JPS58172869A - Secondary battery - Google Patents

Abstract

PURPOSE:To provide a secondary battery having small size and good performance by using one or more of ATiNbO5 (A; K, H, Li, or Na) as a positive active mass, Li as a negative active mass, and a material which is chemically stable and in which Li<+> can migrate as an electrolyte. CONSTITUTION:One or more of ATiNbO5 (A; K, H, Li, or Na) is used as a positive active mass. Li is used as a negative active mass. A material which is chemically stable to the positive active mass and Li, and in which Li ion can migrate to conduct electrochemical reaction with the positive active mass is used as an electrolyte. A secondary battery constructed with above materials has small size and large discharge capacity.

Description

[Detailed Description of the Invention] The present invention relates to a small-sized and large-sized secondary battery that is free of charge.
More specifically, this applies to batteries that use lithium as the negative electrode active material.

Traditionally, lithium has been used as a negative electrode active material ^ Energy f
A lot of work has been done on lBIjL1, and as a positive electrode active m*, Q-gens such as Br2 and I2, CuF2, AgF2, AgFNiF'2, Cu
Cl2, Agel, NiCl2, CoF3, CrF″4
．． MinF5, b bFx, CdF2, AsF3, Hg
F2, CuBr, CdCl2, PbCl2, Ni
Metal halides such as Cl2 and Coc12, etc.
Ag5cN, CuSCN and Ni (SON) 2
Gold rotanide, krno2. Cr2C)
ss V'20! h 5n02s P602% Ti0
2s Bi20sCrt) 3, i'@sO<, Nio
XAgo, ago, Cu2L), euO, Ag2W
O', gold enemies such as Ag 2Cr04%, NiS
x, AgB5. CuB5. Pb1iBzSs and
mn8484% gold Jllll 91C compound, 1゛IS2
．． 1Jss・2 and WS2, etc., are used for layered calibration, fluorinated graphite, benzoquinones, dinitrobenzene, and other compounds, and POCl3.5UC12 and 5O2.
Oxyhalides such as Cl2 etc. are used.9'#l
iike is proposed. And specifically? In this case, an intercalation compound of graphite and fluorine was used as the positive electrode active material, and lithium gold ring was used as the negative electrode active material. iLb is known (see Thu.M!4+H No. 3,514,337 specification honor), and lithium batteries (Matsushita Ichibansha) using fluoride black sushi as a stationary active material and divalent manganese are known. Lithium battery as positive electrode active material (Santo i)
(manufactured by Mki Co., Ltd.) is already commercially available.

However, these batteries were not necessarily sufficient due to their release properties of 7.

The present invention has been made in consideration of such a block, and its purpose is to provide a battery that is small in size and has excellent characteristics.

To summarize the present invention, in the battery of the present invention, the pressure active material is KTiNbOs, iri'tN05, LiT
iN'l) U5, N&TiN05, the negative electrode active material is lithium, and the electrolytic material is chemically incompatible with the positive electrode active material and lithium. %, and lithium ions are a substance that moves to perform an electrochemical reaction with the positive electrode active material.

The above kKTiNb as the positive electrode active material in the present invention
5, HTiN&Qs, Li'i'1NbOs> NJL
When using TiNIe (Js above the -axis as a positive electrode, powder of these compounds or a combination of this and binder powder I#l:J is deposited on a support such as nickel or steel in the form of a film.
To re-shape or mix these 7 compound powders with carbon rot to give conductivity, put this mixture into a gold maple container, or mix the @1 mixture with a binder solution and add nickel, It can be formed by other means than coating it on a temple support, drying it, and forming it into a film. Positive electrode activity? ! The actual lithium is formed in the form of a sheet in the same way as 1 meter of general lithium, or the sheet is placed in a nickel or copper mesh to form a negative electrode.

'141. As a shoulder, non-pro)/a[et
Solvent and LIC104, LIAICl4, LiBF4,
Combinations with lithium salts such as LICl, or electrolytes or molten salts in which Ll+ is the main conductor, and known *m-conductivity used in batteries using lithium as the negative electrode active material can be used. I can do it.

In addition, if necessary, 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 will not be put to rest by these Examples.

In addition, in the examples, all of the kimono pond production was carried out under a clear argon gas atmosphere.

Example 1 FIG. 1 is a schematic diagram showing the configuration of a button-type electric device, which is a specific example of this @Ming.
2 is a lithium negative electrode, 3 is a porous polypropylene diaphragm,
4 was used as a toilet by impregnating felt 4 made of carbon fiber. The positive electrode mixture 5 is 0.02 g of KTiNipOs.
A powder and 0.02g of acetylene black were mixed with the above electrolyte to form. A lithium sheet was used as the lithium negative electrode 2 with a porous polypropylene partition 3 sandwiched therebetween.

The battery prepared in this way was initially heated to 0.32 mA/c.
Apply constant current photoelectric charge of m2, OK in KTiNl>05
0.32 mA/c after being completely electrochemically treated
The results of constant ta discharge at m2 are shown in A in FIG. The average electromotive force until the voltage reaches 1V is 1.5V. Similarly, Hoshokyado is 150Ah/kg and the energy capacity is 22 seconds.
It was wh/kg.

Fig. 3B The Sakaku branch was discharged at 0.32 mA/cm2 for 2 hours, and the wave number was 1 after photoelectric discharge at 0.32 mA/cm2 for 2 hours! This shows the result of repeated practice of performing metal removal, and the KTiN605 is a positive electrode active in a light XOJ cage. Become. The KTiN40s used here was obtained by subjecting a chemical mixture of 2CO3, TiOz and Nb2O5 to a solid phase reaction at 1100°C for 20 hours in air.

Flood Example 2 The same procedure as in Example 1 was carried out, except that 0.02 g of H, TiN 05 seedlings and 0.02 g of acetylene black were mixed and formed with the same electrolytic number as in the example as the positive electrode mixture 5. A battery shown in FIG. 1 was manufactured.

Nine batteries thus prepared were electrochemically (ITiN) prepared in the same manner as in Example 1, and then initially charged at 0.32 mA/am2 until the Hlr in 05 was completely extracted.
The results of constant current discharge at 2 mA/am2 are shown in FIG. 2B. XF-y until the voltage becomes IV; J electromotive force is 1.7V, discharge capacity is also 200Ah/kg, and energy sound level is a+owh/kg.

Figure 4 shows that the battery pauses for 2 hours after discharging at 0.32 mA/cm2, then it pauses for 1 minute after charging for 2 hours at 0.32 mA/cm2, and then clings to the wave number turtle. This shows the results of repeated operations, and HTiNbO
s is a rechargeable positive electrode lubricant, and the battery constructed with this positive electrode becomes a secondary battery that can be charged and discharged. (used here) IT
i N bos is KT prepared in the same manner as in Example 1.
iN405 in 2Ni-1cl for 60'C1hr
It was prepared by stirring and then ion exchange of + - + H +.

Example 3 As positive electrode mixture 5, 0.02 g of 1TiNbOs
The cell shown in Figure 1 was prepared in the same manner as in Example 1, except that the powder and 0.02 g of acetylene black were used in the same formulation as the ts standard.

The battery produced in this manner was treated in the same manner as in Example 1 to
'l' l, itl in 1NbOs - Initial charge at 0.32 mA/cm2 until electrochemical extraction into the original metal, followed by constant L discharge at 0.32 mA/crn2. The results are shown in C of Figure 2.The average electromotive force until the voltage reaches 1■ is 1°6V, and the discharge capacity is 215Ah/
kg energy*JN- was 344Wh/kg. Figure 5 shows that after discharging at 0.32 mA/cm2 for 2 hours, the battery is separated and stopped, and after being charged at 0.32 zuA/cm2 for 2 hours, the battery is separated and stopped at a wave number of 11t. This is the result of the repetition, LiT1
NbO5 is a rechargeable positive electrode, and the ll1c battery configured with this positive electrode becomes a secondary battery with 110% charge/discharge capability.

The LiT1NbO5 used here was obtained by adding excess Lihos to KTiNiOs tabulated in the same manner as in Example 1.
Ion replacement was performed by heating in a platinum crucible at 0° C. for 10 hours.

Real =? lJ 4 As positive electrode mixture 5, 0.02 g of NaTiN105
Powder and 0.02 g of acetylene black? lJ
A 91/IL cell shown in FIG. 1 was prepared in the same manner as in Example 1 except that it was mixed with the same cell 7111I'& as in Example 1 and used.

The open-circuit voltage of the 'llL cell prepared in this holiday was 2.6■
I failed. The results of constant current discharge at 0.32 mA/cm2 are shown in D in FIG. The average electromotive force until the voltage reaches IV is 1.4V, and the discharge capacity is 11UAh/
The kg energy density was 154Wh/kg. When a photodischarge cycle test similar to the three examples described above was carried out, NaTi Heshi05 was cured by the positive electrode lubricant capable of being recharged, and the battery made with this positive electrode was a secondary battery which could be photodischarged. It becomes a battery. NaTiN1. used here. Os is Na2CO
3. A chemical mixture of TiO2 and Nb2O5 was subjected to an in-phase reaction at 1050 DEG C. for 20 hours in air.

As is clear from the above description, the battery of the present invention has the advantage that it can be divided into multiple packages as a photodischargeable secondary battery.

[Brief explanation of the drawing]

Figure 1 shows the configuration of a button-type battery that is a specific example of the present invention, and is a schematic diagram on the 11-r plane. Figure 3 is a graph showing the photodischarge cycle of a battery using KTilJ)05 as the positive electrode oil, and the fourth symbol is M'l'1N.
Graph showing the charging and discharging 11L Nykle characteristics of a battery with bOs (i-stop active offshore), 5th - bos to LiTi
1! It is a graph showing other photodischarge cycle shrines. 1...Stainless Steel Container, 2...Lithium Container, 3
...Takashi Hishiko Polypropylene #l! Diaphragm, 4... Carbon fiber felt, 5-... Positive electrode assembly, 6.
...Nylon front pocket. Applicant's agent Masa Lee Minamiya

Claims (1)

[Claims] Cathode active material tiKTiNbos, HTiNJ) 05, L
The group consisting of iTiN&pOsNATiNbOs was selected (more than enough), the negative electrode active material is lithium,
A secondary battery characterized in that the electrolyte material is chemically stable with respect to the positive electrode active material and lithium, and is a material that allows lithium ions to move for an electrochemical reaction with the positive electrode active material.