JP5417852B2 - Positive electrode active material, and positive electrode and nonaqueous electrolyte secondary battery using the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a positive electrode active material, a positive electrode using the same, and a nonaqueous electrolyte secondary battery, and more specifically, a positive electrode active material capable of suppressing gas generation inside the battery, and a positive electrode and a non-electrode using the same. The present invention relates to a water electrolyte secondary battery.

  In recent years, the technology of portable electronic devices has been remarkably developed, and electronic devices such as mobile phones and notebook computers have begun to be recognized as basic technologies that support an advanced information society. In addition, research and development related to the enhancement of the functions of these electronic devices have been energetically advanced, and the power consumption of these electronic devices has been increasing proportionally. On the other hand, these electronic devices are required to be driven for a long time, and a high energy density of a secondary battery as a driving power source is inevitably desired. In addition, it has been desired to extend the cycle life for environmental reasons.

  From the standpoint of the occupied volume and mass of the battery built in the electronic device, the higher the energy density of the battery, the better. At present, lithium ion secondary batteries have a high voltage and an excellent energy density as compared with other battery systems, and thus have been built into most devices.

Usually, in lithium ion secondary batteries, lithium transition metal composite oxides such as lithium cobaltate (LiCoO ₂ ) and lithium nickelate (LiNiO ₂ ) are used for the positive electrode, and a carbon material is used for the negative electrode. It is used in the range of 4.2V to 2.5V. In the unit cell, the terminal voltage can be increased to 4.2 V largely due to excellent electrochemical stability such as a non-aqueous electrolyte material and a separator.

  Many studies have been conducted for the purpose of further enhancing the performance and expanding the applications of such lithium ion secondary batteries. As one of them, for example, it has been studied to increase the energy density of a positive electrode active material such as lithium cobaltate by increasing the charging voltage to increase the capacity of the lithium ion secondary battery.

  However, when charging / discharging is repeated at a high capacity, there is a problem that the capacity is deteriorated and the battery life is shortened. Further, when used in a high temperature environment, gas is generated inside the battery, causing problems such as leakage and battery deformation.

  Thus, for example, Patent Document 1 below discloses a method of improving battery characteristics such as charge / discharge cycle characteristics by coating a surface of a positive electrode with a metal oxide. Patent Document 2 listed below describes a method for improving the structural stability and thermal stability by coating the surface of a positive electrode active material with a metal oxide.

  In addition, in the surface coating of the positive electrode active material, the effect of improving the cycle characteristics and the thermal stability due to the coating form has been studied. For example, the following Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, and Patent Literature 8 describe a method of uniformly coating a lithium transition metal composite oxide. Patent Document 9 below describes a positive electrode active material in which a lump of metal oxide is attached on a metal oxide layer.

  Further, elements used for surface coating have also been studied. For example, Patent Document 10 below discloses a positive electrode active material in which one or more surface treatment layers containing two or more coating elements are formed on the surface of a lithium compound serving as a core. Have been described.

  The following Patent Document 11 discloses a battery having excellent charge / discharge characteristics by using a material whose particle surface is coated with phosphorus (P). Patent Document 12 below discloses a battery having excellent charge / discharge cycle characteristics and large current charge / discharge characteristics by using a positive electrode to which phosphorus (P) is added. Patent Document 13 below discloses a method for forming a layer containing boron (B), phosphorus (P), or nitrogen (N). Furthermore, the following patent document 14, the following patent document 15, and the following patent document 16 disclose a method of containing a phosphate compound or the like in the positive electrode.

Japanese Patent No. 3172388 Japanese Patent No. 3691279 JP 7-235292 A JP 2000-149950 A JP 2000-156227 A JP 2000-164214 A JP 2000-195517 A JP 2002-231227 A Japanese Patent Laid-Open No. 2001-256969 JP 2002-164053 A Japanese Patent No. 3054829 JP 05-36411 A Japanese Patent No. 3192855 JP-A-10-154532 Japanese Patent Laid-Open No. 10-241681 JP-A-11-204145

  However, in the covering element, the covering method, and the covering form disclosed in Patent Document 1 and Patent Document 2, since lithium ion diffusion is inhibited, a sufficient capacity cannot be obtained with a charge / discharge current value in a practical range. There is.

  According to the methods disclosed in Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, and Patent Literature 8, although high capacity can be maintained, the cycle characteristics are improved to a high degree and further gas generation is achieved. It is not enough to suppress this. In addition, when a positive electrode active material having a structure in which a lump of metal oxide was adhered on a metal oxide layer by the method disclosed in Patent Document 9, sufficient charge / discharge efficiency was not obtained, and the capacity was large. The result decreased.

  The effect of Patent Document 10 is limited to the improvement of thermal stability. Moreover, when a positive electrode active material was produced by the manufacturing method disclosed in Patent Document 10, a uniform multilayer was formed, and not only an effect was not recognized particularly for suppressing gas generation, but gas generation increased on the contrary. As a result.

  In Patent Document 11, Patent Document 12, and Patent Document 13, the cycle characteristics are improved by adding or coating phosphorus to the positive electrode active material, but these techniques using only light elements that are inert to lithium. Then, sufficient reversible capacity cannot be obtained.

  Patent Document 14 is a technology related to safety during overcharge. In addition, simply mixing a phosphate compound or the like in the positive electrode does not actually provide a sufficient effect. Similarly, in Patent Document 15 and Patent Document 16 described above, since a phosphate compound or the like is simply mixed in the positive electrode, the effect is insufficient.

  Thus, by modifying the positive electrode active material, cycle characteristics or thermal stability can be improved to some extent, but on the other hand, battery capacity tends to decrease. Further, the degree of improvement in battery characteristics obtained by the above-described method is not sufficient, and further improvement is desired for suppression of gas generation inside the battery that occurs in a high temperature environment.

  Accordingly, an object of the present invention is to provide a positive electrode that has a high capacity, is excellent in charge / discharge cycle characteristics, and can suppress gas generation, and a nonaqueous electrolyte secondary battery using the positive electrode.

（式（１）中、ＭはＬｉである。ａ、ｃ、ｄはそれぞれ０以上の整数である。ｂは１以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする炭化水素基である。）

（式（１）’中、ＭはＭｇである。ａは１である。ｂは１であり、ｃ＝ｄ＝０である。ａ、ｂ、ｃ、ｄの和は２である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ３は２価の炭化水素基である。） In order to solve the above-mentioned problem, the first invention
Particles comprising a cathode material capable of occluding and releasing electrode reactants;
A positive electrode active material provided with at least a part of the particles and a coating containing at least one of metal salts represented by the formulas (1) to (1) ′ .

(In Formula (1), M is Li . Each of a, c and d is an integer of 0 or more. B is an integer of 1 or more. The sum of a, b, c and d is an integer of 2 or more.) And the sum of a and b is an integer equal to or greater than 1. e, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are all monovalent groups and are bonded to each other. (R3 is a hydrocarbon group having a valence of the sum of a, b, c, and d.)

(In Formula (1) ′, M is Mg, a is 1, b is 1, and c = d = 0. The sum of a, b, c, and d is 2. e, f, g and h are each an integer of 1 or more, and R3 is a divalent hydrocarbon group.

  In the first invention, R1 and R2 in the above formula (1) are an alkyl group, an alkenyl group, an alkynyl group, a trialkylsilyl group, or a group obtained by halogenating them, and R3 is a hydrocarbon group. preferable.

In the first invention, the metal salt represented by the formula (1) is dilithium ethanedisulfonate, dilithium propanedisulfonate, dilithium sulfoacetate, dilithium sulfopropionate, dilithium sulfobutanoate, sulfobenzoate. It is preferably at least one selected from the group consisting of dilithium acid, dilithium succinate, and trilithium sulfosuccinate .
Metal salt represented by the formula (1) 'is magnesium scan Ruhopuropion acid, magnesium Suruhobutan acid is preferably at least one selected from the group consisting of sulfobenzoic acid magnesium.

Moreover, in 1st invention, it is preferable that a film contains alkali metal salt or alkaline-earth metal salt other than the metal salt represented by Formula (1)-Formula (1) ' .

  In the first invention, the particles preferably include at least lithium and one or more transition metals.

  In the first invention, the particles preferably include cobalt (Co) as a main transition metal element and have a layered structure. Furthermore, it is preferable that at least a part of the surface of the particle contains one or more elements different from the main transition metal element constituting the particle. The element different from the main transition metal element constituting the particles preferably contains at least one of nickel (Ni), manganese (Mn), and phosphorus (P).

（式（１）中、ＭはＬｉである。ａ、ｃ、ｄはそれぞれ０以上の整数である。ｂは１以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする炭化水素基である。）

（式（１）’中、ＭはＭｇである。ａは１である。ｂは１であり、ｃ＝ｄ＝０である。ａ、ｂ、ｃ、ｄの和は２である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ３は２価の炭化水素基である。） The second invention is
A conductive substrate;
A positive electrode active material layer provided on a conductive substrate and including at least a positive electrode active material,
The positive electrode active material is
Particles comprising a cathode material capable of occluding and releasing electrode reactants;
It is a positive electrode provided with at least one part of particle | grains and the film containing at least any one of the metal salts represented by Formula (1)-Formula (1) ' .

(In Formula (1), M is Li . Each of a, c and d is an integer of 0 or more. B is an integer of 1 or more. The sum of a, b, c and d is an integer of 2 or more.) And the sum of a and b is an integer equal to or greater than 1. e, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are all monovalent groups and are bonded to each other. (R3 is a hydrocarbon group having a valence of the sum of a, b, c, and d.)

(In Formula (1) ′, M is Mg, a is 1, b is 1, and c = d = 0. The sum of a, b, c, and d is 2. e, f, g and h are each an integer of 1 or more, and R3 is a divalent hydrocarbon group.

（式（１）中、ＭはＬｉである。ａ、ｃ、ｄはそれぞれ０以上の整数である。ｂは１以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする炭化水素基である。）

（式（１）’中、ＭはＭｇである。ａは１である。ｂは１であり、ｃ＝ｄ＝０である。ａ、ｂ、ｃ、ｄの和は２である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ３は２価の炭化水素基である。） The third invention is
A positive electrode having a positive electrode active material, a negative electrode, a separator, and an electrolyte;
The positive electrode active material is
Particles comprising a cathode material capable of occluding and releasing electrode reactants;
A non-aqueous electrolyte secondary battery comprising: a coating film provided on at least a part of the particles and including at least one of metal salts represented by formulas (1) to (1) ′ .

(In Formula (1), M is Li . Each of a, c and d is an integer of 0 or more. B is an integer of 1 or more. The sum of a, b, c and d is an integer of 2 or more.) And the sum of a and b is an integer equal to or greater than 1. e, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are all monovalent groups and are bonded to each other. (R3 is a hydrocarbon group having a valence of the sum of a, b, c, and d.)

(In Formula (1) ′, M is Mg, a is 1, b is 1, and c = d = 0. The sum of a, b, c, and d is 2. e, f, g and h are each an integer of 1 or more, and R3 is a divalent hydrocarbon group.

  In 3rd invention, it is preferable that an upper limit charging voltage is 4.25V or more and 4.80V or less, and a lower limit discharge voltage is 2.00V or more and 3.30V or less. This is because the energy density can be improved.

In this invention, at least one of the metal salts represented by the above formulas (1) to (1) ′ is included in at least a part of the particles including the positive electrode material capable of occluding and releasing the electrode reactant. Since the film containing these is formed, the chemical stability of the positive electrode active material can be improved. When a positive electrode having this positive electrode active material is used in an electrochemical device such as a battery together with an electrolytic solution, the electrode reactant is efficiently transmitted and decomposition of the electrolytic solution is suppressed. Therefore, in the battery using the positive electrode active material of the present invention, it is possible to realize a high charge voltage property and a high energy density property associated therewith, a good charge / discharge cycle characteristic even under a high charge voltage, and a gas inside the battery Occurrence can be suppressed.

  According to the present invention, it is possible to realize a non-aqueous electrolyte secondary battery having a high capacity, excellent charge / discharge cycle characteristics, and less gas generation inside the battery.

It is an expanded sectional view showing the composition of the cathode by one embodiment of this invention. It is sectional drawing showing the structure of the battery by the 1st example of this invention. FIG. 3 is an enlarged sectional view showing a part of a wound electrode body in the battery shown in FIG. 2. It is sectional drawing showing the structure of the battery by the 2nd example of this invention. It is sectional drawing along the II line of the winding electrode body shown in FIG. It is a graph which shows the result by TOF-SIMS analysis.

  An embodiment of the present invention will be described below with reference to the drawings.

(1) Configuration of Positive Electrode Active Material In the positive electrode active material according to one embodiment of the present invention, a coating is provided on at least a part of particles including a positive electrode material capable of occluding and releasing an electrode reactant. Is.

  The positive electrode material capable of occluding and releasing the electrode reactant is preferably a compound capable of occluding and releasing lithium. Specifically, as the positive electrode material, for example, a lithium-containing compound such as lithium oxide, lithium phosphorus oxide, lithium sulfide, or an intercalation compound containing lithium is suitable, and a mixture of two or more of these is used. Also good. In order to increase the energy density, a lithium-containing transition metal oxide containing at least lithium (Li) and one or more transition metal elements is preferable. Among them, lithium cobaltate, lithium nickelate, nickel cobalt manganese composite lithium oxide A lithium-containing compound having a layered structure such as a product is more preferable from the viewpoint of increasing the capacity. In particular, a lithium cobaltate-containing transition metal oxide mainly composed of lithium cobaltate is preferable because of its high filling property and high discharge voltage. The lithium cobaltate-containing transition metal oxide may be substituted with at least one element selected from Groups 2 to 15 or subjected to fluorination treatment.

  Examples of such lithium-containing compounds include lithium composite oxides having an average composition represented by chemical formula I, more specifically chemical formula II, and lithium composite oxides having an average composition represented by chemical formula III. be able to.

(Chemical I)
_{Li p Ni (1-qr)} Mn q M1 r O (2-y) X z
(In the formula, M1 represents at least one element selected from Group 2 to Group 15 excluding nickel (Ni) and manganese (Mn). X represents Group 16 element and Group 17 element other than oxygen (O). P, q, r, y, and z are 0 ≦ p ≦ 1.5, 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.0, −0.10 ≦ y ≦. (The values are within the range of 0.20 and 0 ≦ z ≦ 0.2. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of p represents the value in a fully discharged state.)

(Chemical II)
Li _a Co _(1-b) M2 _b O _(2-c)
(Wherein M2 is vanadium (V), copper (Cu), zirconium (Zr), zinc (Zn), magnesium (Mg), aluminum (Al), gallium (Ga), yttrium (Y) and iron (Fe). Represents at least one of the group consisting of: values of a, b and c are 0.9 ≦ a ≦ 1.1, 0 ≦ b ≦ 0.3, −0.1 ≦ c ≦ 0.1 Note that the composition of lithium varies depending on the state of charge and discharge, and the value of a represents the value in a fully discharged state.)

(Chemical III)
Li _w Ni _x Co _y Mn _z M3 _(1-xyz) O _(2-v)
(Wherein M3 is vanadium (V), copper (Cu), zirconium (Zr), zinc (Zn), magnesium (Mg), aluminum (Al), gallium (Ga), yttrium (Y) and iron (Fe). It represents at least one of the group consisting of: v, w, x, y and z have values of −0.1 ≦ v ≦ 0.1, 0.9 ≦ w ≦ 1.1, 0 <x <. 1, 0 <y <1, 0 <z <0.5, 0 ≦ 1-xyz The composition of lithium varies depending on the state of charge and discharge, and the value of w is a complete discharge. Represents the value in the state.)

Further, examples of the lithium-containing compound include a lithium composite oxide having a spinel structure represented by Formula IV, more specifically, Li _d Mn ₂ O ₄ (d≈1). .

(Chemical IV)
_{Li p Mn (2-q)} M4 q O r F s
(In the formula, M4 is cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe ), Copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W). q, r, and s are values within the range of 0.9 ≦ p ≦ 1.1, 0 ≦ q ≦ 0.6, 3.7 ≦ r ≦ 4.1, and 0 ≦ s ≦ 0.1. Note that the composition of lithium varies depending on the state of charge and discharge, and the value of p represents a value in a fully discharged state.

Furthermore, examples of the lithium-containing compound may include, for example, a chemical compound V, more specifically, a lithium composite phosphate having an olivine type structure represented by chemical compound VI. _e FePO ₄ (e≈1).

(Chemical V)
Li _a M5 _b PO ₄
(In the formula, M5 represents at least one element selected from Group 2 to Group 15. a and b are in the range of 0 ≦ a ≦ 2.0 and 0.5 ≦ b ≦ 2.0. Value.)

(Chemical VI)
Li _t M6PO ₄
(In the formula, M6 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V ), Niobium (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W) and zirconium (Zr) T is a value in a range of 0.9 ≦ t ≦ 1.1, wherein the composition of lithium varies depending on the state of charge and discharge, and the value of t represents a value in a complete discharge state. )

  Such particles can be used as starting materials that are usually available as positive electrode active materials, but in some cases, they can be used after pulverizing secondary particles using a ball mill or a grinder. .

Alternatively, lithium composite oxide particles in which an element different from the main transition metal is present on the surface by coating with an element different from the main transition metal constituting the lithium composite oxide may be used. This is because higher electrochemical stability can be obtained. The element different from the main transition metal preferably includes at least one of nickel (Ni), manganese (Mn), and phosphorus (P). The main transition metal constituting the lithium composite oxide particles means the transition metal having the largest ratio among the transition metals constituting the particles. For example, when lithium cobaltate having an average composition of LiCo _0.98 Al _0.01 Mg _0.01 O ₂ is used as the lithium composite oxide, the main transition metal is cobalt, and it is preferable that the coating treatment is performed with nickel, manganese, phosphorus, or the like. .

  In addition to the above, the positive electrode material capable of occluding and releasing the electrode reactant is, for example, an oxide such as titanium oxide, vanadium oxide or manganese dioxide, iron disulfide, titanium disulfide, molybdenum sulfide, etc. Examples include disulfides, chalcogenides such as niobium selenide, and conductive polymers such as sulfur, polyaniline, and polythiophene.

  The coating provided on at least a part of the particles may be formed so as to cover the entire surface of the particle including the positive electrode material capable of occluding and releasing the electrode reactant, or a part or more of the surface. It may be formed. This coating contains a metal salt represented by the formula (1).

（Ｍは金属元素である。ａ、ｂ、ｃ、ｄはそれぞれ０以上の整数である。ａ、ｂ、ｃ、ｄの和は２以上の整数であり、ａとｂとの和は１以上の整数である。ｅ、ｆ、ｇ、ｈはそれぞれ１以上の整数である。Ｒ１およびＲ２は、いずれも１価の基であり、互いに結合して環を形成してもよい。Ｒ３は、ａ、ｂ、ｃ、ｄの和を価数とする基である。）

(M is a metal element. Each of a, b, c and d is an integer of 0 or more. The sum of a, b, c and d is an integer of 2 or more, and the sum of a and b is 1 or more. E, f, g, and h are each an integer equal to or greater than 1. Each of R1 and R2 is a monovalent group, and may be bonded to each other to form a ring. It is a group having the valence as the sum of a, b, c, and d.)

  Among these, a metal salt in which b or d in formula (1) is 1 or more is preferable. It is because it can have inertness and high oxidation resistance by including a sulfonic acid.

  R1 and R2 in Formula (1) are, for example, an alkyl group, an alkenyl group, an alkynyl group, a trialkylsilyl group, or a group obtained by halogenating them. Here, the “group in which they are halogenated” means a group in which at least a part of hydrogen groups are substituted with halogen groups. In addition, R1 and R2 in Formula (1) may mutually be the same, and may differ. Furthermore, in the trialkylsilyl group, the alkyl groups adjacent to the silicon atom may be the same as or different from each other. Moreover, R3 in Formula (1) is a hydrocarbon group, for example.

  Such a coating contributes to the improvement of the chemical stability of the positive electrode active material. When a positive electrode using a positive electrode active material provided with such a coating is used in an electrochemical device such as a battery together with an electrolytic solution, the electrode reactant is efficiently permeated and the decomposition of the electrolytic solution is suppressed. It is possible to achieve both suppression of gas generation from the battery and increase in the capacity of the battery. Further, cycle characteristics can be improved by suppressing the decomposition of the electrolytic solution. In addition, the decomposition product may be contained in the film with the metal salt shown in Formula (1).

  As M shown in Formula (1), it is desirable to use an alkali metal element (Group 1A element excluding hydrogen) or an alkaline earth metal element (Group 2A element). In particular, lithium is preferable among alkali metal elements, and magnesium or calcium is preferable among alkaline earth metal elements. This is because higher effects can be obtained by using these lithium, magnesium, or calcium.

  Examples of the metal salts represented by the formula (1) are listed below. First, as for M which is lithium among alkali metal elements, dilithium methanedisulfonate, dilithium ethanedisulfonate, dilithium propanedisulfonate, dilithium benzenedisulfonate, dilithium naphthalenedisulfonate, biphenyldisulfonic acid. Dilithium salts having two sulfonic acid groups such as dilithium, sulfonic acid groups and carboxylic acids such as dilithium sulfoacetate, dilithium sulfophenylacetate, dilithium sulfopropionate, dilithium sulfobutanoate and dilithium sulfobenzoate Or a dilithium salt having a group, or dilithium succinate, dilithium maleate, dilithium fumarate, dilithium itaconate, dilithium mesaconic acid, dilithium citraconic acid, dilithium phthalate, naphthalenedicarboxylic acid It includes dilithium salt having two carboxylic acid groups, such as lithium. In addition, dilithium salts partially fluorinated include dilithium tetrafluoroethanedisulfonate, dilithium hexafluoropropanedisulfonate, dilithium tetrafluorosulfopropionate, dilithium hexafluorosulfobutanoate, and tetrafluorosulfobenzoic acid. Examples thereof include a dilithium salt having two sulfonic acid groups such as dilithium, or a dilithium salt having a sulfonic acid group and a carboxylic acid group such as dilithium tetrafluorosuccinate and dilithium tetrafluorophthalate.

  Of the metal salts represented by the formula (1), as M being lithium, not only the above-mentioned dilithium salts, but also trilithium salts, tetralithium salts, pentalithium salts, and the like can be used. Examples of the trilithium salt include trilithium disulfobenzoate, trilithium sulfophthalate, trilithium sulfoisophthalate, trilithium sulfoterephthalate, trilithium methanetricarboxylate, and trilithium aconitic acid. Tetralithium salts include propanetetracarboxylic acid tetralithium, cyclopentanetetracarboxylic acid tetralithium, tetrahydrofurantetracarboxylic acid tetralithium, butanetetracarboxylic acid tetralithium, benzenetetracarboxylic acid tetralithium, disulfonaphthalenedicarboxylic acid tetralithium. Examples thereof include lithium, tetralithium naphthalene tetracarboxylate, and tetralithium biphenyl tetracarboxylate. Furthermore, examples of the pentalithium salt include pentalithium biphenylsulfotetracarboxylate.

  In addition to the above, among the metal salts represented by the formula (1), trilithium sulfosuccinate, dilithium ethylsulfosuccinate, lithium diethylsulfosuccinate and the like can be used as M.

  As mentioned above, although the metal salt shown by Formula (1) whose M is lithium was enumerated, M may be sodium (Na), magnesium (Mg), or calcium (Ca). For example, sodium salts include disodium ethanedisulfonate, disodium propanedisulfonate, disodium sulfopropionate, disodium sulfobutanoate, disodium sulfobenzoate, and the like, Examples include disodium salts having two carboxylic acid groups such as disodium acid, disodium maleate, disodium fumarate, disodium phthalate, disodium squarate, and disodium croconate. Examples of the magnesium salt include magnesium ethanedisulfonate, magnesium propanedisulfonate, magnesium sulfoacetate, magnesium sulfopropionate, magnesium sulfobenzoate, magnesium succinate, dimagnesium trisulfosuccinate, and magnesium squarate. Examples of calcium salts include calcium ethanedisulfonate, calcium propanedisulfonate, calcium sulfoacetate, calcium sulfopropionate, calcium sulfobenzoate, calcium succinate, tricalcium disulfosuccinate, and calcium squarate.

  In particular, the coating is a metal salt represented by the formula (1), and the dithane ethanedisulfonate, dilithium propanedisulfonate, dilithium sulfoacetate, disulfopropionic acid shown in the order of the formulas (2) to (9). Lithium, dilithium sulfobutanoate, dilithium sulfobenzoate, dilithium succinate, trilithium sulfosuccinate, magnesium ethanedisulfonate, magnesium propanedisulfonate, magnesium sulfoacetate shown in the order of formulas (10) to (17), Magnesium sulfopropionate, magnesium sulfobutanoate, magnesium sulfobenzoate, magnesium succinate, trimagnesium disulfosuccinate, or calcium ethanedisulfonate, calcium propanedisulfonate, sulfoacetic acid sequentially shown in formulas (18) to (25) Mosquito A high effect can be obtained by including at least one selected from the group consisting of calcium, calcium sulfopropionate, calcium sulfobutanoate, calcium sulfobenzoate, calcium succinate, and tricalcium disulfosuccinate. Therefore, it is preferable. Among these, it is preferable to include dilithium sulfopropionate, trilithium sulfosuccinate, and magnesium sulfopropionate because higher effects can be obtained.

  In the coating, any of the above-described metal salts represented by the formula (1) may be mixed and used.

Further, the coating preferably contains an alkali metal salt or an alkaline earth metal salt other than the metal salt represented by the formula (1) in addition to the above compound, and among them, other lithium salts are included. It is preferable. This is because the film resistance is reduced and the cycle characteristics can be further improved. Examples of other alkali metal salts or other alkaline earth metal salts include carbonates, halide salts, borates, and phosphates of alkali metal elements or alkaline earth metal elements. Specific examples include, for example, lithium carbonate (Li ₂ CO ₃ ), lithium fluoride (LiF), lithium tetraborate (Li ₂ B ₄ O ₇ ), lithium metaborate (LiBO ₂ ), lithium pyrophosphate (Li _4). P ₂ O ₇ ), lithium tripolyphosphate (Li ₅ P ₃ O ₁₀ ), lithium orthosilicate (Li ₄ SiO ₄ ), lithium metasilicate (Li ₂ SiO ₃ ), or the like. Of course, these may be mixed and used.

In addition, the film containing such a metal salt is confirmed by analyzing the surface of the positive electrode active material by, for example, TOF-SIMS (Time of Flight secondary Ion Mass Spectrometry). Can do. For example, C ₇ H ₄ SO ₅ Li ₃ ⁺ , C ₂ H ₄ S ₂ O ₆ Li ₃ ⁺ , C ₃ H ₄ SO ₅ Li ₃ ⁺ , and C ₃ H ₆ S _{2 are obtained} by surface analysis by TOF-SIMS of the positive electrode. Positive secondary ions composed of O ₆ Li ₃ ⁺ , C ₄ H ₄ O ₄ Li ₃ ⁺ , C ₄ H ₈ S ₂ O ₆ Li ₃ ⁺ and C ₄ O ₄ Li ₃ ⁺ , and C ₂ H ₃ SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , C ₆ H ₄ SO ₃ Li ⁻ , C ₆ H ₄ SO ₄ Li ⁻ , C ₇ H ₅ SO ₄ ⁻ , C ₇ H ₄ SO ₅ Li ⁻ C ₂ H ₄ S ₂ O ₆ Li ⁻ , C ₃ H ₄ SO ₅ Li ⁻ , C ₃ H ₆ S ₂ O ₆ Li ⁻ , C ₄ H ₄ O ₄ Li ⁻ , C ₄ H ₈ S ₂ O ₆ Li ^- and C ₄ O ₄ Li ^- peak of at least one of the secondary ions selected from among the negative secondary ions consisting of is obtained. The same applies to the case where the positive electrode is present in an electrochemical device such as a secondary battery. In this case, an electrochemical device is prepared, disassembled, and the positive electrode is taken out. The surface analysis may be performed by SIMS.

  The average particle diameter of the positive electrode active material is preferably in the range of 2.0 μm to 50 μm. If the thickness is less than 2.0 μm, the positive electrode active material is easily peeled off from the positive electrode current collector in the pressing step when the positive electrode is produced, and the surface area of the positive electrode active material is increased, so that a conductive agent or a binder is added. This is because the amount must be increased, and the energy density per unit mass becomes small. On the other hand, when the thickness exceeds 50 μm, there is a high possibility that the positive electrode active material penetrates the separator and causes a short circuit.

(2) Configuration of Positive Electrode Next, a usage example of the positive electrode active material described above will be described with reference to FIG. FIG. 1 shows a cross-sectional structure of a positive electrode according to an embodiment of the present invention. This positive electrode is used for, for example, an electrochemical device such as a battery, and has a positive electrode current collector 1 having a pair of opposed surfaces and a positive electrode active material layer 2 provided on the positive electrode current collector 1. doing.

  The positive electrode current collector 1 is preferably made of a material having good chemical stability, electrical conductivity, and mechanical strength. Examples of such a material include metal materials such as aluminum, nickel, and stainless steel.

  The positive electrode active material layer 2 includes, for example, any one or more of the positive electrode active materials as described above, and includes a conductive agent and a binder as necessary. The positive electrode active material layer 2 may be provided on both sides of the positive electrode current collector 1 or may be provided on one side.

  Examples of the conductive agent include carbon materials such as graphite, carbon black, acetylene black, and ketjen black. These may be used alone or in combination of two or more. Note that the conductive agent may be a metal material or a conductive polymer as long as it is a conductive material.

  Examples of the binder include synthetic rubbers such as styrene butadiene rubber, fluorine rubber or ethylene propylene diene, and polymer materials such as polyvinylidene fluoride. These may be used alone or in combination of two or more.

  Since this positive electrode has a positive electrode active material on the surface of which a coating containing the metal salt represented by the above formula (1) is formed, when this positive electrode is used in an electrochemical device such as a battery, it has a high capacity. And charge / discharge cycle characteristics can be improved, and gas generation can be suppressed.

(3) Positive electrode active material and positive electrode manufacturing method A positive electrode active material and a positive electrode according to an embodiment of the present invention are manufactured, for example, by the following procedure. First, for example, particles including a positive electrode material that can be normally stored as a positive electrode active material and capable of inserting and extracting an electrode reactant are prepared as a starting material, and the particle surface is coated as necessary.

  The coating treatment is performed, for example, by pulverizing and mixing lithium-containing composite oxide particles as a positive electrode material and a compound containing an element different from the main transition metal constituting the lithium-containing composite oxide. Thereby, an element different from the main transition metal constituting the lithium-containing composite oxide is deposited on the surface of the lithium-containing composite oxide particles. As the deposition means, for example, a ball mill, a jet mill, a pulverizer, a fine pulverizer or the like can be used. In this case, it is also effective to add some liquid, which can be exemplified by water. Further, it can be deposited by a mechanochemical treatment such as mechanofusion, or a vapor phase method such as a sputtering method or a chemical vapor deposition (CVD) method. Furthermore, it can be applied by a wet method such as a method of mixing raw materials in water or a solvent such as ethanol, a neutralization titration method, or a sol-gel method using metal alkoxide as a raw material.

  Further, the lithium-containing composite oxide particles deposited with an element different from the main transition metal may be baked at a temperature of, for example, 300 ° C. to 1000 ° C. in an oxidizing atmosphere such as air or pure oxygen. Further, after firing, the particle size may be adjusted by light pulverization or classification operation, if necessary. Further, different coating layers may be formed by performing the coating treatment twice or more.

  Then, a metal salt layer containing the metal salt represented by the above formula (1) is formed on at least a part of the surface of the starting material particles or the particles provided with the coating layer as described above. The positive electrode active material according to the embodiment is prepared. In this specification, a layer on the surface of the positive electrode active material before battery assembly is referred to as a coating layer, and a layer on the surface of the positive electrode active material after battery assembly is referred to as a coating as appropriate. Examples of a method for forming a metal salt layer on the particles include a liquid phase method such as a coating method, a dipping method, or a dip coating method, and a vapor phase method such as a vapor deposition method, a sputtering method, or a CVD method. As a method of forming the metal salt layer, any of these methods may be used alone, or two or more methods may be used. Especially, as a liquid phase method, it is preferable to form a metal salt layer using the solution containing the metal salt shown to Formula (1). Specifically, for example, particles containing a positive electrode material capable of occluding and releasing an electrode reactant are mixed and stirred in a solution containing the above metal salt, and then the solvent is removed.

  The amount of the metal salt represented by the formula (1) added to the solvent by the liquid phase method is, for example, 0 with respect to the particles of the starting material or the particles provided with the coating layer as described above. It is preferably larger than 1% by weight and smaller than 5% by weight, more preferably 0.2% by weight to 3.0% by weight. When the addition amount is smaller than this range, it becomes difficult to improve the discharge capacity and charge / discharge cycle characteristics and to obtain the effect of suppressing gas generation. If the amount added exceeds this range, it will be difficult to increase the energy density of the positive electrode active material, and the effect of improving the discharge capacity and charge / discharge cycle characteristics will be reduced.

  Next, a positive electrode is produced using the produced positive electrode active material. The method for producing the positive electrode is not limited. For example, a known binder, a conductive agent, etc. are added to the positive electrode active material, and a solvent is added to apply on the positive electrode current collector 1. A known binder, a conductive agent, etc. are added to the positive electrode active material. A method of heating and applying on the positive electrode current collector 1 is employed. Further, a method of producing a molded body electrode on the positive electrode current collector 1 by taking a treatment such as molding by mixing the positive electrode active material alone or with a conductive agent or a binder, and the like can be used. However, the method for manufacturing the positive electrode is not limited thereto.

  More specifically, first, for example, a positive electrode active material, a conductive agent, and a binder are mixed to prepare a positive electrode mixture, and this positive electrode mixture is mixed with a solvent such as 1-methyl-2-pyrrolidone. A positive electrode mixture slurry is prepared by dispersing, and this positive electrode mixture slurry is applied to the positive electrode current collector 1. Then, after drying the solvent, the positive electrode active material layer 2 can be formed by compression molding using a roll press or the like, and a positive electrode can be obtained. Alternatively, regardless of the presence or absence of the binder, it is also possible to produce a positive electrode having strength by pressure molding while applying heat to the positive electrode active material.

  As another method for producing the positive electrode active material and the positive electrode, first, particles containing a positive electrode material capable of occluding and releasing the electrode reactant are prepared as a starting material, and this positive electrode material is bound to the positive electrode material as necessary. A positive electrode is prepared using an agent and a conductive agent. Subsequently, the metal salt represented by the above formula (1) is deposited on the surface of the positive electrode active material layer 2 to deposit the metal salt on at least a part of the surface of the positive electrode active material.

  The method for depositing the metal salt on the surface of the positive electrode active material layer 2 is similar to the method for depositing the metal salt on the surface of the positive electrode active material, for example, a liquid such as a coating method, a dipping method or a dip coating method. Examples include a phase method, a vapor phase method such as a vapor deposition method, a sputtering method, or a CVD method. As a method of forming the metal salt layer, any of these methods may be used alone, or two or more methods may be used. Especially, as a liquid phase method, it is preferable to form a metal salt layer using the solution containing the metal salt shown to Formula (1). Specifically, for example, in the immersion method, the positive electrode current collector 1 on which the positive electrode active material layer 2 is formed is immersed in a solution containing the above metal salt. The metal salt penetrates into the positive electrode active material layer 2 and exists between the particles containing the positive electrode material, the binder, and the conductive agent, and adheres to the surface of the particles. Thereby, a metal salt layer containing a metal salt is formed on the particle surface.

  Next, a non-aqueous electrolyte secondary battery using a positive electrode active material and a positive electrode according to an embodiment of the present invention will be described.

(4) First Example of Nonaqueous Electrolyte Secondary Battery (4-1) Configuration of Nonaqueous Electrolyte Secondary Battery FIG. 2 shows a cross-sectional structure of the battery according to the first embodiment of the present invention. This battery is, for example, a non-aqueous electrolyte secondary battery, using lithium (Li) as an electrode reactant, and a so-called lithium ion secondary battery in which the capacity of the negative electrode is represented by a capacity component due to insertion and extraction of lithium (Li). Next battery.

  This battery is called a so-called cylindrical type, and is a wound electrode in which a pair of strip-like positive electrode 21 and strip-like negative electrode 22 are wound through a separator 23 inside a substantially hollow cylindrical battery can 11. It has a body 20. The battery can 11 is made of, for example, iron (Fe) plated with nickel (Ni), and has one end closed and the other end open. Inside the battery can 11, a pair of insulating plates 12 and 13 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 20.

  At the open end of the battery can 11, a battery lid 14, a safety valve mechanism 15 provided inside the battery lid 14 and a heat sensitive resistance element (Positive Temperature Coefficient; PTC element) 16 are interposed via a gasket 17. It is attached by caulking, and the inside of the battery can 11 is sealed.

  The battery lid 14 is made of, for example, the same material as the battery can 11. The safety valve mechanism 15 is electrically connected to the battery lid 14 via the heat sensitive resistance element 16. The safety valve mechanism 15 causes the disk plate 15A to reverse and disconnect the electrical connection between the battery lid 14 and the wound electrode body 20 when the internal pressure of the battery exceeds a certain level due to internal short circuit or external heating. It has become. When the temperature rises, the heat sensitive resistance element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface.

  For example, a center pin 24 is inserted in the center of the wound electrode body 20. A positive electrode lead 25 made of aluminum (Al) or the like is connected to the positive electrode 21 of the spirally wound electrode body 20, and a negative electrode lead 26 made of nickel (Ni) or the like is connected to the negative electrode 22. The positive electrode lead 25 is electrically connected to the battery lid 14 by being welded to the safety valve mechanism 15, and the negative electrode lead 26 is welded to and electrically connected to the battery can 11.

[Positive electrode]
FIG. 3 is an enlarged cross-sectional view showing a part of the spirally wound electrode body 20 shown in FIG. The positive electrode 21 has, for example, the same structure as the positive electrode shown in FIG. 1, and is provided with a positive electrode active material layer 21B on both surfaces of a strip-shaped positive electrode current collector 21A. Although not shown, a region where the positive electrode active material layer 21B exists may be provided only on one surface of the positive electrode current collector 21A. The configurations of the positive electrode current collector 21A and the positive electrode active material layer 21B are the same as the configurations of the positive electrode current collector 1 and the positive electrode active material layer 2 described above, respectively.

[Negative electrode]
As shown in FIG. 3, the negative electrode 22 includes, for example, a negative electrode current collector 22A having a pair of opposed surfaces, and a negative electrode active material layer 22B provided on both surfaces or one surface of the negative electrode current collector 22A. Yes. In addition, you may make it have the area | region in which the negative electrode active material layer 22B was provided only in the single side | surface of 22 A of negative electrode collectors. The anode current collector 22A is made of a metal foil such as a copper (Cu) foil.

  The negative electrode active material layer 22B includes, for example, a negative electrode active material, and may include other materials that do not contribute to charging, such as a conductive agent, a binder, or a viscosity modifier, as necessary. Examples of the conductive agent include graphite fiber, metal fiber, and metal powder. Examples of the binder include a fluorine-based polymer compound such as polyvinylidene fluoride, or a synthetic rubber such as styrene butadiene rubber or ethylene propylene diene rubber. Examples of the viscosity modifier include carboxymethylcellulose.

  The negative electrode active material includes one or more negative electrode materials capable of electrochemically inserting and extracting lithium (Li) at a potential of lithium metal of 2.0 V or less. Yes.

Examples of negative electrode materials capable of inserting and extracting lithium (Li) include carbonaceous materials, metal compounds, oxides, sulfides, lithium nitrides such as LiN ₃ , lithium metals, and alloys with lithium. Examples thereof include metals and polymer materials.

  Examples of carbonaceous materials include non-graphitizable carbon, graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon Blacks, carbon fibers or activated carbon can be used. Among these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body refers to a carbonized material obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as: In addition, examples of the polymer material include polyacetylene and polypyrrole.

  Among such negative electrode materials capable of inserting and extracting lithium (Li), those having a charge / discharge potential relatively close to lithium metal are preferable. This is because the lower the charge / discharge potential of the negative electrode 22, the easier it is to increase the energy density of the battery. Among these, a carbon material is preferable because a change in crystal structure that occurs during charge / discharge is very small, a high charge / discharge capacity can be obtained, and good cycle characteristics can be obtained. In particular, graphite is preferable because it has a high electrochemical equivalent and can provide a high energy density. Moreover, non-graphitizable carbon is preferable because excellent cycle characteristics can be obtained.

  Examples of the negative electrode material capable of inserting and extracting lithium (Li) include lithium metal alone, a metal element or a metalloid element capable of forming an alloy with lithium (Li), an alloy, or a compound. These are preferable because a high energy density can be obtained, and in particular, when used together with a carbon material, a high energy density can be obtained and excellent cycle characteristics can be obtained, and therefore, it is more preferable. Note that in this specification, alloys include those composed of one or more metal elements and one or more metalloid elements in addition to those composed of two or more metal elements. The structures include solid solutions, eutectics (eutectic mixtures), intermetallic compounds, or those in which two or more of them coexist.

Examples of such metal elements or metalloid elements include tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si), zinc (Zn), antimony (Sb), and bismuth. (Bi), cadmium (Cd), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), zirconium (Zr), yttrium (Y) or hafnium (Hf). These alloys or compounds, for example, those represented by the chemical formula Ma _s Mb _t Li _u or a chemical formula Ma _p Mc _q Md _r,. In these chemical formulas, Ma represents at least one of a metal element and a metalloid element capable of forming an alloy with lithium, Mb represents at least one of a metal element and a metalloid element other than lithium and Ma, Mc represents at least one of nonmetallic elements, and Md represents at least one of metallic elements and metalloid elements other than Ma. The values of s, t, u, p, q, and r are s> 0, t ≧ 0, u ≧ 0, p> 0, q> 0, and r ≧ 0, respectively.

  Among these, a simple substance, alloy or compound of Group 4B metal element or semimetal element in the short-period type periodic table is preferable, and silicon (Si) or tin (Sn), or an alloy or compound thereof is particularly preferable. These may be crystalline or amorphous.

Examples of the negative electrode material capable of inserting and extracting lithium further include oxides, sulfides, and other metal compounds such as lithium nitrides such as LiN ₃ . Examples of the oxide include MnO ₂ , V ₂ O ₅ , V ₆ O ₁₃ , NiS, and MoS. In addition, examples of oxides that have a relatively low potential and can occlude and release lithium include iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide. Examples of the sulfide include NiS and MoS.

  In the non-aqueous electrolyte secondary battery according to the first example, by adjusting the amount between the positive electrode active material and the negative electrode active material capable of occluding and releasing lithium, the charge capacity of the positive electrode active material is more than that. The charge capacity of the negative electrode active material described above is larger, so that lithium metal does not deposit on the negative electrode 22 even during full charge.

  Further, in this nonaqueous electrolyte secondary battery, the electrochemical equivalent of the negative electrode material capable of inserting and extracting lithium is larger than the electrochemical equivalent of the positive electrode 21, and the negative electrode 22 is charged with lithium during the charging. The metal is not deposited.

[Separator]
The separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes.

  The separator 23 is made of, for example, a synthetic resin porous film made of polytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE), or the like, or a ceramic porous film. The separator 23 may have a structure in which two or more of the above porous films are stacked. Among them, a porous film made of polyolefin is preferable because it is excellent in short-circuit preventing effect and can improve battery safety by a shutdown effect. In particular, polyethylene can obtain a shutdown effect within a range of 100 ° C. or more and 160 ° C. or less, and is a resin having electrochemical stability, and is copolymerized with polyethylene or polypropylene, You may hit with a blend. Alternatively, a separator in which a porous resin layer such as polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) is formed on a polyolefin porous film may be used.

  The separator 23 is impregnated with an electrolytic solution as a liquid electrolyte.

[Electrolytes]
As the electrolyte, for example, a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent can be used. These can utilize what has been used for the conventional nonaqueous electrolyte secondary battery.

  Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3- Examples include dioxolane, 4-methyl 1,3-dioxolane, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, propionitrile, anisole, acetate ester, butyrate ester, propionate ester and the like. These may be used alone or in admixture of two or more. Among them, for example, it is preferable that at least one kind is selected from cyclic carbonates such as propylene carbonate and ethylene carbonate, and chain carbonates such as diethyl carbonate and dimethyl carbonate. This is because the cycle characteristics can be improved. In this case, it is particularly preferable to contain a mixture of a high viscosity (high dielectric constant solvent) such as propylene carbonate and ethylene carbonate and a low viscosity solvent such as diethyl carbonate and dimethyl carbonate. This is because the dissociation property of the electrolyte salt and the ion mobility are improved, so that a higher effect can be obtained.

  As an electrolyte salt, for example, a lithium salt can be cited as one that generates ions by dissolving or dispersing in the above non-aqueous solvent.

Examples of the lithium salt include lithium perchlorate (LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), LiB (C ₆ H ₅ ) ₄ , CH ₃ SO ₃ Li, CF ₃ SO ₃ Li, LiCl, LiBr and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, lithium hexafluorophosphate (LiPF ₆ ) is preferable because high ion conductivity can be obtained and cycle characteristics can be improved.

  In addition, the content of such an electrolyte salt is preferably within a range of 0.1 mol to 3.0 mol, for example, with respect to 1 liter (l) of the solvent, and more preferably within a range of 0.5 mol to 2.0 mol. preferable. This is because higher ion conductivity can be obtained within this range.

  In the nonaqueous electrolyte secondary battery according to the first example, when charged, for example, lithium ions are released from the positive electrode active material layer 21B and inserted into the negative electrode active material layer 22B through the electrolytic solution. Further, when discharging is performed, for example, lithium ions are released from the negative electrode active material layer 22b and inserted into the positive electrode active material layer 21B through the electrolytic solution.

  The upper limit charging voltage of this nonaqueous electrolyte secondary battery may be, for example, 4.20V, but is preferably designed to be higher than 4.20V and within a range of 4.25V to 4.80V. Furthermore, it is more preferable that the upper limit charging voltage of this nonaqueous electrolyte secondary battery is designed to be in the range of 4.35V to 4.65V. Moreover, it is preferable that a minimum discharge voltage shall be 2.00V or more and 3.30V or less. For example, when the battery voltage is set to 4.25 V or higher, the amount of lithium released per unit mass is increased even with the same positive electrode active material as compared with a 4.2 V battery. The amount of the active material and the negative electrode active material is adjusted, and a high energy density is obtained. Moreover, according to one embodiment of the present invention, since the coating containing the metal salt represented by the above formula (1) is formed on the positive electrode active material, excellent cycle characteristics can be obtained even when the battery voltage is increased. As a result, gas generation inside the battery can be suppressed.

(4-2) Method for Manufacturing Nonaqueous Electrolyte Secondary Battery Next, an example of a method for manufacturing the nonaqueous electrolyte secondary battery according to the first example of the present invention will be described.

  First, the positive electrode 21 is obtained by the same method as the positive electrode active material and the positive electrode manufacturing method according to the embodiment of the present invention described above.

  The negative electrode 22 is, for example, a method in which a known binder or conductive agent is added to the negative electrode active material, a solvent is added, and the negative electrode current material 22A is applied onto the negative electrode current collector 22A. It can be produced by a method of adding and heating to the negative electrode current collector 22A. The negative electrode 22 can be produced by a method of producing a molded electrode on the negative electrode current collector 22A by subjecting the negative electrode active material alone or mixed with a conductive agent or a binder to a treatment such as molding. However, the method for producing the negative electrode is not limited to them. More specifically, first, for example, a negative electrode active material and a binder are mixed to prepare a negative electrode mixture, and the negative electrode mixture is dispersed in a solvent such as 1-methyl-2-pyrrolidone to form a negative electrode. A mixture slurry is prepared, this negative electrode mixture slurry is applied to the negative electrode current collector 22A, and the solvent is dried. Thereafter, the negative electrode active material layer 22B is formed by compression molding using a roll press or the like, and the negative electrode 22 is obtained. Alternatively, regardless of the presence or absence of the binder, it is also possible to produce a strong negative electrode by pressure molding while applying heat to the negative electrode active material.

  Next, the positive electrode lead 25 is attached to the positive electrode current collector 21A by welding or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A by welding or the like. Thereafter, the positive electrode 21 and the negative electrode 22 are wound through the separator 23, and the tip of the positive electrode lead 25 is welded to the safety valve mechanism 15, and the tip of the negative electrode lead 26 is welded to the battery can 11. Then, the wound positive electrode 21 and negative electrode 22 are sandwiched between the pair of insulating plates 12 and 13 and stored in the battery can 11. After the positive electrode 21 and the negative electrode 22 are accommodated in the battery can 11, an electrolyte is injected into the battery can 11 and impregnated in the separator 23. Thereafter, the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are fixed to the opening end of the battery can 11 by caulking through the gasket 17. Thus, the secondary battery shown in FIG. 2 is manufactured.

(5) Second Example of Nonaqueous Electrolyte Secondary Battery (5-1) Configuration of Nonaqueous Electrolyte Secondary Battery FIG. 4 shows the configuration of the nonaqueous electrolyte secondary battery according to the second example. This non-aqueous electrolyte secondary battery is a so-called laminate film type, in which a wound electrode body 30 to which a positive electrode lead 31 and a negative electrode lead 32 are attached is housed in a film-like exterior member 40. .

  The positive electrode lead 31 and the negative electrode lead 32 are led out from the inside of the exterior member 40 to the outside, for example, in the same direction. The positive electrode lead 31 and the negative electrode lead 32 are made of, for example, a metal material such as aluminum, copper, nickel, or stainless steel, and each have a thin plate shape or a mesh shape.

[Exterior material]
The exterior member 40 is made of, for example, a rectangular aluminum laminated film in which a nylon film, an aluminum foil, and a polyethylene film are bonded together in this order. For example, the exterior member 40 is disposed so that the polyethylene film side and the wound electrode body 30 face each other, and the outer edge portions are in close contact with each other by fusion bonding or an adhesive. An adhesive film 41 is inserted between the exterior member 40 and the positive electrode lead 31 and the negative electrode lead 32 to prevent intrusion of outside air. The adhesion film 41 is made of a material having adhesion to the positive electrode lead 31 and the negative electrode lead 32, for example, a polyolefin resin such as polyethylene, polypropylene, modified polyethylene, or modified polypropylene.

  The exterior member 40 may be made of a laminated film having another structure, a polymer film such as polypropylene, or a metal film instead of the above-described aluminum laminated film.

[Wound electrode body]
FIG. 5 shows a cross-sectional structure taken along line II of the spirally wound electrode body 30 shown in FIG. The electrode winding body 30 is obtained by laminating a positive electrode 33 and a negative electrode 34 via a separator 35 and an electrolyte layer 36 and winding them, and the outermost periphery is protected by a protective tape 37.

  The positive electrode 33 has a structure in which a positive electrode active material layer 33B is provided on one or both surfaces of a positive electrode current collector 33A. The negative electrode 34 has a structure in which a negative electrode active material layer 34B is provided on one surface or both surfaces of a negative electrode current collector 34A, and the negative electrode active material layer 34B and the positive electrode active material layer 33B are arranged to face each other. Yes. The configurations of the positive electrode current collector 33A, the positive electrode active material layer 33B, the negative electrode current collector 34A, the negative electrode active material layer 34B, and the separator 35 are the same as those of the positive electrode current collector 21A, the positive electrode active material layer 21B, and the first embodiment described above. This is the same as the anode current collector 22A, the anode active material layer 22B, and the separator 23.

  The electrolyte layer 36 includes an electrolytic solution and a polymer compound serving as a holding body that holds the electrolytic solution, and has a so-called gel shape. A gel electrolyte is preferable because high ion conductivity can be obtained and battery leakage can be prevented. The configuration of the electrolytic solution (that is, the solvent and the electrolyte salt) is the same as that of the secondary battery according to the first embodiment.

  As the polymer material, various polymers that can be gelled by absorbing the above-described electrolyte can be used. Specifically, for example, a fluorine-based polymer such as poly (vinylidene fluoride) or poly (vinylidene fluoride-co-hexafluoropropylene), an ether-based polymer such as poly (ethylene oxide) or a crosslinked product thereof, or Poly (acrylonitrile) can be used. In particular, in view of redox stability, it is desirable to use a fluorine-based polymer such as a polymer of vinylidene fluoride.

  The operation and effect of the non-aqueous electrolyte secondary battery according to the second example are the same as those of the non-aqueous electrolyte secondary battery according to the first example described above. In addition, according to the second example, since gas generation inside the battery is suppressed, expansion and deformation of the nonaqueous electrolyte secondary battery can be suppressed.

(5-2) Manufacturing Method of Nonaqueous Electrolyte Secondary Battery The nonaqueous electrolyte secondary battery according to the second example can be manufactured by, for example, the following three manufacturing methods.

  In the first production method, first, a precursor solution containing an electrolytic solution, a polymer compound, and a mixed solvent is applied to each of the positive electrode 33 and the negative electrode 34, and the mixed solvent is volatilized to form the electrolyte layer 36. . Thereafter, the positive electrode lead 31 is attached to the end portion of the positive electrode current collector 33A by welding, and the negative electrode lead 32 is attached to the end portion of the negative electrode current collector 34A by welding. Next, the positive electrode 33 and the negative electrode 34 on which the electrolyte layer 36 is formed are laminated via a separator 35 to form a laminated body, and then the laminated body is wound in the longitudinal direction, and a protective tape 37 is attached to the outermost peripheral portion. The wound electrode body 30 is formed by bonding. Finally, for example, the wound electrode body 30 is sandwiched between the exterior members 40, and the outer edges of the exterior members 40 are sealed and sealed by heat fusion or the like. At that time, the adhesion film 41 is inserted between the positive electrode lead 31 and the negative electrode lead 32 and the exterior member 40. Thereby, the nonaqueous electrolyte secondary battery shown in FIGS. 4 and 5 is completed.

  In the second manufacturing method, first, the positive electrode 33 and the negative electrode 34 are prepared as described above, and after the positive electrode lead 31 and the negative electrode lead 32 are attached to the positive electrode 33 and the negative electrode 34, the positive electrode 33 and the negative electrode 34 are connected to the separator 35. Are laminated and wound, and a protective tape 37 is adhered to the outermost peripheral portion to form a wound body that is a precursor of the wound electrode body 30. Next, the wound body is sandwiched between the exterior members 40, and the outer peripheral edge except for one side is heat-sealed to form a bag shape, which is then stored inside the exterior member 40. Subsequently, an electrolyte composition including an electrolytic solution, a monomer that is a raw material of the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary is prepared, and the interior of the exterior member 40 Inject.

  After injecting the electrolyte composition, the opening of the exterior member 40 is heat-sealed and sealed in a vacuum atmosphere. Next, the gelled electrolyte layer 36 is formed by applying heat to polymerize the monomer to obtain a polymer compound. As described above, the nonaqueous electrolyte secondary battery shown in FIGS. 4 and 5 is obtained.

  In the third manufacturing method, the wound body is formed to form the inside of the bag-shaped exterior member 40 in the same manner as in the first manufacturing method described above, except that the separator 35 coated with the polymer compound on both sides is used. Store in. Examples of the polymer compound applied to the separator 35 include a polymer containing vinylidene fluoride as a component, that is, a homopolymer, a copolymer, or a multi-component copolymer. Specifically, polyvinylidene fluoride, binary copolymers containing vinylidene fluoride and hexafluoropropylene as components, and ternary copolymers containing vinylidene fluoride, hexafluoropropylene and chlorotrifluoroethylene as components. Etc. In addition, the high molecular compound may contain the other 1 type, or 2 or more types of high molecular compound with the polymer which uses the above-mentioned vinylidene fluoride as a component.

  Subsequently, after the electrolytic solution or the like is adjusted and injected into the exterior member 40, the opening of the exterior member 40 is sealed by thermal fusion or the like. Finally, the exterior member 40 is heated while applying a load, and the separator 35 is brought into close contact with the positive electrode 33 and the negative electrode 34 through the polymer compound. As a result, the electrolytic solution is impregnated into the polymer compound, and the polymer compound is gelled to form the electrolyte layer 36. Thus, the nonaqueous electrolyte secondary battery is completed.

  In the third manufacturing method, the swollenness characteristics are improved as compared with the second manufacturing method. Further, in the third manufacturing method, compared to the second manufacturing method, the monomer or solvent that is a raw material of the polymer compound hardly remains in the electrolyte layer 36, and the polymer compound forming process is excellent. Be controlled. For this reason, sufficient adhesion is obtained between the positive electrode 33, the negative electrode 34, and the separator 35 and the electrolyte layer 36.

  The improvement behavior of the battery characteristics of the nonaqueous electrolyte secondary batteries according to the first and second examples is not clear, but is presumed to be due to the following mechanism.

  In a battery charged to 4.20 V or more, the positive electrode active material generates a high electromotive force, and thus the electrolyte in contact with the positive electrode active material is in a strong oxidizing environment. As a result, it is considered that the metal component is eluted from the positive electrode active material which has become unstable by extracting more lithium (Li) and the positive electrode active material is deteriorated or oxidative decomposition of the electrolyte occurs. And, since the eluted metal component is reduced and deposited on the negative electrode side, the surface of the negative electrode is covered and the occlusion and release of lithium is hindered, so that it is estimated that the charge / discharge cycle characteristics deteriorate. Further, it is conceivable that the electrolyte is oxidized and decomposed on the positive electrode to generate gas, or a film is formed on the positive electrode, so that the battery swells or the impedance increases.

  On the other hand, in the positive electrode active material according to one embodiment of the present invention, the coating represented by the above formula (1) is formed on the particle surface. This coating is considered stable against the high electromotive force of the positive electrode, suppresses the reaction between the positive electrode and the electrolytic solution, and suppresses the decomposition of the electrolytic solution and the generation of a coating with low lithium ion permeability such as LiF. It is thought that you can. Therefore, it is thought that it contributes to coexistence with the high capacity | capacitance by high charge pressure improvement, the improvement of charging / discharging cycling characteristics, and the suppression of the battery swelling by gas generation.

  The non-aqueous electrolyte secondary batteries according to the first and second examples have light weight, high capacity, and high energy density characteristics, and are portable such as video cameras, notebook personal computers, word processors, radio cassette recorders, and cellular phones. It can be widely used for small electronic devices.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

<Example 1>
A method for manufacturing the positive electrode active material is described below. First, 100 parts by weight of lithium cobaltate having an average composition of LiCo _0.98 Al _0.01 Mg _0.01 O ₂ and an average particle diameter of 13 μm measured by a laser scattering method is weighed so as to be 1 part by weight of dilithium sulfopropionate. These were stirred in 100 ml of pure water for 1 hour. After stirring, the water was removed by an evaporator and then dried in an oven at 120 ° C. for 12 hours to obtain a positive electrode active material in which lithium cobaltate was coated with dilithium sulfopropionate.

When the obtained positive electrode active material powder is analyzed by ToF-SIMS, C ₃ H ₄ SO ₅ Li ₃ ⁺ as positive secondary ions and C ₃ H ₄ SO ₅ Li ⁻ as negative secondary ions are observed. It was confirmed that a film containing dilithium sulfopropionate was formed on the surface of the positive electrode active material.

  Using the positive electrode active material obtained as described above, the nonaqueous electrolyte secondary battery shown in FIGS. 4 and 5 was produced as described below. First, 98% by weight of a positive electrode active material, 0.8% by weight of amorphous carbon powder (Ketjen Black) as a conductive agent, and 1.2% by weight of polyvinylidene fluoride (PVdF) as a binder are mixed to form a positive electrode. A mixture was prepared. After this positive electrode mixture was dispersed in N-methyl-2-pyrrolidone (NMP) to produce a positive electrode mixture slurry, this positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector 33A made of a strip-shaped aluminum foil having a thickness of 20 μm. It was applied evenly. The obtained coated material was dried with hot air and then compression molded with a roll press to form the positive electrode active material layer 33B. Thereafter, an aluminum positive electrode lead 31 was attached to one end of the positive electrode current collector 33A.

  The negative electrode 34 was produced as follows. First, a negative electrode mixture was prepared by mixing 90% by weight of graphite powder as a negative electrode active material and 10% by weight of polyvinylidene fluoride (PVdF) as a binder. After this negative electrode mixture was dispersed in N-methyl-2-pyrrolidone (NMP) to produce a negative electrode mixture slurry, the negative electrode mixture slurry was uniformly applied to both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 15 μm. The negative electrode active material layer 34B was formed by coating and further heat-press molding it. Thereafter, a nickel negative electrode lead 32 was attached to one end of the negative electrode current collector 34A.

  The separator 35 was produced as follows. First, N-methyl-2-pyrrolidone (NMP) is added in a mass ratio of PVdF: NMP = 10: 90 to poly (bilidenidene fluoride) (PVdF) having a weight average molecular weight of 150,000, and is sufficiently dissolved. Of N-methyl-2-pyrrolidone (NMP) was prepared.

  Next, the produced slurry was applied onto a microporous film that is a mixture of polyethylene (PE) and polypropylene (PP) having a thickness of 7 μm used as a base material layer. Next, the microporous membrane coated with this slurry was phase-separated in a water bath and then dried with hot air to obtain a separator 35 made of a microporous membrane having a PVdF microporous layer having a thickness of 4 μm.

Next, the separator 35, the positive electrode 33, and the negative electrode 34 were laminated | stacked in order of the negative electrode 34, the separator 35, the positive electrode 33, and the separator 35, and it wound many times, and produced the wound electrode body 30. The wound electrode body 30 is sandwiched between exterior members 40 made of a moisture-proof aluminum laminate film, and the outer peripheral edge except one side is heat-sealed and stored in the exterior member 40 as a bag shape. An electrolyte was injected inside. As the electrolytic solution, a non-aqueous electrolytic solution in which LiPF ₆ was dissolved in a mixed solution having a volume mixing ratio of 1: 1 between ethylene carbonate (EC) and diethyl carbonate (DEC) to a concentration of 1 mol / dm ^3. Was used.

  Then, vacuum sealing and thermocompression bonding were performed by heat-sealing the opening of the exterior member 40 under reduced pressure, and a flat-type nonaqueous electrolyte secondary battery having dimensions of approximately 34 mm × 50 mm × 3.8 mm was produced.

  About the obtained non-aqueous electrolyte secondary battery, the battery characteristics were evaluated as follows.

(A) Initial capacity About the produced nonaqueous electrolyte secondary battery, it discharged after performing constant current constant voltage charge on the conditions of environmental temperature 45 degreeC, charging voltage 4.20V, charging current 800mA, and charging time 2.5 hours. Discharging was performed at a current of 400 mA and a final voltage of 3.0 V, and the initial capacity was measured.

When the secondary battery whose initial capacity was evaluated was disassembled, the positive electrode was taken out and the electrode surface was analyzed by ToF-SIMS, C ₃ H ₄ SO ₅ Li ₃ ⁺ as the positive secondary ion and C as the negative secondary ion ₃ H ₄ SO ₅ Li ^- and are observed, that the coatings containing sulfo acid dilithium on the surface of the positive electrode active material is formed has been confirmed. The results of ToF-SIMS positive secondary ion analysis and ToF-SIMS negative secondary ion analysis at this time are shown in FIG.

(B) Charging / discharging cycle characteristics Charging / discharging was repeated under the same conditions as when the initial capacity was determined, and the discharge capacity at the 200th cycle was measured to determine the capacity retention ratio relative to the initial capacity.

(C) Increasing rate of cell thickness After the non-aqueous electrolyte secondary battery whose initial capacity was determined was subjected to constant current and constant voltage charging under conditions of a charging voltage of 4.20 V, a charging current of 800 mA, and a charging time of 2.5 hours, Storage was performed at 90 ° C. for 4 hours, and the increase rate of the cell thickness before and after storage was determined by {(cell thickness after storage−cell thickness before storage) / cell thickness before storage} × 100.

<Example 2>
In the evaluation of battery characteristics, (a) initial capacity, (b) charge / discharge cycle characteristics, and (c) increase rate of cell thickness were evaluated in the same manner as in Example 1 except that the charging voltage was 4.35V.

<Example 3>
In the evaluation of battery characteristics, (a) initial capacity, (b) charge / discharge cycle characteristics, and (c) increase rate of cell thickness were evaluated in the same manner as in Example 1 except that the charging voltage was 4.40V.

<Example 4>
In the evaluation of battery characteristics, (a) initial capacity, (b) charge / discharge cycle characteristics, and (c) increase rate of cell thickness were evaluated in the same manner as in Example 1 except that the charging voltage was 4.50V.

<Example 5>
A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 3 except that in the production of the positive electrode active material, dilithium sulfopropionate was weighed to 0.2 parts by weight with respect to 100 parts by weight of lithium cobaltate. The battery characteristics were evaluated.

<Example 6>
In the production of the positive electrode active material, a nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 3 except that 100 parts by weight of lithium cobaltate was weighed so that dilithium sulfopropionate was 0.5 parts by weight. The battery characteristics were evaluated.

<Example 7>
In the production of the positive electrode active material, a nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 3 except that 100 parts by weight of lithium cobaltate was weighed so that dilithium sulfopropionate was 3.0 parts by weight. The battery characteristics were evaluated.

<Example 8>
In the production of the positive electrode active material, a nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 3 except that 100 parts by weight of lithium cobaltate was weighed so that dilithium sulfopropionate was 5.0 parts by weight. Fabricated and battery characteristics were evaluated.

<Example 9>
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 3 except that dilithium sulfopropionate of Example 3 was changed to magnesium sulfopropionate, and battery characteristics were evaluated. In Example 9, it was confirmed by analysis using TOF-SIMS that a film containing magnesium sulfopropionate was formed on the surface of the positive electrode active material.

<Example A>
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that dilithium sulfopropionate of Example 1 was changed to dilithium propanedisulfonate, and battery characteristics were evaluated. In addition, also in Example A, by analysis using TOF-SIMS, C ₃ H ₆ S ₂ O ₆ Li ₃ ⁺ as a positive secondary ion and C ₃ H ₆ S ₂ O ₆ Li ⁻ as a negative secondary ion It was confirmed that a film containing dilithium propanedisulfonate was formed on the surface of the positive electrode active material.

<Example B>
A nonaqueous electrolyte secondary battery was prepared and the battery characteristics were evaluated in the same manner as in Example 3 except that dilithium sulfopropionate of Example 3 was changed to dilithium propanedisulfonate. In addition, also in Example B, C ₃ H ₆ S ₂ O ₆ Li ₃ ⁺ as a positive secondary ion and C ₃ H ₆ S ₂ O ₆ Li ⁻ as a negative secondary ion are obtained by analysis using TOF-SIMS. It was confirmed that a film containing dilithium propanedisulfonate was formed on the surface of the positive electrode active material.

<Example C>
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that dilithium sulfopropionate of Example 1 was changed to dilithium ethanedisulfonate, and battery characteristics were evaluated. In addition, also about Example C, by analysis using TOF-SIMS, C ₂ H ₄ S ₂ O ₆ Li ₃ ⁺ as a positive secondary ion and C ₂ H ₄ S ₂ O ₆ Li ⁻ as a negative secondary ion It was confirmed that a film containing dilithium propanedisulfonate was formed on the surface of the positive electrode active material.

<Example D>
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that dilithium sulfopropionate of Example 1 was changed to dilithium butanedisulfonate, and battery characteristics were evaluated. In addition, also in Example D, C ₄ H ₈ S ₂ O ₆ Li ₃ ⁺ as a positive secondary ion and C ₄ H ₈ S ₂ O ₆ Li ⁻ as a negative secondary ion are obtained by analysis using TOF-SIMS. It was confirmed that a film containing dilithium propanedisulfonate was formed on the surface of the positive electrode active material.

<Example 10>
A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 3 except that trilithium sulfopropionate of Example 3 was changed to trilithium sulfosuccinate, and battery characteristics were evaluated. In addition, also in Example 10, it was confirmed by analysis using TOF-SIMS that a film containing trilithium sulfosuccinate was formed on the surface of the positive electrode active material.

<Example 11>
First, lithium carbonate (Li ₂ CO ₃ ), manganese carbonate (MnCO ₃ ), and ammonium phosphate ((NH ₄ ) H ₂ PO ₄ ) are mixed with lithium (Li): manganese (Mn): phosphorus (P). = 3: 3: 2 were weighed and mixed so as to have a molar ratio of 3: 3: 2. The obtained mixed powder was weighed so as to be 2 parts by weight with respect to 100 parts by weight of lithium cobaltate having an average composition of LiCo _0.98 Al _0.01 Mg _0.01 O ₂ and an average particle diameter measured by a laser scattering method of 13 μm. Subsequently, the mixed powder and lithium cobalt oxide are treated for 1 hour using a mechanochemical apparatus, and Li ₂ CO ₃ , MnCO ₃ , and (NH ₄ ) H ₂ PO ₄ are applied to the surface of the lithium cobalt oxide. A fired precursor was prepared by deposition. The calcined precursor was heated at a rate of 3 ° C. per minute, held at 900 ° C. for 3 hours and then gradually cooled, and a powder obtained by coating manganese (Mn) or phosphorus (P) on the surface of lithium cobaltate Obtained.

  The obtained powder was observed with a scanning electron microscope (SEM) (hereinafter referred to as SEM / EDX) equipped with an energy dispersive X-ray analyzer (EDX: Energy Dispersive X-ray). Manganese (Mn) was distributed over the entire surface of the lithium cobalt oxide particles, and it was confirmed that P was locally scattered on the surface of the lithium cobalt oxide particles.

Further, when a powder X-ray diffraction (XRD) pattern using a long wavelength CuKα was measured for this powder, Li ₃ PO ₄ in addition to a diffraction peak corresponding to LiCoO ₂ having a layered rock salt structure. The diffraction peak of was confirmed.

  Furthermore, the element ratio on the particle surface was measured by a scanning X-ray photoelectron spectrometer (ESCA: Quantera SXM manufactured by ULVAC-PHI). Co / (Co + Mn + P) was 0.40.

  A non-aqueous electrolyte secondary battery was produced and battery characteristics were evaluated in the same manner as in Example 3 except that the lithium cobalt oxide particles that had been coated as described above were used.

<Example 12>
First, lithium carbonate (Li ₂ CO ₃ ), nickel hydroxide (Ni (OH) ₂ ), and manganese carbonate (MnCO ₃ ) are mixed with Li ₂ CO ₃ : Ni (OH) ₂ : MnCO ₃ = 1.08. : Weighed to a molar ratio of 1: 1 (corresponding to Li _1.08 Ni _0.5 Mn _0.5 O ₂ ), pulverized to a mean particle size of 1 μm or less by a wet method using a ball mill, and then dried under reduced pressure at 70 ° did. The obtained mixed powder was weighed so that the average composition was 5 parts by weight with respect to 100 parts by weight of lithium cobaltate having an average particle diameter of 13 μm as measured by the LiCo _0.98 Al _0.01 Mg _0.01 O ₂ laser scattering method. Subsequently, this mixed powder and lithium cobalt oxide are treated for 1 hour using a mechanochemical apparatus to deposit Li ₂ CO ₃ , Ni (OH) ₂ , and MnCO ₃ on the surface of the lithium cobalt oxide. Thus, a calcined precursor was produced. The calcined precursor was heated at a rate of 3 ° C. per minute, held at 800 ° C. for 3 hours and then gradually cooled, and a powder obtained by coating manganese (Mn) or nickel (Ni) on the surface of lithium cobaltate Obtained.

When the obtained powder was analyzed by atomic absorption analysis, the composition of LiCo _0.94 Ni _0.02 Mn _0.02 Al _0.01 Mg _0.01 O ₂ was confirmed. Moreover, when the particle size was measured by the laser diffraction method, the average particle size was 13.5 μm.

  Moreover, when the powder was observed by SEM / EDX, a nickel manganese metal compound having a particle size of about 0.1 to 5 μm was deposited on the surface of lithium cobaltate, and Ni and Mn were almost uniform over the entire surface. Was observed.

  A non-aqueous electrolyte secondary battery was produced and battery characteristics were evaluated in the same manner as in Example 3 except that the lithium cobalt oxide particles that had been coated as described above were used.

<Example E>
Weighing so that 1 part by weight of dilithium propanedisulfonate is 100 parts by weight of nickel-cobalt composite oxide having an average composition of LiNi _0.80 Co _0.15 Al _0.05 O ₂ and an average particle diameter of 13 μm as measured by a laser scattering method. did. Then, these were treated for 1 hour using a mechanochemical apparatus, and the positive electrode active in which dilithium propanedisulfonate was coated on the surface of lithium nickel cobaltate and the nickel cobalt composite oxide was coated with dilithium propanedisulfonate. Obtained material.

When the obtained positive electrode active material powder was analyzed by ToF-SIMS, C ₃ H ₆ S ₂ O ₆ Li ₃ ⁺ as a positive secondary ion and C ₃ H ₆ S ₂ O ₆ Li ⁻ as a negative secondary ion It was confirmed that a film containing dilithium propanedisulfonate was formed on the surface of the positive electrode active material. A non-aqueous electrolyte secondary battery was produced and battery characteristics were evaluated in the same manner as in Example 1 except that the nickel cobalt oxide particles subjected to the coating treatment as described above were used.

<Comparative Example 1>
A secondary battery was produced in the same manner as in Example 1 except that lithium cobaltate not coated with dilithium sulfopropionate was used as the positive electrode active material, and battery characteristics were evaluated.

<Comparative example 2>
In the evaluation of battery characteristics, (a) initial capacity, (b) charge / discharge cycle characteristics, and (c) increase rate of cell thickness were evaluated in the same manner as in Comparative Example 1 except that the charging voltage was 4.35V.

<Comparative Example 3>
In the evaluation of battery characteristics, (a) initial capacity, (b) charge / discharge cycle characteristics, and (c) increase rate of cell thickness were evaluated in the same manner as in Comparative Example 1 except that the charging voltage was 4.40V.

<Comparative Example 4>
In the evaluation of battery characteristics, (a) initial capacity, (b) charge / discharge cycle characteristics, and (c) increase rate of cell thickness were evaluated in the same manner as in Comparative Example 1 except that the charging voltage was 4.50V.

<Comparative Example 5>
A secondary battery was produced in the same manner as in Example 11 except that lithium cobaltate not coated with dilithium sulfopropionate was used as the positive electrode active material, and battery characteristics were evaluated.

<Comparative Example 6>
A secondary battery was produced in the same manner as in Example 12 except that lithium cobaltate not coated with dilithium sulfopropionate was used as the positive electrode active material, and battery characteristics were evaluated.

<Comparative Example 7>
A non-aqueous electrolyte secondary battery was prepared and the battery characteristics were evaluated in the same manner as in Example 3 except that lithium carbonate was used as the dilithium sulfopropionate of Example 3.

<Comparative Example A>
A secondary battery was produced in the same manner as in Example E except that a nickel cobalt composite oxide not coated with dilithium propanedisulfonate was used as the positive electrode active material, and the battery characteristics were evaluated.

  Table 1 below summarizes the results of evaluation of battery characteristics of Examples 1 to 12, Examples A to E, Comparative Examples 1 to 7, and Comparative Example A.

  As can be seen from Table 1 by comparing, for example, Examples 1 to 4 and Comparative Examples 1 to 4, respectively, by forming a film containing a metal salt on the particle surface, a decrease in capacity retention rate and An increase in the rate of increase in thickness could be suppressed. In addition, as the charging voltage increases, the energy density increases and the initial capacity increases. On the other hand, the capacity retention rate decreases and the thickness increase rate also increases, but a film containing a metal salt is formed. As a result, it was found that a decrease in capacity retention rate and an increase in thickness increase rate can be suppressed.

  Further, for example, as can be seen by comparing Example A to Example B with Comparative Example 1 and Comparative Example 3, respectively, and comparing Example C to Example D with Comparative Example 1, respectively, a metal salt is formed on the particle surface. By forming the coating film containing, it was possible to suppress a decrease in capacity retention rate and an increase in thickness increase rate.

  Further, in Example 8 and Comparative Example 3, the capacity retention rate is approximately the same, and therefore the upper limit of the amount of the coating material added is preferably smaller than 5.0 parts by weight with respect to 100 parts by weight of the particles. I understood that. In particular, from Example 3 and Examples 5 to 8, a higher effect can be obtained when the amount of coating material added is in the range of 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the particles. I understood.

  Further, in Comparative Example 7 in which a film containing lithium carbonate was formed, the capacity retention rate was lower than that in Comparative Example 3 in which no film was provided, and the thickness increase rate was significantly increased. This is considered to be because in the coating film containing lithium carbonate, gas generation from the positive electrode increased due to lithium carbonate on the particle surface, and the distortion of the cells occurred due to gas generation.

  Further, according to Example 11 and Comparative Example 5, and Example 12 and Comparative Example 6, capacity was maintained by forming a film containing a metal salt on the particles on which a coating layer containing manganese, nickel, and phosphorus was formed. It has been found that higher effects are obtained with respect to the rate of increase in thickness and the rate of increase in thickness.

  Further, from the comparison between Example E and Comparative Example A, it is possible to suppress a decrease in capacity retention rate and an increase in thickness increase rate by forming a coating containing a metal salt on the surface of the nickel cobalt composite oxide particles. did it.

  From the above results, the particles containing the positive electrode material capable of occluding and releasing the electrode reactant are expressed by the above formula (1) such as dilithium sulfopropionate, magnesium sulfopropionate, trilithium sulfosuccinate and the like. It was found that by forming a coating containing the metal salt represented, both a high initial capacity and a capacity retention ratio can be achieved, and the thickness increase rate at high temperatures can be suppressed.

  Although the present invention has been described with reference to the embodiments and examples, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made. For example, in the above-described embodiments and examples, the secondary battery having a winding structure has been described. However, the present invention is similarly applied to a secondary battery having a structure in which a positive electrode and a negative electrode are folded or stacked. be able to. In addition, the present invention can also be applied to so-called coin-type, button-type, and square-type secondary batteries.

  In the above-described embodiment, the secondary battery using the nonaqueous electrolytic solution or the gel electrolyte as the electrolyte has been described. However, the present invention can be similarly applied to a secondary battery using a solid electrolyte. As the solid electrolyte, any inorganic solid electrolyte or polymer solid electrolyte can be used as long as it is a material having ionic conductivity. Examples of the inorganic solid electrolyte using an ion conductive inorganic material include lithium nitride, lithium iodide, ion conductive ceramics, ion conductive crystals, and ion conductive glass. A polymer solid electrolyte using an ion conductive polymer is composed of an electrolyte salt and a polymer compound that dissolves the electrolyte salt. Examples of the polymer compound include ether polymers such as poly (ethylene oxide) and cross-linked products thereof. , Poly (methacrylate) ester, acrylate, etc., specifically, polyether, polyester, polyphosphazene, polysiloxane, etc. may be mentioned, and these may be used alone or copolymerized or mixed in the molecule it can.

  Further, in the above-described embodiments and examples, a so-called lithium ion secondary battery in which the capacity of the negative electrode is expressed by a capacity component due to insertion and extraction of lithium has been described. However, the present invention, for example, inserts and releases lithium. By making the charging capacity of the negative electrode material that can be smaller than the charging capacity of the positive electrode, the capacity of the negative electrode includes a capacity component due to insertion and extraction of lithium and a capacity component due to precipitation and dissolution of lithium, and The present invention can be similarly applied to a secondary battery expressed as a sum.

DESCRIPTION OF SYMBOLS 1 ... Positive electrode collector 2 ... Positive electrode active material layer 11 ... Battery can 12, 13 ... Insulation board 14 ... Battery cover 15 ... Safety valve mechanism 15A ... Disc board 16. .. Thermal resistance element 17 ... Gasket 20, 30 ... Wound electrode body 21,33 ... Positive electrode 21A, 33A ... Positive electrode current collector 21B, 33B ... Positive electrode active material layer 22, 34 ... Negative electrode 22A, 34A ... Negative electrode current collector 22B, 34B ... Negative electrode active material layer 23, 35 ... Separator 24 ... Center pin 25, 31 ... Positive electrode lead 26, 32 ..Negative electrode lead 36 ... Electrolyte layer 37 ... Protective tape 40 ... Exterior member 41 ... Adhesion film

Claims (15)

Particles comprising a cathode material capable of occluding and releasing electrode reactants;
A positive electrode active material comprising: a coating film provided on at least a part of the particles and including at least one of metal salts represented by formulas (1) to (1) ′ .

(In Formula (1), M is Li . Each of a, c and d is an integer of 0 or more. B is an integer of 1 or more. The sum of a, b, c and d is an integer of 2 or more.) And the sum of a and b is an integer equal to or greater than 1. e, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are all monovalent groups and are bonded to each other. (R3 is a hydrocarbon group having a valence of the sum of a, b, c, and d.)

(In Formula (1) ′, M is Mg, a is 1, b is 1, and c = d = 0. The sum of a, b, c, and d is 2. e, f, g and h are each an integer of 1 or more, and R3 is a divalent hydrocarbon group. 2. The positive electrode active material according to claim 1, wherein R1 and R2 in the formula (1) are an alkyl group, an alkenyl group, an alkynyl group, a trialkylsilyl group, or a group obtained by halogenating them. The positive electrode active material according to claim 2, wherein the c and d in the formula (1) are 0. The positive electrode active material according to claim 3, wherein b in the formula (1) is 1 or 2. 5. The sum of a, b, c and d in the above formula (1) is an integer of 2 or more and 3 or less,
5. The positive electrode active material according to claim 4, wherein R 3 in the formula (1) is a divalent to trivalent hydrocarbon group whose valence is the sum of a, b, c, and d. The metal salt represented by the above formula (1) is dilithium ethanedisulfonate, dilithium propanedisulfonate, dilithium sulfoacetate, dilithium sulfopropionate, dilithium sulfobutanoate, dilithium sulfobenzoate, disuccinate. lithium, Ri least one der selected from the group consisting of sulfosuccinic tribasic lithium,
The positive electrode active material according to claim 1 , wherein the metal salt represented by the formula (1) ′ is at least one selected from the group consisting of magnesium sulfoacetate, magnesium sulfopropionate, and magnesium sulfobutanoate . The said coating film is a positive electrode active material in any one of Claims 1-6 containing alkali metal salt or alkaline-earth metal salt other than the metal salt represented by Formula (1)-Formula (1) ' . The positive electrode active material according to claim 1, wherein the particles include at least lithium and one or more transition metals. The positive electrode active material according to claim 8 , wherein the particles include cobalt (Co) as a main transition metal element and have a layered structure. The positive electrode active material according to claim 8, wherein one or more elements different from the main transition metal element constituting the particle are present in at least a part of the surface of the particle. The positive electrode active material according to claim 10 , comprising at least one of nickel (Ni), manganese (Mn), and phosphorus (P) as an element different from the main transition metal element constituting the particles. In surface analysis by time-of-flight secondary ion mass spectrometry, C ₇ H ₄ SO ₅ Li ₃ ⁺ , C ₂ H ₄ S ₂ O ₆ Li ₃ ⁺ , C ₃ H ₄ SO ₅ Li ₃ ⁺ , C ₃ H ₆ Positive secondary ions composed of S ₂ O ₆ Li ₃ ⁺ , C ₄ H ₄ O ₄ Li ₃ ⁺ , C ₄ H ₈ S ₂ O ₆ Li ₃ ⁺ and C ₄ O ₄ Li ₃ ⁺ , and C ₂ H ₃ SO _{3 ^{-, C 6 H 4 SO 3}} -, C 6 H 5 SO 3 -, C 6 H 4 SO 3 Li -, C 6 H 4 SO 4 Li -, C 7 H 5 SO 4 -, C 7 H 4 SO 5 Li ⁻ , C ₂ H ₄ S ₂ O ₆ Li ⁻ , C ₃ H ₄ SO ₅ Li ⁻ , C ₃ H ₆ S ₂ O ₆ Li ⁻ , C ₄ H ₄ O ₄ Li ⁻ , C ₄ H ₈ S ₂ O ₆ Li ^- and C ₄ O ₄ Li ^- positive electrode active material according to at least one of the one peak of claims 1 to 11 obtained secondary ion selected from among negative secondary ions consisting of. A conductive substrate;
A positive electrode active material layer including at least a positive electrode active material provided on the conductive substrate,
The positive electrode active material is
Particles comprising a cathode material capable of occluding and releasing electrode reactants;
A positive electrode comprising: a coating provided on at least a part of the particles and including at least one of metal salts represented by formulas (1) to (1) ′ .

(In Formula (1), M is Li . Each of a, c and d is an integer of 0 or more. B is an integer of 1 or more. The sum of a, b, c and d is an integer of 2 or more.) And the sum of a and b is an integer equal to or greater than 1. e, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are all monovalent groups and are bonded to each other. (R3 is a hydrocarbon group having a valence of the sum of a, b, c, and d.)

(In Formula (1) ′, M is Mg, a is 1, b is 1, and c = d = 0. The sum of a, b, c, and d is 2. e, f, g and h are each an integer of 1 or more, and R3 is a divalent hydrocarbon group. A positive electrode having a positive electrode active material, a negative electrode, a separator, and an electrolyte;
The positive electrode active material is
Particles comprising a cathode material capable of occluding and releasing electrode reactants;
A non-aqueous electrolyte secondary battery comprising: a coating provided on at least a part of the particles and including at least one of metal salts represented by formulas (1) to (1) ′ .

(In Formula (1), M is Li . Each of a, c and d is an integer of 0 or more. B is an integer of 1 or more. The sum of a, b, c and d is an integer of 2 or more.) And the sum of a and b is an integer equal to or greater than 1. e, f, g, and h are each an integer equal to or greater than 1. R1 and R2 are all monovalent groups and are bonded to each other. (R3 is a hydrocarbon group having a valence of the sum of a, b, c, and d.)

(In Formula (1) ′, M is Mg, a is 1, b is 1, and c = d = 0. The sum of a, b, c, and d is 2. e, f, g and h are each an integer of 1 or more, and R3 is a divalent hydrocarbon group. The nonaqueous electrolyte secondary battery according to claim 14, wherein the upper limit charging voltage is 4.25 V or more and 4.80 V or less and the lower limit discharge voltage is 2.00 V or more and 3.30 V or less .

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