CN111164817A - Lithium ion secondary battery - Google Patents
Lithium ion secondary battery Download PDFInfo
- Publication number
- CN111164817A CN111164817A CN201780095520.7A CN201780095520A CN111164817A CN 111164817 A CN111164817 A CN 111164817A CN 201780095520 A CN201780095520 A CN 201780095520A CN 111164817 A CN111164817 A CN 111164817A
- Authority
- CN
- China
- Prior art keywords
- ion secondary
- secondary battery
- lithium ion
- positive electrode
- 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.)
- Granted
Links
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 113
- 239000007774 positive electrode material Substances 0.000 claims abstract description 50
- 239000007773 negative electrode material Substances 0.000 claims abstract description 39
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 8
- 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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- 239000011230 binding agent Substances 0.000 claims description 31
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Images
Classifications
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- 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
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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
- H01M10/052—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
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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
- H01M4/13—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
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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
- H01M4/36—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
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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
- H01M4/36—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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- 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
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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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- 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
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Abstract
The lithium ion secondary battery of the present invention contains in a container: the battery includes 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 electrolytic solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode. When a center portion of the lithium ion secondary battery is pierced with a nail made of SUS304 having a diameter of 3mm and a length of 70mm at a speed of 80mm/sec in a fully charged state in an environment of 25 ℃ to perform a nail piercing test for short-circuiting the lithium ion secondary battery, the lithium ion secondary battery is short-circuited and, after the nail piercing test, the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery when the voltage is in a range of 0.001V to 0.100V is 0.1 Ω to 300 Ω.
Description
Technical Field
The present invention relates to a lithium ion secondary battery.
Background
Lithium ion secondary batteries are characterized by high energy density and are widely used as power sources for mobile phones, notebook-size personal computers, electric vehicles, and the like.
Lithium ion secondary batteries use a flammable organic solvent as a main solvent for an electrolyte solution, and therefore require safety against ignition and explosion.
As a technique relating to the safety of such a lithium ion secondary battery, for example, a technique described in patent document 1 (japanese patent application laid-open No. 2013-251281) is cited.
Patent document 1 (japanese patent application laid-open No. 2013-251281) describes a lithium secondary battery including an electrode body including a positive electrode having a positive electrode active material layer containing a positive electrode active material on a surface of a positive electrode collector, a negative electrode having a negative electrode active material layer containing a negative electrode active material on a surface of a negative electrode 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 a ratio of a surface area of the battery case to an energy capacity when the battery is fully charged is 4.5cm2Wh or more, and the positive electrode has a resistivity of 10 Ω · cm or more and 450 Ω · cm or less.
Documents of the prior art
Patent document
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 energy density of lithium ion secondary batteries, further improvement in safety of lithium ion secondary batteries has been demanded.
Here, it is clear from the study of the present inventors that: when a high-capacity type positive electrode active material such as a lithium nickel-containing composite oxide is used to increase the energy density of a lithium ion secondary battery, or when the thickness of the collector layer of the positive electrode or 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 reduced, and the safety of the battery may be deteriorated.
Further, it was clarified from the study of the present inventors that: when the resistance of the electrode is increased in order to improve the safety of the battery, the battery characteristics such as the cycle characteristics may be deteriorated.
Namely, the present inventors found that: conventional lithium ion secondary batteries have a trade-off 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 made extensive studies to achieve the above object. The results are clear: by setting the dc resistance between the positive and negative electrodes of the lithium ion secondary battery after the nail penetration test performed under the predetermined conditions to a predetermined range, the trade-off relationship between the battery characteristics such as the cycle characteristics and the battery safety can be improved, and a lithium ion secondary battery having both the battery characteristics such as the cycle characteristics and the battery safety excellent in characteristics can be obtained.
Namely, the following are found: the present invention has been achieved because the dimension of the direct current resistance between the positive and negative electrodes of a lithium ion secondary battery after a nail penetration test performed under predetermined conditions is effective as a design indicator for a lithium ion secondary battery having an excellent balance between battery characteristics such as cycle characteristics and battery safety.
The present invention has been made based on this finding.
That is, according to the present invention, the following lithium ion secondary battery is provided.
According to the present invention, there is provided a lithium ion secondary battery comprising a container containing: 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 electrolytic solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode,
when a nail penetration test for short-circuiting the lithium ion secondary battery was performed by piercing the center of the lithium ion secondary battery with a nail made of SUS304 having a diameter of 3mm and a length of 70mm at a speed of 80mm/sec in a fully charged state in an environment of 25 ℃,
after the nail penetration test, the lithium ion secondary battery is short-discharged, and the DC resistance between the positive electrode and the negative electrode of the lithium ion secondary battery is 0.1 Ω to 300 Ω when the voltage is in the range of 0.001V to 0.100V.
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 and other objects, features and advantages will be further apparent from the following description of the preferred embodiments and the accompanying drawings.
Fig. 1 is a schematic diagram showing an example of the laminated battery according to the present embodiment.
Fig. 2 is a schematic diagram showing an example of the wound battery in 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 description thereof is omitted. In the drawings, the respective constituent elements schematically show shapes, sizes, and arrangement relationships to the extent that the present invention can be understood, and are different from actual sizes. In the present embodiment, "a to B" in the numerical range means a to B unless otherwise specified.
< lithium ion Secondary Battery >
The lithium-ion secondary battery according to the present embodiment includes: the battery includes 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 electrolytic solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode. When a center portion of the lithium ion secondary battery is pierced with a nail made of SUS304 having a diameter of 3mm and a length of 70mm at a speed of 80mm/sec in a fully charged state in an environment of 25 ℃ to perform a nail piercing test for short-circuiting the lithium ion secondary battery, the lithium ion secondary battery is short-circuited and, after the nail piercing test, the direct current resistance between the positive electrode and the negative electrode of the lithium ion secondary battery when the voltage is in a range of 0.001V to 0.100V is 0.1 Ω to 300 Ω.
According to the study of the present inventors, it is clear that: when a high-capacity type positive electrode active material such as a lithium nickel-containing composite oxide is used to increase the energy density of a lithium ion secondary battery, or when the thickness of the collector layer of the positive electrode or 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 reduced, and the safety of the battery may be deteriorated.
Further, it was clarified from the study of the present inventors that: when the resistance of the electrode is increased in order to improve the safety of the battery, the battery characteristics such as the cycle characteristics may be deteriorated.
Namely, the present inventors found that: conventional lithium ion secondary batteries have a trade-off relationship between battery characteristics such as cycle characteristics and battery safety.
Accordingly, the present inventors have made extensive studies to achieve the above object. The results are clear: by setting the dc resistance between the positive and negative electrodes of the lithium ion secondary battery after the nail penetration test performed under the above conditions to the above range, the trade-off relationship between battery characteristics such as cycle characteristics and battery safety can be improved, and a lithium ion secondary battery having both good characteristics of battery characteristics such as cycle characteristics and battery safety can be obtained.
Namely, it was found first: the measure of the dc resistance between the positive and negative electrodes of a lithium ion secondary battery after a nail penetration test performed under predetermined conditions is effective as a design guideline for a lithium ion secondary battery that is excellent in the 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 direct current 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, further preferably 10 Ω or more, further preferably 40 Ω or more, further 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 direct current 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, further preferably 150 Ω or less, and particularly preferably 130 Ω or less.
In the lithium ion secondary battery according to the present embodiment, by setting the dc resistance between the positive electrode and the negative electrode after the nail penetration test to the upper limit value or less, 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 at a constant current of 1C at 25 ℃ to a voltage of 4.2V by a constant current-constant voltage (CC-CV) method, and then charged at a constant voltage of 4.2V to a charge termination current of 0.015C.
The dc resistance between the positive and negative electrodes after the nail penetration test in the lithium ion secondary battery according to the present embodiment can be achieved by appropriately selecting (a) the mixing ratio of the positive electrode active material layer or the negative electrode active material layer, (B) the type of the separator, (C) the type of the collector layer, and the like.
Among these, as an element for setting the dc resistance between the positive electrode and the negative electrode of the lithium ion secondary battery after the nail penetration test to a desired numerical range, for example, a predetermined range is set for the amount of the conductive aid in the positive electrode active material layer, a separator having high heat resistance and high elongation is used, a separator having a tensile elongation larger than that of the positive electrode current collector layer or the negative electrode current collector layer is used, and the like are cited.
The reason why the lithium ion secondary battery according to the present embodiment is excellent in battery safety is not clearly understood, and it is considered that this is because: in such a lithium ion secondary battery, for example, even if a foreign substance enters the battery and a short circuit occurs, the resistance of the battery can be maintained in a high range, and therefore, the flow of a large current can be suppressed, and as a result, thermal runaway of the battery can be suppressed.
The battery cell rated capacity of the lithium-ion secondary battery according to the present embodiment is preferably 5Ah or more, and more preferably 7Ah or more.
In addition, the number of stacked layers or the number of 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 makes it possible to increase the capacity of the lithium-ion secondary battery according to the present embodiment. 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 of the present embodiment are not particularly limited, and the following configurations may be adopted, 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 multiple layers with separators 20 interposed therebetween, and these battery elements are accommodated in a container including a flexible film 30 together with an electrolyte (not shown). The following constitution 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 are drawn out to the outside 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 collector layer 3, 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 collector layer 8.
The uncoated portion of the positive electrode active material in the positive electrode collector layer 3 was formed as 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 was formed as a negative electrode tab 5 for connection to the negative electrode terminal 16.
The positive electrode tabs 10 are joined to each other at the positive electrode terminal 11 and are connected to each other together with the positive electrode terminal 11 by ultrasonic welding or the like, and the negative electrode tabs 5 are joined to each other at the negative electrode terminal 16 and are connected to each other together with the negative electrode terminal 16 by ultrasonic welding or the like. One end of the positive electrode terminal 11 is drawn out of the flexible film 30, and one end of the negative electrode terminal 16 is also drawn out of the flexible film 30.
An insulating member may be formed, as necessary, at the boundary 4 between the coated portion (positive electrode active material layer 2) and the uncoated portion of the positive electrode active material, not only at the boundary 4, but also in the vicinity of the boundary between the positive electrode tab 10 and the positive electrode active material.
Similarly, an insulating member may be formed as necessary at the boundary 9 between the coated portion (negative electrode active material layer 7) and the uncoated portion of the negative electrode active material, 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 outer dimension of the anode active material layer 7 is larger than the outer dimension of the cathode active material layer 2 and smaller than the outer dimension of the separator 20.
[ winding type Battery ]
Fig. 2 schematically shows the structure of the wound battery, and the container and the like are not shown. The wound battery 101 includes a battery element in which a positive electrode 1 and a negative electrode 6 are stacked and wound with a separator 20 interposed therebetween, and the battery element is accommodated in a container including a flexible film together with an electrolyte (not shown).
The above description of the wound battery 101 is omitted because the battery elements are also electrically connected to the positive electrode terminal, the negative electrode terminal, and the like, and other configurations are basically the same as those of the laminated battery 100.
Next, each configuration used in the lithium-ion secondary battery of the present embodiment will be described.
(Anode for absorbing and releasing lithium)
The positive electrode 1 used in the present embodiment can be appropriately selected from known positive electrodes that can be used in lithium ion secondary batteries, depending on the application and the like. The active material used for the positive electrode 1 is preferably a material having high electron conductivity so that lithium ions can be reversibly released and stored and electron transport can be easily performed.
The positive electrode active material used for 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. As the lithium composite oxide, lithium manganate (LiMn) may be mentioned2O4) (ii) a Lithium cobaltate (LiCoO)2) (ii) a Lithium nickelate (LiNiO)2) (ii) a Those in which at least a part of manganese, cobalt, and nickel portions in these lithium compounds is substituted with another metal element such as aluminum, magnesium, titanium, and zinc; nickel-substituted lithium manganate in which at least a part of manganese in the lithium manganate is substituted by nickel; cobalt-substituted lithium nickelate obtained by substituting at least part of nickel of lithium nickelate with cobalt; a substance in which a part of manganese in nickel-substituted lithium manganate is substituted with other metal (for example, at least one of aluminum, magnesium, titanium, and zinc); cobalt-substituted lithium nickelate is a substance in which a part of nickel of cobalt-substituted lithium nickelate is substituted with another metal element (for example, at least one of aluminum, magnesium, titanium, zinc, and manganese). These lithium composite oxides may be used alone or in combination of two or more.
Examples of the lithium-containing composite oxide having a layered crystal structure include a composite oxide containing lithium and nickel. 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, and In.
In the lithium nickel-containing composite oxide, Co is preferably contained as a metal other than Ni occupying the nickel site. Further, the lithium nickel containing composite oxide more preferably contains Mn or Al in addition to Co, that is, a lithium nickel cobalt manganese composite oxide (NCM) having a layered crystal structure, a lithium nickel cobalt aluminum composite oxide (NCA) having a layered crystal structure, or a mixture thereof may be suitably used.
As the lithium nickel-containing composite oxide having a layered crystal structure, for example, a compound represented by the following formula (1) can be used.
Li1+a(NibCocMe1aMe21-b-c-d)O2(1)
(wherein Mel is Mn or Al, Me2 is at least 1 selected from Mn, Al, Mg, Fe, Cr, Ti and In (excluding the same metal as Me 1), -0.5. ltoreq. a.ltoreq.0.1, 0.1. ltoreq. b.ltoreq.1, 0. ltoreq. c.ltoreq.0.5, 0. ltoreq. d.ltoreq.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 still more preferably 2 to 25 μm, from the viewpoint of reactivity with an electrolyte solution, rate characteristics, and the like. Here, the average particle diameter means a particle diameter (median diameter: D) at which the cumulative value in the particle size distribution (volume basis) by 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 such that the positive electrode active material layer 2 faces the negative electrode active material layer 7 on the negative electrode current collector layer 8 with a separator interposed therebetween.
The positive electrode 1 in the present embodiment can be manufactured by a known method. For example, the following method or the like can be employed: after a positive electrode slurry is obtained by dispersing a positive electrode active material, a binder resin, and a conductive auxiliary agent in an organic solvent, 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 for producing the positive electrode, for example, N-methyl-2-pyrrolidone (NMP) can be used.
As the binder resin, for example, a resin generally used as a binder resin for a positive electrode, such as Polytetrafluoroethylene (PTFE) or 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 part 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, when the total amount of the positive electrode active material layer 2 is 100 parts by mass. When the content of the binder resin is within the above range, the positive electrode slurry has a better balance of coatability, binder adhesion, and battery characteristics.
When the content of the binder resin is equal to or less than the upper limit, 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 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 aid is not particularly limited as long as it improves the conductivity of the positive electrode, and examples thereof include carbon black, ketjen black, acetylene black, natural graphite, artificial graphite, and carbon fiber. These conductive aids may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the conductive auxiliary 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, further 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, when the total amount of the positive electrode active material layer 2 is 100 parts by mass. When the content of the conductive additive is within the above range, the coating property of the positive electrode slurry, the adhesive property of the binder resin, and the battery characteristics are more well balanced.
When the content of the conductive auxiliary agent is less than the upper limit value or less, 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 conductive auxiliary is not less than the lower limit, 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 collector layer 3, aluminum, stainless steel, nickel, titanium, or an alloy thereof 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, as the thickness of the positive electrode current collector layer 3 becomes thinner, the positive electrode current collector layer 3 is more likely to be deformed or damaged, and thus the safety of the lithium ion secondary battery is more likely to deteriorate. However, the lithium ion secondary battery according to the present embodiment can suppress deterioration in battery safety even if the thickness of the positive electrode collector layer 3 is small. 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 6.3 of 2010 is preferably less than 10%, more preferably less than 8%. This can suppress extension of the positive electrode collector layer 3 even if the separator 20 is damaged by a sharp metal such as lithium dendrite, and thus can suppress contact between the metal piercing the separator 20 and the positive and negative electrodes. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and 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 example3Above and 4.0g/cm3Less than, more preferably 2.4g/cm3Above and 3.8g/cm3The lower, more preferably 2.8g/cm3Above and 3.6g/cm3The following.
Here, the higher the density of the positive electrode active material layer 2, the more likely the battery characteristics such as the cycle characteristics of the lithium ion secondary battery deteriorate. However, the lithium-ion secondary battery according to the present embodiment can suppress deterioration of battery characteristics such as cycle characteristics. Therefore, the energy of the obtained lithium ion secondary battery is further improved from the viewpoint of improving the battery characteristics such as cycle characteristicsFrom the viewpoint of density, the density of the positive electrode active material layer 2 is preferably 3.0g/cm3Above, more preferably 3.2g/cm3Above, particularly preferably 3.3g/cm3The above. In addition, the density of the positive electrode active material layer 2 is preferably 4.0g/cm from the viewpoint of further suppressing deterioration of cycle characteristics at high temperatures3Less than, more preferably 3.8g/cm3The concentration is preferably 3.6g/cm or less3The following.
The thickness (total thickness of both surfaces) 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 can be set to be thick from the viewpoint of energy density, and the thickness can be set to be thin from the viewpoint of output characteristics. The thickness (total thickness of both surfaces) of the positive electrode active material layer 2 can be set as appropriate within a range of, for example, 20 μm to 500 μm, preferably 40 μm to 400 μm, and more preferably 60 μm to 300 μm.
The thickness (thickness on one side) 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 can be set to be thick from the viewpoint of energy density, and the thickness can be set to be thin from the viewpoint of output characteristics. The thickness (thickness on one side) of the positive electrode active material layer 2 can be set as appropriate in a range of, for example, 10 μm to 250 μm, preferably 20 μm to 200 μm, and more preferably 30 μm to 150 μm.
(negative electrode for absorbing and releasing lithium)
The negative electrode 6 according to the present embodiment can 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 may be appropriately set according to the application, as long as it can be used for the negative electrode.
The negative electrode 6 has a structure including a negative electrode current collector layer 8 and a negative electrode active material layer 7 formed on the negative electrode 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 assistant from the viewpoint of improving conductivity.
As the negative electrode active material, any material capable of storingThe active material for a negative electrode that releases lithium ions is not particularly limited, and a carbonaceous material can be used. Examples of the carbonaceous material include graphite, amorphous carbon (e.g., graphitizable carbon and graphitization-resistant carbon), diamond-like carbon, fullerene, carbon nanotube, and carbon nanohorn. As the graphite, natural graphite or artificial graphite can be used, and inexpensive natural graphite is preferable from the viewpoint of material cost. Examples of the amorphous carbon include amorphous carbons obtained by heat-treating coal pitch coke, petroleum pitch coke, acetylene pitch coke, and the like. As other negative electrode active material, a lithium metal material, an alloy material such as silicon or tin, Nb, or the like can be used2O5Or TiO2And oxide-based materials or composites thereof.
The negative electrode active material may be used alone, or two or more kinds may be used in combination.
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 during 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 and output characteristics and from the viewpoint of negative electrode production (smoothness of the negative electrode surface and the like). Here, the average particle diameter means a particle diameter (median diameter: D) at which the cumulative value in the particle size distribution (volume basis) by the laser diffraction scattering method is 50%50)。
The negative electrode 6 in the present embodiment can be produced by a known method. For example, the following method or the like can be employed: after a slurry is obtained by dispersing a negative electrode active material and a binder resin in a solvent, the slurry is applied to the negative electrode current collector layer 8 and dried, and a negative electrode active material layer 7 is formed by applying pressure as necessary.
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 defoaming agents and surfactants may be added to the slurry as necessary.
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, further preferably 1.0 part by mass or more and 5.0 parts by mass or less, and particularly preferably 1.0 part by mass or more and 3.0 parts by mass or less, when the entire negative electrode active material layer 7 is 100 parts by mass. When the content of the binder resin is within the above range, the balance of the coating property of the negative electrode slurry, the binding property of the binder resin, and the battery characteristics is more excellent.
When the content of the binder resin is not more than the above upper limit, the proportion of the negative electrode active material increases, and the capacity per unit mass of the negative electrode increases, which is preferable. When the content of the binder resin is not less than the 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 (e.g., SBR (styrene butadiene rubber)) or an acrylic binder resin can be used. As the aqueous binder resin, those in the form of an emulsion can be used. When water is used as the solvent, it is preferable to use an aqueous binder and a thickener such as CMC (carboxymethyl cellulose) in combination.
The negative electrode active material layer 7 may contain a conductive assistant as needed. As the conductive assistant, a conductive material generally used as a conductive assistant for a negative electrode, such as a carbonaceous material, e.g., carbon black, ketjen black, or acetylene black, can be used.
The content of the conductive auxiliary in the negative electrode 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, and particularly preferably 0.2 part by mass or more and 1.0 part by mass or less, when the entire negative electrode active material layer 7 is 100 parts by mass. When the content of the conductive auxiliary agent is within the above range, the balance between the coating property of the negative electrode slurry, the adhesion property of the binder resin, and the battery characteristics is more excellent.
When the content of the conductive auxiliary agent is not more than the above upper limit, the proportion of the negative electrode active material increases, and the capacity per unit mass of the negative electrode increases, which is preferable. When the content of the conductive auxiliary is not less than the lower limit, the conductivity of the negative electrode is more favorable, which is preferable.
The average particle diameter (primary particle diameter) of the conductive assistant used in 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 assistant is preferably 10nm or more, more preferably 30nm or more, and is preferably 100nm or less, more preferably 80nm or less, from the viewpoint of being able to form a sufficient number of contact points and form a good conductive path, from the viewpoint of suppressing excessive aggregation of the conductive assistant and uniformly dispersing the conductive assistant in the negative electrode. When the conductive auxiliary is in the form of a fiber, the conductive auxiliary has an average diameter of 2 to 200nm and an average fiber length of 0.1 to 20 μm.
Here, the average particle diameter of the conductive assistant is the median particle diameter (D)50) The term "particle size" refers to a particle size 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 (the total thickness of both surfaces) is not particularly limited, and may be appropriately set according to desired characteristics. For example, the thickness can be set to be thick from the viewpoint of energy density, and the thickness can be set to be thin from the viewpoint of output characteristics. The thickness (total thickness of both surfaces) of the negative electrode active material layer 7 can be set as appropriate within a range of, for example, 40 μm to 1000 μm, preferably 80 μm to 800 μm, and more preferably 120 μm to 600 μm.
The thickness (thickness on one side) 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 can be set to be thick from the viewpoint of energy density, and the thickness can be set to be thin from the viewpoint of output characteristics. The thickness (thickness on one side) of the negative electrode active material layer 7 can be set as appropriate in a range of, for example, 20 μm to 500 μm, preferably 40 μm to 400 μm, and more preferably 60 μm to 300 μm.
The density of the negative electrode active material layer 7 is not particularly limited, and is preferably 1.2g/cm, for example3Above and 2.0g/cm3Less than, more preferably 1.3g/cm3Above and 1.9g/cm3The following further advantagesIs selected to be 1.4g/cm3Above and 1.8g/cm3The following.
As the negative electrode 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 collector layer 8 is not particularly limited, and is, for example, 1 μm or more and 20 μm or less.
Here, as the thickness of the negative electrode collector layer 8 becomes thinner, the negative electrode collector layer 8 is more likely to be deformed or damaged, and therefore, the safety of the lithium ion secondary battery is more likely to deteriorate. However, the lithium ion secondary battery according to the present embodiment can suppress deterioration in battery safety even if the negative electrode 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 negative electrode current collector layer 8 measured at 6.3 of 2010 is preferably less than 10%, more preferably less than 5%. This can suppress extension of the negative electrode collector layer 8 even if the separator 20 is damaged by a sharp metal such as lithium dendrite, and thus can suppress contact between the metal piercing the separator 20 and the positive and negative electrodes. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and safety can be further improved.
(nonaqueous electrolyte solution containing lithium salt)
The nonaqueous electrolytic solution containing a lithium salt used in the present embodiment may be appropriately selected from known ones depending on the kind of the electrode active material, the application of the lithium ion secondary battery, and the like.
Specific examples of the lithium salt include LiClO4、LiBF6、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiB10Cl10、LiAlCl4、LiCl、LiBr、LiB(C2H5)4、CF3SO3Li、CH3SO3Li、LiC4F9SO3、Li(CF3SO2)2N, 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), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), ethyl methyl carbonate (MEC), and Vinylene Carbonate (VC); lactones such as γ -butyrolactone and γ -valerolactone; ethers such as trimethoxymethane, 1, 2-dimethoxyethane, diethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxolanyls such as 1, 3-dioxolane and 4-methyl-1, 3-dioxolane; nitrogen-containing solvents such as acetonitrile, nitromethane, formamide, and dimethylformamide; organic acid esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and ethyl propionate; phosphoric acid triesters, diethylene glycol dimethyl ethers; triethylene glycol dimethyl ethers; sulfolanes such as sulfolane and methylsulfolane; oxazolidinones such as 3-methyl-2-oxazolidinone; sultones such as 1, 3-propane sultone, 1, 4-butane sultone and naphthalene sultone, and the like. These may be used alone or in combination of two or more.
(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. As the flexible film 30, a film in which a resin layer is provided on the front and back surfaces of a metal layer serving as a base material can be used. The metal layer may be selected from those having a barrier property against leakage of the electrolyte solution and intrusion 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, facing the heat-fusible resin layers of the flexible film 30 with the battery element interposed therebetween, and heat-fusing 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 outer package opposite to the surface on which the heat-fusible resin layer is formed.
(terminal)
In the present embodiment, the positive electrode terminal 11 may be made of aluminum or an aluminum alloy, and the negative electrode terminal 16 may be made of copper or a copper alloy, or a nickel-plated terminal thereof. The terminals may be drawn out of the container, and a heat-fusible resin may be provided in advance in portions of the terminals located at portions where the periphery of the exterior body is heat-fused.
(insulating Member)
When the boundary portions 4 and 9 between the coated portion and the uncoated portion of the active material are formed as an insulating member, polyimide, glass fiber, polyester, polypropylene, or a composition containing any of these may be used. These members are welded to the boundary portions 4 and 9 by applying heat thereto, or an insulating member can be formed by applying a gel-like resin to the boundary portions 4 and 9 and drying the resin.
(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 a proportion of 50% by mass or more in the resin layer, and means: 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 the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, m-phenylene terephthalate, poly (m-phenylene terephthalate), polycarbonate, polyester carbonate, aliphatic polyamide, wholly aromatic polyamide, semi-aromatic polyamide, wholly aromatic polyester, polyphenylene sulfide, poly (p-phenylene benzobisoxazole), polyimide, polyarylate, polyether imide, polyamideimide, polyacetal, polyether ether ketone, polysulfone, polyether sulfone, fluorine-based resin, polyether nitrile, and modified polyphenylene ether.
Among these, from the viewpoint of excellent balance among heat resistance, mechanical strength, stretchability, price, and the like, one or more selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, aliphatic polyamide, wholly aromatic polyamide, semi-aromatic polyamide, and wholly aromatic polyester is preferable, one or more selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, aliphatic polyamide, wholly aromatic polyamide, and semi-aromatic polyamide is more preferable, one or more selected from the group consisting of polyethylene terephthalate and wholly aromatic polyamide is further preferable, and polyethylene terephthalate is further 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, further preferably 240 ℃ or higher, and particularly preferably 250 ℃ or higher.
When the melting point or the decomposition temperature of the separator 20 according to the present embodiment is equal to or higher than the lower limit value, even if the battery generates heat and reaches a high temperature, the heat 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 lower, and preferably 400 ℃ or lower 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 lower, and preferably 400 ℃ or lower from the viewpoint of stretchability.
According to JIS L1913: the average values of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the separator according to the present embodiment, which are measured at 6.3 of 2010, are preferably larger than the tensile elongations of the positive electrode collector layer 3 and the negative electrode collector layer 8, respectively. Thus, even if the separator 20 is damaged by a sharp metal such as lithium dendrite, the separator 20 is more elongated than the positive and negative electrode collectors, and therefore the positive and negative electrodes are easily covered with the separator 20. Therefore, the elongated spacer 20 can suppress contact between the metal that has punctured the spacer 20 and the positive and negative electrodes. As a result, thermal runaway and the like of the lithium ion secondary battery can be suppressed, and 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 separator 20 measured at 6.3 of 2010 is preferably 10% or more, more preferably 12% or more, and particularly preferably 13% or more. When 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, even if the separator 20 is damaged by sharp metal such as lithium dendrite, the separator 20 stretches to effectively cover the positive and negative electrodes, and therefore, contact between the metal of the pricked 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 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 separator 20 measured at 6.3 of 2010 is not particularly limited, but is preferably 100% or less, more preferably 70% or less, and even more preferably 50% or less, from the viewpoint of the heat resistance of the separator 20.
Further, according to JIS L1913: the tensile elongation in the MD of the separator 20 measured at 6.3 of 2010 is preferably 10% or more, and more preferably 12% or more.
According to JIS L1913: the upper limit of the tensile elongation in the MD of the separator 20 measured at 6.3 of 2010 is not particularly limited, but is preferably 100% or less, more preferably 70% or less, and still more preferably 50% or less.
The resin layer constituting the spacer 20 according to the present embodiment is preferably a porous resin layer. Thus, when an abnormal current occurs in the lithium ion secondary battery or the battery temperature rises, the micropores of the porous resin layer are closed to interrupt the flow of current, and thermal runaway of the battery can be avoided.
From the viewpoint of balance between mechanical strength and lithium ion conductivity, 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.
The porosity can be determined by the following equation.
ε＝{1-Ws/(ds·t)}×100
Here, ε: porosity (%), Ws: weight per unit area (g/m)2) Ds: true density (g/cm)3) T: film thickness (. mu.m).
The planar shape of the spacer 20 according to the present embodiment is not particularly limited, and may be appropriately selected according to the shapes of the electrode and the current collector, and may be, for example, a rectangular shape.
From the viewpoint of the balance between mechanical strength and lithium ion conductivity, the thickness of the separator 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.
In order to further improve the 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 only on one surface of the resin layer from the viewpoint of handling property, productivity, and the like of the spacer 20 described in the present embodiment, and may be provided on both surfaces of the resin layer from the viewpoint of further improving heat resistance of the spacer 20.
The spacer 20 according to the present embodiment further includes the ceramic layer, so that thermal shrinkage of the spacer 20 can be further reduced, and short-circuiting between electrodes can be further prevented.
The ceramic layer may be formed by, for example, applying a ceramic layer forming material to 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, an oxide, a nitride, a sulfide, a carbide, or the like having high insulating properties is preferable, and a material obtained by adjusting one or two or more kinds of ceramics selected from alumina, boehmite, titanium oxide, silicon oxide, magnesium oxide, barium oxide, zirconium oxide, zinc oxide, iron oxide, or the like into a particulate state is more preferable. Among these, alumina, boehmite, and titanium oxide are preferable.
The binder resin is not particularly limited, and examples thereof include cellulose resins such as carboxymethyl cellulose (CMC); an acrylic resin; and fluorine-based resins 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, water, alcohols such as ethanol, N-methylpyrrolidone (NMP), toluene, dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and the like.
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 further preferably 1 μm or more and 15 μm or less, from the viewpoint of balance among heat resistance, mechanical strength, handling properties, and lithium ion conductivity.
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-described configurations may be adopted.
The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like are included within a range in which the object of the present invention can be achieved.
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 >
Lithium nickel-containing composite oxygen for use as a positive electrode active materialCompound (chemical formula: LiNi)0.8Co0.15Al0.05O2Average particle diameter: 6 μm), 3.0 parts by mass of carbon black as a conductive aid, and 3.0 parts by mass of polyvinylidene fluoride (PVDF) as a binder resin. These were dispersed in an organic solvent to prepare a positive electrode slurry. This positive electrode slurry was continuously applied to an aluminum foil (tensile elongation: 6%) having a thickness of 15 μm as a positive electrode current collector, dried, and then pressurized to prepare an application portion provided with a positive electrode current collector (positive electrode active material layer: one side of which has a thickness of 60 μm and a density of 3.35 g/cm)3) And an uncoated portion of the positive electrode roll.
The positive electrode roll was punched out to form a positive electrode so as to leave an uncoated portion serving as a tab for connection to a positive electrode terminal.
< 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 part by mass of carbon black was used as the conductive auxiliary, 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 pressed to prepare a coated portion having a negative electrode current collector (negative electrode active material layer: one-side thickness: 90 μm, density: 1.55 g/cm)3) And an uncoated portion of the negative roll.
The negative electrode roll was punched out so as to leave an uncoated portion serving as a tab for connection to a negative electrode terminal, thereby producing a negative electrode.
< production of laminated Battery >
The positive electrode and the negative electrode were stacked via a separator in a repeated folding structure, and a negative electrode terminal and a positive electrode terminal were provided to obtain a stacked body. Next, LiPF obtained by dissolving 1M in a solvent containing ethylene carbonate, diethyl carbonate and ethylmethyl carbonate6The resulting electrolyte and the resulting laminate are contained in a flexible filmThereby, a laminated type laminated battery was obtained. The rated capacity of the laminated multilayer 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 direction: 19 percent of
Average value of tensile elongation in MD and tensile elongation in TD: 19.5 percent
Melting point: 250 deg.C
< evaluation >
(1) Tensile elongation of the separator and collector
According to JIS L1913: 2010 6.3 was measured.
(2) Porosity of porous resin layer
The following equation was used.
ε＝{1-Ws/(ds·t)}×100
Here, ε: porosity (%), Ws: weight per unit area (g/m)2) Ds: true density (g/cm)3) T: film thickness (. mu.m).
(3) DC resistance between positive and negative electrodes after nail penetration test
The laminated battery thus obtained was fully charged by constant current charging at 25 ℃ with a constant current of 1C until a voltage of 4.2V and then constant voltage charging at a constant voltage of 4.2V until a charge termination current of 0.015C using a constant current constant voltage (CC-CV) method.
Next, a nail-piercing test was performed in which nails made of SUS304 (manufactured by whitewater manufacturing) having a diameter of 3mm and a length of 70mm were pierced in a direction perpendicular to the electrode surface at a speed of 80mm/sec at the central portion of the stacked type laminated battery in a fully charged state under an environment of 25 ℃.
Then, after the nail penetration test, short-circuit discharge was caused in the laminated battery, and for a laminated battery having a voltage in the range of 0.001V or more and 0.100V or less, a direct current resistance between the positive electrode and the negative electrode was measured at room temperature (25 ℃) by using a resistance measuring instrument (product name: Digital Multimeter 7544-01) manufactured by Yokogawa Meters & instruments corporation.
(4) Cycle test
The obtained laminated type laminate battery was evaluated for cycle characteristics at a temperature of 25 ℃, charged at a constant current of 0.5C until a voltage of 4.2V was reached, then charged at a constant voltage of 4.2V until a charge termination current of 0.015C, then subjected to CC discharge at a discharge rate of 3.0C and a discharge termination voltage of 2.5V, and subjected to 300 cycles, and a capacity retention (%) was a value obtained by dividing a discharge capacity (mAh) after 300 cycles by a discharge capacity (mAh) at a 10 th cycle, and a capacity retention (%) was 80% or more, and when less than 80% was 80%, ○ was obtained.
(5) Safety test
In the center of the laminated type laminate battery in a fully charged state, nails made of SUS304 (manufactured by white water manufacturing) having a diameter of 3mm and a length of 70mm were pricked at a speed of 80mm/sec in a direction perpendicular to the electrode surface in an environment of 25 ℃, thereby causing a short circuit in the laminated type laminate battery. Next, the state of the battery was observed after 6 hours, and the safety of the battery was evaluated according to the following criteria.
○ the lithium ion battery has no smoke and fire
X: at least one of smoke and fire of the lithium ion battery occurs
The evaluation results are shown in table 1. In example 1, the voltage of the laminate battery when the dc resistance between the positive and negative electrodes was measured was 0.0582V.
(example 2)
A laminated multilayer 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 the separator, and each evaluation was performed. Here, the physical properties of the spacer 2 are as follows.
Tensile elongation in MD: 40 percent of
Tensile elongation in TD direction: 35 percent of
Average value of tensile elongation in MD and tensile elongation in TD: 37.5 percent
Thermal decomposition temperature: 400 deg.C
In example 2, the voltage of the laminate battery when the dc resistance between the positive and negative electrodes was measured 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 type 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 laminate battery when the dc resistance between the positive and negative electrodes was measured 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 conductive additive: 4.0 parts by mass of binder resin: a laminated type 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 laminated multilayer battery was produced in the same manner as in example 1 except that a spacer 3 (thickness: 25 μm, porosity: 54%) including a porous resin layer made of polypropylene and a ceramic layer (alumina) was used as the spacer, and each evaluation was performed. Here, the physical properties of the spacer 3 are as follows.
Tensile elongation in MD: 125 percent
Tensile elongation in TD direction: 630 percent
Average value of tensile elongation in MD and tensile elongation in TD: 377.5%
Melting point: 160 deg.C
Comparative example 3
A laminated type laminated battery was produced in the same manner as in example 1 except that the separator 4 including a porous resin layer (thickness: 25 μm, porosity: 55%) containing polypropylene was used as the 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 direction: 400 percent
Average value of tensile elongation in MD and tensile elongation in TD: 225 percent
Melting point: 160 deg.C
Comparative example 4
A laminated-type laminated battery was produced in the same manner as in example 1 except that a separator 5 including a porous resin layer (thickness: 18 μm, porosity: 54%) containing polypropylene and a ceramic layer (thickness: 7 μm) containing alumina was used as the separator, and the respective evaluations were performed. Here, the physical properties of the spacer 5 are as follows.
Tensile elongation in MD: 50 percent of
Tensile elongation in TD direction: 400 percent
Average value of tensile elongation in MD and tensile elongation in TD: 225 percent
Melting point: 160 deg.C
Comparative example 5
A laminated type laminated battery was produced in the same manner as in example 1 except that a separator 6 including a nonwoven fabric layer containing glass fibers and a layer containing ceramic (magnesium oxide) (thickness: 30 μm, porosity: 76%) was used as the separator, and each evaluation was performed. Here, the physical properties of the spacer 6 are as follows.
Tensile elongation in MD: 8.9 percent
Tensile elongation in TD direction: 14.3 percent
Average value of tensile elongation in MD and tensile elongation in TD: 11.6 percent
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 part by mass of a binder resin: a laminated type 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]
Claims (13)
1. 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 electrolytic solution containing a lithium salt, and a separator interposed between the positive electrode and the negative electrode,
when a nail penetration test for short-circuiting the lithium ion secondary battery was performed by piercing the center of the lithium ion secondary battery with a nail made of SUS304 having a diameter of 3mm and a length of 70mm at a speed of 80mm/sec in a fully charged state in an environment of 25 ℃,
after the nail penetration test, short-circuit discharge is caused in the lithium ion secondary battery, and the DC resistance between the positive electrode and the negative electrode of the lithium ion secondary battery is 0.1 Ω to 300 Ω when the voltage is in the range of 0.001V to 0.100V.
2. The lithium-ion secondary battery according to claim 1, wherein the melting point or decomposition temperature of the separator is 220 ℃ or higher.
3. The lithium ion secondary battery according to claim 1 or 2, wherein the ratio of the total amount of lithium ions in the lithium ion secondary battery is in accordance with JIS L1913: 2010, 6.3, wherein the average values of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the separator are greater than the tensile elongation of the positive electrode collector layer and the negative electrode collector layer, respectively.
4. The lithium ion secondary battery according to any one of claims 1 to 3, wherein the ratio of the total mass of the lithium ion secondary battery according to JIS L1913: an average value of the tensile elongation in the MD direction and the tensile elongation in the TD direction of the separator measured at 6.3 of 2010 is 10% or more.
5. The lithium ion secondary battery according to any one of claims 1 to 4, wherein the positive electrode active material layer contains a positive electrode active material, a binder resin, and a conductive auxiliary agent.
6. The lithium-ion secondary battery according to claim 5, wherein a content of the conductive auxiliary exceeds 1.0 part by mass and is less than 4.0 parts by mass when the whole of the positive electrode active material layer is 100 parts by mass.
7. The lithium ion secondary battery according to claim 5 or 6, wherein the conductive auxiliary agent contains one or more selected from carbon black, ketjen black, acetylene black, natural graphite, artificial graphite, and carbon fiber.
8. The lithium ion secondary battery according to any one of claims 5 to 7, wherein the positive electrode active material comprises a composite oxide containing lithium nickel.
9. The lithium-ion secondary battery according to claim 8, wherein the lithium-nickel containing composite oxide is represented by the following formula (1),
Li1+a(NibCocMe1dMe21-b-c-d)O2(1)
in the formula (1), Me1 is Mn or Al, Me2 is at least 1 selected from Mn, Al, Mg, Fe, Cr, Ti and In, but does not include metals of the same kind as Me1, a is more than or equal to 0.5 and less than 0.1, b is more than or equal to 0.1 and less than 1, c is more than 0 and less than 0.5, and d is more than 0 and less than 0.5.
10. The lithium ion secondary battery according to any one of claims 1 to 9, wherein the density of the positive electrode active material layer is 3.0g/cm3The above.
11. The lithium ion secondary battery according to any one of claims 1 to 10, wherein a battery cell rated capacity of the lithium ion secondary battery is 5Ah or more.
12. The lithium ion secondary battery according to any one of claims 1 to 11, wherein the number of stacked layers or the number of windings of the positive electrode in the central portion of the lithium ion secondary battery is 10 or more.
13. The lithium ion secondary battery according to any one of claims 1 to 12, wherein the thickness of the separator is 5 μm or more and 50 μm or less.
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| CN113809278A (en) * | 2021-09-15 | 2021-12-17 | 珠海冠宇电池股份有限公司 | Electrode assembly and application thereof |
| WO2022001987A1 (en) * | 2020-06-28 | 2022-01-06 | 华为技术有限公司 | Secondary battery and terminal |
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| CN112750978B (en) * | 2020-12-30 | 2022-03-15 | 珠海冠宇电池股份有限公司 | Pole piece and battery |
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| WO2019073595A1 (en) | 2019-04-18 |
| JPWO2019073595A1 (en) | 2020-10-22 |
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