IE49259B1 - A positive active material for an electric cell with a non-aqueous electrolyte - Google Patents
A positive active material for an electric cell with a non-aqueous electrolyteInfo
- Publication number
- IE49259B1 IE49259B1 IE274/80A IE27480A IE49259B1 IE 49259 B1 IE49259 B1 IE 49259B1 IE 274/80 A IE274/80 A IE 274/80A IE 27480 A IE27480 A IE 27480A IE 49259 B1 IE49259 B1 IE 49259B1
- Authority
- IE
- Ireland
- Prior art keywords
- bismuth
- aqueous electrolyte
- active material
- chromate
- silver
- Prior art date
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 title description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000011149 active material Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 229910052716 thallium Inorganic materials 0.000 description 6
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 6
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- FCSCTLGIPUOGOC-UHFFFAOYSA-N disilver;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Ag+].[Ag+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O FCSCTLGIPUOGOC-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- -1 dichromate anion Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Glass Compositions (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Secondary Cells (AREA)
Abstract
1. Active positive material for electrochemical generator with non aqueous electrolyte, characterized in that it is constituted of a double chromate of bismuth which belongs to the group comprising bismuth-silver-bichromate AgBi(Cr2 O7 )2 , bismuth-thallium-bichromate TlBi(Cr2 O7 )2 and bismuth-thallium-chromate TlBi(CrO4 )2 .
Description
The invention relates to a positive active material for an electric cell with a non-aqueous electrolyte and more particularly to cells which include a negative electrode 4 based on an alkali or alkali-earth metal, in particular lithium.
Cells with non-aqueous electrolyte are known in which the active materials are silver chromate and lithium. The discharge voltage of these cells is higher than 2 volts and is particularly suitable for some applications. Unfortunate10 ly, silver chromate is an expensive active material because it contains silver.
The invention aims to replace silver chromate by an active material which contains less silver or which does not contain any and which has a similar discharge potential.
The invention provides an active positive material for electrochemical generator with non aqueous electrolyte, characterized in that it is constituted of a double chromate of bismuth which belongs to the group comprising bismuthsilver-bichromate AgBi(Cr2O^)2, bismuth-thallium-bichromate TXBi(Cr2O^)2 and bismuth-thallium-chromate TIBi(CrO4)2· Bismuth double chromate is taken to mean a double salt of bismuth whose anion is formed by oxygen and hexa2valent chromium and may be either the chromate anion CrO. or 2- 4 the dichromate anion Cr20^ · Bismuth and silver double dichromate contains 14.4% by weight of silver instead of 65.0% as in silver chromate.
The invention also provides an electrochemical generator comprising a positive electrode, a non aqueous electrolyte and a negative electrode based on an alkaline metal or an alkalo-terrene metal, characterized in that the positive electrode contains an active material according to claim 1.
The invention will be better understood from the examples described hereinbelow by way of non-limiting illustrations with reference to the accompanying drawings in which figures 1 to 3 show discharge curves of electric cells in accordance with the invention.
Curves A, B and C in figure 1 relate to the discharge of three primary cells containing bismuth and silver double dichramate AgBi(Cr207)2 as their positive active material.
These cells are button cells of the type often designated 10 by the numerical symbol 44, i.e. diameter 11.4 mm and height .35 mm. The quantity of positive active material in these cells is less than that in cells of this type found commercially.
The difference in quantity is compensated by a shim. They contain 130 mg of an active mass containing 95% dichromate and 5% graphite compressed at 1.5 metric tonnes to obtain a thickness σ of 0.6 nm, the surface area of the electrode being 0.6 cm . The negative electrode contains a quantity of lithium whose capacity greatly exceeds the positive capacity. The electrolyte is a molar solution of lithium perchlorate in propylene carbonate.
The graph in figure 1 plots the voltage V in volts of the cells as a function of the duration t in hours of the discharge of such cells through a resistance of 150 kQ and at a temperature of 37°C. The capacity obtained is 30 mAh down to 2.5 volts for all three cells»and 45 to 50 mAh down to 2 volts. The corresponding specific capacities (by weight) are comparable to those obtained with silver chromate.
Curve D in figure 2 relates to the discharge of a cell wnich contains bismuth and thallium double dichromate TlBi(Cr2O7)2 as its positive active material.
The cell differs from those described hereinabove only by the nature of its positive active material and by the weight of the active mass which is 200 mg. The curve of the figure represents the discharge of the cell through a resistance of 150 ko and at ambient temperature. The capacity obtained is 30 mAh down to 2.5 V,and 54 mAh down to 2V. 492S9 Figure 3 shows a discharge curve E of a cell which contains bismuth and thallium double chromate TIBi (CrOi,) j as its positive active material.
The cell has the same geometrical characteristics as the 5 preceding cells. 560 mg of positive active mass containing % of graphite is inserted therein. Xt is discharged through a resistance of 62 kfl at ambient temperature. The discharge voltage is lower than that of the preceding cells but sufficient for devices which merely require a supply voltage higher than 10 2 volts. With this voltage as end voltage, a capacity of 85 mAh is obtained.
To make it easier to reproduce the invention, a nonlimiting description is given hereinafter of a method.of preparing each of the active materials in accordance with the invention.
Bismuth and silver double dichromate is obtained by preparing a saturated aqueous solution of CrCb at ambient temperature, i.e. about 20°C. 800 g of solid bismuth nitrate Bi (NQ3) >5H;>0 is added per litre of solution. The mixture is shaken for about an hour, then small quantities of silver dichromate Ag2Cr2O? are added so as to make the atomic ratio between the silver and the bismuth equal to one, i.e. 356 g of silver dichromate for 800 g of bismuth nitrate. The reaction mixture is shaken for about 24 hours to obtain optimum effi25 ciency i.e. of about 95%. The solid is filtered and washed with a solvent such as acetone or tetrahydrofuran - water would cause hydrolysis - then dried,preferably in an oven under vacuum conditions.
Bismuth and thallium double dichromate can be obtained by the same method, replacing the silver dichromate by the corresponding quantity of thallium dichromate.
Simple washing in water transforms the bismuth and thallium double dichromate into bismuth and thallium double chromate. of course, the invention is not limited to the embodiments which have just been described.
Claims (4)
1. Active positive material for electrochemical generator with non aqueous electrolyte, characterized in that it is constituted of a double chromate of bismuth which 5 belongs to the group comprising bismuth-silver-bichromate AgBi (Cr 2 O^) 2 , bismuth-thallium-bichromate TIBi (Cr^·?) 2 and bismuth-thallium-chromate TIBi(CrO^) 2 .
2. Electrochemical generator comprising a positive electrode, a non aqueous electrolyte and a negative 10 electrode based on an alkaline metal or an alkalo-terrene metal, characterized in that the positive electrode contains an active material according to claim 1.
3. A material as claimed in claim 1, substantially as herein described. 15
4. An electric cell as claimed in claim 2, substantially as herein described.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7903772A FR2457017A1 (en) | 1979-02-14 | 1979-02-14 | POSITIVE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROCHEMICAL GENERATOR |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE800274L IE800274L (en) | 1980-08-14 |
| IE49259B1 true IE49259B1 (en) | 1985-09-04 |
Family
ID=9221968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE274/80A IE49259B1 (en) | 1979-02-14 | 1980-02-13 | A positive active material for an electric cell with a non-aqueous electrolyte |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0014909B1 (en) |
| JP (1) | JPS55108173A (en) |
| AT (1) | ATE1345T1 (en) |
| AU (1) | AU527821B2 (en) |
| BR (1) | BR8000862A (en) |
| CA (1) | CA1134607A (en) |
| DE (1) | DE3060660D1 (en) |
| DK (1) | DK61480A (en) |
| ES (1) | ES488595A1 (en) |
| FR (1) | FR2457017A1 (en) |
| IE (1) | IE49259B1 (en) |
| IL (1) | IL59318A (en) |
| NO (1) | NO150739C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56132690A (en) * | 1980-03-19 | 1981-10-17 | Hochiki Co | Fire detector |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2159665A5 (en) * | 1971-11-08 | 1973-06-22 | Mallory & Co Inc P R | High energy density cell - having metal chromate cathode depolariser light metal anode and organic electrolyte soln |
-
1979
- 1979-02-14 FR FR7903772A patent/FR2457017A1/en active Granted
-
1980
- 1980-02-05 IL IL59318A patent/IL59318A/en unknown
- 1980-02-07 AT AT80100632T patent/ATE1345T1/en not_active IP Right Cessation
- 1980-02-07 EP EP80100632A patent/EP0014909B1/en not_active Expired
- 1980-02-07 DE DE8080100632T patent/DE3060660D1/en not_active Expired
- 1980-02-12 NO NO800368A patent/NO150739C/en unknown
- 1980-02-13 IE IE274/80A patent/IE49259B1/en unknown
- 1980-02-13 AU AU55503/80A patent/AU527821B2/en not_active Ceased
- 1980-02-13 BR BR8000862A patent/BR8000862A/en unknown
- 1980-02-13 CA CA000345590A patent/CA1134607A/en not_active Expired
- 1980-02-13 DK DK61480A patent/DK61480A/en not_active Application Discontinuation
- 1980-02-14 ES ES488595A patent/ES488595A1/en not_active Expired
- 1980-02-14 JP JP1610380A patent/JPS55108173A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DK61480A (en) | 1980-08-15 |
| CA1134607A (en) | 1982-11-02 |
| JPS55108173A (en) | 1980-08-19 |
| NO150739C (en) | 1984-12-05 |
| IL59318A0 (en) | 1980-05-30 |
| AU5550380A (en) | 1980-08-21 |
| ES488595A1 (en) | 1980-10-01 |
| NO150739B (en) | 1984-08-27 |
| DE3060660D1 (en) | 1982-09-02 |
| BR8000862A (en) | 1980-10-29 |
| IE800274L (en) | 1980-08-14 |
| NO800368L (en) | 1980-08-15 |
| IL59318A (en) | 1983-06-15 |
| FR2457017B1 (en) | 1981-10-16 |
| EP0014909B1 (en) | 1982-07-14 |
| FR2457017A1 (en) | 1980-12-12 |
| EP0014909A1 (en) | 1980-09-03 |
| ATE1345T1 (en) | 1982-07-15 |
| AU527821B2 (en) | 1983-03-24 |
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