CN111164817B - Lithium ion secondary battery - Google Patents
Lithium ion secondary battery Download PDFInfo
- Publication number
- CN111164817B CN111164817B CN201780095520.7A CN201780095520A CN111164817B CN 111164817 B CN111164817 B CN 111164817B CN 201780095520 A CN201780095520 A CN 201780095520A CN 111164817 B CN111164817 B CN 111164817B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium ion
- ion secondary
- secondary battery
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 107
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- 239000007773 negative electrode material Substances 0.000 claims abstract description 35
- 238000009782 nail-penetration test Methods 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The lithium ion secondary battery of the present invention is accommodated in a container: a positive electrode having a positive electrode collector layer and a positive electrode active material layer, a negative electrode having a negative electrode collector layer and a negative electrode active material layer, a nonaqueous electrolyte solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode. In addition, when a nail made of SUS304 having a diameter phi 3mm and a length 70mm is used to pierce the center portion of the lithium ion secondary battery at a speed of 80mm/sec in a fully charged state in an environment of 25 ℃, and a nail penetration test for shorting the lithium ion secondary battery is performed, after the nail penetration test, the lithium ion secondary battery is subjected to a short-circuit discharge, and when the voltage reaches a range of 0.001V to 0.100V, the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery is 0.1 omega to 300 omega.
Description
Technical Field
The present invention relates to a lithium ion secondary battery.
Background
Lithium ion secondary batteries have a characteristic of high energy density, and are widely used as power sources for mobile phones, notebook personal computers, electric vehicles, and the like.
Since a flammable organic solvent is used as a main solvent for an electrolyte solution in a lithium ion secondary battery, safety against fire and explosion is required.
As a technique related to the safety of such a lithium ion secondary battery, for example, a technique described in patent document 1 (japanese patent application laid-open publication No. 2013-251281) is cited.
Patent document 1 (japanese patent application laid-open No. 2013-251281) describes a lithium secondary battery comprising an electrode body composed of a positive electrode having a positive electrode active material layer containing a positive electrode active material on the surface of a positive electrode current collector, a negative electrode having a negative electrode active material layer containing a negative electrode active material on the surface of a negative electrode current collector, and a separator arranged between the positive electrode and the negative electrode, and a battery case accommodating the electrode body and an electrolyte together, wherein the ratio of the surface area of the battery case to the energy capacity when the battery is fully charged is 4.5cm 2 And the positive electrode has a resistivity of 10 to 450 Ω·cm.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-251281
Disclosure of Invention
Problems to be solved by the invention
With the increase in size and the increase in energy density of lithium ion secondary batteries, further improvement in safety of lithium ion secondary batteries is demanded.
Here, it is clear from the study of the present inventors that: in order to achieve high energy density of a lithium ion secondary battery, for example, when a high capacity type positive electrode active material such as a lithium nickel-containing composite oxide is used, the thickness of the current collector layers of the positive electrode and the negative electrode is reduced, or the density of the positive electrode active material layer is increased, the thermal stability of the lithium ion secondary battery may be lowered, and the battery safety may be deteriorated.
Furthermore, it is clear from the study of the present inventors that: when the resistance of the electrode is increased to improve the safety of the battery, battery characteristics such as cycle characteristics may be deteriorated.
That is, the present inventors found that: conventional lithium ion secondary batteries have a relationship between battery characteristics such as cycle characteristics and battery safety.
The present invention has been made in view of the above circumstances, and provides a lithium ion secondary battery having excellent battery characteristics such as cycle characteristics and battery safety.
Means for solving the problems
The present inventors have conducted intensive studies in order to achieve the above-described object. The result can be clearly defined: by setting the dc resistance between the positive electrode and the negative electrode of the lithium ion secondary battery after the nail penetration test performed under a predetermined condition to a predetermined range, it is possible to improve the relationship between the battery characteristics such as cycle characteristics and the battery safety, and to obtain a lithium ion secondary battery having excellent characteristics such as cycle characteristics and battery safety.
Namely, found that: the present invention has been achieved by considering that a dimension of a direct current resistance between the positive electrode and the negative electrode of a lithium ion secondary battery after a nail penetration test performed under a predetermined condition is effective as a design pointer for realizing a lithium ion secondary battery excellent in balance between battery characteristics such as cycle characteristics and battery safety.
The present invention has been made based on this knowledge.
That is, according to the present invention, a lithium ion secondary battery shown below is provided.
According to the present invention, there is provided a lithium ion secondary battery, which contains, in a container: a positive electrode having a positive electrode collector layer and a positive electrode active material layer, a negative electrode having a negative electrode collector layer and a negative electrode active material layer, a nonaqueous electrolyte solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode,
when a nail made of SUS304 having a diameter of 3mm and a length of 70mm was used to pierce the center portion of the lithium ion secondary battery at a speed of 80mm/sec in a fully charged state at 25℃and to perform a nail penetration test for shorting the lithium ion secondary battery,
after the nail penetration test, the lithium ion secondary battery is short-circuited and discharged, and when the voltage reaches a range of 0.001V to 0.100V, the DC resistance between the positive electrode and the negative electrode of the lithium ion secondary battery is 0.1 to 300 Ω.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a lithium ion secondary battery having excellent battery characteristics such as cycle characteristics and excellent battery safety can be improved.
Drawings
The above objects and other objects, features and advantages will be further apparent from the following preferred embodiments and the accompanying drawings.
Fig. 1 is a schematic diagram showing an example of a laminated battery according to the present embodiment.
Fig. 2 is a schematic diagram showing an example of a wound battery according to the present embodiment.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the appropriate description thereof is omitted. In the drawings, each component schematically shows a shape, a size, and a layout relationship to the extent that the present invention can be understood, and is different from the actual size. In the present embodiment, "a to B" in the numerical range indicates a or more and B or less unless otherwise specified.
< lithium ion Secondary Battery >
The lithium ion secondary battery according to the present embodiment is accommodated in a container: a positive electrode having a positive electrode collector layer and a positive electrode active material layer, a negative electrode having a negative electrode collector layer and a negative electrode active material layer, a nonaqueous electrolyte solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode. In addition, when a nail made of SUS304 having a diameter phi 3mm and a length 70mm is used to pierce the center portion of the lithium ion secondary battery at a speed of 80mm/sec in a fully charged state in an environment of 25 ℃, and a nail penetration test for shorting the lithium ion secondary battery is performed, after the nail penetration test, the lithium ion secondary battery is subjected to a short-circuit discharge, and when the voltage reaches a range of 0.001V to 0.100V, the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery is 0.1 omega to 300 omega.
From the studies by the inventors it is clear that: in order to achieve high energy density of a lithium ion secondary battery, for example, when a high capacity type positive electrode active material such as a lithium nickel-containing composite oxide is used, the thickness of the current collector layers of the positive electrode and the negative electrode is reduced, or the density of the positive electrode active material layer is increased, the thermal stability of the lithium ion secondary battery may be lowered, and the battery safety may be deteriorated.
Furthermore, it is clear from the study of the present inventors that: when the resistance of the electrode is increased to improve the safety of the battery, battery characteristics such as cycle characteristics may be deteriorated.
That is, the present inventors found that: conventional lithium ion secondary batteries have a relationship between battery characteristics such as cycle characteristics and battery safety.
Accordingly, the present inventors have conducted intensive studies to achieve the above object. The result can be clearly defined: by setting the dc resistance between the positive electrode and the negative electrode of the lithium ion secondary battery after the nail penetration test performed under the above conditions to the above range, the relationship between the battery characteristics such as cycle characteristics and battery safety, which is present between them, can be improved, and a lithium ion secondary battery having excellent characteristics such as cycle characteristics and battery safety can be obtained.
Namely, it was found that: the dimension of the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery after the nail penetration test performed under the predetermined conditions is effective as a design pointer for realizing a lithium ion secondary battery excellent in balance between battery characteristics such as cycle characteristics and battery safety.
In the lithium ion secondary battery according to the present embodiment, the lower limit of the dc resistance between the positive electrode and the negative electrode after the nail penetration test is 0.1 Ω or more, preferably 1 Ω or more, more preferably 2 Ω or more, still more preferably 10 Ω or more, still more preferably 40 Ω or more, still more preferably 60 Ω or more, and particularly preferably 80 Ω or more.
In the lithium ion secondary battery according to the present embodiment, the dc resistance between the positive electrode and the negative electrode after the nail penetration test is set to the lower limit value or more, whereby the safety of the lithium ion secondary battery can be effectively improved.
In the lithium ion secondary battery according to the present embodiment, the upper limit of the dc resistance between the positive electrode and the negative electrode after the nail penetration test is 300 Ω or less, preferably 250 Ω or less, more preferably 200 Ω or less, still more preferably 150 Ω or less, and particularly preferably 130 Ω or less.
In the lithium ion secondary battery according to the present embodiment, the direct current resistance between the positive electrode and the negative electrode after the nail penetration test is set to the upper limit value or less, whereby battery characteristics such as cycle characteristics of the lithium ion secondary battery can be effectively improved.
Here, in the present embodiment, the fully charged state means: the lithium ion secondary battery was charged with a constant current at 25 ℃ and a constant current of 1C using a constant current constant voltage (CC-CV) method until a voltage of 4.2V, and then charged with a constant voltage of 4.2V and a state at a charge termination current of 0.015C.
The direct current resistance between the positive electrode and the negative electrode after the above-described nail penetration test of the lithium ion secondary battery according to the present embodiment can be achieved by appropriately selecting the mixing ratio of (a) the positive electrode active material layer or the negative electrode active material layer, (B) the kind of the separator, (C) the kind of the collector layer, and the like.
Among these, examples of the elements for setting the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery after the above-mentioned nail penetration test to a desired value range include setting the amount of the conductive auxiliary agent in the positive electrode active material layer to a predetermined range, using a separator having high heat resistance and high elongation, using a separator having a tensile elongation larger than that of the positive electrode current collector layer or the negative electrode current collector layer, and the like.
The reason why the lithium ion secondary battery described in the present embodiment is excellent in battery safety is not clear, and it is considered that this is because: in such a lithium ion secondary battery, for example, even if a short circuit occurs due to the entry of foreign matter into the battery, the resistance of the battery can be maintained in a high range, and thus, the flow of a large current can be suppressed, and as a result, thermal runaway of the battery can be suppressed.
The rated capacity of the battery cell of the lithium ion secondary battery according to the present embodiment is preferably 5Ah or more, and more preferably 7Ah or more.
The number of layers or windings of the positive electrode in the central portion of the lithium ion secondary battery according to the present embodiment is preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more.
This enables the lithium ion secondary battery according to the present embodiment to have a high capacity. In addition, even with such a high capacity, the lithium ion secondary battery according to the present embodiment is excellent in short-circuit resistance, and can suppress thermal runaway of the battery.
The form and type of the lithium ion secondary battery according to the present embodiment are not particularly limited, and may be configured as follows, for example.
[ laminated Battery ]
Fig. 1 schematically shows the structure of a laminated battery. The laminated battery 100 includes battery elements in which positive electrodes 1 and negative electrodes 6 are alternately laminated in a plurality of layers with separators 20 interposed therebetween, and these battery elements are housed together with an electrolyte (not shown) in a container including a flexible film 30. The following composition is presented: the positive electrode terminal 11 and the negative electrode terminal 16 are electrically connected to the battery element, and a part or all of the positive electrode terminal 11 and the negative electrode terminal 16 is led out of the flexible film 30.
The positive electrode 1 has a positive electrode active material coated portion (positive electrode active material layer 2) and an uncoated portion on the front and back of the positive electrode current collector layer 3, respectively, and the negative electrode 6 has a negative electrode active material coated portion (negative electrode active material layer 7) and an uncoated portion on the front and back of the negative electrode current collector layer 8.
The uncoated portion of the positive electrode active material in the positive electrode collector layer 3 is made into a positive electrode tab 10 for connection to the positive electrode terminal 11, and the uncoated portion of the negative electrode active material in the negative electrode collector layer 8 is made into a negative electrode tab 5 for connection to the negative electrode terminal 16.
The positive electrode tabs 10 are collected together at the positive electrode terminal 11 and connected together with the positive electrode terminal 11 by ultrasonic welding or the like, and the negative electrode tabs 5 are collected together at the negative electrode terminal 16 and connected together with the negative electrode terminal 16 by ultrasonic welding or the like. One end of the positive electrode terminal 11 is led out of the flexible film 30, and one end of the negative electrode terminal 16 is also led out of the flexible film 30.
An insulating member may be formed as needed at the boundary portion 4 between the coated portion (positive electrode active material layer 2) and the uncoated portion of the positive electrode active material, and the insulating member may be formed not only at the boundary portion 4 but also in the vicinity of the boundary portion between the positive electrode tab 10 and the positive electrode active material.
An insulating member may be formed in the same manner as the boundary 9 between the coated portion (negative electrode active material layer 7) and the uncoated portion of the negative electrode active material, if necessary, and may be formed in the vicinity of the boundary between the negative electrode tab 5 and the negative electrode active material.
In general, the external dimension of the anode active material layer 7 is larger than the external dimension of the cathode active material layer 2 and smaller than the external dimension of the separator 20.
[ winding type Battery ]
Fig. 2 schematically shows the structure of a wound battery, and the illustration of a container and the like is omitted. The wound battery 101 includes a battery element in which the positive electrode 1 and the negative electrode 6 are stacked and wound with the separator 20 interposed therebetween, and the battery element is housed in a container including a flexible film together with an electrolyte (not shown).
The battery elements of the wound battery 101 are also electrically connected to a positive electrode terminal, a negative electrode terminal, and the like, and other configurations are substantially identical to those of the laminated battery 100, and therefore, the above description is omitted here.
Next, each configuration used in the lithium ion secondary battery of the present embodiment will be described.
(cathode for lithium absorption and release)
The positive electrode 1 used in the present embodiment may be appropriately selected from known positive electrodes that can be used in lithium ion secondary batteries, depending on the application and the like. As the active material used for the positive electrode 1, a material having high electron conductivity is preferable in order to be able to reversibly release and store lithium ions and to be able to easily transport electrons.
The positive electrode active material used in the positive electrode 1 is not particularly limited, and for example, a lithium composite oxide having a layered rock salt type structure or a spinel type structure, lithium iron phosphate having an olivine type structure, or the like can be used. Lithium composite oxides include lithium manganate (LiMn 2 O 4 ) The method comprises the steps of carrying out a first treatment on the surface of the Lithium cobalt oxide (LiCoO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Lithium nickelate (LiNiO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the A lithium compound in which at least a part of manganese, cobalt, or nickel is replaced with another metal element such as aluminum, magnesium, titanium, or zinc; nickel-substituted lithium manganate obtained by substituting at least a part of manganese in lithium manganate with nickel; cobalt-substituted lithium nickelate in which at least a part of nickel in the lithium nickelate is substituted with cobalt; a material obtained by substituting a part of manganese of lithium manganate with other metals (for example, at least one of aluminum, magnesium, titanium, and zinc); a substance obtained by substituting cobalt for a part of nickel in lithium nickelate with other metal elements (for example, at least one of aluminum, magnesium, titanium, zinc, and manganese). These lithium composite oxides may be used singly or in combination of two or more.
As the lithium-containing composite oxide having a layered crystal structure, a lithium-nickel-containing composite oxide can be mentioned. The lithium-nickel-containing composite oxide may be one in which a part of nickel in the nickel site is replaced with another metal. Examples of the metal other than Ni occupying the nickel site include at least one metal selected from Mn, co, al, mg, fe, cr, ti, in.
In the lithium nickel-containing composite oxide, co is preferably contained as a metal other than Ni occupying nickel sites. Further, the lithium nickel-containing composite oxide more preferably contains Mn or Al in addition to Co, that is, lithium nickel cobalt manganese composite oxide (NCM) having a layered crystal structure, lithium nickel cobalt aluminum composite oxide (NCA) having a layered crystal structure, or a mixture thereof can be suitably used.
As the lithium-nickel-containing composite oxide having a layered crystal structure, for example, those represented by the following formula (1) can be used.
Li 1+a (Ni b Co c Me1 a Me2 1-b-c-d )O 2 (1)
(wherein Mel is Mn or Al, me2 is at least 1 selected from Mn, al, mg, fe, cr, ti, in (excluding the same metals as Me 1), -0.5.ltoreq.a < 0.1, 0.1.ltoreq.b < 1, 0 < c < 0.5, 0 < d < 0.5)
The average particle diameter of the positive electrode active material is, for example, preferably 0.1 to 50 μm, more preferably 1 to 30 μm, and even more preferably 2 to 25 μm from the viewpoints of reactivity with an electrolyte, rate characteristics, and the like. The average particle diameter herein means a particle diameter (median diameter: D) at which the cumulative value in the particle size distribution (volume basis) based on the laser diffraction scattering method is 50% 50 )。
The positive electrode 1 is composed of a positive electrode current collector layer 3 and a positive electrode active material layer 2 on the positive electrode current collector layer 3. The positive electrode 1 is disposed so that the positive electrode active material layer 2 faces the negative electrode active material layer 7 on the negative electrode current collector layer 8 via a separator.
The positive electrode 1 in the present embodiment can be manufactured by a known method. For example, the following methods and the like can be employed: after dispersing a positive electrode active material, a binder resin, and a conductive auxiliary agent in an organic solvent to obtain a positive electrode slurry, the positive electrode slurry is applied to a positive electrode current collector layer 3, dried, and pressurized as necessary, thereby forming a positive electrode active material layer 2 on the positive electrode current collector layer 3.
As a slurry solvent used in the production of the positive electrode, for example, N-methyl-2-pyrrolidone (NMP) can be used.
As the binder resin, for example, a resin that is generally used as a binder resin for a positive electrode, such as Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), can be used.
The content of the binder resin in the positive electrode active material layer 2 is preferably 0.1 part by mass or more and 10.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less, and still more preferably 1.0 part by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the entire positive electrode active material layer 2. When the content of the binder resin is within the above range, the balance of the coatability of the positive electrode slurry, the adhesion of the binder, and the battery characteristics is more excellent.
In addition, when the content of the binder resin is equal to or less than the upper limit value, the proportion of the positive electrode active material increases, and the capacity per positive electrode mass increases, which is preferable. When the content of the binder resin is not less than the above lower limit, electrode peeling is suppressed, which is preferable.
The positive electrode active material layer 2 may contain a conductive auxiliary agent in addition to the positive electrode active material and the binder resin. The conductive auxiliary agent is not particularly limited as long as the conductivity of the positive electrode is improved, and examples thereof include carbon black, ketjen black, acetylene black, natural graphite, artificial graphite, carbon fiber, and the like. These conductive assistants may be used alone or in combination of 1 or more than 2.
When the total amount of the positive electrode active material layer 2 is set to 100 parts by mass, the content of the conductive auxiliary agent in the positive electrode active material layer 2 is preferably more than 1.0 part by mass and less than 4.0 parts by mass, more preferably 1.2 parts by mass or more and 3.5 parts by mass or less, still more preferably 1.5 parts by mass or more and 3.5 parts by mass or less, and particularly preferably 2.0 parts by mass or more and 3.5 parts by mass or less. If the content of the conductive auxiliary agent is within the above range, the balance of the coatability of the positive electrode slurry, the adhesiveness of the binder resin, and the battery characteristics is more excellent.
In addition, if the content of the conductive additive is less than the upper limit value or equal to or less than the upper limit value, the proportion of the positive electrode active material increases, and the capacity per positive electrode mass increases, which is preferable. If the content of the conductive auxiliary agent is equal to or greater than the lower limit value, the conductivity of the positive electrode becomes better, and the battery characteristics of the lithium ion secondary battery are improved, which is preferable.
As the positive electrode current collector layer 3, aluminum, stainless steel, nickel, titanium, an alloy thereof, or the like can be used. Examples of the shape include foil, flat plate, and mesh. Aluminum foil is particularly preferably used.
The thickness of the positive electrode collector layer 3 is not particularly limited, and is, for example, 1 μm or more and 30 μm or less.
Here, the thinner the thickness of the positive electrode collector layer 3 is, the more easily the positive electrode collector layer 3 is deformed or broken, and therefore, the safety of the lithium ion secondary battery is easily deteriorated. However, the lithium ion secondary battery according to the present embodiment can suppress deterioration of battery safety even when the thickness of the positive electrode current collector layer 3 is thin. Therefore, from the viewpoint of improving the safety of the lithium ion secondary battery, reducing the proportion of the positive electrode current collector layer 3 in the lithium ion secondary battery, and further increasing the energy density of the lithium ion secondary battery, the thickness of the positive electrode current collector layer 3 is preferably less than 25 μm, more preferably less than 20 μm, and particularly preferably less than 18 μm.
Further, according to JIS L1913: the tensile elongation of the positive electrode current collector layer 3 measured at 2010.3 is preferably less than 10%, more preferably less than 8%. As a result, even if the separator 20 is broken due to sharp metal such as lithium dendrites, for example, the elongation of the positive electrode current collector layer 3 can be suppressed, and therefore, contact between the metal that pierces the separator 20 and the positive and negative electrodes can be suppressed. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and the safety can be further improved.
The density of the positive electrode active material layer 2 is not particularly limited, and is preferably 2.0g/cm, for example 3 4.0g/cm above 3 Hereinafter, it is more preferably 2.4g/cm 3 Above and 3.8g/cm 3 The following is more preferably 2.8g/cm 3 Above and 3.6g/cm 3 The following is given.
Here, the higher the density of the positive electrode active material layer 2, the more likely the battery characteristics such as cycle characteristics of the lithium ion secondary battery deteriorate. However, the lithium ion secondary battery according to the present embodiment can suppress degradation of battery characteristics such as cycle characteristics. Therefore, from the viewpoint of improving battery characteristics such as cycle characteristics and further improving the energy density of the obtained lithium ion secondary battery, the density of the positive electrode active material layer 2 is preferably 3.0g/cm 3 The above, more preferably 3.2g/cm 3 The above, particularly preferably 3.3g/cm 3 The above. Further, from the viewpoint of further suppressing deterioration of cycle characteristics at high temperature, the density of the positive electrode active material layer 2 is preferably 4.0g/cm 3 Hereinafter, it is more preferably 3.8g/cm 3 The following are more preferable3.6g/cm 3 The following is given.
The thickness of the positive electrode active material layer 2 (total thickness of both surfaces) is not particularly limited, and may be appropriately set according to desired characteristics. For example, the thickness may be set to be relatively thick from the viewpoint of energy density, and the thickness may be set to be relatively thin from the viewpoint of output characteristics. The thickness of the positive electrode active material layer 2 (total thickness of both surfaces) can be set appropriately in a range of, for example, 20 μm to 500 μm, preferably 40 μm to 400 μm, more preferably 60 μm to 300 μm.
The thickness (thickness of one surface) of the positive electrode active material layer 2 is not particularly limited, and may be appropriately set according to desired characteristics. For example, the thickness may be set to be relatively thick from the viewpoint of energy density, and the thickness may be set to be relatively thin from the viewpoint of output characteristics. The thickness (thickness of one surface) of the positive electrode active material layer 2 may be appropriately set in a range of, for example, 10 μm or more and 250 μm or less, preferably 20 μm or more and 200 μm or less, and more preferably 30 μm or more and 150 μm or less.
(negative electrode for lithium absorption and release)
The negative electrode 6 according to the present embodiment may be appropriately selected from known negative electrodes that can be used in lithium ion secondary batteries, depending on the application and the like. The negative electrode active material used for the negative electrode 6 can be appropriately set according to the application or the like as long as it can be used for the negative electrode.
The anode 6 has a structure including an anode current collector layer 8 and an anode active material layer 7 formed on the anode current collector layer 8. The negative electrode active material layer 7 contains a negative electrode active material and a binder resin, and preferably further contains a conductive auxiliary agent from the viewpoint of improving conductivity.
The negative electrode active material is not particularly limited as long as it is an active material for a negative electrode capable of absorbing and releasing lithium ions, and a carbonaceous material can be used. Examples of the carbonaceous material include graphite, amorphous carbon (e.g., graphitizable carbon and non-graphitizable carbon), diamond-like carbon, fullerene, carbon nanotube, and carbon nanohorn. As the graphite, natural graphite or artificial graphite can be used, and from the viewpoint of material cost, it is preferable to be inexpensive Natural graphite. Examples of the amorphous carbon include amorphous carbon obtained by heat-treating coal pitch coke, petroleum pitch coke, acetylene pitch coke, and the like. As other negative electrode active materials, lithium metal materials, alloy materials such as silicon and tin, nb, and the like can be used 2 O 5 Or TiO 2 An oxide material, or a composite thereof.
The negative electrode active material may be used alone or in combination of two or more.
The average particle diameter of the negative electrode active material is preferably 2 μm or more, more preferably 5 μm or more from the viewpoint of suppressing side reactions at the time of charge and discharge and suppressing a decrease in charge and discharge efficiency, and is preferably 40 μm or less, more preferably 30 μm or less from the viewpoint of input/output characteristics and the viewpoint of negative electrode production (smoothness of the negative electrode surface, etc.). The average particle diameter herein means a particle diameter (median diameter: D) at which the cumulative value in the particle size distribution (volume basis) based on the laser diffraction scattering method is 50% 50 )。
The negative electrode 6 in the present embodiment can be manufactured by a known method. For example, the following method or the like can be employed: after dispersing the negative electrode active material and the binder resin in a solvent to obtain a slurry, the slurry is applied to the negative electrode current collector layer 8 and dried, and pressurized as necessary to form the negative electrode active material layer 7.
Examples of the method for applying the negative electrode slurry include a doctor blade method, a die coating method, and a dip coating method. Additives such as an antifoaming agent and a surfactant may be added to the slurry as needed.
The content of the binder resin in the negative electrode active material layer 7 is preferably 0.1 part by mass or more and 10.0 parts by mass or less, more preferably 0.5 part by mass or more and 8.0 parts by mass or less, still more preferably 1.0 part by mass or more and 5.0 parts by mass or less, particularly preferably 1.0 part by mass or more and 3.0 parts by mass or less, based on 100 parts by mass of the entire negative electrode active material layer 7. When the content of the binder resin is within the above range, the balance of the coatability of the negative electrode slurry, the adhesion of the binder resin, and the battery characteristics is more excellent.
In addition, when the content of the binder resin is equal to or less than the upper limit value, the proportion of the negative electrode active material increases, and the capacity per unit negative electrode mass increases, which is preferable. When the content of the binder resin is not less than the above lower limit, electrode peeling is suppressed, which is preferable.
As the solvent, an organic solvent such as N-methyl-2-pyrrolidone (NMP) or water can be used. When an organic solvent is used as the solvent, a binder resin for an organic solvent such as polyvinylidene fluoride (PVDF) can be used. When water is used as the solvent, a rubber-based binder (for example, SBR (styrene butadiene rubber)), and an acrylic-based binder resin may be used. Such an aqueous binder resin may be in the form of an emulsion. When water is used as the solvent, it is preferable to use a water-based binder and a thickener such as CMC (carboxymethyl cellulose).
The anode active material layer 7 may contain a conductive auxiliary agent as needed. As the conductive auxiliary agent, a conductive material that is generally used as a conductive auxiliary agent for a negative electrode, such as a carbonaceous material including carbon black, ketjen black, and acetylene black, can be used.
The content of the conductive auxiliary in the anode active material layer 7 is preferably 0.1 part by mass or more and 3.0 parts by mass or less, more preferably 0.1 part by mass or more and 2.0 parts by mass or less, particularly preferably 0.2 parts by mass or more and 1.0 part by mass or less, based on 100 parts by mass of the entire anode active material layer 7. If the content of the conductive auxiliary agent is within the above range, the balance of the coatability of the negative electrode slurry, the adhesiveness of the binder resin, and the battery characteristics is more excellent.
In addition, when the content of the conductive additive is equal to or less than the upper limit value, the proportion of the negative electrode active material increases, and the capacity per unit negative electrode mass increases, which is preferable. If the content of the conductive additive is not less than the above lower limit, the conductivity of the negative electrode is more favorable, and thus it is preferable.
The average particle diameter (primary particle diameter) of the conductive auxiliary agent used for the positive electrode active material layer 2 and the negative electrode active material layer 7 is preferably in the range of 10 to 100 nm. The average particle diameter (primary particle diameter) of the conductive auxiliary agent is preferably 10nm or more, more preferably 30nm or more from the viewpoint of suppressing excessive aggregation of the conductive auxiliary agent and uniformly dispersing it in the negative electrode, and is preferably 100nm or less, more preferably 80nm or less from the viewpoint of enabling formation of a sufficient number of contact points and formation of a good conductive path. When the conductive auxiliary is fibrous, the average diameter is 2 to 200nm and the average fiber length is 0.1 to 20. Mu.m.
Here, the average particle diameter of the conductive auxiliary agent is the median particle diameter (D 50 ) The particle diameter is the particle diameter at which the cumulative value in the particle size distribution (volume basis) by the laser diffraction scattering method is 50%.
The thickness of the negative electrode active material layer 7 (total thickness of both surfaces) is not particularly limited, and may be appropriately set according to desired characteristics. For example, the thickness may be set to be relatively thick from the viewpoint of energy density, and the thickness may be set to be relatively thin from the viewpoint of output characteristics. The thickness of the negative electrode active material layer 7 (total thickness of both surfaces) may be set appropriately in a range of, for example, 40 μm or more and 1000 μm or less, preferably 80 μm or more and 800 μm or less, and more preferably 120 μm or more and 600 μm or less.
The thickness (thickness of one surface) of the negative electrode active material layer 7 is not particularly limited, and may be appropriately set according to desired characteristics. For example, the thickness may be set to be relatively thick from the viewpoint of energy density, and the thickness may be set to be relatively thin from the viewpoint of output characteristics. The thickness (thickness of one surface) of the negative electrode active material layer 7 may be set appropriately in a range of, for example, 20 μm or more and 500 μm or less, preferably 40 μm or more and 400 μm or less, and more preferably 60 μm or more and 300 μm or less.
The density of the negative electrode active material layer 7 is not particularly limited, and is preferably 1.2g/cm, for example 3 Above and 2.0g/cm 3 Hereinafter, more preferably 1.3g/cm 3 Above and 1.9g/cm 3 The following is more preferably 1.4g/cm 3 Above and 1.8g/cm 3 The following is given.
As the negative electrode current collector layer 8, copper, stainless steel, nickel, titanium, or an alloy thereof can be used. Examples of the shape include foil, flat plate, and mesh.
The thickness of the negative electrode current collector layer 8 is not particularly limited, and is, for example, 1 μm or more and 20 μm or less.
Here, the thinner the thickness of the anode current collector layer 8 is, the more easily the anode current collector layer 8 is deformed or broken, and therefore, the safety of the lithium ion secondary battery is easily deteriorated. However, the lithium ion secondary battery according to the present embodiment can suppress deterioration of battery safety even when the negative electrode current collector layer 8 is thin. Therefore, from the viewpoint of improving the safety of the lithium ion secondary battery, reducing the proportion of the negative electrode current collector layer 8 in the lithium ion secondary battery, and further increasing the energy density of the lithium ion secondary battery, the thickness of the negative electrode current collector layer 8 is preferably less than 15 μm, more preferably less than 12 μm, and particularly preferably less than 10 μm.
Further, according to JIS L1913: the tensile elongation of the anode current collector layer 8 measured at 2010.3 is preferably less than 10%, more preferably less than 5%. As a result, even if the separator 20 is broken due to sharp metal such as lithium dendrites, the elongation of the negative electrode current collector layer 8 can be suppressed, and therefore, contact between the metal that pierces the separator 20 and the positive and negative electrodes can be suppressed. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and the safety can be further improved.
(lithium salt-containing nonaqueous electrolyte)
The nonaqueous electrolyte solution containing a lithium salt used in the present embodiment may be appropriately selected from known materials depending on the type of electrode active material, the use of the lithium ion secondary battery, and the like.
Specific examples of the lithium salt include LiClO 4 、LiBF 6 、LiPF 6 、LiCF 3 SO 3 、LiCF 3 CO 2 、LiAsF 6 、LiSbF 6 、LiB 10 Cl 10 、LiAlCl 4 、LiCl、LiBr、LiB(C 2 H 5 ) 4 、CF 3 SO 3 Li、CH 3 SO 3 Li、LiC 4 F 9 SO 3 、Li(CF 3 SO 2 ) 2 N, lithium lower fatty acid carboxylate, and the like.
The solvent for dissolving the lithium salt is not particularly limited as long as it is a solvent generally used as a liquid for dissolving the electrolyte, and examples thereof include carbonates such as Ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), dimethyl carbonate (DMC), ethylene Methyl Carbonate (EMC), diethyl carbonate (DEC), ethylmethyl carbonate (MEC), and Vinylene Carbonate (VC); lactones such as gamma-butyrolactone and gamma-valerolactone; ethers such as trimethoxy methane, 1, 2-dimethoxyethane, diethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxapentanes such as 1, 3-dioxolane and 4-methyl-1, 3-dioxolane; nitrogen-containing solvents such as acetonitrile, nitromethane, formamide, dimethylformamide, and the like; organic acid esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and ethyl propionate; triesters of phosphoric acid, diethylene glycol dimethyl ether; triethylene glycol dimethyl ether; sulfolanes such as sulfolane and methyl sulfolane; oxazolidinones such as 3-methyl-2-oxazolidinone; sultones such as 1, 3-propane sultone, 1, 4-butane sultone, and naphthalene sultone. One kind of them may be used alone, or two or more kinds may be used in combination.
(Container)
In the present embodiment, a known member can be used for the container, and the flexible film 30 is preferably used from the viewpoint of weight reduction of the battery. The flexible film 30 may be a film having a resin layer provided on the front and rear surfaces of a metal layer serving as a base material. The metal layer may be selected from those having a barrier property against leakage of electrolyte and invasion of moisture from the outside, and aluminum, stainless steel, or the like may be used. The exterior body is formed by providing a heat-fusible resin layer such as a modified polyolefin on at least one surface of the metal layer, disposing the heat-fusible resin layers of the flexible film 30 so as to face each other with the battery element interposed therebetween, and heat-welding the periphery of the portion accommodating the battery element. A resin layer such as a nylon film or a polyester film may be provided on the surface of the exterior body which is the surface opposite to the surface on which the heat-fusible resin layer is formed.
(terminal)
In the present embodiment, a terminal made of aluminum or an aluminum alloy may be used as the positive electrode terminal 11, and copper or a copper alloy, a terminal obtained by plating nickel on these, or the like may be used as the negative electrode terminal 16. The terminals are led out of the container, and a heat-fusible resin may be provided in advance at a portion of each terminal located at a portion where the periphery of the exterior body is heat-fused.
(insulating part)
When the insulating member is formed by the boundary portions 4 and 9 between the coated portion and the uncoated portion of the active material, polyimide, glass fiber, polyester, polypropylene, or a material containing these components may be used. These members can be welded to the boundary portions 4 and 9 by applying heat thereto, or the boundary portions 4 and 9 can be coated with a gel-like resin and dried, whereby an insulating member can be formed.
(spacer)
The spacer 20 according to the present embodiment preferably includes a resin layer containing a heat-resistant resin as a main component.
Here, the resin layer is formed of a heat-resistant resin as a main component. Here, "main component" means that the proportion in the resin layer is 50 mass% or more, and means that: the content is preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass.
The resin layer constituting the spacer 20 according to the present embodiment may be a single layer or two or more layers.
Examples of the heat-resistant resin forming the resin layer include one or more selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, polycarbonate, polyester carbonate, aliphatic polyamide, wholly aromatic polyester, polyphenylene sulfide, poly-p-phenylene benzobisoxazole, polyimide, polyarylate, polyetherimide, polyamideimide, polyacetal, polyether ether ketone, polysulfone, polyether sulfone, fluorine-based resin, polyether nitrile, modified polyphenylene ether, and the like.
Among these, from the viewpoint of excellent balance of heat resistance, mechanical strength, stretchability, price, and the like, one or two or more selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, aliphatic polyamide, wholly aromatic polyamide, semiaromatic polyamide, and wholly aromatic polyester are preferable, one or two or more selected from polyethylene terephthalate, polybutylene terephthalate, aliphatic polyamide, wholly aromatic polyamide, and semiaromatic polyamide are more preferable, and one or two or more selected from polyethylene terephthalate and wholly aromatic polyamide are more preferable.
The melting point of the separator 20 according to the present embodiment is preferably 220 ℃ or higher, more preferably 230 ℃ or higher, and still more preferably 240 ℃ or higher, from the viewpoint of improving the safety of the lithium ion secondary battery. Alternatively, from the viewpoint of improving the safety of the lithium ion secondary battery, the separator 20 according to the present embodiment preferably does not exhibit a melting point, and the decomposition temperature is preferably 220 ℃ or higher, more preferably 230 ℃ or higher, still more preferably 240 ℃ or higher, and particularly preferably 250 ℃ or higher.
By setting the melting point or the decomposition temperature of the separator 20 described in this embodiment to the above lower limit value or more, even if the battery heats up to a high temperature, thermal shrinkage of the separator 20 can be suppressed, and as a result, the contact area between the positive electrode and the negative electrode can be suppressed. This can suppress thermal runaway and the like of the lithium ion secondary battery, and can further improve safety.
The upper limit of the melting point of the spacer 20 according to the present embodiment is not particularly limited, and is, for example, 500 ℃ or less, and preferably 400 ℃ or less from the viewpoint of stretchability. Alternatively, the upper limit of the decomposition temperature of the spacer according to the present embodiment is not particularly limited, and is, for example, 500 ℃ or less, and preferably 400 ℃ or less from the viewpoint of stretchability.
According to JIS L1913: the average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the separator described in this embodiment, which are measured at 2010.3, is preferably greater than the tensile elongation of the positive electrode current collector layer 3 and the negative electrode current collector layer 8, respectively. As a result, even if the separator 20 is broken by sharp metal such as lithium dendrites, the separator 20 stretches more than the positive and negative electrode current collectors, and therefore, the positive and negative electrodes are easily covered with the separator 20. Therefore, contact between the metal of the puncture spacer 20 and the positive and negative electrodes can be suppressed by the elongated spacer 20. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and the safety can be further improved.
Further, according to JIS L1913: the average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the spacer 20 measured at 2010.3 is preferably 10% or more, more preferably 12% or more, and particularly preferably 13% or more. If the average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the separator 20 is equal to or greater than the lower limit value, the separator 20 stretches and effectively covers the positive and negative electrodes even if the separator 20 is broken by sharp metal such as lithium dendrites, and therefore contact between the metal of the puncture separator 20 and the positive and negative electrodes can be suppressed. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and the safety can be further improved.
According to JIS L1913: the upper limit value of the average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the spacer 20 measured at 6.3 of 2010 is not particularly limited, but is preferably 100% or less, more preferably 70% or less, and further preferably 50% or less from the viewpoint of heat resistance of the spacer 20.
Further, according to JIS L1913: the tensile elongation in the MD direction of the spacer 20 measured at 2010.3 is preferably 10% or more, more preferably 12% or more.
According to JIS L1913: the upper limit value of the tensile elongation in the MD direction of the spacer 20 measured at 2010.3 is not particularly limited, but is preferably 100% or less, more preferably 70% or less, and further preferably 50% or less.
The resin layer constituting the spacer 20 according to the present embodiment is preferably a porous resin layer. In this way, when an abnormal current or a battery temperature rise occurs in the lithium ion secondary battery, the micropores of the porous resin layer are blocked, and the flow of current can be blocked, so that thermal runaway of the battery can be avoided.
The porosity of the porous resin layer is preferably 20% or more and 80% or less, more preferably 30% or more and 70% or less, and particularly preferably 40% or more and 60% or less, from the viewpoint of balance between mechanical strength and lithium ion conductivity.
The porosity can be determined by the following formula.
ε＝{1-Ws/(ds·t)}×100
Here, ε: porosity (%), ws: weight per unit area (g/m) 2 ) And ds: true density (g/cm) 3 ) And t: film thickness (μm).
The planar shape of the separator 20 according to the present embodiment is not particularly limited, and may be appropriately selected according to the shape of the electrode or the current collector, and may be rectangular, for example.
The thickness of the spacer 20 according to the present embodiment is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 40 μm or less, and still more preferably 10 μm or more and 30 μm or less, from the viewpoint of balance between mechanical strength and lithium ion conductivity.
From the viewpoint of further improving heat resistance, the spacer 20 according to the present embodiment preferably further includes a ceramic layer on at least one surface of the resin layer. Here, the ceramic layer is preferably provided on only one side of the resin layer from the viewpoint of handling properties, productivity, and the like of the spacer 20 described in the present embodiment, and may be provided on both sides of the resin layer from the viewpoint of further improving the heat resistance of the spacer 20.
The spacer 20 according to the present embodiment can further reduce thermal shrinkage of the spacer 20 by further providing the ceramic layer, and can further prevent short-circuiting between electrodes.
The ceramic layer may be formed by, for example, coating a ceramic layer forming material on the resin layer and drying the material. As the ceramic layer forming material, for example, a material obtained by dissolving or dispersing an inorganic filler and a binder resin in an appropriate solvent can be used.
The inorganic filler used in the ceramic layer may be appropriately selected from known materials used for a separator of a lithium ion secondary battery. For example, it is preferably an oxide, nitride, sulfide, carbide, or the like having high insulation properties, and more preferably a material in which one or more ceramics selected from the group consisting of alumina, boehmite, titania, silica, magnesia, barium oxide, zirconia, zinc oxide, iron oxide, and the like are adjusted to be in a particulate form. Among these, alumina, boehmite and titania are preferable.
The binder resin is not particularly limited, and examples thereof include cellulose resins such as carboxymethyl cellulose (CMC); an acrylic resin; and fluororesins such as polyvinylidene fluoride (PVDF). The binder resin may be used alone or in combination of two or more.
The solvent for dissolving or dispersing these components is not particularly limited, and may be appropriately selected from, for example, alcohols such as water and ethanol, N-methylpyrrolidone (NMP), toluene, dimethyl carbonate (DMC), and Ethyl Methyl Carbonate (EMC), and the like.
From the viewpoint of balance of heat resistance, mechanical strength, handleability and lithium ion conductivity, the thickness of the ceramic layer is preferably 0.1 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less, and still more preferably 1 μm or more and 15 μm or less.
The present invention has been described above based on the embodiments, but these are examples of the present invention, and various configurations other than the above may be adopted.
The present invention is not limited to the above-described embodiments, and includes modifications, improvements, and the like within a range that can achieve the object of the present invention.
Examples
The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.
Example 1
< preparation of Positive electrode >
As the positive electrode active material, a lithium-nickel-containing composite oxide (chemical formula: liNi 0.8 Co 0.15 Al 0.05 O 2 Average particle diameter: 6 μm) 94.0 parts by mass, 3.0 parts by mass of carbon black was used as a conductive auxiliary agent, and 3.0 parts by mass of polyvinylidene fluoride (PVDF) was used as a binder resin. They were dispersed in an organic solvent to prepare a positive electrode slurry. The positive electrode slurry was continuously applied to an aluminum foil having a thickness of 15 μm as a positive electrode current collector(tensile elongation: 6%) and then dried, followed by pressurization, whereby a coated portion having a positive electrode collector (positive electrode active material layer: thickness of 60 μm, density: 3.35g/cm on one side) was produced 3 ) And a positive electrode roll of an uncoated portion that is not coated.
The positive electrode roll was punched to leave an uncoated portion serving as a tab for connection to a positive electrode terminal, and a positive electrode was produced.
< preparation of negative electrode >
96.7 parts by mass of natural graphite (average particle diameter: 16 μm) was used as the negative electrode active material, 0.3 parts by mass of carbon black was used as the conductive auxiliary agent, 2.0 parts by mass of styrene-butadiene rubber was used as the binder resin, and 1.0 part by mass of carboxymethyl cellulose was used as the thickener. They were dispersed in water to prepare a negative electrode slurry. The negative electrode slurry was continuously applied to a copper foil (tensile elongation: 4%) having a thickness of 8 μm as a negative electrode current collector, dried, and then pressurized, thereby producing a coated portion (negative electrode active material layer: thickness of 90 μm on one side, density: 1.55 g/cm) having a negative electrode current collector 3 ) And a negative electrode roll of an uncoated portion that is not coated.
The negative electrode roll was punched to leave an uncoated portion serving as a tab for connection to a negative electrode terminal, and a negative electrode was produced.
< production of laminated Battery >
The positive electrode and the negative electrode are laminated in a repeatedly folded structure with a separator interposed therebetween, and a negative electrode terminal and a positive electrode terminal are provided thereon, thereby obtaining a laminate. Next, 1M LiPF was dissolved in a solvent containing ethylene carbonate, diethyl carbonate, and ethylene methyl carbonate 6 And the resulting electrolyte and the resulting laminate are contained in a flexible film, thereby obtaining a laminated battery. The rated capacity of the laminated battery was set to 9.2Ah, the positive electrode was set to 28 layers, and the negative electrode was set to 29 layers.
As the spacer, a spacer 1 (thickness: 25 μm, porosity: 56%) having a porous resin layer containing polyethylene terephthalate (PET) and a ceramic layer containing boehmite particles was used. Here, the physical properties of the spacer 1 are as follows.
Tensile elongation in MD: 20 percent of
Tensile elongation in TD: 19%
Average value of tensile elongation in MD direction and tensile elongation in TD direction: 19.5%
Melting point: 250 DEG C
< evaluation >
(1) Tensile elongation of separator and current collector
According to JIS L1913: 2010.3, was measured.
(2) Porosity of porous resin layer
The expression is as follows.
ε＝{1-Ws/(ds·t)}×100
Here, ε: porosity (%), ws: weight per unit area (g/m) 2 ) And ds: true density (g/cm) 3 ) And t: film thickness (μm).
(3) DC resistance between positive electrode and negative electrode after nailing test
The obtained laminated battery was charged at a constant current and constant voltage (CC-CV) at 25 ℃ with a constant current of 1C until a voltage of 4.2V was reached, and then charged at a constant voltage of 4.2V until a charge termination current of 0.015C was reached.
Next, a nail (manufactured by white water manufacturing) made of SUS304 having a diameter of 3mm and a length of 70mm was punched in the vertical direction against the electrode surface at a speed of 80mm/sec at the center of the laminated battery in a fully charged state at 25 ℃.
Then, after the nail penetration test, the laminate battery was short-circuited, and a resistance measuring instrument (product name: digital Multimeter 7544-01) made of Yokogawa Meters & Instruments Corporation was used for the laminate battery having a voltage in the range of 0.001V to 0.100V, and the positive electrode terminal and the negative electrode terminal were brought into contact with the tester at 25℃and the direct current resistance between the positive electrode and the negative electrode was measured at room temperature (25 ℃).
(4) Cycle test
The cycle characteristics of the obtained laminated battery were evaluated. At a temperature of 25 ℃, constant current charging was performed at a constant current of 0.5C until a voltage of 4.2V, and then constant voltage charging was performed at a constant voltage of 4.2V until a charging termination current of 0.015C. Then, CC discharge was performed under conditions of a discharge rate of 3.0C and a discharge termination voltage of 2.5V. The charge and discharge were performed for 300 cycles. The capacity maintenance ratio (%) is a value obtained by dividing the discharge capacity (mAh) after 300 cycles by the discharge capacity (mAh) at the 10 th cycle. The capacity retention (%) was marked as o when 80% or more and as x when less than 80%.
(5) Safety test
In the center of the laminate battery in the fully charged state, a nail made of SUS304 (manufactured by white water manufacturing) having a diameter of 3mm and a length of 70mm was punched in the vertical direction against the electrode surface at a speed of 80mm/sec at 25 ℃. Next, the state of the battery was observed after 6 hours passed, and the battery safety was evaluated according to the following criteria.
O: the lithium ion battery has no smoke and fire
X: at least one of smoking and igniting the lithium ion battery
The evaluation results are shown in table 1. In example 1, the voltage of the laminated battery at the time of measuring the direct current resistance between the positive electrode and the negative electrode was 0.0582V.
Example 2
A laminate type laminate battery was produced in the same manner as in example 1, except that a separator 2 including a porous resin layer (thickness: 15 μm, porosity: 65%) made of wholly aromatic polyamide (also referred to as aramid) was used as a separator. Here, the physical properties of the spacer 2 are as follows.
Tensile elongation in MD: 40 percent of
Tensile elongation in TD: 35%
Average value of tensile elongation in MD direction and tensile elongation in TD direction: 37.5%
Thermal decomposition temperature: 400 DEG C
In example 2, the voltage of the laminated battery at the time of measuring the direct current resistance between the positive electrode and the negative electrode was 0.0011V.
Example 3
Except that the mixing ratio of the positive electrode was changed to the positive electrode active material: 95.0 parts by mass of a conductive additive: 2.0 parts by mass of a binder resin: a laminated battery was produced in the same manner as in example 2 except for 3.0 parts by mass, and each evaluation was performed. In example 3, the voltage of the laminated battery at the time of measuring the direct current resistance between the positive electrode and the negative electrode was 0.0582V.
Comparative example 1
Except that the mixing ratio of the positive electrode was changed to the positive electrode active material: 93.0 parts by mass of a conductive additive: 4.0 parts by mass of a binder resin: a laminated battery was produced in the same manner as in example 1 except for 3.0 parts by mass, and each evaluation was performed.
Comparative example 2
A laminate type laminated battery was produced in the same manner as in example 1, except that a separator 3 (thickness: 25 μm, porosity: 54%) including a porous resin layer made of polypropylene and a ceramic layer (alumina) was used as a separator, and each evaluation was performed. Here, the physical properties of the spacer 3 are as follows.
Tensile elongation in MD: 125%
Tensile elongation in TD: 630%
Average value of tensile elongation in MD direction and tensile elongation in TD direction: 377.5%
Melting point: 160 DEG C
Comparative example 3
A laminate type laminated battery was produced in the same manner as in example 1, except that a separator 4 including a porous resin layer (thickness: 25 μm, porosity: 55%) containing polypropylene was used as a separator, and each evaluation was performed. Here, the physical properties of the spacer 4 are as follows.
Tensile elongation in MD: 50 percent of
Tensile elongation in TD: 400 percent of
Average value of tensile elongation in MD direction and tensile elongation in TD direction: 225%
Melting point: 160 DEG C
Comparative example 4
A laminate type laminated battery was produced in the same manner as in example 1, except that a separator 5 having a porous resin layer (thickness: 18 μm, porosity: 54%) including polypropylene and a ceramic layer (thickness: 7 μm) including alumina was used as a separator. Here, the physical properties of the spacer 5 are as follows.
Tensile elongation in MD: 50 percent of
Tensile elongation in TD: 400 percent of
Average value of tensile elongation in MD direction and tensile elongation in TD direction: 225%
Melting point: 160 DEG C
Comparative example 5
A laminate type laminated battery was produced in the same manner as in example 1, except that a separator 6 having a nonwoven fabric layer containing glass fibers and a layer containing ceramics (magnesium oxide) (thickness: 30 μm, porosity: 76%) was used as a separator, and each evaluation was performed. Here, the physical properties of the spacer 6 are as follows.
Tensile elongation in MD: 8.9%
Tensile elongation in TD: 14.3%
Average value of tensile elongation in MD direction and tensile elongation in TD direction: 11.6%
Comparative example 6
Except that the mixing ratio of the positive electrode was changed to the positive electrode active material: 96.0 parts by mass of a conductive additive: 1.0 parts by mass of a binder resin: a laminated battery was produced in the same manner as in example 1 except for 3.0 parts by mass, and each evaluation was performed.
TABLE 1
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Claims (10)
1. A lithium ion secondary battery, which is accommodated in a container: a positive electrode having a positive electrode collector layer and a positive electrode active material layer, a negative electrode having a negative electrode collector layer and a negative electrode active material layer, a nonaqueous electrolyte containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode,
in a fully charged state at 25 ℃, a nail made of SUS304 having a diameter of 3mm and a length of 70mm was used to pierce the center portion of the lithium ion secondary battery at a rate of 80mm/sec, and a nail penetration test for shorting the lithium ion secondary battery was performed,
after the nail penetration test, short-circuit discharge is generated in the lithium ion secondary battery, and when the voltage reaches a range of 0.001V or more and 0.100V or less, the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery is 0.1 omega or more and 300 omega or less,
the positive electrode active material layer contains a conductive auxiliary agent, and the content of the conductive auxiliary agent exceeds 1.0 mass parts and is less than 4.0 mass parts when the total mass of the positive electrode active material layer is set to 100 mass parts,
the melting point or decomposition temperature of the spacer is 220 ℃ or higher,
the average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the separator measured in accordance with JIS L1913:2010 is larger than the tensile elongation of the positive electrode current collector layer and the negative electrode current collector layer, respectively,
The average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the spacer measured according to 6.3 of JIS L1913:2010 is 10% or more.
2. The lithium ion secondary battery according to claim 1, wherein the positive electrode active material layer contains a positive electrode active material, a binder resin, and the conductive auxiliary agent.
3. The lithium ion secondary battery according to claim 1 or 2, wherein the conductive auxiliary agent comprises one or two or more selected from carbon black, natural graphite, artificial graphite, and carbon fiber.
4. The lithium ion secondary battery according to claim 1 or 2, wherein the positive electrode active material comprises a composite oxide containing lithium nickel.
5. The lithium ion secondary battery according to claim 4, wherein the lithium-nickel containing composite oxide is represented by the following formula (1),
Li 1+a (Ni b Co c Me1 d Me2 1-b-c-d )O 2 (1)
in the formula (1), me1 is Mn or Al, me2 is at least 1 selected from Mn, al, mg, fe, cr, ti, in, but does not comprise metals of the same species as Me1, -0.5.ltoreq.a <0.1, 0.1.ltoreq.b <1, 0< c <0.5, 0< d <0.5.
6. The lithium ion secondary battery according to claim 1 or 2, wherein the density of the positive electrode active material layer is 3.0g/cm 3 The above.
7. The lithium ion secondary battery according to claim 1 or 2, wherein a cell rated capacity of the lithium ion secondary battery is 5Ah or more.
8. The lithium ion secondary battery according to claim 1 or 2, wherein the number of layers or windings of the positive electrode in the central portion of the lithium ion secondary battery is 10 or more.
9. The lithium ion secondary battery according to claim 1 or 2, wherein the thickness of the spacer is 5 μm or more and 50 μm or less.
10. The lithium ion secondary battery according to claim 3, wherein the carbon black contains one or two or more selected from ketjen black and acetylene black.
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