JPH0765816A - Manufacture of sheet electrode and chemical battery manufactured thereby - Google Patents

Abstract

PURPOSE:To reduce manufacture variation of a discharge capacity, and improve cycle characteristics of a battery assembly by discharging electrode material application liquid from an injector, and applying it to a conductive support body wound around a backup roll to run in a specified thickness. CONSTITUTION:Regulated application liquid of electrode material is supplied continuously to a liquid reservoir 8 in an extrusion type injector 7 through a flow gauge 12 from a tank 13 of the application liquid by a constant flow supply device 11 such as a constant flow pump or the like which is suitable. The applied liquid is supplied from the liquid reservoir 8 through a slot 5 to be discharged from a slot nozzle 6, and it is applied on a support body 1 which is running continuously. The liquid reservoir 8 has action of reducing fluctuation of a supply ratio of the application liquid, so the application liquid is discharged uniformly. A backup roll 2 keeps the support body 1 and the injector 7 at a constant distance from each other, and it keeps a transfer speed of the support body 1 constant. In this application method, viscosity of the application liquid is within a range of 0.5-500Pas at 25 deg.C, it is desirably 0.6-100Pas, and it is more desirably 0.7-50Pas.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a sheet-like electrode plate for reducing the manufacturing fluctuation of discharge capacity and improving the cycleability of an assembled battery, and a chemical battery using the electrode plate.

[0002]

2. Description of the Related Art Generally, a non-aqueous electrolyte battery has a lower electric conductivity than a non-aqueous electrolyte battery,
It is necessary to reduce the thickness of the electrode layer formed on the conductive support that is the current collector. Therefore, in the cylindrical battery, a spiral structure in which a sheet-shaped electrode is wound is adopted in order to increase the filling amount of the active material.

Conventionally, as a method for manufacturing a sheet-like electrode plate,
A roll rolling method is used. That is, the active material is kneaded with a conductive agent, a binder and the like, and is roll-rolled and press-filled into the support to form a sheet electrode. Further, a method of extruding the kneading mixture on both sides of the support (Japanese Patent Laid-Open No. 4-28)
2558), a pulling method (Japanese Patent Laid-Open No. 62-25636).
5, JP-A-63-114058) and a pulling-down method (JP-A-1-267953, JP-A-1-194265). These methods are efficient because they can be coated on both sides at the same time, but have the problem that it is difficult to position the support in the center of the electrode plate sheet, and it is not possible to form a thin sheet having a uniform thickness. A combination of a plurality of rolls, a roll coating method in which the coating liquid is applied to the support by passing through the roll gap has been proposed as a method for producing a sheet-like electrode plate, and as an example, a reverse roll method, There is a gravure roll method. However, in the case of these roll coat methods, surface states called ribbing (unevenness) and unevenness are seen, and it is difficult to smooth the coated surface of the sheet-like electrode plate. Japanese Patent Laid-Open No. 1-184069,
JP-A-1-194265 and JP-A-4-242071
The doctor blade method disclosed in U.S.A., etc. has been proposed as a method for manufacturing a thin sheet-like electrode plate. According to this method, a doctor blade is provided with a predetermined gap from the surface of the support to be coated, an active material is mixed with a conductive agent, and a binder or the like is further added and kneaded to form an electrode material coating solution. Is stored in the front side of the doctor blade, and the electrode material liquid is drawn out in layers in an amount corresponding to the gap between the doctor blade and the traveling support, whereby a sheet-shaped electrode plate is manufactured.

Although it is possible to prepare a thin sheet-like electrode plate by this doctor blade method, the solvent evaporates during coating because the coating is performed while the electrode material coating liquid is stored in front of the doctor blade. The liquid concentration changes with time. Therefore, it is difficult to perform stable coating because the liquid properties of the coating liquid change with the change of the coating liquid concentration. Further, in the doctor blade method as proposed in JP-A-4-242071, since the coating liquid stored in the front side of the doctor blade is continuously supplied onto the conductive support, it is possible to prevent the coating solution from passing through the joint portion of the support. In this case, it is necessary to finish applying the stored coating liquid before passing. After passing through the joining, the supply of the coating solution is restarted, but the original coating width cannot be applied until the front side of the doctor blade is filled with the coating solution. There are problems that it is difficult to start and stop the application freely and that both sides cannot be applied simultaneously. As a coating method, there is an extrusion method. The extrusion method is a method of supplying the coating liquid to the liquid injector, discharging the coating liquid from the slot nozzle, and coating it on the running support.Control the coating amount by setting the discharge amount of the constant flow pump. In addition, since there is almost no contact with the outside air, the concentration of the coating liquid does not change due to evaporation of the solvent. When the liquid injector is provided so as to face the backup roll (Japanese Patent Laid-Open No. 56-1766).
1, JP-A-57-19060, JP-A-1-18026
7, JP-A-2-164480) or in the case where a backup roll or plate is not provided on the side of the support opposite to the liquid injector (JP-A-60-150866, JP-A-62-9516).
9, JP-A-4-4071), and has been proposed in the fields of photographic films, plate-making materials and magnetic recording materials. However, the electrode sheet used as the electrode material for chemical batteries has a significantly thicker coating film than photographic film, plate-making material, etc., and in the conventional extrusion type coating method, the manufacturing fluctuation (variation) in discharge capacity is small and the cycle is small. It is not possible to manufacture a sheet-shaped electrode plate having improved properties.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a sheet-like electrode plate for a chemical battery, which reduces the manufacturing fluctuation of the discharge capacity and improves the cycleability of the assembled battery.

[0006]

The thickness of a coating film of an electrode material is usually large (for example, 30 to 1000 μm in a wet state),
Since the drying load is large, it is necessary to reduce the coating speed. When coating with an extrusion type liquid injector at a low speed region of less than 10 m / min with this film thickness, liquid dripping occurs in coating of photographic film, and streaks due to aggregation in coating of magnetic recording material. May occur.
The present inventors have made diligent studies on the application of the electrode material, and surprisingly, using an extrusion type liquid injector and a backup roll on the opposite side of the support, for the electrode material coating liquid, It was found that when the viscosity is within a predetermined range, the problem of streaks due to the liquid dripping and aggregation does not occur, and a good coated product can be obtained, and the present invention has been completed based on this finding. The above-mentioned object of the present invention is, in the production of a chemical battery having a positive electrode, a negative electrode, and an electrolyte, discharging an electrode material coating liquid from an extrusion type liquid injector having a slot nozzle, and winding the conductive support to run a conductive support. This has been achieved by a method for producing a sheet-like electrode plate, which is characterized by being applied on the body.

In the extrusion type liquid injector used in the present invention, two lips are opposed to each other so as to keep a gap, and a slot is formed, and a liquid reservoir communicating with the slot is provided inside. The coating liquid is quantitatively supplied to this liquid reservoir by a liquid supply facility provided outside the liquid injector, and is further discharged from a slot nozzle through a communicating slot. It is installed so that the slot nozzle keeps a distance from the traveling body,
The coating liquid discharged from the slot nozzle is applied in layers on the support. Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is an end view of a coating apparatus which is an embodiment of the manufacturing method of the present invention, and the liquid injector is shown in section. However, it is not limited to this embodiment. In FIG. 1, a conductive support 1 (hereinafter referred to as “support”) is in close contact with the surface of a rotating backup roll 2 and continuously runs in a winding manner. The liquid injector 7 is installed so that the slot nozzle 6 and the backup roll 2 are spaced from the support. The liquid injector 7 comprises a slot 5 formed by an inlet lip 3 and an outlet lip 4 provided with an inlet lip surface 9 and an outlet lip surface 10 of the support 1, respectively.
It is composed of a liquid reservoir 8 continuous to the slot 5. Figure 2
Fig. 1 shows a liquid supply flow chart of the electrode material coating liquid (hereinafter referred to as coating liquid). The prepared electrode material coating solution is continuously supplied from a tank 13 for the coating solution through a flow meter 12 to a liquid reservoir 8 in a liquid injector 7 by a constant flow rate supply device 11 such as an appropriate constant flow rate pump. . The coating liquid supplied from the tank 13 is
The liquid is supplied to the liquid reservoir 8 through a passage (not shown) in the liquid injector 7 that connects the liquid reservoir 8 and the line from the tank 13. The coating liquid is discharged from the liquid reservoir 8 through the slot 5 and the slot nozzle 6, and is applied onto the continuously running support 1. Since the liquid reservoir has a function of buffering the fluctuation of the supply rate of the coating liquid, the coating liquid is uniformly discharged. The backup roll keeps the support and the liquid injector at a constant distance, and also keeps the transport speed of the support constant. In the coating method,
The viscosity of the electrode material coating liquid is 0.5 Pas to 500 Pa at 25 ° C. as measured by a B-type viscometer (manufactured by Tokimec).
The range of s is good, and preferably 0.6 Pas to 100 Pa.
s, more preferably 0.7 Pas to 50 Pas. As shown in FIG. 3, the slot clearance 29 (L1) of the liquid injector 7 used in the present invention is determined by the liquid physical properties of the electrode material coating liquid, the coating thickness, and the like, and is not particularly limited. 1 mm to 2 mm is preferable, and 0.3 mm to 1 mm is particularly preferable.

Further, the width 30 (L2) of the support inlet side lip surface 9 of the liquid injector 7 used in the present invention (the width of the lip surface is the projected width with respect to the tangent at the position of the slot 5 with respect to the backup roll 2). Is 0.2 mm or more.
5 mm is preferable, and 0.3 mm to 3 mm is particularly preferable. Furthermore, the width 31 (L3) of the support outlet side lip surface 10 of the liquid injector 7 used in the present invention (the width of the lip surface is
The projection width with respect to the tangent line at the position of the slot 5 with respect to the backup roll 2. ) Is 0.2 mm to 5 m
m is preferable, and 0.3 mm to 3 mm is particularly preferable. Further, the gap 32 between the liquid injector 7 and the support 1 used in the present invention is 32.
(L4) (which is the shorter of the shortest distance between the inlet-side lip surface 9 and the support 1 and the shortest distance between the outlet-side lip surface 10 and the support 1) is not particularly limited, but is 0.1 m.
m to 3 mm is preferable, and 0.3 mm to 1 mm is particularly preferable. Furthermore, the length 33 (L5) of the slot 5 of the liquid injector 7 used in the present invention is not particularly limited, but is preferably 10 to 200 mm, and particularly 20 to 150 mm.
mm is preferred. Liquid reservoir 8 of the liquid injector 7 used in the present invention
The cross-sectional shape is not particularly limited as long as the coating liquid does not stay therein, but when the cross-sectional shape is circular, the inner diameter 34 (D) is 5 to
100 mm is preferable, and 10 mm to 50 mm is particularly preferable. Further, the respective shapes of the inlet side lip surface 9 and the outlet side lip surface 10 of the liquid injector used in the present invention are not particularly limited, but are flat surfaces, combinations of flat surfaces, arcs,
Combinations of planes and arcs are preferred, and planes and combinations of planes are particularly preferred. Furthermore, regarding the combination of the shapes of the inlet side lip surface 9 and the outlet side lip surface 10, the plane 9 and the plane 1
0 (FIGS. 4 (a) and 4 (b)), arc 10 and plane 9 (FIG. 4).
(C)), plane combination 10 and plane 9 (FIG. 4 (d)),
The combination 10 of planes and the circular arc 9 (FIG. 4 (e)), the circular arc 9 and the circular arc 10 (FIG. 4 (f)), and the like are given as examples, but the invention is not limited thereto. 4A and 4B show examples of the shape of the lip surface and the combination thereof, the present invention is not limited to these.

As shown in FIG. 5, the position of the liquid injector 7 used in the present invention with respect to the backup roll 2 is not particularly limited, and is a range in which the support 1 is wound in close contact with the backup roll 2. If so, a liquid injector can be installed. A preferred position of the liquid injector 7 with respect to the backup roll 2 will be described with reference to FIG. In FIG. 5A, an example having two liquid injectors 7 and 7 on one backup roll 2 is shown for the purpose of explaining the angles (α, β) below. From the point 37 at which the support 1 starts to be wound around the backup roll 2 to the support running side of the liquid injector 7 at an angle 35 (α) and from the point 38 at which the winding of the support 1 ends, the support of the liquid injector 7 The angle 36 (β) to the opposite side of traveling is preferably 3 ° or more,
Particularly preferably, it is 5 ° or more. Within the above range, on the vertical line 39 passing through the center of the backup roll 2, the upper side of the backup roll 2 (FIG. 5B) and the lower side of the backup roll 2 (FIG. 5C) are infused. The vessel 7 can also be installed. The transport speed of the support in the invention is not particularly limited, but is preferably 0.1 to 100 m / min, particularly preferably 0.1 to 50 m / min. Further, the amount of the electrode material coating liquid supplied to the liquid injector used in the present invention is determined by the coating thickness, the transport speed of the support, etc., but the average flow velocity in the slot (supply flow rate / slot cross-sectional area) is 0. 0.1 cm / min to 100 m / min is preferable, and 0.5 cm / min to 30 m / min is particularly preferable. The coating thickness of the electrode material coating liquid applied according to the present invention is preferably 10 μm to 2000 μm in a wet state before drying, and particularly preferably 30 μm to 1000 μm. The thickness of the coating film after drying is preferably 5 μm to 1800 μm, particularly 15 to 90 μm.
0 μm is preferable. The material of the liquid injector used in the present invention is selected to have corrosion resistance when the coating liquid is corrosive, but metal, alloy, material containing at least metal, ceramic, plastic or the like can be used. .
The temperature of the electrode material coating liquid supplied to the liquid injector used in the present invention can be controlled as necessary. The liquid temperature is preferably in the range of 10 ° C to 60 ° C, particularly 15 ° C to 45 ° C.
Is preferred.

As shown in FIG. 6, in the present invention, when the coating speed is fast, the coating thickness is thin, or when it is necessary depending on the physical properties of the coating liquid, the liquid injector 7 and the support are provided on the inlet side of the liquid injector. A decompression chamber 14 that closes the space between the two can be provided. The decompression chamber 14 has a box-like shape, and a conduit 15 is connected to a decompressor (not shown) and is maintained at a decompression of 0 to 300 mmH ₂ O.

FIG. 7 shows an example without a backup roll for reference. As shown in FIG. 7, the liquid injectors 7 and 7 can be installed on both sides of the support 1 so as to keep a space therebetween. In this case, the liquid injectors 7 and 7 are installed so as to face each other. It is also possible (Fig. 7 (a)) to be installed at a certain distance (Fig. 7 (b)). The electrode material can be coated on both surfaces of the support at the same time by the above-mentioned method, but in this case, since there is no backup roll, the distance between the support and the slot nozzle fluctuates, which causes uneven coating film thickness.

The electrode material coating liquid applied according to the present invention may contain an electrode active material, a conductive agent, a binder, a solvent and the like. As the electrode active material, H ⁺ , Li ⁺ , Na
^Any compound capable of inserting and / or releasing ⁺ and K ⁺ may be used. Among them, transition metal oxides, chalcogenides of transition metals, carbonaceous materials, oxides mainly composed of Group IVB and VB semimetals of the periodic table may be used. It can be used, and in particular, a lithium-containing transition metal oxide, a transition metal oxide, a carbonaceous material, and an oxide mainly composed of a group IVB or VB semimetal of the periodic table are preferable. (The transition metal is preferably mainly composed of Mn, Co, Ni, V and Fe, and Group IVB and VB of the periodic table are Ge and S.
It is preferable to mainly use n, Pb, Bi, and Si. )
Specifically, LiCoO ₂ , LiNiO ₂ , LiCo _0.5
Ni _0.5 O ₂ , LiMn ₂ O ₄ , LiCoVO ₄ , Li
NiVO ₄ , LiCo _0.9 Sn _0.1 O ₂ , LiCo _0.9
Ti _0.1 O ₂ , LiCo _0.9 Al _0.1 O ₂ , LiCo _0.9
In _0.1 O ₂ , LiCo _0.9 Y _0.1 O ₂ , LiCo _{0.9
Ce 0.1 O 2, Fe 3 O} 4, V 6 O 13, V 2 O 5, and the like. As a preferable carbonaceous material, 002
The surface spacing is 3.35 to 3.80 A (angstrom-
And a density of 1.1 to 1.7 g / m ³ , preferably graphite, petroleum coke, cresol resin fired carbon, furan resin fired carbon, polyacrylonitrile fiber fired carbon, vapor grown carbon, mesophase pitch fired carbon. And so on. Examples of oxides mainly composed of Group IVB and VB semimetals in the periodic table include GeO, GeO ₂ , SnO,
SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₃ O
₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , Bi ₂ O
₃ , Bi ₂ O ₄ , Bi ₂ O ₅ , SiSnO ₃ , Li ₂ S
iO ₃ , Li ₄ SiO ₄ , Li ₂ Si ₃ O ₇ , Li ₂ S
i ₂ O ₅ , Li ₈ SiO ₆ , Li ₆ Si ₂ O ₇ , Li ₄
Ge ₉ O ₂₀ , Li ₆ Ge ₈ O ₁₉ , Li ₄ Ge ₅ O ₁₂ , L
i ₆ Ge ₂ O ₇ , α-Li ₄ GeO ₄ , Li ₄ GeO
₄ , β-Li ₈ GeO ₆ , Li ₂ Ge ₇ O ₁₅ , Li ₂ G
eO ₃ , Li ₂ Ge ₄ O ₉ , Li ₂ SnO ₃ , Li ₈ S
nO ₆ , Li ₂ PbO ₃ , β-Li ₂ PbO ₃ , Li ₈
PbO ₆ , Li ₄ PbO ₄ , Li ₇ SbO ₆ , LiSb
O ₃ , Li ₃ SbO ₄ , Li ₃ BiO ₄ , Li ₇ BiO
₆ , Li ₅ BiO ₅ , LiBiO ₂ , Li ₄ Bi ₆
O ₁₁ , Li ₄ MgSn ₂ O ₇ , Li ₂ MgSn ₂ O ₅ ,
Li ₂ MgSn ₂ O ₆ , Li ₂ Mg ₃ SnO ₆ , Li ₄
Examples thereof include, but are not limited to, Mg ₂ SnO ₆ . The electrode material coating liquid applied according to the present invention may include an active material of 0.01 to 100 μm. The conductive agent may be any electron conductive material that does not cause a chemical change in the constructed battery. Usually, one or a mixture of conductive materials such as natural graphite (scaly graphite, flake graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder, metal fiber or polyphenylene derivative. Can be included as The combined use of graphite and acetylene black is particularly preferred. As the binder, at least one kind of a polymer having a polysaccharide, a thermoplastic resin and a rubber elasticity, or a mixture thereof can be used. The binder may be dissolved in a solvent or may be precipitated such as dispersed or suspended. As the solvent, water or at least one organic solvent or a mixture thereof can be used. The solvent is not particularly limited, and N-
Methylpyrrolidone, xylene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, methanol, methyl acetate, ethyl acetate, butyl acetate, methylene chloride, ethylene chloride and the like are preferable. In the present invention, the composition of the electrode material coating liquid is not particularly limited, but the coating liquid is usually 1 to 50 parts by weight of the conductive agent to 100 parts by weight of the electrode active material,
It comprises 0.1 to 50 parts by weight of binder and 30 to 600 parts by weight of solvent.

The conductive support in the present invention is not particularly limited, but conductive materials such as metal foils (aluminum, copper, nickel, stainless steel, etc.), inorganic oxides, organic polymer materials, carbon, etc. A film can be used.
The form of the support may be continuous, perforated, net,
A continuous body is particularly preferable. The thickness of the conductive support is 1 to 20.
0 μm is preferable. Further, the tension acting on the support in the present invention is not particularly limited, but is 10 g / c.
m to 500 g / cm is preferable, and particularly 20 g / cm to 3
00 g / cm is preferred. In the present invention, when the position variation of the support on the backup roll is large, the support traveling position is E on the support entry side of the backup roll.
It is controlled by a PC (edge position controller). As shown in FIG. 8, when the electrode material is sequentially coated on each side, the support is conveyed to the drying chamber after each side of the support is coated. Drying may be performed using hot air drying, far infrared rays, and the like. In the case of hot air drying, the temperature is selected depending on the solvent, binder, etc., but 40 to 250 ° C. is preferable, and 50 to 200 ° C. is particularly preferable. If the water cannot be sufficiently removed by the drying, a dehydration step may be provided. As the dehydration process, vacuum drying, far infrared rays,
High temperature drying, combinations of these and the like can be used.
In FIG. 8, 16 is a delivery roll of the support 1 before coating the electrode material, 17 and 18 are front and back electrode material coating portions, 19 and 19 are drying chambers, 20 and 20 are tension control rolls, 21 Indicates a winding roll of the support 1 after applying the electrode material.

As the shape of the chemical battery, coins, buttons,
It can be used for both cylindrical and square types. When manufacturing a battery using the sheet electrode of the positive electrode and the negative electrode according to the present invention, as a separator for separating the positive electrode sheet and the negative electrode sheet, for example, polyethylene, polypropylene such as microporous polypropylene film separator, glass fiber, etc. Can be mentioned. As the electrolyte, for example, a solvent obtained by mixing at least one of aprotic organic solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, and 1,2-dimethoxyethane as the organic solvent. And a lithium salt soluble in the solvent, such as LiClO ₄ , LiBF ₄ , LiPF ₆ ,
A solution composed of one or more salts such as LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF _{6 and the} like can be mentioned. Among them, propylene carbonate or a mixed solution of ethylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate is mixed with LiCF ₃ SO ₃ ,
Electrolytes containing LiClO ₄ , LiBF ₄ and / or LiPF ₆ are preferred. The sheet-shaped electrode plate manufactured by the method of the present invention can be used for primary batteries and secondary batteries. That is, the present invention is also applied to primary batteries.

[0015]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Example 1 88 parts by weight of LiCoO ₂ as a positive electrode active material and 9 parts by weight of acetylene black as a conductive agent were mixed, 3 parts by weight of polyvinylidene fluoride as a binder was added, and N- was used as a solvent. A slurry having a solid content concentration of 60%, which was kneaded by adding methylpyrrolidone, had a thickness of 20 μm.
The aluminum foil was coated on both sides by the method of the present invention using a coating apparatus as shown in FIG. The distance between the slot nozzle and the support is 0.5 mm, the slot clearance is 0.5 mm, the width of the inlet and outlet lip surfaces is 3 mm,
The coating was carried out at a support transportation speed of 1 m / min. The solid content of the electrode material coating liquid was 60% by weight, and the apparent viscosity was 1 Pas. The coated material was dried with hot air and compression-molded with a roller press to form a positive electrode sheet having a thickness of 370 μm.

LiCoVO ₄ (lithium carbonate, cobalt oxide and vanadium pentoxide in air was used as the negative electrode active material
85 parts by weight (calcined at 000 ° C. for 24 hours), 6 parts by weight of acetylene black as a conductive agent, and 6 parts by weight of graphite, and ethyl acrylate as a binder.
Add 3 parts by weight of a copolymerization compound of ethylene and maleic anhydride, add toluene as a solvent, and knead and mix the resulting slurry with a solid content concentration of 50% onto both sides of a copper foil having a thickness of 20 μm in the same manner as the positive electrode. According to the invention, each side was applied. The gap between the slot nozzle and the support is 0.5 mm, the slot clearance is 0.5 mm, and the width of the inlet and outlet lip surfaces is 3
mm, and the transport speed of the support was 1 m / min. The solid content of the slurry electrode material coating liquid is 50% by weight,
The apparent viscosity was 1 Pas. The coated material was dried and compression-molded with a roller press to form a negative electrode sheet having a thickness of 220 μm.

Using the electrode sheet prepared above, a cylindrical battery having an internal structure as shown in FIG. 9 was prepared. This figure is a perspective view showing a cylindrical battery in a cut-away manner.
7, microporous polypropylene film separator 28,
The negative electrode sheet 26 and the separator 28 are laminated in this order and are spirally wound. The length of each wound sheet was 25 cm. This winding state was housed in a bottomed cylindrical battery can 25 made of iron and plated with nickel and also serving as a negative electrode terminal. Furthermore, 1 mol / liter Li as an electrolyte
PF ₆ (equal volume mixture of ethylene carbonate and dimethyl carbonate) was injected into the battery can. The battery lid 22 having the electrode terminals was caulked via the gasket 23 to produce a cylindrical battery. The positive electrode terminal is the positive electrode sheet 27.
Then, the battery can 25 was connected to the negative electrode sheet 26 in advance by a lead terminal. 24 is a safety valve. The prepared cylindrical battery had a diameter of 1.4 cm and a height of 5 cm. The conductive support serves as a collector. An assembled battery was created using three created cylindrical batteries.

Example 2 A petroleum-based coke as an anode active material.
8 parts by weight of polyvinylidene fluoride as a binder and 4 parts by weight of polyvinylidene fluoride as a binder, and N-methylpyrrolidone as a solvent, and kneaded to form a slurry on both sides of a copper foil having a thickness of 20 μm, as shown in FIG. By using a different coating device, the coating was performed on each side according to the present invention. Distance between slot nozzle and support is 0.5m
m, slot clearance 0.5 mm, width of inlet and outlet lip surfaces 3 mm, carrier speed 1 m / m
I went in. The solid content of the slurry electrode material coating liquid was 50% by weight, and the apparent viscosity was 1.5 Pas. The coated material was dried with hot air and compression-molded with a roller press to form a negative electrode sheet having a thickness of 220 μm. As the positive electrode, the one prepared in Example 1 was used, a cylindrical battery was prepared in the same manner as in Example 1, and a two-pack battery was prepared.

Example 3 SnO 8 was used as the negative electrode active material.
6 parts by weight, 3 parts by weight of acetylene black as a conductive agent and 6 parts by weight of graphite are mixed, and further 4 parts by weight of polyvinylidene fluoride and 1 part by weight of carboxymethyl cellulose are added as a binder, and water is added as a solvent. The mixture was kneaded and dispersed to prepare a coating liquid for negative electrode material. The slurry-like coating liquid was applied to both sides of a copper foil having a thickness of 20 μm by the method of the present invention using a coating apparatus as shown in FIG. The distance between the slot nozzle and the support was 0.5 mm, the slot clearance was 0.5 mm, the width of the lip surfaces on the inlet and outlet sides was 3 mm, and the transport speed of the support was 1 m / min. The solid content of the slurry electrode material coating liquid is 5
At 0% by weight, the apparent viscosity was 3 Pas. The coated product was dried with hot air and compression-molded with a roller press to have a thickness of 220 μm. The positive electrode prepared in Example 1 was used to prepare a cylindrical battery in the same manner as in Example 1, and
This assembled battery was created.

[Example 4] SiSnO as a negative electrode active material
₃ 86 parts by weight, 3 parts by weight of acetylene black as a conductive agent and graphite 6 were mixed in a ratio of parts by weight Furthermore, polyvinylidene fluoride 4 parts by weight of carboxymethyl cellulose 1 part by weight as a binder, water as a solvent The mixture was added, kneaded, and dispersed to prepare a negative electrode material coating solution.
The slurry-form coating solution was applied to both sides of a copper foil having a thickness of 20 μm by the method of the present invention by using a coating apparatus as shown in FIG. The interval between the slot nozzle outlet and the support was 0.5 mm, the slot clearance was 0.5 mm, the width of the inlet and outlet lip surfaces was 3 mm, and the support was transported at a speed of 1 m / min. The solid content of the slurry electrode material coating liquid is 50% by weight, and the apparent viscosity is 2.5 Pa.
It was s. The coated product was dried with hot air and compression-molded with a roller press to have a thickness of 220 μm. As the positive electrode, the one prepared in Example 1 was used, a cylindrical battery was prepared in the same manner as in Example 1, and a two-pack battery was prepared.

Example 5 LiCoO 2 as a positive electrode active material
88 parts by weight of ₂ and 9 parts of acetylene black as a conductive agent
3 parts by weight of polyvinylidene fluoride as a binder is added, and N-methylpyrrolidone as a solvent is added and kneaded at different amounts to give an apparent viscosity of 0.1 Pas.
0.5Pas, 50Pas, 500Pas, 1000P
An as electrode material coating solution was prepared and applied by the method of the present invention. Distance between slot nozzle and support is 0.5m
m, slot clearance 0.7 mm, lip width 2 each
mm, a conveying speed of 10 m / min, a constant amount pump was applied so that the coating thickness in a wet state was 440 μm, and coating was carried out. As a result, 0.5 Pas, 50 Pas, 500 Pa
With the electrode material coating solution of s, a smooth and good surface was obtained,
When the electrode material coating amount of 0.1 Pas was settled in the liquid reservoir 8 of the liquid injector 7, the dispersion state was poor and the discharge of the coating liquid from the liquid injector was non-uniform, and a smooth surface could not be obtained. 1000P
With the as electrode material coating solution, an uncoated portion called coating blank was generated, and a satisfactory smooth surface could not be obtained.

[Comparative Example 1] The same positive electrode mixture coating solution as in Example 1 was applied to both sides of an aluminum foil having a thickness of 20 μm by the doctor blade method on each side. The transport speed of the support was 1 m / min. The coated material was dried with hot air and compression-molded with a roller press to give a positive electrode sheet having a thickness of 370 μm.
Created. The same negative electrode mixture coating liquid as in Example 1 was applied to both sides of a copper foil having a thickness of 20 μm, one side at a time, in the same manner as the positive electrode, by the doctor blade method. The coated material was dried with hot air and compression-molded with a roller press to form a negative electrode sheet having a thickness of 220 μm. A cylindrical battery was prepared from the prepared positive electrode sheet and negative electrode sheet in the same manner as in Example 1 to prepare a three-pack battery.

Comparative Example 2 The same negative electrode mixture coating solution as in Example 2 was applied to both sides of a copper foil having a thickness of 20 μm by the doctor blade method on each side. Transport speed of support is 1m /
It was done in min. The coated material was dried with hot air and compression-molded with a roller press to form a negative electrode sheet having a thickness of 220 μm. As the positive electrode, the one prepared in Comparative Example 1 was used, a cylindrical battery was prepared in the same manner as in Example 2, and a two-pack battery was prepared.

Comparative Example 3 The same negative electrode mixture coating solution as in Example 3 was applied to both sides of a copper foil having a thickness of 20 μm by the doctor blade method on each side. Transport speed of support is 1m /
It was done in min. The coated material was dried with hot air and compression-molded with a roller press to form a negative electrode sheet having a thickness of 220 μm. As the positive electrode, the one prepared in Comparative Example 1 was used, a cylindrical battery was prepared in the same manner as in Example 2, and a two-pack battery was prepared.

[Comparative Example 4] The same negative electrode mixture coating solution as in Example 4 was applied to both sides of a copper foil having a thickness of 20 μm by using a coating apparatus as shown in FIG. The transport speed of the support was 1 m / min. The coated material was dried with hot air and compression-molded with a roller press to form a negative electrode sheet having a thickness of 220 μm. As the positive electrode, the one prepared in Comparative Example 1 was used, a cylindrical battery was prepared in the same manner as in Example 2, and a two-pack battery was prepared. [Discharge Capacity Test and Charge / Discharge Cycle Test] The discharge capacity of the prepared cylindrical battery was measured under conditions of a current density of 1 mA / cm 2, a charge end voltage of 4.3 V and a discharge end voltage of 1.8 V. The three-pack battery has a charge end voltage of 12.9 V and a discharge end voltage of 5.4 V, and the two-pack battery has a charge voltage of 8.
A charge / discharge cycle test was performed at 6 V and a discharge end voltage of 3.6 V, and the number of cycles when the discharge capacity decreased to 60% of the initial capacity was defined as the charge / discharge cycle life. Table 1 shows 50 of each of Examples 1, 2, 3, 4 and Table 2 of Comparative Examples 1, 2, 3, 4.
The test results of individual battery packs are shown.

[0026]

[Table 1]

[0027]

[Table 2]

As is clear from Tables 1 and 2, when the sheet-like electrode plate obtained by the manufacturing method of the present invention is used, the manufacturing fluctuation of the discharge capacity of the cylindrical battery can be reduced and a plurality of assembled batteries can be assembled. Since it is hard to be over-discharged and over-charged, cycleability can be improved.

[0029]

When the sheet-like electrode plate obtained by the manufacturing method of the present invention is used, the manufacturing fluctuation of the discharge capacity of the cylindrical battery can be reduced, and the plurality of assembled batteries are less likely to be over-discharged and over-charged. The cycleability can be improved. Since the discharge capacity of a battery with small manufacturing fluctuations can be obtained, the manufacturing yield is improved, and sorting by 100% inspection is unnecessary,
Manufacturing efficiency is achieved.

[Brief description of drawings]

FIG. 1 is an end view showing a main part of a coating apparatus used in the present invention, in which a liquid injector is shown in section.

FIG. 2 shows a coating liquid supply flow chart used in the present invention.

FIG. 3 is a cross-sectional view showing a configuration of a main part of a coating device used in the present invention.

FIG. 4 is an enlarged cross-sectional view showing a lip shape of the liquid injector used in the present invention.

FIG. 5 shows the position of the coating device used in the present invention.

FIG. 6 shows a coating apparatus provided with a decompression chamber used in the present invention.

FIG. 7 shows a double-sided simultaneous coating apparatus for a support.

FIG. 8 is a flowchart showing the overall manufacturing process of the sheet electrode having the coating apparatus used in the present invention.

FIG. 9 is a perspective view showing a cylindrical battery by cutting a part thereof.

[Explanation of symbols] 1 support 2 backup roll 3 inlet side lip 4 outlet side lip 5 slot 6 slot nozzle 7 injector 8 liquid reservoir 9 inlet side lip surface 10 outlet side lip surface 11 pump 12 flow meter 13 tank 14 pressure reduction Chamber 15 Conduit 16 Delivery Roll 17 Front Side Coating Section 18 Back Side Coating Section 19 Drying Zone 20 Tension Control Roll 21 Winding Roll 22 Battery Lid 23 Gasket 24 Safety Valve 25 Battery Can 26 Negative Electrode 27 Positive Electrode 28 Separator 29 (L1) Slot Clearance 30 (L2) Width of inlet side lip surface 31 (L3) Width of outlet side lip surface 32 (L4) Distance between lip surface and support 33 (L5) Slot length 34 (D) Liquid reservoir inner diameter 35 (α) Support Angle to traveling side 36 (β) Angle to the opposite side of support traveling 37 Rolling start point 38 Winding end point 39 Vertical line

Claims (3)

[Claims] 1. A conductive support, which is used for manufacturing a chemical battery having a positive electrode, a negative electrode, and an electrolyte, in which an electrode material coating liquid is discharged from an extrusion type liquid injector having a slot nozzle and wound around a backup roll to run. A method for producing a sheet-shaped electrode plate, which comprises applying the same to a predetermined thickness. 2. The viscosity of the electrode material coating liquid is 0.5 Pas or more.
It is 500 Pas, The manufacturing method of the sheet-shaped electrode of Claim 1 characterized by the above-mentioned. 3. A non-aqueous electrolyte battery comprising a sheet-like electrode manufactured by the method according to claim 1 or 2.