JPH07220759A - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery

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Publication number
JPH07220759A
JPH07220759A JP6010091A JP1009194A JPH07220759A JP H07220759 A JPH07220759 A JP H07220759A JP 6010091 A JP6010091 A JP 6010091A JP 1009194 A JP1009194 A JP 1009194A JP H07220759 A JPH07220759 A JP H07220759A
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JP
Japan
Prior art keywords
active material
material layer
negative electrode
protective film
non
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP6010091A
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Japanese (ja)
Other versions
JP3371301B2 (en
Inventor
Hiroshi Benno
Takeshi Koike
武志 小池
博 辨野
Original Assignee
Sony Corp
ソニー株式会社
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Filing date
Publication date
Application filed by Sony Corp, ソニー株式会社 filed Critical Sony Corp
Priority to JP01009194A priority Critical patent/JP3371301B2/en
Publication of JPH07220759A publication Critical patent/JPH07220759A/en
Application granted granted Critical
Publication of JP3371301B2 publication Critical patent/JP3371301B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

(57) [Summary] [Non-aqueous electrolysis having negative electrode 1 having negative electrode active material layer 32 formed on current collector 9 and positive electrode 2 having positive electrode active material layer 33 formed on current collector 10] In the liquid secondary battery, the porous protective film 31 having a thickness of 0.1 to 200 μm is formed on the surface of either the negative electrode active material layer 32 or the positive electrode active material layer 33. [Effect] The protective film formed on the surface of the active material layer can prevent the active material from falling off and redepositing after the active material layer is formed and before the electrodes are housed in the battery can. Therefore, an internal short circuit of the battery caused by the active material redeposited on the electrode surface can be prevented, and a highly reliable and safe non-aqueous electrolyte secondary battery can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses, for example, a material such as a carbon material that can be doped with lithium ions and dedoped, as a negative electrode active material, and a lithium complex such as a lithium cobalt complex oxide as a positive electrode active material. The present invention relates to a non-aqueous electrolyte secondary battery using an oxide.

[0002]

2. Description of the Related Art In recent years, due to advances in electronic technology, high performance, miniaturization, and portability of electronic devices have been advanced, and batteries used in these electronic devices are also strongly required to have high energy density. It has become so.

Conventionally, secondary batteries used in these electronic devices include aqueous electrolyte secondary batteries such as nickel-cadmium batteries and lead batteries. These batteries have low discharge voltage and high energy density. It is insufficient in terms of obtaining a battery.

Therefore, recently, as a secondary battery replacing the above-mentioned nickel-cadmium battery or the like, a material capable of doping / dedoping lithium ions such as a carbon material is used as a negative electrode active material and a positive electrode active material is used. Research and development of non-aqueous electrolyte secondary batteries using lithium composite oxides such as lithium cobalt composite oxides and non-aqueous electrolytes prepared by dissolving lithium salt in a non-aqueous solvent as electrolytes have been actively conducted. ing.

This battery has the advantages that the battery voltage is high and self-discharge is small, and exhibits a high energy density.

In order to actually use the above-mentioned carbon materials and lithium composite oxides as active materials, these are used with an average particle size of 5-50.
A powder having a diameter of μm is dispersed in a solvent together with a binder to prepare a negative electrode mixture slurry and a positive electrode mixture slurry. Then, each of the slurries is applied to a metal foil serving as a current collector to form a negative electrode active material layer and a positive electrode active material layer. A negative electrode and a positive electrode each having a negative electrode active material layer and a positive electrode active material layer laminated on this current collector are separated from each other with a separator interposed therebetween, and housed in the battery can in this state.

Here, a point to be noted in the above-mentioned non-aqueous electrolyte secondary battery is that the non-aqueous electrolyte used therein has an electric conductivity that is about two orders of magnitude smaller than that of the aqueous electrolyte. Therefore, in order to obtain sufficient battery performance, it is necessary to make the structure of the battery such that the electrolyte can move as easily as possible.

Therefore, in the above non-aqueous electrolyte secondary battery,
As a separator to separate the positive and negative electrodes, thickness 1
A very thin separator of about 0 to 50 μm is used.

[0009]

By the way, in the non-aqueous electrolyte secondary battery as described above, the electrode is coated with the mixture slurry containing the powdered active material on the current collector to form the active material layer. It is produced by that, and then stored in a battery can.

At this time, the electrode on which the active material layer is formed is
Before being stored in the battery can, the process of stacking the electrode and the separator, the process of cutting into a predetermined electrode shape, etc.
Passes through various processes. Usually, in these processes, for the purpose of mass production, the electrode is manufactured as a long electrode raw material, which is run using a running system such as an unwinding roll, a winding roll, a guide roller, etc. Then do.

However, when the raw material of the electrode is traveling,
When the active material layer comes into contact with a guide roller or the like, the active material drops off from the active material layer, and a part of the dropped active material reattaches to the surface of the electrode.

Since the drop-out active material redeposited on the electrode surface has a particle size of 5 to 50 μm, which is about the same as the thickness of the separator, there is a problem that it penetrates the separator in the assembled battery and causes an internal short circuit. Induce.

Therefore, the present invention has been proposed in view of such a conventional situation, and it is possible to prevent the active material from falling off from the electrode during manufacturing and prevent the occurrence of internal short circuit. The purpose is to provide a secondary battery.

[0014]

In order to achieve the above-mentioned object, a non-aqueous electrolyte secondary battery of the present invention comprises a negative electrode formed by laminating a negative electrode active material coating layer on a current collector, and a current collector. In a non-aqueous electrolyte secondary battery having a positive electrode having a positive electrode active material coating layer laminated thereon and a non-aqueous electrolyte solution, a thickness is provided on at least one surface of the negative electrode active material coating layer and the positive electrode active material coating layer. 0.1
It is characterized in that a porous protective film having a thickness of up to 200 μm is formed.

Further, the porous protective film is characterized by being a non-woven fabric. Furthermore, the porous protective film is characterized by comprising a resin binder and solid particles.

The non-aqueous electrolyte secondary battery to which the present invention is applied includes a negative electrode formed by stacking a negative electrode active material layer on a current collector, and a positive electrode formed by stacking a positive electrode active material layer on a current collector. It has a non-aqueous electrolyte.

In the present invention, in order to suppress the occurrence of an internal short circuit in such a non-aqueous electrolyte secondary battery, a porous protective film is formed on the surface of at least one of the positive electrode and negative electrode active material layers. To do.

That is, in such a non-aqueous electrolyte secondary battery, the positive electrode and the negative electrode are each formed by applying a mixture slurry containing a powdered active material onto a current collector to form an active material layer. It is manufactured and then stored in a battery can. Here, the electrode on which the active material layer is formed passes through various steps such as a step of stacking with a separator and a step of cutting until it is housed in the battery can. During the period from the preparation to the storage in the battery can, the active material existing particularly near the surface of the active material layer may drop off, and a part of the dropped active material may reattach to the electrode. The active material redeposited on the electrodes causes an internal short circuit in the completed battery.

Therefore, in the present invention, in order to suppress an internal short circuit caused by such a dropout active material, a porous protective film is formed on the surface of the active material layer of at least one of the positive electrode and the negative electrode, and the active material layer is formed. The active material should be prevented from falling off.

When the porous protective film is formed on the surface of the active material layer after formation, the active material existing on the surface of the active material layer is firmly bonded to the protective film. After such a protective film is formed, the active material on the surface is firmly bonded to the protective film even if there is some contact with the surface before the electrode is housed in the battery can. Therefore, the active material does not fall off the electrode. Therefore, the internal short circuit caused by the redeposition of the drop-off active material is prevented.

The reason why the protective film is porous is to prevent the protective film from interfering with the original function of the electrode, that is, the electrode reaction with the electrolyte ions in the electrolytic solution.

The thickness of this porous protective film is 0.1.
It is necessary to be in the range of up to 200 μm. When the thickness of the porous protective film is less than 0.1 μm, the protective effect is insufficient,
It is not possible to sufficiently prevent the active material from falling off. Further, when the thickness of the porous protective film exceeds 200 μm, the protective film hinders the reaction of the electrodes with the ions in the electrolytic solution, which deteriorates the battery performance.

Examples of such a porous protective film include a non-woven fabric and a coating film formed by applying a fine particle slurry in which fine particles are dispersed in a solvent together with a binder.

As a non-woven fabric, it withstands the temperature during film formation,
It is necessary to select a material that is insoluble in the non-aqueous solvent of the electrolytic solution, and it is desirable that the weight per unit area can be made as small as possible without impairing the effect of preventing the active material from falling off. For example, Manila hemp or the like can be used. Also,
The material is not limited to an insulating material such as Manila hemp, but may be one having electron conductivity in consideration of smoothness of electrode reaction.

To retain the nonwoven fabric on the surface of the active material layer,
Although an adhesive agent or the like may be used, the slurry containing the active material 22 is applied to both surfaces of the current collector 21 and the active material coating film 23 as shown in FIG. While the active material coating film 23 is wet, the nonwoven fabric 24 may be directly placed on the coating film 23 and dried. As the active material coating film 23 is dried, the non-woven fabric 24 is attached to the surface thereof, and an active material layer is formed in the form of a non-woven fabric being attached to the surface.

On the other hand, the porous protective film may be a coating film formed by applying a fine particle slurry other than the non-woven fabric as described above.

That is, as shown in FIG.
When the fine particle slurry 28 in which the fine particles 27 are dispersed in a solvent together with the binder is applied to the surface of the electrode active material layer 26 containing, the binder in the slurry 28 forms a contact interface between the solid fine particles 27 or the solid fine particles 27. Collect near the contact interface with the active material layer 26. As a result, a portion other than the contact interface becomes, so to speak, a hole, and a protective film having many such hole portions is formed.

The fine particles to be contained in the fine particle slurry must be insoluble in the non-aqueous solvent of the electrolytic solution. Alumina powder, SiO 2 powder (silica), insulating fine particles such as polyethylene resin, and electrode reaction. In consideration of the above, a carbon powder or the like having electron conductivity may be used.

However, when carbon powder is used for the protective film, if it falls off and reattaches to the electrode surface,
As in the case where the active material in the active material layer is dropped and redeposited, this may cause an internal short circuit. Therefore, in order to reliably prevent such carbon powder from falling off, it is desirable to increase the amount of the binder with respect to the carbon powder to some extent within a range in which the effect of forming pores at the contact interface can be maintained. For example, the protective film may contain the binder in an amount 1.5 times the binder content in the active material layer.

The particle size of these fine particles is 0.1 to 50 μm.
However, the thickness is preferably 5 to 10 μm from the viewpoints of permeability of the electrolytic solution, control of the thickness of the protective film, and the like.

Further, as the binder, in addition to polyvinylidene fluoride, a rubber resin or the like can be used as long as it has resistance to the electrolytic solution.

Although various materials used for the protective film have been exemplified above, when an insulating material is used for the protective film, the separator is excluded so that the protective film also has a function as a separator. May be. As a result, the cost of the separator can be reduced, which is advantageous for improving production efficiency.

As the negative electrode provided with such a porous protective film, the negative electrode active material used for the positive electrode, and the positive electrode active material, those usually used in this type of non-aqueous electrolyte secondary battery are used. It is possible.

For example, as the negative electrode active material, it is possible to use an alkali metal such as lithium, or a material that is doped / dedoped with an alkali metal such as lithium in association with charge / discharge reaction. As an example of the latter, a conductive polymer such as polyacetylene or polypyrrole, or a carbon material such as coke, polymer carbon, or carbon fiber can be used, but a carbonaceous material is used because of its large energy density per unit volume. It is desirable to use. Carbonaceous materials include pyrolytic carbons, cokes (petroleum coke,
Pitch coke, coal coke, etc.), carbon black (acetylene black, etc.), glassy carbon, organic polymer material fired body (organic polymer material at an appropriate temperature of 500 ° C. or higher in an inert gas stream or in a vacuum) Fired), carbon fiber, etc. are used.

On the other hand, examples of the positive electrode active material include transition metal oxides such as manganese dioxide and vanadium pentoxide, transition metal chalcogenides such as iron sulfide and titanium sulfide, and composite compounds of these with lithium. Can be used. In particular, high voltage and high energy density are obtained,
Lithium-cobalt composite oxide and lithium-cobalt-nickel composite oxide are preferable because they have excellent cycle characteristics.

As the electrolytic solution used in the battery, for example, an electrolytic solution in which a lithium salt is used as an electrolyte and this is dissolved in an organic solvent is used. Here, the organic solvent is not particularly limited, but for example, propylene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran. , 1,3-dioxolane, 4
-Methyl-1,3-dioxolane, diethyl ether,
A single solvent or a mixed solvent of two or more kinds such as sulfolane, methylsulfolane, cetonitrile and propionitrile can be used.

Any known electrolyte may be used as the electrolyte.
Can be used, LiClOFour, LiAsF 6, LiPF6, L
iBFFour, LiB (C6HFive)Four, LiCl, LiB
r, CH3SO3LI, CF3SO3There are Li and the like.

[0038]

[Function] A negative electrode formed by laminating a negative electrode active material layer on a current collector,
In a non-aqueous electrolyte secondary battery having a positive electrode in which a positive electrode active material layer is laminated on a current collector and a non-aqueous electrolytic solution, a thickness is formed on at least one surface of the negative electrode active material layer and the positive electrode active material layer. When the porous protective film having a thickness of 0.1 to 200 μm is formed, the active material existing on the surface of the active material layer is firmly bonded to the protective film. After forming such a protective film, the active material on the surface is firmly bonded to the protective film even if there is some contact with the electrode surface before the electrode is housed in the battery can. Therefore, the active material does not fall off the electrode. Therefore, before the electrode is housed in the battery can, the internal short circuit of the battery caused by the active material that has fallen off and redeposited on the electrode surface is prevented.

Further, since this protective film is porous,
By forming this, the original function of the electrode, that is, the electrode reaction with the electrolyte ions in the electrolytic solution is not hindered, and the above effect is obtained without degrading the battery performance.

[0040]

EXAMPLES Preferred examples of the present invention will be described below based on experimental results.

Example 1 In this example, a non-woven fabric is used as a protective film formed on the surface of an active material layer.

The structure of the non-aqueous electrolyte secondary battery produced in this example is shown in FIG. The non-aqueous electrolyte secondary battery was manufactured as follows.

First, the negative electrode 1 was manufactured as follows.
Petroleum pitch was used as a starting material, and this was fired to obtain coarse-grained pitch coke. This coarse-grained pitch coke was crushed into a powder having an average particle size of 20 μm, and the powder was fired in an inert gas at a temperature of 1000 ° C. to remove impurities, thereby producing a coke material powder.

The coke material powder thus produced was used as a negative electrode active material carrier, and 90 parts by weight of this coke material powder was used as a binder for polyvinylidene fluoride (PVd).
F) 10 parts by weight were mixed to prepare a negative electrode mixture. This negative electrode mixture was dispersed in N-methylpyrrolidone as a solvent to prepare a negative electrode mixture slurry.

Next, this negative electrode mixture slurry is applied to both surfaces of a strip-shaped copper foil having a thickness of 10 μm to be the negative electrode current collector 9 and, at the same time, while the coating film is still wet, it is applied onto the coating film. A non-woven fabric as a protective film was placed and dried. As a result, the negative electrode active material layer 32 in the form of the non-woven fabric 31 being attached to the surface was formed.

In this embodiment, the non-woven fabric is Manila.
I used hemp. This Manila hemp is 1m 2Weight per hit is 1
The thickness is 1 g and the thickness is 40 μm.

Then, the protective film 31 is formed on the surface in this manner.
The strip-shaped negative electrode was produced by compression-molding the negative electrode active material layer 32 formed by having a roller press. In addition, in the strip-shaped negative electrode 1, the negative electrode active material layer 32 after molding has the same film thickness of 90 μm on both surfaces, the width is 55.6 mm, and the length is 551.5 mm.

Next, the positive electrode 2 was produced as follows.
LiCoO 2 was obtained by mixing 0.5 mol of lithium carbonate and 1 mol of cobalt carbonate and baking in air at a temperature of 900 ° C. for 5 hours.

Using this LiCoO 2 as a positive electrode active material, 91 parts by weight of this LiCoO 2 was mixed with 6 parts by weight of graphite as a conductive agent and 3 parts by weight of PVdF as a binder to prepare a positive electrode mixture. This positive electrode mixture was dispersed in N-methylpyrrolidone to prepare a positive electrode mixture slurry.

Next, this positive electrode mixture slurry is uniformly applied to both surfaces of a strip-shaped aluminum foil having a thickness of 20 μm to be the positive electrode current collector 10 and dried to form the positive electrode active material layer 33, and compression molding is performed. By doing so, the strip positive electrode 2 was produced. The strip-shaped positive electrode 2 has the same thickness of the positive electrode active material layer 33 after molding of 70 μm on both sides, the width is 53.6 mm, and the length is 523.5 mm.

The strip-shaped negative electrode 1 and the strip-shaped positive electrode 2 produced as described above are used as a separator 3 with a thickness of 25 μm and a width of 5 μm.
A negative electrode 1, a separator 3, a positive electrode 2, and a separator 3 were laminated in this order via a 8.1 mm microporous polypropylene film to obtain a laminated electrode body having a four-layer structure. Then, this laminated electrode body is spirally wound many times along the length direction with the negative electrode 1 inside, and further the end portion of the separator located at the outermost periphery is fixed with the tape 20 to form the spirally wound electrode body. It was made. In this spiral electrode body, the hollow portion at the center has an inner diameter of 3.5 mm and an outer diameter of 17.0 mm.

The spirally wound electrode body manufactured as described above was housed in a nickel-plated iron battery can 5, and insulating plates 4 were placed on the upper and lower surfaces of the spirally wound electrode body. Then, in order to collect the current of the negative electrode 1 and the positive electrode 2, the lead 12 made of aluminum is drawn out from the positive electrode current collector 10 to the battery lid 7, and the negative electrode lead 11 made of nickel is drawn out from the negative electrode current collector 9 to form a battery can. Welded to 5.

Next, the battery can 5 containing the spiral electrode body.
5.0 g of a non-aqueous electrolytic solution prepared by dissolving LiPF 6 in a mixed solvent of equal volume of propylene carbonate and diethyl carbonate at a ratio of 1 mol / l was injected into the solution to impregnate the spirally wound electrode body.

The battery lid 5 is fixed by caulking the battery can 5 through the insulating sealing gasket 6 whose surface is coated with asphalt, so that the battery can be kept airtight and have a diameter of 1 mm.
A cylindrical non-aqueous electrolyte secondary battery having a size of 8 mm and a height of 65 mm was prepared.

Example 2 In this example, a coating film is used as a protective film formed on the surface of the active material layer.

A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the formation of the negative electrode active material layer and the protective film of the negative electrode was carried out as follows. However, here, the positive electrode active material layer of the positive electrode had a thickness of 65 μm on both sides, and a microporous film having a thickness of 15 μm was used as a separator.

That is, a negative electrode active material layer was formed by applying the negative electrode mixture slurry prepared in the same manner as in Example 1 to both surfaces of a copper foil which will be the negative electrode current collector, and drying.

On the other hand, 72 parts by weight of alumina powder having an average particle size of about 10 μm, 3 parts by weight of PVdF as a binder and 25 parts by weight of N-methylpyrrolidone as a solvent were mixed to prepare a fine particle slurry as a protective film material. .

Then, this fine particle slurry was applied to the surface of the negative electrode active material layer formed on the negative electrode current collector at a coating thickness of about 20 μm and dried to form a porous protective film. Next, the negative electrode active material layer having the protective film formed on its surface was compression-molded by a roller press machine to prepare a strip-shaped negative electrode. The strip-shaped negative electrode has the same thickness of the negative electrode active material layer after molding, which is 85 μm on both surfaces.

Example 3 This example is an example in which a coating film was used as a protective film formed on the surface of the electrode active material layer, and the separator was omitted.

In producing the laminated electrode body, a separator is not interposed between the strip-shaped negative electrode and the strip-shaped positive electrode, only the strip-shaped negative electrode and the strip-shaped positive electrode are stacked, and the spiral winding is performed many times so that the negative electrode is inside. A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 2 except for the above. However, in this case as well, in the spiral electrode body, the inner diameter of the hollow portion at the center is 3.5 mm and the outer diameter is 17.0 mm. In addition, the thickness of the negative electrode active material layer is 90
μm, and the thickness of the positive electrode active material layer was 70 μm.

Comparative Example A non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that a non-woven fabric was not attached to the surface of the negative electrode active material layer.

The rate of occurrence of internal short circuit was examined for each battery manufactured as described above.

In order to measure the rate of occurrence of internal short circuit, the prepared battery was initially charged immediately after preparation and left for 2 weeks. Then, after being left for 2 weeks, the open circuit voltage was measured, and a voltage at which this voltage was lower than the reference was judged to be “with internal short circuit”. Table 1 shows the occurrence rate of the internal short circuit of the battery measured as described above.

[0065]

[Table 1]

As can be seen from Table 1, all the batteries of Examples 1 to 3 in which the protective film was formed on the surface of the active material layer had a lower occurrence rate of internal short circuit than the batteries of Comparative Example. From this, it was found that forming a protective film on the surface of the active material layer is extremely effective in suppressing the occurrence of internal short circuits in the battery.

Further, in the battery of Example 3, the internal short circuit is surely suppressed even though the separator is not used, and the absence of the separator causes no trouble. From this, it was found that if an insulating film is used as the protective film, it can be used together as a separator, and a secondary effect that the cost of the separator can be reduced can be obtained.

In the above examples, the case where the protective film is formed only on the negative electrode is taken as an example, but of course, the case where the protective film is formed only on the positive electrode or the protective film is formed on both the negative electrode and the positive electrode. Even in this case, the same effect can be obtained.

[0069]

As apparent from the above description, the non-aqueous electrolyte secondary battery of the present invention has a thickness of 0.1 to 200 μm on either surface of the negative electrode active material layer or the positive electrode active material layer. Since the porous protective film is formed, the protective film can prevent the active material from falling off and redepositing after the active material layer is formed and before the electrode is housed in the battery can. Therefore, an internal short circuit of the battery caused by the active material redeposited on the electrode surface can be prevented, and high reliability and safety can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing a state in which a nonwoven fabric is stuck as a protective film on an active material layer of an electrode.

FIG. 2 is a schematic view showing a state in which a coating film containing fine particles is applied as a protective film on an active material layer of an electrode.

FIG. 3 is a schematic vertical cross-sectional view showing one structural example of a non-aqueous electrolyte secondary battery to which the present invention is applied.

[Explanation of symbols]

 1 Negative electrode 2 Positive electrode 3 Separator 9 Negative electrode current collector 10 Positive electrode current collector 31 Porous protective film 32 Negative electrode active material layer 33 Positive electrode active material layer

Claims (3)

[Claims]
1. A non-aqueous electrolyte solution having a non-aqueous electrolyte, a negative electrode formed by laminating a negative electrode active material coating layer on a current collector, a positive electrode formed by laminating a positive electrode active material coating layer on a current collector. In the secondary battery, a non-aqueous electrolyte secondary battery in which a porous protective film having a thickness of 0.1 to 200 μm is formed on the surface of either the negative electrode active material coating layer or the positive electrode active material coating layer. .
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the porous protective film is a non-woven fabric.
3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the porous protective film comprises a resin binder and solid particles.
JP01009194A 1994-01-31 1994-01-31 Non-aqueous electrolyte secondary battery Expired - Fee Related JP3371301B2 (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
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JP3371301B2 JP3371301B2 (en) 2003-01-27

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