US20120321926A1 - Processing device of nonaqueous electrolyte secondary battery and manufacturing method thereof - Google Patents

Processing device of nonaqueous electrolyte secondary battery and manufacturing method thereof Download PDF

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Publication number
US20120321926A1
US20120321926A1 US13/133,428 US201013133428A US2012321926A1 US 20120321926 A1 US20120321926 A1 US 20120321926A1 US 201013133428 A US201013133428 A US 201013133428A US 2012321926 A1 US2012321926 A1 US 2012321926A1
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battery
nonaqueous electrolyte
electrolyte secondary
secondary battery
foreign bodies
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English (en)
Inventor
Katsuyuki Hojo
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Tongji University
Toyota Motor Corp
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Tongji University
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Assigned to TOYOTA JIDOSHA KABUSHIKI KAISHA reassignment TOYOTA JIDOSHA KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOJO, KATSUYUKI
Publication of US20120321926A1 publication Critical patent/US20120321926A1/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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0468—Compression means for stacks of electrodes and separators
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0481—Compression means other than compression means for stacks of electrodes and separators
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • 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
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the present invention relates to a processing device for a nonaqueous electrolyte secondary battery and a manufacturing method thereof and, more particularly, to a processing device before initial charging and a manufacturing method including a pre-initial charging process.
  • nonaqueous electrolyte secondary batteries free from internal short-circuits, voltage drop defects, and the like are desirable, with some attention focusing on prevention of the immixing of metallic foreign bodies during the process of manufacturing such a nonaqueous electrolyte secondary battery has been pointed out.
  • immixed metallic foreign bodies may melt and be disposed within a battery in such a manner as to penetrate a separator and cause a short-circuit has been noted.
  • Patent Document 1 discloses, as a method for testing a lithium ion secondary battery, which is a nonaqueous electrolyte secondary battery in which reliable and quick discovery of defective batteries, a method in which a lithium ion battery is held in an environment in which the temperature is 45° C. or hotter for ten or more days, or 60° C. to 70° C. for four or more days, before detection of a voltage drop, and presence of electrically conductive foreign bodies in the lithium ion battery is determined upon detection of a voltage drop larger than a predetermined voltage drop reference.
  • Patent Document 2 discloses a method for suppressing occurrence of minute short-circuiting between a cathode and an anode by initially charging a lithium ion secondary battery which is a nonaqueous electrolyte secondary battery to 0.01% to 0.1% of the battery capacity to thereby set the anode potential to 1.5 v or larger under the Li/Li + reference and the cathode potential to 3.5 v or larger under the Li/Li + reference, and then allowing the battery to stand for one to 48 hours.
  • a lithium ion secondary battery which is a nonaqueous electrolyte secondary battery
  • Patent Document 1 Japanese Patent Laid-open Publication No. 2005-158643
  • Patent Document 2 Japanese Patent Laid-open Publication No. 2005-243537
  • Patent Document 1 it is necessary to leave a lithium ion secondary battery alone in a heating environment for four to ten days, which problematically increases manufacturing costs.
  • Patent Document 2 a charging device is necessary to charge a battery to 0.01% to 0.1% of the battery capacity, which also problematically increases manufacturing costs. In view of these problems, a more efficient selection method has been desired.
  • An object of the present invention is to provide a processing device for a nonaqueous electrolyte secondary battery capable of melting and diffusing metallic foreign bodies immixed in the nonaqueous electrolyte secondary battery before initially charging the battery, and to provide a method of manufacturing a nonaqueous electrolyte secondary battery.
  • a processing device for a nonaqueous electrolyte secondary battery is a processing device for a nonaqueous electrolyte secondary battery having electrodes accommodated, together with nonaqueous electrolyte, in a battery case, the electrodes including a cathode plate and an anode plate arranged with a separator in-between, for melting and diffusing metallic foreign bodies immixed in the electrodes, the processing device comprising a space reducing unit for reducing a space present in the electrodes being uncharged, to thereby place the nonaqueous electrolyte secondary battery in a space-reduced state, and a holding unit for holding a cathode potential at a melting potential of the metallic foreign bodies for a predetermined period of time in the space-reduced state, the melting potential of the metallic foreign bodies being lower than a charge-discharge cathode potential for use in charging and discharging the nonaqueous electrolyte secondary battery.
  • the space reducing unit may be a battery fixing unit for fixing the battery case on an outer surface thereof by applying a predetermined surface pressure sufficient to bring the cathode plate into contact with the metallic foreign bodies.
  • the battery fixing unit may use a surface pressure between 0.1 MPa and 5.0 MPa as the predetermined surface pressure.
  • the battery fixing unit may further have a battery heating unit for heating the nonaqueous electrolyte secondary battery.
  • the holding unit may hold a cathode potential of the nonaqueous electrolyte secondary battery in an open-circuit state in a case where the metallic foreign bodies are assumed to be of iron.
  • a manufacturing method for a nonaqueous electrolyte secondary battery is a method for manufacturing a nonaqueous electrolyte secondary for melting and diffusing metallic foreign bodies immixed in a nonaqueous electrolyte secondary battery having electrodes accommodated, together with nonaqueous electrolyte, in a battery case, the electrodes including a cathode plate and an anode plate arranged with a separator in-between, the method comprising a space reducing step of reducing a space in the uncharged electrodes to thereby place the nonaqueous electrolyte secondary battery in a space-reduced state, and a holding step of holding a cathode potential at a melting potential of the metallic foreign bodies for a predetermined period of time in the space-reduced state, the melting potential of the metallic foreign bodies being lower than a charge-discharge cathode potential for use in charging and discharging the nonaqueous electrolyte secondary battery
  • the space reducing step may be a battery binding step of binding the battery case on an outer surface thereof by applying a predetermined surface pressure sufficient to bring the cathode plate into contact with the metallic foreign bodies.
  • the space reducing step may be a battery depressurizing step of reducing pressure in the battery case.
  • the space reducing step may be a battery heating step of heating the battery, based on a predetermined heating condition, after the battery binding step, and thereafter releasing the battery.
  • a cathode potential of the nonaqueous electrolyte secondary battery in an open-circuit state may be held in a case where the metallic foreign bodies are assumed to be of iron.
  • a processing device for a nonaqueous electrolyte secondary battery having the above described structure and a method for manufacturing a nonaqueous electrolyte secondary battery with an arrangement in which metallic foreign bodies are kept contacting the cathode plate having a potential equal to that at which the metallic foreign bodies melt, the metallic foreign bodies will melt and be diffused before initial charging. This can suppress occurrence of internal short-circuiting, voltage drop defects, and other problems which may result from the inmixing of metallic foreign bodies in a nonaqueous electrolyte secondary battery.
  • FIG. 1 is a diagram explaining a device for processing a nonaqueous electrolyte secondary battery in an embodiment according to the present invention
  • FIG. 2 is a diagram explaining a structure of a battery in an embodiment according to the present invention.
  • FIG. 3 is a diagram explaining a structure of electrodes in an embodiment according to the present invention.
  • FIG. 4 is a diagram explaining batteries fixed in the processing device according to an embodiment of the present invention.
  • FIG. 5 is a flowchart explaining a procedure of a method for manufacturing a nonaqueous electrolyte secondary battery in an embodiment according to the present invention
  • FIG. 6 is diagram explaining a result of observation of a cathode plate, an anode plate, and a separator in an example in an embodiment according to the present invention
  • FIG. 7 is a flowchart explaining a procedure of a method of manufacturing a nonaqueous electrolyte secondary battery when a space reducing step and a holding step are not performed in the embodiment according to the present invention
  • FIG. 8 is diagram explaining a result of observation of a cathode plate, an anode plate, and a separator in a comparative example in an embodiment according to the present invention.
  • FIG. 9 is a flowchart explaining a procedure of a method of manufacturing a nonaqueous electrolyte secondary battery in an embodiment according to the present invention, in which the space reducing step is a battery heating step;
  • FIG. 10 is a diagram explaining batteries placed in the processing device and further in a high temperature furnace in an embodiment according to the present invention.
  • FIG. 11 is a diagram explaining a structure of a heating function-equipped processing device in an embodiment according to the present invention.
  • FIG. 12 is a flowchart of a procedure of a method of manufacturing a nonaqueous electrolyte secondary battery in an embodiment according to the present invention, in which the cathode potential is adjusted and maintained;
  • FIG. 13 is a diagram explaining a structure of a power source device, processing device, and batteries in an embodiment according to the present invention.
  • FIG. 14 is a diagram explaining a structure in which surface pressure is applied to batteries, using a vacuum furnace in an embodiment according to the present invention.
  • FIG. 15 is a diagram explaining a structure in which surface pressure is applied to batteries, using a high pressure furnace in an embodiment according to the present invention.
  • a lithium ion secondary battery having a lithium nickel oxide cathode and a graphite anode is described as an object to be processed, a nonaqueous electrolyte secondary battery having a cathode and an anode made of any other appropriate material may be used.
  • a lithium ion secondary battery will be referred to simply as “a battery”.
  • a polyethylene separator is used instead of a polyethylene separator.
  • a polyolefin-based insulating porous film may be used instead.
  • a polyethylene film, a film made of laminated polyethylene and polypropylene or the like may be desirably used.
  • rolled-up electrodes including a cathode plate, an anode plate, and a separator will be described in the following, multi-plate stacked electrodes or the like may be used instead. Further, although flat electrodes will be described in the following, cylindrical electrodes or the like may be used instead.
  • nonaqueous electrolyte produced by mixing ethylene carbonate and diethyl carbonate, or nonaqueous solvent, at a volume ratio 4:6 and dissolving lithium hexafluorophosphate, or solute, with a density of 1.0 mol/L is used will be described in the following, any other appropriate nonaqueous solvent and solute may be used instead.
  • FIG. 1 is a diagram explaining a processing device 10 for a nonaqueous electrolyte secondary battery.
  • the XYZ axis shown in FIG. 1 is defined such that the x direction corresponds to the width direction of the processing device 10 , the y direction corresponds to the thickness thereof, and the z direction corresponds to the height direction thereof.
  • the processing device 10 is a device for holding one or more batteries 14 to be described in detail referring to FIG. 2 in a frame 11 , then applying constant surface pressure to the batteries 14 , using a pressing portion 13 , preferably, via a fixing element 12 , to thereby reduce the space d between the cathode plate 20 and the anode plate 22 to be described in detail referring to FIG.
  • the processing device 10 can apply surface pressure to one or more batteries 14 at the same time.
  • the processing device 10 comprises the frame 11 , the fixing element 12 , and the pressing portion 13 , with the fixing element 12 being omissible.
  • the frame 11 has a function of serving as an outer frame of the processing device 10 , and at least the fixing element 12 , the pressing portion 13 , and the battery 14 can be accommodated in the frame 11 .
  • At least one or more batteries 14 can be accommodated in the frame 11 , and the number of fixing elements 12 same as that of the batteries 14 accommodated are used. In the example below, it is assumed that five batteries 14 are accommodated.
  • a battery 14 is put onto a fixed side wall disposed on the shorter edge of the frame 11 , and thereafter the fixing element 12 is positioned on the battery 14 . Five batteries and five fixing elements 12 are alternately placed in this order. Thereafter, the pressing portion 13 is set in a position next to the fixing element 12 last placed.
  • the frame 11 can be made of, for example, aluminum alloy. Alternatively, a material such as stainless steel or the like which is unlikely to rust, can be used. In these cases, preferably, an insulating layer may be provided on the outermost surface of the frame 11 . Other materials available for the frame 11 may include polytetrafluoroethylene or the like.
  • the dimensions of the frame 11 can be determined in accordance with the shape and dimension of a battery 14 to be accommodated therein. If a battery 14 to be accommodated has a width 100 mm, thickness 20 mm, and height 150 mm, the dimensions of the frame 11 can be width 120 mm, thickness 200 mm, and height 170 mm.
  • the fixing element 12 has a function of binding the installed battery 14 , and may be of the same width and height as the battery 14 to be accommodated. While the fixing element 12 can be made using a flat panel of the same material as that of the frame 11 , desirably, fire-resistive heat insulating material may be used for the fixing element 12 . Preferably, an insulating layer may be provided on the outermost surface of the fixing element 12 , similar to the frame 11 , because the fixing element 12 is to contact a battery 14 .
  • the dimensions of the fixing element 12 may be set in accordance with the shape and dimension of a battery 14 to be accommodated. If the dimensions of the battery 14 to be accommodated are width 100 mm, thickness 20 mm, and height 150 mm, the fixing element 12 may be designed with dimensions of width 100 mm, thickness 10 mm, and height 150 mm.
  • the pressing portion 13 is a flat panel having, for example, four pressing pins coupled on one side thereof and with an external force applied to the other side of the flat panel can apply pressure to the fixing element 12 via the pressing pins.
  • Use of four pressing pins makes it possible to apply substantially constant pressure onto the fixing element 12 . That is, the pressing portion 13 has a function of applying substantially constant surface pressure to a surface having a larger area of the battery 14 by means of pressure applied to the fixing element 12 .
  • a screw mechanism or the like for moving the pressing portion 13 relative to the frame 11 can be used.
  • a screw mechanism comprises a fixing panel, a nut and a bolt, in which the nut and the bolt are fixed to the fixing panel with, when necessary, an elastic member or the like, such as a spring or rubber, interposed between the fixing panel and the nut, the fixing panel having a threaded hole formed thereon for receiving the bolt. Then, by turning the bolt around, the pressing portion 13 is pressed by the tip end of the bolt, whereby an external force is applied to the pressing portion 13 .
  • a surface pressure can be measured using a load cell attached to the pressing portion 13 .
  • another method may be used for the measurement, including use of a surface pressure measurement sheet provided between the battery 14 and the fixing element 12 .
  • the function of the screw mechanism which generates a predetermined surface pressure by turning the bolt corresponds to a space-reducing function or unit of the processing device 10 .
  • FIG. 2 is a diagram explaining a structure of the battery 40 .
  • a vehicle battery to be mounted on a vehicle is a battery assembly comprising two or more electric cells.
  • the electric cells constituting an assembled battery e.g., a lithium ion secondary battery having an average voltage being about 3.5 v is available, wherein the average voltage is a average of inter-electrode potential differences between a lithium nickel oxide cathode and a graphite anode in the plurality of electric cells constituting the battery assembly.
  • an electric cell of a lithium ion secondary battery is used as a battery 14 .
  • a battery 14 is placed in the processing device 10 , and subjected to a pre-initial charging processing.
  • a battery 14 comprises electrodes 18 and electrolyte (not shown) in a battery case 16 having a sealing valve 17 , a cathode terminal 21 , and an anode terminal 23 .
  • the battery case 16 is made of aluminum or made using an aluminum and resin-laminated sheet, or the like.
  • the battery case 16 has a sealing valve 17 on an upper portion thereof.
  • the sealing valve 17 is kept open when pouring electrolyte and then closed after the pouring.
  • the cathode terminal 21 is a terminal adapted to electrical connection to the cathode plate 20
  • the anode terminal 23 is a terminal adapted to electrical connection to the anode plate 22 .
  • FIG. 3 is a diagram explaining a structure of the electrodes 18 .
  • the electrodes 18 comprise a cathode plate 20 , an anode plate 22 , and a separator 24 .
  • the electrodes 18 are wound such that the separator 24 sandwiched by the cathode plate 20 and the anode plate 22 .
  • the battery 14 When the battery 14 is charged, lithium ions are discharged from the cathode plate 20 and lithium ions are absorbed by the anode plate 22 , causing the electrodes 18 to expand.
  • the battery 14 has the dimensions defined in consideration of change in thickness of the electrodes 18 due to the expansion.
  • An uncharged battery 14 before expansion leaves a small space “d” between the cathode plate 20 and anode plate 22 of the electrodes 18 .
  • FIG. 4 is a diagram explaining batteries 14 installed and fixed in the processing device 10 .
  • the battery 14 is accommodated in the frame 11 of the processing device 10 , and the fixing element 12 is provided on the side of the battery 14 where the pressing portion 13 is located. Thereafter, a predetermined surface pressure is applied to the battery 14 by the pressing portion 13 .
  • FIG. 5 is a flowchart explaining a procedure within a method of manufacturing a nonaqueous electrolyte secondary battery.
  • a battery 14 having electrodes 18 in the battery case 16 is provided; electrolyte is introduced and allowed to permeate through the electrodes 18 ; surface pressure is applied to the battery 14 ; and a space-reduced state with the space “d” reduced is maintained for a predetermined period of time; and thereafter the pre-initial charging process is terminated.
  • electrodes 18 such that the cathode plate 20 and the anode plate 22 sandwich the separator 24 are installed in the battery case 16 .
  • electrolyte is poured into the battery case 16 in which the electrodes 18 has been installed (S 12 ).
  • the sealing valve 17 provided on the battery case 16 is opened for the pouring procedure, and closed after pouring has been completed. After the pouring, the electrolyte may be allowed to permeate (S 14 ) by allowing the battery 14 to sit.
  • surface pressure is applied using the processing device 10 to eliminate the space “d” and ensure that, e.g., iron-based foreign bodies contact the cathode plate 20 , because it can be expected that any metallic foreign bodies 26 which are the iron-based foreign bodies, present near the cathode plate 20 , may not contact the cathode plate 20 when there exists in such the space “d”.
  • a surface pressure of between at least 0.1 MPa and 5.0 MPa, more preferably, between at least 0.1 MPa and 2.0 MPa is applied.
  • the applied pressure must be no less than 0.1 Mpa because a surface pressure of less than 0.1 MPa is too small to maintain a constant surface pressure, such that an inconstant surface pressure will be applied to the electrodes 18 . Meanwhile, because application of a too high surface pressure when a porous film is used for the separator may crush the pores of the separator, the upper limit of the surface pressure is defined such that the extent of porousness of the separator does not drop.
  • the space-reduced state is maintained for between at least one to 35 hours (S 18 ). While the holding time may differ depending on the nature, dimensions, and the like, of metallic foreign bodies 26 which can be removed by the time of initial charging, it can be understand based on the melting speed of the metallic foreign bodies 26 that such a state must be held for at least one hour. A longer holding time ensures reliable melting of metallic foreign bodies 26 . However, as the copper or the like constituting the anode charge collector which is a component of the electrodes 18 could melt at some potential, the holding time must be limited to, for example, 35 hours or shorter, that is, within a range which will not adversely affect the battery functionality.
  • the pre-initial charging process step is terminated (S 20 ).
  • the initial charging is applied after the holding step (S 18 ) because it has been confirmed through experimental observation that, because the melting potential of metallic foreign bodies 26 is lower than the charge/discharge cathode potential when the battery 14 has yet to be charged and remains in an open-circuit state, electrically conductive metallic foreign bodies 26 contacting the cathode plate 20 will gradually melt and be diffused, even if the battery 14 is not yet charged. In other words, so-called galvanic corrosion will occur, whereas such metallic foreign bodies 26 will not melt when not contacting the cathode plate 20 .
  • the electrically conductive iron-based foreign bodies are brought into reliable contact with the cathode plate 20 before initial charging with the cathode potential being equal to the melting potential of the iron-based foreign bodies, so that the iron-based foreign bodies melt and iron ions of the iron-based foreign bodies solvated in the electrolyte are diffused in the battery 14 before application of initial charging.
  • the above processing it is possible to suppress occurrence of internal short-circuiting of the battery 14 , voltage drop defects, and other disadvantages.
  • a battery 14 was prepared (S 10 ).
  • electrodes 18 wound with the cathode plate 20 and the anode plate 20 sandwiching the separator 18 were installed in the battery case 16 .
  • the sealing valve 17 of the battery case 16 having the electrodes 18 therein was opened, and the battery case was filled with electrolyte (S 12 ). After the pouring of the electrolyte, the sealing valve 17 was closed, and the electrolyte was allowed to permeate (S 14 ).
  • FIG. 6 is a diagram explaining results of observation of the cathode plate 20 , the anode plate 22 , and the separator 24 in the example.
  • disk-like iron-based foreign bodies having a diameter of 100 ⁇ m and thickness of 20 ⁇ m were placed in advance in the vicinity of the cathode plate 20 when performing the example, following the procedure shown in FIG. 5 .
  • the battery 14 was decomposed and structural components, namely, the cathode plate 20 , the anode plate 22 , and the separator 24 , were removed and observed with a microscope appropriate to the observation of metal.
  • FIG. 6A shows an observation of the cathode plate 20 , in which a trace where the disk-like iron-based foreign bodies were placed could be observed.
  • FIG. 6B shows an observation of a position on the separator 24 on the cathode plate 20 side, the position being opposed to the position where the iron-based foreign bodies were placed on the cathode plate 20 , in which the iron-based foreign bodies were observed diffused in a larger area, leaving a stain.
  • FIG. 6C shows an observation of a position on the separator 24 on the anode plate 22 side, the position being opposed to the position where the iron-based foreign bodies were placed on the cathode plate 20 , in which the iron-based foreign bodies were observed diffused in a larger area, leaving a stain.
  • FIG. 6A shows an observation of the cathode plate 20 , in which a trace where the disk-like iron-based foreign bodies were placed could be observed.
  • FIG. 6B shows an observation of a position on the separator 24 on the ca
  • 6D shows an observation of a position on the anode plate 22 , the position being opposed to the position where the iron-based foreign bodies were placed on the cathode plate 20 , in which the iron-based foreign bodies were observed diffused in a larger area, leaving a stain.
  • FIG. 7 is a flowchart explaining a procedure of a manufacturing method for a nonaqueous electrolyte secondary battery in which the battery fixing step (S 16 ) and the holding step (S 18 ), which correspond to the space reducing step, were not performed.
  • the comparative example was carried out following the procedure shown in FIG. 7 . Specifically, following a procedure similar to that shown in FIG. 5 , respective steps from preparation (S 10 ) to electrolyte permeation (S 14 ) were performed. Thereafter, without performing the battery fixing step (S 16 ) and the holding step (S 18 ), corresponding to the space reducing step, the pre-initial charging process was terminated (S 20 ).
  • FIG. 8 is a diagram explaining results of observation of the cathode plate 20 , the anode plate 22 , and the separator 24 in the comparative example. Similar to the example of the embodiment, in order to verify the effects of the comparative example, disk-like iron-based foreign bodies having a diameter of 100 ⁇ m and thickness of 20 ⁇ m were placed in advance in the vicinity of the cathode plate 20 , following the procedure shown in FIG. 7 . After initial charging, in order to verify the effects of the comparative example, the battery 14 was decomposed and structural components, namely, the cathode plate 20 , the anode plate 22 , and the separator 24 , were removed and observed with the above microscope.
  • FIG. 8A shows results of observation of the cathode plate 20 , in which a trace where the disk-like iron-based foreign bodies were placed could be observed.
  • FIG. 8B shows an observation of a position on the separator 24 on the cathode plate 20 side, the position being opposed to the position where the iron-based foreign bodies were placed on the cathode plate 20 , in which the iron-based foreign bodies were observed locally deposited, causing internal short-circuiting.
  • FIG. 8C shows an observation of a position on the separator 24 on the anode plate 22 side, the position being opposed to the position where the iron-based foreign bodies were placed on the cathode plate 20 , in which locally deposited iron-based foreign bodies were observed.
  • FIG. 8D shows an observation of a position on the anode plate 22 , the position being opposed to the position where the iron-based foreign bodies were placed on the cathode plate 20 , in which locally deposited iron-based foreign bodies were observed.
  • the battery 14 is fixed and held for a predetermined period of time.
  • the battery 14 may be heated while fixed, then released from being fixed, and maintained for a predetermined period of time.
  • the battery heating step corresponds to the space reducing step.
  • FIG. 9 is a flowchart explaining processes in a method of manufacturing a nonaqueous electrolyte secondary battery, in which the space reducing step is replaced by the battery heating step (S 17 a ). Specifically, respective steps until the battery fixing step (S 16 ) are performed, following a procedure similar to that shown in FIG. 5 . Then, the battery 14 is heated while fixed, using the structure shown in FIG. 10 or FIG. 11 until the temperature inside the battery 14 reaches 25° C. to 60° C. (S 17 a ). After the heating, the battery 14 is released (S 17 b ). Then, respective steps from the holding step (S 18 ) to the pre-initial charging process are performed, following a procedure similar to that shown in FIG. 5 .
  • FIGS. 10 and 11 are diagrams explaining devices having a function of heating the battery 14 . These devices can heat the fixed battery 14 so that the electrodes 18 are brought to and maintained in a closely contacting state, even after the battery 14 is released. With such configuration, a battery fixing device need only be used for a shorter period of time to maintain a reliable connection of the metallic foreign bodies 26 with the cathode plate 20 . This can enable further cost reductions.
  • FIG. 10 is a diagram showing batteries 14 placed in the processing device 10 within a high temperature furnace 38 .
  • the batteries 14 arranged in the processing device 10 are placed in the high temperature furnace 38 , which is then operated to heat the batteries 14 so that the temperature inside the batteries 14 increases to 25° C. to 60° C.
  • the upper limit of the temperature is set to 60° C. in order to suppress dissolution of electrolyte which is known to begin dissolving at about 70° C. or higher.
  • the electrodes 18 are maintained in a closely contacting state and remain so thereafter, even after the batteries 14 are released from being fixed.
  • FIG. 11 is a diagram explaining a structure of a heating function-equipped processing device 40 .
  • the heating function-equipped processing device 40 includes a heating function-equipped fixing element 42 and a heating control device 44 . That is, the fixing element 12 of the above described processing device 10 is replaced by the heating function-equipped fixing element 42 , and the heating control device 44 for controlling the heating function-equipped fixing element 42 is additionally provided.
  • the heating function-equipped fixing element 42 has a function of heating the battery 14 to the above described temperature of, for example, 25° C. to 60° C., while applying a surface pressure between at least 0.1 MPa and 5.0 MPa to the batteries 14 .
  • the heating control device 44 has a function of controlling the heat temperature of the heating function-equipped fixing element 42 .
  • stainless steel foreign bodies are known to be passivated at a potential lower than that required for foreign bodies made of iron. Therefore, if 18% of the mass of Cr is comprised of stainless steel foreign bodies, the cathode potential is adjusted to ⁇ 0.25 v to +0.25 v according to the Standard Hydrogen Electrode Reference (2.8 v to 3.2 v according to the Li/Li + Reference) and so held.
  • FIG. 12 is a flowchart explaining processes of a method of manufacturing a nonaqueous electrolyte secondary battery when the cathode potential is adjusted and so held.
  • respective steps up to the battery fixing step (S 16 ) are performed following a procedure similar to that shown in FIG. 5 , and thereafter the cathode potential is adjusted and maintained using a power source device 36 having the structure shown in FIG. 13 (S 19 ).
  • the state of holding corresponds to a state in which a surface pressure is maintained at a predetermined value and the cathode potential is kept at a potential which is lower than the charge/discharge cathode potential and at which metallic foreign bodies 26 melt.
  • a pre-initial charging process is terminated (S 20 ), similarly as in FIG. 5 .
  • FIG. 13 is a diagram explaining structures of the power source device 36 , the processing device 10 , and the battery 14 .
  • the power source device 36 can be connected to the cathode terminal 21 and the anode terminal 23 of the battery 14 , and has a function of adjusting and maintaining the cathode potential.
  • the power source device 36 has a function of adjusting and maintaining the cathode potential while the battery is kept fixed.
  • the cathode potential can be adjusted to ⁇ 0.25 v to +0.25 v according to the Standard Hydrogen Electrode Reference.
  • the battery voltage may be adjusted based on the relationship between the battery voltage and the desired cathode potential.
  • the holding time is set to between at least one hour and 35 hours for the reasons described above.
  • the battery fixing step is described as a step corresponding to the space reducing step, while the battery fixing step (S 16 ) is a step at which a surface pressure is externally applied to the battery 14 .
  • the pressure inside the battery 14 is reduced to thereby eliminate the space “d” in the electrodes 18 so that the metallic foreign bodies 26 contact the cathode plate 20 .
  • This procedure includes a battery depressurizing step instead of the battery fixing step (S 16 ) corresponding to the space reducing step in the flowchart shown in FIG. 5 . That is, respective steps until electrolyte permeation (S 14 ) are performed.
  • the battery 14 is depressurized using the structure shown in FIG. 14 or FIG. 15 , which are described below. Thereafter, respective steps from the holding step (S 18 ) to termination of the pre-initial charging process (S 20 ) are performed.
  • FIGS. 14 and 15 are diagrams explaining the operation and structure of a device having a function of applying a surface pressure to the electrodes 18 .
  • a surface pressure between at least 0.1 MPa and 5.0 MP may be applied to the battery 14 at the space reducing step (S 16 ).
  • the device shown in FIGS. 14 and 15 may be used instead of the processing device 10 .
  • FIG. 14 is a diagram explaining a structure for applying surface pressure to the battery 14 using a vacuum furnace 30 .
  • five (for example) batteries 14 are placed in the vacuum furnace 30 , and depressurized to between 10 kPa and 100 kPa, and surface pressure is externally applied to the batteries 14 .
  • the batteries 14 are placed in the vacuum furnace 30 while the sealing valve 17 kept open, and then depressurized. Then, the sealing valve 17 is closed while the batteries 14 remain depressurized, and the batteries 14 are removed from the vacuum furnace 30 .
  • an effect similar to that obtained with the configuration shown in FIG. 4 can be attained.
  • FIG. 15 is a diagram explaining a structure for applying surface pressure to the battery 14 using a high pressure furnace 34 . Because the pressure of the high pressure furnace 34 can be increased and maintained at a relatively high pressure, an effect similar to that described with reference to FIG. 14 can be produced using the high pressure furnace 34 .
  • a processing device for a nonaqueous electrolyte secondary battery and a manufacturing method thereof according to the present invention are useful for nonaqueous electrolyte secondary batteries and their manufacture because of their ability to melt and diffuse metallic foreign bodies immixed in the nonaqueous electrolyte secondary battery before performance of initial charging.
  • 10 processing device 11 frame, 12 fixing element, 13 pressing portion, 14 battery, 16 battery case, 17 sealing valve, 18 electrodes, 20 cathode plate, 21 cathode terminal, 22 anode plate, 23 anode terminal, 24 separator, 26 metallic foreign bodies, 30 vacuum furnace, 34 high pressure furnace, 36 power source device, 38 high temperature furnace, 40 heating function-equipped processing device, 42 heating function-equipped fixing element, 44 heating control device.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Mounting, Suspending (AREA)
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US9917331B2 (en) 2012-11-13 2018-03-13 Toyota Jidosha Kabushiki Kaisha Method for producing a secondary battery and the metal contaminant deactivation of the same
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JPWO2011111153A1 (ja) 2013-06-27
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CN102273001A (zh) 2011-12-07
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EP2546917B1 (en) 2018-04-25
US20190103628A1 (en) 2019-04-04

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