JP2002158012A - Slurry mixture for manufacturing nonaqueous cell electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slurry mixture for manufacturing a nonaqueous cell electrode with an excellent volume density, self-discharging property, and especially with an excellent charge-discharge cycle. SOLUTION: The slurry mixture for manufacturing a nonaqueous cell is a mixture of an electrode activator powder, a binder, and an aqueous medium, and the slurry mixture contains acetyleneglycol, or a derivative of the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a slurry composition for manufacturing an electrode body of a non-aqueous battery such as a lithium ion battery having excellent characteristics, an electrode body of a non-aqueous battery using the slurry composition, and a method of manufacturing the same. About.

[0002]

2. Description of the Related Art In recent years, as devices have become more portable and cordless, demand for non-aqueous electrolyte type secondary batteries having a small size, light weight and high energy density has been increasing. The positive electrode active material for a non-aqueous electrolyte secondary battery includes L
iCoO ₂ , LiNiO ₂ , LiNi _0.8 Co _0.2 O ₂ , L
Composite oxides of lithium and a transition metal such as iMn ₂ O ₄ and LiMnO ₂ are known. Further, as the negative electrode active material, carbonaceous materials, metal oxides, lithium transition metal nitrides, and the like are known.

In particular, a lithium secondary battery using lithium-cobalt composite oxide (LiCoO ₂ ) as a positive electrode active material and carbon such as a lithium alloy, graphite, and carbon fiber as a negative electrode can obtain a high voltage of 4V. Therefore, it is widely used as a battery having a high energy density.

[0004] However, non-aqueous secondary batteries, in particular, have further improved capacity densities per unit volume of the electrode layers of the positive electrode and the negative electrode, or are more excellent in terms of charge-discharge cycle characteristics and self-discharge characteristics. An electrode assembly is desired. Heretofore, as a method of manufacturing a large-area electrode body, a binder such as polyvinylidene fluoride and an electrode active material are dispersed in an organic solvent such as N-methylpyrrolidone to form a slurry, and then the slurry composition is formed of aluminum foil. Alternatively, a method of applying an electrode body to a current collector foil such as a copper foil and removing the organic solvent by drying is often used.

However, organic solvents such as N-methylpyrrolidone have a high boiling point and require a large amount of heat energy for drying and removal, and there is a risk of ignition and toxicity to human bodies. Therefore, there is a demand for a production method using a solvent that can improve the safety and workability. It is also conceivable to apply a slurry composition comprising an electrode active material, an organic polymer binder and water to a current collector foil without using an organic solvent such as N-methylpyrrolidone to produce an electrode body. The properties and adhesion are unsatisfactory, and there is no known method capable of satisfying all of these properties.

[0006] On the other hand, as the demand for non-aqueous secondary batteries further increases, including the expansion of applications, there is an increasing demand for electrode volume capacity density, mass capacity density, charge / discharge cycle characteristics, safety, etc. It is getting higher and higher levels are being demanded.

[0007]

DISCLOSURE OF THE INVENTION The present invention is excellent in the capacity, self-discharge characteristics and charge / discharge cycle characteristics which are the characteristics of the above-mentioned non-aqueous battery electrode, and especially excellent in charge / discharge cycle durability. The electrode body of the non-aqueous battery, without using an organic solvent having the above-mentioned problems,
Provided are a slurry composition that can be manufactured safely and with good workability, an electrode body for a non-aqueous battery using the slurry composition, and a method for manufacturing the same.

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventor has conducted research on the production of an electrode body for the above non-aqueous battery. As a result, a slurry containing an electrode active material powder, a binder and an aqueous medium was obtained. When the composition is formed, and the slurry composition is applied to a current collector or the like to form an electrode body, by adding acetylene glycol or a derivative thereof to the slurry composition for producing the electrode body, a conventional composition can be obtained. It has been found that an electrode body having remarkably excellent characteristics can be obtained. That is, when acetylene glycol or a derivative thereof is contained in the slurry composition for producing an electrode body of the nonaqueous battery, even if the slurry is an aqueous medium such as water, the obtained electrode body is In particular, they have found that the charge-discharge cycle characteristics are greatly improved, and that the surface uniformity of the electrode body and the workability and safety during the manufacture of the electrode body are also excellent.

Although it is not clear why these excellent effects are obtained by including acetylene glycol or a derivative thereof in the slurry composition, the presence of acetylene glycol or a derivative thereof depends on the presence of the above-mentioned electrode medium containing the aqueous medium. It lowers the dynamic interfacial tension of the slurry composition for production, improves the wettability of the metal surface, and lowers the viscosity.As a result, it prevents the entrainment of air and the generation of bubbles when applying the slurry composition, This is probably because the dispersibility of the substance in the slurry composition was improved, and the adhesion between the current collector and the electrode active material layer was improved. In fact, the slurry composition for manufacturing an electrode body in the present invention, despite the high concentration of the electrode active material powder, the viscosity of the slurry is reduced, and the application of the slurry composition to the current collector at the time of manufacturing the electrode body, A uniform and highly smooth coating film without bubbles and uneven lines can be obtained.

Thus, the present invention provides a slurry composition for producing an electrode body of a non-aqueous battery comprising an electrode active material powder, a binder and an aqueous medium, wherein the slurry composition contains acetylene glycol or a derivative thereof. A slurry composition is provided.

The present invention also provides a slurry composition containing at least an electrode active material powder, a binder and an aqueous medium, wherein the slurry composition contains acetylene glycol or a derivative thereof as a current collector. Provided are an electrode body for a non-aqueous battery, which carries the aqueous medium and removes the aqueous medium, and a method for producing the same. Further, the present invention provides a non-aqueous battery in which the above-mentioned electrode body for a non-aqueous battery is incorporated.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The acetylene glycol used in the present invention means a compound having an acetylene bond and one hydroxyl group at each of two carbon atoms adjacent to the triple bond of alkyne. In addition, the derivative means a compound in which the hydroxyl group is substituted or added with various groups by an ether bond or an ester bond. The acetylene glycol or a derivative thereof of the present invention may have one or more hydrogen atoms in the molecule substituted with a halogen atom.

The acetylene glycol in the present invention is preferably a compound represented by the following formula (1).

Embedded image However, R ¹ , R ² , R ³ and R ⁴ in the formula (1) each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom.

As the acetylene glycol and its derivative in the present invention, a compound represented by the following formula (2) is preferably cited as a preferred example having a large dynamic surface tension reducing effect.

Embedded image However, the symbols in the formula (2) have the following meanings. m, n: 0, 1, or 2 independently of each other. p, q: 0-30 independently of each other, and the sum of p + q is 0-40. A ^1, A _^2: -CH ² independently of one another CH ₂ -, - CH ₂ C
H ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ CH ₂ —.

According to the study of the present inventor, when m or n is 3 or more, the solubility of the compound of the formula (2) in the slurry composition for producing an electrode body is reduced, or the compound itself is produced. Is not preferred because it becomes difficult. m and n are
Particularly preferably, all are 1. Further, p and q are particularly preferably independently 0 to 8 and the sum (p + q) is particularly preferably 1 to 10.

In the formula (2), the acetylene glycol derivative is usually obtained by adding an alkylene oxide to acetylene glycol, and thus is usually obtained as a mixture having different p and q. For example, a compound with p = 3, q = 3, p = 4,
A mixture of a compound having q = 4 and a compound having p = 3 and q = 4 is exemplified. Thus, p and q are integers in each molecule since they are usually produced in a mixture, but are represented as an average of their values in a mixture.

Preferred examples of acetylene glycol or a derivative thereof contained in the above formula (2) include m = n =
1, A ¹ and A ² are each —CH ₂ CH ₂ —, p + q = 10
Wherein m = n = 1, A ¹ and A ² are each —CH ₂ C
H ₂ −, compound of p + q = 1.5, m = n = 2, A ¹ , A
² are both _{-CH 2 CH 2 -, p +} q = compounds of 3.5, m = n = 1, A 1, also A ² are both -CH ₂ CH ₂ CH
_2- , p + q = 5 and the like.

In the present invention, the content of acetylene glycol or a derivative thereof in the slurry composition is 2%.
0 to 5000 ppm is preferred. If the content of acetylene glycol or a derivative thereof is less than 20 ppm, the above-described effect of addition is undesirably reduced. On the other hand, if the content exceeds 5000 ppm, the effect of addition is saturated and the cost is increased, and the density of the electrode layer after pressing may be undesirably reduced. A particularly preferred content is 20 to 1000 ppm.

In the present invention, acetylene glycol or
Or a slurry composition containing the derivative thereof,
Contains substance powder, binder and aqueous medium. electrode
Active materials include lithium secondary batteries as non-aqueous batteries.
In the case of a positive electrode, lithium can be inserted and removed.
LiCoO_Two, LiCo_0.8Ni_0.2O_Two, LiMn _Two
O_FourPreferred are lithium transition metal composite oxides such as
Can be

In the case of a negative electrode of a lithium secondary battery as a non-aqueous battery, a material capable of inserting and removing lithium is used. For example, a lithium metal, a lithium alloy, a carbon material, an oxide mainly composed of a metal belonging to Groups 14 and 15 of the periodic table, a carbon compound, a silicon carbide compound, a silicon oxide compound, a titanium sulfide, and a boron carbide compound are preferable. As the carbon material, those obtained by thermally decomposing organic substances under various thermal decomposition conditions, artificial graphite, natural graphite, soil graphite, expanded graphite, flaky graphite, and the like can be used. As the oxide, a compound mainly composed of tin oxide can be used. Among them, carbon materials, metals, metals or metal oxides,
Lithium transition metal nitrides are preferred.

The average particle diameter of the above-mentioned positive and negative electrode active material powders is preferably 3 to 30 μm, and more preferably 5 to 15 μm, although it depends on the use of the battery. The content of the electrode active material in the slurry composition is 20 to
It is preferably 60% by mass, and particularly preferably 30 to 40% by mass.

The binder contained in the slurry composition is preferably an aqueous dispersion of polytetrafluoroethylene, an aqueous dispersion of polyvinylidene fluoride, carboxymethyl cellulose, an aqueous latex of a styrene-butadiene copolymer, a (meth) acrylate ester -Styrene dibunylbenzene copolymer aqueous latex, acrylonitrile-butadiene-methacrylic acid-methyl methacrylate copolymer aqueous latex, water-soluble binder such as polyacrylate, aqueous latex, polymer aqueous dispersion alone or mixture Is used. The binder is preferably 2 to 15 parts by mass, particularly 2 to 1 part by mass with respect to 100 parts by mass of the electrode active material powder.
It is preferable to contain 2 parts by mass.

The aqueous medium in the present invention means an aqueous medium or a medium containing water, preferably at least 50% by weight, particularly preferably at least 70% by weight. As a medium other than water contained in the aqueous medium, a medium compatible with water is preferable. Examples of such a medium include low-boiling alcohols such as methanol, ethanol, and isopropanol;
Organic media such as methylpyrrolidone are preferred. The aqueous medium may be used alone, or may contain a water-insoluble organic solvent as long as it does not separate. As the aqueous medium in the present invention, it is preferable to use only water from the viewpoint of workability during production of the electrode body. The content of the aqueous medium in the slurry composition column is preferably 1 to 30% by mass in the slurry composition.

The slurry composition preferably further contains a fluorine-containing surfactant. By including a fluorine-containing surfactant, the dynamic surface tension provided by acetylene glycol or a derivative thereof can be further synergistically reduced, and the required content of acetylene glycol or a derivative thereof can be reduced. Such a fluorinated surfactant has a fluoroalkyl group in the molecule,
It preferably has a structure having a perfluoroalkyl group and a hydrophilic functional group. As the preferred fluorine-containing surfactant, nonionic and anionic surfactants are particularly suitable, and specifically, “SUFLON” S-381,
S-145, KH-20, S-113 (all are trade names of Seimi Chemical Co.), [ZONYL] FS
O-100, FSN-100, FSO, FSN (all trade names of DuPont), "Fluorad (FLUORA)
D) FC-143, FC-430, FC = 431 (all are 3M company names). The content of the fluorinated surfactant in the slurry composition is preferably 1 to 100 parts by mass of acetylene glycol or a derivative thereof.
-100 parts by mass, particularly preferably 5-30 parts by mass.

Further, the slurry composition of the present invention may further contain, if necessary, other components, for example, acetylene black,
Carbon-based conductive additives such as graphite and ketchen black can also be added, thereby improving the performance of the non-aqueous battery. In that case, the content is preferably 3 to 10 parts by mass with respect to 100 parts by mass of the electrode active material.

In the present invention, the solid content in the slurry composition comprises the electrode active material powder, a binder and, if necessary, a fluorine-containing surfactant and a carbon-based conductive additive. Content is preferably 30 to 60% by mass. Although the viscosity of the slurry composition also depends on the coating method, it is preferably 0.2 to 5 Pa / from the viscosity for coating and the coating density.
s.

In the present invention, when the electrode body of a non-aqueous battery is manufactured from the above slurry composition, the electrode body is manufactured by applying the slurry composition to a current collector forming the electrode body by coating or the like. Preferably, a production method in which the slurry composition is applied to a current collector and the aqueous medium is dried is exemplified.

As the current collector, a metal foil, a metal porous sheet, a metal mesh or the like is used. For the positive electrode, an aluminum foil or a stainless steel foil is used. On the other hand, for the negative electrode, a copper foil, a nickel foil or the like is used. Is used. The above-mentioned slurry composition is applied to such a current collector by means such as a doctor blade, a roll star, and a curtain coater. In the present invention, in the application step, as described above, the application of the slurry composition to the current collector does not cause entrainment of air or generation of bubbles, and has a high smoothness without uniformity and without bubbles and uneven lines. It has the feature that a coating film can be obtained. Next, the coating film for forming the obtained electrode layer is preferably subjected to drying to remove the aqueous medium, and then preferably subjected to consolidation by a roll press or the like to produce an electrode body.

When a non-aqueous battery, for example, a lithium secondary battery is constructed using the electrode body produced according to the present invention, a porous polyethylene or porous polypropylene film is preferably used as a separator. . Various solvents such as ethers and esters can be used as the solvent for the electrolyte solution of the battery, and among them, carbonate is preferable. In this case, both cyclic and chain carbonates can be used. Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate (EC). Preferred chain carbonates include dimethyl carbonate, diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate, methyl isopropyl carbonate and the like. As the solvent for the electrolyte solution, carbonate esters can be used alone or in combination of two or more. Moreover, you may mix and use it with another solvent. In addition, when a chain carbonate and a cyclic carbonate are used in combination, discharge characteristics, cycle durability, and charge / discharge efficiency can be sometimes improved.

As a solvent constituting the electrolyte solution, a gel polymer containing a vinylidene fluoride-hexafluoropropylene copolymer (for example, manufactured by Atochem Co., Ltd., trade name: Kynar) or a vinylidene fluoride-perfluoropropyl vinyl ether copolymer is used. An electrolyte can also be used.

In a lithium secondary battery as a non-aqueous battery, the solute constituting the electrolyte solution is ClO ₄
−, CF ₃ SO ₃ −, BF ₄ −, PF ₆ −, AsF ₆ −, S
Any one or more of lithium salts having anion such as bF ₆ —, CF ₃ CO ₂ —, (CF ₃ SO ₂ ) ₂ N— are preferably used. Such a solute is 0.2 to 2.0 mol / l (liter) based on the solvent or the polymer electrolyte.
Is preferably contained at a concentration of Outside of this range, the ionic conductivity decreases and the electrical conductivity of the electrolyte decreases. Among them, the concentration of solute is 0.5-1.5 mol
/ L is particularly preferred.

The shape of the lithium battery as a non-aqueous battery produced according to the present invention is not particularly limited. A sheet shape, a film shape, a folded shape, a rolled bottomed cylindrical shape, a button shape, and the like are selected according to the application.

Although the lithium secondary battery has been mainly described as the non-aqueous battery of the present invention, the non-aqueous battery of the present invention is not limited to this, but may be a lithium primary battery or another non-aqueous battery. Primary or secondary batteries, and even though they have different names, function substantially the same as batteries, such as charge / discharge functions.For example, the present invention can be similarly applied to non-aqueous electric double layer capacitors. Including.

That is, for example, a non-aqueous electric double layer capacitor is a slurry composition comprising an electrode active material comprising an inorganic fine powder such as a carbonaceous material having a high specific surface area such as activated carbon, a binder such as carboxymethyl cellulose, and an aqueous medium. Has a positive electrode and a negative electrode formed by applying the compound on a metal current collector, has a charge / discharge function, and functions substantially the same as a battery. Examples of the carbonaceous material include activated carbon, polyacene, and mesophase carbon. In addition to such a carbonaceous material, a highly conductive carbonaceous powder such as acetylene black or Ketjen black can be added to impart conductivity.

The carbonaceous material described above differs from graphite powder in that a considerable amount of an aqueous medium is adsorbed. As a result, the content of the carbonaceous material in the slurry composition is preferably from 10 to 30% by mass. Also,
The specific surface area of the carbonaceous material is preferably from 300 to 3000 m ² / g. As the binder and the aqueous medium, the same binder and aqueous medium as described for the lithium battery described above can be used. As the positive and negative electrode current collectors, for example, the same aluminum foil as the positive electrode current collector in a lithium battery can be particularly preferably used.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition,
In the following, Examples 1 to 3 are Examples, and Examples 4 and 5 are Comparative Examples. In the examples, unless otherwise specified, “parts” and “%” for content are based on mass.

Example 1 In an autoclave, 175 g of methyl methacrylate, 55 g of styrene, and 5 parts of divinylbenzene
g, 200 g of pure water, and heated to 80 ° C. while stirring,
Polymerized. Further, 350 g of 1,3-butadiene, 100 g of styrene, 5 g of divinylbenzene, 25 g of sodium dodecylbenzenesulfonate, 1500 g of pure water, and 15 g of azobisbutyronitrile were charged and polymerized, and when the monomer consumption reached 99.8%. The reaction was stopped by cooling, the unreacted monomer was removed, and the pH was adjusted to 7 with alkali to obtain a polymer latex having a binder polymer A (hereinafter, referred to as binder polymer A). The particle size of the polymer was 0.26 μm.

An acetylene glycol derivative {structural formula CH ₃ —CH (CH ₃ ) —CH ₂ —C (CH ₃ ) ((O—
_{CH 2 CH 2) p -OH)} -C≡C-C (CH 3) ((O-
_{CH 2 CH 2) q -OH)} -CH 2 -CH (CH 3) -CH 3
Where p and q are mixtures having various values, and p + q = 3.5 ° was dissolved in isopropanol to prepare a 1% by mass solution (solution B).

95 parts by mass of mesophase carbon microbeads (MCMB) having an average particle size of 6.1 μm and calcined at 2800 ° C., a latex containing 3 parts by mass of binder polymer A, 2 parts by mass of sodium salt of carboxymethyl cellulose, and 3 parts by mass of ethyl alcohol , And pure water 65
Parts by mass were mixed, and further, solution B was added, and the whole was mixed with a ball mill to obtain a slurry composition for manufacturing a negative electrode body. The content of the acetylene glycol derivative in the slurry composition was 150 ppm.

Using the above slurry composition, copper foil (18 μm thick) was coated on one side with a doctor blade.
There were no streaks on the coated surface, and a smooth coated surface was obtained. The adhesion was also good. The coated product was dried for 10 hours, and then roll-pressed to produce a negative electrode sheet for a lithium battery. When the density of the electrode layer was measured from the thickness of the negative electrode body after rolling and the mass per unit area of the electrode layer, it was 1.36 g / cm ³ .

The negative electrode obtained above was subjected to a single-electrode durability test using a coin-type lithium battery having lithium metal as a counter electrode in order to evaluate the performance of the negative electrode body of the lithium battery as follows.

That is, the above-mentioned negative electrode sheet was circularly punched, vacuum-dried at 120 ° C. for 3 hours and used as a negative electrode, and a metallic lithium foil (thickness 200 μm) was used as a counter electrode.
A nickel foil (20 μm thick) was used for the counter electrode current collector, a 25 μm thick porous polypropylene sheet was used for the separator, and a 1 M LiPF ₆ /
Using an EC + DEC (1: 1) solution, a coin-type lithium battery (diameter 20 mm, thickness 3 mm) using a SUS304 negative electrode cap and a SUS316L positive electrode case
Was assembled in an argon glove box.

For such a coin-type lithium battery, 2
Charge / discharge cycle test by charging at a constant current and constant voltage for 10 hours to 0.01 V at a load current of 40 mA per 1 g of the negative electrode active material at 5 ° C. and discharging to 1.5 V at a load current of 40 mA per 1 g of the negative electrode active material Was performed 30 times. as a result,
The capacity retention rate after 30 charge / discharge cycles was 82%.

[Example 2] In an autoclave, 175 g of methyl methacrylate, 55 g of styrene, and 5 of divinylbenzene were added.
g, 200 g of pure water, and heated to 80 ° C. while stirring,
Polymerized. Further, 350 g of 1,3-butadiene, 100 g of styrene, 5 g of divinylbenzene, 25 g of sodium dodecylbenzenesulfonate, 1500 g of pure water, and 15 g of azobisbutyronitrile were charged and polymerized, and when the monomer consumption reached 99.8%. The reaction was stopped by cooling, the unreacted monomer was removed, the pH was adjusted to 7 with alkali, and a polymer latex having binder polymer A was obtained. The particle size of the polymer was 0.26 μm.

Further, an acetylene glycol derivative {structural formula CH ₃ —CH (CH ₃ ) —CH ₂ —C (CH ₃ ) ((O—
_{CH 2 CH 2) p -OH)} -C≡C-C (CH 3) ((O-
_{CH 2 CH 2) q -OH)} -CH 2 -CH (CH 3) -CH 3
Where p and q are mixtures having various values, and p + q = 3.5 ° was dissolved in isopropanol to prepare a 1% by mass solution (solution B).

92 parts by mass of LiCoO _{2 having an} average particle size of 8.2 μm, 5 parts by mass of acetylene black, a latex containing 2 parts by mass of binder polymer A, 2 parts by mass of sodium salt of carboxymethylcellulose, 4 parts by mass of ethyl alcohol, and 60 parts by mass of water were mixed, and further, solution B and “Surflon S-381” (trade name of nonionic fluorine-containing surfactant manufactured by Seimi Chemical Co., Ltd.) were added,
The whole was mixed with a ball mill to obtain a slurry composition for producing a positive electrode body. The content of the acetylene glycol derivative in the slurry composition was 100 ppm. The content of Surflon S-381 was 50 ppm.

Using the above slurry composition, aluminum foil (thickness: 20 μm) was coated on one side with a doctor blade. There were no streaks on the coated surface, and a smooth coated surface was obtained. The adhesion was also good. The coated material was dried at 120 ° C. for 1 hour and roll-pressed to prepare a positive electrode sheet for a lithium battery. When the density of the electrode layer was measured from the thickness of the positive electrode body after rolling and the mass per unit area of the electrode layer, it was 3.15 g / cm ³ .

The positive electrode obtained above was subjected to a single-electrode durability test using a coin-type lithium battery having lithium metal as a counter electrode in order to evaluate the performance as a positive electrode body of a lithium ion battery. .

That is, the above-mentioned positive electrode sheet was punched out in a circular shape, vacuum-dried at 120 ° C. for 5 hours and used as a positive electrode, and a metallic lithium foil (thickness 200 μm) was used as a negative electrode.
A nickel foil (20 μm thick) was used for the negative electrode current collector, a 25 μm thick porous polypropylene sheet was used for the separator, and a 1 M LiPF ₆ /
An EC + DEC (1: 1) solution (a mixed solution of LiPF ₆ as a solute at a mass ratio of EC and DEC (1: 1); the same applies hereinafter) was used, and a negative electrode cap made of SUS304 and a positive electrode made of SUS316L were used. Using the case, a coin-type lithium battery (diameter 20 mm, thickness 3 mm) was assembled in an argon glove box.

For such a coin-type lithium battery, 2
The battery was charged at a constant current of 4.3 V with a load current of 75 mA per 1 g of the positive electrode active material at 5 ° C.
A constant current discharge was performed to 2.5 V at a load current of mA to perform a charge / discharge cycle test 30 times. As a result, the capacity retention after 30 charge / discharge cycles was 92%.

Example 3 In Example 1, in addition to the acetylene glycol derivative, “Surflon S-381” (a nonionic fluorine-containing surfactant manufactured by Seimi Chemical Co., Ltd.) was added to the slurry composition used in the production of the negative electrode. Product name)
Was prepared in the same manner as in Example 1 except that was added so that the concentration became 100 ppm, and a charge / discharge cycle test was conducted. As a result, the capacity retention ratio at the 30th cycle was 86%.

[Example 4] A slurry composition for producing a negative electrode was prepared in the same manner as in Example 1 except that no acetylene glycol derivative was added. I got Streaks were partially observed on the surface of the negative electrode body. The obtained negative electrode body was subjected to a charge / discharge cycle durability test using a coin-type lithium battery in the same manner as in Example 1, and as a result, the capacity retention after 30 charge / discharge cycles was 78%.

Example 5 A slurry composition for producing a positive electrode was prepared in the same manner as in Example 2 except that the acetylene glycol derivative and Surflon 381 were not added. Thus, a positive electrode body was obtained. Streaks were partially observed on the surface of the positive electrode body. The obtained positive electrode body was subjected to a charge / discharge cycle durability test using a coin-type lithium battery in the same manner as in Example 2, and as a result,
The capacity retention after 30 charge / discharge cycles was 86%.

Example 6 Latex containing 85 parts by mass of high-purity activated carbon powder having a specific surface area of 1600 m ² / g and an average particle size of 7 μm, 12 parts by mass of Ketjen black and 2 parts by mass of binder polymer A, and sodium carboxymethylcellulose 2 parts by mass, 4 parts by mass of ethyl alcohol, and 60 parts by mass of pure water were mixed, further, solution B was added, and the whole was mixed by a ball mill to obtain a slurry composition for manufacturing a capacitor electrode body. The content of the acetylene glycol derivative in the slurry composition is 25
It was 0 ppm. This slurry composition was applied to a width of 10c.
m, an electrode layer was formed by applying it to one side of an etched aluminum foil having a thickness of 29 μm, dried at 120 ° C. for 2 hours, and then press-rolled to produce an electrode body having a thickness of 100 μm.

From the above electrode body, an effective electrode area of 4 cm × 6
cm of the electrode body were obtained, and these were used as a positive electrode body and a negative electrode body, and were placed so as to face each other with a 160 μm-thick glass fiber mat separator interposed therebetween. Then 1
Vacuum drying was performed at 90 ° C. for 5 hours to remove impurities. Then, in a nitrogen glove box, 1.2 mol / l of (C
A propylene carbonate solution of ₂ H ₅ ) ₃ (CH ₃ ) NBF ₄ was used as an electrolytic solution in vacuum impregnation to produce an element impregnated with the electrolytic solution to produce an electric double layer capacitor.

After measuring the initial discharge capacity and internal resistance of the electric double layer capacitor, the electric discharge was measured in a thermostat at 45 ° C.
The charge and discharge with a constant current of 2 A between 2.8 V is repeated 2,000 cycles, the discharge capacity and internal resistance after 2,000 cycles are measured, and the performance change before and after is observed. Reliability was evaluated at an accelerated rate. The initial capacity was 6.29 F, the initial internal resistance was 0.28Ω, and the capacity after the cycle test was 6.22.
F, the internal resistance was 0.30Ω.

[0057]

According to the present invention, the electrode of a non-aqueous battery has excellent characteristics such as capacity density, self-discharge characteristics, and charge-discharge cycle characteristics. The present invention also provides a slurry composition which is highly safe and can produce an electrode body of a non-aqueous battery excellent in uniformity of application to a current collector and the like.

Continued on the front page (72) Inventor Hidemasa Taka 3-2-10 Chigasaki, Chigasaki-shi, Kanagawa F-term (reference) in Seimi Chemical Co., Ltd. 5H029 AJ03 AJ04 AJ05 AK03 AL01 AL02 AL06 AL12 CJ02 CJ08 CJ22 DJ08 EJ11 HJ01 HJ02 5H050 AA07 AA08 AA09 BA17 CA08 CA09 CB01 CB02 CB07 DA04 DA09 DA11 EA22 FA17 GA02 GA10 GA22 HA01 HA02

Claims (10)

[Claims] 1. A slurry composition for producing an electrode body for a non-aqueous battery comprising an electrode active material powder, a binder and an aqueous medium, wherein the slurry composition contains acetylene glycol or a derivative thereof. Slurry composition. 2. The slurry composition according to claim 1, wherein the acetylene glycol or a derivative thereof is a compound represented by the formula (1). Embedded image However, R ¹ , R ² , R ³ , and R ⁴ in the formula each independently represent an alkyl group having 1 to 20 carbon atoms or a hydrogen atom. 3. The slurry composition according to claim 1, wherein the acetylene glycol or a derivative thereof is a compound represented by the formula (2). Embedded image However, the symbols in the formula have the following meanings. m, n: 0, 1, or 2 independently of each other. p and q: 0 to 30 independently of each other, and p + q is 0 to 4
0. A ^1, A _^2: -CH ² independently of one another CH ₂ -, - CH ₂ C
H ₂ CH ₂ — or —CH ₂ CH ₂ CH ₂ CH ₂ —. 4. A slurry composition wherein the content of acetylene glycol or a derivative thereof is from 20 to 2000 pp.
The slurry composition according to any one of claims 1 to 3, wherein m is m. 5. The slurry composition according to claim 1, wherein the slurry composition contains a fluorine-containing surfactant. 6. The slurry composition according to claim 1, wherein the electrode active material is a positive electrode electrode active material and a lithium transition metal composite oxide capable of inserting and removing lithium. . 7. An electrode active material for a negative electrode, wherein the electrode active material is one of a carbonaceous powder, a metal oxide powder, a metal powder and a lithium transition metal nitride capable of inserting and removing lithium. 6. The slurry composition according to any one of 1 to 5. 8. An electrode assembly for a non-aqueous battery, wherein the slurry composition according to claim 1 is supported on a current collector and an aqueous medium is removed. 9. A method for producing an electrode assembly for a non-aqueous battery, comprising applying the slurry composition according to claim 1 to a current collector and drying an aqueous medium. 10. A non-aqueous battery in which the electrode for a non-aqueous battery according to claim 8 is incorporated.