JP2011253629A - Positive electrode active material, positive electrode and nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive electrode active material required for a nonaqueous electrolyte secondary battery exhibiting excellent cycle characteristics.SOLUTION: The positive electrode active material has a composition represented by LiFeMPSiO(where, M is at least one kind of metal element selected from Zr, Sn, Y, and Al, 0.05≤x<1, 0.05≤y<1, and 0≤a≤0.05(a is an occupation ratio of iron obtained in the lithium site by Rietveld analysis from a powder X-ray diffraction pattern using a CuKα-ray as a radiation source)).

Description

  The present invention relates to a positive electrode active material, a positive electrode, and a nonaqueous electrolyte secondary battery. More specifically, the present invention relates to a positive electrode active material that provides a nonaqueous electrolyte secondary battery having excellent cycle characteristics, a positive electrode using the same, and a nonaqueous electrolyte secondary battery.

As a non-aqueous electrolyte secondary battery, a lithium secondary battery has been put into practical use and is widely used. Further, in recent years, lithium secondary batteries are attracting attention not only as small-sized batteries for portable electronic devices but also as large-capacity devices for on-vehicle use and power storage. Therefore, demands for safety, cost, life, etc. are higher.
The lithium secondary battery has a positive electrode, a negative electrode, an electrolytic solution, a separator, and an exterior material as main components. The positive electrode includes a positive electrode active material, a conductive material, a current collector, and a binder (binder).
In general, a layered transition metal oxide typified by LiCoO ₂ is used as the positive electrode active material. However, the layered transition metal oxide easily causes oxygen desorption at a relatively low temperature of about 150 ° C. in a fully charged state, and the thermal desorption reaction of the battery can occur due to the oxygen desorption. Therefore, when a battery having such a positive electrode active material is used for a portable electronic device, there is a risk that an accident such as heat generation or ignition of the battery may occur.

For this reason, lithium iron phosphate (LiFePO ₄ ) having an olivine type structure that is stable and does not release oxygen when abnormal and is cheaper than LiCoO ₂ is expected.
LiFePO ₄ is known to have a large volume change rate of about 7% between insertion and desorption of Li, and it is known that capacity deterioration occurs due to repeated charge / discharge cycles. The reason for causing the capacitance change is as follows. That is, the volume change due to repeated charge / discharge causes destruction of the particulate positive electrode active material made of LiFePO ₄ , disconnection of the conductive path, and the like. Due to destruction, disconnection, etc., an increase in internal resistance in the positive electrode or an inactive portion occurs, resulting in capacity deterioration (decrease).
Volume change rate = (A−B) × 100 / A
A is the crystal lattice volume before lithium desorption, B is the crystal lattice volume after lithium desorption, and it is also known that the capacity deteriorates due to the reaction product formed between the nonaqueous electrolyte and the positive electrode interface at high temperatures. Yes.

Various solutions for the capacity degradation have been proposed.
For example, in JP-A-2005-340056 (Cited document 1), an attempt is made to suppress capacity deterioration by putting Al ₂ O ₃ that does not contribute to charging / discharging in the positive electrode.
Japanese Patent Laid-Open No. 2008-166207 (Cited Document 2) also attempts to suppress capacity degradation by putting an inorganic substance that does not contribute to charge / discharge into the positive electrode to increase the dispersibility of the positive electrode active material. .

JP 2005-340056 A JP 2008-166207 A

  However, none of the positive electrode active materials described in the above publication has been able to sufficiently suppress capacity deterioration.

The inventors of the present invention have studied,
(I) Substituting part of the P site of LiFePO ₄ with Si and substituting part of the Fe site (ii) Lithium-containing metal oxidation by reducing the occupation ratio of iron in the lithium site to a predetermined value or less The present inventors have found that the volume change rate of an object can be suppressed, and as a result, capacity deterioration due to charging / discharging can be suppressed, and that the initial capacity reduction can be prevented.

Thus, according to the present invention, the following general formula (1)
Li _a Fe _{1-x + a} M _x P _1-y Si _y O ₄ (1)
(Wherein, M is at least one metal element selected from Zr, Sn, Y, and Al, x is 0.05 ≦ x <1, and y is 0.05 ≦ y <1. Where a is 0 ≦ a ≦ 0.05 (where a is the occupation ratio of iron in the lithium site determined by Rietveld analysis from a powder X-ray diffraction pattern using CuKα rays as a radiation source) )
The positive electrode active material characterized by having the composition represented by these is provided.
Moreover, according to this invention, the positive electrode characterized by including the said positive electrode active material, a electrically conductive material, and a binder is provided.
Furthermore, according to the present invention, there is provided a nonaqueous electrolyte secondary battery comprising a positive electrode including the positive electrode active material, a negative electrode, an electrolyte, and a separator.

In the present invention, a decrease in the initial capacity due to iron occupying the lithium site can be suppressed. Furthermore, it is possible to provide a positive electrode and a non-aqueous electrolyte secondary battery that can suppress capacity change and initial capacity reduction.
When the positive electrode active material has a volume change rate of 5% or less, capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction can be further suppressed.
When M has a valence of +4, capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction can be further suppressed.
When the positive electrode active material has a composition in which M is Zr, it is possible to further suppress capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction.

When the positive electrode active material has a composition defined by x in the range of 0.05 ≦ x ≦ 0.25, capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction can be further suppressed.
When the positive electrode active material has a composition defined by y in the range of 0.10 ≦ y ≦ 0.50, capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction can be further suppressed.
When the positive electrode active material has a composition of 2x = y, capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction can be further suppressed.

In the X-ray diffraction pattern in which the positive electrode active material uses CuKα rays, the ratio (A / B) of peak intensity (A) to (B) of 0.7 or more (however, the peak intensity (A) is 25.4). The peak intensity derived from the (111) plane and the (201) plane around ˜25.6 degrees, and the peak intensity (B) means the peak intensity derived from the (101) plane around 20.5 to 21.0 degrees) When it has, it can suppress the capacity degradation by the repetition of a charging / discharging cycle, and a first time capacity | capacitance fall more.
When the positive electrode active material has a surface coated with carbon, capacity deterioration due to repeated charge / discharge cycles and initial capacity reduction can be further suppressed.

2 is a powder X-ray diffraction pattern of the positive electrode active material of Example 1. FIG. 2 is a powder X-ray diffraction pattern of the positive electrode active material of Example 2. FIG. 2 is a powder X-ray diffraction pattern of a positive electrode active material of Comparative Example 1. It is a schematic sectional drawing of a secondary battery.

_{"The defect chemistry of LiFePO 4 prepared by} hydrothermal method at different pH values Journal of Power Sources, Volume 194, Issue 1,20 October 2009, Pages 536-540 Jiali Liu, Rongrong Jiang, Xiaoya Wang, Tao Huang, Aishui Yu " to According to the report, it has been reported that in LiFePO ₄ , iron can occupy the lithium site slightly. As a result of investigation, the inventors of the present invention, as a result of substituting part of the P site of LiFePO ₄ with Si and substituting part of the Fe site with M, the ratio of iron occupying the lithium site is 10 It has been found that it increases to more than%. It has been found that the increase causes the lithium diffusion path to be interrupted and lithium cannot be removed, resulting in a decrease in initial capacity. Therefore, according to the present invention, by setting the occupation ratio of iron in the lithium site to a predetermined value or less, it is possible to further suppress the capacity deterioration and the initial capacity reduction due to repeated charge / discharge cycles.

The present invention will be described in detail below.
(I) Cathode Active Material The cathode active material is represented by the following general formula (1)
Li _1-a Fe _{1-x + a} M _x P _1-y Si _y O ₄ (1)
(Wherein, M is at least one metal element selected from Zr, Sn, Y, and Al, x is 0.05 ≦ x <1, and y is 0.05 ≦ y <1. Where a is 0 ≦ a ≦ 0.05 (where a is the occupation ratio of iron in the lithium site determined by Rietveld analysis from a powder X-ray diffraction pattern using CuKα rays as a radiation source) )
It is a lithium containing metal oxide which has a composition represented by these. The general formula (I) can be rewritten as (Li _1−a Fe _a ) (Fe _1−x M _x ) (P _1−y Si _y ) O ₄ .

The a value can take a value in the range of 0 to 0.05. When the a value is as small as possible, the amount of lithium in the positive electrode active material increases, and in particular, the decrease in the initial capacity can be suppressed (the initial discharge capacity can be increased). In order to adjust the a value to around 0.05, the firing temperature should be lower than 700 ° C., which is reported to be optimal for conventional LiFePO ₄ , and the composition of Li: Fe should be such that the feed composition becomes excessive. The ratio is set to 0.95: 1.05, etc. In order to prepare it near 0, the firing temperature is set to 650 to 700 ° C., the ratio of Li: Fe is set to 1: 1, and the like. Can be mentioned.
Most lithium-containing metal oxides having the composition of the general formula (1) have an olivine type structure, but may have a configuration not having an olivine type structure.

In general formula (1), M is at least one metal element selected from Sn, Zr, Y, and Al. Further, the valence of M is not particularly limited. Specifically, Y and Al can be trivalent, Sn can be divalent and tetravalent, and Zr can be 2 to 4 valent. Moreover, Fe can take 2-4 valence and 6 valence. For Sn, Zr, and Fe, a single valence metal element can be used, and a mixture of a plurality of valence metal elements can also be used. Among these valences, it is preferable to use tetravalent ones for Sn and Zr from the viewpoint of little change in valence during the production of the lithium-containing metal oxide and during charge and discharge. Since Y and Al are only trivalent, if these are used, the change in valence can be reduced during the production of the lithium-containing metal oxide and during charge and discharge. About Fe, it is preferable to use a bivalent thing from a viewpoint of improving the insertion and detachment | desorption property of Li. In addition, when using a mixture, the valence for prescribing x in General formula (1) means an average value for convenience.
M is preferably a trivalent or tetravalent metal element, and more preferably tetravalent Zr, from the viewpoint that the effect of suppressing the volume change rate is large.

x may be in the range of 0.05 ≦ x <1, and y may be in the range of 0.05 ≦ y <1. From the viewpoint of reducing the volume change rate of the lithium-containing metal oxide, x is preferably in the range of 0.05 ≦ x ≦ 0.25 and / or y is preferably in the range of 0.10 ≦ y ≦ 0.50. , 0.075 ≦ x ≦ 0.25 and / or 0.15 ≦ y ≦ 0.5.
More specifically, when the value of x is large (the amount of substitution at the Fe site with M is large) and / or the value of y is large (the amount of substitution of Si at the P site is large), the volume change rate becomes small. The discharge capacity tends to be small. Therefore, the values of x and y can be determined from the selected type of M and the desired volume change rate and discharge capacity.

Here, the lithium-containing metal oxide preferably has a volume change rate of 5% or less. The reason is that there are many lithium-containing metal oxides in which the slope with respect to the volume change rate of the capacity maintenance ratio (the ratio of the capacity after the charge / discharge cycle to the initial capacity) changes at 5% as a boundary. That is, when the volume change rate is higher than about 5%, the degree of decrease in the capacity maintenance rate with respect to the increase in the volume change rate may increase. Therefore, if the volume change rate is 5% or less, a decrease in the capacity maintenance rate can be further suppressed.
From the viewpoint of setting the volume change rate to 5% or less, it is particularly preferable that x is in the range of 0.05 ≦ x ≦ 0.25 and / or y is in the range of 0.1 ≦ y ≦ 0.5. Within this range, it is possible to suppress volume changes that occur during lithium insertion / extraction without greatly reducing the discharge capacity of the battery.

Furthermore, the larger the value of x and / or the larger the value of y, the more the volume change rate can be suppressed, so that the capacity maintenance rate can be improved. If the volume change rate is 4% or less, the capacity maintenance rate can be 90% or more.
Conversely, the larger the value of x and / or the larger the value of y, the lower the initial capacity. For example, when replacing Fe with Zr, from the viewpoint of obtaining an initial capacity of 100 mAh / g or more, x is preferably 0.35 or less and / or y is 0.7 or less, and an initial capacity of 110 mAh / g or more. From the viewpoint of obtaining x, it is more preferable that x is 0.3 or less and / or y is 0.6 or less, and from the viewpoint of obtaining an initial capacity of 120 mAh / g or more, x is 0.25 or less and / or y is More preferably, it is 0.5 or less.

When replacing Fe with Sn, from the viewpoint of obtaining an initial capacity of 100 mAh / g or more, x is preferably 0.33 or less and / or y is 0.66 or less, and an initial capacity of 110 mAh / g or more is obtained. From the viewpoint, x is preferably 0.29 or less and / or y is 0.58 or less. From the viewpoint of obtaining an initial capacity of 120 mAh / g or more, x is 0.23 or less and / or y is 0.00. More preferably, it is 46 or less.
When replacing Fe with Y, from the viewpoint of obtaining an initial capacity of 100 mAh / g or more, x is preferably 0.35 or less and / or y is preferably 0.35 or less, and an initial capacity of 110 mAh / g or more is obtained. From the viewpoint, x is preferably 0.35 or less and / or y is preferably 0.35 or less. From the viewpoint of obtaining an initial capacity of 120 mAh / g or more, x is 0.25 or less and / or y is 0.00. More preferably, it is 25 or less.

When replacing Fe with Al, from the viewpoint of obtaining an initial capacity of 100 mAh / g or more, x is preferably 0.45 or less and / or y is 0.45 or less, and an initial capacity of 110 mAh / g or more is obtained. From the viewpoint, x is preferably 0.4 or less and / or y is 0.4 or less, and from the viewpoint of obtaining an initial capacity of 120 mAh / g or more, x is 0.35 or less and / or y is 0.00. More preferably, it is 35 or less.
In the case where Fe is substituted with a trivalent metal atom and all of the Fe is divalent, Si can have the same amount as the substitution amount of Fe in order to maintain electrical neutrality. In this case, from the viewpoint of setting the volume change rate to 4% or less, the substitution amount is preferably 0.35 or more for Al and 0.2 or more for Y.

  In the case where Fe is substituted with a +4 valent metal atom and all of the Fe is +2 valent, Si can be double the amount of substitution of Fe in order to maintain electrical neutrality. In this case, from the viewpoint of setting the volume change rate to 4% or less, the substitution amount is preferably 0.15 or more for Zr and 0.25 or more for Sn. Further, from the viewpoint of setting the volume change rate to 3% or less, the substitution amount is preferably 0.2 or more for Zr and 0.3 or more for Sn. Furthermore, from the viewpoint of setting the volume change rate to 2% or less, the substitution amount is preferably 0.25 or more for Zr.

More specifically, as the lithium-containing metal oxide,
_{Li 1-a Fe 1-x} + a Zr x P 1-y Si y O 4 (a is 0.05 or less, 0.05 ≦ x ≦ 0.35,0.1 ≦ y ≦ 0.7)
Li _1-a Fe _{1-x + a} Sn _x P _1-y Si _y O ₄ (a is 0.05 or less, 0.05 ≦ x ≦ 0.33, 0.1 ≦ y ≦ 0.66)
Li _1-a Fe _{1-x + a} Y _x P _1-y Si _y O ₄ (a is 0.05 or less, 0.05 ≦ x ≦ 0.35, 0.1 ≦ y ≦ 0.7)
Li _1-a Fe _{1-x + a} Al _x P _1-y Si _y O ₄ (a is 0.05 or less, 0.05 ≦ x ≦ 0.45, 0.05 ≦ y ≦ 0.9)

Li _1-a Fe _{1-x + a} (Zr, Sn) _x P _1-y Si _y O ₄
(A is 0.05 or less, 0.05 ≦ x ≦ 0.33, 0.1 ≦ y ≦ 0.7, atomic ratio of Zr and Sn 0.99: 0.01 to 0.01: 0.99)
Li _1-a Fe _{1-x + a} (Zr, Y) _x P _1-y Si _y O ₄
(A is 0.05 or less, 0.05 ≦ x ≦ 0.35, 0.1 ≦ y ≦ 0.7, atomic ratio of Zr and Y 0.99: 0.01 to 0.01: 0.99)
Li _1-a Fe _{1-x + a} (Zr, Al) _x P _1-y Si _y O ₄
(A is 0.05 or less, 0.05 ≦ x ≦ 0.45, 0.05 ≦ y ≦ 0.7, atomic ratio of Zr and Al 0.99: 0.01 to 0.01: 0.99)
Li _1-a Fe _{1-x + a} (Sn, Y) _x P _1-y Si _y O ₄
(A is 0.05 or less, 0.05 ≦ x ≦ 0.35, 0.05 ≦ y ≦ 0.66, atomic ratio of Sn and Y 0.99: 0.01 to 0.01: 0.99)
Li _1-a Fe _{1-x + a} (Sn, Al) _x P _1-y Si _y O ₄
(A is 0.05 or less, 0.05 ≦ x ≦ 0.45, 0.05 ≦ y ≦ 0.66, atomic ratio of Sn and Al 0.99: 0.01 to 0.01: 0.99)
Li _1-a Fe _{1-x + a} (Y, Al) _x P _1-y Si _y O ₄
(A is 0.05 or less, 0.05 ≦ x ≦ 0.45, 0.05 ≦ y ≦ 0.45, atomic ratio of Y and Al 0.99: 0.01 to 0.01: 0.99)
Is mentioned.

  Further, when M is +4, x and y preferably have a relationship of 2x = y. When M is +3 valent, x and y preferably have a relationship of x = y. The lithium-containing metal oxide having this relationship gives an effect that oxygen deficiency and elemental defects such as P and Li are less likely to occur in the positive electrode active material, and the crystal structure is strengthened.

(B) Method for Producing Positive Electrode Active Material Lithium-containing metal oxides are prepared by combining combinations of carbonates, hydroxides, chlorides, sulfates, acetates, oxides, oxalates, nitrates, etc. of each element as raw materials. It can be manufactured by using. As the production method, methods such as a firing method, a solid phase method, a sol-gel method, a melt quench method, a mechanochemical method, a coprecipitation method, a hydrothermal method, and a spray pyrolysis method can be used. Among these methods, a firing method under an inert atmosphere (for example, a nitrogen atmosphere) (firing conditions are 400 to 800 ° C. for 1 to 48 hours) is simple.

(C) Others The surface of the positive electrode active material may be coated with carbon in order to improve conductivity. The coating may be on the entire surface of the positive electrode active material or a part thereof.
The ratio of carbon to be coated is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the positive electrode active material. When the amount is less than 1 part by weight, the effect of covering carbon may not be sufficiently obtained. When the amount is more than 10 parts by weight, the capacity of the battery may be decreased in order to inhibit the diffusion of lithium at the interface between the positive electrode active material and the electrolytic solution. A more desirable ratio is in the range of 1.5 to 7 parts by weight.

  The carbon coating method is not particularly limited, and a known method can be used. For example, the lithium-containing metal oxide and / or metal oxide raw material is mixed with a compound serving as a carbon source, and the obtained mixture is fired in an inert atmosphere to coat the mixture. As the compound serving as the carbon source, it is necessary to use a compound that does not prevent the raw material from changing to a lithium-containing metal oxide and / or metal oxide. Examples of such compounds include saccharides such as sucrose and fructose, glycols such as polyethylene glycol, fatty acids such as lauric acid, pitch, and tar.

(II) Nonaqueous electrolyte secondary battery The nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, a nonaqueous electrolyte, and a separator. Hereinafter, each constituent material will be described.
(A) Positive Electrode The positive electrode includes a positive electrode active material, a conductive material, a binder, and a current collector. For example, a known mixture of an active material, a conductive material, and a binder mixed with an organic solvent is applied to the current collector. It can produce by the method of.

As binders (binders), polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, ethylene propylene diene polymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, fluororubber, polyvinyl acetate, polymethyl methacrylate, polyethylene, Nitrocellulose or the like can be used.
As the conductive material, acetylene black, carbon, graphite, natural graphite, artificial graphite, needle coke, or the like can be used.
As the current collector, foamed (porous) metal having continuous pores, metal formed in a honeycomb shape, sintered metal, expanded metal, non-woven fabric, plate, foil, perforated plate, foil, and the like can be used. .

As the organic solvent, N-methyl-2-pyrrolidone, toluene, cyclohexane, dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, methyl acrylate, diethyltriamine, N, N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, etc. are used. be able to.
The thickness of the positive electrode is preferably about 0.01 to 20 mm. If it is too thick, the conductivity is lowered, and if it is too thin, the capacity per unit area is lowered. In addition, you may compress the positive electrode obtained by application | coating and drying with a roller press etc. in order to raise the packing density of an active material.

(B) Negative electrode A negative electrode can be produced by a known method. Specifically, it can be manufactured in the same manner as described in the method for manufacturing the positive electrode. That is, after mixing the known binder and the known conductive material described in the method for producing the positive electrode with the negative electrode active material, the mixed powder is formed into a sheet shape, and the formed body is made of a conductor such as stainless steel or copper. What is necessary is just to crimp | bond to a net | network (current collector). Moreover, it can also produce by apply | coating the slurry obtained by mixing the said mixed powder with the well-known organic solvent demonstrated by the positive electrode preparation method on metal substrates, such as copper.
A known material can be used as the negative electrode active material. In order to constitute a high energy density battery, it is preferable that the potential at which lithium is inserted / desorbed is close to the deposition / dissolution potential of metallic lithium. A typical example is a carbon material such as natural or artificial graphite in the form of particles (scale-like, lump-like, fibrous, whisker-like, spherical, pulverized particles, etc.).

Examples of the artificial graphite include graphite obtained by graphitizing mesocarbon microbeads, mesophase pitch powder, isotropic pitch powder, and the like. Also, graphite particles having amorphous carbon attached to the surface can be used. Among these, natural graphite is more preferable because it is inexpensive, close to the redox potential of lithium, and can constitute a high energy density battery.
Further, lithium transition metal oxide, lithium transition metal nitride, transition metal oxide, silicon oxide, and the like can be used as the negative electrode active material. Among these, Li ₄ Ti ₅ O ₁₂ is more preferable because of high potential flatness and small volume change due to charge and discharge.

(C) Nonaqueous electrolyte As the nonaqueous electrolyte, for example, an organic electrolyte, a gel electrolyte, a polymer solid electrolyte, an inorganic solid electrolyte, a molten salt, or the like can be used. After injecting the nonaqueous electrolyte, the opening of the secondary battery container is sealed. Gas generated by energization before sealing may be removed.

Examples of the organic solvent constituting the organic electrolyte include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC) and butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, dipropyl carbonate, and the like. Chain carbonates, lactones such as γ-butyrolactone (GBL) and γ-valerolactone, furans such as tetrahydrofuran and 2-methyltetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane , Ethers such as ethoxymethoxyethane, dioxane, dimethyl sulfoxide, sulfolane, methyl sulfolane, acetonitrile, methyl formate, methyl acetate and the like. it can.
Moreover, since cyclic carbonates such as PC, EC and butylene carbonate are high-boiling solvents, they are suitable as solvents to be mixed with GBL.

Examples of the electrolyte salt constituting the organic electrolyte include lithium borofluoride (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium trifluoroacetate (LiCF ₃ COO) ), Lithium salts such as lithium bis (trifluoromethanesulfone) imide (LiN (CF ₃ SO ₂ ) ₂ ), and one or more of these may be used in combination. The salt concentration of the electrolytic solution is preferably 0.5 to 3 mol / l.

(D) Separator Examples of the separator include porous materials and nonwoven fabrics. As the material of the separator, the above-described one that does not dissolve or swell in the organic solvent contained in the electrolyte is preferable. Specific examples include polyester polymers, polyolefin polymers (for example, polyethylene and polypropylene), ether polymers, and inorganic materials such as glass.

(E) Other members Various materials used for conventionally known nonaqueous electrolyte secondary batteries can be used for other members such as battery containers, and there is no particular limitation.

(F) Manufacturing method of nonaqueous electrolyte secondary battery The nonaqueous electrolyte secondary battery includes, for example, a laminate including a positive electrode, a negative electrode, and a separator sandwiched therebetween. The laminate may have, for example, a strip-like planar shape. Moreover, when producing a cylindrical or flat battery, the laminate may be wound.
One or more of the laminates are inserted into the battery container. Usually, the positive electrode and the negative electrode are connected to the external conductive terminal of the battery. Thereafter, the battery container is sealed to block the positive electrode, the negative electrode, and the separator from the outside air.

  In the case of a cylindrical battery, the sealing method is generally a method in which a lid having a resin packing is fitted into the opening of the battery container and the battery container and the lid are caulked. In the case of a square battery, a method of attaching a lid called a metallic sealing plate to the opening and performing welding can be used. In addition to these methods, a method of sealing with a binder and a method of fixing with a bolt via a gasket can also be used. Furthermore, a method of sealing with a laminate film in which a thermoplastic resin is attached to a metal foil can also be used. An opening for electrolyte injection may be provided at the time of sealing.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example. The reagents used in the examples were special grade reagents manufactured by Kishida Chemical Co. unless otherwise specified.
[Example 1]
First, 30 ml of ethanol was weighed into a sample bottle as a solvent. As a starting material, 1.3196 g of LiCH ₃ COO as a lithium source was weighed, Fe (NO ₃ ) ₃ · 9H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, silicon Si (OC ₂ H ₅ ) ₄ as a source was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.75: 0.25: 0.5: 0.5, and the solvent It was dissolved in order. After all the raw materials are dissolved in a solvent, the mixture is stirred for 1 week at room temperature with a stirrer, and then left in a constant temperature bath at 40 ° C. for 24 hours to evaporate ethanol to obtain a brown powder. It was.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.75 Zr _0.25 P _0.5 Si _0.5 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as A1.
Sample A1 was pulverized in an agate mortar, and the powder X-ray diffraction pattern shown in FIG. 1 was obtained using an X-ray analyzer MiniFlexII manufactured by Rigaku Corporation. The measurement conditions were a range of 2θ of 10 ° to 90 °, a step of 0.02 °, and a measurement time per step of FT mode of 3 s.

Next, with respect to the obtained powder X-ray diffraction pattern, using “RIETA-2000” (F. IzumI AND T. Ikeda, Mater. Sci. Forum, 321-324 (2000) 198-203), Table 1 Structural analysis by Rietveld analysis using the indicated parameters as initial values was performed. The occupancy ratio of iron and Li at the 4a site was refined under conditions that satisfy the following formula.
4a site iron occupancy + 4a site lithium occupancy = 1
The other occupancy rates were fixed at the initial values shown in Table 1, and the structure was refined.

  The a value obtained from the structural analysis results is obtained by using the occupancy ratio of lithium and iron in the 4a site (lithium site) and the peak intensity composed of the (111) plane and the (201) plane in the vicinity of 25.4 to 25.6 degrees. Table 2 shows the ratio (A / B) of the peak intensity (B) composed of the (101) plane near 20.5 to 21.0 degrees with respect to (A).

[Example 2]
First, 30 ml of ethanol was weighed into a sample bottle as a solvent. As a starting material, 1.3196 g of LiCH ₃ COO as a lithium source was weighed, Fe (NO ₃ ) ₃ · 9H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, silicon Si (OC ₂ H ₅ ) ₄ as a source was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.85: 0.15: 0.7: 0.3, and the solvent It was dissolved in order. After all the raw materials are dissolved in a solvent, the mixture is stirred for 1 week at room temperature with a stirrer, and then left in a constant temperature bath at 40 ° C. for 24 hours to evaporate ethanol to obtain a brown powder. It was.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.85 Zr _0.15 P _0.7 Si _0.3 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as A2. In the same manner as in Example 1, a powder X-ray diffraction pattern A2 shown in FIG. 2 was obtained. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and strength ratio (A / B) of lithium and iron in the 4a site.

Example 3
First, 30 ml of ethanol was weighed into a sample bottle as a solvent. As a starting material, 1.3196 g of LiCH ₃ COO as a lithium source was weighed, Fe (NO ₃ ) ₃ · 9H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, silicon Si (OC ₂ H ₅ ) ₄ as a source was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.875: 0.125: 0.75: 0.25, and the solvent It was dissolved in order. After all the raw materials are dissolved in a solvent, the mixture is stirred for 1 week at room temperature with a stirrer, and then left in a constant temperature bath at 40 ° C. for 24 hours to evaporate ethanol to obtain a brown powder. It was.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked in a nitrogen atmosphere at 600 ° C. for 12 hours to obtain a sample made of Li _a Fe _0.875 Zr _0.125 P _0.75 Si _0.25 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as A3. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and ratio (A / B) of lithium and iron in the 4a site.

Example 4
First, 30 ml of methanol was weighed as a solvent in a sample bottle. As a starting material, 1.3196 g of LiCH ₃ COO as a lithium source was weighed, Fe (NO ₃ ) ₃ · 9H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, silicon Si (OC ₂ H ₅ ) ₄ as a source was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.9: 0.1: 0.8: 0.2, and the solvent It was dissolved in order. After all the raw materials are dissolved in a solvent, the mixture is stirred for 1 week at room temperature with a stirrer, and then left in a constant temperature bath at 40 ° C. for 24 hours to evaporate ethanol to obtain a brown powder. It was.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.9 Zr _0.1 P _0.8 Si _0.2 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as A4. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and ratio (A / B) of lithium and iron in the 4a site.

Example 5
First, 30 ml of methanol was weighed as a solvent in a sample bottle. As a starting material, 1.3196 g of LiCH ₃ COO as a lithium source was weighed, Fe (NO ₃ ) ₃ · 9H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, silicon Si (OC ₂ H ₅ ) ₄ as a source was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.925: 0.075: 0.85: 0.15, and the solvent It was dissolved in order. After all the raw materials are dissolved in a solvent, the mixture is stirred for 1 week at room temperature with a stirrer, and then left in a constant temperature bath at 40 ° C. for 24 hours to evaporate ethanol to obtain a brown powder. It was.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.925 Zr _0.075 P _0.85 Si _0.15 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as A5. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratios of lithium and iron in the 4a site.

[Comparative Example 1]
First, 30 ml of ethanol was weighed into a sample bottle as a solvent. As a starting material, 1.3788 g of LiNO ₃ as a lithium source was weighed, FeCl ₃ .6H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, Si (OC as a silicon source) ₂ H ₅ ) ₄ is weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.75: 0.25: 0.5: 0.5 and dissolved in the solvent in order. I went. After all the raw materials were dissolved in the solvent, the mixture was stirred with a stirrer at room temperature for 1 week, and then left in a constant temperature bath at 40 ° C. for 24 hours to obtain a brown powder.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.75 Zr _0.25 P _0.5 Si _0.5 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as B1. In the same manner as in Example 1, the powder X-ray diffraction pattern of B1 shown in FIG. 3 was obtained. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and ratio (A / B) of lithium and iron in the 4a site.

[Comparative Example 2]
First, 30 ml of ethanol was weighed into a sample bottle as a solvent. As a starting material, 0.4789 g of LiOH was weighed as a lithium source, FeCl ₃ .6H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, and Si (OC ₂ as a silicon source). H ₅ ) ₄ was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.875: 0.125: 0.75: 0.25 and dissolved in the solvent in order. It was. After all the raw materials were dissolved in the solvent, the mixture was stirred with a stirrer at room temperature for 1 week, and then left in a constant temperature bath at 40 ° C. for 24 hours to obtain a brown powder.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked in a nitrogen atmosphere at 600 ° C. for 12 hours to obtain a sample made of Li _a Fe _0.875 Zr _0.125 P _0.75 Si _0.25 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as B2. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and ratio (A / B) of lithium and iron in the 4a site.

[Comparative Example 3]
First, 30 ml of methanol was weighed as a solvent in a sample bottle. 0.4789 g of LiOH as a lithium source was weighed as a starting material, FeCl ₃ · 6H ₂ O as an iron source, ZrOCl ₂ · 8H ₂ O as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, and a silicon source Si (OC ₂ H ₅ ) ₄ was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.9: 0.1: 0.8: 0.2, It was dissolved in order. After all the raw materials were dissolved in the solvent, the mixture was stirred with a stirrer at room temperature for 1 week, and then left in a constant temperature bath at 40 ° C. for 24 hours to obtain a brown powder.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.9 Zr _0.1 P _0.8 Si _0.2 O ₄ . It was confirmed that 2.5 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as B3. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and ratio (A / B) of lithium and iron in the 4a site.

[Comparative Example 4]
First, 30 ml of ethanol was weighed into a sample bottle as a solvent. As a starting material, 1.3196 g of LiCH ₃ COO as a lithium source was weighed, Fe (NO ₃ ) ₃ · 9H ₂ O as an iron source, ZrCl ₄ as a zirconium source, H ₃ PO ₄ (purity 85%) as a phosphorus source, silicon Si (OC ₂ H ₅ ) ₄ as a source was weighed in a molar ratio of Li: Fe: Zr: P: Si = 1: 0.98: 0.02: 0.96: 0.04 to obtain a solvent. It was dissolved in order. After all the raw materials were dissolved in the solvent, the mixture was stirred with a stirrer at room temperature for 1 week, and then left in a constant temperature bath at 40 ° C. for 24 hours to obtain a brown powder.

15 wt% sucrose was added to the obtained powder, mixed well in an agate mortar, and then pressed into a pellet. The obtained pellet-like mixture was baked at 600 ° C. for 12 hours in a nitrogen atmosphere to obtain a sample made of Li _a Fe _0.98 Zr _0.02 P _0.96 Si _0.04 O ₄ . It was confirmed that 2.4 parts by weight of carbon adhered to 100 parts by weight of the sample on the surface of the sample. The obtained sample is designated as B4. In the same manner as in Example 1, the a value is shown in Table 2 together with the occupation ratio and strength ratio (A / B) of lithium and iron in the 4a site.

  From Table 2, it can be seen that the samples of the examples all have a value of 0.05 or less. Moreover, it turns out that the intensity | strength ratio A / B of all the samples of an Example is 0.7 or more.

(Measurement of positive electrode capacity and volume change rate)
For each sample, a positive electrode capacity and volume change rate measurement cell was prepared by the following method.
About 1 g each of A1 to A5 and B1 to B4 are weighed and pulverized in an agate mortar, and about 10 wt% acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive agent and about 10 wt% as a binder. Teflon (registered trademark) resin powder (Kureha KF Polymer Kureha KF Polymer) was mixed.
This mixture was dissolved in N-methyl-2-pyrrolidone to form a slurry, which was applied to both surfaces of an aluminum foil having a thickness of 20 μm by a doctor blade method. The coating amount was about 5 mg / cm ² . After drying this coating film, it was cut so that the electrode application surface was 2 cm × 2 cm, and pressed to obtain a positive electrode.

About 30 ml of electrolyte composed of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate in which 1 mol / liter of LiPF ₆ was dissolved was poured into a 50 ml beaker. A cell was obtained by immersing the positive electrode and metallic lithium as the negative electrode active material in the electrolyte as a counter electrode.
The cell obtained in an environment of 25 ° C. was charged for the first time. The charging current was 0.1 mA, and the charging was terminated when the cell potential reached 4V. After charging was completed, discharging was performed at 1 mA, and discharging was terminated when the cell potential reached 2.0V. The capacity (measured capacity: initial discharge capacity) was calculated from the charging and discharging conditions. The obtained measured capacity is shown in Table 3 together with the theoretical capacity and capacity ratio (measured capacity × 100 / theoretical capacity) of each positive electrode.

The cell was further charged to 4 V with a current of 0.1 mA, and lithium was desorbed. The positive electrode in this state was taken out and subjected to powder X-ray diffraction measurement using CuKα rays to determine the lattice constants (a axis, b axis and c axis) of the positive electrode active material before and after lithium desorption.
The lattice volume before and after lithium desorption was calculated by integrating the a-axis, b-axis, and c-axis, and the volume change rate was calculated by the formula: volume change rate = (A−B) × 100 / A (A is lithium Crystal lattice volume before desorption, B means crystal lattice volume after lithium desorption).
Table 3 shows the lattice constant, the lattice volume, and the volume change rate before and after charging.

(Evaluation of secondary battery)
A secondary battery was prepared for the obtained sample by the following method. About 1 g of each of A1 to A5 and B1 to B4 are weighed and pulverized in an agate mortar, and about 10 wt% acetylene black as a conductive agent and about 10 wt% Teflon (registered trademark) resin powder as a binder. Mixed.
This mixture was dissolved in N-methyl-2-pyrrolidone to form a slurry, which was applied to both surfaces of an aluminum foil having a thickness of 20 μm by a doctor blade method. The coating amount was about 5 mg / cm ² . After drying this coating film, pressing was performed to produce a positive electrode.

As the negative electrode active material, natural graphite powder or lithium titanate (Li ₄ Ti ₅ O ₁₂ ) was used. About 10 wt% of Teflon (registered trademark) resin powder was mixed with this negative electrode active material as a binder. Further, when lithium titanate was used as the negative electrode active material, 10 wt% acetylene black was further mixed as a conductive agent. This mixture was dissolved in N-methyl-2-pyrrolidone to form a slurry, which was applied to both sides of a copper foil having a thickness of 20 μm, dried, and then pressed to produce a negative electrode.
The positive electrode and the negative electrode produced as described above were cut out to a size of 30 mm × 30 mm, respectively, and the positive electrode was provided with a 3 mm wide and 50 mm long aluminum tab as the battery current introduction terminal, and the negative electrode was 3 mm wide and long. A 50 mm copper tab was welded.

A porous polyethylene separator was sandwiched between the positive electrode and the negative electrode. The obtained laminate was sandwiched between a laminate film in which a thermoplastic resin was bonded to two metal foils as a battery exterior, and the periphery was sealed by heat welding. The laminate is provided with an opening for electrolyte injection.
The opening was impregnated with 50% by volume of ethylene carbonate in which 1 mol / liter of LiPF ₆ was dissolved and 50% by volume of diethyl carbonate as an electrolyte. Next, the opening was sealed to obtain a secondary battery shown in FIG. FIG. 4 is a schematic cross-sectional view of a secondary battery. In FIG. 4, 1 is a positive electrode, 2 is a negative electrode, 3 is a separator, 4 is a positive electrode and a negative electrode tab, and 5 is a laminate.

The battery thus produced was charged and discharged in an environment at 25 ° C. The charging current was 0.3 mA, and the charging was terminated when the battery potential reached 4V. After charging was completed, discharging was performed at 0.3 mA, and discharging was completed when the battery potential reached 2.0V. Furthermore, charging / discharging was repeated at a current of 0.3 mA, the discharge capacity at the 100th time was measured, and the capacity retention rate was obtained by the following formula. The results are shown in Table 4.
Capacity retention = 100th discharge capacity / first discharge capacity

Table 4 shows that the positive electrode active materials A1 to A5 in which the occupation ratio of iron in the lithium site is 5% or less have the same type and charge / discharge temperature of the negative electrode active material as compared to the positive electrode active materials B1 to B4. Then, it is clearly shown that a secondary battery having a high discharge capacity and an excellent capacity retention rate is provided.
If the volume change rate is 4% or less, 0.075 ≦ x ≦ 0.25, 0.15 ≦ y ≦ 0.50, 2x = y and an intensity ratio A / B of 0.7 or more is satisfied, 95 It is clearly shown to give a secondary battery with a high capacity retention of more than% and good cycle characteristics.

1: Positive electrode 2: Negative electrode 3: Separator 4: Positive electrode and negative electrode tab 5: Laminate

Claims (11)

The following general formula (1)
Li _1-a Fe _{1-x + a} M _x P _1-y Si _y O ₄ (1)
(Wherein, M is at least one metal element selected from Zr, Sn, Y, and Al, x is 0.05 ≦ x <1, and y is 0.05 ≦ y <1. Where a is 0 ≦ a ≦ 0.05 (where a is the occupation ratio of iron in the lithium site determined by Rietveld analysis from a powder X-ray diffraction pattern using CuKα rays as a radiation source) )
The positive electrode active material characterized by having the composition represented by these.   The positive electrode active material according to claim 1, wherein the positive electrode active material has a volume change rate of 5% or less.   The positive electrode active material according to claim 1, wherein the M has a valence of +4.   The positive electrode active material according to claim 1, wherein the positive electrode active material has a composition in which M is Zr.   The positive electrode active material according to claim 1, wherein the positive electrode active material has a composition defined by x in a range of 0.05 ≦ x ≦ 0.25.   The positive electrode active material according to claim 1, wherein the positive electrode active material has a composition defined by y in a range of 0.10 ≦ y ≦ 0.50.   The positive electrode active material according to claim 1, wherein the positive electrode active material has a composition of 2x = y.   In the X-ray diffraction pattern using CuKα rays, the positive electrode active material has a ratio (A / B) of peak intensity (A) to (B) of 0.7 or more (provided that the peak intensity (A) is 25. The peak intensity derived from the (111) plane and the (201) plane near 4 to 25.6 degrees, and the peak intensity (B) refers to the peak intensity derived from the (101) plane near 20.5 to 21.0 degrees. 8) The positive electrode active material according to any one of claims 1 to 7.   The positive electrode active material according to claim 1, wherein the positive electrode active material has a surface coated with carbon.   A positive electrode comprising the positive electrode active material according to claim 1, a conductive material, and a binder.   A nonaqueous electrolyte secondary battery comprising a positive electrode including the positive electrode active material according to claim 1, a negative electrode, an electrolyte, and a separator.

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