CA1192946A - Electroactive material for power cells - Google Patents
Electroactive material for power cellsInfo
- Publication number
- CA1192946A CA1192946A CA000417567A CA417567A CA1192946A CA 1192946 A CA1192946 A CA 1192946A CA 000417567 A CA000417567 A CA 000417567A CA 417567 A CA417567 A CA 417567A CA 1192946 A CA1192946 A CA 1192946A
- Authority
- CA
- Canada
- Prior art keywords
- electroactive material
- power
- power cell
- transition metal
- power cells
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Secondary Cells (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
An electroactive material for power cells, especially secondary electrochemical power-producing cells. It is composed of a complex compound of a transition metal and basic organic ligands, especially Schiff bases dissolved in polar organic solvents, water or their mixtures.
Description
~lec~roactiv3 mat~rial Eor pow~r c911s r~his invention relates to an ~lectroactive matsrial for power cells, the secondary electrochemical p~wer producing cells in particulsr, The operation o~ an electric power cell is based OIl hete-rog~neous o~idation and reduction reac-tions OI th~ elsctro~
active material,, The release o~ electric energy is possible only if the di~ference o~ standard electrode potentials o~
the red-ox systems undergoing elec-trode processas in the ano-dic and cathodic potential rengss is sufficiently high, a~d ~ihen the current density is su~ficiently hi~h"
During an electrode ~rocess in ~ po~er cell, the electro-active material is oxidiz~d on anode, and reduced on cathode, n'ypically used electroactiv~ materials are liquid sodium for anode and liquid sulfur for cathode in a solid electroly-te, containing ~.g. sodium ions.
~ he usa of such m3terizls, though, is inconv~nient and no~ious becau=,e OI, among other r~asons, high to~icit~,~ of liquid sodium, In designs 3ccording to U.S. I`atents ~os~ 3791867, 3827910, 3~64167 and a German OfIe~ No. 2937717~ alkali metaLs or alkali earths metaLs of low slectronega tl~ity are used ~or anode materials in non-aqueous reversible cells~
while the cathodic electroactivs material is compos~d o~ a .
~i2~
~ixture o halogens or chalcogens fixed in a conductive matrix. The eleetrolyte used consists of a salt contain-ing alkali metal or alkali earth metal ions. In many cases it is necessary to remove the products of electrode reac-tions from the electrodes or their immediate vicinity, which hinders the use of these electroactive materials on larger scale.
In case of the most known power cells, careful separation of cathodie and anodic 20nes is necessary to avoid mixing of the electrolytie substances leading to an irreversible deaetivation of the cell.
In such a known and widely used power cell, as a reversible lead cell, the electroactive material of both anode and cathode consists of a Pb ~II/ in 30 % sulfuric acid solution. During the charging cycle, Pb /II/ is reduced to Pb /0/ and oxidiæed to Pb /IV/ on anode and eathode, respectively. Major drawbacks of such a cell are the heavy weight of the electrodes and highly corrosive properties of the electrolyte solution.
It was found, that -the electroactive material for power cells according to the invention displays suffi-cient difference of standard electrode potentials and low charging overpotential in relation to the working potential.
It also allows for the use of low-cost ant low-weight electrode materials and has no metal-corroding properties.
Moreover, it does not deposit on the electrodes, nor precipitate within the electrode zones~ making the removal of the products of electrode reactions unnecessary.
The present invention provides a power cell having an electroactive material comprised of a complex of a transi-tion metal, wherein said electroactive material is a complex of a transition metal and a schiff base dissolved in a polar organic solvent, water or their mixtures.
The power cell in accordance with the pr~sen-t invention may be a secondary power cell.
The transiti~n metals used to compose the electroactive material according to ~he invention are such metals, as:
nickelt cobalt~ iron, chromium, manganese, copperO titanium and vanadiums Schiff bases are used as organic liyands, the most advan-tageDus being the ethylenediamine derivatives.
Denoting the electroactive material according to the in-vention as MeL jtvie - transîtion metal, L ~ ligand~, it is re-duced on cathode duriny the power cell char~ing cycle to lvleL .
During the workiny cycle a reversed react~on tal~es place~ Si-milarly, during the charging cycle MeL is oxidized on anode to 1eL~, and this reaction is reversed dur ng the working cycle.
The cathode and anode reactions are electrochemically re-versible, i.e. the same electroactive material works as a re-actant during the charging cycle, and as a product during the workins cycle on both electrDdes. The rate of both these re-actions is controlled by the transport rate.
The additional merit of the electroact~ve material accord-ins to the invention is a relatively lligh energy output froM
a unit of weight, as well as the possibility of application of the power cell containing such a material in low tempera-ture conditions. Moreover, mixing the electroactive material according to the invention contained within the anode and cathode zone does not result in an irreversible deactivation of the power cell, allowiny repeated charging.
The subject o~ this invention is closer described in fol-lowing examples of preferred embodiments, which do not however limi~ the scope of ~his invention~ The enclosed Fig, l and Fig. 2 display cyclic voltammetry curves obtained in condi-~ions described in Examples I and II, respectively.
Example I.
The electrDactivs material for power cells composed of a csmplex c~mpound o, nickel (Ni(II)) and N, N ~ethylene~bis (salicylidenoimine)~ salen) di-ssolved in a O.lM ~C2H5)4 NCl04 -(TEAP) solution in N,N-dimethyl~ormamide (DI~F3. The s~lution was deoxidized by purging with dry nitrogen~ The electrodes were made o~ platinum wire 0.6 ~m in diameter and 8 mm long, The cell dia~ram before charging was:
Pt¦Ni(sale~ (O~lM TEAP in Dl~lr)l Ni (salen),(O.l~1 TEAP in DMF)¦Pt The difference of standard electrode ,ootentials in this cell was, ~ E~ = 2.46 V.
During charging and work, the ~0 = -l.59 V and k = 0.71 x lO 2 cm/s on cathode, and Eo = +0.~7 V and k~ = 0.72 x lO 2 cm~s on anodeO Potential sweep rate, Vp =
= 5~ mV/s, temperature 25 C, Ni (salen) concentration:
active material,, The release o~ electric energy is possible only if the di~ference o~ standard electrode potentials o~
the red-ox systems undergoing elec-trode processas in the ano-dic and cathodic potential rengss is sufficiently high, a~d ~ihen the current density is su~ficiently hi~h"
During an electrode ~rocess in ~ po~er cell, the electro-active material is oxidiz~d on anode, and reduced on cathode, n'ypically used electroactiv~ materials are liquid sodium for anode and liquid sulfur for cathode in a solid electroly-te, containing ~.g. sodium ions.
~ he usa of such m3terizls, though, is inconv~nient and no~ious becau=,e OI, among other r~asons, high to~icit~,~ of liquid sodium, In designs 3ccording to U.S. I`atents ~os~ 3791867, 3827910, 3~64167 and a German OfIe~ No. 2937717~ alkali metaLs or alkali earths metaLs of low slectronega tl~ity are used ~or anode materials in non-aqueous reversible cells~
while the cathodic electroactivs material is compos~d o~ a .
~i2~
~ixture o halogens or chalcogens fixed in a conductive matrix. The eleetrolyte used consists of a salt contain-ing alkali metal or alkali earth metal ions. In many cases it is necessary to remove the products of electrode reac-tions from the electrodes or their immediate vicinity, which hinders the use of these electroactive materials on larger scale.
In case of the most known power cells, careful separation of cathodie and anodic 20nes is necessary to avoid mixing of the electrolytie substances leading to an irreversible deaetivation of the cell.
In such a known and widely used power cell, as a reversible lead cell, the electroactive material of both anode and cathode consists of a Pb ~II/ in 30 % sulfuric acid solution. During the charging cycle, Pb /II/ is reduced to Pb /0/ and oxidiæed to Pb /IV/ on anode and eathode, respectively. Major drawbacks of such a cell are the heavy weight of the electrodes and highly corrosive properties of the electrolyte solution.
It was found, that -the electroactive material for power cells according to the invention displays suffi-cient difference of standard electrode potentials and low charging overpotential in relation to the working potential.
It also allows for the use of low-cost ant low-weight electrode materials and has no metal-corroding properties.
Moreover, it does not deposit on the electrodes, nor precipitate within the electrode zones~ making the removal of the products of electrode reactions unnecessary.
The present invention provides a power cell having an electroactive material comprised of a complex of a transi-tion metal, wherein said electroactive material is a complex of a transition metal and a schiff base dissolved in a polar organic solvent, water or their mixtures.
The power cell in accordance with the pr~sen-t invention may be a secondary power cell.
The transiti~n metals used to compose the electroactive material according to ~he invention are such metals, as:
nickelt cobalt~ iron, chromium, manganese, copperO titanium and vanadiums Schiff bases are used as organic liyands, the most advan-tageDus being the ethylenediamine derivatives.
Denoting the electroactive material according to the in-vention as MeL jtvie - transîtion metal, L ~ ligand~, it is re-duced on cathode duriny the power cell char~ing cycle to lvleL .
During the workiny cycle a reversed react~on tal~es place~ Si-milarly, during the charging cycle MeL is oxidized on anode to 1eL~, and this reaction is reversed dur ng the working cycle.
The cathode and anode reactions are electrochemically re-versible, i.e. the same electroactive material works as a re-actant during the charging cycle, and as a product during the workins cycle on both electrDdes. The rate of both these re-actions is controlled by the transport rate.
The additional merit of the electroact~ve material accord-ins to the invention is a relatively lligh energy output froM
a unit of weight, as well as the possibility of application of the power cell containing such a material in low tempera-ture conditions. Moreover, mixing the electroactive material according to the invention contained within the anode and cathode zone does not result in an irreversible deactivation of the power cell, allowiny repeated charging.
The subject o~ this invention is closer described in fol-lowing examples of preferred embodiments, which do not however limi~ the scope of ~his invention~ The enclosed Fig, l and Fig. 2 display cyclic voltammetry curves obtained in condi-~ions described in Examples I and II, respectively.
Example I.
The electrDactivs material for power cells composed of a csmplex c~mpound o, nickel (Ni(II)) and N, N ~ethylene~bis (salicylidenoimine)~ salen) di-ssolved in a O.lM ~C2H5)4 NCl04 -(TEAP) solution in N,N-dimethyl~ormamide (DI~F3. The s~lution was deoxidized by purging with dry nitrogen~ The electrodes were made o~ platinum wire 0.6 ~m in diameter and 8 mm long, The cell dia~ram before charging was:
Pt¦Ni(sale~ (O~lM TEAP in Dl~lr)l Ni (salen),(O.l~1 TEAP in DMF)¦Pt The difference of standard electrode ,ootentials in this cell was, ~ E~ = 2.46 V.
During charging and work, the ~0 = -l.59 V and k = 0.71 x lO 2 cm/s on cathode, and Eo = +0.~7 V and k~ = 0.72 x lO 2 cm~s on anodeO Potential sweep rate, Vp =
= 5~ mV/s, temperature 25 C, Ni (salen) concentration:
2 x lO 311 Stanoard potentials to, relati.ve to saturated calomel electrode, SC~, v~ere determin2d as arithmetic means of anode and cathode peal~ poten~ials /Fig. l/, while the standard of rate constants charge exchange, I~s, were calculated using Nicholson method /~.nal~ Chem. 44, 19.6;(1955)/ from the re~
lation between the anode and cathode pea!c potentials, Example IIo The electroac~ive material f3r power cells ~omposed of N,N -ethylene-bis (salicylidenoiminate)-cobalt(II)-(Co (salen)) * N,N-bis salicylidene ethylenediamine dianion dissolved ln O~l~i Tr:,`\P solutiorl :in llc~amethylphospllo-~riami~e Tile cell dia~ram beFor^ ~he cl~3rgin~ wa~:
Pt¦~o(salen)~(0~1ll T~ P ln ~-lr~lP~ Co (5alen)~(oo~ TE,~P in ~IrlPT)¦
The dirferencs oF s~andard electrode po~entials in this cell Y~as ~ 0 = 1~35 v, ~ Fter joinin~ the electl~odes ~cnar~in~ and worlc~, ~-0 a le20 V and ks ~ 0~4~ x 10 2 cm~s on ca~hode, and Eo = ~0 rl5 V~ kS = ~20 x lo 2 cm/5 on anode e Potentials ~ and rate constan-ts Qf C)larSe exchan~c were determined as in Fx3Mple ~0 The cyclic voltammetry curve ~i'ig~ 2~ was recorded in Followiny conditions:
Co(salen) concentraticn: 2 x ~0 3~1 ~otential sweep rate: ~0 mV/s Temperature: 20 C
r
lation between the anode and cathode pea!c potentials, Example IIo The electroac~ive material f3r power cells ~omposed of N,N -ethylene-bis (salicylidenoiminate)-cobalt(II)-(Co (salen)) * N,N-bis salicylidene ethylenediamine dianion dissolved ln O~l~i Tr:,`\P solutiorl :in llc~amethylphospllo-~riami~e Tile cell dia~ram beFor^ ~he cl~3rgin~ wa~:
Pt¦~o(salen)~(0~1ll T~ P ln ~-lr~lP~ Co (5alen)~(oo~ TE,~P in ~IrlPT)¦
The dirferencs oF s~andard electrode po~entials in this cell Y~as ~ 0 = 1~35 v, ~ Fter joinin~ the electl~odes ~cnar~in~ and worlc~, ~-0 a le20 V and ks ~ 0~4~ x 10 2 cm~s on ca~hode, and Eo = ~0 rl5 V~ kS = ~20 x lo 2 cm/5 on anode e Potentials ~ and rate constan-ts Qf C)larSe exchan~c were determined as in Fx3Mple ~0 The cyclic voltammetry curve ~i'ig~ 2~ was recorded in Followiny conditions:
Co(salen) concentraticn: 2 x ~0 3~1 ~otential sweep rate: ~0 mV/s Temperature: 20 C
r
Claims (4)
1. A power cell, having an electroactive material comprised of a complex of a transition metal, wherein said electroactive material is a complex of a transition metal and a schiff base dissolved in a polar organic solvent, water or their mixtures.
2. A power cell according to claim 1, wherein the transition metal is one of the following metals: nickel, cobalt, iron, chromium, manganese, copper, titanium or vanadium.
3. A power cell according to claim 3, wherein said Schiff base is an ethylenediamine derivative.
4. A power cell according to claim 1, which is a secondary electrochemical power-producing cell.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL1981234354A PL134200B1 (en) | 1981-12-21 | 1981-12-21 | Electroactive material for supply sources |
| PLP-234354 | 1981-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1192946A true CA1192946A (en) | 1985-09-03 |
Family
ID=20010961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000417567A Expired CA1192946A (en) | 1981-12-21 | 1982-12-13 | Electroactive material for power cells |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS58111268A (en) |
| CA (1) | CA1192946A (en) |
| DE (1) | DE3247309C2 (en) |
| GB (1) | GB2113208B (en) |
| IT (1) | IT1155433B (en) |
| PL (1) | PL134200B1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69432428D1 (en) * | 1993-11-17 | 2003-05-08 | Pinnacle Vrb Ltd | STABILIZED ELECTROLYTE SOLUTIONS, METHODS AND THEIR PRODUCTION AND REDOX CELLS AND BATTERIES THAT CONTAIN THESE SOLUTIONS |
| US6468688B2 (en) | 1995-05-03 | 2002-10-22 | Pinnacle Vrb Limited | High energy density vanadium electrolyte solutions, methods of preparation thereof and all-vanadium redox cells and batteries containing high energy vanadium electrolyte solutions |
| JP4553731B2 (en) * | 2002-10-03 | 2010-09-29 | ゲン３ パートナーズ インコーポレイテッド | Electrochemical capacitor and method of using the same |
| EP1550170B1 (en) * | 2002-10-07 | 2010-08-18 | Gen3 Partners, Inc. | Method of manufacture of an energy storage device |
| CA2647744A1 (en) | 2006-03-24 | 2007-10-04 | Gen 3 Partners, Inc. | Method for manufacturing an energy storage device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2070648A1 (en) * | 1969-10-27 | 1971-09-17 | Usm Corp | Redox fuel element |
| FR2309046A1 (en) * | 1975-04-24 | 1976-11-19 | Alsthom Cgee | PROCESS FOR THE REGULATION OF AN ELECTROCHEMICAL SYSTEM OF THE REDOX TYPE AND IMPLEMENTATION DEVICE |
| US4192910A (en) * | 1978-11-29 | 1980-03-11 | Nasa | Catalyst surfaces for the chromous/chromic redox couple |
-
1981
- 1981-12-21 PL PL1981234354A patent/PL134200B1/en unknown
-
1982
- 1982-12-06 GB GB08234730A patent/GB2113208B/en not_active Expired
- 1982-12-13 CA CA000417567A patent/CA1192946A/en not_active Expired
- 1982-12-20 IT IT24868/82A patent/IT1155433B/en active
- 1982-12-20 JP JP57223651A patent/JPS58111268A/en active Pending
- 1982-12-21 DE DE3247309A patent/DE3247309C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT8224868A1 (en) | 1984-06-20 |
| DE3247309C2 (en) | 1985-04-25 |
| PL134200B1 (en) | 1985-07-31 |
| IT1155433B (en) | 1987-01-28 |
| GB2113208A (en) | 1983-08-03 |
| IT8224868A0 (en) | 1982-12-20 |
| PL234354A1 (en) | 1983-07-04 |
| JPS58111268A (en) | 1983-07-02 |
| GB2113208B (en) | 1985-09-04 |
| DE3247309A1 (en) | 1983-06-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |