JPH0922735A - Laminate type polymer electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate type polymer electrolyte secondary battery with which it is possible to sense the voltages of a plurality of element cells at the time of charging and discharging. SOLUTION: A polymer electrolyte secondary battery includes element cells 21 -23 equipped with an active material, a positive electrode containing non- aqueous electrolytic solution and polymer for retaining the solution, a negative electrode containing a carbonaceous material to occlude and release lithium ions and retaining non-aqueous electrolytic solution, and a solid polymer electrolyte layer interposed between the positive and negative electrodes and containing non-aqueous electrolytic solution and a polymer for retaining the solution, wherein the element cells 21 -23 are laminated and connected in series. The element cells 21 -23 are provided with terminals 16, 17 for measuring their voltages.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminated polymer electrolyte secondary battery in which a plurality of polymer electrolyte cells are connected in series.

[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 Equipped with unit cells.

By the way, as one of the uses of the unit cell, there is provided a laminated polymer electrolyte secondary battery in which a plurality of the unit cells are laminated so as to be connected in series and the voltage is increased by the number of lamination of a single unit cell. It is considered to be assembled. In this laminated polymer electrolyte secondary battery, charging / discharging can be performed by connecting a charger / discharger to the electrode (eg, positive electrode) of the uppermost unit cell and the negative electrode of the lowermost unit cell.

However, since the plurality of unit cells forming the secondary battery do not always have the same battery performance, the voltage of one unit cell during charging may be higher than that of another unit cell. When the voltage of a certain unit cell becomes higher than that of the other unit cell as described above, the unit cell is overcharged and the battery performance is impaired. Further, even during discharging, a certain unit cell is in an over-discharged state due to the above-mentioned variation in performance among unit cells. When such over-discharging occurs, the current collector of the negative electrode is dissolved or the negative electrode active material deteriorates, which hinders subsequent charging.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to provide a laminated polymer electrolyte secondary battery capable of detecting the voltages of a plurality of unit cells during charging and discharging. The present invention provides a highly reliable laminated polymer electrolyte secondary battery that prevents a battery reaction between adjacent positive and negative electrodes between the unit cells when the unit cells are stacked to be connected in series. It is the one we are trying to provide.

The present invention provides a highly reliable laminated polymer electrolyte secondary battery which prevents contact between collectors of the positive electrodes of the unit cells when the unit cells are stacked for series connection. It is the one we are trying to provide.

[0009]

The laminated polymer electrolyte secondary battery according to the present invention comprises a positive electrode containing an active material, a non-aqueous electrolytic solution and a polymer holding the electrolytic solution, and a carbonaceous material which absorbs and releases lithium ions. A polymer electrolyte element comprising a negative electrode containing a material and holding a non-aqueous electrolyte solution, and a non-aqueous electrolyte solution interposed between the positive electrode and the negative electrode and a solid polymer electrolyte layer containing a polymer holding the electrolyte solution. A laminated polymer electrolyte secondary battery having a structure in which a plurality of batteries are stacked and connected in series, wherein each of the unit cells is provided with a terminal for measuring the voltage of the battery. Is.

Another laminated polymer electrolyte secondary battery according to the present invention comprises a collector made of aluminum foil, an active material,
A positive electrode laminated with a positive electrode layer containing a non-aqueous electrolytic solution and a polymer holding the electrolytic solution, and a negative electrode layer containing a non-aqueous electrolytic solution containing a carbonaceous material capable of inserting and extracting lithium ions in a copper foil were laminated. A plurality of polymer electrolyte cells including a negative electrode and a solid polymer electrolyte layer containing a nonaqueous electrolytic solution and a polymer holding the electrolytic solution interposed between the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode are laminated. In the laminated polymer electrolyte secondary battery having a structure connected in series, the aluminum foil and the copper foil arranged adjacent to each other in the laminated portion of each unit cell are formed of Al-Cu clad foil. It is characterized by.

Yet another laminated polymer electrolyte secondary battery according to the present invention comprises a positive electrode containing an active material, a non-aqueous electrolytic solution and a polymer holding the electrolytic solution, and a carbonaceous material which absorbs and releases lithium ions. And a plurality of polymer electrolyte unit cells comprising a negative electrode holding a non-aqueous electrolyte solution and a solid polymer electrolyte layer containing a non-aqueous electrolyte solution and a polymer holding the electrolyte solution interposed between the positive electrode and the negative electrode. A laminated type polymer electrolyte secondary battery having a structure in which layers are stacked and connected in series, and a surface along the stacking direction is covered with an insulating film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a laminated polymer electrolyte secondary battery according to the present invention will be described with reference to FIGS. 1 and 2.
Multilayer polymer electrolyte secondary cell 1 is stacked so that the series connection in contact with the anode and the cathode from each other for example three polymers electrolytic frugal battery 2 ₁ to 2 ₃ 1. Each of the unit cells 2 _{1 to} 2 ₃ has a positive electrode having a structure in which a positive electrode layer 4 is laminated on a current collector ₃ made of, for example, aluminum foil,
For example, a negative electrode having a structure in which a negative electrode layer 6 is laminated on a current collector 5 made of copper foil, and a solid polymer electrolyte layer 7 interposed between the positive electrode positive electrode layer 4 and the negative electrode negative electrode layer 6. There is. The first of said unit cells 2 ₁ to the current collector 3 and the negative electrode current collector 5 of the positive electrode, the current collector 3 and the integrated strip-shaped positive electrode terminal 8 and FIG. 2 The strip-shaped negative electrode terminals 9 integrated with the current collector 5 are respectively extended. The negative electrode terminal 9 is the second unit cell 2
_It also serves as the positive terminal of ₂ . The third unit cell 2 ₃
The positive electrode current collector 3 and the negative electrode current collector 5 of
A strip-shaped positive electrode terminal 10 integrated with the current collector 3 and a strip-shaped negative electrode terminal 11 integrated with the current collector 5 are respectively extended. The negative electrode terminal 10 also serves as the negative electrode terminal of the _{second unit} cell 2 ₂ .

The terminals 8 to 11 of the respective unit cells 2 ₁ to 2 ₃
It is connected to the detector 12, the voltage V ₁ ~V ₃ of each unit cell 2 ₁ to 2 ₃ is detected by the detector 12. The charger / discharger 13 is a charger for charging the laminated polymer electrolyte secondary battery 1 or a device driven by the secondary battery 1, and the charger / discharger 13 is the first unit cell 2 The positive electrode terminal ₁ of ₁ and the negative electrode terminal 11 of the _{third unit} cell 2 ₃ are connected. Normally open switch 14, the is interposed between the charging and discharging unit 13 and the third negative terminal 11 of the unit cell 2 _3, so the control signal from the detector 12 is the input off ing.

Next, the above-mentioned positive electrode layer 4, negative electrode layer 6, and solid polymer electrolyte layer 7 will be described in detail. 1) Positive Electrode Layer 2 The positive electrode layer 2 contains an active material, a conductive material, a non-aqueous electrolytic solution, and a polymer holding the electrolytic solution.

Examples of the active material include lithium manganese oxide such as lithium manganese oxide, manganese dioxide, and Li _y NiO ₂ (where y is an atomic ratio of 0.05 <y ≦ 1.0). A lithium-containing cobalt oxide such as Li _y CoO ₂ (where y is an atomic ratio of 0.05 <y ≦ 1.0), Li _y Co _z Ni
_1-z O ₂ (where y and z are each 0.05 in atomic ratio)
<Y ≦ 1.0, 0 <z <1.0), various oxides such as amorphous vanadium pentoxide containing lithium, titanium disulfide, and disulfide. Chalcogen compounds such as molybdenum can be used. In particular, a lithium manganese composite oxide is preferable. Among such lithium manganese composite oxides, it is preferable to use one having a composition formula represented by Li _x Mn ₂ O ₄ (where x is an atomic ratio of 0.05 <x ≦ 2.0). A polymer electrolyte secondary battery provided with a positive electrode containing a lithium manganese composite oxide having such a composition has improved discharge capacity.

As the conductive material, for example, artificial graphite, carbon black such as acetylene black, or the like can be used. The electrolytic solution is prepared by dissolving an electrolyte in a non-aqueous solvent.

Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, sulfolane, acetonitrile, 1,2-dimethoxyethane, 1,3-dimethoxypropane and diethyl ether. , Tetrahydrofuran, 2-
Methyltetrahydrofuran, γ-butyrolactone and the like can be mentioned. The non-aqueous solvent may be used alone or in combination of two or more.

As the electrolyte contained in the non-aqueous electrolyte, for example, lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium borofluoride (LiBF ₄ ), lithium arsenic hexafluoride ( LiAsF
₆ ), lithium trifluorometasulfonate (LiCF
₃ SO ₃ ) and lithium bis (trifluoromethylsulfonylimide) [LiN (CF ₃ SO ₂ ) ₂ ]. The amount of the electrolyte dissolved in the non-aqueous solvent is preferably 0.5 to 2.0 mol / l.

Examples of the polymer include vinylidene fluoride-hexafluoropropylene (VDF-HF).
The copolymer of P) can be used. In such a copolymer, VDF contributes to the improvement of the mechanical strength in the skeleton of the copolymer, and HFP is incorporated into the copolymer in an amorphous state, so that the electrolyte is retained and the lithium ion is retained. Function as a transparent part of the. The copolymerization ratio of the HFP depends on the method of synthesizing the copolymer, but is usually at most about 20% by weight.

2) Negative Electrode Layer 4 This negative electrode layer 4 contains a carbonaceous material which absorbs and releases lithium ions, a non-aqueous electrolyte solution and a polymer which holds this electrolyte solution.

Examples of the carbonaceous material include those obtained by firing an organic polymer compound (for example, phenol resin, polyacrylonitrile, cellulose, etc.), those obtained by firing coke and pitch, mesophase. Examples thereof include those obtained by firing pitch, artificial graphite, natural graphite and the like. Above all, in an atmosphere of an inert gas such as argon gas or nitrogen gas, 500 ° C. to 300 ° C.
It is preferable to use a carbonaceous material obtained by firing the organic polymer compound at a temperature of 0 ° C. under normal pressure or reduced pressure.

As the non-aqueous electrolyte and the polymer, the same ones as described in the above-described positive electrode layer are used. 3) Polymer Electrolyte Layer 5 This polymer electrolyte layer 5 contains a non-aqueous electrolytic solution and a polymer that holds this electrolytic solution.

As the non-aqueous electrolyte and the polymer, the same ones as those explained in the above-mentioned positive electrode layer are used. In the laminated polymer electrolyte secondary battery 1 having the configuration shown in FIGS. 1 and 2 described above, each of the unit cells 2 ₁ to 2 ₃ is the detector 12
Has terminals 8 to 11 connected to. When a predetermined voltage is supplied to the secondary battery 1 through the charger / discharger 13 for a predetermined time for charging, each cell 2 ₁
It can be detected to 2 ₃ of the voltage V ₁ ~V ₃ respectively. In this voltage detection, for example, the voltage V _{2 of the second unit} cell 2 ₂ is set to the other unit cells (first and third unit cells) 2 ₁ , 2
_When it is detected that the voltage is higher than the voltages V ₁ and V _{3 of 3} and exceeds a predetermined value, a control signal is output from the detector 12 to the normally open switch 14, and charging is stopped. The predetermined value is set to the maximum chargeable voltage during charging, for example, 4.3V. As a result, it is possible to prevent the _{second unit} cell 2 _{2 from} being overcharged.

On the other hand, when performing discharge at a predetermined cut-off voltage through the charge and discharge unit 13 to the secondary battery 1, the detector 12 by detecting the voltage V ₁ ~V ₃ of each unit cell 2 ₁ to 2 _3, respectively can do. In this voltage detection, for example, the voltage V _{2 of the second unit} cell 2 ₂ is set to another unit cell (first,
3rd unit cell) lower than voltages V ₁ and V _{3 of} 2 ₁ and 2 ₃ ,
When it is detected that the value is equal to or less than the predetermined value, the control signal is output from the detector 12 to the normally open switch 14, and the discharge is stopped. The predetermined value is set to the minimum dischargeable voltage, for example, 2.7V. As a result, the second unit cell 2 ₂ is in an overdischarged state, and the negative electrode layer 6 of the unit cell 2 ₂ is
Can be prevented from being deteriorated.

Therefore, it is possible to prevent a certain unit cell constituting the laminated polymer electrolyte secondary battery from being overcharged during a charging operation, or a certain unit cell constituting the secondary battery from being overdischarged at the time of discharging. Since this can be prevented, improvement in reliability and improvement in life can be achieved.

In the example shown in FIG. 1, when the detector detects that a certain unit cell is higher than a predetermined value during charging, the unit cell is turned off by turning off the normally open switch from the detector. The overcharge state is prevented, but the present invention is not limited to this. For example, a variable resistor is interposed between the terminals of each unit cell, and when a unit cell having a higher voltage than other unit cells is detected by the detector during charging, the control signal of the detector is used to By controlling so that the resistance value of the variable resistor interposed between the terminals of the high-voltage unit cells becomes large, the voltage between each unit cell is averaged and the specific unit cell is overcharged. You may prevent it. On the other hand, when a low voltage unit cell is detected by the detector during discharging, the resistance value of the variable resistor interposed between the terminals of the low voltage unit cell is reduced by the control signal of the detector. It is also possible to prevent the specific unit cell from being over-discharged by controlling the voltage to average the voltage between the unit cells.

Next, another laminated polymer electrolyte secondary battery according to the present invention will be described with reference to FIGS. Multilayer polymer electrolyte secondary cell 1 is stacked so that the series connection in contact with for example three polymers electrolytic frugal battery 2 ₁ to 2 ₃ to the negative electrode from each other and the positive electrode as shown in FIG.
Each of the unit cells 2 _{1 to} 2 ₃ has a positive electrode having a structure in which a positive electrode layer 4 is stacked on a current collector ₃ made of, for example, an aluminum foil, and a negative electrode layer 6 is stacked at a current collector 5 made of, for example, a copper foil. It is composed of a negative electrode and a solid polymer electrolyte layer 7 interposed between the positive electrode layer 4 of the positive electrode and the negative electrode layer 6 of the negative electrode. Collector of the first cell 2 ₁ of the negative electrode current collector 5 and the second cell 2 ₂ of the positive electrode current collector 3, and the second of said negative electrode of the cell 2 ₂ 5 and the current collector ₃ of the positive electrode of the _{third unit} cell 2 ₃ are shown in FIG.
It is formed by the l-Cu clad foil 15. A strip-shaped positive electrode terminal 8 integrated with the current collector 3 extends to the positive electrode current collector 3 of the _{first unit} cell 21. The Al- between the _first and second unit cells 2 ₁ and 2 ₂
The Cu-clad foil 15 includes the Al-Cu clad foil 1 described above.
A strip-shaped terminal 16 that is integrated with 5 and serves as both a negative electrode and a positive electrode is extended. The second and third unit cells 2
_2, is the Al-Cu clad foil 15 between the two _3, it is integrated with the Al-Cu clad foil 15, strip-like terminal 17 which also serves as a negative electrode and the positive electrode is extended. A strip-shaped negative electrode terminal 11 integrated with the current collector 5 extends to the negative electrode current collector 5 of the _{third unit} cell 23. The terminal of each unit cell 2 ₁ to 2 ₃ 8,11,16,1
7 is connected to the detector similarly to FIG. The positive electrode terminal 8 of the _{first unit} cell 2 ₁ and the third unit cell 2 ₃
A charger / discharger is connected to the negative electrode terminal 11 in the same manner as in FIG.

As the positive electrode layer 4, the negative electrode layer 6 and the solid polymer electrolyte layer 7, the same ones as described in the above items 1) to 3) are used. The laminated polymer electrolyte secondary battery 1 described above is assembled, for example, by the following method.

First, as shown in FIG. 5, between the positive electrode layer 4 and the negative electrode layer 6, the Al-Cu clad foil 15 is provided with the Al current collector 3 on the positive electrode layer 4 side, and the Cu current collector 5 is the negative electrode layer. One unit is formed by arranging and stacking so as to be positioned on the 6 side, respectively, and further stacking the solid polymer electrolyte layer 7 on the positive electrode layer 4 side. Subsequently, two units are stacked, and a solid polymer electrolyte layer 7, a positive electrode layer 4 and a current collector 3 made of Al foil are stacked in this order on the upper surface of the stack, and then the stack made of the two units. A negative electrode layer 6 and a current collector 5 made of Cu foil are laminated on the lower surface of the product in this order to form a laminated polymer electrolyte secondary battery 1 having a structure shown in FIG.
Is assembled.

The laminated polymer electrolyte secondary battery 1 having the above-mentioned structure is constructed by stacking three polymer electrolyte battery cells 2 ₁ to 2 _{3 so} that the negative electrode and the positive electrode are in contact with each other and are connected in series. Since the Al-Cu clad foil 15 is used as the current collector of C, the current collector made of Al foil and C
It is possible to prevent the current collector from corroding due to a battery reaction between the current collectors made of u foil.

That is, in a laminated polymer electrolyte secondary battery, two unit cells are stacked with a negative electrode current collector made of Cu foil of one unit cell and a positive electrode current collector made of Al foil of the other unit cell. When they are connected in series with each other, an electrolytic solution may be present between the current collectors. When the electrolytic solution is thus interposed between the Cu foil current collector and the Al foil current collector, a battery reaction occurs between the current collectors and the current collector corrodes.

According to the present invention, as shown in FIG. 3, by using the Al-Cu clad foil 15 as the current collectors of the negative and positive electrodes of two unit cells (for example, 2 ₁ , 2 ₂ ),
It is possible to prevent the electrolytic solution from entering between the current collectors of the negative electrode and the positive electrode. As a result, the current collector 3 made of Al foil
Since it is possible to prevent a battery reaction between the collector 5 made of Cu foil and the collector 5, it is possible to prevent the collectors 3 and 5 from being corroded. Therefore, it is possible to realize a highly reliable laminated polymer electrolyte secondary battery.

The laminated polymer electrolyte secondary battery shown in FIG. 3 has terminals 8, 11, 16, 17 connected to the detector.
Therefore, as in the case of the laminated polymer electrolyte secondary battery shown in FIG. 1 described above, a unit cell that constitutes the secondary battery is overcharged in the charging operation, or the secondary battery is configured during discharging. Since it is possible to prevent a certain unit cell from being over-discharged, it is possible to achieve improvement in reliability and improvement in life.

Next, another laminated polymer electrolyte secondary battery according to the present invention will be described with reference to FIG. In FIG. 6, the same members as those in FIG. 1 described above are designated by the same reference numerals and the description thereof will be omitted.

Laminated Polymer Electrolyte Secondary Battery 1 of FIG.
The four faces along three stacking direction of the polymer electrolyte frugal battery 2 ₁ to 2 ₃ (side surface) is covered by the insulating tape 18.

[0036] By coating the insulating tape 18 to the four faces along the stacking direction of the three polymer electrolytes frugal battery 2 ₁ to 2 _3, as shown in FIG. 6 (side), two unit cells adjacent vertically ( For example, it is possible to prevent the positive electrode current collectors 3 of 2 ₁ , 2 ₂ ) from coming into contact with each other. In addition, the insulating tape 18 prevents the electrolytic solution from entering between the negative electrode current collector made of the Cu foil and the positive electrode current collector made of the Al foil which are in contact with each other in two unit cells (for example, 2 ₁ and 2 ₂ ). Since it can be prevented, it is possible to prevent a battery reaction from occurring between the current collectors. As a result, it is possible to realize a highly reliable laminated polymer electrolyte secondary battery 1 in which a plurality of unit cells 2 ₁ to 2 ₃ are satisfactorily connected in series.

[0037]

As described in detail above, according to the present invention, it is possible to detect the voltages of a plurality of unit cells during charging / discharging, and a unit cell at the time of charging may be overcharged or at the time of discharging. It is possible to provide a highly reliable and long-life laminated polymer electrolyte secondary battery that prevents the unit cell from being over-discharged.

Further, according to the present invention, when stacking a plurality of unit cells to connect them in series, a highly reliable stack type in which a battery reaction is prevented between the positive and negative electrodes adjacent to each other. A polymer electrolyte secondary battery can be provided.

Further, according to the present invention, when stacking a plurality of unit cells to connect them in series, it is possible to prevent the collectors of the positive electrodes of the unit cells from contacting each other, and to provide a highly reliable laminated polymer electrolyte electrolyte. We can provide the next battery.

[Brief description of drawings]

FIG. 1 is a schematic view showing a charge / discharge system in which a laminated polymer electrolyte secondary battery according to the present invention is incorporated.

FIG. 2 is a plan view showing the laminated polymer electrolyte secondary battery of FIG.

FIG. 3 is a sectional view showing another laminated polymer electrolyte secondary battery according to the present invention.

FIG. 4 is a cross-sectional view showing an Al—Cu clad foil used in the laminated polymer electrolyte secondary battery of FIG.

5 is a sectional view showing a unit having an Al—Cu clad foil used for assembling the laminated polymer electrolyte secondary battery of FIG.

FIG. 6 is a perspective view showing still another laminated polymer electrolyte secondary battery according to the present invention.

[Explanation of symbols]

1 ... multilayer polymer electrolyte secondary battery, 2 ₁ to 2 ₃ ... polymer electrolyte frugal battery, 3,5 ... collector, 4 ... positive electrode layer, 6 ...
Negative electrode layer, 7 ... Polymer electrolyte layer, 8 to 11, 16, 17
... terminal, 12 ... detector, 13 ... charger / discharger, 15 ... Al-
Cu clad foil.

Claims (3)

[Claims] 1. A positive electrode containing an active material, a non-aqueous electrolytic solution and a polymer holding the electrolytic solution, a negative electrode containing a carbonaceous material capable of occluding and releasing lithium ions and holding the non-aqueous electrolytic solution, and the positive electrode. And a laminated polymer electrolyte secondary structure having a structure in which a plurality of polymer electrolyte cells including a non-aqueous electrolyte solution interposed between a negative electrode and a solid polymer electrolyte layer containing a polymer holding the electrolyte solution are stacked and connected in series. A laminated polymer electrolyte secondary battery, wherein each of the unit cells is provided with a terminal for measuring a voltage of the battery. 2. A positive electrode in which a positive electrode layer containing an active material, a nonaqueous electrolytic solution, and a polymer holding the electrolytic solution is laminated on a current collector made of aluminum foil, and a carbonaceous material capable of occluding and releasing lithium ions in a copper foil. And a negative electrode in which a negative electrode layer holding a nonaqueous electrolytic solution is laminated, a nonaqueous electrolytic solution interposed between the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode, and a polymer holding the electrolytic solution. A laminated polymer electrolyte secondary battery having a structure in which a plurality of polymer electrolyte unit cells having a solid polymer electrolyte layer are stacked and connected in series, wherein aluminum foils are arranged adjacent to each other in a stacking portion of the unit cells. A laminated polymer electrolyte secondary battery, wherein the copper foil and the copper foil are formed of an Al-Cu clad foil. 3. A positive electrode containing an active material, a non-aqueous electrolytic solution and a polymer holding the electrolytic solution, a negative electrode containing a carbonaceous material that absorbs and releases lithium ions, and holding the non-aqueous electrolytic solution, and the positive electrode. And a laminated polymer electrolyte secondary structure having a structure in which a plurality of polymer electrolyte cells including a non-aqueous electrolyte solution interposed between a negative electrode and a solid polymer electrolyte layer containing a polymer holding the electrolyte solution are stacked and connected in series. A laminated polymer electrolyte secondary battery, characterized in that the surface of the battery along the stacking direction is covered with an insulating film.