WO2016113863A1 - 非水電解質電池及び電池パック - Google Patents
非水電解質電池及び電池パック Download PDFInfo
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- WO2016113863A1 WO2016113863A1 PCT/JP2015/050795 JP2015050795W WO2016113863A1 WO 2016113863 A1 WO2016113863 A1 WO 2016113863A1 JP 2015050795 W JP2015050795 W JP 2015050795W WO 2016113863 A1 WO2016113863 A1 WO 2016113863A1
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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
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
- B60L50/64—Constructional details of batteries specially adapted for electric vehicles
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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
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
- H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
- H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
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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
- H01M50/538—Connection of several leads or tabs of wound or folded electrode stacks
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/271—Lids or covers for the racks or secondary casings
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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
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
- H01M50/291—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by their shape
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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
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- Embodiments of the present invention relate to a nonaqueous electrolyte battery and a battery pack.
- Non-aqueous electrolyte batteries such as lithium ion secondary batteries have been actively conducted as high energy density batteries.
- Non-aqueous electrolyte batteries are expected as a power source for uninterruptible power supplies of hybrid vehicles, electric vehicles, and mobile phone base stations.
- the voltage obtained from the unit cell is as low as about 3.7V. For this reason, in order to obtain a high output, it is necessary to extract a large current from the large unit cell, so that there is a problem that the entire apparatus is enlarged.
- Bipolar batteries have a positive electrode active material layer formed on one plate surface of a current collector, and a plurality of layers stacked in series with a bipolar electrode and an electrolyte layer forming a negative electrode active material layer on the other plate surface It is a battery of the structure. Since this bipolar battery is stacked in series inside the unit cell, a high voltage can be obtained even in the unit cell. Therefore, when obtaining a high output, an output can be obtained with a high voltage constant current, and furthermore, the electric resistance of the battery connection portion can be greatly reduced.
- a structure using a liquid electrolyte is used.
- the structure using a liquid electrolyte of a lithium ion secondary battery cannot be applied to the bipolar battery. That is, the structure of the bipolar battery needs to have a structure in which the electrodes are made independent so that a short circuit (liquid junction) due to ion conduction does not occur when the electrolytes existing between the electrode layers touch each other.
- bipolar batteries using polymer solid electrolytes that do not contain liquid electrolytes have been proposed.
- this method since the liquid electrolyte is not included in the battery, the possibility of a short circuit (liquid junction) due to ion conduction between the electrode layers is reduced.
- the ionic conductivity of a solid electrolyte is as low as about 1/10 to 1/100 of that of a liquid electrolyte. For this reason, since the problem that the output density of a battery becomes low arises, it has not been put to practical use.
- the gel electrolyte is a gel electrolyte in which a polymer such as polyethylene oxide (PEO) or polyvinylidene fluoride (PVdF) is impregnated with an electrolytic solution.
- PEO polyethylene oxide
- PVdF polyvinylidene fluoride
- the challenge remains to increase the size (high energy density) of bipolar batteries.
- a method of increasing the energy density of a bipolar battery a method of increasing the electrode area of the positive and negative electrodes, a method of connecting small-area bipolar unit cells in parallel, and the like can be considered.
- a lithium ion secondary battery having a conventional electrode structure positive and negative electrodes and a separator are wound in a spiral shape without a gap, and the battery exterior is filled with high density to achieve high energy density.
- the positive electrode and the negative electrode are integrally formed because of the structure thereof, and thus the counter electrodes come into contact with each other by spiral winding. Therefore, there is a problem that a short circuit occurs unless an insulating layer such as a separator or a polymer is sandwiched between the bipolar electrode layers.
- a bipolar battery in which a positive electrode active material layer is formed on one plate surface of a current collector and a negative electrode active material is formed on the other plate surface. It is an object to provide a nonaqueous electrolyte battery and a battery pack.
- the non-aqueous electrolyte battery includes a bipolar electrode and a non-aqueous electrolyte.
- the bipolar electrode includes a current collector, a positive electrode active material layer formed on one surface of the current collector, and a negative electrode active material layer formed on the other surface of the current collector.
- the bipolar electrode is divided into a plurality of predetermined lengths in one direction, and the portions between the divided portions are sequentially folded and folded one after another.
- FIG. 1 is a longitudinal sectional view showing a schematic configuration of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 2 is a perspective view showing a schematic configuration of the bipolar electrode of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 3 is a longitudinal sectional view showing a schematic configuration of the bipolar electrode according to the first embodiment.
- FIG. 4 is a longitudinal sectional view showing a schematic configuration of the electrode laminate of Example 2 of the bipolar electrode.
- FIG. 5 is an enlarged cross-sectional view of a portion A in FIG.
- FIG. 6 is an exploded perspective view showing a schematic configuration of the battery pack of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 1 is a longitudinal sectional view showing a schematic configuration of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 2 is a perspective view showing a schematic configuration of the bipolar electrode of the nonaqueous electrolyte battery according to the
- FIG. 7 is a block diagram showing an electric circuit of the battery pack of FIG.
- FIG. 8 is a side view of a main part showing a schematic configuration of a modification of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 9 is a schematic configuration diagram illustrating an attached state of a current collecting tab of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 10 is a schematic configuration diagram illustrating a modified example of the attached state of the current collecting tab of the nonaqueous electrolyte battery according to the first embodiment.
- FIG. 11 is a longitudinal sectional view showing a schematic configuration of the nonaqueous electrolyte battery of FIG. FIG.
- FIG. 12 is a diagram showing a resistance test result of the current collector in the nonaqueous electrolyte battery of FIGS. 9 and 10.
- 13A is a longitudinal sectional view showing a schematic configuration of a double-sided positive electrode of Comparative Example 1.
- FIG. 13B is a longitudinal sectional view showing a schematic configuration of a double-sided negative electrode of Comparative Example 1.
- FIG. 13C is a longitudinal cross-sectional view illustrating a schematic configuration of the stacked battery of Comparative Example 1.
- FIG. 1 is a schematic cross-sectional view of an example nonaqueous electrolyte battery 60 according to the first embodiment.
- a nonaqueous electrolyte battery 60 shown in FIG. 1 includes a substantially box-shaped exterior member 61 and a zigzag-shaped bipolar electrode 11 housed in the exterior member 61.
- the exterior member 61 is made of, for example, a laminate film in which a metal layer is interposed between two resin films.
- FIG. 2 is a perspective view showing a schematic configuration of the bipolar electrode 11.
- FIG. 3 shows the basic structure of the electrode body 2 of the bipolar electrode 1.
- the electrode body 2 of the bipolar electrode 1 includes a current collector 3, a positive electrode active material layer 4 formed on one surface of the current collector 3, and a negative electrode formed on the other surface of the current collector 3. And an active material layer 5.
- Aluminum was used as the material for the current collector 3, and the current collector 3 was formed into a square having a side of, for example, 5 cm.
- Lithium manganese phosphate (hereinafter, LMP) was used for the positive electrode active material layer 4
- lithium titanate (hereinafter, LTO) was used for the negative electrode active material layer 5.
- the positive electrode active material layer 4 can occlude and release lithium.
- the negative electrode active material layer 5 has a reaction potential in the vicinity of 1.5V.
- LMP or LTO, a conductive additive, and a binder were mixed with 5 wt% carbon and 10 wt% polyvinylidene fluoride based on the total weight of the electrode body 2.
- the bipolar electrode 1 according to Example 1 was produced by molding these mixtures.
- Example 2 As shown in FIG. 4, the electrode body 2 of the bipolar electrode 1 described in Example 1 is used to form a laminated body 2X of the electrode body 2 laminated in three layers (electrode bodies 2A to 2C). There is an electrolyte layer 7 between the electrode bodies 2A to 2C of the laminate 2X so that the electrode bodies 2A to 2C do not touch each other. Further, in FIG. 4, a negative electrode member 2 t 1 is stacked via an electrolyte layer 7 on the upper side of the electrode body 2 A at the uppermost position. In FIG. 4, a positive electrode member 2 t 2 is laminated via an electrolyte layer 7 below the electrode body 2 C at the lowest position.
- Example 3 One side (long side) of the current collector 3 was formed to 45 cm, for example, and the other side (short side) was formed to 5 cm, for example.
- a bipolar electrode 1 was produced in the same manner as in Example 1 except that the obtained rectangular plate-shaped current collector 3 was used. That is, the positive electrode active material layer 4 is formed on one plate surface of the rectangular plate-shaped current collector 3, and the negative electrode active material layer 5 is formed on the other plate surface.
- Example 4 A laminated body 2X of the electrode body 2 in which the electrode body 2 of the bipolar electrode 1 described in Example 3 is laminated in three layers (electrode bodies 2A to 2C), a negative electrode member 2t1, and a positive electrode member 2t2 are integrally laminated. A rectangular plate-shaped electrode laminate 6 is formed. And the bipolar battery of Example 4 was obtained by producing similarly to Example 2. Further, the rectangular plate-like electrode laminate 6 was folded in a zigzag shape and overlapped to obtain a zigzag bipolar electrode 11 (see FIG. 2) according to Example 4. At this time, as shown in FIG.
- the electrode laminate 6 is divided into a plurality of plates with a predetermined length in one direction, and the sections 8 are sequentially bent alternately and folded in a zigzag manner. It is piled up with.
- the bipolar electrode 11 is formed by folding each segmented portion 8 so as to be alternately folded at intervals of 5 cm. Note that a folded portion between adjacent divided portions 8 is referred to as a folded portion 12.
- Example 5 (Modification of the first embodiment)
- the length from the bottom in FIG. 8 to the folded portion 12 of each divided portion 8 is 5 cm, 6 cm, 5 cm, 4 cm, 5 cm, 6 cm, 5 cm, and 5 cm.
- a bipolar electrode 11 shown in FIG. 8 was produced in the same manner as in Example 4 except that the sheets were folded in order. Accordingly, as shown in FIG. 8, when the bipolar electrode 11 is zigzag folded, folded portions 12 are alternately formed at the left and right ends of the divided portion 8.
- the center point position O of the folded portion 12 on one end side of the divided portion 8 is bent in a state where adjacent portions with respect to the overlapping direction of the folded portion 12 are alternately shifted in a direction orthogonal to the overlapping direction.
- one positive electrode current collecting tab 13a is formed in one of the folded portions 12 on one end side.
- One of the folded portions 12 on the other end side is provided with one negative current collecting tab 13b.
- the bipolar electrode 11 having the structure of Example 5 is housed in an exterior member (case) 61.
- An insulating member 62 such as a nonwoven fabric or a resin material is disposed on the inner peripheral surface of the exterior member 61.
- the positive current collecting tab 13a is connected to the current collector 3 of the positive electrode member 2t2, and the negative current collecting tab 13b is connected to the current collector 3 of the negative electrode member 2t1. It is connected.
- the negative electrode current collecting tab 13b and the positive electrode current collecting tab 13a are extended to the outside from an opening (not shown) of the exterior member 61, and the negative electrode terminal 63 (see FIG. 6) and the positive electrode terminal 64 (see FIG. 6)).
- the bipolar electrode 11 and the non-aqueous electrolyte are completely sealed by heat-sealing the opening of the exterior member 61 with the current collecting tab 13b for the negative electrode and the current collecting tab 13a for the positive electrode interposed therebetween.
- FIG. 6 is an exploded perspective view showing a schematic configuration of the battery pack 90 of the nonaqueous electrolyte battery 60 according to the first embodiment.
- FIG. 7 is a block diagram showing an electric circuit of the battery pack 90 of FIG.
- the battery pack 90 shown in FIGS. 6 and 7 includes a plurality of unit cells 91.
- the unit cell 91 is the nonaqueous electrolyte battery 60 described with reference to FIG.
- the plurality of single cells 91 are stacked such that the negative electrode terminal 63 and the positive electrode terminal 64 extending to the outside are aligned in the same direction, and are fastened with an adhesive tape 65 to constitute an assembled battery 66. These unit cells 91 are electrically connected to each other in series as shown in FIG.
- the printed wiring board 67 is disposed to face the side surface from which the negative electrode terminal 63 and the positive electrode terminal 64 of the unit cell 91 extend.
- a thermistor 68, a protection circuit 69, and a terminal 70 for energizing external devices are mounted on the printed wiring board 67.
- An insulating plate (not shown) is attached to the surface of the printed wiring board 67 facing the assembled battery 66 in order to avoid unnecessary wiring and wiring of the assembled battery 66.
- the positive electrode side lead 71 is connected to a positive electrode terminal 64 located in the lowermost layer of the assembled battery 66, and the tip thereof is inserted into the positive electrode side connector 72 of the printed wiring board 67 and electrically connected thereto.
- the negative electrode side lead 73 is connected to the negative electrode terminal 63 located on the uppermost layer of the assembled battery 66, and the tip thereof is inserted into the negative electrode side connector 74 of the printed wiring board 67 and electrically connected thereto.
- These connectors 72 and 74 are connected to the protection circuit 69 through wirings 75 and 76 formed on the printed wiring board 67.
- the thermistor 68 detects the temperature of the unit cell 91, and the detection signal is transmitted to the protection circuit 69.
- the protection circuit 69 can cut off the plus side wiring 77a and the minus side wiring 77b between the protection circuit 69 and the terminal 70 for energization to an external device under a predetermined condition.
- An example of the predetermined condition is, for example, when the temperature detected by the thermistor 68 is equal to or higher than a predetermined temperature.
- Another example of the predetermined condition is when, for example, overcharge, overdischarge, overcurrent, or the like of the unit cell 91 is detected. This detection of overcharge or the like is performed on each individual cell 91 or the entire assembled battery 66.
- the battery voltage When detecting the individual cells 91, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each unit cell 91. In the case of the battery pack 90 of FIGS. 6 and 7, a wiring 78 for voltage detection is connected to each unit cell 91. A detection signal is transmitted to the protection circuit 69 through these wirings 78.
- Protective sheets 79 made of rubber or resin are disposed on the three side surfaces of the assembled battery 66 excluding the side surfaces from which the positive electrode terminal 64 and the negative electrode terminal 63 protrude.
- the assembled battery 66 is stored in the storage container 80 together with each protective sheet 79 and the printed wiring board 67. That is, the protective sheet 79 is disposed on each of the inner side surface in the long side direction and the inner side surface in the short side direction of the storage container 80, and the printed wiring board 67 is disposed on the inner side surface on the opposite side in the short side direction.
- the assembled battery 66 is located in a space surrounded by the protective sheet 79 and the printed wiring board 67.
- the lid 81 is attached to the upper surface of the storage container 80.
- a heat shrink tape may be used instead of the adhesive tape 65 for fixing the assembled battery 66.
- the protective sheets 79 are arranged on both side surfaces of the assembled battery 66, the heat shrinkable tube is circulated, and then the heat shrinkable tube is thermally contracted to bind the assembled battery 66.
- FIGS. 6 and 7 show the configuration in which the unit cells 91 are connected in series, but in order to increase the battery capacity, they may be connected in parallel.
- the assembled battery pack 90 can also be connected in series and / or in parallel.
- the mode of the battery pack 90 is appropriately changed depending on the use.
- a use of the battery pack 90 one in which cycle characteristics with a large current characteristic are desired is preferable.
- Specific applications include power supplies for digital cameras, and in-vehicle applications such as two-wheel to four-wheel hybrid electric vehicles, two-wheel to four-wheel electric vehicles, and assist bicycles.
- the battery pack 90 is particularly suitable for in-vehicle use.
- the electrode group can hold a non-aqueous electrolyte.
- the nonaqueous electrolyte can also be stored in the main part of the exterior member 61 together with the electrode group.
- the nonaqueous electrolyte battery 60 according to the first embodiment prevents leakage of the nonaqueous electrolyte through the opening provided in the lead holding portion, that is, leakage of the nonaqueous electrolyte from the inside of the battery to the outside of the battery. You can also.
- the electrode lead whose heat is sealed at the periphery of the opening provided in the lead sandwiching portion exhibits high sealing performance. Therefore, leakage of the nonaqueous electrolyte from the inside of the battery to the outside of the battery can be further prevented.
- the electrode group can include a positive electrode and a negative electrode. Further, the electrode group can include a separator interposed between the positive electrode and the negative electrode.
- the positive electrode can include a positive electrode current collector and a positive electrode material layer formed on the positive electrode current collector.
- the positive electrode material layer may be formed on both sides of the positive electrode current collector, or may be formed only on one side. Further, the positive electrode current collector may include a positive electrode material layer unsupported portion in which the positive electrode material layer is not formed on any surface.
- the positive electrode material layer can contain a positive electrode active material.
- the positive electrode material layer can further include a conductive agent and a binder.
- the conductive agent can be blended in order to improve current collection performance and suppress contact resistance between the positive electrode active material and the positive electrode current collector.
- the binder can be blended to fill a gap between the dispersed positive electrode active materials and bind the positive electrode active material and the positive electrode current collector.
- the positive electrode can be connected to the electrode lead, that is, the positive electrode lead, for example, via the positive electrode material layer unsupported portion of the positive electrode current collector.
- the positive electrode and the positive electrode lead can be connected by, for example, welding.
- the negative electrode can include a negative electrode current collector and a negative electrode material layer formed on the negative electrode current collector.
- the negative electrode material layer may be formed on both sides of the negative electrode current collector, or may be formed only on one side.
- the negative electrode current collector may include a negative electrode material layer unsupported portion in which the negative electrode material layer is not formed on any surface.
- the negative electrode material layer can contain a negative electrode active material.
- the negative electrode material layer can further include a conductive agent and a binder.
- the conductive agent can be blended in order to enhance the current collecting performance and suppress the contact resistance between the negative electrode active material and the negative electrode current collector.
- a binder can be mix
- the negative electrode can be connected to the electrode lead, that is, the negative electrode lead, for example, via the negative electrode material layer unsupported portion of the negative electrode current collector.
- the connection between the negative electrode and the negative electrode lead can be performed by welding, for example.
- Negative electrode The negative electrode is produced, for example, by applying a negative electrode agent paste obtained by dispersing a negative electrode active material, a conductive agent and a binder in a suitable solvent to one or both sides of a negative electrode current collector and drying the paste. be able to. After drying, the negative electrode paste can be pressed.
- Examples of the negative electrode active material include carbonaceous materials, metal oxides, metal sulfides, metal nitrides, alloys, and light metals that can occlude and release lithium ions.
- Examples of the carbonaceous material that can occlude and release lithium ions include coke, carbon fiber, pyrolytic vapor phase carbonaceous material, graphite, resin fired body, mesophase pitch-based carbon fiber, or mesophase spherical carbon fired body. Can do. Among them, it is preferable to use mesophase pitch-based carbon fiber or mesophase spherical carbon graphitized at 2500 ° C. or higher because the electrode capacity can be increased.
- the metal oxide examples include titanium-containing metal composite oxides, for example, tin-based oxides such as SnB 0.4 P 0.6 O 3.1 and SnSiO 3, and silicon-based oxides such as SiO, such as WO 3. And tungsten-based oxides.
- titanium-containing metal composite oxides for example, tin-based oxides such as SnB 0.4 P 0.6 O 3.1 and SnSiO 3, and silicon-based oxides such as SiO, such as WO 3.
- tungsten-based oxides examples include titanium-containing metal composite oxides, for example, tin-based oxides such as SnB 0.4 P 0.6 O 3.1 and SnSiO 3, and silicon-based oxides such as SiO, such as WO 3. And tungsten-based oxides.
- titanium-containing metal composite oxides for example, tin-based oxides such as SnB 0.4 P 0.6 O 3.1 and SnSiO 3
- silicon-based oxides such as SiO, such as WO 3.
- titanium-containing metal composite oxides examples include titanium-based oxides that do not contain lithium during lithium oxide synthesis, lithium titanium oxides, and some of the constituent elements of lithium titanium oxides such as Nb, Mo, W, P, A lithium titanium composite oxide substituted with at least one kind of different element selected from the group consisting of V, Sn, Cu, Ni and Fe can be given.
- lithium titanium oxide examples include lithium titanate having a spinel structure (for example, Li 4 + x Ti 5 O 12 (x can be changed within a range of 0 ⁇ x ⁇ 3 by charge / discharge)), bronze Titanium oxide having a structure (B) or anatase structure (for example, Li x TiO 2 (0 ⁇ x ⁇ 1), composition before charging is TiO 2 ), ramsteride type lithium titanate (for example, Li 2 + y Ti 3 O 7 ( y can be changed within a range of 0 ⁇ y ⁇ 3 by charging / discharging), and niobium titanium oxide (for example, Li x NbaTiO 7 (0 ⁇ x, more preferably 0 ⁇ x ⁇ 1) 1 ⁇ a ⁇ 4)).
- a spinel structure for example, Li 4 + x Ti 5 O 12 (x can be changed within a range of 0 ⁇ x ⁇ 3 by charge / discharge)
- titanium-based oxide examples include metal composite oxides containing TiO 2 , Ti, and at least one element selected from the group consisting of P, V, Sn, Cu, Ni, Co, and Fe.
- TiO 2 is preferably anatase type and low crystalline having a heat treatment temperature of 300 to 500 ° C.
- the metal composite oxide containing Ti and at least one element selected from the group consisting of P, V, Sn, Cu, Ni, Co, and Fe include TiO 2 —P 2 O 5 , TiO 2.
- the metal composite oxide preferably has a microstructure in which a crystal phase and an amorphous phase coexist or exist alone. With such a microstructure, the cycle performance can be greatly improved.
- a lithium titanium oxide, a metal composite oxide containing at least one element selected from the group consisting of Ti and P, V, Sn, Cu, Ni, Co, and Fe is preferable.
- metal sulfide examples include lithium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), iron sulfide (FeS, FeS 2 , Li x FeS 2 (where 0 ⁇ x ⁇ 1)).
- metal sulfide examples include lithium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), iron sulfide (FeS, FeS 2 , Li x FeS 2 (where 0 ⁇ x ⁇ 1)).
- metal sulfide examples include lithium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), iron sulfide (FeS, FeS 2 , Li x FeS 2 (where 0 ⁇ x ⁇ 1)).
- lithium cobalt nitride Li x Co y N (where 0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 0.5)
- lithium titanate having a spinel structure is desirable to use as the negative electrode active material.
- a carbon material can be used as the conductive agent.
- the carbon material include acetylene black, carbon black, coke, carbon fiber, and graphite.
- binder for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), or the like is used.
- PTFE polytetrafluoroethylene
- PVdF polyvinylidene fluoride
- EPDM ethylene-propylene-diene copolymer
- SBR styrene-butadiene rubber
- CMC carboxymethylcellulose
- the negative electrode current collector various metal foils and the like can be used depending on the negative electrode potential.
- examples thereof include aluminum foil, aluminum alloy foil, stainless steel foil, titanium foil, copper foil, and nickel foil.
- the thickness of the foil at this time is preferably 8 ⁇ m or more and 25 ⁇ m or less.
- the negative electrode potential can be nobler than 0.3 V with respect to metallic lithium, for example, when lithium titanium oxide is used as the negative electrode active material, the use of aluminum foil or aluminum alloy foil reduces the battery weight. Is preferable.
- the average crystal grain size of the aluminum foil and the aluminum alloy foil is preferably 50 ⁇ m or less.
- the aluminum foil or aluminum alloy foil having an average crystal particle size range of 50 ⁇ m or less is affected by many factors such as material composition, impurities, processing conditions, heat treatment history and annealing conditions, and the crystal The particle diameter (diameter) is adjusted by combining the above factors in the production process.
- the thickness of the aluminum foil and the aluminum alloy foil is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
- the purity of the aluminum foil is preferably 99% or more.
- As the aluminum alloy an alloy containing at least one element such as magnesium, zinc, or silicon is preferable.
- the content of transition metals such as iron, copper, nickel and chromium is preferably 1% or less. In the case of in-vehicle use, it is particularly preferable to use an aluminum alloy foil.
- the mixing ratio of the negative electrode active material, the conductive agent and the binder should be in the range of 80 to 95% by weight of the negative electrode active material, 3 to 20% by weight of the conductive agent, and 1.5 to 7% by weight of the binder. preferable.
- Positive electrode The positive electrode is produced, for example, by applying a positive electrode agent paste obtained by dispersing a positive electrode active material, a conductive agent, and a binder in a suitable solvent to one or both sides of a positive electrode current collector and drying it. be able to. After drying, the positive electrode paste can be pressed.
- a positive electrode agent paste obtained by dispersing a positive electrode active material, a conductive agent, and a binder in a suitable solvent to one or both sides of a positive electrode current collector and drying it. be able to. After drying, the positive electrode paste can be pressed.
- the positive electrode active material examples include various oxides and sulfides.
- LiMn y Co 1-y O 2 (where 0 ⁇ y ⁇ 1)
- spinel type lithium manganese nickel composite oxide (Li x Mn 2-y Ni y O 4 (where 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ In a)
- lithium phosphates having an olivine structure Li x FePO 4, Li x Fe 1-y Mn y PO 4, Li x MnPO 4, Li x Mn 1-y Fe y PO 4, Li x CoPO 4 (Where 0 ⁇ x ⁇ 1.2 and 0 ⁇ y ⁇ 1)
- iron sulfate Fe 2 (SO 4 ) 3
- vanadium oxide eg, V 2 O 5
- examples of the positive electrode active material include conductive polymer materials such as polyaniline and polypyrrole, disulfide polymer materials, organic materials such as sulfur (S) and carbon fluoride, and inorganic materials.
- More preferable positive electrode active materials are spinel-type manganese lithium (Li x Mn 2 O 4 (where 0 ⁇ x ⁇ 1.1)) and olivine-type lithium iron phosphate (Li x FePO 4 ) having high thermal stability.
- olivine type lithium manganese phosphate Li x MnPO 4 (where 0 ⁇ x ⁇ 1)
- olivine type lithium manganese iron phosphate Li x Mn 1-y Fe y PO 4 (where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.5)).
- acetylene black, carbon black, artificial graphite, natural graphite, conductive polymer, or the like can be used as the conductive agent.
- binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), modified PVdF obtained by substituting at least one of hydrogen or fluorine of PVdF with another substituent, and vinylidene fluoride-6 fluoride.
- PTFE polytetrafluoroethylene
- PVdF polyvinylidene fluoride
- modified PVdF obtained by substituting at least one of hydrogen or fluorine of PVdF with another substituent
- vinylidene fluoride-6 fluoride vinylidene fluoride-6 fluoride.
- a copolymer of propylene fluoride, a terpolymer of polyvinylidene fluoride-tetrafluoroethylene-6propylene fluoride, or the like can be used.
- NMP N-methyl-2-pyrrolidone
- DMF dimethylformamide
- Examples of the positive electrode current collector include aluminum foil, aluminum alloy foil, stainless steel foil, and titanium foil having a thickness of 8 to 25 ⁇ m.
- the positive electrode current collector is preferably an aluminum foil or an aluminum alloy foil.
- the average crystal grain size of the aluminum foil or aluminum alloy foil is preferably 50 ⁇ m or less. More preferably, the average crystal grain size of the aluminum foil or aluminum alloy foil is 30 ⁇ m or less, and more preferably 5 ⁇ m or less.
- the strength of the aluminum foil or the aluminum alloy foil can be dramatically increased, the positive electrode can be densified with a high press pressure, and the battery capacity can be increased. Can be increased.
- Aluminum foil or aluminum alloy foil having an average crystal grain size in the range of 50 ⁇ m or less is affected by a number of factors such as material structure, impurities, processing conditions, heat treatment history, and annealing conditions, and the crystal grain size is It is adjusted by combining the above factors in the manufacturing process.
- the thickness of the aluminum foil and the aluminum alloy foil is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
- the purity of the aluminum foil is preferably 99% or more.
- As the aluminum alloy an alloy containing elements such as magnesium, zinc and silicon is preferable.
- the content of transition metals such as iron, copper, nickel and chromium is preferably 1% or less.
- the mixing ratio of the positive electrode active material, the conductive agent and the binder should be in the range of 80 to 95% by weight of the positive electrode active material, 3 to 20% by weight of the conductive agent, and 1.5 to 7% by weight of the binder. preferable.
- a porous separator can be used as the separator.
- the porous separator include a porous film containing polyethylene, polypropylene, cellulose, or polyvinylidene fluoride (PVdF), and a synthetic resin nonwoven fabric.
- PVdF polyvinylidene fluoride
- porous films made of polyethylene or polypropylene, or both are easy to add a shutdown function that closes the pores and significantly attenuates the charge / discharge current when the battery temperature rises. This is preferable because the property can be improved. From the viewpoint of cost reduction, it is preferable to use a cellulose separator.
- Non-aqueous electrolytes include LiBF 4 , LiPF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , Li (CF 3 SO 2 ) Examples thereof include organic electrolytes in which one or more lithium salts selected from 3 C, LiB [(OCO) 2 ] 2 and the like are dissolved in an organic solvent at a concentration in the range of 0.5 to 2 mol / L.
- organic solvents examples include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), chain carbonates such as diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC), and dimethoxy.
- Chain ethers such as ethane (DME) and diethoxyethane (DEE), cyclic ethers such as tetrahydrofuran (THF) and dioxolane (DOX), ⁇ -butyrolactone (GBL), acetonitrile (AN), sulfolane (SL), etc. It is preferable to use a single solvent or a mixed solvent.
- a room temperature molten salt (ionic melt) containing lithium ions can be used as the non-aqueous electrolyte.
- a secondary battery having a wide operating temperature can be obtained by selecting an ionic melt composed of lithium ions, an organic cation and an anion, which is liquid at 100 ° C. or less, preferably at room temperature or less.
- the thickness of the stainless steel member that can be used as the case is desirably 0.2 mm or less.
- the stainless steel member is composed of a composite film material in which a metal foil made of stainless steel and a rigid organic resin film are laminated in this order on a heat-fusible resin film (thermoplastic resin film) located in the innermost layer. It is possible.
- heat-fusible resin film for example, a polyethylene (PE) film, a polypropylene (PP) film, a polypropylene-polyethylene copolymer film, an ionomer film, an ethylene vinyl acetate (EVA) film, or the like can be used.
- a polyethylene terephthalate (PET) film, a nylon film, etc. can be used, for example.
- the case may be composed of a case main body having a concave portion that can be a main portion for accommodating the electrode group, and an outer portion outside the concave portion, and a lid.
- the case main body and the lid may be an integrated member that is seamless and continuous.
- Electrode lead As the electrode lead that can be electrically connected to the positive electrode, that is, the positive electrode lead, for example, aluminum, titanium, an alloy based on them, stainless steel, or the like can be used.
- the negative electrode lead that can be electrically connected to the negative electrode that is, the negative electrode lead, for example, nickel, copper and alloys based on them can be used.
- the negative electrode potential is nobler than 1 V with respect to metallic lithium, for example, when lithium titanate is used as the negative electrode active material, aluminum or an aluminum alloy can be used as the negative electrode lead material. In this case, it is preferable to use aluminum or an aluminum alloy for both the positive electrode lead and the negative electrode lead because the light weight and the electric resistance can be kept small.
- the positive electrode lead and the negative electrode lead are not much higher than the strength of the positive electrode current collector or the negative electrode current collector connected to the positive electrode lead because stress concentration at the connection portion is reduced.
- ultrasonic welding which is one of the preferred methods, is applied as means for connecting to the current collector, stronger welding can be easily performed when the Young's modulus of the positive electrode lead or the negative electrode lead is smaller.
- annealed pure aluminum JIS 1000 series is preferable as a material for the positive electrode lead or the negative electrode lead.
- the thickness of the positive electrode lead is desirably 0.1 to 1 mm, and a more preferable range is 0.2 to 0.5 mm.
- the thickness of the negative electrode lead is desirably 0.1 to 1 mm, and a more preferable range is 0.2 to 0.5 mm.
- the folded bipolar electrode 11 is housed in the exterior member 61.
- the electrode body 2 of the bipolar electrode 1 is used to form a laminate 2X of the electrode body 2 laminated in three layers (electrode bodies 2A to 2C), and the laminate 2X of the electrode body 2 and the negative electrode
- the electrode laminate 6 was formed by integrally laminating the member 2t1 and the positive electrode member 2t2. And this electrode laminated body 6 divides one plate body into a plurality of parts with a predetermined length in one direction, and sequentially folds the divided parts 8 alternately and folds them in a zigzag shape, 1, the zigzag bipolar electrode 11 shown in FIG. 2 is formed. Therefore, by folding the bipolar electrode 11 in a zigzag manner, the energy density can be improved with a small volume.
- FIG. 8 shows a first modification of the nonaqueous electrolyte battery 60 of the first embodiment.
- the bipolar electrode 11 is folded in a zigzag manner as shown in the fifth embodiment, the center point position O of the folded portion 12 on one side of the folded portion 12 adjacent to the overlapping direction of the folded portion 12 is The portions are bent in a state where the portions are alternately shifted in the direction orthogonal to the overlapping direction.
- the current collection efficiency of the bipolar batteries according to Example 5 (see FIG. 9) and Example 6 (see FIG. 10) was measured. The measurement was performed by reading the resistance value when a current of 50 mA, 100 mA, and 500 mA was passed. The result is shown in FIG. In FIG. 12, the measurement value A is a measurement result when the current collecting tab is one place, and the measurement value B is a measurement result when the current collecting tab is five places. As is clear from FIG. 12, the resistance was reduced by about half by increasing the number of current collecting tabs to five compared to the case where the number of current collecting tabs was only one.
- Example 2 the constant current charge / discharge test in Example 2 and Comparative Example 2 was performed.
- the average operating voltage was calculated from the test results, and the obtained values are shown in Table 1.
- the bipolar battery in which the positive electrode active material layer is formed on one plate surface of the current collector and the negative electrode active material is formed on the other plate surface is intended to increase the energy density and reduce the resistance.
- a bipolar battery, a method of manufacturing the same, and a battery pack can be provided.
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Abstract
Description
図1乃至図7は、第1の実施の形態を示す。図1は、第1の実施形態に係る一例の非水電解質電池60の概略断面図である。図1に示す非水電解質電池60は、ほぼ箱形の外装部材61と、この外装部材61内に収納されたつづら折り状のバイポーラ電極11とを有する。外装部材61は、例えば2枚の樹脂フィルムの間に金属層を介在したラミネートフィルムからなる。図2は、バイポーラ電極11の概略構成を示す斜視図である。
図3は、バイポーラ電極1の電極本体2の基本構造を示す。図3に示すようにバイポーラ電極1の電極本体2は、集電体3と、集電体3の一面に形成された正極活物質層4と、集電体3の他面に形成された負極活物質層5とを有する。集電体3の素材にはアルミニウムを用い、1辺が例えば5cmの正方形に成形した。正極活物質層4にはリン酸マンガンリチウム(以下LMP)、負極活物質層5にはチタン酸リチウム(以下LTO)を用いた。正極活物質層4は、リチウムを吸蔵及び放出可能である。負極活物質層5は、1.5V付近に反応電位が存在する。LMPもしくはLTOと導電助剤、粘結材をそれぞれ電極本体2の総重量に対してカーボンを5wt%、ポリフッ化ビニリデンを10wt%混合した。これらの混合物を成形することで、実施例1に係るバイポーラ電極1を作製した。
図4に示すように実施例1に記載のバイポーラ電極1の電極本体2を用いて3層(電極本体2A~2C)に積層した電極本体2の積層体2Xを形成する。この積層体2Xの各電極本体2A~2C間にはそれぞれ電解質層7があり、電極本体2A~2C同士が触れないようにする。さらに、図4中で、最上段の位置の電極本体2Aの上側には負極部材2t1が電解質層7を介して積層されている。図4中で、最下段の位置の電極本体2Cの下側には正極部材2t2が電解質層7を介して積層されている。ここで、負極部材2t1は、集電体3の下面側に負極活物質層5のみが形成されている。正極部材2t2は、集電体3の上面側に正極活物質層4のみが形成されている。これらの電極本体2の積層体2Xと、負極部材2t1と、正極部材2t2とが一体的に積層されて電極積層体6を形成し、バイポーラ電池を作製した。これにより、実施例2に係るバイポーラ電池を得た。
集電体3の1辺(長辺)を例えば45cmとし、もう1辺(短辺)を例えば5cmに成形した。得られた長方形の板状の集電体3を用いた以外は、実施例1と同様にバイポーラ電極1を作製した。すなわち、長方形の板状の集電体3の一方の板面に正極活物質層4を形成するとともに、同他方の板面に負極活物質層5を形成している。
実施例3に記載のバイポーラ電極1の電極本体2を3層(電極本体2A~2C)に積層した電極本体2の積層体2Xと、負極部材2t1と、正極部材2t2とが一体的に積層された長方形の板状の電極積層体6を形成する。そして、実施例2と同様に作製することで、実施例4のバイポーラ電池を得た。さらに、この長方形の板状の電極積層体6をつづら折り状に折り畳んで重ねて実施例4に係るつづら折りバイポーラ電極11(図2参照)を得た。このとき、図2に示すように電極積層体6は、1つの板体を一方向に所定の長さで複数に区分けし、各区分け部分8間を順次、互い違いにそれぞれ折り曲げてつづら折り状に折り畳んで重ねてある。各区分け部分8は、例えば、5cm毎に順次、互い違いにそれぞれ折り返すようにつづら折りにすることでバイポーラ電極11が形成されている。なお、隣接する区分け部分8間の折り返し部分を折り返し部12と称する。
実施例4に記載のつづら折りバイポーラ電極11を作製するとき、各区分け部分8の折り返し部12までの長さを図8中の下から5cm、6cm、5cm、4cm、5cm、6cm、5cm、5cmの順につづら折りにした以外は、実施例4と同様に図8に示すバイポーラ電極11を作製した。これにより、図8に示すようにバイポーラ電極11は、つづら折りにするとき、区分け部分8の左右の両端に交互に折り返し部12が形成される。そして、区分け部分8の一端側の折り返し部12の中心点位置Oは、折り返し部12の重ね合わせ方向に対して隣接する部分が重ね合わせ方向と直交する方向に交互にずらした状態で折り曲げてある。ここでは、図9に示すように一端側の折り返し部12の1つに1つの正極用の集電用タブ13aが形成されている。他端側の折り返し部12の1つに1つの負極用の集電用タブ13bとが設けられている。
実施例5に記載のつづら折りバイポーラ電極11において、図10に示すように各折り返し地点に集電用タブを正負極の各5ヶ所、合計10ヶ所に溶接して設置した。図10中で、14aは、正極の集電用タブ、14bは、負極の集電用タブである。これ以外は、実施例5と同様につづら折りバイポーラ電極11を作製した。
負極は、例えば、負極活物質、導電剤及び結着剤を適当な溶媒に分散させて得られる負極剤ペーストを、負極集電体の片側又は両面に塗布し、これを乾燥させることにより作製することができる。乾燥後、負極剤ペーストを、プレスをすることもできる。
d=2(S/π)1/2 (A)
平均結晶粒子径の範囲が50μm以下の範囲にあるアルミニウム箔又はアルミニウム合金箔は、材料組成、不純物、加工条件、熱処理履歴ならび焼なましの加熱条件など多くの因子に複雑に影響され、前記結晶粒子径(直径)は、製造工程の中で、前記諸因子を組み合わせて調整される。
正極は、例えば、正極活物質、導電剤及び結着剤を適当な溶媒に分散させて得られる正極剤ペーストを、正極集電体の片側又は両面に塗布し、これを乾燥させることにより作製することができる。乾燥後、正極剤ペーストは、プレスを行うこともできる。
セパレータとしては、例えば、多孔質セパレータを用いることができる。多孔質セパレータとしては、例えば、ポリエチレン、ポリプロピレン、セルロース、又はポリフッ化ビニリデン(PVdF)を含む多孔質フィルム、合成樹脂製不織布等を挙げることができる。中でも、ポリエチレンか、あるいはポリプロピレン、又は両者からなる多孔質フィルムは、電池温度が上昇した場合に細孔を閉塞して充放電電流を大幅に減衰させるシャットダウン機能を付加しやすく、二次電池の安全性を向上できるため、好ましい。低コスト化の観点からは、セルロース系のセパレータを用いることが好ましい。
非水電解質としては、LiBF4、LiPF6、LiAsF6、LiClO4、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、Li(CF3SO2)3C、LiB[(OCO)2]2などから選ばれる一種以上のリチウム塩を0.5~2mol/Lの範囲内にある濃度で有機溶媒に溶解した有機電解液が挙げられる。
ケースとして使用され得るステンレス部材の厚さは、0.2mm以下にすることが望ましい。例えば、ステンレス部材は、最内層に位置する熱融着性樹脂フィルム(熱可塑性樹脂フィルム)の上にステンレスからなる金属箔及び剛性を有する有機樹脂フィルムをこの順序で積層した複合フィルム材から構成することが可能である。
正極に電気的に接続され得る電極リード、すなわち正極リードとしては、例えばアルミニウム、チタン及びそれらをもとにした合金、ステンレスなどを用いることができる。
図8は、第1の実施の形態の非水電解質電池60の第1の変形例を示す。本変形例は、実施例5で示したようにバイポーラ電極11を、つづら折りにするとき、片側の折り返し部12の中心点位置Oが折り返し部12の重ね合わせ方向に対して隣接する折り返し部12の部分が重ね合わせ方向と直交する方向に交互にずらした状態で折り曲げたものである。
図10および図11は、第1実施形態の非水電解質電池60の第2の変形例を示す。本変形例は、図10に示すようにバイポーラ電極11を、つづら折りにするとき、折り返し部12毎に集電タブ(正極の集電用タブ14aおよび負極の集電用タブ14b)を取り付ける構成にしたものである。
図13Aに示すように集電体21の両面に正極活物質層22を形成した。また、図13Bに示すように集電体21の両面に負極活物質層23を形成した。これにより、比較例1に係る第1電極24と第2電極25とを得た。
図13Cは、比較例1に記載の第1電極24と第2電極25とを用いて交互に5層に積層し、積層型電池26を作製した。電極間には電解質層27があり、電極同士が触れないようにする。これにより、比較例2に係る積層型電池26を得た。
Claims (8)
- 集電体と、前記集電体の一面に形成された正極活物質層と、前記集電体の他面に形成された負極活物質層とを有するバイポーラ電極と、
非水電解質と、を具備し、
前記バイポーラ電極は、一方向に所定の長さで複数に区分けし、各区分け部分間を順次、互い違いにそれぞれ折り曲げて折り畳んで重ねてある非水電解質電池。 - 前記負極活物質層は、1.5V付近に反応電位が存在する請求項1に記載の非水電解質電池。
- 前記集電体は、アルミニウムを用いている請求項1に記載の非水電解質電池。
- 前記正極活物質層は、リチウムを吸蔵及び放出可能であり、
前記負極活物質と、
前記正極活物質層と、
非水電解質と、を含むことを特徴とする請求項2に記載の非水電解質電池。 - 前記バイポーラ電極を複数積層させた積層体を設け、
前記積層体は、前記バイポーラ電極を一方向に所定の長さで複数に区分けし、各区分け部分間を順次、互い違いにそれぞれ折り曲げて折り畳んで重ねてある請求項1に記載の非水電解質電池。 - 前記バイポーラ電極は、片側の折り返し部の中心点位置が前記折り返し部の重ね合わせ方向に対して隣接する部分が前記重ね合わせ方向と直交する方向に交互にずらした状態で折り曲げてある請求項5に記載の非水電解質電池。
- 前記バイポーラ電極は、前記折り返し部毎に集電タブを取り付けてある請求項6に記載の非水電解質電池。
- 請求項1または5のいずれかに記載の非水電解質電池と、
前記非水電解質電池を収容する外装部材と、
を有する非水電解質電池の電池パック。
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