JPH07134984A - Cylindrical nonaqueous electrolyte secondary battery - Google Patents

Abstract

PURPOSE:To provide a smooth progress of battery reaction, to secure a high battery capacity, and to provide an excellent cycle property. CONSTITUTION:In a cylindrical non-aqueous electrolyte secondary battery, a mixture consisting of a carbon material, which has (002) face spacing of 3.70Angstrom or more, a true density of less than 1.70g/cm<3>, and no heat generating peak at 700 deg.C or more by a differential thermal analysis in air flow, carbon fabric, and a binder at least is used as a negative electrode binding material. In this way, a negative electrode is sufficiently expands its volume, so that a clearance between a spiral electrode body outer circumference and a battery can inner circumference is filled up, and winding looseness of the electrode is prevented, and consequently, a proper pressure is generated between the negative electrode and the positive electrode.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cylindrical non-aqueous electrolyte secondary battery, and more particularly to improving charge / discharge cycle characteristics.

[0002]

2. Description of the Related Art Recent remarkable advances in electronic technology have made electronic devices smaller and lighter one after another. As a result, even smaller batteries are being used for mobile power sources.
Light weight and high energy density are required.

Conventionally, an aqueous solution type battery such as a lead battery or a nickel-cadmium battery has been mainly used as a secondary battery for general use. However, although these batteries have excellent cycle characteristics, they cannot be said to be sufficiently satisfactory in terms of battery weight and energy density.

On the other hand, recently, a non-aqueous electrolyte secondary battery using lithium or a lithium alloy for the negative electrode has been attracting attention. This battery has high energy density, less self-discharge,
Moreover, it is lightweight and has excellent characteristics as a secondary battery. However, as the charge / discharge cycle is repeated, lithium grows into dendrite-like crystals, and
There are drawbacks such as passing through the voids of the fiber and finally reaching the positive electrode to cause an internal short circuit, and lithium deactivating and precipitating in powder form, which is a major obstacle to practical use. ing.

Therefore, there has been proposed a non-aqueous electrolyte secondary battery using a carbonaceous material such as coke, graphite, or a sintered body of an organic polymer capable of doping / dedoping lithium or lithium ions in the negative electrode. This battery has high expectations because it does not cause dendrite-like crystal growth of lithium due to repeated charge / discharge cycles as described above, and has a high battery voltage and high energy density.

In this case, examples of the carbonaceous material used for the negative electrode include, for example, JP-A-62-122066 and JP-A-6-62126.
As disclosed in Japanese Patent Publication No. 2-90863, etc., (0
It is usual to use those having a 02) plane spacing of 3.40 to 3.60Å and a true density of about 1.70 to 2.20 g / cm ³ . However, carbonaceous materials having morphological parameters such as (002) plane spacing and true density in the above ranges are insufficient in the amount of lithium that can be doped, and are a major factor in determining the energy density of a battery. The capacity per unit weight of carbon (mAh / g) can be obtained only about half of the theoretical value (theoretically, one carbon atom is doped to six carbon atoms). It's known.

Therefore, in Japanese Patent Laid-Open No. 63-21795, the (002) plane spacing is 3.70 Å or more, the true density is less than 1.70 g / cm ³ , and the differential heat in air flow is It has been shown by analysis that when a carbonaceous material having no exothermic peak at 700 ° C. or higher is used for the negative electrode, a non-aqueous electrolyte secondary battery having not only excellent cycle life but also large discharge capacity is realized.

[0008]

However, Japanese Patent Laid-Open No. Sho 63-63
A carbonaceous material having a morphological parameter as disclosed in Japanese Patent Publication No. -21795 has a drawback in that it has a large lithium doping amount but has a small volume expansion coefficient due to lithium doping.

That is, the carbonaceous material capable of being doped / dedoped with lithium has a characteristic that its volume expands when it is doped with lithium. In a non-aqueous electrolyte secondary battery using a carbonaceous material as a negative electrode, the volume expansion of such a carbonaceous material is used to increase the pressure between the members to ensure contact. Therefore, when a carbonaceous material having a small volume expansion coefficient due to lithium doping is used, such an effect cannot be obtained, resulting in poor contact and impairing the smoothness of the electrode reaction.

In order to eliminate such inconvenience, in Japanese Patent Laid-Open No. 5-234593, a negative electrode pellet of a coin-type non-aqueous electrolyte secondary battery is used, in addition to the carbonaceous material having the above-mentioned morphological parameters, lithium. By adding a carbonaceous material that undergoes a large volume expansion due to the dope, the contact property between the negative electrode pellet and the negative electrode current collector laminated thereon is ensured.

However, the non-aqueous electrolyte secondary battery using these carbonaceous materials as the negative electrode has a relatively large current consumption due to its high energy density and light weight. It is considered that the application to mobile electronic devices will become mainstream. As a type of power supply used for electronic devices having a relatively large current consumption, a spirally wound electrode body in which a plate-shaped negative electrode and a plate-shaped positive electrode are laminated with a separator interposed therebetween, and the laminated body is spirally wound A cylindrical form, housed in a cylindrical battery can, is preferred. This is because the spiral electrode body has a large electrode area and is excellent in heavy load resistance.

However, in the case of the cylindrical non-aqueous electrolyte secondary battery, unlike the coin type, the volume expansion of the carbonaceous material increases the capacity of the spirally wound electrode body to increase the outer circumference of the spirally wound electrode body. It is hoped that the clearance around the inner circumference of the battery can will be filled in to prevent the electrode from loosening and that an appropriate pressure be generated between the positive electrode and the negative electrode. Therefore, it is considered that the non-aqueous electrolyte secondary battery of coin type is different in the volume expansion coefficient required for the carbonaceous material and the effect of the volume expansion of the carbonaceous material on the electrode reaction.

Therefore, even if the method and conditions used for the coin type non-aqueous electrolyte secondary battery are directly applied to the cylindrical non-aqueous electrolyte secondary battery, the charge and discharge cycle characteristics are not further improved. It is necessary to set the conditions in detail.

Therefore, the present invention has been proposed in view of such a conventional situation, in which the negative electrode is sufficiently expanded in volume, the clearance between the outer circumference of the spiral electrode body and the inner circumference of the battery can is proper, and the negative electrode is / Providing an appropriate pressure between the positive electrodes, it is an object of the present invention to provide a cylindrical non-aqueous electrolyte secondary battery having a high battery capacity and excellent cycle characteristics.

[0015]

In order to achieve the above object, a cylindrical non-aqueous electrolyte secondary battery of the present invention has a plate-shaped negative electrode and a plate-shaped positive electrode laminated via a separator, and the laminated The plate-shaped negative electrode has a spiral electrode formed by spirally winding a body, and the plate-shaped negative electrode has a surface interval of at least a (002) plane of 3.70 Å or more on the surface of the plate-shaped negative electrode current collector. The plate has a true density of less than 1.70 g / cm ³ and a negative electrode mixture consisting of a carbonaceous material and a binder, which has no exothermic peak at 700 ° C. or higher in a differential thermal analysis in an air stream, and is applied to the above plate. The positive electrode is a non-aqueous electrolyte secondary battery in which a positive electrode mixture composed of at least a lithium-transition metal complex oxide, a conductive agent and a binder is applied to the surface of a plate-shaped positive electrode current collector, A carbon fiber is added to the agent. .

The negative electrode mixture is characterized in that it expands at a coefficient of expansion of 3 to 14% by absorbing a non-aqueous electrolyte or doping lithium.

In the cylindrical non-aqueous electrolyte secondary battery, a plate-shaped negative electrode and a plate-shaped positive electrode are laminated via a separator, and the spirally wound electrode body formed by spirally winding the laminated body has a cylindrical shape. It is housed and configured in a battery can.

In the present invention, the negative electrode mixture used for the plate-shaped negative electrode has a surface spacing of at least (002) planes of 3.70.
By using a mixture of carbonaceous material having a true density of Å or more and a true density of less than 1.70 g / cm ³ and having no exothermic peak at 700 ° C or more in a differential thermal analysis in an air stream, and carbon fiber and a binder. , Both battery capacity and cycle characteristics should be achieved.

That is, the carbonaceous material having the above-mentioned morphological parameters has a large lithium doping amount and is suitable for increasing the battery capacity. However, the volume expansion coefficient when lithium is doped is small, and most of the functions are to expand the volume of the negative electrode mixture to fill the clearance between the outer circumference of the spirally wound electrode body and the inner circumference of the battery can, and to increase the pressure between the negative electrode and the positive electrode. I can't get it. Therefore, the smoothness of the electrode reaction cannot be obtained even if the negative electrode mixture is composed of only this and the binder.

Here, when carbon fiber is added to the negative electrode mixture in addition to the carbonaceous material having the above-mentioned morphological parameters, the carbon fiber is doped with lithium between the carbon layers and absorbs the electrolytic solution. Because of the large volume expansion of the carbonaceous material having the above morphological parameters, the carbon fiber fills the clearance between the outer circumference of the spirally wound electrode body and the inner circumference of the battery can, so that the pressure between the negative electrode and the positive electrode is sufficient. To be enhanced. Therefore, the electrode reaction proceeds smoothly, a high battery capacity is secured, and excellent charge / discharge cycle characteristics are obtained.

When selecting the above-mentioned carbon fiber, it is desirable to pay attention to the shape when expanded in volume, the coefficient of volume expansion caused in the negative electrode mixture, and the performance as the negative electrode active material.

First, it is preferable that the shape when expanded in volume expands in the direction perpendicular to the axial direction of the fiber, that is, the one having a so-called crystal structure that expands in the radial direction of the fiber. This is because the swelling of the carbon fibers due to the overlapping of the carbon fibers is directly reflected in the increase of the electrode volume, and efficient volume expansion can be obtained.

Further, it is desirable to select a material which can expand the negative electrode mixture by 3 to 14% in the thickness direction, and more preferably a material which can expand the negative electrode mixture by 5 to 12% in the thickness direction. When the volume expansion coefficient of the negative electrode mixture is less than 3%, the pressure between the positive electrode and the negative electrode may be insufficient, and the electrode reaction may not proceed satisfactorily. On the contrary, the volume expansion coefficient of the negative electrode mixture is 1
If it exceeds 4%, the volume occupied by the spirally-wound electrode body in the battery can becomes too large, and a space for injecting the electrolyte cannot be secured, resulting in a shortage of the electrolyte.

Further, a material having a large amount of lithium doping / dedoping and a small amount of lithium which is inactivated by repeated charging / discharging, that is, a material having excellent performance as a negative electrode active material as well as volume expansion performance is used. And more desirable.

Here, it is conceivable that a large amount of this carbon fiber is contained in the negative electrode mixture so that most of the function as the negative electrode active material is fulfilled, but if the content of carbon fiber in the negative electrode mixture becomes too large. , The negative electrode mixture volume density does not increase,
When the negative electrode mixture slurry is applied to the negative electrode current collector, various inconveniences occur due to the fiber shape such as frequent occurrence of electrode defects, which is not preferable. In the usual case, the carbon fiber can be expanded by 3 to 14% in the negative electrode mixture by adding a very small amount, and if the addition amount is such that the volume expansion in this range occurs, There is no inconvenience.

Mixing with the negative electrode mixture as described above, (0
02) surface spacing is 3.70Å or more, and true density is 1.70.
The following are examples of carbonaceous materials having a heat generation peak of less than 700 g / cm ^{3 and} less than 700 ° C. in a differential thermal analysis in an air stream.

That is, a carbonaceous material obtained by carbonizing an organic material by a technique such as firing may be mentioned. A furan resin composed of a furfuryl alcohol or furfural homopolymer or copolymer is suitable as a starting material for carbonization. Specifically, furfural + phenol,
Polymers composed of furfuryl alcohol + dimethylol urea, furfuryl alcohol + formaldehyde, furfuryl alcohol + furfural, furfural + ketones and the like show good characteristics as a negative electrode active material for a non-aqueous electrolyte secondary battery.

Alternatively, petroleum pitch having a hydrogen / carbon atomic ratio of 0.6 to 0.8 is used as a raw material, a functional group containing oxygen is introduced into these, and so-called oxygen cross-linking is performed to obtain an oxygen content of 10 to 20% by weight. A carbonaceous material obtained by firing after the precursor of is also suitable.

Further, it is also possible to use a carbonaceous material having a large doping amount with respect to lithium by adding a phosphorus compound or a boron compound when carbonizing the furan resin or petroleum pitch.

The carbon fibers may be obtained by carbonizing vapor-grown carbon fibers or organic polymer fibers obtained by a vapor phase method by a series of stepwise heat treatment while maintaining the original fiber shape. And those obtained by carbonization after spinning of pitch or the like, infusibilizing treatment, and the like. For example, polyacrylonitrile-based, cellulose-based, polyvinyl alcohol-based, phenol-based, pitch-based carbonaceous and graphite fibers can be used alone or in combination of two or more.

On the other hand, the positive electrode mixture used for the plate-like positive electrode is formed by applying a positive electrode mixture comprising a positive electrode active material, a conductive agent and a binder. As the positive electrode active material, a transition metal compound such as manganese dioxide or vanadium pentoxide, a transition metal chalcogen compound such as iron sulfide, or a composite compound of these and lithium can be used.

As the electrolytic solution, 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. The organic solvent is not particularly limited, for example, propylene carbonate, ethylene carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone,
Tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionitrile and the like can be used alone or in combination of two or more kinds.

Any known electrolyte can be used as the electrolyte.
Can be used, LiClO_Four, LiAsF ₆, LiPF₆, L
iBF_Four, LiB (C₆H_Five)_Four, LiCl, LiB
r, CH₃SO₃Li, CF₃SO₃There are Li and the like.

[0034]

The cylindrical non-aqueous electrolyte secondary battery of the present invention comprises a spirally wound electrode body housed in a cylindrical battery can, and in particular (002) ) Surface spacing is 3.70Å or more, and true density is 1.70 g / cm
Less than ³ and 700 ℃ by differential thermal analysis in air flow
A mixture obtained by mixing the above-mentioned carbonaceous material having no exothermic peak, carbon fiber and a binder is used.

In the cylindrical type non-aqueous electrolyte secondary battery using such a negative electrode mixture, a high battery capacity is obtained because the carbonaceous material having the above-mentioned morphological parameters has a large lithium doping amount.

Further, the carbon fiber mixed with this carbonaceous material expands greatly due to the fact that the carbon layers are doped with lithium and absorbs the electrolytic solution. Therefore, this expansion is reflected and the negative electrode mixture is reflected. Expands in volume, filling the clearance between the outer circumference of the spirally wound electrode body and the inner circumference of the battery can to prevent the electrode from loosening and to generate an appropriate pressure between the negative electrode and the positive electrode. Therefore, the electrode reaction proceeds smoothly, and good charge / discharge cycle characteristics can be obtained.

[0037]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will be described in detail below with reference to FIGS.

Example 1 A longitudinal sectional view of a cylindrical non-aqueous electrolyte secondary battery prepared in this example is shown in FIG. The cylindrical non-aqueous electrolyte secondary battery was prepared as follows.

First, the negative electrode 1 was manufactured as follows.
Petroleum pitch is used as a starting material, and 10 to 20% by weight of a functional group containing oxygen is introduced into this (so-called oxygen cross-linking), followed by firing at 1000 ° C. in an inert gas stream to have properties similar to glassy carbon. A carbonaceous material was obtained. As a result of X-ray diffraction measurement of this material, the spacing between (002) planes was 3.76Å. The true specific gravity was measured by the pycnometer method and found to be 1.58 g / cm ³ .
This carbonaceous material was pulverized to obtain a carbonaceous material powder having an average particle diameter of 10 μm.

The carbonaceous material powder thus obtained was used as a negative electrode active material carrier, 87 parts by weight of this, 3 parts by weight of vapor grown carbon fiber (VGCF: Showa Denko KK), and a binder. Then, 10 parts by weight of polyvinylidene fluoride (PVDF) to be used was weighed and 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 (paste form).

The thickness of the negative electrode current collector 9 is 10 μm.
This negative electrode material mixture slurry was applied to both surfaces of the strip-shaped copper foil of 1 above, dried, and then compression molded to prepare strip-shaped negative electrode 1. The electrode was designed to have a width of 41.5 mm and a length of 720 mm, and the thickness of the negative electrode mixture after molding was 80 μm on both sides and was the same.

The positive electrode 2 was manufactured as follows. 0.5 mol of lithium carbonate and 1 mol of cobalt carbonate were mixed and fired in air at a temperature of 900 ° C. for 5 hours to obtain LiCoO ₂ .

This LiCoO ₂ was used as a positive electrode active material, 91 parts by weight of this, 6 parts by weight of graphite as a conductive agent,
3 parts by weight of polyvinylidene fluoride serving as a binder was weighed and mixed to prepare a positive electrode mixture. This positive electrode mixture is N-
It was dispersed in methylpyrrolidone to obtain a positive electrode slurry (paste form).

This positive electrode slurry was uniformly applied on both sides of a 20 μm thick band-shaped aluminum foil which will be the positive electrode current collector 10, dried, and then compression molded to form a band-shaped positive electrode 2. The electrodes have a width of 39.5 mm and a length of 660.
The thickness of the mixture after molding was 80 μm and the same on both sides.

The strip-shaped negative electrode 1 and the strip-shaped positive electrode 2 produced as described above are used as a negative electrode 1, a separator 3, a positive electrode 2, and a separator 3 with a microporous polypropylene film having a thickness of 25 μm and a width of 44.0 mm as a separator 3. Was laminated in this order, and this laminated body was spirally wound many times. Then, by fixing the final end portion of the separator located at the outermost periphery with a tape having a width of 40 mm, the outer diameter is 19.6 mm and the height is 44.0.
A mm type spiral electrode body was produced.

The spiral electrode body was housed in a nickel-plated iron battery can 5, and insulating plates 4 were arranged on the upper and lower surfaces of the electrode body. Then, the aluminum positive electrode lead 12 was led out from the positive electrode collector 10 to the battery lid 7, and the nickel negative electrode lead 11 was led out from the negative electrode collector 9 and welded to the battery can 5.

An 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 / 1 was injected into the battery can 5 accommodating the spiral electrode body. Then, by caulking the battery can 5 through the insulating sealing gasket 6 whose surface is coated with asphalt, the safety valve device 8 having the current cutoff mechanism and the battery lid 7 are fixed, and the airtightness inside the battery is maintained. A cylindrical non-aqueous electrolyte secondary battery having a diameter of 20 mm and a height of 50 mm was prepared.

Example 2 89 parts by weight of the carbonaceous material mixed as the negative electrode active material carrier in the negative electrode mixture was used, and the vapor grown carbon fiber (VGCF:
A cylindrical non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the mixing amount of (Showa Denko KK) was 1 part by weight.

Example 3 89 parts by weight of the carbonaceous material to be mixed as the negative electrode active material supporting material in the negative electrode mixture, the vapor grown carbon fiber (VGCF:
A cylindrical non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the mixing amount of (Showa Denko KK) was changed to 5 parts by weight.

Comparative Example 1 Without mixing the vapor grown carbon fiber (VGCF: Showa Denko KK) into the negative electrode mixture, the amount of the carbonaceous material mixed as the negative electrode active material carrier was set to 90 parts by weight. A cylindrical non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except for the above.

Further, in the same manner as in Example 1, Example 2, and Comparative Example 1, a total of 20 cylindrical non-aqueous electrolyte secondary batteries were prepared.

Then, with respect to these batteries, constant current charging was performed for 2.5 hours under the conditions of the upper limit voltage of 4.2 V and the current of 1 A, and then the constant resistance was discharged under the conditions of resistance 6Ω and final voltage 2.75 V. The charging / discharging cycle was repeated.
Then, disassemble the battery after one cycle in the charged state,
The thickness of the negative electrode mixture of the strip negative electrode was measured. Further, the capacity at the 10th cycle (hereinafter referred to as the initial capacity) and the capacity at the 150th cycle were measured.

For each battery, the amount of VGCF added to the negative electrode mixture, the thickness of the negative electrode mixture before incorporating the negative electrode into the battery, the thickness of the negative electrode mixture after one charge / discharge cycle, and 1
Table 1 shows the 0th cycle capacity and the 150th cycle capacity (both are the average values of 20 batteries). Further, FIG. 2 shows the relationship between the expansion rate and the capacity retention rate of the negative electrode mixture.

[0054]

[Table 1]

As can be seen from Table 1, VGC was added to the negative electrode mixture.
In the batteries of Examples 1 to 3 to which F was added, the expansion amount of the negative electrode mixture after one cycle of charging and discharging was higher than that of the battery of the comparative example in which carbon fiber was not added to the negative electrode mixture. large.

From this, it is understood that adding the carbon fiber to be added to the negative electrode mixture is effective in increasing the volume expansion coefficient of the negative electrode mixture and smoothing the electrode reaction.

However, as shown in FIG. 2, the expansion coefficient of the negative electrode mixture has an appropriate range, and a high capacity retention rate is obtained in the expansion coefficient range of 3 to 14%, but the expansion coefficient of the negative electrode mixture is high. Three
It can be seen that in the range of less than 14% or the range of more than 14%, sufficient capacity retention cannot be obtained.

When the expansion coefficient of the negative electrode mixture was less than 3%, the capacity retention rate was insufficient because the clearance between the outer circumference of the spirally wound electrode body and the inner circumference of the battery can was not sufficiently filled, and This is because there is not enough pressure generated in. On the other hand, the reason why a sufficient capacity retention ratio could not be obtained in the range where the expansion ratio of the negative electrode mixture exceeded 14% was that the volume occupied by the negative electrode mixture became too large and the space for injecting the electrolyte solution could not be secured. , Because of lack of electrolyte.

Therefore, when the carbon fibers are mixed with the negative electrode mixture, it is desirable to mix them in such an amount that the expansion coefficient of the negative electrode mixture is 3 to 14%, more preferably 5 to 12%. .

[0060]

As is apparent from the above description, the cylindrical non-aqueous electrolyte secondary battery of the present invention has, as a negative electrode mixture, at least a (002) plane spacing of 3.70Å or more and a true density. Of less than 1.70 g / cm ³ and a carbonaceous material having no exothermic peak at 700 ° C. or more in a differential thermal analysis in an air stream, and a mixture of carbon fiber and a binder are used, so that the negative electrode has a sufficient volume. It expands, thereby filling the clearance between the outer circumference of the spirally wound electrode body and the inner circumference of the battery can, and an appropriate pressure is generated between the negative electrode and the positive electrode. Therefore, the battery reaction proceeds smoothly, a high battery capacity can be secured, and excellent cycle characteristics can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic vertical cross-sectional view showing one structural example of a cylindrical non-aqueous electrolyte secondary battery to which the present invention is applied.

FIG. 2 is a characteristic diagram showing the relationship between the expansion rate and the capacity retention rate of a negative electrode mixture.

[Explanation of symbols]

 1 ... Strip negative electrode 2 ... Strip positive electrode 3 ... Separator 4 ... Insulating plate 5 ... Battery can 6 ... Sealing gasket 7 ... Battery lid 8 ... Safety valve device 9 ... Negative electrode current collector 10 ... Positive electrode current collector 11 ... Negative electrode lead 12 ... Positive electrode lead

Claims (2)

[Claims] 1. A plate-shaped negative electrode and a plate-shaped positive electrode are laminated with a separator interposed therebetween, and a spiral electrode is formed by winding the laminated body in a spiral shape. A plate-shaped positive electrode current collector surface is coated with a positive electrode mixture composed of at least a lithium-transition metal composite oxide, a conductive agent and a binder, and the plate-shaped negative electrode is formed on the plate-shaped negative electrode current collector surface. , At least the (002) plane spacing is 3.70 Å or more, and the true density is 1.
A carbonaceous material having an exothermic peak of less than 70 g / cm ³ and having an exothermic peak at 700 ° C. or more in a differential thermal analysis in an air stream, and a negative electrode mixture composed of carbon fiber and a binder, are applied. Cylindrical non-aqueous electrolyte secondary battery. 2. The cylindrical nonaqueous electrolytic solution according to claim 1, wherein the negative electrode mixture undergoes volume expansion at a coefficient of expansion of 3 to 14% due to absorption of the nonaqueous electrolytic solution or dope of lithium. Secondary battery.