JPH09199175A - Manufacture of polymer electrolyte secondary cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remarkably reduce a cavity amount between a sheath member and an element cell stored therein. SOLUTION: In a method of manufacturing a polymer electrolyte secondary cell of structure storing a polymer electrolyte element cell in a sheath film having a thermomelting resin surface, a plurality of element cells 21 are set up with a desired space apart in the lengthwise direction of a film on the thermomelting resin surface of a first long scaled film 1, a thermomelting resin surface of a second long scaled film 2 is superposed so as to cover an upper surface of a plurality of the element cells 21. A guide plate 3 of thickness equal to or a little thicker than the element cell 21 is arranged on the second long scaled film 2 so as to be adjacent at least to a side wall along the lengthwise direction of the film of the element cell 21, two sheets of the long scaled films 1, 2 are made to pass through between a pair of heated elastic rolls 5a, 5b, two sheets of the long scaled films 1, 2 in the periphery of each element cell are pressure heated and thermally sealed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer electrolyte secondary battery provided with a solid polymer electrolyte layer.

[0002]

2. Description of the Related Art In recent years, with the development of electronic equipment, there has been a demand for the development of a secondary battery that is small, lightweight, has a high energy density, and can be repeatedly charged and discharged. As such a secondary battery, a lithium secondary battery including a negative electrode using lithium or a lithium alloy as an active material and a positive electrode using an oxide, sulfide, or selenide such as molybdenum, vanadium, titanium, or niobium as an active material is used. Secondary batteries are known. However, a secondary battery provided with a negative electrode using lithium or a lithium alloy as an active material has a problem that the charge / discharge cycle life is short because lithium dendrites are generated in the negative electrode when charge / discharge cycles are repeated.

[0003] For this reason, the negative electrode, for example coke, graphite, carbon fiber, resin fired body, a lithium ion, such as pyrolytic vapor carbon using a carbonaceous material for absorbing and releasing, electrolytes such as LiPF ₆ A non-aqueous solvent secondary battery using an electrolytic solution comprising a non-aqueous solvent such as ethylene carbonate and propylene carbonate has been proposed.
The non-aqueous solvent secondary battery can improve the negative electrode characteristics due to the precipitation of dendrite, and thus can improve the battery life and safety.

On the other hand, US Pat. No. 5,296,318 discloses a rechargeable lithium intercalation having a hybrid polymer electrolyte which has been made flexible by adding polymers to the cathode, anode and electrolyte layers. A battery, that is, a polymer electrolyte secondary battery is disclosed. Such a polymer electrolyte secondary battery includes a positive electrode in which a positive electrode layer containing an active material, a non-aqueous electrolytic solution, and a polymer holding the electrolytic solution is laminated on a current collector and a carbon capable of inserting and extracting lithium ions in the current collector. Structure in which a solid polymer electrolyte layer containing a non-aqueous electrolyte solution and a polymer holding this electrolyte solution is interposed between a negative electrode in which a negative electrode layer containing a porous material, a non-aqueous electrolyte solution and a polymer holding this electrolyte solution is laminated It has a structure in which the unit cell is included and the unit cell is housed in an exterior member.

By the way, in order to store the unit cell in the exterior member, conventionally, a flat unsealed bag having one side opened is prepared from a heat-fusible film such as polyethylene, and the unsealed bag is then prepared. It has been practiced to insert the unit cell therein, heat seal the opening, and store the unit cell in a sealed bag (exterior member). However, the polymer electrolyte secondary battery manufactured by such a method has a bag-shaped exterior member because the unit cell is inserted into the unsealed bag and sufficient deaeration is not performed in heat sealing the opening. There is a problem in that a high-capacity void is generated between the unit cells, and the non-aqueous electrolyte flows out from the unit cells, resulting in deterioration of the cell performance.

That is, in the polymer electrolyte secondary battery, since the positive electrode layer, the negative electrode layer and the solid polymer electrolyte layer constituting the unit cell repeatedly expand and contract during charging and discharging, the non-aqueous electrolyte solution retained therein is It becomes easy for the unit cell to seep into the exterior member. In particular, at least one of the positive electrode and negative electrode current collectors of the unit cell for supplying the unit cell of the non-aqueous electrolyte described later has a structure in which a non-aqueous electrolyte such as punched metal can flow. With this, the non-aqueous electrolytic solution in the unit cell easily leaks into the exterior member through the collector made of the punched metal during the charge / discharge. In a conventional polymer electrolyte secondary battery, a high-capacity void exists between the exterior member and the unit cell, and a positive electrode layer, a negative electrode layer, and a solid polymer electrolyte that constitute the unit cell during charge / discharge of the secondary battery. Since the layer has a poor effect of suppressing the expansion, the non-aqueous electrolytic solution seeps out from the unit cell. In addition, the exuded non-aqueous electrolyte solution accumulates in the voids, that is, the amount of the non-aqueous electrolyte solution in the unit cell decreases. As a result, there is a problem that the battery capacity is rapidly reduced due to repeated charging and discharging.

[0007]

DISCLOSURE OF THE INVENTION The present invention is intended to provide a method for producing a polymer electrolyte secondary battery capable of remarkably reducing the amount of void between the exterior member and the unit cell housed therein. To do.

The present invention is a method for producing a polymer electrolyte secondary battery capable of remarkably reducing the amount of void between an exterior member having a spacer on at least two parallel side faces and a unit cell housed therein. Is to provide.

[0009]

A polymer electrolyte secondary battery according to the present invention is a positive electrode in which a positive electrode layer containing a polymer holding an active material and a non-aqueous electrolyte is laminated on a current collector, and a lithium electrode on the current collector. A negative electrode in which a negative electrode layer containing a carbonaceous material that absorbs and releases ions is laminated, and a solid polymer electrolyte layer containing a polymer that holds a nonaqueous electrolytic solution interposed between the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode. In a method for producing a polymer electrolyte secondary battery having a structure in which a polymer electrolyte unit cell including the above is housed in an exterior member, a plurality of unit cells are provided on a heat-fusible resin surface of a first long film. In the vertical direction at a desired interval, a step of stacking the heat-fusible resin surface of the second long film so as to cover the plurality of upper surfaces of the unit cells, and a thickness on the second long film. Same as the unit cell Alternatively, a step of arranging a slightly thick guide plate so as to be adjacent to at least a side wall along the length direction of the film of each of the unit cells, and stacking the two long films on each other on the bottom surface of the guide plate, The two long films in which the plurality of unit cells are sandwiched between the guide plates are passed between a pair of heated heat-resistant elastic rolls, and the two long films around the unit cells are provided. And heat-pressing them to heat-seal the heat-sealing resin surfaces thereof.

Another polymer electrolyte secondary battery according to the present invention is a positive electrode in which a positive electrode layer containing a polymer holding an active material and a non-aqueous electrolyte is laminated on a current collector, and a lithium ion is absorbed and released in the current collector. A polymer having a negative electrode in which a negative electrode layer containing a carbonaceous material is laminated, and a solid polymer electrolyte layer containing a polymer that holds a nonaqueous electrolytic solution interposed between the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode. In a method for producing a polymer electrolyte secondary battery having a structure in which an electrolyte unit cell is housed in an exterior member, a plurality of unit cells are desired on the heat-fusible resin surface of a first long film in the length direction of the film. And a spacer made of a polymer resin having a thickness equal to or slightly thicker than the unit cells on the long film at least in the length direction of the film of each unit cell. And a step of placing the second long film so that the heat-fusible resin surface covers the plurality of unit cells and the upper surfaces of the spacers. Two long films sandwiching a spacer therebetween are passed between a pair of heated heat-resistant elastic rolls to heat the two long films around each of the unit cells with at least the spacer interposed therebetween. And a step of heat sealing.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for manufacturing a polymer electrolyte secondary battery according to the present invention will be described in detail with reference to FIGS. First, as shown in FIG. 1, a plurality of, for example, rectangular polymer electrolyte cells 21 are installed on the heat-fusible resin surface of the first long film 1 at desired intervals in the length direction of the film 1. To do. When installing each of the unit cells 21 on the first long film 1, it is preferable to temporarily fix it to the long film 1 with an adhesive. As shown in FIG. 2, the unit cell 21 has a structure in which a solid polymer electrolyte layer 24 is interposed between a positive electrode 22 and a negative electrode 23. The positive electrode 22 is composed of a positive electrode current collector 25 and a positive electrode layer 26 carried by the current collector 25. The negative electrode 23 is composed of a negative electrode current collector 27 and a negative electrode layer 28 carried by the current collector 27.

Next, as shown in FIG. 1, the heat-fusible resin surface of the second long film 2 is overlapped so as to cover the upper surfaces of the unit cells 21, and then the second long film 2 is covered. A frame-shaped guide plate 3 having a thickness equal to or slightly thicker than the unit cells 21 is arranged so as to be close to the peripheral side wall of each unit cell 21, and the two long sheets are provided on the bottom surface of the guide plate 3. Films 1 and 2 are stacked on top of each other. Subsequently, the plurality of unit cells 21 pass the two long films 1 and 2 sandwiched by the guide plate 3 between the heat-resistant elastic rolls 5a and 5b having the shafts 4a and 4b. The rubber rolls 5a and 5b have a length sufficiently longer than the width of the long films 1 and 2, and are heated by a desired heating source to, for example, the softening point of the heat-fusible resin or higher. As shown in FIG. 3, the two long films 1 and 2 are passed between the heated elastic rolls 5 a and 5 b, and the unit cell 21
When the guide plate 3 moves between the elastic rolls 5a and 5b, the elastic rolls 5a and 5b are deformed so as to wrap the unit cell 21 and the guide plate 3 and overlap each other on the bottom surface of the guide plate 3. In the two long films 1 and 2 thus cut, the long film 1 portion on the lower surface side receives heat from the elastic roll 5a on the lower side, and the long film 2 portion on the upper surface side is the elastic roll on the upper side. The heat-fusible resin surfaces are heat-sealed by receiving heat from 5b through the frame-shaped guide plate 3. As a result, the guide plate 3 is removed from the two long films 1 and 2 that have passed between the elastic rolls 5a and 5b, and the two long films 1 and 2 are positioned at the periphery of the guide plate 3. As shown in FIG. 4, the unit cell 21 and the unit cell 21 are accommodated by cutting along the cut portion, and the heat-fusible resin surface having the frame-shaped heat-sealing portion 6 located near the peripheral side wall A polymer electrolyte secondary battery 9 composed of an exterior member 8 formed of the two films 7a and 7b held therein is manufactured.

Next, the solid polymer electrolyte layer 24, the positive electrode current collector 25, the positive electrode layer 26, the negative electrode current collector 27 and the negative electrode layer 28 which constitute the unit cell 21, the long films 1, 2, the guide plate 3 and The elastic rolls 5a and 5b will be described.

1) Solid Polymer Electrolyte Layer 24 This polymer electrolyte layer 24 contains a non-aqueous electrolytic solution and a polymer that holds this electrolytic solution.

The non-aqueous electrolyte is prepared by dissolving an electrolyte in a non-aqueous solvent. As the non-aqueous solvent,
Ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DE
C), ethyl methyl carbonate (EMC), γ-butyrolactone (γ-BL), sulfolane, acetonitrile, 1,2-dimethoxyethane, 1,3-dimethoxypropane, dimethyl ether, tetrahydrofuran (TH
F), 2-methyltetrahydrofuran, etc. can be mentioned. The non-aqueous solvent may be used alone or in combination of two or more.

Examples of the electrolyte include lithium perchlorate (LiClO ₄ ) and lithium hexafluorophosphate (L
iPF _6), boric tetrafluoride lithium (LiBF _4), lithium hexafluoroarsenate (LiAsF _6), lithium trifluoromethanesulfonate (LiCF ₃ SO _3), bis (trifluoromethylsulfonyl) imide lithium [LiN
(CF ₃ SO ₃ ) ₂ ].

The amount of the electrolyte dissolved in the non-aqueous solvent is desirably 0.2 mol / l to 2 mol / l. As the polymer that holds the non-aqueous electrolyte, for example, a polyethylene oxide derivative, a polypropylene oxide derivative, a polymer containing the derivative, a copolymer of vinylidene fluoride (VdF) and hexafluoropropylene (HFP), or the like is used. You can In the solid electrolyte layer, such a polymer may be present in a form in which the molecules are crosslinked. In addition, in the copolymer, VdF contributes to the improvement of mechanical strength in the skeleton of the copolymer, and HFP is incorporated in the copolymer in an amorphous state to retain the non-aqueous electrolyte and lithium. It functions as an ion permeation part. The copolymerization ratio of the HFP depends on the method of synthesizing the copolymer, but is usually 2 at maximum.
It is around 0% by weight.

The solid electrolyte layer 24 can be produced, for example, by the method described below. (1) A polymer solution holding the non-aqueous electrolytic solution is prepared, and a plasticizer such as DBP (dibutyl phthalate) is added to the solution, and the film is formed and dried. A polymer electrolyte layer is produced by immersing the electrolyte solution in the polymer and holding the electrolyte solution in the polymer and by impregnating the electrolyte solution by replacing the plasticizer with the electrolyte solution.

(2) A solution of a polymer holding the non-aqueous electrolyte is prepared, a plasticizer such as DBP (dibutyl phthalate) is added to the solution, and a film is formed and dried. Is removed by extraction with a solvent such as ethanol and the like, and a non-aqueous electrolytic solution is impregnated into the polymer electrolyte layer.

(3) A polymer solution for holding the non-aqueous electrolyte is prepared, and the solution is formed into a film, dried, and then impregnated with the non-aqueous electrolyte to form a polymer electrolyte layer. In the above methods (1) and (2), the plasticizer is
It is added for the purpose of improving mechanical properties such as strength of the solid electrolyte layer and increasing the impregnation amount of the electrolytic solution to improve charge / discharge characteristics. After adding the plasticizer, a film is formed, and a non-aqueous electrolyte solution is impregnated into the polymer electrolyte layer so that the plasticizer and the non-aqueous electrolyte solution are replaced, so that the non-aqueous electrolyte solution is not limited to the polymer. Since the space occupied by the plasticizer can also be impregnated, the impregnation amount of the electrolytic solution can be increased.

In the production methods (1) to (3), the impregnation of the electrolytic solution (including the removal of the plasticizer in the case of adding the plasticizer) is performed after assembling the unit cell not impregnated with the electrolytic solution. Alternatively, the unit cell 21 may be housed in the exterior member 8 shown in FIG.

2) Positive Electrode Current Collector 25 The positive electrode current collector 25 may have a structure such as a punched metal made of aluminum through which a non-aqueous electrolyte can flow. In addition to the punched metal, an aluminum mesh, an aluminum expanded metal, or the like can be used as the positive electrode current collector having a structure in which the nonaqueous electrolytic solution can flow. Further, as the positive electrode current collector, an aluminum foil can be used in addition to the structure in which the non-aqueous electrolyte can flow.

3) Positive Electrode Layer 26 The positive electrode layer 26 contains an active material, a conductive material, a non-aqueous electrolytic solution, and a polymer holding the electrolytic solution.

As the active material, various oxides (for example, lithium manganese composite oxides such as LiMn ₂ O ₄ ,
Manganese dioxide, lithium-containing nickel oxide such as LiNiO ₂ , lithium-containing cobalt oxide such as LiCoO ₂ , lithium-containing nickel cobalt oxide, amorphous vanadium pentoxide containing lithium, etc.)
And chalcogen compounds (for example, titanium disulfide, molybdenum disulfide, and the like). Among them, it is preferable to use a lithium manganese composite oxide, a lithium-containing cobalt oxide, and a lithium-containing nickel oxide.

Examples of the conductive material include artificial graphite, carbon black (for example, acetylene black), nickel powder and the like. As the non-aqueous electrolyte and the polymer, the same ones as those described in the solid polymer electrolyte layer described above are used.

The positive electrode 22 can be manufactured, for example, by the method described below. (1) A solution of a polymer holding the non-aqueous electrolyte is prepared, and a plasticizer such as DBP (dibutyl phthalate), the active material and the conductive material are added to the solution, and then these are mixed to form a mixture. After forming the positive electrode layer by forming a film, the positive electrode layer and the current collector are bonded by, for example, thermocompression bonding. By impregnating the positive electrode layer with the electrolytic solution by substituting the electrolytic solution with the plasticizer in the positive electrode layer while holding the electrolytic solution in the polymer by immersing it in a non-aqueous electrolytic solution, or After removing the plasticizer in the positive electrode layer by extracting it with a solvent such as ethanol, the positive electrode layer is impregnated with a non-aqueous electrolytic solution to prepare a positive electrode.

(2) A solution of a polymer holding the non-aqueous electrolyte is prepared, and a plasticizer such as DBP (dibutyl phthalate), the active material and the conductive material are added to the solution, and then mixed. Then, the positive electrode coating material is prepared. The positive electrode coating material is applied to the current collector and then dried. By impregnating the positive electrode layer with the electrolytic solution by substituting the electrolytic solution with the plasticizer in the positive electrode layer while holding the electrolytic solution in the polymer by immersing it in a non-aqueous electrolytic solution, or After removing the plasticizer in the positive electrode layer by extracting it with a solvent such as ethanol, the positive electrode layer is impregnated with a non-aqueous electrolytic solution to prepare a positive electrode.

(3) A positive electrode layer is prepared by preparing a polymer solution holding the non-aqueous electrolyte solution, adding the active material and the conductive material to the solution, mixing these, and forming a film. After that, the positive electrode layer and the current collector are bonded to each other by, for example, thermocompression bonding and impregnated with the non-aqueous electrolytic solution to produce a positive electrode.

(4) A polymer solution holding the non-aqueous electrolyte is prepared, the active material and the conductive material are added to the solution, and then these are mixed to prepare a positive electrode coating material. The positive electrode coating material is applied to the current collector, dried, and then impregnated with a non-aqueous electrolyte to form a positive electrode.

In the above methods (1) and (2), a plasticizer is added for the purpose of improving mechanical properties such as strength of the solid electrolyte layer and increasing the amount of electrolyte impregnated to improve charge / discharge characteristics. It

In the methods (1) to (4), the impregnation of the electrolytic solution (including the removal of the plasticizer in the case of adding the plasticizer) may be performed after assembling the unit cell not impregnated with the electrolytic solution, or It may be after housing the unit cell 21 in the exterior member 8 shown in FIG.

4) Negative Electrode Current Collector 27 The negative electrode current collector 27 may have a structure such as a punched metal made of copper through which a non-aqueous electrolyte can flow. In addition to the punched metal, a copper mesh, a copper expanded metal, or the like can be used as the positive electrode current collector having a structure in which the nonaqueous electrolytic solution can flow. Further, as the negative electrode current collector, a copper foil may be used in addition to the one having a structure in which the nonaqueous electrolytic solution can flow.

5) Negative Electrode Layer 28 This negative electrode layer 28 contains a carbonaceous material which absorbs and releases lithium ions, a non-aqueous electrolytic solution, and a polymer which holds this electrolytic solution.

Examples of the carbonaceous material that absorbs and releases lithium ions include organic polymer compounds (eg, phenol resin, polyacrylonitrile, cellulose).
Examples of the carbonaceous material include a material obtained by firing a coke, a coke, a material obtained by firing a pitch, an artificial graphite, a natural graphite, and the like. Above all, it is preferable to use a carbonaceous material obtained by calcining the organic polymer compound at a temperature of 500 ° C. to 3000 ° C. in an inert gas atmosphere such as an argon gas or a nitrogen gas at normal pressure or reduced pressure. preferable.

As the non-aqueous electrolytic solution and the polymer, the same ones as those described for the solid polymer electrolyte layer are used. The negative electrode layer 28 is permitted to contain artificial graphite, natural graphite, carbon black, acetylene black, Ketjen black, nickel powder, conductive materials such as polyphenylene derivatives, and fillers such as olefin polymers and carbon fibers.

The negative electrode 23 can be manufactured, for example, by the method described below. (1) A polymer solution holding the non-aqueous electrolyte is prepared, a plasticizer such as DBP (dibutyl phthalate) and the active material are added to the solution, and then these are mixed to form a film. After the negative electrode layer is prepared, the negative electrode layer and the current collector are bonded together by, for example, thermocompression bonding.
By impregnating the negative electrode layer with the electrolytic solution by substituting the electrolytic solution with the plasticizer in the negative electrode layer while holding the electrolytic solution in the polymer by immersing it in a non-aqueous electrolytic solution, or The plasticizer in the negative electrode layer is removed by extraction with a solvent such as ethanol, and then impregnated with a non-aqueous electrolytic solution to produce a negative electrode.

(2) A solution of a polymer holding the non-aqueous electrolytic solution is prepared, and a plasticizer such as DBP (dibutyl phthalate) and the active material are added to the solution, which are then mixed to prepare a negative electrode. Prepare the paint. The negative electrode coating material is applied to the current collector and then dried. By impregnating the negative electrode layer with the electrolytic solution by substituting the electrolytic solution with the plasticizer in the negative electrode layer while holding the electrolytic solution in the polymer by immersing it in a non-aqueous electrolytic solution, or The plasticizer in the negative electrode layer is removed by extraction with a solvent such as ethanol, and then impregnated with a non-aqueous electrolytic solution to produce a negative electrode.

(3) After preparing a polymer solution holding the non-aqueous electrolyte and adding the active material to the solution,
After mixing these and forming a film to form a negative electrode layer, the negative electrode layer and the current collector are bonded to each other by, for example, thermocompression bonding. A negative electrode is produced by impregnating this with a non-aqueous electrolyte.

(4) After preparing a solution of the polymer holding the non-aqueous electrolyte and adding the active material to the solution,
These are mixed to prepare a negative electrode coating material. The negative electrode coating material is applied to the current collector, dried, and then impregnated with a non-aqueous electrolyte to form a negative electrode.

In the above methods (1) and (2), a plasticizer is added for the purpose of improving mechanical properties such as strength of the solid electrolyte layer and improving the amount of electrolyte impregnated to improve charge / discharge characteristics. To be done.

In the methods (1) to (4), the impregnation of the electrolytic solution (including the removal of the plasticizer in the case of adding the plasticizer) may be performed after assembling the unit cell not impregnated with the electrolytic solution, or It may be after housing the unit cell 21 in the exterior member 8 shown in FIG.

When the non-aqueous electrolyte is impregnated after assembling the unit cell not impregnated with the electrolytic solution or after accommodating the unit cell 21 in the exterior member 8 shown in FIG. 4, the positive electrode current collector 25 is used. It is preferable to use one or both of the negative electrode current collectors 27 having a structure in which a non-aqueous electrolytic solution such as punched metal can flow.

6) Long Films 1, 2 At least the opposing surfaces of the long films 1, 2 are made of a heat-fusible resin such as polyethylene. The long films 1 and 2 are specifically a heat-fusible resin film alone; a resin film such as polyethylene terephthalate or nylon or an Al foil or a metal foil such as a copper foil is laminated on the heat-fusible resin film. The above can be used. When such a laminated film is used as a long film, it is arranged such that the heat-fusible resin film is located on the unit cell side.

7) Guide Plate 3 The guide plate 3 may be formed of a material that is non-heat-sealing with respect to the heat-fusible resin, and is particularly formed of a metal such as copper or aluminum having good thermal conductivity. Preferably.

The guide plate is not limited to the frame-like one shown in FIG. 1 described above, but as shown in FIG. 5, after the long film 2 is stacked on a plurality of unit cells 21, the guide film is placed on the long film 2. The two elongated guide plates 3a and 3b may be arranged so as to be close to the side walls of the unit cells 21 along the length direction of the film 2.

8) Elastic rolls 5a, 5b Since these elastic rolls 5a, 5b are heated to heat-bond the long films 1 and 2, they can withstand the softening temperature of the films. There is a need,
For example, silicone rubber or fluororubber can be used.

The first and second long films are heat-sealed to each other through the elastic rolls 5a and 5b and then heat-sealed to stabilize the shape of the battery. Allow the length of film to cool by passing it through another elastic roll that is not heated.

In the method for manufacturing a polymer electrolyte secondary battery according to the present invention described above, for example, as shown in FIG. 1, a plurality of unit cells 21 are formed on the heat-fusible resin surface of the first long film 1 by the film. 1, a step of installing at a desired interval in the length direction, a step of stacking the heat-fusible resin surface of the second long film 2 so as to cover the upper surfaces of the plurality of unit cells 21, and the second length. A frame-shaped guide plate 3 having a thickness equal to or slightly thicker than the unit cells 21 is provided on the length film 2 for each unit cell 21.
And the plurality of unit cells 21 are arranged on the bottom surface of the guide plate 3 so as to overlap each other on the bottom surface of the guide plate 3.
The two long films 1 and 2 sandwiched between the two long films 1 and 2 around the respective unit cells 21 by passing between the pair of heat-resistant elastic rubber rolls 5a and 5b which are heated. 2 is heated and pressed to heat-seal the heat-sealing resin surfaces to each other.

According to such a method, as shown in FIG. 4, the unit cell 21 is covered with the exterior member 8 composed of two films 7a and 7b having the heat-sealed portion 6 around the unit cell 21, and the unit cell 21 is provided. Of the films 7a, 7 on the surfaces of the positive and negative electrodes of
Since b is closely attached, the unit cell 21 can be stored in a state where there is almost no gap between the unit cell 21 and the exterior member 8. As a result, even when the positive electrode layer 26, the negative electrode layer 28, and the solid polymer electrolyte layer 24 that constitute the unit cell 21 repeatedly expand and contract during charging and discharging of the unit cell 21, the positive and negative electrode sides of the unit cell 21 The exterior member 8 closely attached to the surface
Since it can be suppressed by the two films 7a and 7b, it is possible to prevent the nonaqueous electrolytic solution in them from oozing out due to the expansion and contraction of each component. In particular, when a current collector having a structure through which a non-aqueous electrolyte such as punched metal can flow is used for either or both of the positive electrode and the negative electrode of the unit cell, expansion of each component of the unit cell 21 Although the non-aqueous electrolyte solution in them easily oozes out due to the contraction, the oozing out can be effectively suppressed by the two films 7a and 7b of the exterior member 8. Further, even if the non-aqueous electrolyte in the unit cell 21 tries to ooze out due to expansion and contraction of the respective constituent members, there is almost no gap between the unit cell 21 and the exterior member 8, so the amount of oozing out. Can be reduced. Therefore, the unit cell 2 by repeating charging and discharging
Since the decrease in the amount of the non-aqueous electrolyte in 1 can be suppressed, a polymer electrolyte secondary battery having a high capacity for a long period of time can be obtained.

The plurality of unit cells 21 are connected to the guide plate 3
When passing the two long films 1 and 2 sandwiched between the two between the pair of heated heat-resistant elastic rolls 5a and 5b, a frame shape having a thickness equal to or slightly thicker than the unit cell 21. By arranging the guide plate 3 of the above so as to be close to the peripheral side wall of each of the unit cells 21, it is possible to suppress the pressure of the elastic rolls 5a and 5b from being applied to the unit cells 21. As a result, a plurality of unit cells 2 are provided between the elastic rolls 5a and 5b.
When the two long films 1 and 2 sandwiching 1 between the guide plates 3 are passed, even if the unit cell 21 is already impregnated with the non-aqueous electrolytic solution, the electrolytic solution from the unit cell 21 Can be suppressed.

As shown in FIG. 5 described above, after the second long film 2 is stacked on the plurality of unit cells 21, two elongated guide plates 3a and 3b are formed on the long film 2. The elastic rolls 5a and 5b are arranged so as to be close to the side walls of the unit cells 21 along the length direction of the film 2.
Even when it passes through, a polymer electrolyte secondary battery having substantially the same effect as using a frame-shaped guide plate can be obtained. However, the frame-shaped guide plate is used not only in the length direction of the long film but also in the side wall of the unit cell along the width direction thereof, that is, in the peripheral side wall of the unit cell, a heat-sealing portion having good sealing property is provided. Can be formed. Therefore, since the amount of voids in the exterior member accommodating the unit cell can be significantly reduced,
As compared with the case of using the two guide plates 3a and 3b shown in FIG. 5, it is possible to more effectively suppress the decrease in the amount of the non-aqueous electrolyte solution in the unit cell 21 due to the repeated charging and discharging.

Next, another method for manufacturing a polymer electrolyte secondary battery according to the present invention will be described in detail with reference to FIGS. First, as shown in FIG. 6, a plurality of rectangular polymer electrolyte cells 21 having the above-described structure are formed on the heat-fusible resin surface of the first long film 1 at desired intervals in the length direction of the film 1. Set it open. When installing each of the unit cells 21 on the first long film 1, for example, it is preferable that an adhesive is pointedly attached to the back surface of each of the unit cells 21 and temporarily fixed to the long film 1. . Subsequently, a frame-shaped spacer 10 made of a polymer resin having a thickness equal to or slightly thicker than that of the unit cells 21 is placed on the long film 1 so as to be in contact with a peripheral side wall of each unit cell 21. . Continue to the second long film 1
The heat-fusible resin surface of the unit cells 21 and the spacers 10 so as to cover the upper surfaces of the unit cells 21 and the spacers 10.
1 and a spacer 10 sandwiched between two long films 1 and 2 and a heat-resistant elastic roll 5 having axes 4a and 4b.
Pass between a and 5b. The elastic rolls 5a, 5b
Is sufficiently longer than the width of the long films 1 and 2 and is heated by a desired heating source to, for example, the softening point of the resin for heat fusion or higher. As shown in FIG.
The elastic roll 5 obtained by heating a long film 1 or 2
When the unit cell 21 and the spacer 10 are moved between the elastic rolls 5a and 5b, the elastic rolls 5a and 5b are deformed so as to wrap the unit cell 21 and the spacer 10. Then, the two long films 1 and 2 receive heat from the elastic rolls 5a and 5b, and the long films 1 and 2 are heat-sealed to the upper and lower surfaces of the frame-shaped spacer 10, respectively. After that, the two long films 1 and 2 passed between the elastic rolls 5a and 5b are cut along the peripheral edge of the spacer 10 to form a unit cell 21 and the unit cell 21 as shown in FIG. 21 is housed, and is composed of a frame-shaped spacer 10 on the peripheral side wall thereof and an exterior member 11 formed of two films 7a and 7b having a heat-fusible resin surface heat-sealed to the spacer 10. The polymer electrolyte secondary battery 12 is manufactured.

At least opposing surfaces of the long films 1 and 2 are made of a heat-fusible resin such as polyethylene. The long films 1 and 2 are specifically a heat-fusible resin film alone; a resin film such as polyethylene terephthalate or nylon or an Al foil or a metal foil such as a copper foil is laminated on the heat-fusible resin film. The above can be used. When such a laminated film is used as a long film, it is arranged such that the heat-fusible resin film is located on the unit cell side.

The spacer is made of a heat-fusible resin such as polyethylene or a polymer resin such as polypropylene or nylon. In particular, the spacer made of a heat-fusible resin can satisfactorily heat seal the long films 1 and 2 when the elastic rolls 5a and 5b are heated and pressed.

The spacers are not limited to the frame-like ones shown in FIG. 6 described above, and as shown in FIG. 9, a plurality of unit cells 21 are installed on the long film 1 at desired intervals in the length direction. After that, the two elongated spacers 10a and 10b may be arranged so as to be in contact with the side walls of the respective unit cells 21 along the length direction of the film 1. When installing such elongated spacers 10 a and 10 b on the first long film 1, the spacers 10 a and 1
It is preferable to attach an adhesive pointwise to the back surface of 0b and temporarily fix it to the long film 1.

The spacer is allowed to be attached with a pair of terminals for drawing out the positive and negative electrode current collectors of the stored unit cell to the outside. The elastic rolls 5a and 5b are
As described above, since the long films 1 and 2 are heated to heat-bond them, they must withstand the softening point temperature of the films, but it is necessary to use, for example, silicone rubber or fluororubber. Can be used.

The first and second long films are heat-fused to the spacer 10 through the elastic rolls 5a and 5b, and then the first and second long films are heat-fused to stabilize the shape of the battery. The second long film is allowed to pass through another elastic roll which is not heated to be cooled.

Another method of manufacturing a polymer electrolyte secondary battery according to the present invention described above is, for example, as shown in FIG. 6, a plurality of unit cells 2 on the heat-fusible resin surface of the first long film 1.
1 at a desired interval in the length direction of the film 1, and a frame-shaped spacer made of polymer resin having a thickness equal to or slightly thicker than the unit cell 21 on the long film 1. Respectively so as to be in contact with the peripheral side walls of each of the unit cells 21, and so that the heat-fusible resin surface of the second long film 2 covers the upper surfaces of the plurality of unit cells 21 and the spacers 10. The step of stacking and passing the two long films 1 and 2 sandwiching the plurality of unit cells 21 and the spacers 10 between a pair of heat-resistant elastic rolls 5a and 5b that are heated to pass the respective elements. 2 around the battery
The method includes a step of heat-pressing the long films 1 and 2 with the frame-shaped spacer 10 sandwiched therebetween to heat-seal.

According to such a method, as shown in FIG. 8, the unit cell 21 has a frame-like spacer 10 on its peripheral side wall and a heat-fusible resin surface heat-sealed to the spacer 10.
Since the film 7a, 7b is formed by the sheets of film 7a, 7b and is covered with the exterior member 11, and the films 7a, 7b are adhered to the positive and negative electrode side surfaces of the unit cell 21, the unit cell 21 and the exterior The unit cell 21 can be stored in a state where there is almost no gap between the members 11. As a result, the unit cell 21
Even when the positive electrode layer, the negative electrode layer, and the solid polymer electrolyte layer constituting the unit cell 21 repeatedly expand and contract during charging and discharging, the exterior member 11 that is in close contact with the positive electrode side and the negative electrode side surface of the unit cell 21 Since it can be suppressed by the sheets of film 7a, 7b, it is possible to prevent the non-aqueous electrolyte solution therein from oozing out due to the expansion and contraction of each constituent member. In particular, when a current collector having a structure through which a non-aqueous electrolyte such as punched metal can flow is used for either or both of the positive electrode and the negative electrode of the unit cell, expansion of each component of the unit cell 21 Although the non-aqueous electrolyte solution therein easily bleeds due to the contraction, the bleeding can be effectively suppressed by the two films 7a and 7b of the exterior member 11. Further, even if the non-aqueous electrolyte in the unit cell 21 tries to ooze out due to expansion and contraction of each component member, there is almost no gap between the unit cell 21 and the exterior member 11, so the amount of ooze out. Can be reduced. Therefore, a decrease in the amount of the non-aqueous electrolytic solution in the unit cell 21 due to repeated charging and discharging can be suppressed, so that a polymer electrolyte secondary battery having a high capacity for a long period of time can be obtained.

Further, the two long films 1 and 2 sandwiching the plurality of unit cells 21 and the frame-shaped spacer 10 therebetween are passed between the pair of heated heat-resistant elastic rolls 5a and 5b. At this time, since the frame-shaped spacer 10 having the same thickness as or slightly thicker than the unit cells 21 is arranged in contact with the peripheral side wall of each unit cell 21, the elastic rolls 5a and 5b are attached to the unit cells 21. It is possible to suppress the application of pressure.
As a result, when the two long films 1 and 2 having the plurality of unit cells 21 and the spacer 10 sandwiched between the elastic rolls 5a and 5b are passed, the unit cell 21 is already exposed to the non-aqueous electrolyte. Even if impregnated, it is possible to prevent the electrolyte solution from seeping out from the unit cell 21.

Further, since the exterior member 11 has the frame-shaped spacers 10 on the periphery, impacts from the outside can be mitigated by the spacers, so that a highly reliable polymer electrolyte secondary battery can be obtained.

As shown in FIG. 9 described above, a plurality of unit cells 21 are installed on the first long film 1 at desired intervals in the length direction thereof, and two elongated spacers 10a,
10b are installed so as to contact the side walls of each of the unit cells 21 along the length direction of the film 1, respectively, and then the second long film 2 is stacked on the unit cells 21 and the spacers 10a and 10b. Even when the elastic rolls 5a and 5b are passed, a polymer electrolyte secondary battery having substantially the same effect as using the frame-shaped spacer can be obtained. However, it is possible to form an exterior member having a spacer that is in contact with not only the lengthwise direction of the long film but also the side wall of the unit cell along the width direction thereof, that is, the side wall around the unit cell by using the frame-shaped spacer. Therefore, the gap between the unit cell and the exterior member can be made extremely smaller than in the case of using the two spacers 10a and 10b shown in FIG. It can be effectively suppressed.

[0063]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail with reference to the drawings. (Example 1) <Production of positive electrode> Copolymer of vinylidene fluoride-hexafluoropropylene (VdF-HFP) in 20 g of acetone (manufactured by El Fatchem Co .; KYNAR275)
0, the copolymerization ratio [VdF: HFP] was 85:15), 2.8 g of powder was dissolved, and then 4.3 g of dibutyl phthalate (DBP) was added to this acetone solution, and the composition formula was LiCoO ₂ as an active material. 10.5 g of the lithium-containing cobalt oxide and 1.13 g of acetylene black as a conductive material were added, mixed and dispersed to prepare a positive electrode paste. The positive electrode paste is made of aluminum punched metal (hole diameter: 1.5 mm, opening rate 40%)
2.5mA using a knife coater for the positive electrode current collector consisting of
Coating at a coating speed of 1 m / min so that it becomes h / cm ² ,
A positive electrode was produced by drying the coating film with dry air. <Preparation of Negative Electrode> After dissolving 2.0 g of the same vinylidene fluoride-hexafluoropropylene copolymer used in the positive electrode layer in 12 g of acetone, dibutyl phthalate (DBP) 3. was added to the acetone solution. 12 g was added, 7.37 g of mesophase pitch carbon fiber (manufactured by Petka Co., Ltd.) was added as an active material, and these were mixed to prepare a paste for negative electrode. The negative electrode paste is made of copper punched metal (hole diameter: 1.5 m
m, porosity of 40%) for a negative electrode current collector of 2.5 mAh
/ Cm ² was applied under the same conditions as described above using a knife coater, and the coating film was dried with dry air to prepare a negative electrode. <Preparation of Solid Polymer Electrolyte Layer> After dissolving 2.0 g of a copolymer of vinylidene fluoride-hexafluoropropylene similar to that used for the positive electrode layer in 10 g of acetone, dibutyl phthalate ( D
2.0 g of BP) was added and mixed to prepare an electrolyte layer paste. This paste was applied on a smooth glass plate so that the film thickness after drying was 70 μm, dried, and peeled from the glass plate to prepare a solid polymer electrolyte layer. <Preparation of Non-Aqueous Electrolyte> A non-aqueous solvent in which ethylene carbonate (EC) and dimethyl carbonate (DMC) are mixed at a volume ratio of 1: 1 and LiPF ₆ as an electrolyte has a concentration of 1 mol / l. Was dissolved as described above to prepare a non-aqueous electrolytic solution. <Production of unit cell> The obtained positive electrode and negative electrode were 2 cm x 2
The solid polymer electrolyte layer was cut into a size of 2.25 cm × 2.25 cm. The polymer electrolyte layer was interposed between the positive electrode and the negative electrode, and these were thermocompression bonded by a rigid roll heated to 130 ° C. to obtain a unit cell not impregnated with an electrolytic solution. Subsequently, the unit cell not impregnated with the electrolytic solution is immersed in the nonaqueous electrolytic solution for 2 hours to replace the electrolytic solution with the DBP in the positive electrode layer, the negative electrode layer, and the polymer electrolyte layer constituting the unit cell. A unit cell having the structure shown in FIG. 2 was produced by impregnating the electrolytic solution.

Then, as shown in FIG.
0 μm polyethylene (PE) film and thickness 50 μm
On the PE film of the first long film 1 laminated with the polyethylene terephthalate (PET) film, a plurality of unit cells 21 produced by the above-described method are placed at desired intervals in the length direction of the film 1. At the same time, it was temporarily fixed by an adhesive applied to the back surface of the unit cell in a point manner. 50 μm thick PE film and 50
After stacking the PE film surface of the second long film 2 laminated with a PET film having a thickness of μm so as to cover the upper surfaces of the plurality of unit cells 21, the thickness of the unit cell 21 is set on the second long film 2. A frame-shaped guide plate 3 made of slightly thicker copper is arranged close to the peripheral side wall of the unit cell 21, and the two long films 1 and 2 are stacked on each other on the bottom surface of the guide plate 3. . Next, the plurality of unit cells 2
Two long films 1, 2 sandwiched between the guide plates 3 were passed between elastic rolls 5a, 5b made of silicone rubber having shafts 4a, 4b. The elastic rolls 5a and 5b have a length sufficiently longer than the width of the long films 1 and 2, and 110 ° C. depending on a desired heating source.
Heating. As shown in FIG. 3, the two long films 1 and 2 are passed between the heated elastic rolls 5a and 5b, and the unit cell 21 and the guide plate 3 are interposed between the elastic rolls 5a and 5b. The elastic rolls 5a, 5b are deformed so as to wrap the unit cell 21 and the guide plate 3 by moving the two rolls, and the two long films 1, 2 stacked on the bottom surface of the guide plate 3 are overlapped with each other. The parts were heat sealed to each other. Subsequently, the guide plate 3 was removed from the two long films 1 and 2 passed between the elastic rolls 5a and 5b, and the two long films 1 and 2 were positioned at the periphery of the guide plate 3. As shown in FIG. 4, the unit cell 21 is cut by cutting along the location.
A polymer composed of the unit cell 21 and an exterior member 8 formed of two PE / PET laminate films 7a and 7b having a frame-shaped heat-sealing portion 6 located near the side wall of the unit cell 21. The electrolyte secondary battery 9 was manufactured.

Example 2 First, as shown in FIG. 6, a PE film having a thickness of 50 μm and a PET film having a thickness of 50 μm were laminated on the PE film of the first long film 1 in the same manner as in Example 1. The unit cells 21 were respectively installed at desired intervals in the length direction of the film 1, and were temporarily fixed by an adhesive that was pointed on the back surface of the unit cell. Subsequently, a frame-shaped spacer 10 made of polyethylene having a thickness equivalent to that of the unit cell 21 was placed on the long film 1 so as to be in contact with a peripheral side wall of the unit cell 21. PE film with a thickness of 50 μm and a thickness of 5
After stacking the PE surface of the second long film 2 laminated with a 0 μm PET film so as to cover the upper surfaces of the unit cells 21 and the spacers 10, the plurality of unit cells 2
Two long films 1 and 2 sandwiching 1 and a spacer 10 were passed between elastic rolls 5a and 5b made of silicone rubber having shafts 4a and 4b. The elastic rolls 5a and 5b have a length sufficiently longer than the width of the long films 1 and 2, and are heated to 110 ° C. by a desired heating source. As shown in FIG. 7, the two long films 1 and 2 are passed between the heated elastic rolls 5a and 5b, and the unit cell 21 and the spacer 10 are placed between the elastic rolls 5a and 5b. By moving
The elastic rolls 5a and 5b were deformed so as to wrap the unit cell 21 and the spacer 103, and the PE films of the long films 1 and 2 were heat-sealed to the upper and lower surfaces of the frame-shaped spacer 10, respectively. Next, by cutting the two long films 1 and 2 that have passed between the elastic rolls 5a and 5b along the peripheral edge of the spacer 10, as shown in FIG.
And a packaged electrolyte 11 formed on the peripheral side wall of the frame-shaped spacer 10 and an exterior member 11 formed of two PE / PET laminate films 7a and 7b heat-sealed to the spacer 10. Battery 12 was manufactured.

(Comparative Example) An unsealed bag having a structure similar to that of the unit cell of Example 1 in which a PE film having a thickness of 50 μm and a PET film having a thickness of 50 μm were laminated was prepared. Then, the unit cell was inserted from the opening of the unsealed bag, and the opening was heat-sealed to manufacture a polymer electrolyte secondary battery in which the unit cell was housed in a sealed bag as an exterior member.

With respect to the obtained secondary batteries of Examples 1 and 2 and Comparative Example, the positive electrode current collector and the negative electrode current collector of the stored unit cell were drawn out to the outside using a lead, and the charging current 2
After performing constant current constant voltage charging for 10 hours at 4.2 mA for 4.2 mA, charging / discharging for discharging at a current of 2 mA up to 2.7 V was repeated. The discharge capacity retention ratio with respect to the initial capacity after repeating charge and discharge 100 times was measured. The results are shown in Table 1 below.

[0068] As is clear from Table 1, the secondary batteries obtained in Examples 1 and 2 have extremely high discharge capacity retention rates as compared with the secondary batteries of Comparative Examples. This is the case of the first and second embodiments.
The outer packaging film of the secondary battery, the two PE / PET laminate films constituting the outer packaging member are in close contact with the positive and negative electrode side surfaces of the unit cell, and most of the outer packaging member housing the unit cell This is due to the absence of voids.

[0069]

As described in detail above, according to the present invention, the amount of void between the exterior member and the unit cell housed therein is significantly reduced to expand and contract the unit cell during charging and discharging. It is possible to provide a method for producing a polymer electrolyte secondary battery which suppresses the non-aqueous electrolyte solution from seeping out due to the above, and consequently has a high capacity for a long period of time.

[Brief description of drawings]

FIG. 1 is a perspective view for explaining the production of a polymer electrolyte secondary battery according to the present invention.

FIG. 2 is a partially cutaway perspective view of a unit cell used in the present invention.

FIG. 3 is a partially enlarged cross-sectional view near the elastic roll of FIG.

FIG. 4 is a partially cutaway perspective view of a polymer electrolyte secondary battery manufactured by the method shown in FIG.

FIG. 5 is a perspective view for explaining another production mode of the polymer electrolyte secondary battery according to the present invention.

FIG. 6 is a perspective view for explaining the manufacture of another polymer electrolyte secondary battery according to the present invention.

FIG. 7 is a partially enlarged cross-sectional view near the elastic roll of FIG.

8 is a partially cutaway perspective view of a polymer electrolyte secondary battery manufactured by the method shown in FIG.

FIG. 9 is a perspective view for explaining another manufacturing mode in another polymer electrolyte secondary battery according to the present invention.

[Explanation of symbols]

 1 ... 1st long film, 2 ... 2nd long film, 3, 3a, 3b ... Guide plate, 5a, 5b ... Elastic roll, 6 ... Heat-sealing part, 7a, 7b ... It has a heat-fusible resin surface. Films 8, 11 ... Exterior member, 9, 12 ... Polymer electrolyte secondary battery, 10, 10a, 10b ... Spacer, 21 ... Unit cell, 22 ... Positive electrode, 23 ... Negative electrode, 24 ... Solid polymer electrolyte layer.

Claims (5)

[Claims] 1. A positive electrode in which a positive electrode layer containing a polymer holding an active material and a non-aqueous electrolytic solution is laminated on a current collector, and a negative electrode layer containing a carbonaceous material which absorbs and releases lithium ions is laminated on the current collector. A structure in which a polymer electrolyte cell including a negative electrode and a solid polymer electrolyte layer containing a polymer holding a non-aqueous electrolyte interposed between the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode is housed in an exterior member. In a method for producing a polymer electrolyte secondary battery, a step of placing a plurality of the unit cells on a heat-fusible resin surface of a first long film at desired intervals in a length direction of the film, 2 stacking the heat-fusible resin surface of the long film so as to cover the upper surfaces of the plurality of unit cells;
A guide plate having a thickness equal to or slightly thicker than the unit cells on the long film is arranged so as to be close to at least sidewalls of the unit cells along the length direction of the film, and at the bottom surface of the guide plate. Stacking the two long films on top of each other, and passing the two long films sandwiching the plurality of unit cells between a pair of heated heat-resistant elastic rolls A process for producing a polymer electrolyte secondary battery, comprising a step of heating and pressing the peripheral two long films to heat-seal the heat-sealing resin surfaces thereof. 2. The polymer electrolyte secondary battery according to claim 1, wherein one or both of the current collectors used for the positive electrode and the negative electrode has a structure in which the nonaqueous electrolytic solution can flow. Production method. 3. A positive electrode in which a positive electrode layer containing a polymer holding an active material and a non-aqueous electrolytic solution is laminated on a current collector, and a negative electrode layer containing a carbonaceous material which absorbs and releases lithium ions is laminated on the current collector. A structure in which a polymer electrolyte cell including a negative electrode and a solid polymer electrolyte layer containing a polymer holding a non-aqueous electrolyte interposed between the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode is housed in an exterior member. In a method for producing a polymer electrolyte secondary battery, a step of placing a plurality of the unit cells on a heat-fusible resin surface of a first long film at desired intervals in a length direction of the film, and A spacer made of a polymer resin having a thickness equal to or slightly thicker than the unit cells is provided on the long film so as to be in contact with at least sidewalls of the respective unit cells along the length direction of the film. And the extent, the second
The step of stacking the heat-fusible resin surface of the long film so as to cover the upper surfaces of the plurality of unit cells and the spacers, and heating the two long films sandwiching the plurality of unit cells and the spacers. And a heat-sealing process of passing the two long films around each of the unit cells by sandwiching at least the spacer to heat-seal between the pair of heat-resistant elastic rolls. Of manufacturing polymer electrolyte secondary battery. 4. The polymer electrolyte secondary battery according to claim 3, wherein one or both of the current collectors used for the positive electrode and the negative electrode has a structure in which the nonaqueous electrolytic solution can flow. Production method. 5. The method for manufacturing a polymer electrolyte secondary battery according to claim 3, wherein the spacer is made of a heat-fusible resin.