphite Co., Ltd.) Manufactured, CGB10, average particle size 10 μm) was added in the same manner as in Example 201, except that 55 g was added to obtain a positive electrode active material composite F-11 for sodium ion secondary batteries.

[Example 227: (Na-NCA-A 70% + NMP-F 30%) 99% + graphene 1% complex F-12]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, NMP-A was changed to NMP-F obtained in Production Example 206, and graphene (XGsciences, xGNP, average A positive electrode active material composite F-12 for a sodium ion secondary battery was obtained in the same manner as in Example 201 except that 5 g of the particle size was added and the composite treatment was performed.

[Example 228: (Na-NCA-A 70% + NMP-F 30%) 99% + acetylene black 1% complex F-13]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, NMP-A was changed to NMP-F obtained in Production Example 206, and acetylene black (manufactured by Denka, LI- 100, average particle size 50 nm) A positive electrode active material composite F-13 for a sodium ion secondary battery was obtained in the same manner as in Example 201 except that the composite treatment was performed by adding 5 g.

[Example 229: (Na-NCA-A 70% + NMP-F 30%) 99% + polyaniline 1% complex F-14]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, NMP-A was changed to NMP-F obtained in Production Example 206, and 5 g of polyaniline (manufactured by Sigma-Aldrich) was added. A positive electrode active material composite F-14 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that the composite treatment was performed by adding.

[Example 230: (Na-NCM-A35% + Na-NCA-A35% + NMP-A30%) complex EF-1]
A positive electrode active material composite for a lithium ion secondary battery in the same manner as in Example 201 except that 350 g of Na-NCM-A was changed to a mixture of Na-NCM-A175 g and Na-NCA-A175 g obtained in Production Example F. The body EF-1 was obtained.

[Comparative Example 201: (Na-NCM-A 70% + NMP-A 30%) Mixture E-15]
The Na-NCM-A 350 g obtained in Production Example D and the NMP-A 150 g obtained in Production Example 201 were mixed to obtain a positive electrode active material mixture E-15 for sodium ion secondary batteries.

[Comparative Example 202: (Na-NCM-A 70% + NMP-L 30%) Complex E-16]
A positive electrode active material composite E-16 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-L obtained in Production Example 212.

[Comparative Example 203: (Na-NCM-A 99.5% + NMP-A 0.5%) Complex E-17]
A positive electrode active material composite E-17 for sodium ion secondary batteries was obtained in the same manner as in Example 201 except that Na-NCM-A was changed to 497.5 g and NMP-A was changed to 2.5 g.

[Comparative Example 204: (Na-NCM-A 50% + NMP-A 50%) Complex E-18]
A positive electrode active material composite E-18 for sodium ion secondary batteries was obtained in the same manner as in Example 201 except that Na-NCM-A was changed to 250.0 g and NMP-A was changed to 250.0 g.

[Comparative Example 205: (Na-NCM-A 70% + NMP-G 30%) Complex E-19]
A positive electrode active material composite E-19 for sodium ion secondary batteries was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-G obtained in Production Example 207.

[Comparative Example 206: (Na-NCM-A 70% + NMP-C 30%) Complex E-20]
A positive electrode active material composite E-20 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-C obtained in Production Example 203.

[Comparative Example 207: (Na-NCM-A 70% + NMP-K 30%) Complex E-21]
A positive electrode active material composite E-21 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-K obtained in Production Example 211.

[Comparative Example 208: (Na-NCM-A 70% + NMP-H 30%) Complex E-22]
A positive electrode active material composite E-22 for sodium ion secondary battery was obtained in the same manner as in Example 201 except that NMP-A was changed to NMP-H obtained in Production Example 208.

[Comparative Example 209: (Na-NCM-B 70% + NMP-A 30%) Mixture E-23]
A positive electrode active material mixture E-23 for sodium ion secondary batteries was obtained in the same manner as in Comparative Example 201 except that Na-NCM-A was changed to Na-NCM-B obtained in Production Example D.

[Comparative Example 210: (Na-NCA-A 70% + NMP-A 30%) Mixture F-14]
Na-NCA-A 350 g obtained in Production Example F and NMP-A 150 g obtained in Production Example 201 were mixed to obtain a positive electrode active material mixture F-14 for sodium ion secondary batteries. .

[Comparative Example 211: (Na-NCA-A 70% + NMP-L 30%) Complex F-15]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-L obtained in Production Example 212. A positive electrode active material composite F-15 for ion secondary battery was obtained.

[Comparative Example 212: (Na-NCA-A 99.5% + NMP-A 0.5%) Complex F-16]
Na-NCM-A 350 g was changed to 497.5 g of Na-NCA-A obtained in Production Example F, and NMP-A was changed to 2.5 g. A positive electrode active material composite F-16 for batteries was obtained.

[Comparative Example 213: (Na-NCA-A 50% + NMP-A 50%) Complex F-17]
In the same manner as in Example 201 except that 350 g of Na-NCM-A was changed to 250 g of Na-NCA-A obtained in Production Example F and NMP-A was changed to 250 g, the positive electrode active for sodium ion secondary battery A substance complex F-17 was obtained.

[Comparative Example 214: (Na-NCA-A 70% + NMP-G 30%) Complex F-18]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-G obtained in Production Example 207. A positive electrode active material composite F-18 for ion secondary battery was obtained.

[Comparative Example 215: (Na-NCA-A 70% + NMP-C 30%) Complex F-19]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-C obtained in Production Example 203. A positive electrode active material composite F-19 for ion secondary battery was obtained.

[Comparative Example 216: (Na-NCA-A 70% + NMP-K 30%) Complex F-19]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-K obtained in Production Example 211. A positive electrode active material composite F-19 for ion secondary battery was obtained.

[Comparative Example 217: (Na-NCA-A 70% + NMP-H 30%) Complex F-20]
Na-NCM-A was changed to Na-NCA-A obtained in Production Example F, and NMP-A was changed to NMP-H obtained in Production Example 208. A positive electrode active material composite F-20 for ion secondary battery was obtained.

≪Evaluation of polyanion particle coverage on composite particle surface by X-ray photoelectron spectroscopy≫
Positive electrode active material mixture 0-p, 0-x, 1-p, 1-x, 2-p, all positive electrode active material composites for lithium ion secondary batteries except 2-x or sodium ion secondary batteries The positive electrode active material composite was analyzed for elements present on the surface of the composite particles using X-ray photoelectron spectroscopy (XPS). Specifically, from the peak of Ni2p _3/2 derived from the positive electrode active material composite for lithium ion secondary battery or the positive electrode active material composite for sodium ion secondary battery, the positive electrode active material composite for lithium ion secondary battery or NCM according to differential XPS profile obtained by subtracting the peak of trivalent Ni2p _3/2 derived from normalized polyanion particles from the peak of P2p or Si2P derived from the positive electrode active material composite for sodium ion secondary battery From the peak intensity of NCA-derived Ni2p _3/2 and the peak intensity sum of P2p and C1s derived from phosphate-based polyanion particles, or the peak intensity sum of Si2P and C1s derived from silicate-based polyanion particles, the following formula (2 Or XPS peak intensity ratio (A1) or XPS peak intensity ratio (A2). These XPS peak intensity ratios (A1) or XPS peak intensity ratios (A2) indicate that the smaller the value, the more the composite particle surface is coated with polyanions. The results are shown in Tables 1-3.
XPS peak intensity ratio (A1) = (peak intensity of trivalent Ni of Ni2p _3/2 ) /
((P2p peak intensity) + (C1s peak intensity)) (2)
XPS peak intensity ratio (A2) = (peak intensity of trivalent Ni of Ni2p _3/2 ) /
((Peak intensity of Si2p) + (peak intensity of C1s)) (3)

≪Evaluation of polyanion particle coating strength on the surface of composite particles by X-ray photoelectron spectroscopy≫
For the positive electrode active material composite for a lithium ion secondary battery or the positive electrode active material composite for a sodium ion secondary battery, the elements present on the surface of the composite particle after applying a certain shearing force to the composite particle are the same as described above. Using X-ray photoelectron spectroscopy, the XPS peak intensity ratio is obtained in the same manner as in the above formula (2) or (3), and the ratio of the XPS peak intensity ratio before and after applying the shear force is used to determine the polyanion to NCM or NCA. The coating strength was evaluated.
Specifically, the positive electrode active material composite for a lithium ion secondary battery or the positive electrode active material composite for a sodium ion secondary battery and 10 g of N-methyl-2-pyrrolidone were mixed with a high-speed mixer (Primix Co., Ltd., 40 L The mixture was stirred and kneaded at 2000 rpm for 3 minutes. This is an emphasis on the application process of the positive electrode slurry to the current collector in the manufacturing process of the secondary battery, and a force greater than the shearing force applied to the positive electrode active material particles in the application process is applied. ing. After the slurry after stirring and kneading is dried at 80 ° C. for 12 hours using a hot air dryer to obtain a positive electrode active material composite for a lithium ion secondary battery or a positive electrode active material composite for a sodium ion secondary battery Then, the obtained positive electrode active material composite for lithium ion secondary battery or positive electrode active material composite for sodium ion secondary battery was subjected to X-ray photoelectron spectroscopy, and the phosphate system was calculated from the same calculation as in the above formula (2). After obtaining the XPS peak intensity ratio (B1) of the polyanion particles or the XPS peak intensity ratio (B2) of the silicate-based polyanion particles from the same calculation as in the formula (3), the following formula (4) or formula The coating strength ratio (C1) or (C2) was determined from (5). The coating strength ratio (C1) or (C2) is smaller in value and closer to 1, indicating that the surface of the composite particle is more strongly coated with the polyanion particle. A result is shown to Tables 1-3 with the manufacturing conditions of the positive electrode active material composite for lithium ion secondary batteries, or the positive electrode active material composite for sodium ion secondary batteries.
Covering strength ratio (C1) =
(XPS peak intensity ratio (B1)) / (XPS peak intensity ratio (A1)) (4)
Covering strength ratio (C2) =
(XPS peak intensity ratio (B2)) / (XPS peak intensity ratio (A2)) (5)

<< Elution amount of transition metal to electrolyte >>
All positive electrode active material composites for lithium ion secondary batteries or positive electrode active material mixtures for lithium ion secondary batteries, or positive electrode active material composites for sodium ion secondary batteries or positive electrode active material mixtures for sodium ion secondary batteries As a material, a positive electrode of a lithium ion secondary battery or a sodium ion battery was produced. Specifically, the obtained positive electrode active material composite for lithium ion secondary battery or positive electrode active material mixture for lithium ion secondary battery, or positive electrode active material composite for sodium ion secondary battery or for sodium ion secondary battery A positive electrode active material mixture, acetylene black, and polyvinylidene fluoride were mixed at a mass ratio of 90: 5: 5, and N-methyl-2-pyrrolidone was added thereto and kneaded sufficiently to prepare a positive electrode slurry. The positive electrode slurry was applied to a current collector made of an aluminum foil having a thickness of 20 μm using a coating machine, and vacuum dried at 80 ° C. for 12 hours. Thereafter, it was punched into a disk shape of φ14 mm and pressed at 16 MPa for 2 minutes using a hand press to obtain a positive electrode.
Next, a coin-type secondary battery was constructed using the positive electrode. A lithium foil (in the case of a lithium ion secondary battery) or a sodium foil (in the case of a sodium ion battery) punched to φ15 mm was used as the negative electrode. For the electrolyte, LiPF ₆ (in the case of a lithium ion secondary battery) or NaPF ₆ (in the case of a sodium ion secondary battery) is mixed in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate are mixed at a volume ratio of 3: 7. Those dissolved at a concentration of 1 mol / L were used. As the separator, a known one such as a polymer porous film such as polypropylene was used. These battery components were assembled and housed in a conventional manner in an atmosphere with a dew point of −50 ° C. or lower to produce a coin-type secondary battery (CR-2032).

The obtained secondary battery was charged. Specifically, constant current charging with a current of 170 mA / g and a voltage of 4.5 V was performed.
Thereafter, the secondary battery was disassembled, and the taken out positive electrode was washed with dimethyl carbonate and then immersed in an electrolytic solution. In this case, the electrolyte solution was LiPF ₆ (in the case of a lithium ion secondary battery) or NaPF ₆ (in the case of a sodium ion secondary battery) in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 3: 7. ) Was dissolved at a concentration of 1 mol / L. The electrolyte solution in which the positive electrode was immersed was placed in a sealed container and allowed to stand at 70 ° C. for 1 week.
After standing, the electrolyte solution from which the positive electrode was taken out was filtered through a 0.45 μm discic filter and acid-decomposed with nitric acid. NCM-derived Mn, Ni, and Co contained in the acid-decomposed electrolyte were quantified using ICP emission spectroscopy. The results are shown in Tables 4-6.

≪Evaluation of high temperature cycle characteristics≫
The high-temperature cycle characteristics were evaluated using the secondary battery produced by evaluating the amount of transition metal elution into the electrolyte. Specifically, a constant current charge with a current density of 85 mA / g and a voltage of 4.25 V, a constant current discharge with a current density of 85 mA / g and a final voltage of 3.0 V, and a discharge at a current density of 85 mA / g (0.5 CA). The capacity was determined. Furthermore, a 100-cycle repeated test under the same charge / discharge conditions was performed, and the capacity retention rate (%) was determined by the following formula (6). All charge / discharge tests were conducted at 45 ° C. The results are shown in Tables 7-9.
Capacity retention (%) = (discharge capacity after 100 cycles) / (discharge capacity after 1 cycle)
× 100 (6)

<Evaluation of rate characteristics>
The rate characteristic was evaluated using the secondary battery manufactured by evaluation of the amount of transition metal elution into the electrolytic solution. Specifically, a constant current charge at a current density of 34 mA / g and a voltage of 4.25 V, a constant current discharge at a current of 34 mA / g and a final voltage of 3.0 V, and the discharge capacity at a current density of 34 mA / g was determined. Furthermore, constant current charging was performed under the same conditions to obtain a constant current discharge with a current density of 510 mA / g and a final voltage of 3.0 V, and a discharge capacity at a current density of 510 mA / g was determined. The charge / discharge test was performed at 30 ° C.
From the obtained discharge capacity, the capacity ratio (%) was obtained by the following formula (7). The results are shown in Tables 7-9.
Capacity ratio (%) = (discharge capacity at a current density of 510 mA / g) /
(Discharge capacity at a current density of 34 mA / g) × 100 (7)

As is clear from Tables 7 to 9, a lithium ion secondary battery using the positive electrode active material composite for lithium ion secondary battery or the positive electrode active material composite for sodium ion secondary battery obtained in Examples as the positive electrode material Alternatively, the sodium ion battery is a lithium ion secondary battery using a positive electrode active material composite for a lithium ion secondary battery or a positive electrode active material mixture for a lithium ion secondary battery obtained in a comparative example as a positive electrode material, or a comparative example. Compared with the sodium ion battery using the obtained positive electrode active material composite for sodium ion secondary battery or the positive electrode active material mixture for sodium ion secondary battery as the positive electrode material, it can be seen that both the high temperature cycle characteristics and rate characteristics are excellent. .
Further, as is apparent from Tables 4 to 6, lithium ion secondary batteries using the positive electrode active material composite for lithium ion secondary batteries or the positive electrode active material composite for sodium ion secondary batteries obtained in Examples as the positive electrode material. The secondary battery or the sodium ion battery is a lithium ion secondary battery using a positive electrode active material composite for a lithium ion secondary battery or a positive electrode active material mixture for a lithium ion secondary battery obtained as a comparative example, or a comparison. Compared to sodium ion battery using positive electrode active material composite for sodium ion secondary battery or positive electrode active material mixture for sodium ion secondary battery obtained as an example for positive electrode material, the amount of transition metal eluted from the electrode to the electrolyte There are few, and it turns out that it is excellent also in safety.

Claims (21)

The following formula (I):
LiNi _a Co _b Mn _c M ¹ _x O ₂ (I)
(In the formula (I), ^{M 1} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge are shown, a, b, c, and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, (0 ≦ x ≦ 0.3 and 3a + 3b + 3c + (valence of M ¹ ) × x = 3)
Or the following formula (II):
LiNi _d Co _e Al _f M ² _y O ₂ (II)
(In the formula (II), ^{M 2} is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and One or more elements selected from Ge are shown, d, e, f, and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦. (Y ≦ 0.3 and 3d + 3e + 3f + (valence of M ² ) × y = 3)
Only on the surface of the lithium composite oxide secondary particles (A) composed of one or more lithium composite oxide particles represented by the following formula (V):
^{_{Li s Co g Ni h M 5}} i PO 4 ··· (V)
(In the formula (V), M ⁵ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. S, g, h, and i are 0 <s ≦ 1.2, 0 ≦ g ≦ 1.2, 0 ≦ h ≦ 1.2, 0 ≦ i ≦ 0.3, and g + h ≠ 0, and s + (Co valence) × g + ( The valence of Ni) × h + (the valence of M ⁵ ) × i = a number satisfying i = 3).
Following formula (VI):
^{_{Li t Co j Ni k M 6}} l SiO 4 ··· (VI)
(In the formula (VI), M ⁶ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. T, j, k, and l are 0 <t ≦ 2.4, 0 ≦ j ≦ 1.2, 0 ≦ k ≦ 1.2, 0 ≦ l ≦ 1.2, and j + k ≠ 0, and t + (Co valence) × j + ( Ni valence) × k + (M ⁶ valence) × 1 = the number satisfying 4).
Or the following formula (VIII):
^{_{Li v Fe p Mn q M 8}} r SiO 4 ··· (VIII)
(In the formula (VIII), M ⁸ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, V, or Gd. V, p, q and r satisfy 0 <v ≦ 2.4, 0 ≦ p ≦ 1.2, 0 ≦ q ≦ 1.2, 0 ≦ r ≦ 1.2, and p + q ≠ 0, and v + (Fe Valence) × p + (valence of Mn) × q + (valence of M ⁸ ) × r = 4 is satisfied.)
And one or more lithium-based polyanion particles (B) having carbon (c) supported on the surface and lithium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the lithium-based polyanion particles (B) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the lithium-based polyanion particles (B),
The average particle diameter of the lithium-based polyanion particles (B) is 20 nm to 200 nm,
Lithium whose mass ratio ((A) :( B)) of the content of the lithium composite oxide secondary particles (A) and the content of the lithium-based polyanion particles (B) is 95: 5 to 55:45 A positive electrode active material composite for an ion secondary battery. The following formula (I):
LiNi _a Co _b Mn _c M ¹ _x O ₂ (I)
(In the formula (I), ^{M 1} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge are shown, a, b, c, and x are 0.3 ≦ a <1, 0 <b ≦ 0.7, 0 <c ≦ 0.7, (0 ≦ x ≦ 0.3 and 3a + 3b + 3c + (valence of M ¹ ) × x = 3)
Or the following formula (II):
LiNi _d Co _e Al _f M ² _y O ₂ (II)
(In the formula (II), ^{M 2} is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and One or more elements selected from Ge are shown, d, e, f, and y are 0.4 ≦ d <1, 0 <e ≦ 0.6, 0 <f ≦ 0.3, 0 ≦. (Y ≦ 0.3 and 3d + 3e + 3f + (valence of M ² ) × y = 3)
On the surface of the lithium composite oxide secondary particles (A) composed of one or more lithium composite oxide particles represented by the following formula (VII):
^{_{Li u Fe m Mn n M 7}} o PO 4 ··· (VII)
(In the formula (VII), M ⁷ represents Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. U, m, n, and o are 0 <u ≦ 1.2, 0 ≦ m ≦ 1.2, 0 ≦ n ≦ 1.2, 0 ≦ o ≦ 0.3, and m + n ≠ 0, and u + (Fe valence) × m + ( (Mn valence) × n + (M ⁷ valence) × o = 3)
Lithium-based polyanion particles (B) represented by the above and having carbon (c) supported on the surface and lithium composite oxide particles are combined,
The amount of carbon (c) supported on the surface of the lithium-based polyanion particle (B) is 0.1% by mass or more and less than 10% by mass in 100% by mass of the lithium-based polyanion particle (B),
The average particle diameter of the lithium-based polyanion particles (B) is 50 nm to 200 nm,
The mass ratio ((A) :( B)) between the content of the lithium composite oxide secondary particles (A) and the content of the lithium-based polyanion particles (B) is 65:35 to 55:45 (provided that 65:35)). A positive electrode active material composite for a lithium ion secondary battery.   The carbon (c) carried on the surfaces of the lithium-based polyanion particles (B) is carbon (c1) derived from cellulose nanofibers or carbon (c2) derived from a water-soluble carbon material. A positive electrode active material composite for a lithium ion secondary battery.   The positive electrode active material composite for a lithium ion secondary battery according to any one of claims 1 to 3, wherein the lithium composite oxide secondary particles (A) have an average particle size of 1 µm to 25 µm. The electric conductivity of the lithium-based polyanion particle (B) formed by supporting carbon (c) on the surface at a pressure of 20 MPa at 25 ° C. is 1 × 10 ⁻⁷ S / cm or more. The positive electrode active material composite for lithium ion secondary batteries according to any one of 1 to 4. Water-insoluble carbon powder (c3) other than carbon (c1) derived from cellulose nanofiber is lithium composite oxide secondary particles (A), and lithium-based polyanion particles (B) having carbon (c) supported on the surface. Combined with
Content of water-insoluble carbon powder (c3) is 100 parts by mass with respect to the total amount of lithium composite oxide secondary particles (A) and lithium-based polyanion particles (B) formed by supporting carbon (c) on the surface. It is 0.5-24 mass parts, The positive electrode active material composite for lithium ion secondary batteries of any one of Claims 1-5. From the peak of Ni2p _3/2 derived from the positive electrode active material composite for lithium ion secondary battery or the positive electrode active material composite for sodium ion secondary battery by X-ray photoelectron spectroscopy (XPS), the positive electrode for lithium ion secondary battery NCM based on differential XPS profile obtained by subtracting Ni2p _3/2 peak derived from normalized polyanion particles from P2p or Si2P peak derived from active material composite or positive electrode active material composite for sodium ion secondary battery Alternatively, the peak intensity calculated from the peak intensity of Ni2p _3/2 derived from NCA and the peak intensity sum of P2p and C1s derived from phosphate polyanion particles, or the peak intensity sum of Si2P and C1s derived from silicate polyanion particles Ratio ((Ni2p _3/2 peak intensity) / (P2p peak intensity + C1s peak intensity) 7) or ((peak intensity of Ni2p _3/2 ) / (peak intensity of Si2p + peak intensity of C1s)) is 0.05 or less. Positive electrode active material composite for secondary battery.   The lithium ion secondary battery which contains the positive electrode active material composite_body | complex for lithium ion secondary batteries of any one of Claims 1-7 as a positive electrode material.   The lithium composite oxide secondary particles (A) and the lithium-based polyanion particles (B) formed by supporting carbon (c) on the surface are mixed to add a compressive force and a shear force to form a composite. The manufacturing method of the positive electrode active material composite_body | complex for lithium ion secondary batteries of any one of Claims 1-7.   Water-insoluble carbon powder (c3) other than lithium composite oxide secondary particles (A), lithium-based polyanion particles (B) formed by supporting carbon (c) on the surface, and carbon (c1) derived from cellulose nanofibers The manufacturing method of the positive electrode active material composite_body | complex for lithium ion secondary batteries of any one of Claims 1-7 provided with the process which mixes and composites, adding compression force and shear force.   11. The production of a positive electrode active material composite for a lithium ion secondary battery according to claim 9, wherein the compounding step is a step performed in an airtight container including an impeller rotating at a peripheral speed of 15 m / s to 45 m / s. Method. Formula (III) below
NaNi _{a ′} Co _{b ′} Mn _{c ′} M ³ _{x ′} O ₂ (III)
(In the formula (III), ^{M 3} is Mg, Ti, Nb, Fe, Cr, Si, Al, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, 1 or 2 or more elements selected from Bi and Ge, a ′, b ′, c ′ and x ′ are 0.3 ≦ a ′ <1, 0 <b ′ ≦ 0.7, 0 < (c ′ ≦ 0.7, 0 ≦ x ′ ≦ 0.3, and 3a ′ + 3b ′ + 3c ′ + (valence of M ³ ) × x ′ = 3).
Or the following formula (IV):
NaNi _{d ′} Co _{e ′} Al _{f ′} M ⁴ _{y ′} O ₂ (IV)
(In the formula (IV), M ⁴ is Mg, Ti, Nb, Fe, Cr, Si, Ga, V, Zn, Cu, Sr, Mo, Zr, Sn, Ta, W, La, Ce, Pb, Bi and 1 or 2 or more elements selected from Ge, d ′, e ′, f ′, and y ′ are 0.4 ≦ d ′ <1, 0 <e ′ ≦ 0.6, and 0 <f ′. ≦ 0.3,0 ≦ y '≦ 0.3, and 3d' + 3e '+ 3f' + ( valence of ^{M 4)} shows a number satisfying × y '= 3.)
On the surface of the sodium composite oxide secondary particles (D) composed of one or more kinds of sodium composite oxide particles represented by the following formula (IX):
Na _w Cog _′ Ni _{h ′} M ⁹ _{i ′} PO ₄ (IX)
(In the formula (IX), M ⁹ represents Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, or Gd. W, g ′, h ′, and i 'Satisfies 0 <w ≦ 1.2, 0 ≦ g ′ ≦ 1.2, 0 ≦ h ′ ≦ 1.2, 0 ≦ i ′ ≦ 0.3, and g ′ + h ′ ≠ 0, and w + (The valence of Co) × g ′ + (the valence of Ni) × h ′ + (the valence of M ⁹ ) × i ′ = 3.
Formula (X) below:
_{Na x Co j 'Ni k'} M 10 l 'SiO 4 ··· (X)
(.X shown in the formula ^{(X), M 10} is Fe, Mn, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, j ', k', and l 'Satisfies 0 <x ≦ 2.4, 0 ≦ j ′ ≦ 1.2, 0 ≦ k ′ ≦ 1.2, 0 ≦ l ′ ≦ 1.2, and j ′ + k ′ ≠ 0, and x + (Co valence) × j ′ + (Ni valence) × k ′ + (M ¹⁰ valence) × l ′ = 4).
Formula (XI):
Na _y Fem _′ Mn _{n ′} M ¹¹ _{o ′} PO ₄ (XI)
(.Y shown in the formula ^{(XI), M 11} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, and Nd or Gd, m ', n', and o 'Satisfies 0 <y ≦ 1.2, 0 ≦ m ′ ≦ 1.2, 0 ≦ n ′ ≦ 1.2, 0 ≦ o ′ ≦ 0.3, and m ′ + n ′ ≠ 0, and y + (valence of Fe) × m '+ (valence of Mn) × n' + ^(valence of ^{M 11)} × o '= 3 indicates a number satisfying.)
Or the following formula (XII):
Na _z Fe _{p ′} Mn _{q ′} M ¹² _{r ′} SiO ₄ ... (XII)
(In the formula ^{(XII), M 12} is Co, Ni, Ca, Sr, Y, Zr, Mo, Ba, Pb, Bi, La, Ce, Nd, Al, Zn, .z showing a V or Gd, p ' , Q ′, and r ′ are 0 <z ≦ 2.4, 0 ≦ p ′ ≦ 1.2, 0 ≦ q ′ ≦ 1.2, 0 ≦ r ′ ≦ 1.2, and p ′ + q ′ ≠. And 0+ and z + (Fe valence) × p ′ + (Mn valence) × q ′ + (M ¹² valence) × r ′ = 4).
And one or more kinds of sodium-based polyanion particles (E) formed by supporting carbon (c) on the surface and sodium composite oxide particles,
The amount of carbon (c) supported on the surface of the sodium-based polyanion particles (E) is 0.1% by mass or more and less than 20% by mass in 100% by mass of the sodium-based polyanion particles (E),
The average particle diameter of the sodium-based polyanion particles (E) is 50 nm to 200 nm,
Sodium whose mass ratio ((D) :( E)) of the content of the sodium composite oxide secondary particles (D) and the content of the sodium-based polyanion particles (E) is 95: 5 to 55:45 The positive electrode active material complex ion secondary battery.   13. The sodium according to claim 12, wherein the carbon (c) supported on the surface of the sodium-based polyanion particle (E) is carbon (c1) derived from cellulose nanofibers or carbon (c2) derived from a water-soluble carbon material. A positive electrode active material composite for an ion secondary battery.   14. The positive electrode active material composite for a sodium ion secondary battery according to claim 12, wherein the average particle size of the sodium composite oxide secondary particles (D) is 1 μm to 25 μm. The electric conductivity as a powder of a sodium-based polyanion particle (E) having carbon (c) supported on the surface at a pressure of 20 MPa at 25 ° C. is 1 × 10 ⁻⁷ S / cm or more. The positive electrode active material composite for sodium ion secondary batteries according to any one of 12 to 14. Water-insoluble carbon powder (c3) other than carbon (c1) derived from cellulose nanofibers, sodium composite oxide secondary particles (D), and sodium-based polyanion particles (E) having carbon (c) supported on the surface Combined with
The content of the water-insoluble carbon powder (c3) is 100 parts by mass of the total amount of the sodium composite oxide secondary particles (D) and the sodium-based polyanion particles (E) formed by supporting carbon (c) on the surface. It is 0.5-24 mass parts, The positive electrode active material composite_body | complex for sodium ion secondary batteries of any one of Claims 12-15. Peak intensity ratio ((Ni2p _3/2 peak intensity) / (P2p peak intensity + C1s peak intensity)) or ((Ni2p _3/2 peak intensity) / (Si2p peak) by X-ray photoelectron spectroscopy (XPS) The positive electrode active material composite for a sodium ion secondary battery according to any one of claims 12 to 16, wherein the strength + the peak intensity of C1s)) is 0.05 or less.   A sodium ion secondary battery comprising the positive electrode active material composite for a sodium ion secondary battery according to any one of claims 12 to 17 as a positive electrode material.   A step of mixing and complexing the sodium composite oxide secondary particles (D) and the sodium-based polyanion particles (E) having carbon (c) supported on the surface while applying compressive force and shearing force. The manufacturing method of the positive electrode active material composite_body | complex for sodium ion secondary batteries of any one of Claims 12-17.   Water-insoluble carbon powder (c3) other than sodium composite oxide secondary particles (D), sodium-based polyanion particles (E) formed by supporting carbon (c) on the surface, and carbon (c1) derived from cellulose nanofibers The manufacturing method of the positive electrode active material composite_body | complex for sodium ion secondary batteries of any one of Claims 12-17 provided with the process of mixing and adding, adding compressive force and shear force.   21. The production of a positive electrode active material composite for a sodium ion secondary battery according to claim 19 or 20, wherein the compounding step is a step performed in an airtight container including an impeller rotating at a peripheral speed of 15 m / s to 45 m / s. Method.