JPS58201255A - Lithium battery - Google Patents

Abstract

PURPOSE:To obtain a small battery having a large charge-and-discharge capacity and a high energy density by using FeVO4 as a positive active material, using lithium as a negative active material, and employing a matter which allows lithium ions to migrate to electrochemically react with the positive active material. CONSTITUTION:A lithium electrode 2 has a disk-like shape with 19mm. diameter. The electrolyte of the battery is prepared by dissolving 1mol of LiClO4, which is dehydrated with molecular sieves after being dissolved, in 1l of propylene carbonate. It is used by impregnating a diaphragm 3 and a positive mixture 5 with it. FeVO4 used as a positive active material is synthesized by mixing Fe2O3 and V2O5 in a molar ratio of 1:1, and heating the mixture at 560 deg.C for 48hr. FeVO4 thus obtained is mixed with both Koetchen black EC and polytetrafluoroethylene in a molar ratio of 70:27:3 by means of a crushing machine so as to prepare a positive mixture. After that, 0.3g of the positive mixture is pressed and stuck to a titanium net which is fused to a positive case 4 by spot welding, thereby making a positive mixture 5 having 20mm. diameter and 1mm. thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a small-sized photovoltaic battery, specifically a battery capable of photodischarge using lithium as a homopolar active material.

Conventionally, many proposals have been made regarding high-energy dense particles used as lithium negative active materials (for example, intercalation compounds of graphite and fluorine as positive electrodes, negative electrodes). 16 batteries using lithium gold as an active material are known (U.S. Patent No. 3,514,337 Specification IIF8).Also, a lithium battery using fluorinated graphite as an active electrode nail (Matsushita Electric Co., Ltd.) is known. made)
and a lithium battery using magnesium/ga/dioxide as the positive electrode active material (
M) manufactured by Sanyo is already on the market. However, these '(5) batteries were primary batteries and had the disadvantage that they could not be recharged.

For secondary batteries that use lithium as the negative electrode active material, titanium, zirconium, hafnium, niobium, tantalum, vanadium sulfides,
Batteries using selenide and telluride (U.S. Patent No. 4,
009,052) and batteries using chromium hydride, niobium selenide, etc. (Journal Op Electrochemical Society Vol. 124, No. 7, No. 96)
However, these batteries were not necessarily sufficient due to their battery characteristics and MM properties.

Since the present invention is proposed to improve the current situation,
The purpose is to provide a battery that is compact, has excellent characteristics, and can be charged and discharged. In the battery that achieves the above object of the present invention, the positive electrode r-occupied material is F e VO4, the negative electrode active material is lithium, and the 'vL solute material is chemically stable with respect to the positive electrode active material and lithium. Yes, live,
It is characterized in that lithium ions are a substance that can migrate with the positive electrode active material for a total chemical vaporization reaction.

The lithium battery according to the present invention has the advantages of being small, having excellent characteristics, and being able to be charged and discharged easily.

Hereinafter, the present invention will be reviewed in detail.

In the case of forming a positive electrode using FeVQa as a positive reaction material in the present invention, the positive electrode is formed by depositing FeVO4 powder or a mixture of FeVO4 powder and a binder powder such as polytetrafluoroethylene on a support such as nickel or stainless steel. Press and form into a film. Alternatively, the F e VOa powder may be mixed with acetylene black to give it sleep properties, optionally a binder powder such as polytetrafluoroethylene may be added, and the mixture may be placed in a metal container. Alternatively, the mixture may be formed by pressure-molding on a support such as nickel or stainless steel.

Lithium, which is produced in a negative way, is produced in the same way as general lithium batteries in the form of a sheet, or the sheet is made of nickel, nickel, etc.
It is formed as a negative electrode by pressing on a conductor network such as stainless steel.

'KN materials include propylene carbonate, 2-methyldetrahydrofura/, dioxole/, tetrahydrofuran, 1,2-dimethoxyethane, ethylene carbonate, r-butyrolactone, dimethyl sulfoxide, acetonitrile, formamide, dimethylformamide, Aprotic organic solvent such as nitromethane and L i CtO
,,L 1AtC/4,LiBF4,LiC4,Li
Combinations with lithium salts such as PFa and LiAsF5, solid electrolytes or molten salts using Li as a conductor, and the use of direct injection and filters that are generally used in batteries that use lithium as the active negative electrode and wj. be able to.

Furthermore, if necessary in view of the battery configuration, a diaphragm made of porous polypropylene or the like may be used.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

In addition, in the examples, battery preparation and measurements were performed under an argon atmosphere.

Example 1 411 is the If? of a battery cell for measuring time of a button type battery, which is an example of a battery according to the present invention. Check out the schematic diagram.
1 is a brass plate with nickel plating, 2 is a lithium negative electrode, 3 is a porous polypropylene diaphragm, 4 is a stainless steel positive electrode container, 5 is a positive electrode mixture, 6a and 6b are Teflon containers, 7 is a nickel lead Show the line.

Inside the concave chamber of container 1, mold an eyeball with a diameter of 20 mm and a thickness of 1 mm.
A container 44 containing the crushed mixture 5 was put therein, a diaphragm 3 was placed on top of the container 44, the container 6a6b was tightened, and the lithium S1 electrode 2 was placed thereon. The lithium electrode has a disk shape with a diameter of 19 mm. As the scale liquid, a solution of LiCtO, which had been distilled and dehydrated with molecular sieves after steaming IfiI, and 1 mol/carbonate of Probile/Carbonate was used. The electrolytic solution was used by impregnating Separate@3 and positive electrode mixture 5.

FeVO4 as a positive electrode active material is replaced with Fe2O3 and vtO
, were mixed at a molar ratio of 1:1 and heated at 560°C in air.
The mixture was synthesized by heating for 48 hours. This F e VO4, Ketjenblack EC and polytetrafluoroethylene were mixed in a crusher at a weight ratio of 70:27:3 to prepare a genuine and false mixture. This positive electrode mixture 0.32 mm was crimped onto a titanium mesh spot welded to the positive electrode container 4, and
A positive electrode mixture 5 having a thickness of 0 mm and a thickness of 1 mm was prepared. When the battery thus prepared was left at a constant current of 1 mA, a discharge curve as shown in FIG. 2 was obtained. Until the battery's pressure drops to 2V, the voltage of the cathode foil material is 172.9Ah.
/l soybean ←density is) 4 5.5 Wh/~,
The discharge answer tj' density until the voltage drops to IV is 270.
2Ah/odor, energy density is 568.7 Wh/I'
It was l.

Example 2 Using a battery prepared in the same manner as in Example 1 except for using a positive electrode mixture of 0.12 mrn in diameter and 1 mm in thickness, 1.
Charging and discharging were performed at a constant current of mA. The charge/discharge cycle is 8 hours and 30 minutes of discharge, 1 hour of rest, and 1 charge! ! L8 hours 30 minutes,
(1 hour), which corresponds to approximately 60 hours of charging/discharging.

FIG. 3 is a diagram showing the results of a charge/discharge trial run. That is, the duration of the melody shows the first phase, then the resting phase, then the photogenic state, and then the body period. Songs - A, B, C.

D indicates the 1st, 2nd, 10th, and 204th discharge and charge, respectively. The final pressure of the discharge isthmus is I VK! ! ! It was possible to charge and discharge 20 times, and it showed good charging and discharging characteristics with no dust.

As explained above, the X-pond according to the present invention has the advantage that it can be used in the field of construction as a compact and energy-dense pond with a large weight of 8 tons.

[Brief explanation of the drawing]

No. 1M is an actual example of the present invention, and is a schematic diagram of a cell disconnection device for evaluating the characteristics of a button-type battery. Figure 3
The figure is a diagram showing the number of charging/discharging cycles of a battery and the voltage change during charging/discharging in an example of the present invention. 1... Container, 2... Lithium negative electrode,
3... Diaphragm, 4... Positive electrode container, 5...
...Positive electrode mixture, 6a, 6b...Teflon container, 7.
··Lead. Applicant's agent Masashi Yamamiya Procedural amendment (spontaneous) June 22, 1980 Patent Office liquid blindness Kazuo Wakasugi 1 Indication of case 1975 Hide Application No. 83588 2 Title of invention Lyticum battery 3, Relationship with the person making the amendment Patent applicant name (Name) (422) Nippon Electric Power Co., Ltd. 11 Kamegou Corporation 4;
Agent 6, Number of inventions increased by amendment 7, Subject of amendment α) The "Claims" in the same specification are corrected as follows. [The positive electrode active material is FeVO, the negative electrode T8 material is lithium, and the waxy material is chemically stable due to S in the iE active material and lithium, and the lithium ions are chemically stable with the positive active material and lithium. A lithium battery that can also be used as a photodischarge, which is characterized by a substance that moves and reacts in a chemical reaction. ” he corrected. Procedural abstract (spontaneous) September 13, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1 Indication of the case 1983 Patent Application No. 083588 2 Title of the invention Lichiu at Pond 3 Comparison with the case of the person making the amendment Related Patent Applicant Lll JR Ichi (Yuuro) (422) Nippon Electric I6-
Public corporation 46 agent 6, amendment Y The number of inventions increases from this 7, during the application to be amended, the ``patent applicant'' is grasped and ``-Du 157 June 22, 2015, the handbook amendment gate'', S11 is corrected. ``Ministry''
List of attached documents (1) Registration thin copy 14 (2) Statement of reasons 1 copy Procedural amendment (voluntary) June 22, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1, Indication of $ 1978 patent application No. 83585 S32, Title of the invention: Lithium 'Seikeike 3, Relationship with the case of the person making the amendment Total number of patent applicants: 1' + 1°; 1 No. 6, 1-1 Shokuhou, 1-chome, Uchisaiwai-cho, Chiyoda-ku, Tokyo Name inscription) (422) Nippon Telegraph and Telephone Public Corporation 4, Agent 6, Number of inventions increased by amendment 8 Contents of amendment Toosho in attached sheet

Claims (1)

[Claims] The positive electrode active material is FeVO4, the active material is lithium, and the electrolyte, pH! I-quality is chemically locked to the positive electrode active material and lithium, and is capable of transferring lithium ions to undergo a serious conversion reaction with the positive electrode active material. Riteu 7-, which allows photodischarge to be performed on standby.
Yaike.