JP2016192310A - Positive electrode material, nonaqueous electrolyte secondary battery positive electrode and nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive electrode material, a nonaqueous electrolyte secondary battery positive electrode and a nonaqueous electrolyte secondary battery, in which a crystal structure is suppressed from being collapsed during charge/discharge and which are excellent in safety.SOLUTION: A positive electrode material of the present invention is represented by LiNiMMMnO(where, 0.50<α≤1.33, 0.33≤γ≤1.1, 0≤η≤1.00, 0≤β<0.67 and 0≤ε≤1.00 are satisfied, Mrepresents at least one selected from Co and Ga, and Mrepresents at least one selected from among Ge, Sn and Sb), and has a layered structure including a Li layer and a Ni layer. When the positive electrode material is indexed with a space group R3m in measurement of powder X-ray diffraction, the peak intensity ratio (I/I) between a peak intensity (I) of the (003) reflection and a peak intensity (I) of the (104) reflection is 0.9 or more. In a nonaqueous electrolyte secondary battery positive electrode 14 and a nonaqueous electrolyte secondary battery 1 of the present invention, the positive electrode material is used.SELECTED DRAWING: None

Description

  The present invention relates to a positive electrode material, a positive electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery using the same.

  With the widespread use of electronic devices such as notebook computers, mobile phones, and digital cameras, the demand for secondary batteries for driving these electronic devices is increasing. In recent years, these electronic devices have been demanded to improve the performance of secondary batteries because power consumption has increased with the progress of higher functionality and miniaturization is expected. Among secondary batteries, non-aqueous electrolyte secondary batteries (particularly lithium ion secondary batteries) can be increased in capacity, and thus are being used in various electronic devices.

  A nonaqueous electrolyte secondary battery generally includes a positive electrode in which a positive electrode active material layer having a positive electrode material typified by a positive electrode active material is formed on the surface of a positive electrode current collector, and a negative electrode active material layer having a negative electrode active material. The negative electrode formed on the surface of the electric body is connected via a non-aqueous electrolyte (non-aqueous electrolyte solution) and is stored in the battery case.

  In a lithium ion secondary battery that is a typical example of a nonaqueous electrolyte secondary battery, a lithium composite oxide is used as a positive electrode material (positive electrode active material). As this complex oxide, it describes in patent documents 1-6, for example.

Patent Document 1 describes that a positive electrode active material in which Li _x CoMO ₂ and LiNiMnMO ₂ are mixed is used (M: all selected from predetermined elements). This positive electrode active material includes an active material having a high average voltage during discharge and an active material having high thermal stability.

Patent Document 2 describes a positive electrode active material including a crystal layer having a layered rock salt structure of LiNiMnTiO ₂ . When this positive electrode active material contains Ti, a high charge / discharge capacity can be obtained as compared with the case where it does not contain Ti.

Patent Document 3 describes that a positive electrode active material in which Li _x MnMO ₄ and LiNiMO ₂ are mixed is used (M: all selected from predetermined elements). This positive electrode active material is excellent in battery performance after high-temperature storage.

Patent Document 4 describes a positive electrode active material in which a part of Li in a LiMnMO ₂ layer having a polycrystalline structure is deficient (M: all selected from predetermined elements). This positive electrode active material is stabilized in strain and chemical bond in the crystal, and effects such as cycle stability and durability stability during charging and discharging are obtained.

Patent Document 5 describes a positive electrode active material in which Li and Co are partially substituted with a predetermined element M in LiCoO ₂ (M: both are selected from predetermined elements). In this positive electrode active material, each of Li and Co is replaced by the element M, whereby the bonding force between the lithium layer and the cobalt layer is strengthened, and the strain between the layers and the expansion of the crystal lattice are suppressed. Effects such as cycle stability and durability stability can be obtained.

Patent Document 6 describes that a positive electrode active material in which LiNiMnCoO ₂ and Li ₂ MO ₃ are mixed is selected (M: selected from predetermined elements). This positive electrode active material has an active material that exhibits an effect excellent in battery capacity and safety, and an active material that exhibits an effect on cycle characteristics and storage characteristics.

However, all of these positive electrode active materials (positive electrode materials) have a problem in that the collapse of the crystal structure during charge / discharge cannot be sufficiently suppressed, leading to a decrease in the capacity of the nonaqueous electrolyte secondary battery.
Regarding safety, Non-Patent Document 1 describes a technique of using a positive electrode containing Ti, that is, LiNiMnTiO ₂ .
However, as described in Non-Patent Document 1, it is described that there is no overwhelming improvement in safety when about 30% of Ti is added.

As another attempt to achieve both safety and high stabilization of the crystal, a technique for forming a positive electrode containing Si having a strong binding force with oxygen in the same amount as the transition metal, that is, Li ₂ MnSiO ₄ is described in Non-Patent Document 2. It is described in.
However, in this positive electrode, the transition metal has a four-coordinate coordination structure, the structure becomes unstable during charging, and it is not a positive electrode with sufficient durability.

In Patent Document 7, Li [Li _x Me _y M ′ _z ] O _{2 + d} (x + y + z = 1, 0 <x <0.33, 0.05 ≦ y ≦ 0.15, 0 <d ≦ 0.1, Me : At least one selected from Mn, V, Cr, Fe, Co, Ni, Al, and B, and M ′: at least one selected from Ge, Ru, Sn, Ti, Nb, and Pt). A positive electrode active material is described.

  However, in the battery using this positive electrode active material, the improvement in safety was insufficient. Specifically, the addition ratio of the element represented by Me in the transition metal is about 14 at%, and oxygen atoms that are not bonded to the element represented by Me existed. The bond between the element represented by Me and the oxygen atom is strong, and bond breakage (desorption of oxygen) hardly occurs. That is, oxygen atoms that do not bind to the element represented by Me contained in the positive electrode active material of Cited Document 7 become oxygen gas when the battery is formed, and the safety of the battery is lowered.

Patent Document _{8, Li x Ni 1-y} M y O 2 + α (M: Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Al, Bi, Sn, Mg, Ca , B, and Zr, 0.9 ≦ x ≦ 1.2, 0 <y ≦ 0.7, α> 0.1) are described. ing. And, in the powder XRD, the ratio of the peak intensity of the (003) plane to the peak intensity of the (104) plane is 0.9 or less, so that mixing (cation mixing) into the Li ion site of Ni ions is suppressed. High capacity expression can be realized.
However, the effect of suppressing the decrease in safety caused by the increase in charge capacity has not been sufficient.

JP 2007-188703 A JP 2008-127233 A JP 2001-345101 A JP 2001-250551 A Japanese Patent No. 3782058 JP 2006-202702 A U.S. Pat. No. 8,734,994 No. 2011-96522

Seung-Taek Myung and 5 others, "Synthesis of LiNi0.5n0.5-xTixO2 by an Emulsion Drying Method and Effect of Ti on Structure and Electrochem. R. Dominko Li2MSiO4 (M = Fe and / or Mn) cathode materials, Journal of Power Sources, 2008, 184, P462-P468

  The present invention has been made in view of the above circumstances, and has a positive electrode material, a positive electrode for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery that are suppressed in crystal structure during charge and discharge and are excellent in safety. It is an issue to provide.

In order to solve the above problems, the inventors focused on the structure of the positive electrode material, and is a positive electrode material containing a large amount of M ² element that strongly binds to oxygen in addition to Ni element, and has a structure in which cation mixing is suppressed. It has been found that the above problem can be solved.

That is, the positive electrode material of the present invention is Li ₂ Ni _α M ¹ _β M ² _γ Mn _η O _4-ε (0.50 <α ≦ 1.33, 0.33 ≦ γ ≦ 1.1, 0 ≦ η ≦ 1.00, 0 ≦ β <0.67, 0 ≦ ε ≦ 1.00, M ¹ : at least one selected from Co, Ga, M ² : at least one selected from Ge, Sn, Sb) (003) peak intensity of reflection (I ₀₀₃ ) when indexed with space group R3m when measuring powder X-ray diffraction, and having a layered structure comprising a Li layer and a Ni layer, (104) and the reflection peak intensity _{(I 104),} the peak intensity ratio _(I 003 _{/ I 104)} is equal to or less than 0.9.
The positive electrode for a non-aqueous electrolyte secondary battery according to the present invention is characterized by using the positive electrode material according to any one of claims 1 and 2.

  The nonaqueous electrolyte secondary battery of the present invention is a positive electrode for a nonaqueous electrolyte secondary battery using the positive electrode material according to any one of claims 1 to 2, and the nonaqueous electrolyte secondary battery according to claim 3. It is characterized by using at least one of positive electrodes for batteries.

  The positive electrode material of the present invention contains Ni in its composition. This Ni forms a local structure in which oxygen (O) is 6-coordinated (6-coordinated local structure). As a result, stable charging / discharging is performed. Moreover, high capacity is achieved by containing a large amount of Ni as the redox species in the range of 0.50 <α ≦ 1.33.

Further, by containing a large amount of M ¹ element and M ² element, crystal structure is more stable, the crystal structure during charge and discharge is suppressed, decrease in battery capacity can be suppressed as a result. The M ² element strongly fixes oxygen. As a result, the desorption of oxygen, which is a concern during abnormal heat generation, is suppressed, and the safety of the battery is further improved. Furthermore, the amount of M ² element, when became 0.33 or more, on average, all of the oxygen in the Ni layer is adjoin the M ² element, and to have a bond with M ² element Therefore, the oxygen desorption effect is remarkably increased.

The positive electrode material of the present invention has a layered structure including a Li layer and a Ni layer, and thus has excellent Li ion conductivity. The Li layer is a layer formed mainly of Li and is substantially made of Li. The Ni layer is a layer formed with Ni (Ni compound) as a main component and is substantially a layer containing Ni, M ¹ element, and M ² element as main components.

Then, the positive electrode material of the present invention _{is (I 003)} and _{(I 104)} peak intensity ratio of _(I 003 _/ I ₁₀₄₎ is 0.9 or more. This peak intensity ratio indicates so-called cation mixing in which Ni ions (Ni element) in the Ni layer are mixed into the Li layer. In the positive electrode material of the present invention, this peak intensity ratio is 0.9 or more, so that cation mixing is further suppressed.
As described above, the positive electrode material of the present invention can provide a non-aqueous electrolyte secondary battery in which a decrease in battery performance is suppressed and is excellent in safety.
Moreover, the positive electrode for nonaqueous electrolyte secondary batteries and the nonaqueous electrolyte secondary battery of the present invention use the positive electrode material of the present invention, and can exhibit the effects obtained by the positive electrode material of the present invention.

It is a schematic sectional drawing which shows the structure of the coin-type lithium ion secondary battery of embodiment. 4 is a graph showing measurement results of powder XRD of the positive electrode material of Example 1. 2 is a graph showing charging characteristics and discharging characteristics of Example 1. FIG.

Hereinafter, the present invention will be specifically described with reference to embodiments.
[Embodiment]
The present embodiment is a coin-type lithium ion secondary battery 1 whose structure is shown in a schematic sectional view in FIG. The lithium ion secondary battery 1 of the present embodiment is a secondary battery (nonaqueous electrolyte secondary battery) using a positive electrode (a positive electrode for a nonaqueous electrolyte secondary battery) having the positive electrode material of the present invention as a positive electrode active material. .

  The lithium ion secondary battery 1 of this embodiment includes a positive electrode case 11, a sealing material 12 (gasket), a nonaqueous electrolyte 13, a positive electrode 14, a positive electrode current collector 140, a positive electrode mixture layer 141, a separator 15, a negative electrode case 16, and a negative electrode. 17, a negative electrode current collector 170, a negative electrode mixture layer 171, a holding member 18, and the like.

  The positive electrode 14 of the lithium ion secondary battery 1 of this embodiment has a positive electrode mixture layer 141 containing a positive electrode active material made of the positive electrode material of the present invention. The positive electrode mixture layer 141 includes members such as a binder and a conductive material as necessary, in addition to the positive electrode active material.

(Positive electrode material)
The positive electrode material is Li ₂ Ni _α M ¹ _β M ² _γ Mn _η O _4-ε (0.50 <α ≦ 1.33, 0.33 ≦ γ ≦ 1.1, 0 ≦ η ≦ 1.00, 0 ≦ β <0.67, 0 ≦ ε ≦ 1.00, M ¹ : at least one selected from Co, Ga, M ² : at least one selected from Ge, Sn, Sb).

  The positive electrode material contains Ni in its composition. This Ni forms a local structure in which oxygen (O) is 6-coordinated (6-coordinated local structure). As a result, stable charging / discharging is performed. Further, high capacity can be achieved by containing a large amount of Ni, which is a redox species, in the range of 0.50 <α ≦ 1.33.

Further, by containing a large amount of M ¹ element and M ² element, the crystal structure becomes more stable, the crystal structure at the time of charging / discharging is kept stable, and as a result, a decrease in battery capacity is suppressed. The M ¹ element is an element with a trivalent formal valence, and the addition of the M ¹ element is expected to suppress the penetration of Li having a significantly different valence into the Ni layer. The M ² element strongly fixes oxygen, and as a result, the desorption of oxygen, which is a concern during abnormal heat generation, is suppressed, thereby improving the safety of the battery. Furthermore, the amount of M ² element, when became 0.33 or more, on average, all of the oxygen in the Ni layer is adjoin the M ² element, and to have a bond with M ² element Therefore, the oxygen desorption effect is remarkably increased.

Furthermore, it is preferable that the M ¹ element and the M ² element are also in a six-coordinate state, and by this configuration, a structural gap with an adjacent transition metal element (Ni or Mn coordination structure) is reduced. And durability can be further improved.

  The positive electrode material of this embodiment may further contain Mn (a ratio of 0 or more and 1.00 or less) which is a transition metal in the composition. Like Mn, this Mn forms a local structure in which oxygen (O) is 6-coordinated (6-coordinated local structure). By being contained at this ratio, the effect of stabilizing the Ni layer is exhibited.

In a nonaqueous electrolyte secondary battery (lithium ion battery), when overcharge or the like proceeds, there may be a problem of ignition and smoke generation. The ignition smoke in this battery is greatly influenced by oxygen released from the positive electrode active material (positive electrode material) in the process leading to the smoke. Specifically, with charge, electrons are deprived of oxygen of the positive electrode active material, leading to oxygen release. In the positive electrode material of the present invention, the M ² element is added, and the added M ² element is more strongly bonded to oxygen than Ni or Mn (transition metal). That is, by adding the M ² element, oxygen release during charging / discharging can be minimized.

The positive electrode material of this embodiment has a layered structure including a Li layer and a Ni layer. With this configuration, the positive electrode material is excellent in Li ion conductivity. The Li layer refers to a layer formed with Li as a main component, and is a layer substantially made of Li. The Ni layer is a layer formed with Ni (Ni compound) as a main component, and is substantially a layer formed with Ni and elements M ¹ and M ² as main components.

When the powder X-ray diffraction was measured, the positive electrode material of the present invention, when indexed with the space group R3m, (003) peak intensity of reflection (I ₀₀₃ ) and (104) peak intensity of reflection (I ₁₀₄ ) and the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) are 0.9 or more. This peak intensity ratio indicates so-called cation mixing in which Ni ions (Ni element) in the Ni layer are mixed into the Li layer. When cation mixing proceeds, the lithium diffusion path is blocked, and stable capacity expression is not achieved. The positive electrode material of the present invention is a positive electrode material in which cation mixing is suppressed when the peak intensity ratio is 0.9 or more.

As the peak intensity ratio is larger, cation mixing is suppressed, and the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) is more preferably 1.2 or more.
The powder XRD for obtaining the peak intensity ratio can be measured by a conventionally known method. For example, it can be measured using a powder XRD measuring apparatus.

  The positive electrode active material should just have said positive electrode material as a positive electrode active material, and may have another positive electrode active material (positive electrode material) further. The other positive electrode active material may be another material included in the above chemical formula, or may be another compound.

(Configuration other than positive electrode active material)
The configuration of the lithium ion secondary battery 1 of the present embodiment can be the same as that of a conventional lithium ion secondary battery except that the above positive electrode material is used as the positive electrode active material.
In the positive electrode 14, a positive electrode mixture layer 141 is formed by applying a positive electrode mixture obtained by mixing a positive electrode active material, a conductive material, and a binder to the positive electrode current collector 140.

  The conductive material ensures the electrical conductivity of the positive electrode 14. Examples of the conductive material include, but are not limited to, graphite fine particles, acetylene black, ketjen black, carbon black such as carbon nanofiber, and amorphous carbon fine particles such as needle coke.

  The binder binds the positive electrode active material particles and the conductive material. As the binder, for example, PVDF, EPDM, SBR, NBR, fluororubber, and the like can be used, but are not limited thereto.

  The positive electrode mixture is dispersed in a solvent and applied to the positive electrode current collector 140. As the solvent, an organic solvent that normally dissolves the binder is used. Examples thereof include, but are not limited to, NMP, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, and tetrahydrofuran. In some cases, a positive electrode active material is slurried with PTFE or the like by adding a dispersant, a thickener, or the like to water.

  As the positive electrode current collector 140, for example, a material obtained by processing a metal such as aluminum or stainless steel, for example, a foil processed into a plate shape, a net, a punched metal, a foam metal, or the like can be used, but is not limited thereto.

(Non-aqueous electrolyte)
The non-aqueous electrolyte 13 is formed by dissolving a supporting salt in an organic solvent.
The supporting salt of the non-aqueous electrolyte 13 is not particularly limited in kind, but an inorganic salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ and LiAsF ₆ , derivatives of these inorganic salts, LiSO ₃ CF ₃ , Organic salt selected from LiC (SO ₃ CF ₃ ) ₃ and LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ) And at least one of these organic salt derivatives. These supporting salts can further improve the battery performance, and can maintain the battery performance higher even in a temperature range other than room temperature. The concentration of the supporting salt is not particularly limited, and it is preferable to appropriately select the supporting salt and the organic solvent in consideration of the use.

The organic solvent (non-aqueous solvent) in which the supporting salt dissolves is not particularly limited as long as it is an organic solvent used in ordinary non-aqueous electrolytes. For example, carbonates, halogenated hydrocarbons, ethers, ketones, Nitriles, lactones, oxolane compounds and the like can be used. In particular, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, vinylene carbonate and the like, and mixed solvents thereof are suitable. Among these organic solvents mentioned in the examples, in particular, by using one or more non-aqueous solvents selected from the group consisting of carbonates and ethers, the solubility of the supporting salt, the dielectric constant and the viscosity are excellent, and the battery The charge / discharge efficiency is preferable.
In the lithium ion secondary battery 1 of the present embodiment, the most preferable nonaqueous electrolyte 13 is one in which the supporting salt is dissolved in an organic solvent.

(Negative electrode)
In the negative electrode 17, a negative electrode mixture obtained by mixing a negative electrode active material and a binder is applied to the surface of the negative electrode current collector 170 to form a negative electrode mixture layer 171.
As the negative electrode active material, a conventional negative electrode active material can be used. A negative electrode active material containing at least one element of Sn, Si, Sb, Ge, and C can be given. Among these negative electrode active materials, C is preferably a carbon material capable of occluding and desorbing electrolyte ions of the lithium ion secondary battery 1 (having Li storage ability), and is preferably amorphous coated natural graphite. More preferred.

  Of these negative electrode active materials, Sn, Sb, and Ge are alloy materials that have a large volume change. These negative electrode active materials may form an alloy with another metal such as Ti—Si, Ag—Sn, Sn—Sb, Ag—Ge, Cu—Sn, and Ni—Sn.

  As the conductive material, a carbon material, metal powder, conductive polymer, or the like can be used. From the viewpoint of conductivity and stability, it is preferable to use a carbon material such as acetylene black, ketjen black, or carbon black.

As the binder, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluororesin copolymer (tetrafluoroethylene / hexafluoropropylene copolymer) SBR, acrylic rubber, fluororubber, Examples thereof include polyvinyl alcohol (PVA), styrene / maleic acid resin, polyacrylate, and carboxymethyl cellulose (CMC).
Examples of the solvent include organic solvents such as N-methyl-2-pyrrolidone (NMP) or water.

  As the negative electrode current collector 170, a conventional current collector can be used, which is obtained by processing a metal such as copper, stainless steel, titanium or nickel, for example, a foil processed into a plate shape, a net, a punched metal, a foam metal. However, it is not limited to these.

(Other configurations)
The positive electrode case 11 and the negative electrode case 16 seal the built-in material via an insulating sealing material 12. The built-in materials are a non-aqueous electrolyte 13, a positive electrode 14, a separator 15, a negative electrode 17, a holding member 18, and the like.
The positive electrode mixture layer 141 is in surface contact with the positive electrode case 11 through the positive electrode current collector 140 to conduct electricity. The negative electrode mixture layer 171 is in surface contact with the negative electrode case 17 via the negative electrode current collector 170.

  The separator 15 interposed between the positive electrode mixture layer 141 and the negative electrode mixture layer 171 electrically insulates the positive electrode mixture layer 141 and the negative electrode mixture layer 171 and holds the nonaqueous electrolyte 13. As the separator 15, for example, a porous synthetic resin film, particularly a porous film of a polyolefin polymer (polyethylene or polypropylene) is used. The separator 15 is formed with a size larger than that of the mixture layers 141 and 171 in order to ensure electrical insulation between the two mixture layers 141 and 171.

  The holding member 18 plays a role of holding the positive electrode current collector 140, the positive electrode mixture layer 141, the separator 15, the negative electrode mixture layer 171, and the negative electrode current collector 170 in place. When an elastic member such as an elastic piece or a spring is used, it can be easily held in place.

(Other forms)
The lithium ion secondary battery 1 of the present embodiment has a coin shape as described above. However, the shape is not particularly limited, and can be applied to batteries of various shapes such as a cylindrical shape and a square shape, and laminate outer bodies. It can be set as the battery of the irregular shape enclosed.

(Production method)
If the positive electrode material of this form has a said structure, the manufacturing method will not be limited. Examples of production methods include solid-phase synthesis, coprecipitation synthesis, hydrothermal synthesis, complex polymerization synthesis, methods via ion exchange, synthesis by high-temperature and high-pressure treatment, sol-gel method, spray-drying method, supercritical synthesis The method etc. are mentioned, The method of combining these methods individually or in multiple numbers etc. can be mentioned.

Hereinafter, the present invention will be described using examples.
As an example for specifically explaining the present invention, a positive electrode material (positive electrode active material), a positive electrode using the positive electrode material, and a lithium ion secondary battery were manufactured. In the example, the lithium ion secondary battery shown in FIG. 1 was manufactured.

Example 1
First, Na ₂ NiSnO ₄ as a starting material was manufactured. Specifically, a compound containing one or more elements of Na, Ni, and Sn was weighed and mixed so that these elements had a predetermined atomic ratio. And it baked (atmosphere atmosphere) and obtained the starting material which has the crystal structure of a substantially single phase.
Subsequently, the obtained Na ₂ NiSnO ₄ was heated in a molten salt composed of Li nitrate and Li chloride to perform an ion exchange treatment.
Thus, the positive electrode material (Li ₂ NiSnO ₄ powder) of this example was manufactured.

When the produced Li ₂ NiSnO ₄ powder was observed with powder XRD, the diffraction result shown in FIG. 2 was obtained.
According to FIG. 2, it can be confirmed that the compound is almost a single phase.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 7.

(Example 2)
An aqueous solution containing each metal complex of Li, Ni, Mn, and Ge was prepared. The obtained complex solution was mixed so as to have the composition ratio of the target positive electrode material, that is, the atomic ratio of Li: Ni: Mn: Ge was 2.1: 1: 0.67: 0.33. .
The obtained mixed solution was dried in a drying furnace to remove organic components by heat treatment, and then heated and baked.
Thus, the positive electrode material (Li _2.1 NiMn _0.67 Ge _0.33 O ₄ powder) of this example was manufactured.

When the produced Li _2.1 NiMn _0.67 Ge _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
In addition, when indexing was performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection was 0. 91.

Example 3
In the same manner as the starting material of Example 1, almost single-phase Na ₂ NiMn _0.67 Ge _0.33 O ₄ was produced.
Subsequently, the obtained Na ₂ NiMn _0.67 Ge _0.33 O ₄ was subjected to an ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ NiMn _0.67 Ge _0.33 O ₄ powder) of this example was manufactured.

When the produced Li ₂ NiMn _0.67 Ge _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 91.

Example 4
In the same manner as in Example 2, a positive electrode material (Li _2.1 NiMn _0.67 Sn _0.33 O ₄ powder) of this example was produced from an aqueous solution containing a metal complex.

When the manufactured Li _2.1 NiMn _0.67 Sn _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 4.

(Example 5)
In the same manner as the starting material of Example 1, almost single phase Na ₂ NiMn _0.67 Sn _0.33 O ₄ was produced.
Subsequently, the obtained Na ₂ NiMn _0.67 Sn _0.33 O ₄ was subjected to an ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ NiMn _0.67 Sn _0.33 O ₄ powder) of this example was manufactured.

When the produced Li ₂ NiMn _0.67 Sn _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 68.

(Example 6)
In the same manner as in Example 2, the positive electrode material of this example (Li _2.1 Ni _0.67 Co _0.67 Mn _0.33 Ge _0.33 O ₄ powder) was produced from the aqueous solution containing the metal complex. It was done.

When the produced Li _2.1 Ni _0.67 Co _0.67 Mn _0.33 Ge _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. There were 35.

(Example 7)
In the same manner as the starting material of Example 1, almost single phase Na ₂ Ni _0.67 Co _0.67 Mn _0.33 Ge _0.33 O ₄ was produced.
Subsequently, the obtained Na ₂ Ni _0.67 Co _0.67 Mn _0.33 Ge _0.33 O ₄ was subjected to ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ Ni _0.67 Co _0.67 Mn _0.33 Ge _0.33 O ₄ powder) of this example was manufactured.

When the produced Li ₂ Ni _0.67 Co _0.67 Mn _0.33 Ge _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 55.

(Example 8)
In the same manner as in Example 6, the positive electrode material of this example (Li _2.1 Ni _0.88 Co _0.22 Mn _0.44 Ge _0.44 O ₄ powder) was produced from the aqueous solution containing the metal complex. It was done.

When the produced Li _2.1 Ni _0.88 Co _0.22 Mn _0.44 Ge _0.44 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. There was one.

Example 9
Almost single phase Na ₂ Ni _0.88 Co _0.22 Mn _0.44 Ge _0.44 O ₄ was produced in the same manner as in Example 1 (Example 7).
Subsequently, the obtained Na ₂ Ni _0.88 Co _0.22 Mn _0.44 Ge _0.44 O ₄ was subjected to an ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ Ni _0.88 Co _0.22 Mn _0.44 Ge _0.44 O ₄ powder) of this example was manufactured.

When the produced Li ₂ Ni _0.88 Co _0.22 Mn _0.44 Ge _0.44 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 34.

(Example 10)
In the same manner as in Example 4, a positive electrode material (Li _2.1 NiMn _0.33 Sb _0.33 Al _0.33 O ₄ powder) of this example was produced from an aqueous solution containing a metal complex.

When the manufactured Li _2.1 NiMn _0.33 Sb _0.33 Al _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. There were 67.

(Example 11)
In the same manner as in Example 1, nearly single-phase Na ₂ NiMn _0.33 Sb _0.33 Al _0.33 O ₄ was produced.
Subsequently, the obtained Na ₂ NiMn _0.33 Sb _0.33 Al _0.33 O ₄ was subjected to ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ NiMn _0.33 Sb _0.33 Al _0.33 O ₄ powder) of this example was manufactured.

When the produced Li ₂ NiMn _0.33 Sb _0.33 Al _0.33 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 71.

(Example 12)
In the same manner as in Example 2, the positive electrode material (Li ₂ NiMn _0.33 Ge _0.67 O ₄ powder) of this example was produced from the aqueous solution containing the metal complex.

When the produced Li ₂ NiMn _0.33 Ge _0.67 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. There were 54.

(Example 13)
In the same manner as in Example 1, almost single phase Na ₂ NiMn _0.33 Ge _0.67 O ₄ was produced.
Subsequently, the obtained Na ₂ NiMn _0.33 Ge _0.67 O ₄ was subjected to an ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ NiMn _0.33 Ge _0.67 O ₄ powder) of this example was manufactured.

When the produced Li ₂ NiMn _0.33 Ge _0.67 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 55.

(Example 14)
In the same manner as in Example 4, a positive electrode material (Li _2.1 NiMn _0.5 Sn _0.5 O ₄ powder) of this example was produced from an aqueous solution containing a metal complex.

When the produced Li _2.1 NiMn _0.5 Sn _0.5 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 36.

(Example 15)
In the same manner as in Example 1, almost single-phase Na ₂ NiMn _0.5 Sn _0.5 O ₄ was produced.
Subsequently, the obtained Na ₂ NiMn _0.5 Sn _0.5 O ₄ was subjected to an ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ NiMn _0.5 Sn _0.5 O ₄ powder) of this example was manufactured.

When the produced Li ₂ NiMn _0.5 Sn _0.5 O ₄ powder was observed with a powder XRD, it was confirmed that it was a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 72.

(Example 16)
In the same manner as in Example 2, a positive electrode material (Li _2.1 Ni _0.77 Mn _0.66 Ge _0.33 O _3.76 powder) of this example was produced from an aqueous solution containing a metal complex. .

When the produced Li _2.1 Ni _0.77 Mn _0.66 Ge _0.33 O _3.76 powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 32.

(Example 17)
In the same manner as in Example 1, almost single phase Na ₂ Ni _0.77 Mn _0.66 Ge _0.33 O _3.76 was produced.
Subsequently, the obtained Na ₂ Ni _0.77 Mn _0.66 Ge _0.33 O _3.76 was subjected to ion exchange treatment in the same manner as in Example 1.
Thus, the positive electrode material (Li ₂ Ni _0.77 Mn _0.66 Ge _0.33 O _3.76 powder) of this example was manufactured.

When the produced Li ₂ Ni _0.77 Mn _0.66 Ge _0.33 O _3.76 powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 32.

(Example 18)
The positive electrode material of this example is Li ₂ NiGeO ₄ powder. This composition was confirmed by ICP analysis.
When Li ₂ NiGeO ₄ powder, which is the positive electrode material of this example, was observed with powder XRD, it was confirmed that it was a substantially single-phase compound and had a layered rock salt type crystal structure.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 01.

(Example 19)
The positive electrode material of this example is Li ₂ Ni _0.67 Ge _0.67 Al _0.67 O ₄ powder. This composition was confirmed by ICP analysis.
The Li ₂ Ni _0.67 Ge _0.67 Al _0.67 O ₄ powder, which is the positive electrode material of this example, was observed with a powder XRD. As a result, the crystal structure of a layered rock salt type was almost a single phase compound. It was confirmed that it had.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 78.

(Comparative Example 1)
In the same manner as in Example 2, a positive electrode material (Li _2.1 NiTiO ₄ powder) of this example was produced from an aqueous solution containing a metal complex.

When the produced Li _2.1 NiTiO ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing was performed with the space group R3m, the peak intensity (I ₀₀₃ ) of 003 reflection was 0 (the peak of 003 reflection could not be confirmed). That is, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) was 0.

(Comparative Example 2)
In the same manner as in Comparative Example 1, a positive electrode material (Li _2.1 NiMn _0.33 Ti _0.67 O ₄ powder) of this example was produced from an aqueous solution containing a metal complex.

When the manufactured Li _2.1 NiMn _0.33 Ti _0.67 O ₄ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 18

(Comparative Example 3)
In the same manner as in Comparative Example 1, a positive electrode material (Li _1.05 NiO ₂ powder) of this example was produced from an aqueous solution containing a metal complex.

When the produced Li _1.05 NiO ₂ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. 35.

(Comparative Example 4)
In the same manner as in Comparative Example 1, a positive electrode material (Li _1.05 CoO ₂ powder) of this example was produced from an aqueous solution containing a metal complex.

When the produced Li _1.05 CoO ₂ powder was observed with a powder XRD, it was confirmed to be a substantially single-phase compound.
Further, when indexing is performed with the space group R3m, the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) between the peak intensity (I ₀₀₃ ) of ₀₀₃ reflection and the peak intensity (I ₁₀₄ ) of 104 reflection is 1. It was 5.

[Evaluation]
As evaluation of the positive electrode material in each of the above examples, a lithium ion secondary battery was assembled, and charge / discharge characteristics were evaluated. After measuring the charge / discharge characteristics, the coin-type battery was disassembled and the positive electrode was taken out, and safety was evaluated.

(Lithium ion secondary battery)
A test cell (2032 type coin type half cell) made of a lithium ion secondary battery was assembled and evaluated using the positive electrode active material of each of the above examples.
(Coin type half cell)
The test cell (coin-type half cell) has the same configuration as the coin-type lithium ion secondary battery 1 whose configuration is shown in FIG.
The positive electrode was prepared by applying a positive electrode mixture obtained by mixing 91 parts by mass of a positive electrode active material (positive electrode active material of each example), 2 parts by mass of acetylene black, and 7 parts by mass of PVDF to a positive electrode current collector 140 made of aluminum foil. Then, the one in which the positive electrode mixture layer 141 was formed was used.

Metal lithium was used for the negative electrode (counter electrode). It corresponds to the negative electrode mixture layer 171 in FIG.
The nonaqueous electrolyte 13 was prepared by dissolving LiPF ₆ in a mixed solvent of 30% by volume of ethylene carbonate (EC) and 70% by volume of diethyl carbonate (DEC) so as to be 1 mol / liter. .
After the test cell was assembled, an activation process was performed by charge / discharge of 1 / 3C × 2 cycles.
The test cell (half cell) of each example was manufactured by the above.

[Charge / discharge characteristics]
The lithium ion secondary battery was charged and discharged at a 1/50 C rate. Charging was performed by CC charging with 4.5V cut, and discharging was performed by CC discharging with 2.6V cut.

  Table 1 shows the measurement results of the charge capacity and discharge capacity of the lithium ion secondary batteries of each example (Examples 1 to 17 and Comparative Examples 1 to 4). In addition, the charge / discharge characteristics of the lithium ion secondary battery of Example 1 are shown in FIG.

As shown in Table 1, the secondary batteries of each example are superior in charge capacity and discharge capacity as compared with Comparative Examples 1 and 2.
Moreover, as shown in FIG. 3, it was confirmed that the secondary battery of Example 1 has good charge / discharge characteristics.

[Safety test]
The lithium ion secondary battery was charged by CC charging up to 4.8 V at a 1/50 C rate.
After charging, the battery was disassembled and the positive electrode was taken out.

The positive electrode taken out was washed with DMC and then heated at a temperature increase rate of 20 ° C./min from room temperature to 1000 ° C. in a helium atmosphere. At that time, the amount of oxygen generated from the positive electrode was measured by TPD-MS measurement.
The measurement results are shown in Table 1.

  As shown in Table 1, the secondary batteries of each example are superior in the amount of generated oxygen compared to Comparative Examples 3-4.

  From the above tests, the secondary battery of each example is a secondary battery excellent in battery characteristics and safety.

1: Lithium ion secondary battery 11: Positive electrode case 12: Sealing material (gasket)
13: Nonaqueous electrolyte 14: Positive electrode 140: Positive electrode current collector 141: Positive electrode mixture layer 15: Separator 16: Negative electrode case 17: Negative electrode 170: Negative electrode current collector 171: Negative electrode mixture layer 18: Holding member

Claims (4)

Li ₂ Ni _α M ¹ _β M ² _γ Mn _η O _4-ε (0.50 <α ≦ 1.33, 0.33 ≦ γ ≦ 1.1, 0 ≦ η ≦ 1.00, 0 ≦ β <0 .67, 0 ≦ ε ≦ 1.00, M ¹ : at least one selected from Co, Ga, M ² : at least one selected from Ge, Sn, Sb)
Having a layered structure comprising a Li layer and a Ni layer;
When the powder X-ray diffraction was measured and indexed with the space group R3m, (003) peak intensity of reflection (I ₀₀₃ ), (104) peak intensity of reflection (I ₁₀₄ ), and peak intensity ratio A positive electrode material having (I ₀₀₃ / I ₁₀₄ ) of 0.9 or more. The positive electrode material according to claim 1, wherein the peak intensity ratio (I ₀₀₃ / I ₁₀₄ ) is 1.2 or more.   A positive electrode (14) for a non-aqueous electrolyte secondary battery comprising the positive electrode material according to any one of claims 1 to 2.   A positive electrode for a non-aqueous electrolyte secondary battery using the positive electrode material according to any one of claims 1 to 2, and at least one of the positive electrode for a non-aqueous electrolyte secondary battery according to claim 3. A nonaqueous electrolyte secondary battery (1) characterized by comprising:

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