EP0036118A2
Expired / Lapsed
EP
⏱️ 0.0 years remaining
Secondary batteries based on reversible electrochemical doping of conjugated polymers
Assignee: University Patents Inc
•
Filing: 1981-02-28
•
Granted: —
•
Expires: 2001-02-28
Abstract
Abstract Reversible electrochemical doping of conjugated polymers is carried out in an electrochemical cell wherein the polymer to be doped is employed as one or both of the electrodes, and the electrolyte is a compound which is ionizable into ionic dopant species. Upon operation of the cell, the conjugated polymers are doped with the ionic dopant species to a preselected room temperature electrical conductivity ranging from that characteristic of semiconductor behavior to that characteristic of metallic behavior. The electrochemically doped or dopable conjugated polymers are employed as one or both of the electrodes of novel lightweight secondary batteries in which the electrochemical doping reactions and their reverse electrochemical undoping reactions are utilized as the charging and discharging mechanisms.
Inventors
- 👤 Alan G. Macdiarmid
- 👤 Alan J. Heeger
- 👤 Paul J. Nigrey
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-09 13:24
CPC Classifications
H; H01; H01M; H01M10/00; H01M10/36; H01B; H01B1/00; H01B1/06; H01B1/12; H01B1/124; H01B1/125; H10; H10K; H10K71/00; H10K71/30; Y; Y02; Y02E; Y02E60/00; Y02E60/10; Y02P; Y02P70/00; Y02P70/50
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
289 words
A method for modifying the electrical conductivity properties of a conjugated polymer which is dopable with dopant species to a more highly electrically conducting state so as to provide said polymer with a preselected room temperature electrical conductivity ranging from that characteristic of semiconductor behavior to that characteristic of metallic behavior, being characterized in that the conjugated polymer is doped with ionic dopant species by reversible electrochemical procedures comprising the steps of: (a) providing an electrochemical cell comprising an anode means, a cathode means, and an electrolyte, the anode means and/or the cathode means including said dopable conjugated polymer as their electrode-active material, said electrolyte comprising a compound which is ionizable into one or more of said ionic dopant species, said dopant species being an anionic species when said polymer is used as the anode-active material, and said dopant species being a cationic species when said polymer is used as the cathode-active material; - (b) operating said electrochemical cell so as to effect a change in the oxidation state of said polymer by electron transfer from said polymer when said polymer is used as the anode-active material and by electron transfer to said polymer when said polymer is used as the cathode-active material, whereby said polymer becomes doped with said ionic dopant species to a degree dependent upon the degree of change effected in said oxidation state of said polymer and the dopant species concentration in said electrolyte; and (c) coordinating and controlling the degree of change effected in said oxidation state of said polymer and the dopant species concentration in said electrolyte so that the corresponding degree of doping will be such as to provide the resulting doped polymer with said pre- ' selected room temperature electrical conductivity.
Claim 2
Independent Claim
289 words
A method for modifying the electrical conductivity properties of a conjugated polymer which is dopable with dopant species to a more highly electrically conducting state so as to provide said polymer with a preselected room temperature electrical conductivity ranging from that characteristic of semiconductor behavior to that characteristic of metallic behavior, being characterized in that the conjugated polymer is doped with ionic dopant species by reversible electrochemical procedures comprising the steps of: (a) providing an electrochemical cell comprising an anode means, a cathode means, and an electrolyte, the anode means and/or the cathode means including said dopable conjugated polymer as their electrode-active material, said electrolyte comprising a compound which is ionizable into one or more of said ionic dopant species, said dopant species being an anionic species when said polymer is used as the anode-active material, and said dopant species being a cationic species when said polymer is used as the cathode-active material; - (b) operating said electrochemical cell so as to effect a change in the oxidation state of said polymer by electron transfer from said polymer when said polymer is used as the anode-active material and by electron transfer to said polymer when said polymer is used as the cathode-active material, whereby said polymer becomes doped with said ionic dopant species to a degree dependent upon the degree of change effected in said oxidation state of said polymer and the dopant species concentration in said electrolyte; and (c) coordinating and controlling the degree of change effected in said oxidation state of said polymer and the dopant species concentration in said electrolyte so that the corresponding degree of doping will be such as to provide the resulting doped polymer with said pre- ' selected room temperature electrical conductivity.
Claim 3
Dependent Claim
13 words
The method of claim 1, wherein said conjugated polymer is an acetylene polymer.
Claim 4
Independent Claim
46 words
The method of claims 1 and 2, wherein said anionic dopant species is selected from the group consisting of halide ions, ClO 4 , PF 6 - , AsF 6 , AsF 4 - , SO 3 CF 3 - , and BF 4 - ,
Claim 5
Independent Claim
28 words
The method of claims 1 and 2, wherein said cationic dopant species is a metallic cation of a metal whose Pauling electronegativity value is no greater than 1.6.
Claim 6
Independent Claim
59 words
The method of claims 1 and 2, wherein said cationic dopant species is an organic cation selected from the group consisting of R 4-x MH x + and R 3 E+ , wherein R is alkyl or aryl, M is N, P or As, E is 0 or S, and x is an integer ranging from 0 to 4.
Claim 7
Independent Claim
55 words
The method of claims 1 and 2, wherein said electrochemical cell is a voltaic cell whose cathode-active material is said conjugated polymer and whose anode-active material is a metal whose Pauling electronegativity value is no greater than 1.0, and said conjugated polymer becomes doped with said cationic dopant species to an n-type electrically conducting material.
Claim 8
Independent Claim
15 words
The method of claims 1 to 5, wherein said electrochemical cell is an electrolytic cell.
Claim 9
Dependent Claim
52 words
The method of claim 7, wherein said conjugated polymer is used as both the anode-active material and the cathode-active material of said electrolytic cell and the anode-active material and the cathode-active material are opposite surfaces of the same unitary mass of conjugated polymer, and said electrolyte is impregnated within said conjugated polymer.
Claim 10
Dependent Claim
85 words
An n-type electrically conducting polymeric material comprising a conjugated polymer doped to a controlled degree with a cationic dopant species characterized in that the conjugated polymer is doped with a non-metallic dopant cation selected from the group consisting of ' R 4-x MH x + and R 3 E + , wherein R is alkyl or aryl, M is N, P or As, E is 0 or S, and x is an integer ranging from 0 to 4, according to the method of claim 5.
Claim 11
Dependent Claim
160 words
A secondary battery comprising an electrolyte and, as electrode means, an anode means and a cathode means, the battery being characterized in that said electrolyte comprises a compound which is ionizable into one or more ionic dopant species selected from the group consisting of an anionic dopant species and a cationic dopant species, and that at least one of said electrode means includes as its electrode-active material a conjugated polymer doped with said cationic dopant species to an n-type electrically conducting material, a conjugated polymer doped with said anionic dopant species to a p-type electrically conducting polymer, or a conjugated polymer which is dopable either with said anionic dopant species to a higher oxidation state or with said cationic dopant species to a lower oxidation state, with the proviso that the cathode-active material may be a polypyrrole-iodine charge transfer complex only when the anode-active material is a conjugated polymer in a lower oxidation state than the cathode-active anion-doped conjugated polymer.
Claim 12
Dependent Claim
160 words
A secondary battery comprising an electrolyte and, as electrode means, an anode means and a cathode means, the battery being characterized in that said electrolyte comprises a compound which is ionizable into one or more ionic dopant species selected from the group consisting of an anionic dopant species and a cationic dopant species, and that at least one of said electrode means includes as its electrode-active material a conjugated polymer doped with said cationic dopant species to an n-type electrically conducting material, a conjugated polymer doped with said anionic dopant species to a p-type electrically conducting polymer, or a conjugated polymer which is dopable either with said anionic dopant species to a higher oxidation state or with said cationic dopant species to a lower oxidation state, with the proviso that the cathode-active material may be a polypyrrole-iodine charge transfer complex only when the anode-active material is a conjugated polymer in a lower oxidation state than the cathode-active anion-doped conjugated polymer.
Claim 13
Dependent Claim
13 words
The battery of claim 10, wherein said conjugated polymer is an acetylene polymer.
Claim 14
Dependent Claim
18 words
The battery of claims 10 and 11, wherein said conjugated polymer is in the form of a film.
Claim 15
Dependent Claim
116 words
The battery of claims 10 to 12, wherein said anionic dopant species is selected from the group consisting of halide ions, ClO 4 - , PF 6 - , AsF 6 - , AsF 4 - , SO 3 CF 3 - , and BF 4 - , and said cationic dopant species is a metallic cation of a metal whose Pauling electronegativity value is no greater than 1.6 or a non-metallic cation selected from the group consisting of R 4-x MH x - and R 3 E+ , wherein R is alkyl or aryl, M is N, P or As, S is 0 or S, and x is an integer ranging from 0 to 4.
Claim 16
Dependent Claim
28 words
The battery of claims 10 to 13, wherein said ionizable compound is a halide, perchlorate or hexafluorophosphate salt of either an alkali metal or a tetraalkyl ammonium cation.
Claim 17
Dependent Claim
35 words
The battery of claims 10 to 14, wherein the anode-active material is a metal whose Pauling electronegativity value is no greater than 1.0, and the cathode-active material is said cation-doped, anion-doped or dopable conjugated polymer.
Claim 18
Dependent Claim
9 words
The battery of claim 15, wherein said'metal is lithium.
Claim 19
Dependent Claim
26 words
The battery of claims 10 to 14, wherein the anode-active material and the cathode-active material are each one of said anion-doped, cation-doped or dopable conjugated polymer.
Claim 20
Dependent Claim
23 words
The battery of claim 17, wherein the anode-active conjugated polymer and the cathode-active conjugated polymer are each in substantially the same oxidation state.
Claim 21
Dependent Claim
44 words
The battery of claim 17, wherein the anode-active material is a conjugated polymer doped with a cationic dopant species to an n-type electrically conducting material, and the cathode-active material is a conjugated polymer in a higher oxidation state than the anode-active cation-doped conjugated polymer.
Claim 22
Dependent Claim
25 words
The battery of claim 19, wherein said cathode-active material is a conjugated polymer doped with an anionic dopant species to a p-type electrically conducting material.
Claim 23
Dependent Claim
42 words
The battery of claim 19, wherein said anode-active material and said cathode-active material are each said cation-doped conjugated polymer but having different degrees of doping, said anode-active cation-doped conjugated polymer having a higher degree of doping than said cathode-active cation-doped conjugated polymer.
Claim 24
Dependent Claim
44 words
The battery of claim 17, wherein the cathode-active material is a conjugated polymer, doped with an anionic dopant species to a p-type electrically conducting material, and the anode-active material is a conjugated polymer in a lower oxidation state than the cathode-active anion-doped conjugated polymer.
Claim 25
Dependent Claim
42 words
The battery of claim 22, wherein said anode-active material and said cathode-active material are each said anion-doped conjugated polymer but having different degrees of doping, said cathode-active anion-doped conjugated polymer having a higher degree of doping than said anode-active anion-doped conjugated polymer.
Claim 26
Dependent Claim
57 words
The battery of claims 17 to 23, wherein said anode-active material and said cathode-active material are formed respectively as the two opposite surface layers of a three-layered unitary mass of conjugated polymer whose central layer constitutes said conjugated polymer impregnated with said electrolyte and in an oxidation state intermediate between those of said anode-active and cathode-active materials.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
Maintenance schedule is calculated for granted US utility patents.