KR101305712B1 - Positive electrode active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery and lithium ion secondary battery - Google Patents

Positive electrode active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery and lithium ion secondary battery Download PDF

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KR101305712B1
KR101305712B1 KR1020120010123A KR20120010123A KR101305712B1 KR 101305712 B1 KR101305712 B1 KR 101305712B1 KR 1020120010123 A KR1020120010123 A KR 1020120010123A KR 20120010123 A KR20120010123 A KR 20120010123A KR 101305712 B1 KR101305712 B1 KR 101305712B1
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positive electrode
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lithium ion
ion secondary
active material
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KR20120100720A (en
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와따루 오기하라
마나부 와따나베
아쯔시 이또오
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닛산 지도우샤 가부시키가이샤
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0585Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

Provided is a positive electrode active material for a lithium ion secondary battery capable of exhibiting excellent initial charge and discharge efficiency, a positive electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same. The positive electrode active material for a lithium ion secondary battery is a general formula: Li (2-0.5x) y(2-0.5x) (1-y) Mn 1-x M 1.5x O 3 [In general formula, Li is lithium, □ is a vacancy in the crystal structure, Mn is manganese, M is Ni α Co β Mn γ (Ni is nickel, Co is cobalt, Mn is manganese, α, β and γ are 0 <α ≦ 0.5, 0 ≦ β ≤ 0.33, 0 <satisfies γ ≤ 0.5), x and y are represented by 0 <x <1.00, 0 <sa <satisfy the relationship of <y <1.00], and the crystal structure belongs to the space group C2 / m Layered transition metal oxide.

Description

POSITIVE ELECTRODE ACTIVE MATERIAL FOR LITHIUM ION SECONDARY BATTERY, POSITIVE ELECTRODE FOR LITHIUM ION SECONDARY BATTERY AND LITHIUM ION SECONDARY BATTERY}

This invention relates to the positive electrode active material for lithium ion secondary batteries, the positive electrode for lithium ion secondary batteries, and a lithium ion secondary battery. In more detail, this invention relates to the positive electrode active material for lithium ion secondary batteries which can exhibit the outstanding initial stage charging and discharging efficiency, the positive electrode for lithium ion secondary batteries using this, and a lithium ion secondary battery.

In recent years, in order to cope with air pollution and global warming, reduction of carbon dioxide emission is urgently desired. In the automobile industry, expectations are concentrated on the reduction of carbon dioxide emissions by the introduction of electric vehicles (EVs) and hybrid electric vehicles (HEVs), and development of motor-driven secondary batteries, which is a key to their practical use, is actively carried out. have.

As a motor drive secondary battery, the lithium ion secondary battery which has high theoretical energy is attracting attention, and development is currently progressing rapidly. Generally, a lithium ion secondary battery applies the positive electrode formed by apply | coating the positive electrode slurry containing a positive electrode active material or a binder to both surfaces of a positive electrode electrical power collector, and the negative electrode slurry containing a negative electrode active material or a binder to both surfaces of a negative electrode current collector. And a negative electrode formed therebetween, and an electrolyte positioned between them, and is housed in a battery case.

In order to improve capacity characteristics, output characteristics, and the like of the lithium ion secondary battery, the selection of each active material is very important.

Conventionally, as a positive electrode active material for a lithium ion secondary battery having a high discharge capacity, the following general formulas xLi [Mn 1/2 Ni 1/2 ] O 2 yLiCoO 2 zLi [Li 1/3 Mn 2/3 ] O 2 ( A layered positive electrode active material (solid solution) having Li 2 MnO 3 represented by x + y + z = 1, 0 <x <1, 0 ≦ y <0.5, 0 <z <1) as a mother structure is used (patent See Document 1).

Japanese Patent Application Laid-Open No. 2007-287445

However, the positive electrode active material for lithium ion secondary batteries described in the patent document 1 has a problem that the capacity loss (initial irreversible capacity) at the time of initial charge and discharge is large and the initial charge and discharge efficiency is low.

The present invention has been made in view of the problems of the related art. And the objective is to provide the positive electrode active material for lithium ion secondary batteries which can exhibit the outstanding initial stage charging and discharging efficiency, the positive electrode for lithium ion secondary batteries, and the lithium ion secondary battery using the same.

Means for Solving the Problems The present inventors have diligently studied for achieving the above object. As a result, the inventors have found that the above object can be achieved by immersing a predetermined layered transition metal oxide in an acidic solution, and have completed the present invention.

That is, the positive electrode active material for lithium ion secondary batteries of this invention is a layered transition metal oxide represented by General formula (1) and whose crystal structure belongs to space group C2 / m.

[Formula 1]

Figure 112012008299117-pat00001

[In Formula 1, Li represents lithium, □ represents vacancy in the crystal structure, Mn represents manganese, M represents Ni α Co β Mn γ (Ni represents nickel, Co represents cobalt, Mn represents manganese, and α, β And γ satisfy 0 <α ≦ 0.5, 0 ≦ β ≦ 0.33, 0 <γ ≦ 0.5), and x and y satisfy a relationship of 0 <x <1.00, 0 <y <1.00.

Moreover, the positive electrode for lithium ion secondary batteries of this invention is a positive electrode for lithium ion secondary batteries which has a positive electrode active material layer formed in the surface of an electrical power collector.

And the said positive electrode active material layer contains the positive electrode active material for lithium ion secondary batteries of this invention.

Moreover, the lithium ion secondary battery of this invention is at least 1 by which the positive electrode for lithium ion secondary batteries which has the positive electrode active material layer formed in the surface of an electrical power collector, the electrolyte layer, and the negative electrode for lithium ion secondary batteries are laminated | stacked in this order. A lithium ion secondary battery with a battery element comprising two unit cells.

And the said positive electrode active material layer contains the positive electrode active material for lithium ion secondary batteries of this invention.

According to the present invention, since a predetermined layered transition metal oxide is immersed in an acidic solution, lithium using a positive electrode active material for lithium ion secondary batteries and a positive electrode active material for lithium ion secondary batteries capable of exhibiting excellent initial charge and discharge efficiency. A positive electrode for an ion secondary battery and a lithium ion secondary battery can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the outline of an example of the lithium ion secondary battery which concerns on one Embodiment of this invention.
2 is a graph showing the results of powder X-ray diffraction measurements for each example.

Hereinafter, the positive electrode active material for lithium ion secondary batteries, the positive electrode for lithium ion secondary batteries, and the lithium ion secondary battery of this invention are demonstrated in detail.

First, the positive electrode active material for lithium ion secondary batteries which concerns on one Embodiment of this invention is demonstrated in detail.

The positive electrode active material for lithium ion secondary batteries of this embodiment is represented by General formula 1, and is a layered transition metal oxide whose crystal structure belongs to space group C2 / m.

[Formula 1]

Figure 112012008299117-pat00002

[In Formula 1, Li is lithium, □ is a vacancy in the crystal structure, Mn is manganese, M is Ni α Co β Mn γ (Ni is nickel, Co is cobalt, Mn is manganese, and α, β and γ are , 0 <α ≦ 0.5, 0 ≦ β ≦ 0.33, and 0 <γ ≦ 0.5 are satisfied), and x and y satisfy a relationship of 0 <x <1.00, 0 <y <1.00].

Since such a positive electrode active material can exhibit the outstanding initial stage charging / discharging efficiency when it uses for a lithium ion secondary battery, it is used suitably for the positive electrode for lithium ion secondary batteries and a lithium ion secondary battery.

Here, when x is not 0 <x <1.00, the crystal structure does not become a layered transition metal oxide belonging to the space group C2 / m. Further, if x is 0.1 or more, the composition becomes more difficult the closer the Li 2 MnO 3, is preferable because it is easy to charge and discharge. Moreover, since x is 0.5 or less, since the charge / discharge capacity per weight of a positive electrode active material is higher than the existing layered positive electrode active material, and can be 200 mAh / g or more, it is preferable.

When y is not 0 <y <1.00, the crystal structure does not become a layered transition metal oxide belonging to the space group C2 / m. Moreover, since y is 0.94 or more, since the fall of discharge capacity can be suppressed, it is preferable.

In addition, when (alpha) is not (alpha) <= 0.5, nickel (Ni) is included in positive electrode active material in the range of x shown above on condition that nickel (Ni) is bivalent, and a crystal structure is a space group C2 / m. It does not become a layered transition metal oxide attributable.

In addition, when β is not β≤0.33, nickel (Ni) is included in the positive electrode active material within the range of x indicated above, provided that nickel (Ni) is divalent, and cobalt (Co) is contained in the positive electrode active material. It does not become a layered transition metal oxide whose crystal structure belongs to the space group C2 / m.

When γ is not γ ≦ 0.5, nickel (Ni) and cobalt (Co) are included in the positive electrode active material within the range of x shown above, provided that nickel (Ni) is divalent, and manganese ( Under the condition that Mn) is tetravalent, the crystal structure does not become a layered transition metal oxide belonging to the space group C2 / m.

The positive electrode active material can be obtained by immersing, in an acidic solution, a layered transition metal oxide represented by, for example, General Formula 2 and whose crystal structure belongs to the space group C2 / m.

[Formula 2]

Figure 112012008299117-pat00003

[In the general formula 2, Li is lithium, Mn is manganese, M is Ni α Co β Mn γ (Ni is nickel, Co is cobalt, Mn is manganese, and α, β and γ are 0 <α ≦ 0.5, 0 ≤ β ≤ 0.33, 0 <γ ≤ 0.5, and satisfies the relationship of α + β + γ = 1), and x is 0 <x <1.00, preferably 0.1 ≤ x ≤ 0.5.

At this time, examples of the acidic compound to be contained in the acidic solution to be used include strong acids such as hydrochloric acid, sulfuric acid, and nitric acid, and weak acids such as acetic acid. And although it does not specifically limit, It is preferable to use the weak acid whose acid dissociation constant is larger than 0 from a viewpoint that it is easy to obtain the positive electrode active material which has a desired performance.

Furthermore, the ratio of the acidic compound (AC) in the acidic solution (AC) to the lithium (Li) in the layered transition metal oxide represented by the above general formula (2) and whose crystal structure belongs to the space group C2 / m is (AC / Li). From a viewpoint of being easy to obtain the positive electrode active material which has a desired performance, it is preferable that it is 0.01-1.00 in molar ratio, and it is more preferable that it is 0.05-0.20.

Next, the positive electrode active material for lithium ion secondary batteries which concerns on another embodiment of this invention is demonstrated in detail.

The positive electrode active material for lithium ion secondary batteries of this embodiment is represented by General formula 3, and is a layered transition metal oxide whose crystal structure belongs to space group C2 / m.

[Formula 3]

Figure 112012008299117-pat00004

[In general formula 3, Li is lithium, □ is a vacancy in the crystal structure, Mn is manganese, M is Ni α Co β Mn γ M 1 δ {Ni is nickel, Co is cobalt, Mn is manganese, M 1 is aluminum ( At least one selected from the group consisting of Al), iron (Fe), copper (Cu), magnesium (Mg) and titanium (Ti), and α, β, γ and δ are 0 <α ≦ 0.5, 0 ≦ β ≦ 0.33, 0 <γ ≦ 0.5, 0 <δ ≦ 0.1, satisfy the relationship of α + β + γ + δ = 1}, and x and y are 0 <x <1.00, 0 <y <1.00 Satisfies the relationship of.

In general, nickel (Ni), cobalt (Co), and manganese (Mn) have the viewpoints of improving the purity of the material and improving the electronic conductivity, aluminum (Al), iron (Fe), copper (Cu), and magnesium (Mg). And titanium (Ti) is known to contribute to capacity | capacitance and an output characteristic from a viewpoint of stability improvement of a crystal structure.

Therefore, also in the positive electrode active material shown by the said General formula 3, when used for a lithium ion secondary battery, it is estimated to exhibit the outstanding initial charge / discharge efficiency, and such a positive electrode active material is a positive electrode for lithium ion secondary batteries, or lithium ion 2 It is suitably used for a secondary battery.

Here, when x is not 0 <x <1.00, the crystal structure does not become a layered transition metal oxide belonging to the space group C2 / m. Further, if x is 0.1 or more, the composition becomes more difficult the closer the Li 2 MnO 3, is preferable because it is easy to charge and discharge. Moreover, when x is 0.5 or less, since the charge / discharge capacity per weight of a positive electrode active material is higher than the existing layered positive electrode active material, since it can be 200 mAh / g or more, it is preferable.

When y is not 0 <y <1.00, the crystal structure does not become a layered transition metal oxide belonging to the space group C2 / m. Moreover, since y is 0.94 or more, since the fall of discharge capacity can be suppressed, it is preferable.

In addition, when (alpha) is not (alpha) <= 0.5, nickel (Ni) is included in positive electrode active material in the range of x shown above on condition that nickel (Ni) is bivalent, and a crystal structure is a space group C2 / m. It does not become a layered transition metal oxide attributable.

In addition, when β is not β≤0.33, nickel (Ni) is included in the positive electrode active material within the range of x indicated above, provided that nickel (Ni) is divalent, and cobalt (Co) is contained in the positive electrode active material. It does not become a layered transition metal oxide whose crystal structure belongs to the space group C2 / m.

When γ is not γ ≦ 0.5, nickel (Ni) and cobalt (Co) are included in the positive electrode active material within the range of x shown above, provided that nickel (Ni) is divalent, and manganese ( Under the condition that Mn) is tetravalent, the crystal structure does not become a layered transition metal oxide belonging to the space group C2 / m.

When δ is not δ ≦ 0.1, nickel (Ni) and cobalt (Co) are contained in the positive electrode active material within the range of x shown above, provided that nickel (Ni) is divalent and manganese (Mn) is tetravalent. ) And manganese (Mn), and the crystal structure is not a layered transition metal oxide belonging to the space group C2 / m.

The positive electrode active material can be obtained, for example, by dipping a layered transition metal oxide represented by the general formula (4) and whose crystal structure is attributed to the space group C2 / m in an acidic solution.

[Formula 4]

Figure 112012008299117-pat00005

[In Formula 4, Li is lithium, Mn is manganese, M is Ni α Co β Mn γ M 1 δ {Ni is nickel, Co is cobalt, Mn is manganese, M 1 is aluminum (Al), iron (Fe) , At least one selected from the group consisting of copper (Cu), magnesium (Mg) and titanium (Ti), and α, β, γ, and δ are 0 <α ≦ 0.5, 0 ≦ β ≦ 0.33, 0 < γ ≦ 0.5, 0 <δ ≦ 0.1, and α + β + γ + δ = 1, and satisfies the relationship of 0 <x <1.00, preferably 0.1 ≦ x ≦ 0.5.

At this time, examples of the acidic compound to be contained in the acidic solution to be used include strong acids such as hydrochloric acid, sulfuric acid, and nitric acid, and weak acids such as acetic acid. And although it does not specifically limit, It is preferable to use the weak acid whose acid dissociation constant is larger than 0 from a viewpoint that it is easy to obtain the positive electrode active material which has a desired performance.

Furthermore, the ratio of the acidic compound (AC) in the acidic solution (AC) to the lithium (Li) in the layered transition metal oxide represented by the general formula (4) and whose crystal structure belongs to the space group C2 / m is (AC / Li). From a viewpoint of being easy to obtain the positive electrode active material which has a desired performance, it is preferable that it is 0.01-1.00 in molar ratio, and it is more preferable that it is 0.05-0.20.

Next, the positive electrode for lithium ion secondary batteries and lithium ion secondary battery which concerns on one Embodiment of this invention is demonstrated in detail, referring drawings. In addition, the dimensional ratios in the drawings cited in the following embodiments are exaggerated for convenience of explanation, and may differ from the actual ratios.

[Configuration of Lithium Ion Secondary Battery]

1 is a cross-sectional view showing an outline of an example of a lithium ion secondary battery according to one embodiment of the present invention.

As shown in FIG. 1, in the lithium ion secondary battery 1 of the present embodiment, the battery element 10 provided with the positive electrode tab 21 and the negative electrode tab 22 is enclosed in the interior of the exterior body 30. Has a built-in configuration. In addition, in this embodiment, the positive electrode tab 21 and the negative electrode tab 22 are led in the opposite direction from the inside of the exterior body 30 to the outside. In addition, although not shown in figure, the positive electrode tab and the negative electrode tab may be guide | induced in the same direction toward the exterior from the inside of an exterior body. In addition, such a positive electrode tab and a negative electrode tab can be provided in the positive electrode collector and negative electrode collector mentioned later by ultrasonic welding, resistance welding, etc., for example.

[Positive electrode tab and negative electrode tab]

The positive electrode tab 21 and the negative electrode tab 22 are made of, for example, materials such as aluminum, copper, titanium, nickel, stainless steel (SUS) and these alloys. However, the present invention is not limited thereto, and conventionally known materials used as taps for lithium ion secondary batteries can be used.

Moreover, the thing of the same material may be used for the positive electrode tab and the negative electrode tab, and the thing of a different material may be used. In addition, like this embodiment, the tab prepared separately may be connected to the positive electrode collector and negative electrode collector which are mentioned later, and the tab may be formed by extending each positive electrode collector and each negative electrode collector mentioned later, respectively.

[External body]

The exterior body 30 is preferably formed of a film-shaped exterior material from the viewpoint of miniaturization and weight reduction, for example, but is not limited to this, and is known in the art for a exterior body for a lithium ion secondary battery. The material of can be used.

Further, when applied to automobiles, a polymer-metal composite laminate sheet having excellent thermal conductivity, for example, from the viewpoint of efficiently transferring heat from a vehicle heat source and rapidly heating the inside of the battery to the battery operating temperature. It is suitable to use.

[Battery element]

As shown in FIG. 1, the battery element 10 in the lithium ion secondary battery 1 of this embodiment is the positive electrode in which the positive electrode active material layer 11B was formed in the surface of both surfaces of 11 A of positive electrode electrical power collectors. (11), the electrolyte layer 13, and the structure which laminated | stacked the some negative electrode 12 in which the negative electrode active material layer 12B was formed on both surfaces of the negative electrode collector 12A. At this time, the positive electrode active material layer 11B formed on one surface of the positive electrode current collector 11A of one positive electrode 11 and the negative electrode current collector 12A of the negative electrode 12 adjacent to the one positive electrode 11 A plurality of negative electrode active material layers 12B formed on one surface thereof are laminated in the order of the positive electrode, the electrolyte layer, and the negative electrode so as to face each other via the electrolyte layer 13.

Thereby, the adjacent positive electrode active material layer 11B, the electrolyte layer 13, and the negative electrode active material layer 12B comprise one unit cell layer 14. Therefore, the lithium ion secondary battery 1 of this embodiment will have a structure electrically connected in parallel by laminating | stacking the unit cell layer 14 in multiple numbers. In addition, the negative electrode active material layer 12B is formed on only one surface of the negative electrode current collector 12a located at the outermost layer of the battery element 10. In addition, an insulating layer (not shown) may be formed on the outer circumference of the unit cell layer to insulate between adjacent positive electrode current collectors and negative electrode current collectors. Such an insulating layer is preferably formed of a material which holds the electrolyte contained in the electrolyte layer and the like and is formed on the outer circumference of the unit cell layer to prevent leakage of the liquid of the electrolyte. Specifically, polypropylene (PP), polyethylene (PE), polyurethane (PUR), polyamide-based resin (PA), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), polystyrene (PS) General purpose plastics, such as thermoplastic olefin rubber, etc. can be used. A silicone rubber may also be used.

[Positive electrode collector and negative electrode collector]

11 A of positive electrode electrical power collectors and 12 A of negative electrode electrical power collectors are comprised with electroconductive materials, such as aluminum foil, copper foil, stainless steel (SUS) foil, for example. However, it is not limited to these, The conventionally well-known material used as an electrical power collector for lithium ion secondary batteries can be used.

[Positive electrode active material layer]

The positive electrode active material layer 11B contains the positive electrode active material for lithium ion secondary batteries of this invention mentioned above as a positive electrode active material, and may contain a binder and a conductive support agent as needed.

In addition, the positive electrode active material layer may contain another positive electrode active material in addition to the positive electrode active material of the present invention described above. As another positive electrode active material, a lithium containing compound is preferable from a viewpoint of a capacity | capacitance and an output characteristic, for example. As such a lithium-containing compound, for example, a composite oxide containing lithium and a transition metal element, a phosphate compound containing lithium and a transition metal element, a sulfate compound containing lithium and a transition metal element, a lithium and a transition metal element, and Although a solid solution containing is mentioned, lithium-transition metal composite oxide is especially preferable from a viewpoint of obtaining higher capacity | capacitance and an output characteristic.

Specific examples of the composite oxide containing lithium and transition metal elements include lithium cobalt composite oxide (LiCoO 2 ), lithium nickel composite oxide (LiNiO 2 ), lithium nickel cobalt composite oxide (LiNiCoO 2 ), and lithium nickel manganese composite oxide (LiNi 0.5). Mn 1.5 O 4 ), lithium nickel manganese cobalt composite oxide [Li (NiMnCo) O 2 , Li (LiNiMnCo) O 2 ], lithium manganese composite oxide (LiMn 2 O 4 ) having a spinel structure, and the like. Moreover, as a specific example of the phosphate compound containing lithium and a transition metal element, a lithium iron phosphate compound (LiFePO 4 ), a lithium iron manganese phosphate compound (LiFeMnPO 4 ), etc. are mentioned. Moreover, in these complex oxides, the thing which substituted a part of transition metal with another element etc. is mentioned from the objective of stabilizing a structure, etc. are mentioned.

As a specific example of a solid solution containing lithium and a transition metal element, xLiM I O 2. (1-x) Li 2 M II O 3 (0 <x <1, M I has an average oxidation state of 3+, and M II has an average of One or more kinds of transition metal elements having an oxidation state of 4+), LiM III O 2 -LiMn 2 O 4 (M III is a transition metal element such as Ni, Mn, Co, Fe, etc.).

As the binder, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyvinyl acetate, polyimide (PI), polyamide (PA), polyvinyl chloride (PVC), polymethylacrylate (PMA) , Thermoplastic resins such as polymethyl methacrylate (PMMA), polyethernitrile (PEN), polyethylene (PE), polypropylene (PP), polyacrylonitrile (PAN), epoxy resins, polyurethane resins, urea resins ( and thermosetting resins such as urearesin, and rubber-based materials such as styrene butadiene rubber (SBR). However, it is not limited to these, The well-known material conventionally used as a binder for lithium ion secondary batteries can be used. These binders may be used individually by 1 type, and may use 2 or more types together.

As a conductive support agent, carbon materials, such as carbon black, such as acetylene black, graphite, carbon fiber, are mentioned, for example. However, it is not limited to these, The conventionally well-known material used as a conductive support agent for lithium ion secondary batteries can be used. These electrically conductive adjuvant may be used individually by 1 type, and may use 2 or more types together.

[Negative electrode active material layer]

The negative electrode active material layer 12B contains, as the negative electrode active material, any one kind or two or more kinds of negative electrode materials capable of occluding and releasing lithium, and may contain a binder or a conductive aid as necessary. In addition, a binder and a conductive support agent can use the above-mentioned thing.

Examples of the negative electrode material capable of occluding and releasing lithium include graphite (natural graphite, artificial graphite, etc.), high crystalline carbon, low crystalline carbon (soft carbon, hard carbon), and carbon black (Ketjen black, acetylene). Black, channel black, lamp black, oil furnace black, thermal black, etc.), fullerenes, carbon nanotubes, carbon nanofibers, carbon nanohorns, carbon fibrils and the like; Si, Ge, Sn, Pb, Al, In , Zn, H, Ca, Sr, Ba, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, Hg, Ga, Tl, C, N, Sb, Bi, O, S, Se, Te, Cl A single element of an alloy such as lithium and an oxide containing these elements [silicon monoxide (SiO), SiO x (0 <x <2), tin dioxide (SnO 2 ), SnO x (0 <x <2) , SnSiO 3, etc .; carbides (silicon carbide (SiC), etc.); metal materials such as lithium metal; lithium-transition metal composite oxides such as lithium-titanium composite oxide (lithium titanate: Li 4 Ti 5 O 12 ); Can be. However, it is not limited to these, The conventionally well-known material used as a negative electrode active material for lithium ion secondary batteries can be used. These negative electrode active materials may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may use the negative electrode active material of that excepting the above. Moreover, in addition to expressing the effect unique to each active material, when the optimum particle diameter differs, it is necessary to mix and use the optimal particle diameters in addition to expressing each unique effect, and to make the particle diameter of all active materials uniform. There is no.

[Electrolyte Layer]

As the electrolyte layer 13, for example, a layer structure is formed by using an electrolyte solution, a polymer gel electrolyte, or a solid polymer electrolyte held by a separator described later, or a laminated structure using a polymer gel electrolyte or a solid polymer electrolyte. The thing which formed these is mentioned.

As electrolyte solution, it is preferable that it is used normally, for example in a lithium ion secondary battery, and specifically, it has the form which the lithium salt melt | dissolved in the organic solvent. Examples of the lithium salt include inorganic acid anion salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiTaF 6 , LiAlCl 4 , Li 2 B 10 Cl 10 , LiCF 3 SO 3 , and Li (CF 3 SO 2 ) 2 N, Li (C 2 F 5 SO 2) can be cited, at least one kind of lithium salts selected from organic acid anion salts, such as into N 2. As the organic solvent, for example, cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC); chain carbonates such as dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and diethyl carbonate (DEC) Ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and 1,2-dibutoxyethane; lactones such as γ-butyrolactone; Nitriles such as acetonitrile; esters such as methyl propionate; amides such as dimethylformamide; organic solvents such as non-flotone solvents in which at least one or two or more selected from methyl acetate and methyl formate are mixed It may be used and the like. Moreover, as a separator, the microporous film which consists of polyolefins, such as polyethylene and a polypropylene, is mentioned, for example.

As a polymer gel electrolyte, what contains the polymer and electrolyte solution which comprise a polymer gel electrolyte in a conventionally well-known ratio are mentioned.

The polymer gel electrolyte is a solid polymer electrolyte having ion conductivity. The electrolyte solution is usually contained in a lithium ion secondary battery. However, the polymer gel electrolyte is not limited thereto, and the same electrolyte solution is present in a skeleton of a polymer having no lithium ion conductivity. It also includes maintaining.

Examples of the polymer having no lithium ion conductivity used in the polymer gel electrolyte include polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), polyacrylonitrile (PAN), and polymethyl methacrylate (PMMA). Etc. can be used. However, it is not limited to these. In addition, since PAN, PMMA, etc. belong to the class which has little ion conductivity if it is either, it can also be set as the polymer which has the said ion conductivity, but here it is illustrated as a polymer which does not have the lithium ion conductivity used for a polymer gel electrolyte. will be.

As a solid polymer electrolyte, the said lithium salt melt | dissolves in polyethylene oxide (PEO), a polypropylene oxide (PPO), etc. are mentioned, for example.

The thickness of the electrolyte layer is preferably thinner from the viewpoint of reducing the internal resistance. The thickness of an electrolyte layer is 1-100 micrometers normally, Preferably it is 5-50 micrometers.

<Examples>

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

(First embodiment)

<Production of Positive Electrode Active Material>

First, the raw material of the positive electrode active material (solid solution) was synthesize | combined by the composite carbonate method. Specifically, nickel sulfate, cobalt sulfate, and manganese sulfate were weighed so that nickel (Ni), cobalt (Co), and manganese (Mn) were at a predetermined molar ratio. Then, these were dissolved in ion-exchanged water to prepare a mixed aqueous solution. Furthermore, it was added dropwise until the aqueous ammonia to the mixed aqueous solution at pH7, and further precipitate the compound of the carbonate was added dropwise to sodium carbonate (Na 2 CO 3) solution, Ni-Co-Mn. In addition, while the sodium carbonate aqueous solution was dripped, it was made to maintain pH7 with ammonia water. Furthermore, the obtained composite carbonate was suction filtered, washed with water, dried at 120 ° C for 5 hours, and calcined at 500 ° C for 5 hours to obtain a composite oxide of Ni-Co-Mn. In addition, a small excess of lithium hydroxide (LiOH.H 2 O) was added to the obtained composite oxide so as to have a predetermined molar ratio, and the mixture was mixed for 30 minutes by automatic induction, and then calcined at 900 ° C for 12 hours, and rapidly After cooling, the raw material of the positive electrode active material (solid solution) [Li 1.85 Ni 0.18 Co 0.10 Mn 0.87 O 3 (in Formula 2, α = 0.4, β = 0.22, γ = 0.38, and x = 0.3). Active material raw material A ”].

Next, part of lithium (Li) was removed by solution treatment. Specifically, the positive electrode active material A is immersed in an aqueous hydrogen chloride (HCl) aqueous solution (the amount of HCl in the acidic aqueous solution is 0.20 in the molar ratio to lithium in the positive electrode active material A), which is an acidic aqueous solution 20 times the amount of the active material. The mixture was stirred for 2 hours, filtered and washed with water, and the solid was vacuum dried at 80 deg. C to obtain a positive electrode active material of this example.

<Method for Analyzing Element Composition of Positive Electrode Active Material>

A part of the obtained positive electrode active material is taken as a sample, and this is dissolved in an acid, and lithium (Li), nickel (Ni), cobalt (Co), and manganese (Mn) contained in the solution are inductively coupled plasma emission spectroscopy (S Quantitative analysis was carried out by inductively coupled plasma emission spectroscopy (ICP-AES) using IAI Nanotechnology Co., Ltd., ICP-AES SPS-3520UV type).

The manufacturing conditions and the obtained results are shown in Table 1. In addition, Li amount in Table 1 is a relative amount at the time of making Li amount of the 1st comparative example mentioned later into 100 mol%. Nickel (Ni), manganese (Mn), and cobalt (Co) did not change regardless of the treatment solution species.

Figure 112012008299117-pat00006

<Structure Analysis Method of Positive Electrode Active Material>

A part of the obtained positive electrode active material was used as a sample (powder) using an X-ray diffractometer (MXP18VAHF), and powder X was measured under a measurement condition of 40 mA, current 200 mA, and X-ray wavelength: Cu-Kα. Line diffraction measurement was performed.

The obtained result is shown in FIG. 2 with the data of a standard sample.

(2nd Example-4th Example, a 1st comparative example, and a 2nd comparative example)

In the solution treatment, an aqueous solution of sulfuric acid (H 2 SO 4 ) was used as the acidic aqueous solution (Example 2), an aqueous solution of nitric acid (HNO 3 ) was used (Example 3), and an acetic acid (CH 3 COOH) aqueous solution. The same operations as those of the first embodiment were carried out except that the used (fourth example), the solution treatment was not performed (the first comparative example), and the ion exchanged water (H 2 O) was used (the second comparative example). It was repeated and the positive electrode active material of each case was obtained.

In the same manner as in Example 1, elemental composition analysis and structural analysis of the positive electrode active material were performed. The manufacturing conditions and the obtained result are shown in Table 1 or FIG. 2 (not shown in FIG. 2, but the same result is acquired also about a 4th Example).

(Fifth to Ninth Embodiments)

At the time of solution treatment, the amount of CH 3 COOH in the aqueous acetic acid (CH 3 COOH) solution was 0.05 (Example 5), 0.10 (Example 6), 0.30 (Example) in a molar ratio to lithium in the positive electrode active material A. The same operations as those in the fourth embodiment were repeated except that the seventh embodiment, 0.50 (eighth example), and 1.00 (ninth example) were obtained to obtain a positive electrode active material of each example.

As described above, elemental composition analysis and structural analysis of the positive electrode active material were performed. The manufacturing conditions and the obtained results are shown in Table 2. In addition, Li amount in Table 2 is a relative amount at the time of making Li amount of the said 1st comparative example into 100 mol%. Nickel (Ni), manganese (Mn), and cobalt (Co) did not change regardless of the treatment solution species.

Figure 112012008299117-pat00007

(Examples 10 to 14, and Comparative Example 3)

In synthesizing the raw material of the positive electrode active material, nickel sulfate, cobalt sulfate, and manganese sulfate are weighed so that nickel (Ni), cobalt (Co), and manganese (Mn) have different predetermined molar ratios, and Li 1.77 Ni 0.32 Co 0.05 Mn 0.86 O 3 (in Formula 2, α = 0.464, β = 0.072, γ = 0.464, x = 0.46, and hereinafter referred to as “positive electrode active material B”) was obtained. Examples, operations similar to those of the fourth, eighth, ninth, and first comparative examples were repeated to obtain positive electrode active materials of each example.

As described above, elemental composition analysis and structural analysis of the positive electrode active material were performed. The manufacturing conditions and the obtained results are shown in Table 3. In addition, Li amount in Table 3 is a relative amount at the time of making Li amount of the said 3rd comparative example 100 mol%. In addition, nickel (Ni), manganese (Mn), and cobalt (Co) did not change regardless of the treatment solution species.

Figure 112012008299117-pat00008

&Lt; Preparation of positive electrode &

First, 80 parts by mass of the obtained positive electrode active material, 10 parts by mass of acetylene black as a conductive aid, and 10 parts by mass of polyvinylidene fluoride as a binder are kneaded, and N-methyl-2-pyrrolidone (NMP) is added thereto, followed by mixing And a positive electrode slurry were produced.

Next, the obtained positive electrode slurry was apply | coated to the aluminum foil as an electrical power collector so that the thickness of a positive electrode active material layer might be 70 micrometers, and it vacuum-dried at 80 degreeC, and obtained the positive electrode of each case.

<Fabrication of Battery>

First, the said positive electrode obtained and the negative electrode which adhered the metal lithium to the stainless steel disc were made to oppose, and the separator (material: polyolefin, thickness: 20 micrometers) was arrange | positioned in the meantime. Subsequently, a stack of the negative electrode, the separator, and the positive electrode was placed in a coin cell [CR2032, a material: stainless steel (SUS316)], the following electrolyte was injected, sealed, and a lithium ion secondary battery (half cell) of each example. Got.

As the electrolyte, lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt was added to an organic solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a ratio of EC: DEC = 1: 2 (volume ratio). The thing dissolved so that it might become 1 mol / L was used.

<Charge / Discharge Characteristics Evaluation of Lithium Ion Secondary Battery>

About the obtained lithium ion secondary battery, the charge / discharge cycle test was done, the initial charge / discharge capacity was measured, and charge / discharge efficiency was computed. Specifically, the battery was charged to 4.8V by a constant voltage method (CC, current: 0.1C) under a 30 ° C atmosphere, and stopped for 10 minutes, and then discharged to 2V by a constant current method (CC, current: 0.1C). After the discharge, the charging and discharging process was stopped for 10 minutes.

The obtained result is written together to Tables 1-3.

As shown in Table 1, the molar ratio of acid was made constant (0.20) with respect to the amount of Li in the positive electrode active material, and the influence of the kind of acid on the performance was evaluated. From Table 1, when the second comparative example using ion-exchanged water is compared with the first comparative example not subjected to solution treatment, it can be seen that the charge-discharge specification is not significantly changed. In addition, it can be seen from Table 1 that the charge and discharge capacity is significantly reduced in the first example using the hydrogen chloride solution and the second example using the sulfuric acid aqueous solution. And from Table 1, although the charging and discharging efficiency is high, it turns out that discharge capacity is falling large. Moreover, from Table 1, although the 3rd Example which used the nitric acid aqueous solution improves slightly of charging / discharging efficiency, it turns out that a discharge capacity falls. From Table 1, it turns out that charging / discharging efficiency can be improved in 4th Example which used the acetic acid aqueous solution, without reducing a discharge capacity significantly.

2 shows that even if the kind of acid to be immersed differs, there is no difference in crystal structure.

As shown in Table 2, the effect of acetic acid concentration on the performance was evaluated. From Table 2, when the molar ratio of acetic acid is at least 0.05 to 0.20 relative to the amount of Li in the positive electrode active material, it can be seen that the charge and discharge efficiency can be improved without significantly reducing the discharge capacity.

As shown in Table 3, the influence which the concentration of acetic acid has on performance was evaluated in the active material (positive electrode active material raw material B) of a different composition. From Table 3, it turns out that the same tendency as the case where the positive electrode active material A is used is shown. Moreover, it turns out that charging / discharging efficiency can be improved, as long as the molar ratio of acetic acid does not fall to 0.50 with respect to Li amount in a positive electrode active material.

It is understood from the amount of Li shown in Tables 1 to 3 that the discharge capacity tends to decrease when the amount of Li is less than 94 mol%. In addition, Li amount is a relative amount when the Li amount of the 1st comparative example or the 3rd comparative example of a 1st comparative example is 100 mol%.

As mentioned above, although this invention was demonstrated by several embodiment and Example, this invention is not limited to these, A various deformation | transformation is possible within the scope of the summary of this invention. That is, the positive electrode and lithium ion secondary battery for lithium ion secondary batteries of this invention should just be what a positive electrode active material layer contains predetermined | prescribed layered transition metal oxide as a positive electrode active material, and it does not specifically limit about other structural requirements. .

For example, the present invention can be applied not only to the laminate battery described above but also to a conventionally known form and structure such as a button battery or a can battery.

For example, the present invention can be applied not only to the above-described stacked type (flat type) battery but also to a conventionally known form and structure such as a wound type (cylindrical) battery. For example, the present invention is not only a normal (internal parallel connection type) battery described above but also a bipolar (internal series connection type) battery, as seen from the electrical connection form (electrode structure) in a lithium ion secondary battery. The present invention can also be applied to conventionally known forms and structures.

In addition, the battery element in a bipolar battery generally has a structure in which a positive electrode active material layer is formed on one surface of a current collector, and a plurality of bipolar electrodes and electrolyte layers in which a negative electrode active material layer is formed on the other surface are laminated. Have

1: Lithium ion secondary battery
10: Battery element
11: positive electrode
11A: Positive electrode collector
11B: positive electrode active material layer
12: negative electrode
12A: anode collector
12B: Negative electrode active material layer
13: electrolyte layer
14:
21: positive electrode tap
22: negative electrode tab
30: exterior

Claims (6)

  1. [Formula 1]
    Figure 112012008299117-pat00009

    [In Formula 1, Li is lithium, □ is a vacancy in the crystal structure, Mn is manganese, M is Ni α Co β Mn γ (Ni is nickel, Co is cobalt, Mn is manganese, and α, β and γ are , 0 <α ≦ 0.5, 0 ≦ β ≦ 0.33, and 0 <γ ≦ 0.5 are satisfied), and x and y are represented by 0 <x <1.00, 0 <y <1.00 satisfying a relationship of]. The structure is a layered transition metal oxide belonging to space group C2 / m, The positive electrode active material for lithium ion secondary batteries characterized by the above-mentioned.
  2. The method of claim 1,
    In said general formula 1, x and y satisfy | fill the relationship of 0.1 <= <= 0.5, 0.94 <= y <1.00, The positive electrode active material for lithium ion secondary batteries characterized by the above-mentioned.
  3. 3. The method according to claim 1 or 2,
    [Formula 2]
    Figure 112012008299117-pat00010

    [In the general formula 2, Li is lithium, Mn is manganese, M is Ni α Co β Mn γ (Ni is nickel, Co is cobalt, Mn is manganese, and α, β and γ are 0 <α ≦ 0.5, 0 ≦ β ≦ 0.33, 0 <γ ≦ 0.5 is satisfied), x is expressed as 0 <satisfied relationship of x <1.00], and the crystal structure is a layered transition metal oxide belonging to the space group C2 / m. It is obtained by immersing in an acidic solution, The positive electrode active material for lithium ion secondary batteries characterized by the above-mentioned.
  4. The method of claim 3,
    The ratio (AC / Li) of the acidic compound (AC) in the acidic solution to the lithium (Li) in the layered transition metal oxide represented by the general formula (2) and whose crystal structure is attributed to the space group C2 / m is It is 0.01-1.00 in molar ratio, The positive electrode active material for lithium ion secondary batteries.
  5. The positive electrode active material layer which contains the positive electrode active material for lithium ion secondary batteries of Claim 1 or 2 on the surface of an electrical power collector, The positive electrode for lithium ion secondary batteries characterized by the above-mentioned.
  6. The positive electrode for lithium ion secondary batteries which has the positive electrode active material layer containing the positive electrode active material for lithium ion secondary batteries of Claim 1 or 2 on the surface of an electrical power collector, the electrolyte layer, and the negative electrode for lithium ion secondary batteries in this order. A lithium ion secondary battery comprising a battery element comprising at least one unit cell laminated.
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