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CN112020790B - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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Publication number
CN112020790B
CN112020790B CN201980028125.6A CN201980028125A CN112020790B CN 112020790 B CN112020790 B CN 112020790B CN 201980028125 A CN201980028125 A CN 201980028125A CN 112020790 B CN112020790 B CN 112020790B
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CN
China
Prior art keywords
positive electrode
container
negative electrode
mixture layer
nonaqueous electrolyte
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Active
Application number
CN201980028125.6A
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Chinese (zh)
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CN112020790A (en
Inventor
二川秀史
森绫香
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Honda Motor Co Ltd
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Honda Motor Co Ltd
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Publication of CN112020790A publication Critical patent/CN112020790A/en
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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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • 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
    • 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
    • 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
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • 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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a nonaqueous electrolyte secondary battery capable of reliably operating an energization cutting mechanism at the time of overcharge without degrading battery performance. The nonaqueous electrolyte secondary battery 1 includes a positive electrode 41, in-container positive electrode terminals 21 and 23, a negative electrode 42, in-container negative electrode terminals 22 and 24, a nonaqueous electrolyte, and an energization breaking mechanism 68b capable of breaking energization to the outside of the container when the in-container pressure rises. The positive electrode mixture layer non-forming portion 41b or at least one member of the positive electrode terminals 21 and 23 in the container is provided with a positive electrode active material layer capable of generating a gas capable of operating the current supply shutoff mechanism 68b.

Description

Nonaqueous electrolyte secondary battery
Technical Field
The present invention relates to a nonaqueous electrolyte secondary battery.
Background
Conventionally, a nonaqueous electrolyte secondary battery including a positive electrode having a positive electrode mixture layer and a positive electrode current collector, a negative electrode having a negative electrode mixture layer and a negative electrode current collector, and a nonaqueous electrolyte solution in a container is known. In the nonaqueous electrolyte secondary battery, lithium ions are used as charge carriers that carry out a battery reaction, for example.
When the nonaqueous electrolyte secondary battery is in an overcharged state, a nonaqueous solvent or the like of the electrolyte is electrolyzed to generate a gas, and the internal pressure increases. Thus, a nonaqueous electrolyte secondary battery is known that includes an energization cutting mechanism that cuts off energization of a positive electrode or a negative electrode to the outside when the internal pressure rises due to overcharge (for example, see patent literature 1).
In addition, a nonaqueous electrolyte secondary battery is known in which a gas generating agent is contained in an electrolyte solution in order to reliably operate the energization cutting mechanism at the time of overcharge, and the gas generating agent reacts to generate a gas by a voltage equal to or higher than the maximum operating power of the nonaqueous electrolyte secondary battery (for example, see patent document 2). According to the nonaqueous electrolyte secondary battery in which the gas generating agent is contained in the electrolyte, the current-carrying shutoff mechanism can be reliably operated by increasing the internal pressure of the nonaqueous electrolyte secondary battery by the gas generated by the gas generating agent before the gas is generated by electrolysis of the nonaqueous solvent or the like at the time of overcharge.
Prior art literature
Patent literature
Patent document 1: international publication No. 2014/049848
Patent document 2 Japanese patent application laid-open No. 2013-69490
Disclosure of Invention
Problems to be solved by the invention
However, in the nonaqueous electrolyte secondary battery described in patent document 2, the gas generating agent is added to the electrolyte solution, and therefore the gas generating agent may interfere with the battery reaction, and the battery performance such as the input/output characteristics and the energy density may be deteriorated.
In addition, in the nonaqueous electrolyte secondary battery, the gas generating agent may be added to the positive electrode mixture layer or the negative electrode mixture layer, but in this case, the generated gas may be enclosed in the positive electrode mixture layer or the negative electrode mixture layer, and the current-carrying shutoff mechanism may not be operated.
The present invention aims to provide a nonaqueous electrolyte secondary battery which can solve the above-mentioned problems and can reliably operate an energization breaking mechanism at the time of overcharging without degrading the battery performance.
Means for solving the problems
In order to achieve the above object, a nonaqueous electrolyte secondary battery according to the present invention includes: a positive electrode having a positive electrode mixture layer and a positive electrode current collector; a positive electrode terminal in the container, which is electrically connected to a positive electrode mixture layer non-formed portion of the positive electrode current collector; a negative electrode having a negative electrode mixture layer and a negative electrode current collector; a negative electrode terminal in the container, which is electrically connected to a negative electrode mixture layer non-formed portion of the negative electrode current collector; a nonaqueous electrolyte; and a current-carrying shutoff mechanism capable of shutting off current carrying between the positive electrode terminal in the container or the negative electrode terminal in the container and the outside of the container when the internal pressure of the container increases, wherein the positive electrode mixture layer non-formed portion or at least one member of the positive electrode terminals in the container is provided with a positive electrode active material layer that reacts under the action of a voltage equal to or higher than the maximum operating power of the nonaqueous electrolyte secondary battery to generate a gas that increases the internal pressure of the container and enables the current-carrying shutoff mechanism to operate.
According to the nonaqueous electrolyte secondary battery of the present invention, when the battery voltage becomes a voltage equal to or higher than the maximum operating power of the nonaqueous electrolyte secondary battery due to overcharge, the positive electrode active material forming the positive electrode active material layer capable of generating gas is decomposed or degenerated, and the element in the composition of the positive electrode active material is gasified to generate gas. Or the positive electrode active material or the modified positive electrode active material reacts with the conductive auxiliary agent, binder or electrolyte at the interface thereof, so that the conductive auxiliary agent, binder or electrolyte is decomposed to generate gas.
As a result, the internal pressure in the container increases, and the current-carrying shutoff mechanism operates to shut off current carrying between the positive electrode terminal in the container or the negative electrode terminal in the container and the outside of the container, so that overcharge can be prevented.
In this case, since the nonaqueous electrolyte secondary battery of the present invention includes the positive electrode active material layer in the positive electrode mixture layer non-formed portion or in at least one member of the positive electrode terminal in the container, the battery reaction in the positive electrode mixture layer, the negative electrode mixture layer, or the nonaqueous electrolyte solution is not hindered by the positive electrode active material, and a decrease in battery performance such as energy density can be prevented. In addition, there is no case where a gas generated by decomposition or deterioration of the positive electrode active material or decomposition of the conductive auxiliary agent, binder or electrolyte after reaction with the positive electrode active material or the deteriorated positive electrode active material is enclosed in the positive electrode mixture layer or the negative electrode mixture layer, and therefore the energization cutting mechanism can be reliably operated.
In the nonaqueous electrolyte secondary battery of the present invention, the positive electrode active material layer that generates the gas preferably contains LiNi 0.5Mn1.5O4(LNMO).LiNi0.5Mn1.5O4 (LNMO) as the positive electrode active material, and since the reaction potential is high and the reactivity with the electrolyte is high, the gas can be easily generated.
Drawings
Fig. 1 is a perspective view showing an example of the structure of a nonaqueous electrolyte secondary battery according to the present embodiment.
Fig. 2 is an exploded perspective view of the nonaqueous electrolyte secondary battery shown in fig. 1.
Fig. 3 is an exploded perspective view of an electrode body member of the nonaqueous electrolyte secondary battery shown in fig. 1.
Fig. 4 is a partial cross-sectional view showing the configuration of the energization cutting mechanism of the nonaqueous electrolyte secondary battery shown in fig. 1.
Fig. 5 is an exploded perspective view of the components of the configuration shown in fig. 4.
Detailed Description
Next, embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1 and 2, a nonaqueous electrolyte secondary battery 1 of the present embodiment includes a battery case 2, and the battery case 2 includes: a battery can 4 having a square deep-drawn shape; and a battery cover 3 that seals an opening 4a of the battery can 4. The battery case 2 accommodates a power generating element. The power generating element includes an electrode body element 40 wound in a flat shape with separators 43 and 44 interposed therebetween and stacked on a negative electrode 42. The electrode body element 40 is inserted into the battery can 4 together with the positive electrode collector plate 21 and the negative electrode collector plate 31 in a state covered by an insulating sheet (not shown) from the outside thereof.
The battery can 4 and the battery cover 3 are each made of an aluminum alloy, and the battery cover 3 is joined to the battery can 4 by laser welding to seal the opening 4 a. The battery cover 3 is provided with a positive electrode side terminal constituent 60 and a negative electrode side terminal constituent 70 to form a cover assembly.
The positive electrode side terminal structure 60 and the negative electrode side terminal structure 70 have a positive electrode terminal 61 and a negative electrode terminal 71 arranged so as to sandwich the 1 st insulators 64 and 74 with the battery cover 3. The battery cover 3 is provided with, in addition to the positive electrode terminal 61 and the negative electrode terminal 71: a gas discharge valve 13 that opens to discharge the gas in the battery container 2 when the pressure in the battery container 2 is higher than a predetermined value; a liquid injection port 12 for injecting an electrolyte into the battery container 2; and a filling plug 11 for sealing the filling port 12 after filling the electrolyte. The filling plug 11 is joined to the battery cover 3 by laser welding in a state where the filling port 12 is closed, and the filling port 12 is sealed.
The positive electrode terminal 61 and the negative electrode terminal 71 are arranged at positions apart from each other on the outer side of the rectangular battery cover 3 along the longitudinal direction. The positive electrode terminal 61 and the negative electrode terminal 71 hold terminal bolts 63 and 73 for fixing the bus bar connection terminals, and are disposed inside the battery cover 3 to realize conductive connection. The positive electrode terminal 61 is made of aluminum or an aluminum alloy, and the negative electrode terminal 71 is made of a copper alloy.
The positive electrode terminal 61 is electrically insulated from the battery cover 3 by a spacer 66 and a1 st insulator 64 on the outside of the battery cover 3 and by a 2 nd insulator 65 (see fig. 4) on the inside of the battery cover 3. The positive electrode terminal 61 is fixed to the battery cover 3 together with the 2 nd insulator 65 and the connection electrode 67 by caulking.
The positive electrode terminal 61 is electrically connected to the positive electrode collector plate 21 with the current-carrying cutoff mechanism interposed therebetween. The details of the structure of the energization cutting mechanism will be described later. The negative electrode terminal 71 is electrically connected to the negative electrode collector plate 31 with a connection terminal (not shown) interposed therebetween.
The positive electrode collector plate 21 and the negative electrode collector plate 31 have a pair of flat bonding pieces 23 and 33 extending toward the bottom of the battery can 4 and connected to the electrode body element 40 in a conductive manner. The positive electrode collector plate 21 and the bonding piece 23 constitute a positive electrode terminal in the container, and the negative electrode collector plate 31 and the bonding piece 33 constitute a negative electrode terminal in the container. The bonding sheets 23 and 33 are bonded to the positive electrode 41 and the negative electrode 42 provided at both ends of the electrode body element 40 in the winding axis direction by welding. As the welding method, ultrasonic welding, resistance welding, laser welding, or the like can be used.
The electrode assembly element 40 is disposed between the bonding piece 23 of the positive electrode collector plate 21 and the bonding piece 33 of the negative electrode collector plate 31 and supported at both ends, and the power generation element assembly 5 is constituted by the cap assembly and the electrode assembly element 40.
The electrode body element 40 is constituted by: in a state where the winding end side is expanded, the negative electrode 42 and the positive electrode 41 are arranged between the 1 st and 2 nd separators 43 and 44, respectively, as shown in fig. 3, and wound in a flat shape. The positive electrode 41 includes a positive electrode mixture layer 41a and a positive electrode mixture layer non-forming portion 41b formed on a positive electrode current collector, not shown, and the negative electrode 42 includes a negative electrode mixture layer 42a and a negative electrode mixture layer non-forming portion 42b formed on a negative electrode current collector, not shown. As shown in fig. 3, the outermost electrode of the electrode body element 40 is a negative electrode 42, and a separator 44 is further wound around the outermost electrode.
The separators 43 and 44 serve to insulate the positive electrode 41 from the negative electrode 42. The negative electrode mixture layer 42a of the negative electrode 42 is larger in the width direction than the positive electrode mixture layer 41a of the positive electrode 41, and thus the positive electrode mixture layer 41a is necessarily sandwiched between the negative electrode mixture layers 42 a.
The positive electrode mixture layer non-formed portion 41b and the negative electrode mixture layer non-formed portion 42b are bound to the planar portion, and are connected to the positive electrode collector plate 21 and the negative electrode collector plate 31 of each electrode to which the positive electrode terminal 61 and the negative electrode terminal 71 are connected by welding or the like. The separators 43 and 44 are wider than the negative electrode mixture layer 42a in the width direction, but the positive electrode mixture layer non-formed portion 41b and the negative electrode mixture layer non-formed portion 42b are wound around the positions where the metal foil surfaces are exposed, and therefore do not become an obstacle in bundling welding.
In the present embodiment, the electrode body element 40 is configured such that the long negative electrode 42 and the long positive electrode 41 are arranged between the long 1 st and 2 nd separators 43 and 44, respectively, and wound in a flat shape, but the following configuration may be adopted: the 1 st separator 43 is arranged between the elongated positive electrode 41 and the elongated negative electrode 42, and the 2 nd separator 44 is arranged between the units by stacking a plurality of units.
Next, details of the energization cutting mechanism will be described with reference to fig. 4 and 5.
The current-carrying cutoff mechanism is provided in a current path from the positive electrode terminal 61 of the positive electrode-side terminal formation part 60 to the positive electrode collector plate 21.
The positive electrode side terminal structure 60 is composed of a positive electrode terminal 61, a positive electrode terminal bolt 63, a 1 st insulator 64, a 2 nd insulator 65, a gasket 66, a positive electrode connection electrode 67, a conductive plate 68 deformed by an increase in the internal pressure of the battery, and a positive electrode collector plate 21. The positive electrode terminal 61, the 1 st insulator 64, the 2 nd insulator 65, the gasket 66, and the positive electrode connection electrode 67 are integrally fixed by caulking to the battery inner end surface portion of the positive electrode terminal 61, and are attached to the battery cover 3. The positive electrode collector plate 21 is integrally fixed to the 2 nd insulator 65.
The positive electrode terminal 61 includes: a plate-shaped main body portion 61a disposed along an upper surface that is an outer side of the battery cover 3; a bolt insertion hole 61b penetrating the main body 61a and penetrating and supporting the positive electrode terminal bolt 63; and a shaft portion 61c inserted into the opening 3a of the battery cover 3 and protruding inward of the battery cover 3, wherein a through hole 61d penetrating in the axial direction along the center of the shaft portion 61c is provided.
The positive electrode terminal bolt 63 includes: a shaft portion 63a inserted into the bolt insertion hole 61b of the positive electrode terminal 61; and a head portion (bottom flat portion) 63b which is supported by being sandwiched between the main body portion 61a and the 1 st insulator 64.
The 1 st insulator 64 is formed of an insulating plate-like member interposed between the positive electrode terminal 61 and the upper surface of the battery cover 3, and has an opening 64a (see fig. 5) communicating with the opening 3a of the battery cover 3 for inserting the shaft portion 61c of the positive electrode terminal 61.
The gasket 66 is inserted into the opening 3a of the battery cover 3 to insulate and seal between the shaft portion 61c of the positive electrode terminal 61 and the battery cover 3.
The positive electrode connection electrode 67 is formed of a conductive flat plate member disposed inside the battery cover 3, and an opening 67a communicating with the opening 3a of the battery cover 3 to allow the shaft portion 61c of the positive electrode terminal 61 to penetrate therethrough is provided at the center thereof. The positive electrode connection electrode 67 is disposed along the lower surface of the battery cover 3 with the 2 nd insulator 65 interposed between the battery cover 3, and the opening 67a is opened at a planar lower surface (planar portion) 67b, and the distal end of the shaft portion 61c of the positive electrode terminal 61 protruding from the opening 67a is expanded radially outward and crimped, whereby the positive electrode connection electrode is integrally fixed to the battery cover 3 in a state of being electrically connected to the positive electrode terminal 61 and insulated from the battery cover 3. The caulking portion 61e of the shaft portion 61c of the positive electrode terminal 61 protrudes to the lower surface 67b of the positive electrode connection electrode 67, and the through hole 61d communicating with the outside of the battery opens toward the inside of the battery.
The 2 nd insulator 65 is formed of an insulating plate-like member disposed along the lower surface of the battery cover 3, and is interposed between the battery cover 3 and the positive electrode connection electrode 67 and between the battery cover 3 and the positive electrode collector plate 21 to insulate these members from each other. The 2 nd insulator 65 has a predetermined plate thickness, and is provided with a through hole 65a which communicates with the opening 3a of the battery cover 3 to allow the shaft portion 61c of the positive electrode terminal 61 to be inserted therethrough. The 2 nd insulator 65 is integrally caulking-fixed to the battery cover 3 together with the positive electrode connection electrode 67 by the caulking portion 61 e.
The 2 nd insulator 65 is provided with a recess 65b which communicates with the through hole 65a and accommodates the positive electrode connection electrode 67 and the conductive plate 68. The recess 65b is provided in a recessed manner on the lower surface of the 2 nd insulator 65, communicating with other space portions inside the battery.
The conductive plate 68 has: a dome-shaped diaphragm portion 68a that gradually reduces in diameter as it moves in the axial direction; and an annular flange portion 68b that extends radially outward from the outer peripheral edge portion of the diaphragm portion 68 a. The diaphragm portion 68a gradually reduces in diameter as it moves in the axial direction in a direction away from the lower surface 67b of the positive electrode connection electrode 67, and has a curved surface portion having a convex arc-shaped cross section in at least a part of the axial direction, and in this embodiment, has a hemispherical shape having a semi-elliptical cross section. The diaphragm portion 68a covers the through hole 61d that opens to the lower surface 67b of the positive electrode connection electrode 67 so as to face the open end of the through hole 61d, and the flange portion 68b is bonded to the lower surface 67b of the positive electrode connection electrode 67 to be sealed, thereby dividing a space outside the battery and a space inside the battery that communicate with each other through the through hole 61 d.
When the internal pressure of the battery container 2 is higher than the preset upper limit value, the diaphragm portion 68a deforms in a direction to reduce the protruding height thereof by a pressure difference with the outside of the battery container 2, breaks the fragile portion 25 of the positive electrode collector plate 21, separates the joint portion 24 joined to the conductive plate 68 from the base portion 22 of the positive electrode collector plate 21, and cuts off the current path, thereby functioning as the current interruption mechanism of the present invention.
The flange portion 68b provided at the outer peripheral edge portion of the diaphragm portion 68a has a ring shape that extends radially outward along one plane, is continuous in a constant width over the entire circumference, is connected to the lower surface of the positive electrode connection electrode 67, and is continuously joined to the lower surface 67b of the positive electrode connection electrode 67 over the entire circumference by laser welding, thereby achieving hermetic sealing.
The diaphragm portion 68a is formed of a material, a plate thickness, a cross-sectional shape, or the like so that the joint portion 24 can be held at a position separated from the positive electrode collector plate 21 by plastic deformation even after the internal pressure of the battery case 2 is reduced. The top portion, i.e., the central portion 68c of the diaphragm portion 68a is joined to the joint portion 24 of the positive electrode collector plate 21 by laser welding. The joining of the central portion 68c may be performed by resistance welding or ultrasonic welding, in addition to laser welding.
The positive electrode collector plate 21 is attached to and fixed to the 2 nd insulator 65. As shown in fig. 5, the positive electrode collector plate 21 has a flat plate-like base portion (upper surface flat portion) 22 that faces and extends parallel to the lower surface of the battery cover 3, and a plurality of support holes 22b are formed so as to penetrate and extend at predetermined intervals. The base 22 is provided with a pair of edges 22a, and the pair of edges 22a are formed by bending along a pair of long sides in a direction away from the battery cover 3, so as to improve rigidity and maintain a planar shape. The pair of bonding pieces 23 of the positive electrode collector plate 21 are provided so as to protrude continuously from the respective edges 22 a.
The positive electrode collector plate 21 is integrally fixed by inserting a plurality of protruding portions 65c protruding toward the lower surface of the 2 nd insulator 65 into the respective support holes 22b of the base 22, and thermally fusing the tips of the protruding portions 65c to join the 2 nd insulator 65.
The positive electrode collector plate 21 is provided with a joint portion 24 joined to the central portion 68c of the conductive plate 68. The joint 24 is formed of a thin portion formed by thinning a part of the base 22. The fragile portion 25 is formed by providing a groove portion in the thin portion so as to surround the periphery of the joint portion 24, and is blocked at the groove portion by the conductive plate 68 deformed in the battery outer direction when the battery internal pressure rises, so that the joint portion 24 can be separated from the base portion 22.
The fragile portion 25 is set to have the following dimensions and shapes so as to have the following strength: the conductive plate 68 breaks when a force in a direction extending toward the battery cover 3 side acts along with deformation of the conductive plate due to an increase in the internal pressure of the battery case 2, and does not break under normal use conditions such as vibration during traveling. The joining of the central portion 68c of the conductive plate 68 and the joining portion 24 of the positive electrode collector plate 21 is performed by laser welding, but resistance welding, ultrasonic welding, or the like may be used in addition to this.
In the nonaqueous electrolyte secondary battery 1 of the present embodiment, a positive electrode active material layer (not shown, hereinafter abbreviated as a gas generation layer) that reacts to generate a gas when the battery voltage becomes equal to or higher than the maximum operating power of the nonaqueous electrolyte secondary battery 1 is provided in the positive electrode mixture layer non-forming portion 41b or in one member of the positive electrode collector plate 21 and the bonding sheet 23 that is the positive electrode terminal in the container. The energization shut-off mechanism operates when the internal pressure of the battery container 2 increases due to the gas generated by the reaction of the gas generation layer.
In the nonaqueous electrolyte secondary battery 1 of the present embodiment, the positive electrode 41 is formed of a positive electrode current collector, a positive electrode mixture layer 41a formed on one side or both sides of the positive electrode current collector, and a positive electrode mixture layer non-formed portion 41 b.
As the positive electrode current collector, a foil or plate of copper, aluminum, nickel, titanium, stainless steel, a carbon sheet, a carbon nanotube sheet, or the like can be used as a single body. The positive electrode current collector may be a clad foil made of 2 or more materials, if necessary. The positive electrode current collector can be set to a thickness of 5 to 100 μm, and from the viewpoints of structure and performance, it is preferably set to a thickness of 7 to 20 μm.
The positive electrode mixture layer 41a is formed of the 1 st positive electrode active material, a conductive auxiliary agent, and a binder. As the 1 st positive electrode active material, at least one material selected from lithium composite oxide (LiNixCoyMnzO2(x+y+z＝1)、(LiNixCoyAlzO2(x+y+z＝1))、 lithium iron phosphate (LiFePO 4 (LFP)) and the like can be used.
As the conductive additive, at least one material selected from carbon black such as Acetylene Black (AB) and Ketjen Black (KB), carbon material such as graphite powder, conductive metal powder such as nickel powder, and the like can be used.
As the binder, at least one material selected from cellulose-based polymers, fluorine-based resins, vinyl acetate copolymers, rubbers, and the like can be used. As the binder, specifically, at least one material selected from polyvinylidene fluoride (PVdF), polyimide (PI), polyvinylidene chloride (PVdC), polyethylene oxide (PEO), and the like can be used.
The positive electrode mixture layer 41a can be formed by applying a positive electrode mixture slurry obtained by mixing the positive electrode active material, the conductive additive, and the binder in an organic solvent such as N-methylpyrrolidone (NMP) to one or both sides of the positive electrode current collector, and drying the mixture. The drying may also be carried out under reduced pressure.
The positive electrode mixture layer 41a can be appropriately pressed after the drying to adjust the thickness and density. The positive electrode mixture layer 41a formed on the positive electrode current collector is preferably a density of 2.0 to 4.2g/cm 3, more preferably a density of 2.6 to 3.2g/cm 3, in view of good balance between energy density and input/output characteristics.
The negative electrode 42 is formed of a negative electrode current collector, a negative electrode mixture layer non-formed portion 42b, and a negative electrode mixture layer 42a formed on one side or both sides of the negative electrode current collector.
As the negative electrode current collector, a foil or plate of copper, aluminum, nickel, titanium, stainless steel, a carbon sheet, a carbon nanotube sheet, or the like can be used in a single body. The negative electrode current collector may be a clad foil made of 2 or more materials, if necessary. The negative electrode current collector can be set to a thickness of 5 to 100 μm, and from the viewpoints of structure and performance, it is preferably set to a thickness of 7 to 20 μm.
The anode mixture layer 42a is formed of an anode active material, a conductive auxiliary agent, and a binder. As the negative electrode active material, at least one material selected from carbon powder (amorphous carbon) such as soft carbon (easily graphitizable carbon), hard carbon (hard graphitizable carbon), graphite (graphite), silica (SiO x), titanium composite oxide (Li 4Ti5O7、TiO2、Nb2TiO7), tin composite oxide, lithium alloy, metallic lithium, and the like can be used.
As the conductive additive, at least one material selected from carbon black such as Acetylene Black (AB) and Ketjen Black (KB), carbon material such as graphite powder, conductive metal powder such as nickel powder, and the like can be used.
As the binder, at least one material selected from cellulose-based polymers, fluorine-based resins, vinyl acetate copolymers, rubbers, and the like can be used. As the binder in the case of using an organic solvent as a solvent of the negative electrode mixture slurry described later, specifically, at least one material selected from polyvinylidene fluoride (PVdF), polyimide (PI), polyvinylidene chloride (PVdC), polyethylene oxide (PEO), and the like can be used. In addition, as for the binder when an aqueous solvent is used as the solvent of the negative electrode mixture slurry, specifically, at least one material selected from styrene-butadiene rubber (SBR), an acrylic-modified SBR resin (SBR-based latex), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), hydroxypropyl methylcellulose (HPMC), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and the like can be used.
The negative electrode mixture layer 42a can be formed by applying a negative electrode mixture slurry obtained by mixing the negative electrode active material, the conductive additive, and the binder in an organic solvent such as N-methylpyrrolidone (NMP) or an aqueous solvent such as pure water to one or both surfaces of the negative electrode current collector, and drying the mixture. The drying may also be carried out under reduced pressure.
The negative electrode mixture layer 42a can be appropriately pressed after the drying to adjust the thickness and density. The negative electrode mixture layer 42a formed on the negative electrode current collector is preferably a density of 0.7 to 2.0g/cm 3, more preferably a density of 1.0 to 1.7g/cm 3, in view of good balance between energy density and input/output characteristics.
As the electrolyte solution, a substance formed of a nonaqueous solvent and an electrolyte may be used, and the concentration of the electrolyte is preferably set in the range of 0.1 to 10 mol/L.
The nonaqueous solvent includes at least one aprotic solvent selected from carbonates, ethers, sulfones, lactones, and the like. As the aprotic solvent, specifically, at least one compound selected from Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methylethyl carbonate (EMC), 1, 2-Dimethoxyethane (DME), 1, 2-Diethoxyethane (DEE), tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane, 1, 3-dioxolane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, acetonitrile (AN), propionitrile, nitromethane, N-Dimethylformamide (DMF), dimethyl sulfoxide, sulfolane, y-butyrolactone, and the like can be used.
As the electrolyte, at least one compound selected from LiPF6、LiBF4、LiClO4、LiN(SO2CF3)、LiN(SO2C2F5)2、LiCF3SO3、LiC4F9SO3、LiC(SO2CF3)3、LiF、LiCl、LiI、Li2O、Li3N、Li3P、Li10GeP2S12(LGPS)、Li3PS4、Li6PS5Cl、Li7P2S8I、LixPOyNz(x＝2y+3z－5、LiPON)、Li7La3Zr2O12(LLZO)、Li3xLa2/3- xTiO3(LLTO)、Li1+xAlxTi2-x(PO4)3(LATP)、Li1.5Al0.5Ge1.5(PO4)3(LAGP)、Li1+x+yAlxTi2-xSiyP3- yO12、Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12、Li4-2xZnxGeO4(LISICON) and the like, preferably LiPF 6、LiBF4 or a mixture thereof can be used.
Examples of the separator 43 or 44 include a film made of a resin such as Polyethylene (PE), polypropylene (PP), polyester, cellulose, or polyamide, a porous resin sheet such as nonwoven fabric, or a porous structure obtained by sintering an inorganic material or mixing an inorganic material with a binder. As the inorganic material used for the porous structure, at least one compound selected from alumina (Al 2O3), silica (SiO2)、LiF、LiCl、LiI、Li2O、Li2S、Li3N、Li3P、Li10GeP2S12(LGPS)、Li3PS4、Li6PS5Cl、Li7P2S8I、LixPOyNz(x＝2y+3z－5、LiPON)、Li7La3Zr2O12(LLZO)、Li3xLa2/3-xTiO3(LLTO)、Li1+ xAlxTi2-x(PO4)3(LATP)、Li1.5Al0.5Ge1.5(PO4)3(LAGP)、Li1+x+yAlxTi2-xSiyP3-yO12、Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12、Li4-2xZnxGeO4(LISICON), and the like can be used.
The separator 43, 44 may be formed using at least one material selected from the porous resin sheet and the porous structure. The separators 43 and 44 have a single-layer structure in the case of being formed of only 1 of the above materials, and in the case of being formed of 2 or more materials, they may be laminated or mixed, and the mode is not particularly limited.
The gas generation layer is formed of a2 nd positive electrode active material that generates a gas, a conductive auxiliary agent, and a binder. As the 2 nd positive electrode active material, the same material as the 1 st positive electrode active material can be used, and particularly LiNi 0.5Mn1.5O4 (LNMO) is preferable from the viewpoint of high reaction potential and high reactivity with the electrolyte solution, which is liable to generate gas. As the conductive additive or binder used in the gas generation layer, the same substance as that used in the positive electrode mixture layer 41a can be used.
The gas generation layer can be formed by applying a gas generation slurry obtained by mixing the 2 nd positive electrode active material, the conductive additive, and the binder in an organic solvent such as N-methylpyrrolidone (NMP) to the positive electrode mixture layer non-formed portion 41b of the positive electrode current collector, and drying the same. The drying may also be carried out under reduced pressure.
The gas generation layer may be formed by bonding a crystal or sintered body of the 2 nd positive electrode active material to at least one member of the positive electrode mixture layer non-formed portion 41b of the positive electrode current collector or the positive electrode terminals 21 and 23 in the container.
In the present embodiment, the nonaqueous electrolyte secondary battery 1 has the following structure: an electrode body element 40 is housed in a battery case 2 made of an aluminum alloy including a battery can 4 having a rectangular deep-drawn shape and a battery cover 3 sealing an opening 4a of the battery can 4. However, the nonaqueous electrolyte secondary battery 1 is not limited to the configuration of the present embodiment, and for example, aluminum, steel, stainless steel, or the like can be used as the material, and for example, a cylindrical shape, a square shape, a button cell, a pouch-shaped (laminated-type) or the like can be used as the container shape.
In the present embodiment, the membrane portion 68a that deforms in response to an increase in the internal pressure of the battery container 2 to break the fragile portion 25 of the positive electrode collector plate 21 is used as the current-carrying shut-off means, but any configuration may be used as long as the current-carrying shut-off means can shut off the current carrying between the positive electrode terminals 21 and 23 in the container or the negative electrode terminals 22 and 24 in the container and the outside of the container in response to an increase in the internal pressure of the battery container 2. The operating pressure of the energization switching mechanism may be, for example, in the range of 0.1 to 5MPa, and preferably in the range of 0.5 to 2.2 MPa.
Next, examples of the present invention and comparative examples will be described.
Examples
[ Example 1]
In this example, first, liNi xCoyMnzO2 (x+y+z=1, x:y:z=6:2:2, hereinafter abbreviated as NCM 622) as a 1 st positive electrode active material, acetylene Black (AB) as a conductive auxiliary agent, and polyvinylidene fluoride (PVdF) as a binder were prepared as NCM622: AB: PFdV = 94:3:3 (mass ratio) was mixed with N-methylpyrrolidone (NMP) and adjusted so that the solid content ratio became 55 mass%, thereby preparing a positive electrode mixture slurry. Next, the positive electrode mixture slurry was applied to a positive electrode current collector made of aluminum foil 15 μm thick, and dried to form a positive electrode mixture layer 41a of 24mg/cm 2.
Next, liNi 0.5Mn1.5O4 (LNMO) as the 2 nd positive electrode active material of the generated gas, acetylene Black (AB) as a conductive aid, and polyvinylidene fluoride (PVdF) as a binder were prepared as LNMO: AB: PFdV = 94:3:3 (mass ratio) was mixed with N-methylpyrrolidone (NMP) and adjusted so that the solid content ratio became 55 mass%, thereby preparing a gas-generating slurry. Next, the gas generating slurry was applied to the positive electrode mixture layer non-forming portion 41b of the positive electrode current collector and dried to form a gas generating layer of 12mg/cm 2.
Next, the positive electrode current collector including the positive electrode mixture layer 41a and the gas generation layer was dried and pressurized, and the electrode density of the positive electrode mixture layer 41a was adjusted to 3.2g/cm 3, thereby forming the positive electrode 41.
Next, a graphite powder (Gr.) as a negative electrode active material, and Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose (CMC) as binders were mixed to be Gr.: SBR: cmc=98: 1:1 (mass ratio) was mixed with pure water, and the mixture was adjusted so that the solid content ratio became 50 mass%, to prepare a negative electrode mixture slurry. Next, the negative electrode mixture slurry was applied to a negative electrode current collector made of a copper foil having a thickness of 8 μm, and dried to form a negative electrode mixture layer 42a of 2mg/cm 2. Next, the negative electrode current collector including the negative electrode mixture layer 42a was dried and pressed, and the electrode density of the negative electrode mixture layer 42a was adjusted to 1.5g/cm 3, thereby forming the negative electrode 42.
Next, as shown in fig. 3, the positive electrode 41 and the negative electrode 42 are respectively arranged between separators 43 and 44 formed of a double layer structure of aluminum oxide (Al 2O3) and Polyethylene (PE), and wound in a flat shape, thereby forming an electrode body element 40. Next, the positive electrode collector end of the electrode assembly element 40 is joined to the joining piece 23 of the positive electrode collector plate 21 and the negative electrode collector end is joined to the joining piece 24 of the negative electrode collector plate 22 by ultrasonic welding, respectively, to form the power generating element assembly 5.
Next, the periphery of the electrode body element 40 is covered with an insulating sheet (not shown) and inserted into the battery can 4, the opening 4a of the battery can 4 is closed with the battery lid 3, and the battery lid 3 and the battery can 4 are bonded and sealed by laser welding. Then, the electrolyte is injected into the battery container 2 from the injection port 12, the injection port 12 is sealed by the injection plug 11, and the lithium ion secondary battery 1 is formed by bonding and sealing the battery lid 3 by laser welding. As the electrolyte, there are used Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC) in EC: EMC: dmc=3: 4:3, and a nonaqueous electrolyte obtained by dissolving LiPF 6 as a supporting electrolyte in a concentration of 1.2 mol/L in the mixed solvent obtained by mixing the above components.
Next, for the lithium ion secondary battery 1 obtained in this example, the element energy density was calculated from the battery capacity in the range of 2.5 to 4.2V at a current value equivalent to 0.33C. The results are shown in Table 1.
Next, for the lithium ion secondary battery 1 obtained in this example, an overcharge test (SOC 200%) of 2 times the maximum battery capacity was performed at a current value corresponding to 1C, and the overcharge SOC and voltage at which the pressure at which the energization switching mechanism was operated was measured. The results are shown in Table 1.
[ Example 2]
In this example, a lithium ion secondary battery 1 was formed in exactly the same manner as in example 1, except that the negative electrode 42 and the electrolyte were prepared as follows.
First, lithium Titanate (LTO) as a negative electrode active material, acetylene Black (AB) as a conductive auxiliary agent, and polyvinylidene fluoride (PVdF) as a binder were mixed to become LTO: AB: pvdf=96: 2:2 (mass ratio) was mixed with N-methylpyrrolidone (NMP) to prepare a negative electrode mixture slurry, and the mixture was adjusted so that the solid content ratio became 55 mass%. Next, the negative electrode mixture slurry was applied to a negative electrode current collector made of aluminum foil having a thickness of 15 μm, thereby forming a negative electrode mixture layer 42a of 42mg/cm 2. Next, the negative electrode current collector including the negative electrode mixture layer 42a was dried and pressurized, and the electrode density of the negative electrode mixture layer 42a was adjusted to 2.1g/cm 3, thereby forming the negative electrode 42.
Next, as an electrolyte, propylene Carbonate (PC) and diethyl carbonate (DEC) were mixed with PC: dec=2: the LiPF 6 as a supporting electrolyte was dissolved in the mixed solvent having a volume ratio of 1 at a concentration of 1.2 mol/L to form a nonaqueous electrolytic solution.
Next, for the lithium ion secondary battery 1 obtained in this example, the element energy density was calculated from the battery capacity in the range of 1.5 to 2.7V at a current value equivalent to 0.33C, and on the other hand, the overcharge SOC and the voltage at which the energization breaking means reached the operating pressure were measured in exactly the same manner as in example 1. The results are shown in Table 1.
Comparative example 1
In this comparative example, a lithium ion secondary battery 1 was formed exactly the same as in example 1, except that the gas generating layer was not formed at all.
Next, the element energy density of the lithium ion secondary battery 1 obtained in this comparative example was calculated in the same manner as in example 1, and the overcharge SOC and the voltage at which the energization switching mechanism reached the operating pressure were measured. The results are shown in Table 1.
Comparative example 2
In this comparative example, a lithium ion secondary battery 1 was formed in exactly the same manner as in example 2, except that the gas generation layer was not formed at all.
Next, the element energy density of the lithium ion secondary battery 1 obtained in this comparative example was calculated in the same manner as in example 2, and the overcharge SOC and the voltage at which the energization switching mechanism reached the operating pressure were measured. The results are shown in Table 1.
TABLE 1
NCM622：LiNixCoyMnzO2(x+y+z＝1，x：y：z＝6：2：2)
Gr.: graphite powder
LTO: lithium titanate
LMNO：LiNi0.5Mn1.5O4
Element volume energy density: wh/L
Working SOC: %
Operating voltage: v
As is clear from table 1, according to the lithium ion secondary batteries of examples 1 and 2 having the gas generation layer in the positive electrode mixture layer non-formation portion 41b, the operation SOC and the operation voltage of the current supply shut-off mechanism are low, and the current supply shut-off mechanism can be reliably operated at the time of overcharge without lowering the battery performance, although the volume energy densities of the respective elements are the same as those of the lithium ion secondary batteries of comparative examples 1 and 2 having no gas generation layer.
Description of the reference numerals
1 … Nonaqueous electrolyte secondary battery, 2 … battery container, 21, 23 … container positive electrode terminal, 22, 24 … container negative electrode terminal, 41 … positive electrode, 41a … positive electrode mixture layer, 41b … positive electrode mixture layer non-formed portion, 42 … negative electrode, 42a … negative electrode mixture layer, 42b … negative electrode mixture layer non-formed portion, 68b … film portion (energization cutoff mechanism).

Claims (4)

1. A nonaqueous electrolyte secondary battery is characterized by comprising, in a container: a positive electrode having a positive electrode mixture layer and a positive electrode current collector; a positive electrode terminal in the container, which is electrically connected to a positive electrode mixture layer non-formed portion of the positive electrode current collector; a negative electrode having a negative electrode mixture layer and a negative electrode current collector; a negative electrode terminal in the container, which is electrically connected to a negative electrode mixture layer non-formed portion of the negative electrode current collector; a nonaqueous electrolyte; and a current-carrying shutoff mechanism capable of shutting off current carrying between the positive electrode terminal in the container or the negative electrode terminal in the container and the outside of the container when the internal pressure of the container increases,
Wherein the positive terminal in the container is composed of a positive current collecting plate and a positive joint sheet extending towards the bottom of the container,
The negative electrode terminal in the container is composed of a negative electrode collector plate and a negative electrode joint piece extending towards the bottom of the container,
The positive electrode mixture layer non-formed portion extends along the positive electrode bonding sheet toward the bottom of the container,
The negative electrode mixture layer non-formed portion extends along the negative electrode bonding sheet toward the bottom of the container,
The positive electrode mixture layer non-formed portion or at least one member of the positive electrode terminal in the container is provided with a positive electrode active material layer that reacts under the action of a voltage equal to or higher than the maximum operating power of the nonaqueous electrolyte secondary battery to generate a gas that can raise the internal pressure of the container and activate the energization shut-off mechanism,
The current-carrying cutoff mechanism includes a shape-variable member capable of deforming a shape when the internal pressure of the container increases, and the fragile portion breaks with the deformation of the shape-variable member, thereby cutting off the current carrying between the positive electrode terminal in the container or the negative electrode terminal in the container and the outside of the container, and the positive electrode terminal in the container and the fragile portion are joined.
2. The nonaqueous electrolyte secondary battery according to claim 1, wherein the shape-changing member is a membrane.
3. The nonaqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material layer that generates the gas contains at least one material selected from LiNi xCoyMnzO2 that is a lithium composite oxide, liNi xCoyAlzO2 that is a lithium composite oxide, and LiFePO 4 (LFP) that is lithium iron phosphate, wherein x+y+z=1 in the LiNi xCoyMnzO2 and the LiNi xCoyAlzO2.
4. The nonaqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material layer that generates the gas contains LiNi 0.5Mn1.5O4 (LNMO) as a positive electrode active material.
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