JP2002033132A - Nonaqueous secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous secondary battery having safety during high temperature storage while the energy density is kept high. SOLUTION: Firing during high temperature storage in the charged state can be restrained by mixing high molecular powder having endoergic peak from 100 deg.C to 150 deg.C both inclusive in differential thermal analysis with a positive electrode and/or a negative and/or an electrolyte by 0.1 wt.% to 4 wt.% for the positive and negative electrodes, 1 wt.% to 10 wt.% for the electrolyte.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous secondary battery having a high energy density and excellent reliability and safety.

[0002]

2. Description of the Related Art In recent years, with the development of portable equipment and cordless equipment, a battery as a power source thereof is required to have a higher energy density in order to realize long-time operation. In response to this demand, a Li-ion secondary battery using a carbon material for the negative electrode, lithium cobaltate for the positive electrode, and a solution in which a Li salt is dissolved in a non-aqueous solvent as an electrolytic solution is often used.

On the other hand, there is a strong demand for lighter and thinner portable telephones and notebook personal computers, and polymer batteries using a polymer gel electrolyte have attracted attention. The use of a polymer gel electrolyte as the electrolyte eliminates the risk of liquid leakage, and allows the battery case to use a soft case such as a resin laminated film with aluminum in the middle layer, and is a lightweight and thin non-aqueous secondary battery. Becomes possible.

[0004]

However, these non-aqueous secondary batteries have high energy density but have problems in reliability and safety. In particular, there is a danger of ignition in a charge state storage test (UL-94) at a high temperature such as 150 ° C. or a safety test such as continuous overcharge.

On the other hand, a highly safe LiMn is used for the positive electrode.
Countermeasures have been devised, such as using ₂ O ₄ , adding an additive to the electrolyte, or using a separator that melts at a high temperature. These are described in, for example, JP-A-5-205744, JP-A-11-329492, and JP-A-11-32289.

However, when LiMn ₂ O ₄ is used for the positive electrode, the discharge potential drops from mid-discharge to about 3 V, and the battery voltage drops in two stages. For this reason, the energy density is lower than that of the current LiCoO ₂ . In addition, when an additive such as crown ether is added to the electrolyte, the effect is small when added in a small amount, and when added in a large amount, an excessively stable film is formed on the surface of the active material. Causes a decline.

On the other hand, in a separator capable of high-temperature meltdown with a multilayer structure, it is difficult to produce a uniform film.
If there is a thin part, it will cause a short circuit at high temperature,
Each has its own problems, such as firing on the contrary.

[0008]

As a result of intensive studies to solve the above-mentioned problems, a non-aqueous secondary battery comprising a positive electrode, a negative electrode containing lithium as an active material, and an electrolyte containing a lithium salt and a non-aqueous solvent as main components has been obtained. A secondary battery, wherein the positive electrode and / or the negative electrode and / or the electrolyte are subjected to differential thermal analysis,
It has been found that by mixing a polymer powder having an endothermic peak at 100 ° C. or higher and 150 ° C. or lower, ignition during high temperature storage in a charged state can be suppressed. As the endothermic peak, when the polymer powder softens and when glass transition occurs,
Furthermore, it appears when it is dissolved in a solvent. In each case, the effect of suppressing ignition was observed.

As the polymer powder, polyethylene (P
E), polyacrylonitrile (PAN), vinyl chloride-
Acrylonitrile copolymer, vinyl acetate-acrylonitrile copolymer, polymethylene, polybutene-1, poly-
5-methylhexene, polydecamethylene terephthalate, polyvinyl isobutyl ether, polyethylene
2,6-Naphthalate was suitable.

The amount of the polymer powder to be added is 0.1 wt% or more and 4 wt% or less with respect to the positive electrode or the negative electrode.
1 wt% or more and 10 wt% or less with respect to the electrolyte, and the average particle size of the polymer powder is 0.05 μm or more and 5 μm or less (preferably 0.1 μm or more and 1 μm or less). Was effective.
However, in the case of an electrolyte, this addition amount indicates the ratio to the member excluding the solvent and the lithium salt.

As the electrolyte, a polymer gel type electrolyte may be used in addition to the combination of the separator composed of the microporous film and the electrolyte. As the polymer gel, a physically cross-linked polymer gel in which a gel-forming polymer is dissolved in an electrolytic solution, or a chemically cross-linked polymer gel in which a monomer or oligomer is cross-linked and gelled by a thermosetting reaction or the like is used.

The polymer gel electrolyte is slightly inferior to the ionic type in terms of high rate discharge characteristics, but is excellent in terms of safety. In a battery having a polymer gel in the positive electrode and / or the negative electrode and / or the electrolyte, the safety was significantly improved by adding the polymer powder.

The gel-forming polymer is preferably composed of at least one selected from the group consisting of polyethers, polyvinylidene fluorides, polyacrylates and polymethacrylates.

In the present invention, the negative electrode using lithium as an active material includes alloys, oxides, and the like capable of inserting and extracting lithium.
An example is a carbon material. As this alloy, lithium-aluminum alloy, Ti-Sn alloy, Fe-Sn alloy, etc., and as an oxide capable of inserting and extracting lithium, iron oxide,
Examples include tin oxide, niobium oxide, and titanium oxide, and examples of the carbon material include coke, graphite, and a fired organic material.

The active material of the positive electrode in the present invention includes a metal oxide containing at least one metal selected from the group consisting of manganese, cobalt, nickel, vanadium and niobium.

The electrolyte in the present invention is composed of a lithium salt dissolved in a non-aqueous solvent (aprotic organic solvent). Examples of the lithium salt include lithium perchlorate (LiClO ₄ ) and trifluoromethanesulfonic acid. Lithium (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (L
iPF _6), lithium tetrafluoroborate (LiBF _4), lithium hexafluoroarsenate (LiAsF _6), lithium hexafluoro antimonate (LiSbF _6), lithium trifluoromethanesulfonate imide [LiN (CF ₃ SO _{2 2} )
Is exemplified.

Examples of the non-aqueous solvent include ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), and butylene carbonate (B
C), γ-butyrolactone (γ-BL), sulfolane (SL), 1,2-dimethoxyethane (DME), 1,
2-diethoxyethane (DEE), ethoxymethoxyethane (EMC), 1,3-dioxolan (DOXL),
4-methyl-1,3-dioxolane (4M-DOXL)
And the like.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, by adding a small amount of a polymer powder having an endothermic peak at 100 ° C. or more and 150 ° C. or less by differential thermal analysis to the positive electrode or / and / or the negative electrode or / and the electrolyte, the battery can be heated to a high temperature. When exposed, the temperature rise of the battery can be once suppressed. Further, when the polymer powder is dissolved, a short circuit between the electrodes can be prevented. 150
The ignition phenomenon in the storage test in a charged state at ° C occurs while the temperature of the battery rises from 100 ° C to 150 ° C. As a result of intensive studies, it was found that the safety of the battery was significantly improved by delaying the rate of temperature rise of the battery between 100 ° C and 150 ° C. Polymer powder having an average particle diameter of 0.05 μm or more and 5 μm or less (preferably 0.1 μm or more and 1 μm or less) was excellent in dispersibility and was effective. In particular, by adding polyacrylonitrile, the effect of suppressing the generation of dendrites in an overcharged state was high, and it was possible to secure a great reliability.

An embodiment of the present invention will be described below. The battery characteristics were evaluated by assembling a cylindrical battery.

(Embodiment 1) The present invention will be described in more detail based on embodiments, but the present invention is not limited to the following embodiments. LiCoO ₂ classified to 100 mesh or less was used as the positive electrode active material.
Acetylene black (AB) as a conductive agent for 0 g
10 g of powder and polytetrafluoroethylene (P
TFE) 6 g of dispersion and 1 μm in average particle size
After sufficiently mixing 2 g of PAN powder, n-methyl-2-
An appropriate amount of pyrrolidone (NMP) was added, mixed well to form a paste, applied to an aluminum core material (25 μm in thickness), dried and rolled to obtain a 200 μm-thick positive electrode.

As the negative electrode, artificial graphite powder (active material) 10
0 g, 15 g of AB powder as a conductive agent, 8 g of styrene butadiene rubber (SBR) as a binder,
3 g of AN powder are mixed well, and water is used as a dispersion solvent.
The coated material is applied to a copper core material and then
It dried and rolled at ℃, and it was set as the negative electrode (250 micrometers in film thickness).

A positive electrode lead made of aluminum was connected to aluminum of the positive electrode core material by ultrasonic welding, and a copper negative electrode lead was similarly bonded to copper of the negative electrode core material by ultrasonic welding. A band-shaped porous polyethylene separator wider than the two electrode plates was disposed between the positive electrode and the negative electrode, and the whole was spirally wound. Furthermore, an insulating plate made of polypropylene is arranged on each of the upper and lower sides of the electrode body, and inserted into a battery case. EC and D in which 1 mol / l of LiPF ₆ is dissolved as a non-aqueous electrolytic solution are placed therein.
An equal volume mixed solution of ME was injected as an electrolyte. Thereafter, vacuum impregnation was performed, a sealing plate was inserted, mechanical caulking was performed, and sealing was performed to obtain a cylindrical battery (design capacity: 900 mAh).

The cylindrical battery thus manufactured was tested at a test temperature of 20 ° C. and a charging current of 0.2 C (1 C is a one-hour rate current).
Then, constant current charging was performed until the battery voltage reached 4.2 V, and then constant voltage charging (constant current constant voltage CCCV charging) was performed at 4.2 V. The first discharge was at a current of 0.2 C and a battery voltage of 3.
0V, the second time under the same charge condition, only discharge 2C
The current was measured. The second 2C discharge capacity was changed to the first 0C discharge capacity.
The value obtained by dividing by the 2C discharge capacity and multiplying by 100 was defined as the high rate discharge ratio. The closer this ratio is to 100, the better the high-rate discharge is. After the third time, charging and discharging were repeated under the same conditions as the first time. The discharge capacity ratio at the 100th cycle relative to the first cycle was defined as the cycle retention rate. The closer this ratio is to 100, the better the cycle characteristics. After charging the battery which had been charged and discharged for 100 cycles, it was subjected to a high-temperature storage test at 150 ° C. for 2 hours, and an ignition test was performed.

The results are shown in (Table 1). As a comparison, a battery (Comparative Example 1) was prepared in which the PAN powder was removed from the positive and negative electrodes in the above Examples, but the initial discharge capacity, high-rate discharge characteristics, and cycle characteristics were almost the same. However, the battery of this example did not ignite in the high-temperature storage test at 150 ° C.
The battery of Comparative Example 1 ignited during the heating.

[0025]

[Table 1]

(Examples 2 to 5)
The powder was replaced with various polymer powders to produce a battery. Table 1 shows the results of the battery. Table 1 also shows, for comparison, the characteristics of a battery (Comparative Example 2-5) in which a polymer powder having no endothermic peak at 100 ° C or higher and 150 ° C or lower in differential thermal analysis was added in the same manner as in Example 1. Show.

It has been found that the polymer powder having an endothermic peak at 100 ° C. or more and 150 ° C. or less has a large ignition suppressing effect. In the case of a polymer powder having an endothermic peak lower than 100 ° C., an endotherm occurred before the separator was melted, and there was no effect in suppressing ignition. On the other hand, if the endothermic peak is higher than 150 ° C., there is no endothermic peak in the range in which ignition occurs, and thus it is considered that there was no effect.

(Examples 6 to 8) As in Example 1, the positive electrode active material was LiCoOO classified to 100 mesh or less.
₂ , 10 g of AB powder as a conductive agent and 6 g of PTFE as a binder were added to 100 g of the positive electrode active material, mixed well, NMP was added in an appropriate amount, mixed well to form a paste, and an aluminum core material ( 25 μm), dried and rolled, and the same 200 μm thickness as in Example 1.
m of the positive electrode were obtained.

As the negative electrode, artificial graphite powder (active material) 10
15 g of AB powder as a conductive agent, 8 g of SBR as a binder, and various weights of the above-mentioned PAN powder with respect to 0 g, mixed well, and made a paste using water as a dispersing solvent. It was applied to the core material. Thereafter, the resultant was dried and rolled at 100 ° C. to obtain a negative electrode (250 μm in thickness) in the same manner as in Example 1 to produce a cylindrical battery.

The battery characteristics are shown in Table 1. No ignition phenomenon was observed when the amount of PAN added was 0.1 wt% or more and 4 wt% or less. When the addition amount was lower than 0.1 wt% (Comparative Example 6), ignition occurred, and when the addition amount exceeded 4 wt% (Comparative Example 7), the initial discharge capacity was significantly reduced. From this, the addition amount of PAN powder is 0.1 wt% or more and 4 wt%.
The following proved to be effective: The same applies to polymer powders having an endothermic peak of 100 ° C. or more and 150 ° C. or less other than PAN powder, and the same applies to the case where they are added only to the positive electrode or the case where they are added to both electrodes.

(Examples 9 to 11) As in Example 1, the cathode active material was LiCo classified to 100 mesh or less.
Using O ₂ , 10 g of AB powder as a conductive agent and 6 g of PTFE as a binder were added to 100 g of the positive electrode active material, 2 g of PE powder of various particle diameters were added, an appropriate amount of NMP was added, and the mixture was thoroughly mixed into a paste. Example 1 was applied to an aluminum core material (film thickness 25 μm), dried and rolled.
A positive electrode having the same film thickness of 200 μm was obtained.

As the negative electrode, artificial graphite powder (active material) 10
15 g of AB powder as a conductive agent and 8 g of SBR as a binder are added to 0 g, and water is used as a dispersion solvent, mixed well, and the paste is applied to a copper core material. After drying and rolling at 100 ° C., a negative electrode (film thickness 250 μm) was obtained in the same manner as in Example 1 to produce a cylindrical battery.

The battery characteristics are also shown in Table 1. If the average particle diameter of the PE powder is larger than 5 μm (Comparative Example 9) or smaller than 0.05 μm (Comparative Example 8), the temperature is 150 ° C.
An ignition phenomenon occurred during high-temperature storage for 2 hours. On the other hand, no ignition phenomenon was observed when PE powder having an average particle size of 0.05 μm or more and 5 μm or less was used. It is considered that the reason for this is that if the average particle size exceeds 5 μm, the effect of surrounding the negative electrode active material is weakened, whereby the exothermic reaction at the time of temperature rise cannot be suppressed. On the other hand, when the average particle size is smaller than 0.05 μm, it is considered that secondary aggregates are formed and the dispersibility is significantly reduced.

The effect of the average particle size was the same in the case of various polymer powders, and also in the case where it was added only to the positive electrode or the case where it was added to both electrodes.

Example 12 LiCo as a positive electrode active material
After mixing 85 g of O ₂ , 5 g of AB powder as a conductive material, and 5 g of PTFE as a binder, and adding an appropriate amount of NMP to form a paste, the mixture was applied to an aluminum foil in the same manner as in Example 1, dried, and rolled. A positive electrode (thickness: 200 μm) was produced.

As a negative electrode, 85 g of highly crystalline carbon (graphite), 3 g of AB powder and 12 g of PTFE were mixed on a copper foil, and an appropriate amount of NMP was added thereto to form a paste.
A negative electrode (250 μm in thickness) was prepared by coating, drying and rolling.

As electrolytes, polyvinylidene fluoride polymer PVDF and propylene hexafluoride (HFP)
In a solution prepared by dissolving 80 g of the copolymer (HFP ratio: 10%) in 60 g of dibutyl phthalate (DBP) and 200 g of acetone, 20 g of Aerosil and 8 g of polyethylene-2,6-naphthalate powder having an average particle diameter of 1 μm were added, and mixed well. Was prepared. Next, it was coated on a polyethylene terephthalate (PET) film, dried (acetone removed), and then the DBP was removed with diethyl ether (DEE) to produce a polymer porous membrane (thickness: 30 μm).

A cylindrical cell similar to that of Example 1 was formed between the negative electrode and the positive electrode with the above-described polymer porous membrane interposed therebetween. Appropriate amounts of 60 g of EC, 30 g of PC, and 10 g of LiBF ₄ were injected as electrolytes and impregnated in vacuum, followed by aging at 60 ° C. for 2 days to gel the polymer porous membrane. Thereafter, the container was sealed to produce a cylindrical battery.

The battery characteristics are shown in Table 2. The battery characteristics were almost the same as those obtained without the polyethylene-2,6-naphthalate powder (Comparative Example 10). However, in the present example, the firing probability was 0 out of 10 and not 100%, but in the present comparative example, 2 out of 10 fired. From this, it was found that the addition of polyethylene-2,6-naphthalate powder improved the high-temperature storage characteristics.

[0040]

[Table 2]

(Examples 13 and 14) Batteries were prepared in the same manner as in Example 12 except that polyethylene-2,6-naphthalate powder was added in various amounts. Table 2 shows the results of the battery. 1w polyethylene-2,6-naphthalate added
In the range of t% to 10% by weight, the probability of the ignition phenomenon is 10
It became 0 out of pieces. When the addition amount was lower than 1 wt% (Comparative Example 11), 5 out of 10 ignited, and when the addition amount exceeded 10 wt% (Comparative Example 12), no ignition phenomenon was observed, but the initial discharge capacity and the high rate The discharge ratio dropped significantly. From this, it was found that the amount of the polyethylene-2,6-naphthalate powder to be added to the electrolyte was 1 wt% or more and 10 wt% or less. This range was the same even when other polymer powders were added.

Example 15 Using the same positive electrode and negative electrode as in Example 12, a cylindrical cell similar to that of Example 1 was formed via a nonwoven fabric made of polyethylene (thickness: 30 μm). EC 40 g, DEC 50 g, LiPF ₆ 10 g as electrolyte
1.0 g of polymethylene powder having an average particle diameter of 0.1 μm, 10 g of methyldiethylene glycol acrylate as a monofunctional monomer, 1 g of ethylene oxide-modified trimethylolpropane triacrylate (molecular weight 428) as a polyfunctional monomer, and a thermal polymerization initiator And 0.03 g of bis (4-t-butylcyclohexyl) peroxydicarbonate was added and mixed and dissolved to prepare a thermopolymerizable electrolyte. After injection of an appropriate amount of this electrolytic solution and vacuum impregnation, thermal polymerization was carried out at 80 ° C. for 4 hours to cause gelation (polyacrylate polymer gel), followed by sealing to produce a cylindrical battery. In this battery, the gel electrolyte (including polymethylene powder) was also present in the positive and negative electrodes.

The battery characteristics are shown in (Table 2). In the high-temperature storage test of this example, the firing probability was 0 out of 10 batteries, and all the batteries did not fire.

Example 16 The same positive electrode as in Example 12 was used, and the negative electrode containing the same PAN powder as in Example 1 was used. As the electrolyte, 40 g of trifunctional acrylate (molecular weight: 9000) copolymer of ethylene oxide and propylene oxide, 60 g of γ-BL and LiC
A mixture of 10 g of F ₃ SO ₃ and 2 g of polydecamethylene terephthalate having an average particle size of 0.1 μm dissolved therein is cast into a film, and then irradiated with an electron beam to obtain a polyether polymer gel electrolyte (thickness: 30 μm). Was formed.

LiCF ₃ SO ₃ was applied to the positive and negative electrodes by vacuum impregnation.
Was dissolved in 1 mol / l and injected into the space of the electrode plate. A cylindrical battery similar to that of Example 1 was produced with the polymer gel interposed between these electrode plates.

Table 2 shows the battery characteristics.
The probability of ignition in the 0 ° C. high-temperature storage test was 0 out of 10 and not all of them ignited.

(Example 17) Using the same positive electrode containing the same PAN powder as in Example 1 and the same negative electrode as in Example 12, the same procedure as in Example 1 was carried out via a microporous polyethylene separator (thickness: 30 μm). A cylindrical cell was constructed. To 40 g of EC, 50 g of DEC, and 10 g of LiPF ₆ were added 1.2 g of polybutene-1 powder having an average particle size of 4 μm, and 10 g of methyldiethylene glycol methacrylate as a monofunctional monomer, and ethylene oxide-modified trimethylolpropane trimethacrylate as a polyfunctional monomer. 1 g, bis (4-tert-butylcyclohexyl) peroxydicarbonate 0.05 as a thermal polymerization initiator
g was added and mixed and dissolved to prepare a thermopolymerizable electrolytic solution.
After injection of an appropriate amount of this electrolytic solution and vacuum impregnation, thermal polymerization was performed at 80 ° C. for 4 hours to gel (polymethacrylate polymer gel), and then sealed to produce a cylindrical battery. Although the gel electrolyte was also present in the positive electrode and the negative electrode, the polybutene-1 powder did not enter the inside of the electrode plate because of its large particle size.

The battery characteristics are shown in (Table 2). In the high-temperature storage test of this example, the firing probability was 0 out of 10 batteries, and all the batteries did not fire.

It was found that high storage ignition in a charged state can be suppressed by mixing a polymer powder having an endothermic peak at 100 ° C. or more and 150 ° C. or less in differential thermal analysis with the positive electrode and / or the negative electrode and / or the electrolyte. .
Polymer powders include PE, PAN, vinyl chloride-acrylonitrile copolymer, vinyl acetate-acrylonitrile copolymer, polymethylene, polybutene-1, poly-5-methylhexene, polydecamethylene terephthalate, polyvinyl isobutyl ether, and polyethylene-2. , 6-naphthalate was suitable, but 100
It is effective if the polymer powder has an endothermic peak at not less than 150 ° C. and not more than 150 ° C.

The amount of the polymer powder added is 0.1 wt% or more and 4 wt% or less for the positive electrode or the negative electrode.
1 wt% or more and 10 wt% or less with respect to the electrolyte, and the average particle size of the polymer powder is 0.05 μm or more and 5 μm or less (preferably 0.1 μm or more and 1 μm or less). Was effective.
In addition, when the battery was subjected to an overcharge test at 4.3 V, the battery to which the polymer powder of the present invention was added had higher safety than the battery without the addition.

[0051]

According to the present invention, by adding an appropriate amount of a polymer powder having an endothermic peak at 100 ° C. or more and 150 ° C. or less by differential thermal analysis to the positive electrode and / or the negative electrode and / or the electrolyte, the battery can be manufactured without deteriorating the battery characteristics. When exposed to high temperatures,
The temperature rise of the battery is once suppressed, and the operation of the battery can be safely stopped (discharge reaction stopped), and high safety can be secured.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Sato 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. F-term (reference) 5H029 AJ12 AK02 AK03 AL02 AL06 AL07 AL12 AM00 AM02 AM03 AM04 AM05 AM07 AM16 BJ27 DJ08 EJ12 EJ14 HJ01 HJ05 HJ14 5H050 AA15 BA17 CA03 CA04 CA05 CA08 CA09 CB02 CB07 CB08 CB12 DA09 EA23 EA26 EA28 HA01 HA05 HA14

Claims (10)

[Claims] 1. A non-aqueous secondary battery comprising a positive electrode, a negative electrode using lithium as an active material, and an electrolyte mainly containing a lithium salt and a non-aqueous solvent, wherein the non-aqueous secondary battery includes: 100 ° C or more and 150 in differential thermal analysis
A non-aqueous secondary battery comprising a polymer powder having an endothermic peak at a temperature of not more than ° C. 2. A non-aqueous secondary battery comprising a positive electrode, a negative electrode using lithium as an active material, and an electrolyte mainly containing a lithium salt and a non-aqueous solvent, wherein the non-aqueous secondary battery comprises: Furthermore, a non-aqueous secondary battery comprising a polymer powder having an endothermic peak at 100 ° C. or higher and 150 ° C. or lower in a differential thermal analysis in an electrolyte. 3. A non-aqueous secondary battery comprising a positive electrode, a negative electrode containing lithium as an active material, and an electrolyte containing a lithium salt and a non-aqueous solvent as main components. A non-aqueous secondary battery comprising a polymer powder having an endothermic peak at not less than 150 ° C. and not more than 150 ° C. 4. The polymer powder according to claim 1, wherein the polymer powder is polyethylene, polyacrylonitrile, vinyl chloride-acrylonitrile copolymer, vinyl acetate-acrylonitrile copolymer, polymethylene, polybutene-1, poly-5-. Methylhexene, polydecamethylene terephthalate, polyvinyl isobutyl ether, polyethylene
A non-aqueous secondary battery, which is at least one member of the group consisting of 2,6-naphthalate. 5. The polymer powder according to claim 1, wherein the polymer powder is contained in an amount of 0.1 wt% or more and 4 wt% or less.
% Of non-aqueous secondary battery. 6. A non-aqueous secondary battery, wherein the polymer powder is added to the electrolyte according to claim 2 in an amount of 1 wt% or more and 10 wt% or less. 7. The polymer powder according to claim 1, wherein the average particle diameter of the polymer powder is 0.05 μm.
A non-aqueous secondary battery having a length of not less than m and not more than 5 μm. 8. A non-aqueous secondary battery, wherein the electrolyte according to any one of claims 1, 2 and 3 is a polymer gel. 9. A non-aqueous secondary battery, wherein the positive electrode and / or the negative electrode according to any one of claims 1, 2 and 3 has a polymer gel. 10. The polymer forming the polymer gel according to claim 8 or 9, wherein the polymer is at least one selected from the group consisting of polyethers, polyvinylidene fluorides, polyacrylates and polymethacrylates. Non-aqueous secondary battery characterized by the following.