JPH10208778A - Non-aqueous electrolyte battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous electrolyte battery which is excellent in preservation characteristics by preventing degradation and self-discharge, etc., by moving electrolyte an electrode part by connecting electrolyte storages incorporating electrolyte in a sealing state and opening the sealing state when the battery is started to be used, in the electrode part incorporating an electrode plate group. SOLUTION: An electrode A is formed by storing an electrode plate group 14 made by winding positive electrode and negative electrode plural numbers of times via a diaphragm and flattening the electrodes in a sheet-like bag made of plastic-metal foil laminate and exposing leads 15, 16 to the outside. In an electrolyte storage B made of the sheet-like bag, non-aqueous electrolyte is stored. This electrode part A and the electrolyte storage B are connected via a seal part 3. Thus, an electrode plate group 14 does not come into contact with electrolyte during long period preservation and a non-aqueous electrolyte battery 1 preventing degradation and self-discharge due to the reaction is obtained. When the battery is started to be used, the seal part 3 is opened and electrolyte is moved to the electrode part A. As the seal part 3, the one welding the internal wall at a connecting portion or pressing the external wall by interposing a packing on the internal surface is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery in which an electrolyte containing an electrolyte is connected to an electrode containing a group of electrodes, and the electrolyte is transferred to the electrode during use. Things.

[0002]

2. Description of the Related Art Conventionally, as a non-aqueous electrolyte battery, for example, a non-aqueous electrolyte battery in which each of a positive electrode electrode and a negative electrode lead are led out of an electrode case having a built-in electrode plate group has been proposed (Japanese Utility Model Application Laid-Open No. SHO 56). -54568). Here, the electrode case is a bag formed by heat-sealing the peripheral edge of the metal-plastic laminate sheet, has a built-in electrode plate group, and has an insulating ring attached to each of the positive and negative electrode leads. A non-aqueous electrolyte is injected, and the opening is thermally fused.

[0003]

Normally, it takes a considerable number of days for the battery to be distributed and stored before it is actually used. In that period, when the storage period is long, the electrolyte and the electrode plate group are not used. And there was a problem that it could not be used at the time of use. This is because, for example, when metal lithium or Li-GIC (lithium occluded carbon) is used for the negative electrode, they react with the electrolyte and deteriorate, and in the case of Li-GIC, carbon is used. This is because so-called self-discharge in which lithium is automatically released occurs. The inventors considered such a problem, and impregnated the electrode group with an electrolytic solution at the start of use.
Thus, deterioration and self-discharge are prevented.

[0004]

The non-aqueous electrolyte battery of the present invention has an electrolyte in a sealed state in an electrode portion containing a group of electrodes, and releases the sealed state at the start of use. And an electrolyte storage for transferring the electrolyte to the electrode portion.
The sealing of the electrolytic solution storage is performed by fusing the inner wall of the connecting portion to the electrode portion and expanding the inner wall at the start of use, or the outer wall of the portion where the packing is interposed on the inner surface of the connecting portion to the electrode portion. It is made to hold down.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The active material used for the negative electrode in the present invention is not particularly limited, but lithium metal, carbon, Li-GIC (lithium occluded carbon), lithium-aluminum alloy and the like can be used. The active material used for the positive electrode in the present invention is not particularly limited, and transition metal oxides such as vanadium, molybdenum, titanium, chromium, iron, nickel, cobalt, manganese, and cerium, and vanadium, cobalt, nickel, manganese, iron, chromium,
Transition metals such as molybdenum and iron, nickel, cobalt,
Copper, silver, zinc, magnesium, calcium, lithium,
A metal composite oxide containing at least two kinds of metals such as sodium, potassium, rubidium, cesium, and francium can be used. In particular, LixCoO _2, LixN
iO ₂ , LixAl _0.25 Ni _0.75 O ₂ , LixMn ₂ O ₄ , L
i ₁₊ xV ₃ O ₈ is preferred.

The non-aqueous electrolyte battery according to the present invention has good storage characteristics because the electrode group as a power generation element and the electrolyte are separated until the battery is used. Also, the sealing of the electrolyte reservoir is performed by fusing the inner wall of the connecting portion to the electrode portion and expanding the inner wall by pulling a fin at the time of use, or packing is interposed on the inner surface of the connecting portion to the electrode portion. By removing the stopper that presses the outer wall of the place where it was made, the electrolyte can be easily moved to the electrode plate group. Since the electrode portion is a sheet-shaped bag in which a positive electrode lead and a negative electrode lead that are electrically connected to the electrode plate group are exposed to the outside, the electrode portion is excellent in portability. In addition, by previously setting the inside of the electrode portion to a negative pressure state, it is possible to impregnate the electrolyte so that the electrolyte easily moves to the electrode group at the start of use and reaches the entire electrode group.

[0007]

Embodiments of the present invention will be described below. FIG.
FIG. 2 is an explanatory diagram of a non-aqueous electrolyte battery according to an embodiment of the present invention. The non-aqueous electrolyte battery 1 has an electrode portion A and an electrolyte reservoir B connected therebetween via a seal portion 3, and a peripheral portion 2 of the battery case is fused on both sides, and a part of the periphery is fused. As shown in FIG. 1C, the safety valve 8 and the leads 15, 1
6 is partially sandwiched between them. Here, FIG.
As shown in (b), the electrode portion A is sealed with the electrode group 14 and the electrolyte solution storage B is sealed with the electrolyte solution, and the seal portion 3 is provided therebetween. Also, the electrode section A
For the electrolyte solution storage B, a plastic-metal foil laminate having extremely high airtightness is used.

As shown in FIG. 2, the electrode plate group 14 'is formed by winding a positive electrode 11 and a negative electrode 12 a plurality of times, for example, about 15 turns, through a diaphragm 13 into a flat roll shape. I have. The electrode plate group 14 ″ shown in FIG. 3 has a configuration in which a positive electrode 11 ′ and a negative electrode 12 ′ are stacked in multiple layers via a diaphragm 13 ′.
5 and 15 ′ are partially insulated by the insulator 17 and are drawn out of the electrode portion A. On the other hand, the leads 16 and 16 ′ of the negative electrode are also partially insulated by the insulator 17 from the negative electrode and are drawn out of the electrode portion A. This is to prevent a short circuit due to the metal foil laminate. Diaphragm 13,
Reference numeral 13 'is made of an organic material having fine pores that can pass through the electrolytic solution. For example, polyethylene or polypropylene is used.

[0009] As shown in FIG.
The grip portions 3a and 3b which can be pulled by hand are provided, and the fusion portions 4 and 4 'are provided on both sides thereof. Usually, the electrolyte solution is held so that the electrolyte does not enter the electrode portion A. At the start of use, the grips 3a, 3b are pulled in the directions of the arrows, as shown in FIG.
As shown in (b), since the electrode portion A and the electrolyte reservoir B communicate with each other, the electrolyte is transferred to the electrode plate group 14, and as a result, an electromotive force is generated. In addition,
The fusion parts 4, 4 'need not always be provided on both sides of the grip parts 3a, 3b, and only one side of the grip parts 3a, 3b may be used.

Further, as shown in FIG. 5A, the seal portion 3 holds the electrolyte by sandwiching the packing 5 from both sides with a sandwich 6 used with a water pillow or the like, for example. Then, when the pinch 6 is removed at the start of use, it becomes as shown in FIG. The packing 5 may be made of, for example, the same material as the O-ring (Viton). If both ends of the packing 5 are attached to the surrounding portion 2, the packing itself may move even if the electrolyte moves. Absent.
The packing 5 is inserted because the width is small with respect to the pinching force, so that a large concentration force per unit area can be obtained, thereby improving the sealing function.

Further, the non-aqueous electrolyte battery 1 of the present invention has a structure shown in FIG.
As shown in FIG. The safety valve 8
Although it cannot enter from the outside by the outward valve 9, for example, it can be evacuated when the internal pressure increases. In some cases, the safety valve 8 is used to exhaust gas to make the pressure in the electrode portion A negative. This is done by suctioning the outside of the safety valve 8 with a vacuum pump or the like. This is because the electrolyte easily moves to the electrode section and the electrolyte reaches the electrode group 14.

First, a positive electrode and a negative electrode were manufactured under the following conditions. (Positive electrode 1) 100 parts by weight of LiCoO ₂ powder as a positive electrode active material, 10 parts by weight of graphite, polyvinylidene fluoride 1
0 parts by weight were mixed and dissolved in N-methyl-2-pyrrolidone to form a paste. Next, this paste was applied to both sides of an aluminum foil having a thickness of 20 μm, dried, and then pressed with a roller. Thus, a thickness of 0.20 mm and a width of 10
An electrode plate having a length of 0 mm and a length of 100 mm was produced.

(Positive electrode 2) LiV ₃ O ₈ powder 1 of positive electrode active material
To 100 parts by weight, 10 parts by weight of graphite and 10 parts by weight of polyvinylidene fluoride were mixed, dissolved in N-methyl-2-pyrrolidone, and then formed into a paste. Next, this paste was applied to both sides of an aluminum foil having a thickness of 20 μm, dried, and then pressed with a roller. Thus, the thickness 0.20
An electrode plate having a thickness of 100 mm, a width of 100 mm and a length of 100 mm was produced.

(Negative Electrode 1) A commercially available metallic lithium foil was pressure-bonded to a 1 mm thick, 100 mm wide, and 100 mm long nickel metal porous body manufactured by Sumitomo Electric Industries to form a negative electrode.

(Negative electrode 2) 20 parts by weight of polyvinylidene fluoride were mixed with 100 parts by weight of phosphorous natural graphite powder,
After dissolving in methyl-2-pyrrolidone, it was made into a paste. This paste was applied to both sides of a copper foil having a thickness of 20 μm, dried, and then pressed with a roller. Thus, an electrode plate having a thickness of 0.20 mm, a width of 100 mm, and a length of 100 mm was produced. To this electrode, ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 and an electrolytic solution in which lithium hexafluorophosphate was dissolved to 1 mol / l, metal lithium, and an external power supply were used. By electrochemically inserting lithium into graphite, Li-G
An IC electrode was obtained.

(Example 1) A positive electrode prepared under the conditions of the positive electrode 1 and a negative electrode prepared under the conditions of the negative electrode 1 was used.
1: 1 ethylene carbonate and diethyl carbonate
At a volume ratio of 1 mol of lithium hexafluorophosphate
1 / l dissolved in advance to 100
I put cc. Leads were attached to the thus obtained positive and negative plates, respectively, with a thickness of 0.025 mm and a width of 105 m.
m, a plurality of layers are laminated together with a polyethylene diaphragm having a length of 105 mm to form an electrode plate group, a width of 5 mm and a length of 130 m
The test battery was housed in an electrode part having a height of 130 mm and a height of 130 mm. In addition, the seal | sticker part 3 used what was heat-sealed.

(Example 2) A positive electrode was prepared under the condition of the positive electrode 2 and a negative electrode was prepared under the condition of the negative electrode 2.
A test battery manufactured under the same conditions as in Example 1 was used as a test battery.

(Embodiment 3) A pressing seal method in which the same material (Viton) as an O-ring is used as a packing at a boundary between an electrolyte storage B and an electrode portion A of a power generating element is used. Except for, a test battery was produced in exactly the same manner as in Example 1.

(Embodiment 4) A pressing and sealing method in which the same material (Viton) used for the O-ring is used as a packing at the boundary between the electrolyte storage B and the electrode portion A of the power generating element is used. Except for, a test battery was produced in exactly the same manner as in Example 2.

(Comparative Example 1) A test battery was prepared under exactly the same conditions as in Example 1 except that the electrolyte and the power generating element were not separated and the electrolyte was previously injected into the power generating element.

(Comparative Example 2) A test battery was prepared under exactly the same conditions as in Example 2 except that the electrolyte and the power generating element were not separated and the electrolyte was injected into the power generating element in advance.

(Comparative Example 3) A test battery was prepared under exactly the same conditions as in Example 3 except that the electrolytic solution and the power generating element were not separated and the electrolytic solution was previously injected into the power generating element.

(Comparative Example 4) A test battery was prepared under exactly the same conditions as in Example 4 except that the electrolytic solution and the power generating element were not separated and the electrolytic solution was previously injected into the power generating element.

In each of the test cells described above, in Examples 1 and 3, Comparative Example 1 and Comparative Example 3, first, the storage part was stored at normal temperature and normal pressure for one year, and then the seal parts 3 of Examples 1 and 3 were opened. Then, the electrolyte was injected into the power generating element. Then, LixC
Since oO ₂ was used, the positive and negative leads were connected to external charge / discharge power supplies, respectively, and the current was 250 mA.
Charged to 2V. Thereafter, 3.0 V at a current of 250 mA.
A cycle test was carried out under the condition of discharging to the maximum, and evaluation was made based on a change in discharge capacity with the cycle. As shown in Table 1, Examples 1 and 3 showed that the cycle life was longer than Comparative Examples 1 and 3. I understand.

In each of the test batteries described above, in Example 2, Example 4, Comparative Example 2, and Comparative Example 4, the seal portion 3 of Examples 2 and 4 was opened after storage under normal temperature and normal pressure for one year. Then, the electrolyte was injected into the power generating element. Then, Li ₁₊ x
Since V ₃ O ₈ was used, the positive and negative leads were connected to external charge / discharge power supplies, respectively, and the current was 250 mA and the current was 1.
Discharged to 5V. After that, 3.8V at 250mA
A cycle test was performed under the conditions of charging up to the maximum, and evaluation was made based on a change in discharge capacity with the cycle. As shown in Table 1, Examples 2 and 4 showed that the cycle life was longer than Comparative Examples 2 and 4. I understand.

[0026]

[Table 1]

[0027]

According to the nonaqueous electrolyte battery of the present invention, the electrode group as a power generation element and the electrolyte are separated until the battery is used, so that the storage characteristics are good and the expiration date is long. long. Further, the sealing of the electrolyte reservoir is performed by fusing the inner wall of the connecting portion to the electrode portion and expanding the inner wall at the time of use, or the outer wall of the portion where the packing is interposed on the inner surface of the connecting portion to the electrode portion. , And the electrolyte can be easily moved to the electrode group. The electrode section is
Since it is a sheet-like bag in which the positive electrode lead and the negative electrode lead that are electrically connected to the electrode plate group are exposed to the outside, it is excellent in portability. Furthermore, the inside of the electrode section is previously in a negative pressure state,
The electrolyte can easily move to the electrode group at the start of use, and can reach the electrode group.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view showing a configuration in an embodiment of the present invention.

FIG. 2 is a schematic perspective view showing a configuration of an electrode plate group in the embodiment of the present invention.

FIG. 3 is a schematic perspective view showing a configuration of an electrode group according to another embodiment of the present invention.

FIG. 4 is a partial cross-sectional view of a seal portion 3 according to the embodiment of the present invention.

FIG. 5 is a partial sectional view of a seal portion 3 according to another embodiment of the present invention.

FIG. 1 is a vertical cross-sectional view taken along a line C-C of a periphery 2 of an embodiment of the present invention.

[Explanation of symbols]

 A: Electrode part B: Electrolyte storage 1: Non-aqueous electrolyte battery 2: Peripheral part 3: Seal part 3a, 3b: Grip part 6: Clamping 8: Safety valve 11, 11 ': Positive electrode 12, 12': Negative electrode 13, 13 ': diaphragm 14, 14', 14 ": electrode group 15: lead

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[Procedure amendment]

[Submission date] March 18, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a schematic perspective view showing a configuration in an embodiment of the present invention.

FIG. 2 is a schematic perspective view showing a configuration of an electrode plate group in the embodiment of the present invention.

FIG. 3 is a schematic perspective view showing a configuration of an electrode group according to another embodiment of the present invention.

FIG. 4 is a partial cross-sectional view of a seal portion 3 according to the embodiment of the present invention.

FIG. 5 is a partial sectional view of a seal portion 3 according to another embodiment of the present invention.

FIG. 6 is a vertical cross-sectional view taken along the line C-C in a periphery 2 of the embodiment of the present invention.

Claims (4)

[Claims] 1. An electrolyte solution in which an electrolytic solution is built in a sealed state in an electrode section containing a group of electrode plates, and the sealed state is opened to transfer the electrolytic solution to the electrode section at the beginning of use. And a non-aqueous electrolyte battery. 2. The non-aqueous electrolyte battery according to claim 1, wherein the sealing of the electrolyte reservoir is performed by fusing the inner wall of the connecting portion to the electrode portion and expanding the inner wall when used. 3. The non-aqueous electrolyte battery according to claim 1, wherein the sealing of the electrolyte storage is performed by pressing an outer wall of a portion where a packing is interposed on an inner surface of a connection portion to the electrode portion. 4. The electrode according to claim 1, wherein the electrode portion is a sheet-shaped bag, and exposes a positive electrode lead and a negative electrode lead that are electrically connected to the electrode plate group. Non-aqueous electrolyte battery.