JP2986946B2 - Inorganic non-aqueous 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 inorganic nonaqueous electrolyte battery regulated by lithium. More specifically, the present invention relates to a lithium regulated inorganic non-aqueous electrolyte battery capable of detecting the end of discharge before the end of the battery life.

[0002]

2. Description of the Related Art In an inorganic nonaqueous electrolyte battery using lithium as a negative electrode active material and an oxyhalide such as thionyl chloride as a positive electrode active material and a solvent for an electrolyte, for example, as shown in FIG. The positive electrode 3 is made of cylindrical lithium disposed along the inner peripheral surface of the bottom cylindrical battery case 2.
Is formed of a columnar carbon porous molded body, a cylindrical separator 4 is disposed between the negative electrode 1 and the positive electrode 3, and the oxyhalide of the positive electrode active material also serves as a solvent for the electrolytic solution. , A large amount of electrolyte 5 is injected into the battery [for example, “the latest technical manual for high-performance batteries”,
Published by Sogo Gijutsu Center, p. 129].

[0003] The inorganic non-aqueous electrolyte battery has excellent characteristics such as high energy density and operation even at a low temperature.

[0004]

However, in the above-mentioned inorganic non-aqueous electrolyte battery, the discharge proceeds by a heterogeneous reaction, and especially in a lithium regulated battery, the internal resistance does not change until the end of discharge. As shown in FIG. 9, the battery is flat until the end of discharge, and when lithium is exhausted, the battery voltage drops sharply, ending the life of the battery.

[0005] Therefore, in this battery, the end of discharge cannot be known before the end of the life of the battery, and as a result, it is difficult to replace the battery at an appropriate time.

Accordingly, the present invention solves the above-mentioned problems of the conventional inorganic non-aqueous electrolyte battery and provides an inorganic non-aqueous electrolyte battery capable of detecting the end of discharge before the end of the battery life. With the goal.

[0007]

The present invention has achieved the above object by disposing a calcium disk at the bottom of a battery case in the above-mentioned lithium-regulated inorganic non-aqueous electrolyte battery.

[0008] The calcium disk is composed of calcium metal or a calcium alloy. Since the calcium metal or calcium alloy has a more noble potential than lithium, the calcium disk does not cause a discharge reaction while lithium is present. Only the lithium discharge reaction proceeds, and a flat discharge characteristic is exhibited.

However, when lithium is exhausted, the calcium or calcium alloy of the calcium disk reacts with the oxyhalide of the positive electrode active material and discharges at a voltage different from that of lithium, resulting in a so-called two-step discharge.

Therefore, the end of discharge can be detected before the end of the life of the battery by the voltage change, and as a result, the battery can be replaced at an appropriate time.

The above-mentioned calcium disk is composed of metallic calcium or a calcium alloy. Examples of the calcium alloy include a calcium-lithium alloy and a calcium-sodium alloy.

[0012] These calcium and calcium alloys,
It is more malleable and ductile than iron, nickel, etc., and can be easily formed into a disc.However, it has poor adhesion to the battery case, and peels off during use only by crimping to the bottom of the battery case. As a result, electrical contact with the battery case may not be obtained.

Therefore, in the present invention, the calcium disk is spot-welded to the bottom of the battery case, and the calcium disk is pressure-bonded to the metal porous body, so that the calcium disk is stably arranged at the bottom of the battery case. Every
The electrical contact between the calcium disk and the battery case is ensured.

The amount of electricity of the calcium disk may be such that the discharge voltage of the calcium or calcium alloy constituting the calcium disk can be detected, and it is sufficient that the theoretical amount of electricity is 20 mAh or more, preferably 40 mAh or more. However, as the amount of electricity of the calcium disk increases, the amount of electricity of lithium and the positive electrode active material decreases accordingly, so the amount of electricity of the calcium disk should be at most 10% of the theoretical amount of lithium. Is preferred.

In the present invention, the reason why the amount of discharge electricity of the battery is regulated by lithium is that if the positive electrode active material does not exist after the discharge of lithium, the discharge of calcium or a calcium alloy of the calcium disk and the positive electrode active material will occur. This is because no reaction can be caused, and therefore, the end of discharge cannot be detected.

Further, the calcium disk is arranged at the bottom of the battery case for the following reason. In the battery of the present invention, an oxyhalide which is liquid at room temperature, such as thionyl chloride, also serves as a positive electrode active material and a solvent for an electrolytic solution.

Therefore, when the discharge reaction of the battery proceeds,
The oxyhalide is consumed, resulting in a decrease in the amount of electrolyte and by the time lithium discharge is complete, the electrolyte can only be present near the bottom of the battery case.

Therefore, if the calcium disk is arranged at the bottom of the battery case, even when the amount of the electrolyte at the end of discharge is small, the calcium disk contacts the electrolyte and calcium in the calcium or calcium alloy is ionized.
A discharge reaction occurs to cause a two-stage discharge, and the end of discharge can be detected before the end of the battery life.

However, if the calcium disk is located far from the bottom of the battery case, the calcium disk cannot come into contact with the electrolyte when the amount of electrolyte decreases at the end of discharge, and calcium and calcium Calcium in the alloy is ionized and cannot cause a discharge reaction, and the end of discharge cannot be detected before the end of the battery life.

In the battery of the present invention, an oxyhalide which is liquid at normal temperature (25 ° C.) such as thionyl chloride, sulfuryl chloride and phosphoryl chloride is used as the positive electrode active material.

These oxyhalides are used as a positive electrode active material and as a solvent for an electrolytic solution. The electrolytic solution contains LiAlCl ₄ , LiAl
It is prepared by dissolving a supporting electrolyte such as Br ₄ , LiGaCl ₄ , LiB ₁₀ Cl ₁₀ . Incidentally, when the preparation of the electrolytic solution, presence of a supporting electrolyte LiCl and AlCl _3, such as LiAlCl ₄ in the form of LiAlCl ₄ in added to the oxyhalide electrolyte (however, Li ⁺ ions and AlCl ₄ to ionize ^- Present with ions)
You may make it.

Next, an example of the configuration of the inorganic non-aqueous electrolyte battery of the present invention will be described with reference to FIG. In the figure, reference numeral 1 denotes a negative electrode, and the negative electrode 1 is disposed along the inner peripheral surface of the battery case 2 by pressing a lithium sheet on the inner peripheral surface of a cylindrical battery case 2 made of stainless steel and having a bottom. It consists of cylindrical lithium.

Reference numeral 3 denotes a positive electrode. The positive electrode 3 is made of, for example, a columnar carbon porous molded body mainly composed of acetylene black and carbon to which a small amount of polytetrafluoroethylene is added as a binder. 1 is disposed at the center of the battery case 2 via the separator 4.

The separator 4 is made of a glass fiber non-woven fabric, has a cylindrical shape, and separates the cylindrical negative electrode 1 from the cylindrical positive electrode 3. Reference numeral 5 denotes an electrolytic solution. The electrolytic solution 5 includes thionyl chloride, sulfuryl chloride,
An oxyhalide such as phosphoryl chloride is used as a solvent.
It is those prepared by dissolving a supporting electrolyte such as l _4. In this battery, unlike the other batteries, a large amount of the electrolyte 5 is injected into the battery because the oxyhalide of the positive electrode active material also serves as a solvent for the electrolyte.

As can be seen from the fact that the oxyhalide is a positive electrode active material, the positive electrode 3 does not react by itself, but is ionized and eluted from the oxyhalide of the positive electrode active material and the negative electrode 1. It becomes a reaction site for the lithium ions.

Reference numeral 6 denotes a positive electrode current collector made of a nickel rod.
Denotes a battery cover, the battery cover 7 has a body 8, an insulating layer 9, and a positive electrode terminal 10, and the body 8 is formed of stainless steel.
Is welded to the open end of the wire.

The insulating layer 9 is made of glass and is formed on the inner peripheral side of the body 8. The insulating layer 9 insulates the body 8 from the positive electrode terminal 10, and the constituent glass is formed on the outer peripheral surface of the body 8. And the constituent glass is fused to the outer peripheral surface of the positive electrode terminal 10 on the inner peripheral surface to seal between the body 8 and the positive electrode terminal 10.

The positive electrode terminal 10 is made of stainless steel, a part of which is formed in a pipe shape at the time of assembling the battery and is used as an electrolyte injection port. The upper end of the positive electrode terminal is inserted into the hollow portion after the electrolyte is injected. It is welded to the upper part of the electric body 6 and sealed.

Reference numeral 11 denotes a calcium disk, and 12 denotes a porous metal body. The porous metal body 12 is spot-welded to the bottom of the battery case 2, and the calcium disk 11 is pressed to the above-described porous metal body 12.

As the porous metal body 12, an expanded metal, a punching metal, a wire mesh, a metal foam, or the like is used, and a material made of stainless steel or nickel is suitable.

Reference numeral 13 denotes a lower separator, which is made of the same glass fiber nonwoven fabric as the separator 4 and insulates the positive electrode 2 and the calcium disk 11 from each other. Thereafter, the calcium ions ionized from the calcium disk 11 and eluted into the electrolytic solution pass through the lower separator 13 and reach the positive electrode 3, where they react with the oxyhalide of the positive electrode active material.

Reference numeral 14 denotes an upper separator, which is also made of glass fiber non-woven fabric so that the positive electrode 3 does not directly contact the body 8 of the battery lid 7 which also functions as a negative electrode terminal.

Next, another configuration example of the inorganic non-aqueous electrolyte battery of the present invention will be described with reference to FIG. In the battery shown in FIG. 2, an explosion-proof thin portion 1 is provided at the center of the bottom of the battery case 2.
5 are provided. Normally, since the thin portion 15 is provided in a cross shape, the calcium disc 1
1 and the metal porous body 12 are formed in a ring shape so as not to hinder the function of preventing the battery from rupture under high pressure due to the destruction of the thin portion 15, that is, the so-called explosion-proof function.

That is, the ring-shaped porous metal body 12 is attached to the battery case 2 so as not to cover the thin portion 15 for explosion protection.
Spot-welded to the bottom of the ring-shaped metal porous body 1
2, a ring-shaped calcium disk 11 is pressed.

In the battery of the present invention, the battery case 2 is formed in a cylindrical shape with a bottom.
Since the cross-sectional shape is most often cylindrical with a bottomed cylinder having a circular cross-sectional shape, the above configuration examples and the later-described examples illustrate the case where a bottomed cylindrical battery case 2 is used.

However, the battery case 2 is not limited to such a case. For example, the battery case 2 may have a rectangular cross section with a rectangular cross section or a bottomed cylindrical shape with a cross section other than circular or square. May be used.

Further, in the above configuration examples and those shown in the embodiments described later, the negative electrode 1 and the separator 4 are cylindrical and the positive electrode 3
Has a columnar shape, but these shapes may vary depending on the shape of the battery case 2 and other circumstances.

The calcium disk 11 can also take various shapes depending on the shape of the battery case 2 and the presence or absence of the explosion-proof thin portion 14. A typical example of the calcium disk 11 is as shown in FIGS.

FIG. 3A is a plan view of the calcium disk 11 and FIG. 3B is a sectional view thereof. The calcium disk 11 shown in FIG. 3 has a disk shape and has the same shape as the calcium disk 11 used in the battery shown in FIG.

FIG. 4A is a plan view of the calcium disk 11 and FIG. 4B is a sectional view thereof. The calcium disk 11 shown in FIG. 4 has a ring shape and has the same shape as the calcium disk 11 used in the battery provided with the explosion-proof thin portion 15 shown in FIG.

FIG. 5A is a plan view of the calcium disk 11 and FIG. 5B is a sectional view thereof. The calcium disk 11 shown in FIG. 5 is in the shape of a square plate, and is used for a battery using a battery case having a rectangular tube shape with a bottom.

FIG. 6A is a plan view of the calcium disk 11 and FIG. 6B is a sectional view thereof. The calcium disk 11 shown in FIG. 6 is a battery using a battery case having a rectangular outer peripheral surface and a circular inner peripheral surface, a rectangular tube with a bottom, and a thin portion for explosion proof provided at the bottom. Used.

[0043]

Next, the present invention will be described more specifically with reference to examples. Example 1 Thionyl chloride was used as a positive electrode active material, a solution prepared by dissolving 1.2 mol / liter of LiAlCl _{4 in} this thionyl chloride was used as an electrolytic solution, and a disk made of metallic calcium was used as a calcium disk. Using a disc-shaped expanded metal made of stainless steel as a porous metal body, a 2 / 3A cylindrical inorganic non-aqueous electrolyte battery having the structure shown in FIG. did.

The lithium used as the negative electrode active material was 4
00, and the theoretical quantity of electricity of this lithium is 1545
mAh. Acetylene black of the positive electrode is 670 mg.
The injection amount of the electrolyte was 3 ml, and the theoretical electric quantity of thionyl chloride as the positive electrode active material was 1980 mAh. The calcium content of the calcium disk is 50 mg, and the theoretical quantity of calcium is 67 mAh.

The potential of calcium with respect to thionyl chloride is about -3.06 V, and the potential of lithium with respect to thionyl chloride is about -3.68 V. Since calcium discharges at a more noble potential than lithium, the battery discharges. As for the voltage, calcium is lower than lithium.

The expanded metal used as the porous metal body has a SW (center-to-center distance in the shorter direction of the mesh) of 1.15 mm, an LW (center-to-center distance in the longer direction of the mesh) of 3.0 mm, and W ( 0.18mm, T
(Plate thickness) is 0.1 mm.

The expanded metal is spot-welded to the bottom of the battery case at three locations along the outer periphery by resistance spot welding, and the calcium disk is crimped to the expanded metal.

The battery of Example 1 was charged at 20 ° C. under a load of 10 k.
FIG. 7 shows discharge characteristics when a continuous discharge was performed at Ω. FIG.
As shown in the figure, in the battery of Example 1, a second-stage discharge is observed at about 2.9 V following the flat discharge at about 3.6 V. The second-stage discharge is based on calcium, and the battery of Example 1 can detect the end of discharge before the end of the life of the battery by the above-described two-stage discharge. Battery replacement is possible.

Comparative Example 1 Thionyl chloride was used as the positive electrode active material, and an electrolyte obtained by dissolving 1.2 mol / l of LiAlCl _{4 in} this thionyl chloride was used. The lithium-thionyl chloride system is shown in FIG. A 2 / 3A cylindrical inorganic non-aqueous electrolyte battery having a structure was manufactured.

The amount of lithium used and the amount of electrolyte injected were the same as those in Example 1. The battery of Comparative Example 1 was equivalent to a conventional battery, and the calcium disk 11 of the battery of Example 1 was used. Although the second embodiment is different from the battery of the first embodiment in that the second embodiment does not use the porous metal body 12, all other configurations are the same as those of the first embodiment.

The battery of Comparative Example 1 was charged at 20 ° C. under a load of 10 k.
FIG. 9 shows discharge characteristics when a continuous discharge was performed at Ω. FIG.
As shown in the figure, in the battery of Comparative Example 1, after flat discharge at about 3.6 V, the battery voltage sharply drops, and the life of the battery ends. Therefore, the end of discharge cannot be detected before the end of the life of the battery, and it is difficult to replace the battery at an appropriate time.

Comparative Example 1 Without using the expanded metal as in Example 1,
A lithium-thionyl chloride-based 2 / 3A cylindrical inorganic non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that the calcium disk was directly pressed to the bottom of the battery case. The amount of lithium used, the amount of electrolyte injected, the amount of calcium, and the like are the same as in the first embodiment.

Thirty batteries of the control example 1 were continuously discharged at 20 ° C. and a load of 10 kΩ, and it was examined whether or not a second-stage discharge occurs at the end of discharge. The results are shown in Table 1 in comparison with the results obtained by examining 30 batteries in Example 1.

[0054]

In Table 1, the denominator is the total number of batteries subjected to the test, and the numerator is the number of batteries in which two-step discharge has occurred. As shown in Table 1, the battery of Example 1 was subjected to the test. Two-stage discharge occurred in all the batteries, but only 20 of the 30 batteries of Comparative Example 1 had the two-stage discharge.

This is because, in the battery of Example 1, the expanded metal is spot-welded to the bottom of the battery case, and the calcium disk is crimped to the expanded metal, so that the calcium disk is stably disposed at the bottom of the battery case. However, the electrical contact with the battery case was ensured, and the calcium discs all contributed to the two-step discharge. However, in the battery of Comparative Example 1, the calcium disc was just pressed directly to the bottom of the battery case. It is considered that the calcium disk peeled off from the bottom of the battery case, and electrical contact between the calcium disk and the battery case could not be made, so that there was something that could not be discharged.

[0057]

As described above, according to the present invention, in a lithium regulated inorganic nonaqueous electrolyte battery, the end of discharge can be detected by causing a second-stage discharge before the end of the life of the battery. Is now available.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of an inorganic non-aqueous electrolyte battery according to the present invention.

FIG. 2 is a sectional view showing another example of the inorganic non-aqueous electrolyte battery of the present invention.

FIG. 3 is a view showing a calcium disk used in the inorganic non-aqueous electrolyte battery of the present invention, wherein a is a plan view and b is a cross-sectional view.

FIG. 4 is a diagram showing a calcium disk used in the inorganic non-aqueous electrolyte battery of the present invention, wherein a is a plan view and b is a cross-sectional view.

FIG. 5 is a view showing a calcium disk used for the inorganic non-aqueous electrolyte battery of the present invention, wherein a is a plan view and b is a cross-sectional view.

FIG. 6 is a view showing a calcium disk used in the inorganic non-aqueous electrolyte battery of the present invention, wherein a is a plan view and b is a cross-sectional view.

FIG. 7 is a diagram showing discharge characteristics of the battery of Example 1 of the present invention.

FIG. 8 is a cross-sectional view showing a conventional inorganic non-aqueous electrolyte battery.

FIG. 9 is a view showing the discharge characteristics of the battery of Comparative Example 1.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Negative electrode 2 Battery case 3 Positive electrode 4 Separator 5 Electrolyte 11 Calcium disk 12 Metal porous body 13 Lower separator

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Jun Sato 1-88, Ushitora, Ibaraki-shi, Osaka Hitachi Maxell, Inc. (72) Inventor Taku Sasama 1-188, Ushitora 1-chome, Ibaraki, Osaka Hitachi Maxell (72) Inventor Kaoru Hisatomi 1-1-88 Ushitora, Ibaraki-shi, Osaka Hitachi Maxell, Inc. (56) References JP-A-4-137364 (JP, A) JP-A-55-59667 (JP) , A) JP-A-54-116639 (JP, A) JP-A-56-28472 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) H01M 2/02 H01M 2/04 H01M 6/14

Claims (6)

(57) [Claims] In a lithium-regulated inorganic nonaqueous electrolyte battery using lithium as a negative electrode active material and a liquid oxyhalide at room temperature as a positive electrode active material and a solvent for an electrolyte, a negative electrode 1 has a bottomed cylindrical shape. The positive electrode 3 is made of a porous carbon body, and a separator 4 is disposed between the negative electrode 1 and the positive electrode 3. The positive electrode 3 is made of lithium disposed along the inner peripheral surface of the battery case 2. A porous metal body 12 is spot-welded to the bottom, a calcium disk 11 is pressed on the porous metal body 12, and an ion-permeable lower separator 13 is disposed between the calcium disk 11 and the positive electrode 3. Features inorganic lithium non-aqueous electrolyte battery regulated by lithium. 2. The lithium non-aqueous inorganic electrolyte battery according to claim 1, wherein the porous metal body 12 is an expanded metal, a punched metal, or a wire mesh. 3. The lithium non-aqueous inorganic non-aqueous electrolyte battery according to claim 1, wherein the calcium disk is disk-shaped. 4. The lithium non-aqueous inorganic non-aqueous electrolyte battery according to claim 1, wherein the calcium disk 11 has a ring shape. 5. The lithium non-aqueous inorganic non-aqueous electrolyte battery according to claim 1, wherein the calcium disk has a square plate shape. 6. The lithium-regulated inorganic non-aqueous electrolyte battery according to claim 1, wherein the calcium disk 11 has a ring shape with a rectangular outer peripheral surface and a circular inner peripheral surface.