JP3537165B2 - Organic electrolyte battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electrolyte battery.

[0002]

2. Description of the Related Art Demand for organic electrolyte batteries represented by manganese dioxide-lithium batteries is increasing due to high voltage of 3 V or more and high energy density.

[0003] Conventionally, an organic electrolyte (hereinafter, referred to as an organic electrolyte) for this type of battery.
Except when referring to batteries, simply referred to as "electrolyte")
Although LiClO ₄ has been used as an electrolyte, recently, importance has been placed on the safety of batteries, and the use of dangerous substances such as LiClO ₄ has become less preferred.

As a lithium salt other than LiClO ₄ , for example, a boron-based lithium salt such as LiBF ₄ or LiB (C ₆ H ₅ ) ₄ is used as an electrolyte.

[0005]

However, the above-mentioned LiB
An electrolyte solution using F ₄ , LiB (C ₆ H ₅ ) _4, or the like as an electrolyte causes discoloration when stored, or causes some of the electrolyte solution solvent to polymerize. In addition, when the electrolytic solution is used in a battery, the storability of the battery is reduced.

Accordingly, an object of the present invention is to solve the problems of the above-mentioned conventional products and to provide an electrolyte and an organic electrolyte battery having excellent storage properties.

[0007]

The present invention is characterized in that an anion of an alkali metal salt used as an electrolyte of an electrolyte in an organic electrolyte battery has a specific structure and has a steric hindrance barrier structure. Here, the steric hindrance barrier structure refers to a structure in which the cation is hard to approach the charge center of the anion. More specifically, the maximum distance between the atom serving as the charge center in the anion and the center of another atom is 4 mm or more, Preferably, it is a metal salt containing an organic anion of 5 ° or more, most preferably 6 ° or more.

It is necessary that the organic anion further has a fluoroalkyl group. The number of fluoroalkyl groups is desirably 4 or more in total. When the number is 5 or more, it is more preferable. When the number is 6 or more, the storage property is most desirably further improved.

The function of the above fluoroalkyl group is to stabilize the metal salt due to its own electron withdrawing property and to improve the storage property of the electrolytic solution. The number of the fluoroalkyl groups is desirably four or more. In order to further enhance the storage property, the number is preferably five or more, and when the number is six or more, more preferable characteristics are obtained.

The atom serving as the center of the anion includes O (oxygen), N (nitrogen), C (carbon), B (boron), Al (aluminum), etc., and is an atom belonging to group IIIb-VIb of the periodic table. is there. Among them, III capable of bonding three or more substituents
A group b-IVb atom is preferred, and a group IIIb atom is particularly preferred, which can have four bonds when the group IIIb atom, such as B (boron), is the anion center and is sterically hindered by substituents around the anion center. Is easy to form. Further, among group IIIb atoms, B (boron) atom is desirable because it has the smallest molecular weight and can reduce the molecular weight of anion. By using a metal salt containing such an anion, the storability of the electrolytic solution is improved,
In addition, by using the electrolytic solution, the storage property of the organic electrolytic solution battery can be improved.

In the present invention, the reason why the use of the above-mentioned electrolyte improves the storability of the electrolyte and the battery will be clarified in the concrete description of the above-mentioned electrolyte.

First, it is desirable that the cation forming the salt is composed of an alkali metal or an alkaline earth metal, and lithium is particularly preferable.

Specific examples of metal salts containing a fluoroalkyl group and an anion having a sterically hindered barrier structure include:
(CF ₃ SO ₂ ) ₂ · N · ME, (CF ₃ SO ₂ ) ₃ C
・ ME, [C ₆ H ₄ (F)] ₄ B ・ ME, [C ₆ H
₄ (Cl)] ₄ B. ME and the like (here, ME is a metal such as Li, Na and K). Also,
Those having more than 2 carbon atoms, especially those having more than 4 carbon atoms, such as C ₄ F ₉ SO ₃ Li, also have a steric hindrance barrier structure. Specific examples of particularly desirable metal salts include, for example, LiB [C ₆ H ₄ (CF ₃ )] ₄ and LiB
[C ₆ H ₃ (CF ₃ ) ₂ ] ₄ (lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate) (hereinafter referred to as LiTFB), LiB (C ₆ H
₃ A ₂ ] ₄ (where A is —C (CF ₃ ) ₂ OCH ₃ ]
And the like.

In particular, the organic boron-based metal salt having a fluoroalkyl group can improve the storability of the electrolytic solution and the battery for the following reasons.

[0015] Boron (B) is capable of forming four bonds more than oxygen (O) and nitrogen (N) as an element contained in an organic substance. It has the ability to bind to a substituent having attractive properties. Moreover, boron has a higher metallicity than carbon (C) having four bonds, and is a convenient element for ionizing the bonded metal.

However, LiBR in which an electron donating alkyl group or a benzene ring is simply bonded to the boron (B) atom.
₄ (R is an alkyl group or a phenyl group) has a higher electron density on the B atom, and thus emits electrons more easily.

That is, if a positive electrode active material which is more easily oxidized and has high activity at a high voltage such as a metal oxidizing agent is used,
The storage property of the battery is rather impaired by, for example, partially reacting with the positive electrode.

Therefore, it is necessary to further introduce a fluoroalkyl group into the substituent connecting the B atom to prevent the concentration of electrons on the B atom. When this fluoroalkyl group is introduced into the substituent bonded to the B atom, electrons are less likely to be emitted, and the electrolyte is less likely to be oxidized, thereby improving the storability.

In particular, the above-mentioned LiTFPB is used in the examples described below, but the ortho position of the phenyl group bonded to the B atom,
It has two trifluoromethyl groups at the meta position, and has a total of eight fluoroalkyl groups, and is particularly excellent in characteristics. The maximum distance between the center of the anion charge center atom and the center of another atom is B atom and F in the case of LiTFPB.
The drug is 6.1% between atomic centers.

Here, the chemical formula of the above LiTFPB is shown as follows.

[0021]

Embedded image

When these metal salts having a steric hindrance barrier structure are dissolved in an electrolyte solvent, they simply have a bulk.
Assuming that the metal component of this is eluted into the electrolyte,
Usually, the metal component is a divalent or higher cation, and when these cations and the anion part of the metal salt having the steric hindrance barrier structure are counterions, the steric hindrance increases because the metal salt is bulky. It is considered that the reaction does not proceed as described above and elution of the metal component of the positive electrode current collector is suppressed.

As the material of the positive electrode current collector, Al (aluminum) or an alloy containing it as a main component is used.
Above all, when the metal material of the positive electrode current collector elutes, the higher the valence of the cation is, the more difficult it is to elute, and in this sense, Al is trivalent, and is harder to elute than other divalent metals. .

In the electrolyte comprising the metal salt having the steric hindrance barrier structure, it is desirable that the anion portion is not only an anion having a large steric hindrance, but the anion itself is stable to oxidation.

In preparing a battery using the above-mentioned electrolyte, a negative electrode in which an alkali metal or a compound containing an alkali metal is integrated with a current collecting material such as a stainless steel net is used. For example, lithium, sodium, potassium and the like can be mentioned. As the compound containing an alkali metal, for example, an alkali metal and an alloy of aluminum, lead, indium, potassium, cadmium, tin, magnesium, etc., and further a compound of an alkali metal and a carbon material And a compound of a low potential alkali metal with a metal oxidizing agent and a sulfide.

In preparing the electrolytic solution, examples of the organic solvent used for dissolving the above-mentioned electrolyte include:
1,2-dimethoxyethane, 1,2-dimethoxymethane, dimethoxypropane, 1,3-dioxolan, tetrahydrofuran, 2-methyltetrahydrofuran, 4-
Examples thereof include ethers such as methyl-1,3-dioxolan, esters such as propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, and γ-valerolactone, and sulfolane. Among them, esters are used in combination with a metal salt containing an anion having the steric hindrance barrier structure, particularly a metal salt containing four or more fluoroalkyl groups or an organic boron-based metal salt having a fluoroalkyl group. Sometimes, it is preferable because the storability of the electrolytic solution is further improved.

The concentration of the electrolyte in the electrolyte is not particularly limited, but usually, the electrolyte or the above-mentioned organic solvent contains, as an electrolyte, a metal salt or a fluoroalkyl group containing at least four fluoroalkyl groups. 0.01 to 2 mol / l, especially 0.05 to 2 mol / l
It is preferable to dissolve about 1 mol / l.

Here, it is more preferable that the metal salt used for the battery is preliminarily treated with a non-halogen solvent because it is easily dissolved in the solvent. The present inventors first tried to dissolve various lithium salts in CH ₂ Cl ₂ , which is a typical halogen-containing solvent that is difficult to dissolve metal salts, but many lithium salts are dissolved in this CH ₂ Cl ₂ It hardly dissolves and precipitates. Even if the conductivity as an electrolyte is measured, it is several tens μS / c.
m or less.

The same applies to other halogen-containing solvents such as perfluorotrialkylamines, which are freon-based solvents.

However, while repeating various studies, the above-mentioned LiTFPB was dissolved in ether, dried in vacuum, and then CH ₂ Cl ₂ was added.
20 mmol / l could be immediately dissolved in ₂ CL ₂ , the conductivity reached 820 μS / cm, and the conductivity improved 10 times or more. Such an effect was confirmed not only with a halogen-containing solvent but also with an ester having a high viscosity.

From the above, it has been found that the dissolution rate and solubility in a solvent can be increased by treating a metal salt which is hardly soluble in a halogen-containing solvent, an ester or the like with a non-halogen solvent in advance.

A more desirable electrolytic solution of the present invention is prepared by treating a metal salt with a non-halogen solvent in advance (for example, dissolving, adhering, impregnating) and then adding a solvent to dissolve the alkali metal salt in the solvent. You. It is particularly desirable that the weight ratio of the non-halogen solvent to the metal salt after treatment is 0.1 or less, more preferably 0.05 or less. The content of the non-halogen solvent with respect to the metal salt is preferably 0.0005 or more by weight, more preferably 0.005 or more.

Here, the solvent effective for the non-halogen solvent treatment is a halogen-containing solvent such as CH ₂ Cl ₂ , CH ₂
Cl ₃ , CCl ₄ , CBrF ₃ , CF ₃ CF ₂ CHCl
₂ , a solvent containing a halogen element such as CCIF ₂ CF ₂ CHClF, propylene carbonate, ethylene carbonate, butylene carbonate, γ
-It is also effective for esters such as butyrolactone and γ-valerolactone, and also for sulfolane. The viscosity of a high-viscosity solvent that is effectively treated with a non-halogen solvent is desirably 1 cp (centipoise) or more at 25 ° C.
p or more is more desirable, and 2.0 cp or more is still more desirable.

Examples of the non-halogen solvent include ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, glyme, and polyethylene oxide; esters such as propylene carbonate, γ-butyrolactone, and methyl formate; and amines;
Ketones, sulfur-containing compounds, further alcohols, protic solvents such as water and the like, ethers,
Esters are preferred, and ethers are particularly preferred because of high solubility of the alkali metal salt and low reactivity with the negative electrode.

It should be noted that a protic solvent such as an alcohol easily reacts with lithium or the like and often has a bad influence on a negative electrode. In the method, since the protic solvent is strongly bound by the alkali metal salt, the reactivity with the negative electrode is low.

For the positive electrode, for example, a metal oxidizing agent such as manganese dioxide, vanadium pentoxide, chromium oxidizing agent, lithium cobalt oxidizing agent, lithium nickel oxidizing agent or a metal sulfide such as molybdenum disulfide or a positive electrode active material thereof is used. A mixture obtained by appropriately adding a conductive additive, a binder such as polytetrafluoroethylene, or the like to a molded body using a current collector material such as an aluminum foil or a stainless steel net as a core material is used.

When a metal oxidizing agent is used as the positive electrode active material, a high voltage can be obtained. However, when such a high voltage is used, the conventional LiBF ₄ or LiB (C ₆ H ₅ ) ₄ has a higher storage property. Although worse, the electrolyte used in the present invention does not lower the storability even under such a high voltage,
Its significance is great.

Taking the case where Al is used for the positive electrode current collector as an example, the effect of suppressing the elution of Al into the electrolytic solution will be described. The electrolyte (metal salt having a steric hindrance barrier structure containing a fluorine atom) used in the present invention will be described. Is the conventional CF ₃ SO ₃ L
A difference starts to appear from around 3.1 V as compared with the case where i is used.

At a higher potential, CF ₃ SO
_{In the} 2Li system, the oxidation current completely rises (that is, the oxidation current flows through Al and the Al itself is oxidized and elutes into the electrolytic solution), whereas, for example, C ₄ F ₉ SO ₃ L
When i is used, almost no oxidation current flows and a remarkable difference appears, and the oxidation current rises at about 4.6 V
It is. Furthermore, when LiTFB is used, about 10 V
In this case, there was no region where the current suddenly increased, and the metal salt was very stable.

When Al or an alloy thereof is used for the positive electrode current collector when using the electrolyte of the present invention, the combination is preferable in terms of safety.

That is, when the potential of the positive electrode becomes 350 mV or less on the basis of Li at the time of abnormal discharge of the battery, the positive electrode current collector alloys and becomes tattered, so that the current cannot be collected from the positive electrode and the current is cut off. This is because abnormal heat generation can be prevented.

For this purpose, the structural design is made appropriate,
The following items should be noted.

First, the setting of the place where the current is cut off is most suitable for cutting off the current. The tab portion of the current collector (connected to one side of the plate-like positive electrode and made of metal) This is a lead portion connecting the positive electrode and the positive electrode terminal portion with the formed positive electrode current collecting member, and is indicated by a lead body 14 in the battery shown in FIG. 1). When this portion is alloyed, only this portion is formed. The current is interrupted just by falling off and falling off.

Second, the place where the current should be cut off is wet with the electrolyte. That is, aluminum alloying occurs only in the presence of the electrolytic solution.
Therefore, it is desirable to fill the electrolyte up to the place where the current is interrupted, or cover it with an electrolyte permeable material and keep it wet with the electrolyte.

Third, a tensile stress is applied to the portion where the current should be interrupted. This is because if a compressive stress is applied, even if a certain amount of the Al alloy falls off, it will adhere again.

However, the direction of the tensile stress does not matter. This is because if any part of the part is dislodged, the parts are separated in the lateral direction, so that the current can be reliably cut off.

A desirable condition is that the current interrupting portion is thinner than other portions. This is because if the lead body is cut at a portion other than the desired portion, a sufficient effect may not be obtained when a shrinkage stress is applied to the portion.

Here, such tensile stress may impair the stability of the current collector made of aluminum at 4.2 V or more, but when the organic metal salt of the present invention is used, the effect is slightly suppressed. is there. For example, between aluminum with high strain and aluminum with low strain annealed from high temperature formed by cold rolling, aluminum with low strain was more stable. When LiCF ₃ SO ₃ or the like is used as the electrolyte, when aluminum having large strain is used, aluminum is easily eluted at a high voltage. However, in the case of the metal salt of the present invention, even aluminum having large strain is stable. Was excellent. Therefore, when the metal salt of the present invention is used, even if distortion occurs due to tensile stress in the aluminum current collector, the effect is small.

By the way, aluminum which has increased strain by rolling has an advantage. The grain boundary of aluminum is reduced by rolling, so that alloying of aluminum and lithium progresses more uniformly during abnormal discharge of the battery, thereby contributing to reliable current interruption, and having a tensile strength of 10 μm even with a thin current collector of 30 μm or less. sufficient strength will ~12kg / mm ² or more is because to obtain.

Further, when the surface area of the positive electrode active material is reduced, the storability is further improved. The positive electrode active material used in the battery of the present invention preferably has a surface area of 50 m ² / g or less, preferably 30 m ² / g or less, and more preferably 2 m ² / g or less.
0 m ² / g or less.

[0051]
Further, it is preferable to treat the active surface of the metal oxidizing agent of the positive electrode active material with an alkali metal or alkaline earth metal compound to contain an alkali metal or an alkaline earth metal, because the storage property is further improved. In addition, storability can be improved to some extent by performing a preliminary discharge after the production of the battery.

[0052]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Example 1 (CF ₃ SO ₂ ) ₃ C.Li, C ₄ F ₉ SO ₃ Li, L
iTFB was dissolved in ethyl ether as a non-halogen solvent, vacuum-dried, and the weight ratio of ethyl ether to lithium salt was adjusted to about 0.04. Then, propylene carbonate was added and mixed, and 0.1 mol / l LiTFL was added.
PB + 0.1 mol / l (CF ₃ SO ₂ ) ₃ C · Li +
An electrolytic solution having a composition of 0.1 mol / l C ₄ F ₉ SO ₃ Li / PC was prepared.

LiTFB in the above electrolyte is an abbreviation for lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate as described above, and PC is an abbreviation for propylene carbonate. Therefore, 0.1 mol / l LiTFPB + 0.
1 mol / l (CF ₃ SO ₂ ) ₃ C · Li + 0.1 m
ol / l C ₄ F ₉ SO ₃ Li / PC is prepared by using lithium tetrakis [3,5
[Bis (trifluoromethyl) phenyl] borate, (CF ₃ SO ₂ ) ₃ C.Li and C ₄ F ₉ SO ₃ Li were each dissolved in 0.1 mol / l. Here, the viscosity of propylene carbonate at 25 ° C. is 2.5 cp.

After heat-treating the electrolytic manganese dioxide, heat-treat it with an aqueous solution of lithium hydroxide to obtain an active material having a surface area of 18 m ² / g. Then, 100 parts by weight of the manganese dioxide, 5 parts by weight of carbon black, and polytetrafluoroethylene were added. After mixing 5 parts by weight (in terms of solid content) of the dispersed water-solvent mixed solution, this was applied to both sides using a 20-micron thick aluminum foil as a core material, dried, and then 0.4 m in thickness.
m, formed into a sheet having a width of 30 mm, and a lead portion (thickness: 3 mm).
At 0 micron, the strain is large by rolling and the tensile tension is 17
kg / mm ² . Its shape is shown in FIG. )
The belt-shaped positive electrode with attached is dried at 250 ° C., and after drying,
Cool to room temperature in a dry atmosphere.

Next, the strip-shaped positive electrode was sandwiched by a separator made of a microporous polypropylene film having a thickness of 25 μm, and a sheet-shaped lithium sheet having a sheet-like lithium sheet having a thickness of 0.18 mm and a width of 30 mm was pressure-bonded to a stainless steel mesh. After being overlapped and spirally wound to form a spiral electrode body, the outer diameter 15
After filling the inside of a cylindrical battery case with a bottom of 0.2 mm and performing spot welding of the positive and negative electrode lead bodies, the above-mentioned electrolytic solution was injected into the battery case.

Next, the opening of the battery case was sealed according to a conventional method to produce a cylindrical organic electrolyte battery having the structure shown in FIG.

However, a stress in the tensile direction is applied to the above-described positive electrode current collector in a specific manner at a portion immersed in the electrolytic solution, as described later in detail.

Referring to the battery shown in FIG. 1, reference numeral 1 denotes the positive electrode and 2 denotes the negative electrode. However, FIG. 1 does not show a current collector used for manufacturing the positive electrode 1 and the negative electrode 2 in order to avoid complication. Reference numeral 3 denotes a separator, and reference numeral 4 denotes an electrolytic solution.

Reference numeral 5 denotes a battery case made of stainless steel.
This battery case 5 also serves as a negative electrode terminal. An insulator 6 made of a polytetrafluoroethylene sheet is arranged at the bottom of the battery case 5, and an insulator 7 made of a polytetrafluoroethylene sheet is also arranged at the inner periphery of the battery case 5. The spiral electrode body composed of the negative electrode 2 and the separator 3, the electrolyte 4, and the like are accommodated in the battery case 5.

Reference numeral 8 denotes a sealing plate made of stainless steel, and a gas ventilation hole 8a is provided in the center of the sealing plate 8. 9 is an annular packing made of polypropylene, 10 is a flexible thin plate made of titanium, and 11 is a thermally deformable member made of an annular polypropylene.

The above-mentioned heat deformable member 11 has an effect of changing the breaking pressure of the flexible thin plate 10 by being deformed by the temperature.

Reference numeral 12 denotes a nickel-plated rolled steel terminal plate. The terminal plate 12 is provided with a cutting edge 12a and a gas discharge hole 12b. The pressure is increased, and the internal pressure is increased, so that the flexible thin plate 10 is broken, and the gas inside the battery is discharged from the gas discharge hole 12b to the outside of the battery, so that the battery is prevented from being broken.

Reference numeral 13 denotes an insulating packing. Reference numeral 14 denotes a lead (a part of the positive electrode current collector). The lead 14 serving as a lead portion of the positive electrode current collector electrically connects the positive electrode 1 and the sealing plate 8. The terminal plate 12 is in contact with the sealing plate 8 and functions as a positive terminal. Reference numeral 15 denotes a lead for electrochemically connecting the negative electrode 2 and the battery case 5.

Then, a stress in the tensile direction is applied to a portion of the lead body 14 as a lead portion of the positive electrode current collector, which is immersed in the electrolytic solution 4, as shown below.

That is, the terminal plate 12 is shifted in the direction A in advance for sealing, and the terminal plate 12 is shifted in the horizontal direction to be closed at a predetermined position, thereby sealing the lead as a lead portion of the positive electrode current collector. At point C of the body 14, stress in the B direction (similar to the stress in the horizontal direction in the figure,
A stress in the tensile direction is applied to the lead body 14 as a lead part of the positive electrode current collector). The point C of the lead 14 as a lead of the positive electrode current collector is:
As shown in FIG. 2, it is thinner than the other parts.

Comparative Example 1 LiB (C ₆ H ₅ ) ₄ was dissolved in a PC solvent, and 0.3 m
ol / l LiB (C ₆ H ₅ ) ₄ / PC to prepare an electrolytic solution having a composition indicated by:

PC in the above electrolyte is an abbreviation for propylene carbonate. Therefore, 0.1 mol / l LiB (C ₆ H ₅ ) ₄ / PC indicating the above-mentioned electrolytic solution is such that the electrolytic solution is LiB (C
₆ H ₅ ) ₄ was dissolved in 0.3 mol / l. The maximum distance between the anion center of LiB (C ₆ H ₅ ) ₄ and the other atom was about 5.6 °. However, it does not contain halogen atoms.

Comparative Example 2 0.3 mol of CF ₃ SO ₃ Li was dissolved in a PC solvent.
An electrolytic solution having a composition of / l CF ₃ SO ₃ Li / PC was prepared.

PC in the above electrolyte is an abbreviation for propylene carbonate. Thus, the electrolytic solution _{0.1mol / l CF 3 SO 3 Li} / PC showing a shows that the electrolytic solution is obtained by 0.3 mol / l dissolved CF ₃ SO ₃ Li in propylene carbonate solvent . CF ₃ SO ₃ Li contains a halogen atom, but the maximum distance between the center of the anion and the other atom is about 3.
It is only 9Å.

Further, a cylindrical organic electrolyte battery having the structure shown in FIG. 1 was produced in the same manner as in Example 1 using the above-mentioned electrolyte.

Next, the minimum voltage when the battery of Example 1 and the batteries of Comparative Examples 1 and 2 were discharged at 0.3 A for 10 milliseconds was measured. Further, both batteries were discharged at a constant current of 50 mA, and the capacities after storage at 80 ° C. for 10 days were measured and compared with the capacities before storage. Table 1 shows the results.

[0073]

[Table 1]

As shown in Table 1, the battery of Example 1
The voltage after discharge at 0.3 A for 10 milliseconds was high, the capacity deterioration due to storage was small, and the storability was excellent. On the other hand, after storage of Comparative Examples 1 and 2, almost no discharge was possible, and the storability was poor.

Further, the lead body as the lead part of the positive electrode current collector is not thin and is not stressed, or a battery produced by applying a stress in the compression direction is forcibly overdischarged at 10 A, After the voltage reached 3 V, an overdischarge experiment was performed at a constant voltage of -3 V. As a result, the interruption of current was sometimes insufficient, and a highly reliable function was not obtained. On the other hand, all the batteries of Example 1 exhibited safe behavior because the current was interrupted during the overdischarge.

[0076]

As described above, according to the present invention,
The storage properties of the electrolyte and the organic electrolyte battery can be improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing one example of an organic electrolyte battery according to the present invention.

FIG. 2 is an enlarged view showing a stressed part of a lead body as a lead part of a positive electrode current collector of the battery shown in FIG. 1;

[Explanation of symbols]

1 positive electrode 2 Negative electrode 3 separator 4 Electrolyte

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H01M 10/40 H01M 10/40 A (72) Inventor Takaaki Sonoda 2-1-23 Hikaricho, Hakata-ku, Fukuoka City, Fukuoka Prefecture (72) Inventor Hiroshi Kobayashi 2-1-23 Hikaricho, Hakata-ku, Fukuoka City, Fukuoka (56) References JP-A-60-20477 (JP, A) JP-A-5-62690 (JP, A) JP-A-5-82139 (JP, A) Japanese Utility Model sho 59-195670 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 2/26 H01M 6/16 H01M 4/02 H01M 4/66 H01M 10 / 40

Claims (7)

(57) [Claims] 1. An organic electrolyte battery having a spiral electrode body in which an aluminum current collector is used as a positive electrode, a positive electrode and a negative electrode are spirally wound through a separator, and having a voltage of 3.1 V or more. Wherein at least one fluoroalkyl group is bonded via an intermediate skeleton to a charge center atom of an anion composed of any one element selected from Groups IIIb to VIb of the Periodic Table. (CF ₃ SO ₂ ) ₂ .N.ME, (CF ₃ SO ₂ ) ₃ C in which the maximum distance between the center of the charge center atom and the center of another atom is 4 ° or more
・ ME, [C ₆ H ₄ (F)] ₄ B ・ ME, [C ₆ H
₄ (Cl)] ₄ B.ME (where ME is Li, Na or
Is _{K), C n F 2n +} 1 SO 3 Li ( where n is an integer of 2 or more), LiB [C ₆ H ₄ (CF _{3)] 4,} LiB
[C ₆ H ₃ (CF ₃ ) ₂ ] ₄ or LiB (C ₆ H ₃ A
₂ ] ₄ [where A is —C (CF ₃ ) ₂ OCH ₃ ], wherein an organic electrolyte obtained by dissolving a metal salt containing an organic anion in an organic solvent is used. battery. 2. The organic electrolyte battery according to claim 1, wherein the maximum distance between the charge center atom of the organic anion and the center of another atom is 5 ° or more. 3. A lead portion of the aluminum current collector.
All lead bodies are connected to one side of the plate-shaped positive electrode,
In a state where it can come in contact with the liquor and is subject to tensile stress
The organic electrolyte battery according to claim 1, wherein: 4. An organic electrode connected to one side of a plate-shaped positive electrode.
Gold containing aluminum ready for contact with the liquor
Lead as a lead part of the positive electrode current collector made of
Formed by cold rolling , tensile of 12 kg / mm ² or more
4. The method according to claim 1, wherein the member is disposed under a stress.
An organic electrolyte battery according to any one of the preceding claims. 5. An organic electrode connected to one side of a plate-shaped positive electrode.
Gold containing aluminum ready for contact with the liquor
Lead as a lead part of the positive electrode current collector made of
Formed by cold rolling , tensile of 17 kg / mm ² or more
4. The method according to claim 1, wherein the member is disposed under a stress.
An organic electrolyte battery according to any one of the preceding claims. 6. The metal salt containing an organic anion is non-halogen.
Metal salt containing the organic anion is treated with an organic solvent.
Contains 0.0005 or more and 0.1 or less by weight
The organic electrolyte battery according to claim 1. 7. The method according to claim 1, wherein the metal salt containing an organic anion is non-halogen.
Metal salt containing the organic anion is treated with an organic solvent.
Containing 0.005 or more and 0.1 or less by weight of a logene solvent,
An organic solvent that dissolves the metal salt containing the organic anion
Using an organic solvent having a viscosity of 1 cp or more at 25 ° C.
Item 7. The organic electrolyte battery according to any one of Items 1 to 6.