JPS58192268A - Lithium battery - Google Patents

Abstract

PURPOSE:To provide a battery having large charge-discharge capacity, small size, high energy density, and wide application. CONSTITUTION:A positive active mass is a compound indicated in Cu2(MxV1-x)2 O7 (M is one or more elements selected from Mo, W, Cr, X is a real number less than 1). A positive electrode is formed by press-bonding the active mass powder or a mixture with a binder powder such as polytetrafluoroethylene on a supporting body such as nickel, stainless steel in a film state. Lithium of a negative active mass is formed in a sheet same as a conventional lithium battery. The lithium sheet is press-bonded to a conductive net such as nickel, stainless steel to form a negative electrode. Substances which are chemically stable to the positive active mass and lithium, and lithium ion can move in the substances can be used as an electrolyte in the same way as a conventional lithium battery.

Description

[Detailed Description of the Invention] The present defense is based on a large battery of Sumire Kameya that emits light in a small size, and a salmon axis.
Using lithium as the negative electrode active material, Cuz (Le1xV+
-1) Photodischarge using 2 (J7 (M: mmo, Vv, Cr, hexavalent - 11 or more, especially 0.3 or less *) as a positive electrode active material also has iiJ ability. It is related to batteries.

Kenki has made many proposals regarding the use of lithium as a negative electrode active material.
Eleven ponds are known in which lead-free and fluorocarbon intercalation compounds are used as positive electrode active materials, and lithium*M is used as negative electrode active materials. (US lj1% II + 3rd
, 514, 337).

In addition, a lithium battery a (manufactured by Matsushita Electric Co., Ltd.) using fluorinated graphite as a positive electrode active material and a 9 lithium battery (manufactured by Sanyo Electric Co., Ltd.) using two-wire manganese as a positive electrode active material are already on the market. However, these IIL batteries were primary batteries and had the disadvantage that they could not be recharged.

Lithium [For secondary batteries used as negative electrode active materials, 11IL turtles (wood - pin number 4,
009,052) and Kameike using niobium selenide descendants (Journal of Y,
Leftrochemical Society Vol. 124 No. 7 96111
Jk and 325th negative 1977 birth) have been proposed, but these batteries have not always been sufficient due to their unique characteristics and economical efficiency.

Furthermore, a nine Li battery using metal vanadate as the positive electrode active material is disclosed in U.S. Patent No. 3,681.143, but this company uses Cu5 as the metal vanadate.
(VO4) Only - having the structure 2 is shown as an example 9, and there is no description of charging characteristics. We have already proposed rechargeable Cu2V207.

When Cu2V20y is used as a positive electrode active material, it must be mixed with a conductive agent such as acetylene black or graphite to improve the electronic number in the positive electrode mixture.

However, adding a thin layer that does not act as an active material will reduce the energy of the positive electrode unit and its weight, which is contrary to increasing the energy density of the battery. Therefore, in order to increase the light Yokotani Sumire, it is necessary to lower the mixing ratio of the conductive agent within the yoke i that can maintain the desired battery performance. For this purpose, it is important to improve the conductivity of the positive electrode active material.

The present invention was proposed to improve the current situation,
Its purpose is to make lithium 11 with a small size and a dredged % property.
The goal is to provide La. In a battery that achieves the above object of the present invention, the positive electrode active material is Cu2 (Mz
Vl-X) 207 (M: MoeW, 6 of Cr
Lithium is used as the negative electrode active material, and the electrolytic material is chemically stable with respect to the positive electrode active material and lithium, and the lithium ion has an electrochemical reaction with the positive electrode active material. It is characterized by being a substance that moves in order to

The lithium battery according to the present invention has the advantage of being able to provide a lithium battery 1 that is small in size and has a low specificity.

To explain the present invention in detail, the positive electrode active material used in the lithium battery according to the present invention has the following general formula (1): % formula % (1) where M#'i, 6 Price Mo, W, Cr (D indicates one sleeve or two or more poles.

Further, x represents a real number less than Fi1, and in the lithium battery according to the present invention, the value of X is preferably 0.3 or less. This is because if X exceeds 0.3, the solid solubility limit is exceeded, resulting in a mixed state, which may lower the battery voltage and reduce the cycle life.

Cu2 (MxVl-
1) When forming a positive electrode using 207, positive & is Cu
2 (MXVl-207 powder or this and polyteto)
A mixture with a binder powder such as fluoroethylene is pressure molded into a film on a nickel or stainless steel support.

Alternatively, the Cuz (IV+zV1-z) 20y powder is mixed with a conductor powder such as rounded acetylene black to impart conductivity, optionally with the addition of a binder powder such as polytetrafluoroethylene, and this mixture is mixed with gold powder. ! It is formed by inserting the mixture into a nickel or stainless steel support or by pressing and molding the mixture onto a nickel or stainless steel support.

Lithium, which is the negative electrode active material, can be used in the same sheet form as that of general lithium batteries, or the sheet can be made of nickel, nickel, etc.
The negative electrode is formed by compressing it into a 4# stainless steel housing mesh.

Examples include propylene carbonate, 2-methyltetrahydrofuran, oxolene, tetrahydrofuran, 1-2-dimethoxyethane, ethylene carbonate, and-butyrolactone, dimethylsulfoquine, acetonitrile, borumamide, dimethylformamide, nitromethane, etc. 'h machine mk and LiClO4
,L+AlCl4,LiBF4゜LiC1,LmuPk
In combination with lithium salts such as ``6 * L s Ata F' 6, solid electrolyte SL or molten salt using FiLi+ as a conductive material, use in 'I&L turtles' in which lithium is used as a negative electrode active material. You can use the known one.

In addition, if necessary, a film made of polypropylene, etc., made of polypropylene, etc., may be used.

To make Cu2 (MXV 1-X) 207,
Cub.

V2O5 and MOx (Moss eWOs ecrO
s%) at a ratio of 2=1x:2x in terms of mo/l/ratio, and synthesized by heating in air at 620°C for 24 hours.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these K in any way.

In addition, in the examples, the production and measurement of batteries were performed under an argon atmosphere.

Example 1 FIG. 1 is a schematic drawing of the moving surface of a battery cell for measuring the characteristics of a phosphor type battery, which is an example of a battery according to the present invention, where l is a nickel-plated yellow fIi4 valley device, and 2iilJ Tew& Negative electrode, 31d porous polypropylene tube, 4 stainless steel plate, 5 positive electrode mixture, 6m, 5b Teflon container, 7 nickel lead wire.

Pressure molded into the 4th part of Valley 5 N1 to diameter aJmm and thickness 1mm.
The positive electrode mixture 5 prepared above was crimped and placed in a Kutani 4-metal plate, the diaphragm 3 was placed on top of it, the lithium negative electrode 2 was tightened with a sacrificial plate 6 and 6b, and the lithium negative electrode 2 was placed thereon. The lithium electrode has a disc shape with a diameter of 19 mm. To dissolve Ltcto4 dehydrated with steamed moleki =-')-sieves and 1 mol/propylene carbonate, a bath solution was used. The electrolyte solution was used by impregnating the electrode mixture 3 and the positive electrode mixture 5. Cu2 (M
Oo, 2VD, 8) 207 ks Cub.

M OQ 3 and VzOst% ratio 2:0.4
; Mixed at a ratio of 0.8 and heated at 620″C2 in air.
The mixture was synthesized by heating for 4 hours. This Cuz (MOo, 2V
0.8) 207 and Ketchump EC and polytetrafluoroethylene in a weight ratio of 80:27
: 3 in a ratio of 1 to 3 in a pickler to prepare a positive electrode mixture. 0.4g of this mixture was added to the cathode container 4.
A positive electrode mixture 5 having a diameter of I mm and a depth of 1 mm was prepared by pressure bonding to a titanium net that was in spot bath contact with the substrate. When the battery prepared in this way was discharged with a current of 1 mA, the discharge was 1 as shown in Figure 2A. It became an L curve.

Until the voltage of the Ill pond drops to 2 ■, the overcoating activity P@Jitsu's Hokai Dondo 1 &i#l: Fi330Ah/kg, the energy configuration is 861 □Wh/kg,
The discharge v'mvBi until the voltage drops to 1■ is 520
Ah/kg x Nerky L degree n1150Wh/kg
I failed. In addition, a 11L battery was fabricated as a conventional battery with a relatively soft Nodame, except that CuzV207, which did not contain Mo and was subjected to the same heat treatment, was used as the positive electrode active material, and a 1mA constant current discharge test was conducted. The discharge 11- occurred as shown in Figure 2B. Discharge capacity of positive electrode active material ILWj degree Fi301Ah/kg until battery voltage decreases by 2VK
Energy m degree ti 749Wb/1g), discharge capacity density until voltage drops to 1■ is 473Ah/kg
The energy density was 1005*h/kg. As described above, the electrode aA#'i of the present invention exhibits excellent characteristics in both the flatness of the discharge voltage and the discharge capacity.

In addition, wt of kto under the same discharge conditions as in [i%l]
The relationship between the exchange rate (X) and the discharge capacity density at the end of 1V is shown in the third
As shown in the figure. As is clear from the figure, as the number of Mo electrified children increases, the released 1 volume weight increases.

Example 2 Nine Cuz (Moo, zV) was produced in the same manner as in Example 1.
o, a) Using a 11111 tortoise with 207 as the positive electrode active material, a photodischarge meeting was carried out with a 1 mA rhinoelectric current. The charging and discharging time is 1 hour and 1 hour, and the time is 1 hour, and this corresponds to approximately 1 hour of charging and discharging.

FIG. 4 is a diagram showing the result of photodischarge pure iron. That is, this 4- is a discharge shape, then a pause j-1, and then a Marugame shape-1.
Next, telogen phase l&11 is shown. 1 Spider A, B, C.

DFi shows the 1st, 2nd, 101st, and 101st discharges and photoelectric charges, respectively.

The 10th (b) release')ILk final voltage -〇) is 2.
40V.

The discharge peak pressure (1 test) was 2.32 V at 1 cycle, which showed good photodischarge characteristics.

Example 3 Cu2(WO2VO8) 2(J
Cub 7.

Wo3 and V2O5 were mixed in a molar ratio of 2:0.4:O8, and synthesized by heating in air at 620'C for 24 hours. This Cu2 (Wo, 2V0.8)
2L) Vi refreshing example 1 and It except that 7 was used as the positive electrode active material
A battery was prepared using iJ. When the electric current produced in this state was subjected to KMC stimulation at 1 mA, the discharge curve as shown in Fig. 5 was obtained. Positive +1 until the battery voltage drops to 2■! , IjLij
320Ab/rig energy table is 840Wb
/kg, and the radiation 14 until the voltage drops to lV is -
The city power was 500 Ah/kg and the energy density was 1100 Wh/kg. As described above, the battery of the present invention exhibits superior characteristics in both discharge voltage flatness and discharge capacity compared to conventional batteries. Furthermore, the relationship between the tR* violet of W and the emission tolerance 'IL density showed the same tendency as shown in FIG. 3, and the discharge cap density increased as the Wt cap increased. Furthermore, charging and discharging was also possible.

Example 4 Cu2 (Cro, 2Vo, a) 2 as positive electrode active material
07 to CuO, CrO3*V2O5 molar ratio Te2
: 0.4 : 0.8(7) 114 times were mixed and heated in air at 620°C for 124 hours to synthesize. This C
A battery was prepared in the same manner as in Example 1, except that u2(Cro2Vo, a) 207 was used as the positive electrode active material.

When the battery prepared in this manner was subjected to a wave number curve at a constant voltage of 1 mA, a discharge curve as shown in FIG. 6 was obtained.

The storage plate in the discharge valley of the positive electrode active material until the XaOt pressure decreases by 2VK is 316Ah/kg, and the energy density is 810W.
h/kg, the discharge level until the voltage reaches IVKtT' is 490Ah/kg, and the energy density is 10
80 W″h/kg.
L seaweed is h compared to promotion rice 01ka! Flatness and release of lt% pressure 11! Both L-Yado shows excellent percentage properties. In addition, the relationship between the a-side ratio of Cr and the cage response density shows the same tendency as shown in Fig. 3, and Crt! As the amount of L chivalry increased, the density of free game answerers increased. Historically, photodischarge also has i=J rudder.

As explained above, the first point of the battery of the present invention is that it can be used as a small-sized energy density battery with a large charge/discharge capacity in many SR applications.

Figure 1 shows a schematic cross-section of a 1st Asahi cell for characterizing a photanic battery, which is a fruitful example of the present invention. A diagram showing
FIG. 3 shows t#iM of Mo of the battery in the embodiment of the present invention.
Figure 4 is a diagram showing the relationship between Momme and Hokametani disturbance level, and Figure 4 is a diagram showing the charge/repetition rate of 1 Ri of the battery in the embodiment of the present invention and the turtle pressure during photodischarge. Figure 5.6 The figure shows the release N'r waiting time voltage F! of U in the embodiment of the present invention. This is a diagram showing the IiU section.

l...container, 2...lithium shellfish, 3...diaphragm,
4...Teflon device, 5...Shosai combination agent, 6a, 6b Kawa Teflon parent device, 7...Reed spinning.

Taganjin's agent Tadashi Sue Miya Li procedure amendment, 'F (method) August 6, 1980 Patent Office Commissioner Kazuo Wakasugi 1 Indication of gravity Showafu 57 Jl Patent Application No. 074511
jji 2 Title of the invention Lithium battery 3 Relationship with famous event to be amended e1 Hanho applicant fl +1+ Higashiguto Chiyoda-ku Uchisaracho 1-1 (1
Mr. No. 6 6 (Ko J.) (422) Nippon Electric Power Company 5 Date of amendment order P. 9, 1982 (Shipping date 5
7.7.27) 6 Number of inventions increased by amendment 1 8 Supplementary Internal Medicine Attachment '&li \-,,/
'α) Insert "Detailed explanation of drawings" between the 9th line and the 10th line of the specification cylinder 126.

Claims (1)

[Claims] 1. Stop practice @ Kenwa Cu2 (MXV+ -X) 2U7
C1mhlc (M represents one or more molecules selected from the liver consisting of tViO, W, and Cr, and X is a real number less than 1) is a compound where tl = t, the negative electrode active material is lithium, The electronic device is chemically stable with respect to the positive electrode active material and lithium), and the lithium ions move to undergo a chemical reaction with the positive electrode active material at once. A lithium battery that can be charged and discharged.