JPH09232003A - Lithium secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithium secondary battery having a structure for decreasing the current loss in a collector part and able to take out heavy current. SOLUTION: A lithium secondary battery is provided with a laminated body in which a base plate 4 in which a positive electrode material layer 1 is arranged on only one surface, and having electronic conductivity, at least one base plate 5 in which a positive electrode material layer 1 is arranged on one surface and a negative electrode material layer 2 is arranged on the other surface, and having electronic conductivity, and a base plate 5 in which a negative electrode material layer 2 is arranged on only one surface are so laminated that all positive electrode material layers 1 may face the negative electrode material layers 2 through lithium ion conductive electrolytic layers 3 and that respective base plates and the positive electrode material layers 1 and the negative electrode material layers 2 may not brought in direct-contact with each other, and at least the positive electrode material layers, the negative electrode material layers and the electrolytic layers of the laminated body are shut off from the outside air.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly to improvement of its structure.

[0002]

2. Description of the Related Art Lithium secondary batteries have attracted attention because they have advantages such as high energy density and weight reduction. In particular, recently, a lithium ion secondary battery using a carbon material capable of inserting and extracting lithium ions in the negative electrode is becoming widespread. A lithium-ion secondary battery, which is shown in FIG. 4 and has a cylindrical shape as disclosed in JP-A-6-310142, is the mainstream. The reason for this is that by adopting a so-called winding type in which a positive electrode and a negative electrode are rolled up through a separator and inserted into a battery can, which is a typical configuration of a cylindrical secondary battery, a current flows from the positive electrode and the negative electrode to the outside of the battery. This is because it is possible to simplify the current collecting structure for taking out. If the laminated prismatic battery proposed in Japanese Unexamined Patent Publication No. 6-333544 shown in FIG. 5 is constructed, its current collecting structure must be complicated. Therefore, recently, as in Japanese Patent Laid-Open No. 6-260172, it has been proposed to employ a winding type structure even in a prismatic lithium ion secondary battery. Further, as the electrolyte of the lithium secondary battery, a non-aqueous solution system containing an organic solvent is mainly selected instead of an aqueous solution system. The ionic conductivity of the non-aqueous system is significantly inferior to that of the aqueous system. Other than the non-aqueous system, solid electrolytes have been investigated, but the solid electrolytes are inferior in ionic conductivity to the non-aqueous system electrolytes. Therefore, it is said that it is difficult to extract a large current with a lithium secondary battery. Therefore, in order to extract a certain amount of current, the electrodes are made thinner to increase the electrode area and increase the reaction area,
Further, it is common for lithium ion secondary batteries to employ the above-described wound structure. Even in the case of a lithium secondary battery in which metallic lithium is used as the negative electrode, it is conceivable to thin the electrode and increase the electrode area in the same manner as above in order to extract a large current.

[0003]

In order to reduce the thickness of the electrode and increase the electrode area as described above, it is necessary to use a long metal foil having a large area as a current collector. In a wound-type battery, a current is sent to the outside of the battery through a terminal portion from a very small part of the current collector, so the current density across the metal foil is not constant. That is, the current density of the current collector portion decreases as the distance from the terminal portion increases. The ohmic loss in the current collector part cannot be ignored. The resulting current loss is one of the causes that a large current cannot be taken out in the case of a lithium secondary battery using a non-aqueous electrolyte. Naturally, this problem becomes remarkable as the size of the electrode is increased, that is, as the size of the battery is increased. An object of the present invention is to provide a lithium secondary battery having a structure capable of reducing current loss in the current collector portion and taking out a large current.

[0004]

In order to solve the above-mentioned problems, a lithium secondary battery of the present invention comprises an electronically conductive substrate having a positive electrode material layer on only one side and at least one sheet on one side. A positive electrode material layer, an electronically conductive substrate having a negative electrode material layer on the other surface, and an electronically conductive substrate having a negative electrode material layer on only one surface, all through a lithium ion conductive electrolyte layer Of the positive electrode material layer of the negative electrode material layer facing each other, and comprising a laminated body laminated so that the respective substrates and the positive electrode material layer and the negative electrode material layer do not come into direct contact, at least the positive electrode material layer of the laminated body, the negative electrode material layer, It is characterized in that it has means for shielding the electrolyte layer from the outside air. The means for shutting off from the outside air may be one that covers the entire laminated body with a frame or the like except for the terminal portion for taking out an electric current. At this time, the thickness of the lithium ion conductive electrolyte layer is preferably 1 mm or less. The reason for this is that if the thickness of the electrolyte layer exceeds 1 mm, it is difficult to take advantage of the advantage of high energy density per volume, which is the advantage of the lithium secondary battery, which is disadvantageous.

In the above structure, the lithium ion conductive electrolyte layer is a liquid, and the positive electrode material layer is disposed on one surface and the negative electrode material layer is disposed on the other surface. A material having means for preventing liquid junction with the liquid on the side of the negative electrode material layer, and means for insulating at least the positive electrode plate layer, the negative electrode plate layer, and the electrolyte layer of the laminate from the outside air is an electrically insulating and electrolytic solution resistant material. It is preferable that at least the positive electrode material layer, the negative electrode material layer, and the electrolyte layer of the laminate are shielded from the outside air. In this structure, a separator may be interposed in the electrolyte layer. The presence of the separator can prevent direct contact between the substrates and between the positive electrode material layer and the negative electrode material layer, that is, a short circuit can be prevented. However, when the separator is interposed, the internal resistance of the battery is slightly increased as compared with the case where the separator is not interposed, which is somewhat disadvantageous. The battery does not function effectively if the liquid on the positive electrode material layer side and the liquid on the negative electrode material layer side of the electronically conductive substrate having the positive electrode material layer on one surface and the negative electrode material layer on the other surface are liquid junctioned. Therefore, this point requires careful attention.

A material used for a means for shielding at least the positive electrode material layer, the negative electrode material layer, and the electrolyte layer of the laminate from the outside air, and / or the liquid on the positive electrode material layer side and the liquid on the negative electrode material layer side are not liquid-junctioned. Specific examples of the material used for the means include one or more selected from fluororesin rubber, butyl rubber and silicone rubber. The reason for this is
This is because these materials are extremely stable with respect to the organic solvent that is often used in the electrolytic solution of the lithium secondary battery. However, it is not particularly limited to these.

In the above structure, the negative electrode material layer preferably contains a carbon material capable of inserting and extracting lithium ions as a main component. Alternatively, Ge, Sn, Pb, Sb, Bi,
It is preferable to contain at least one oxide containing an element selected from Si, In, Mg, Al, and Zn. This is because these materials have the advantage that dendrite formation during charging when metal lithium or a lithium alloy is used as the negative electrode material is prevented and a battery with a long life can be constructed. When the carbon material or the oxide is used as the main component of the negative electrode material layer, a subcomponent is a binder or the like for adhering the carbon material or the oxide to the current collector.

In the above structure, it is preferable that the positive electrode material layer contains a composite oxide containing lithium and one or more selected from cobalt, manganese, nickel and vanadium as main components. This is because these materials exhibit a high potential and thus have an advantage that a high voltage battery can be constructed. However, it is not particularly limited to these.

In the above structure, the surface of the substrate on which the positive electrode material layer is arranged is preferably at least one selected from aluminum, aluminum alloy, nickel, nickel alloy, and stainless steel. This is because these materials are relatively cheaper than silver, which is a metal having the highest electron conductivity. Aluminum is a metal that is relatively stable even in an oxidizing environment and has a small specific gravity, so it has the advantage of being lightweight, and although it can be said that it is the most preferable of these, it is not particularly limited thereto. Further, in the above structure, the substrate surface on the side where the negative electrode material layer is arranged is preferably at least one selected from copper, copper alloy, nickel, nickel alloy, and stainless steel. This is because these materials are relatively cheaper than silver, which is a metal having the highest electron conductivity. Copper is the most preferable because it has the highest electron conductivity among them, but is not particularly limited thereto. From the above, the substrate on which the positive electrode material layer is arranged on one surface and the negative electrode material layer on the other surface is that aluminum or aluminum alloy and copper or copper alloy are bonded by a method such as pressure bonding. It can be said that it is the most suitable material. Particularly, from the viewpoints of weight reduction of the battery and mechanical strength of the substrates, it can be said that the thickness of the aluminum or aluminum alloy of the joined substrates is preferably thicker than the thickness of copper or the copper alloy. Further, it is preferable that at least one of the substrate surface on the side where the positive electrode material layer is arranged and the substrate surface on the side where the negative electrode material layer is arranged is roughened. This is because the adhesion between the positive electrode material layer and the surface of the substrate is improved, and the contact area between the positive electrode material layer and the surface of the substrate is increased, whereby a large current can be taken out. Specific examples of a method of joining aluminum or an aluminum alloy and copper and / or a method of roughening the copper surface include electrodeposition of copper on the surface of aluminum or an aluminum alloy, electroless plating, vapor deposition, mechanical However, the polishing is not limited to these.

In the above structure, it is preferable that the laminated body is pressed in the laminating direction. However, when the electrolyte layer is a liquid, it is necessary to dispose a separator in the electrolyte layer. The optimum value of the degree of pressurization varies depending on the difference between the positive electrode material layer, the negative electrode material layer, and the electrolyte layer used.
However, the positive electrode material layer and the negative electrode material layer are advantageous in that the adhesion with the substrate is improved and the utilization rate of the active material is improved by applying pressure. When the above pressure is applied, the substrates at both ends of the laminate, here the substrate having the positive electrode material layer or the negative electrode material layer arranged on only one surface, the substrate other than both ends of the laminate, here the positive electrode material layer on one surface, The rigidity is preferably higher than that of the substrate having the negative electrode material layer on the other surface. The reason for this is that although it depends on the method of pressing, it is the substrates at both ends of the laminate that directly receive the pressing force, and this part prevents deformation. It is considered that it is not necessary to consider the high rigidity of the substrates other than the both ends of the laminate. Examples of means for increasing the rigidity of the substrate include increasing the thickness when the materials and configurations of the substrates in the laminate are the same, but are not particularly limited thereto.

Further, in the above structure, the minimum value / maximum value of the actual capacity of each of the plurality of cells formed in the laminated body is
It is preferably 0.8 or more. This is not directly related to obtaining a large current, but in the configuration in which the plurality of cells are arranged in series, there is a possibility that a cell having a small actual capacity may be overcharged or overdischarged. For example, in a non-aqueous solution type lithium secondary battery, if the battery is overcharged or overdischarged, the electrolytic solution is decomposed and deteriorated, which causes a reduction in life. For secondary batteries that require cycle life performance, the minimum / maximum value of the actual capacity of each cell is important in design. The above-mentioned actual capacity is the discharge capacity when each cell is charged in advance to the extent that the electrolyte is not substantially decomposed and deteriorated, and then discharged until the electrolyte is not substantially decomposed and deteriorated. This can be verified by actually charging and discharging one unit of each cell before the battery is constructed or by measuring the positive electrode active material amount and the negative electrode active material amount of the unit cell. At this time, the positive electrode material layer, the negative electrode material layer used,
The value (discharge capacity) varies depending on the electrolyte layer and charging / discharging conditions.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, description will be given with reference to the sectional view of the lithium secondary battery of the present invention shown in FIG. For the positive electrode material layer 1, a mixture of LiCoO ₂ powder and a predetermined amount of polyvinylidene fluoride as a binder was used. For the negative electrode material layer 2, a mixture of graphite powder and a predetermined amount of polyvinylidene fluoride as a binder was used. The lithium ion conductive electrolyte layer 3 was prepared by dissolving a predetermined amount of LiPF _{6 in} a mixed solvent of ethylene carbonate and dimethyl carbonate, and impregnated into a polypropylene non-woven fabric separator having a thickness of 0.2 mm. An aluminum plate 4 having a thickness of 0.5 mm was used as a substrate having the electron conductivity in which the positive electrode material layer 1 was arranged only on one surface. The positive electrode material layer 1 was applied on one surface thereof. A copper plate 5 having a thickness of 0.5 mm was used as a substrate having the electron conductivity in which the negative electrode material layer 2 was arranged only on one surface. The negative electrode material layer 2 was applied on one surface thereof. These are 1 each
I prepared them one by one. As shown in FIG. 3, a positive electrode material layer 1 is arranged on one surface and a negative electrode material layer 2 is arranged on the other surface. As a substrate having electron conductivity, an aluminum plate 4 having a thickness of 20 μm is used.
A clad material 6 obtained by pressure-bonding a copper plate 5 of 0 μm by a known method was used. Three pieces of this were prepared, and the positive electrode material layer 1 was applied on the aluminum surface side and the negative electrode material layer 2 was applied on the copper surface side. As shown in FIG. 1, the above-mentioned members are laminated so that all the positive electrode material layers 1 and the negative electrode material layers 2 face each other with the electrolyte layer 3 in between, and the respective substrates, and the positive electrode material layer 1 and the negative electrode material are laminated. The cell was formed such that layer 2 was not in direct contact. At this time, the amount of active material in each of the positive electrode material layer 1 and the negative electrode material layer 2 of each cell is adjusted in advance so that the minimum value / maximum value of the actual capacity of each cell formed in the laminated body is 1.0. did.
Since the same material was selected for the positive electrode active material and the negative electrode active material used for each cell in the battery, the maximum / minimum value of the actual capacity of each cell does not change even if the charge rate and the discharge rate are changed.
The thickness of the electrolyte layer here is 0.2 mm. Further, since the positive electrode material layer 1, the negative electrode material layer 2, and the electrolyte layer 3 may be deteriorated when exposed to moisture in the outside air, especially in the atmosphere, as shown in FIG. 1, the fluororesin rubber 7 and the silicone sealant (not shown) are used. Was used to seal the battery. All of these series of operations were performed in a glove box from which water in the atmosphere was removed.

In the lithium secondary battery having the structure shown in FIG. 1, the entire clad material 6 in contact with the positive electrode material layer 1 and the negative electrode material layer 2 has a collector and a connection terminal for connecting each cell in series. There is. Further, the entire aluminum plate 4 or copper plate 5 with which the positive electrode material layer 1 or the negative electrode material layer 2 is in contact with one surface also serves as a current collector and a positive electrode terminal and a negative electrode terminal to the outside of the battery. That is, it is a structure in which ohmic loss does not occur in the current collector portion that occurs when electricity is taken out from each single cell to the outside. Therefore, there is no current loss due to the ohmic loss, and a large current can be taken out. In addition, since the battery of this configuration is composed of single cells connected in series, almost any voltage can be obtained by adjusting the number of stacked cells. It is also possible to design a high density lithium secondary battery.

[0014]

【Example】

(Experiment 1) The results of a comparative study of the lithium secondary battery of the present invention and a conventional lithium secondary battery having a wound structure will be described below. A positive electrode material layer material and its total amount, a negative electrode material layer material and its total amount, an electrolyte layer material and its total amount, a separator, a current collector of the positive electrode material layer and the negative electrode material layer of a conventional wound-type lithium secondary battery, and The total contact area, the material of the current collector in contact with the positive electrode material layer and the negative electrode material layer, and the thickness of the electrolyte layer were adjusted in the same manner as in the lithium secondary battery of the present invention described above. The lithium secondary battery of the present invention described above (hereinafter abbreviated as Example 1) and the lithium secondary battery having the wound structure (hereinafter abbreviated as conventional example) were each completely charged at a charge rate of 0.5 CmA. After charging, 0.5CmA, 1.0CmA,
Table 1 shows the quantity of electricity discharged when discharged at a discharge rate of 3.0 CmA.
Is shown as a relative value. Here, the battery of Example 1 is 0.5C.
The quantity of electricity discharged when discharged at a discharge rate of mA was 1.00.

[0015]

[Table 1]

As is apparent from Table 1, the battery of Example 1 has a dramatically increased amount of discharged electricity as compared with the battery of the conventional example. This is synonymous with the fact that the battery of Example 1 can extract a large current as compared with the battery of the conventional example.

(Experiment 2) In the battery of Example 1, the surface of the substrate in contact with the positive electrode material layer and the negative electrode material layer was polished with SiC polishing paper (No. 400) to roughen the surface. A battery produced under the same conditions as the battery of Example 1 except for this was used as the battery of Example 2, and the same test as in Experiment 1 was performed. Table 2 shows the results. Also in this case, the amount of electricity discharged when the battery of Example 1 was discharged at a discharge rate of 0.5 CmA was 1.00, and the relative value was shown.

[0018]

[Table 2]

As is clear from Tables 1 and 2, the amount of discharged electricity was further increased by roughening the substrate surface. In other words, it was possible to extract a larger current. As means for roughening the surface of the substrate, there are vapor deposition, electrodeposition, electroless plating, thermal spraying, etc. in addition to polishing, and the same effect can be obtained by these methods.

(Experiment 3) As shown in FIG. 2, the battery of Example 1 was replaced with a bolt 8, a nut 9, and an insulating washer 10 to obtain 5 parts.
A battery was produced in which the laminate was pressed in the stacking direction at kg / cm ² . Using this as the battery of Example 3, the same test as in Experiment 1 was performed. Table 2 shows the results. Also in this case, the amount of electricity discharged when the battery of Example 1 was discharged at a discharge rate of 0.5 CmA was 1.00, and the relative value was shown.

[0021]

[Table 3]

As is clear from Tables 1 and 3, the amount of discharged electricity was further increased by pressurizing the laminate. In other words, it was possible to extract a larger current. When the laminated body is pressed in the stacking direction, it depends on the pressing force, the pressing method, or the battery structure. For example, as shown in FIG. 2, pressure stress is applied to the substrates at both ends of the laminated body. In a battery having such a structure, it is desirable that the substrate on which the positive electrode material layer or the negative electrode material layer is disposed on at least only one surface has high rigidity to withstand pressure. However, it is considered that it is not necessary to consider the high rigidity of the substrate having the positive electrode material layer on one surface and the negative electrode material layer on the other surface.

(Experiment 4) In the battery of Example 1, the minimum / maximum values of the actual capacities of the cells formed in the laminate were 0.9 (Example 4) and 0.8 (Example). 5), 0.7
A battery was produced by adjusting the active material amounts of the positive electrode material layer and the negative electrode material layer so as to be the same as in (Example 6). Each of the batteries of Example 1, Example 4, Example 5, and Example 6 was subjected to a cycle test in which the battery of Example 1 was charged with a current equivalent to 0.5 CmA and repeatedly discharged with a current equivalent to 0.5 CmA. The time when the discharged electricity amount reached 70% of the initial value was determined to be the life period, and the number of charge / discharge cycles up to that point was shown as a relative value in Table 4. Example 1 here
Was set to 1.00.

[0024]

[Table 4]

As is clear from Table 4, when the minimum / maximum value of the actual capacity of each cell formed in the laminated body falls below 0.8, the cycle life sharply decreases.
The reason for this is not clear, but the cell with the minimum actual capacity configured in the stacked body is charged at a high rate and discharged at a high rate as compared with the other cells. It is considered that when the battery was charged at the charge rate or discharged at a discharge rate higher than a certain value, the electrolyte was severely deteriorated. However, in the battery of Example 6, the same result as that of the battery of Example 1 was obtained in the initial charging / discharging stage under the test conditions of Experiment 1, so there is no problem in the performance of extracting a large current.

Examples 1 to 6 are so-called lithium ion secondary batteries using graphite for the negative electrode. However, even if metallic lithium or a lithium alloy is used for the negative electrode, by adopting the battery structure of the present invention, a metal is used for the negative electrode. A large current can be obtained as compared with a battery having a wound structure using lithium or a lithium alloy. When a carbon material is used for the negative electrode, the same effect as that of this embodiment can be obtained as long as it is a carbon material capable of occluding and releasing lithium ions even with so-called amorphous carbon other than graphite having high crystallinity. Further, as a material capable of inserting and extracting lithium ions, Ge, Sn, Pb, Sb, Bi, Si,
You may use at least 1 type or more of the oxide containing the element selected from In, Mg, Al, and Zn. As a specific example, G
eO, GeO ₂ , SnO, SnO ₂ , PbO, PbO ₂ ,
Sb ₂ O ₃ , Sb ₂ O ₄ , Bi ₂ O ₃ , SiO, In ₂ O, M
gO, Al ₂ O ₃ , ZnO, Sn _x Si _y O ₂ (x + y =
1) etc. Also, non-stoichiometric compounds of these oxides can be used. Further, in Examples 1 to 6, a liquid containing an organic solvent was used as the electrolyte layer, but it is not particularly limited thereto, and a solid electrolyte such as lithium nitride may be used as long as it has lithium ion conductivity. good. The advantage of using a solid electrolyte is that it does not require a separator even when the laminated body is pressed, and thus the production is facilitated. In addition, in Examples 1 to 6, LiC was added to the positive electrode material layer.
Although the one containing oO ₂ as a main component was used, LiNi _x Co _y
O ₂ (x + y = 1), LiMnO ₂ , LiMn ₂ O ₄ , Li
Similar results were obtained by using one or more of NiO ₂ , LiV ₂ O _{5 and the} like. Also, graphite or a conductive agent in the positive electrode material,
Carbon black such as acetylene black or metal powder such as aluminum may be included. In that case, Example 1
There is a possibility that an even larger current than -6 can be obtained. Further, in Examples 1 to 6, polyvinylidene fluoride was used as the binder used in the positive electrode material layer and the negative electrode material layer, but polytetrafluoroethylene, ethylene-propylene-diene terpolymer, styrene-butadiene rubber, fluororubber were used. Etc. may be used. Further, in Examples 1 to 6, an aluminum plate, a copper plate, and a clad material in which aluminum and copper are pressure-bonded to the substrate are used, but the substrate is not limited to these, and aluminum alloy, copper alloy, nickel, nickel alloy, stainless Similar results can be obtained by using steel or the like. Further, in Examples 1 to 6, fluororesin rubber was used as the electrolytic solution resistant material used for the battery sealing material and the means for preventing the liquid on the positive electrode material layer side and the liquid on the negative electrode material layer side from causing liquid junction. However, one or more selected from butyl rubber and silicone rubber may be used. Further, in Examples 1 to 6, a non-woven fabric separator having a thickness of 0.2 mm was used as a separator, but a polypropylene microporous membrane having a thickness of several tens of μm or the like can also be used.

[0027]

By adopting the battery structure of the present invention, it is possible to provide a lithium secondary battery having a structure capable of reducing the current loss in the current collector portion and taking out a large current. Further, the battery structure of the present invention enables the design of a high energy density lithium secondary battery.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a lithium secondary battery of the present invention.

FIG. 2 is a cross-sectional view of a lithium secondary battery of the present invention.

FIG. 3 is a cross-sectional view of a substrate having a positive electrode material layer on one surface and a negative electrode material layer on the other surface.

FIG. 4 is a cross-sectional view of a conventional lithium secondary battery.

FIG. 5 is a cross-sectional view of a conventional lithium secondary battery.

[Explanation of symbols]

 1. Positive electrode material layer 2. Anode material layer 3. Electrolyte layer 4. Aluminum plate 5. Copper plate 6. Clad material 7. Fluororesin rubber 8. Bolt 9. Nut 10. Insulation washer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location H01M 10/36 H01M 10/36 A (72) Inventor Tatsuo HORIBA 2-1, Nishishinjuku, Shinjuku-ku, Tokyo No. 1 Shinjin Todenki Co., Ltd. (72) Inventor Hiroki Tamura 2-1-1 Nishishinjuku, Shinjuku-ku, Tokyo Shinjin Todenki Co., Ltd.

Claims (20)

[Claims] 1. An electronically conductive substrate having a positive electrode material layer disposed on only one surface, and at least one substrate having electronic conductivity having a positive electrode material layer on one surface and a negative electrode material layer on the other surface. , A substrate having an electron conductivity in which a negative electrode material layer is arranged only on one side, all positive electrode material layers face the negative electrode material layer via a lithium ion conductive electrolyte layer, and each substrate and positive electrode material layer And a negative electrode material layer are laminated so as not to come into direct contact with each other, and a means for cutting off at least the positive electrode material layer, the negative electrode material layer and the electrolyte layer of the laminated body from the outside air is provided. 2. The lithium ion conductive electrolyte layer has a thickness of 1
The lithium secondary battery according to claim 1, wherein the lithium secondary battery is less than or equal to mm. 3. A liquid and a negative electrode material layer on the positive electrode material layer side of a substrate having electron conductivity in which a lithium ion conductive electrolyte layer is a liquid, and a positive electrode material layer is arranged on one surface and a negative electrode material layer is arranged on the other surface. The material used for the means for shielding at least the positive electrode plate layer, the negative electrode plate layer, and the electrolyte layer of the laminated body from the outside air, which has means for preventing liquid junction with the liquid on the side, is electrically insulating and electrolytic solution resistant. The lithium secondary battery according to claim 1 or 2, wherein: 4. The lithium secondary battery according to claim 3, wherein a separator is provided in the lithium ion conductive electrolyte layer. 5. A material used for a means for shielding the positive electrode plate layer, the negative electrode plate layer, and the electrolyte layer from the outside air and / or a positive electrode material layer on one side,
Of a substrate having an electron conductivity in which the negative electrode material layer is arranged on the other surface,
The material used for the means for preventing the liquid on the positive electrode material layer side and the liquid on the negative electrode material layer side from being liquid-junctioned is at least one selected from fluororesin rubber, butyl rubber, and silicone rubber. Rechargeable lithium battery. 6. The lithium secondary battery according to claim 1, wherein the negative electrode material layer is made of a material whose main component is a carbon material capable of inserting and extracting lithium ions. 7. The negative electrode material layer contains a material capable of inserting and extracting lithium ions, and the material is Ge, Sn, Pb, Sb,
The lithium secondary battery according to claim 1, comprising at least one oxide containing an element selected from Bi, Si, In, Mg, Al, and Zn. 8. The positive electrode material layer is mainly composed of a composite oxide composed of lithium and one or more selected from cobalt, manganese, nickel and vanadium.
7. The lithium secondary battery according to any one of to 7. 9. The surface of the substrate on which the positive electrode material layer is disposed is aluminum, aluminum alloy, nickel, nickel alloy,
9. The lithium secondary battery according to claim 1, wherein the lithium secondary battery is at least one selected from stainless steel. 10. The substrate surface on the side on which the negative electrode material layer is arranged is copper,
2. At least one selected from copper alloy, nickel, nickel alloy, and stainless steel.
10. The lithium secondary battery according to any one of 9 to 10. 11. A substrate having a positive electrode material layer on one surface and a negative electrode material layer on the other surface is made by joining aluminum or an aluminum alloy and copper or a copper alloy, and the side on which the positive electrode material layer is arranged is The lithium secondary battery according to claim 1, wherein aluminum or an aluminum alloy, and the side on which the negative electrode material layer is arranged is copper or a copper alloy. 12. The lithium secondary battery according to claim 11, wherein the thickness of the aluminum or aluminum alloy of the bonded substrates is larger than that of copper or the copper alloy. 13. The lithium secondary battery according to claim 11, wherein the substrate is aluminum or an aluminum alloy and copper or a copper alloy is pressure-bonded thereto. 14. The lithium secondary battery according to claim 11, wherein the substrate is aluminum or an aluminum alloy on which copper is electrodeposited or electroless plated. 15. The substrate is aluminum or an aluminum alloy on which copper is vapor-deposited.
1. The lithium secondary battery according to 1. 16. The substrate is formed by spraying copper on aluminum or an aluminum alloy.
1. The lithium secondary battery according to 1. 17. The surface of the substrate on which the positive electrode material layer is arranged and the surface of the substrate on which the negative electrode material layer is arranged are roughened. A lithium secondary battery according to claim 2. 18. The lithium secondary battery according to claim 1, wherein the stack is pressed in the stacking direction. 19. A substrate having a positive electrode material layer or a negative electrode material layer only on one surface has higher rigidity than a substrate having a positive electrode material layer on one surface and a negative electrode material layer on the other surface. 18
The lithium secondary battery described. 20. The minimum value / maximum value of the actual capacity of each of the plurality of cells formed in the laminated body is 0.8 or more, and any one of claims 1 to 19 is characterized. Rechargeable lithium battery.