JP3253859B2 - Non-aqueous solvent secondary battery and method for granulating negative electrode mixture thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to relates to how to prepare a negative electrode mixture of the non-aqueous solvent secondary battery.

[0002]

2. Description of the Related Art Conventionally, in the manufacture of a battery mixture, the mixture powder is granulated and granulated before forming or filling the mixture, thereby reducing the variation in the weight of the mixture during molding. And the improvement of the packing density. There are various methods for granulating the mixture, and an extrusion granulation method can be mentioned as one of the methods that can be most easily granulated.

In the extrusion granulation method, a raw material powder is kneaded by adding a solvent mainly composed of water, alcohol or the like to form a wet mixture, and the wet mixture is pressed against a screen having fine pores, and the outside of the screen is pressed. This is a method of extruding into cylindrical granules. The obtained cylindrical granules are dried,
It is sized by crushing, classification, etc., and has the target particle size distribution.
A powdery battery mixture having excellent flowability can be obtained.

FIG. 4 shows an example of a conventional extrusion granulator. The wet mixture 2 is supplied to the mixture input hopper 1 and extruded forward by an extrusion screw 4 rotated by a power unit 3. The extruded wet mixture 2 comes into contact with the holding plate 7 and has no place to go, so that it tries to escape in the outer peripheral direction. A cylindrical screen 8 having fine pores is arranged in the outer circumferential direction of the extrusion screw. The wet mixture 2 is extruded from the cylindrical screen 8 to form a cylindrical granular mixture 6. After collecting and drying this columnar granule mixture 6,
Crush and classify to obtain the desired mixture powder.

[0005]

However, when the above-mentioned extrusion granulator is used, the wet mixture 2 once hits the holding plate 7, and the direction in which the stress acts is forcibly changed.
Since the cylindrical screen 8 is pressurized, there is a problem that a large stress loss occurs and only a material excellent in lubricity and flexibility can be extruded. Further, since the frictional resistance between the holding plate 7 and the cylindrical screen 8 and the wet mixture 2 is large, heat is easily generated, and further, the wet mixture 2 easily stagnates around the pressing plate 7, so that the generated heat is generated. Are easily accumulated inside the screen. Therefore, even when a solvent having a relatively high boiling point such as water is used as a lubricant as well as a solvent having a low boiling point, the solvent in the wet mixture volatilizes, and the fluidity is further reduced. There was a drawback of causing clogging.

Further, when an organic substance having a low film-forming temperature or a low crosslinking temperature is contained in the wet mixture, there is a disadvantage that film-forming or crosslinking occurs and clogging occurs. In particular, in the case of a negative electrode mixture for a non-aqueous solvent secondary battery using a carbonaceous material for the support, the carbonaceous material generally has severe irregularities on the particle surface, a large specific surface area, a small particle size, Since the frictional resistance between them is very large, even when this is used as a wet mixture, lubricating properties are remarkably lacking, and it is very difficult to granulate with a conventional extrusion granulator, resulting in poor workability. Was.

SUMMARY OF THE INVENTION The present invention has been made to address the above problems, and has as its object to improve the workability in producing a negative electrode mixture for a non-aqueous solvent secondary battery, and to further reduce the water content of a wet mixture. It is an object of the present invention to produce a negative electrode mixture having a high packing density, and to obtain a high-capacity battery using the negative electrode mixture having a high packing density.

[0008]

That is, the present invention provides a negative electrode
A carrier powder capable of supporting an active material and a wetting agent
Non-aqueous granulation of wet mixture containing by extrusion granulator
In the method of granulating a negative electrode mixture for a solvent secondary battery, an extrusion molding method is used.
The granulator is composed of a wet mixture input hopper, an extrusion mechanism for extruding the input wet mixture, and a hemispherical screen having pores installed in front of the extrusion mechanism ,
The wet mixture is charged into the charging hopper, and the hemisphere
And removing the granulated wet mixture from the screen . Still further, the present invention relates to a non-aqueous solvent secondary battery using the negative electrode mixture thus manufactured.

In the extrusion granulator used in the present invention , a hemispherical screen having pores is provided in front of the extruding mechanism, so that the wet mixture extruded forward by the extruding mechanism is directed in a direction in which stress acts. Is extruded directly from a hemispherical screen to the outside with almost no change. As a result, it is possible to extrude even a wet mixture having a relatively low wettability, and workability during granulation is remarkably improved. further,
Dead space is hardly formed around the hemispherical screen, the wet mixture hardly stays, and heat hardly accumulates. Therefore, a common solvent such as water or alcohol can be used as a wetting agent for the wet mixture, and the mixture can be produced at low cost without requiring special equipment.

Further, as described above, the workability at the time of granulation is improved, so that the amount of the wetting agent added to the wetting mixture can be reduced as compared with the conventional case, and as a result, the packing density of the obtained negative electrode mixture can be reduced. Therefore, a battery having a higher capacity than that of a conventional battery can be obtained.

[0011]

Embodiments of the present invention will be described with reference to the drawings. (Example 1) First, a novolak resin was placed in a nitrogen atmosphere for 9 hours.
After calcining at 50 ° C., it was further carbonized by heating at 2000 ° C., and pulverized so as to have an average particle diameter of 10 μm to obtain a carbonaceous material powder to be a support of the active material. Next, to 95 parts by weight of the obtained carbonaceous material powder, an alkyl methacrylate-butadiene copolymer latex was added as a negative electrode binder so as to have a solid content of 5 parts by weight, and water was added as a wetting agent to the mixture. Was added so as to have a water content of 15%, and these were mixed to obtain a wet mixture.

Next, the wet mixture was granulated by an extrusion granulator. This extrusion granulator will be described with reference to the sectional view shown in FIG. In FIG. 1, reference numeral 1 denotes a mixture input hopper, 2 denotes a wet mixture, 3 denotes a power unit, and 4 denotes an extrusion screw rotated by the power unit 3. 5 is a hemispherical screen having pores, and 6 is an extruded cylindrical granule mixture.

When the wet mixture 2 is charged into the mixture input hopper 1, the wet mixture 2 is rotated by the rotating extrusion screw 4.
Is pushed forward and reaches a hemispherical screen in the direction of travel. The wet mixture 2 is extruded from the pores of the screen to form columnar granules 6. The obtained columnar granules 6 are dried at 80 ° C. for 12 hours, and then pulverized and classified to obtain a desired negative electrode mixture.

In the present embodiment, the water content was reduced from about 35% in the prior art to 15%, but the workability of the granulation was good, and the extruding was carried out smoothly without heat generation of the wet mixture and clogging of the screen. Grains could be done.

Subsequently, the obtained negative electrode mixture powder was reduced to about 1 mm in diameter.
5 mm, weigh a predetermined amount to be about 0.9 mm thick,
A negative electrode body was prepared by press-molding with a pressing force of 2 t / cm2.

Next, a battery shown in FIG. 2 was prepared using the obtained negative electrode body. In FIG. 2, reference numeral 9 denotes a positive electrode container made of stainless steel having a thickness of 0.25 mm. A positive electrode current collector 10 made of stainless steel is inscribed on the inner surface of the container 9. Further, a positive electrode body 11 is accommodated in the positive electrode container 9. The cathode body 11 is composed of 90 parts by weight of V2 O5 powder and 10 parts of artificial graphite 10.
After mixing parts by weight, 5 parts by weight of polytetrafluoroethylene were mixed and pressure-molded to a thickness of about 0.9 mm.

A separator 12 made of a polypropylene nonwoven fabric is provided on the positive electrode body 11, and the separator 12 holds an electrolytic solution obtained by dissolving lithium perchlorate in propylene carbonate at a concentration of 0.7 mol / l. ing. Further, on the upper surface of the separator 12, the negative electrode body 16 manufactured as described above is disposed. In the figure, reference numeral 13 denotes a negative electrode container made of stainless steel having a thickness of 0.25 mm. A negative electrode current collector 14 is inscribed on the inner surface of the container 13, and an inner surface of the negative electrode container 13 including the current collector 14 is provided. Is press-bonded with metallic lithium 15.

A negative electrode container 13 is fitted into the opening of the positive electrode container 9 via an insulating gasket 17, and the positive electrode container 9 and the negative electrode container 13 are formed by caulking the positive electrode container 9.
A positive electrode current collector 10, a positive electrode body 11, a separator 12, a negative electrode body 16, a metallic lithium 15, and a negative electrode current collector 14 are hermetically sealed therein.

After assembling the above-mentioned battery, the metallic lithium 15 was doped into the negative electrode body 16 by aging to produce a desired non-aqueous solvent secondary battery. The battery manufactured according to this embodiment is designated as A.

Example 2 The moisture content in the wet mixture was 2
A battery was prepared in the same manner as in Example 1 except that the content was set to 0%.
This battery was designated as B.

Example 3 The moisture content in the wet mixture was 2
A battery was prepared in the same manner as in Example 1 except that the content was 5%.
This battery was designated as C.

(Comparative Example 1) The moisture content in the wet mixture was 3
A battery was prepared in the same manner as in Example 1 except that the content was set to 0%.
This battery was designated as D.

Comparative Example 2 Moisture content in the wet mixture was 3
The wet mixture was produced at 0% in the same manner as in Example 1, and then subjected to extrusion granulation using the conventional extrusion granulator shown in FIG. The obtained columnar granule mixture was dried, crushed and classified to obtain a negative electrode mixture powder. Using the obtained negative electrode mixture powder, a battery was prepared in the same manner as in Example 1, and this battery was
And However, in this comparative example, when the wet mixture was extruded and granulated, the flowability of the wet mixture was reduced, causing clogging of the screen, and the workability was significantly deteriorated.

Comparative Example 3 The moisture content in the wet mixture was 3
A battery was prepared in the same manner as in Comparative Example 2 except that the content was 5%, and this battery was designated as F.

Comparative Example 4 Moisture content in the wet mixture was 2
Extrusion granulation was attempted using a conventional extrusion granulator in the same manner as in Comparative Example 2 except that the content was set to 5%. However, heat was generated around the screen due to frictional heat, and water was evaporated and the binder was solidified, so that a cylindrical granular mixture could not be obtained.

(Discharge Test) The batteries of the above Examples and Comparative Examples were continuously discharged to 2.0 V with a constant resistance of 15 kΩ.
The discharge capacity at that time was measured. The results are shown in FIG. As is clear from the figure, all of the batteries A, B and C of the example have a larger discharge capacity than the batteries D, E and F of the comparative example. This is because the battery of the example is different from the battery of the comparative example
Because the moisture content of the wet mixture during extrusion granulation is low, a denser mixture powder can be obtained after drying, the molding density is improved, and more negative electrode mixture can be held in the same container. It is.

Since the present invention relates to a negative electrode, it is needless to say that the present invention is not limited to the above-described embodiment such as a positive electrode and an electrolytic solution. For example, as a cathode material, LiCoO2, LiNiO2, LiMn2 O4, L
iMnO2 and the like are also applicable.
EC, BC, DEC, DMC, EMC, DME, γ-B
LBF such as LiBF4, LiPF6, LiCF3
It may be one in which an electrolyte such as SO3 is dissolved.

Further, in the present embodiment, a fired body of novolak resin is used as the carbonaceous material as the active material carrier, but the present invention is not particularly limited and can be applied to any carbonaceous material. . Further, the negative electrode binder is not limited thereto, and other rubbers such as a styrene-butadiene copolymer and an ethylene-propylene copolymer, a resin such as polytetrafluoroethylene and polyethylene, or cellulose may be used. Further, the dispersant is not limited thereto, and an organic solvent such as ethanol or toluene can be used.

[0029]

As described above, the granulation method of the present invention
According to the method , the workability of granulation is improved, and therefore, the water content in the wet mixture is reduced, whereby the negative electrode mixture can be manufactured. Since the negative electrode mixture obtained from the wet mixture in which the water content has been reduced in this way has a high packing density, the nonaqueous solvent secondary battery manufactured using such a negative electrode mixture has a higher capacity than before. It will be.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a wet mixture extrusion granulator according to the present invention.

FIG. 2 is a cross-sectional view of a non-aqueous solvent secondary battery according to one embodiment of the present invention.

FIG. 3 is a diagram showing the results of a discharge test of a battery of an example of the present invention and a battery of a comparative example.

FIG. 4 is a cross-sectional view of a conventional wet mixture extrusion granulator.

[Explanation of symbols]

Reference numeral 1 denotes a mixture input hopper, 2 denotes a wet mixture, 3 denotes a power unit, 4
... extrusion screw, 5 ... hemispherical screen, 6 ... columnar granule mixture, 7 ... holding plate, 8 ... cylindrical screen,
Reference numeral 9: positive electrode container, 10: positive electrode current collector, 11: positive electrode body, 12
... separator, 13 ... negative electrode container, 14 ... negative electrode current collector, 1
5 ... metal lithium, 16 ... negative electrode body, 17 ... insulating gasket.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-9-180709 (JP, A) JP-A-6-357 (JP, A) JP-A-4-215832 (JP, A) JP-A-6-180632 60865 (JP, A) JP-A-7-335218 (JP, A) JP-A-3-263757 (JP, A) WO 96-13542 (WO, A1) (58) Fields investigated (Int. Cl. ⁷⁾ H01M 4/04 H01M 4/02 H01M 4/58 H01M 4/62 H01M 10/40

Claims (4)

(57) [Claims] 1. A support capable of supporting a negative electrode active material.
Extrusion of wet mixture containing body powder and wetting agent into granulator
Therefore, a method of granulating a negative electrode mixture for a non-aqueous solvent secondary battery to be granulated
In the extrusion granulator, the wet mixture input hopper,
An extrusion mechanism for extruding the input wet mixture, and a hemispherical screen having fine holes installed in front of the extrusion mechanism, the wet mixture is supplied to the input hopper.
Wet and granulated from the hemispherical screen
A negative electrode for non-aqueous solvent secondary batteries characterized by taking out the mixture
Granulation method of extreme mix . 2. Part or all of the carrier powder in the wet mixture
The negative electrode for a non-aqueous solvent secondary battery according to claim 1, wherein is a carbon material.
Granulation method of mixture. 3. Granulation side of the negative electrode mixture for a non-aqueous solvent secondary battery water content of the wet mixture is claim 1, wherein 25% or less
Law. 4. A granulation method produced by the granulation method according to claim 1.
Non-aqueous solvent secondary battery using the negative electrode mixture.