CA1230874A - Solid electrolyte cell and iodine-doped metal complexes as the cathode material - Google Patents
Solid electrolyte cell and iodine-doped metal complexes as the cathode materialInfo
- Publication number
- CA1230874A CA1230874A CA000470805A CA470805A CA1230874A CA 1230874 A CA1230874 A CA 1230874A CA 000470805 A CA000470805 A CA 000470805A CA 470805 A CA470805 A CA 470805A CA 1230874 A CA1230874 A CA 1230874A
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- Prior art keywords
- iodine
- formula
- solid electrolyte
- electrolyte cell
- complexes
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/10—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/182—Cells with non-aqueous electrolyte with solid electrolyte with halogenide as solid electrolyte
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
Solid electrolyte cell and iodine-doped petal complexes as the cathode material Abstract Charge-transfer complexes of the formula I
(I) IMAGE
in which M represents a divalent metal atom, R1 to R6 represent a range of hydrocarbon groups, and x represents a number from 1 to 300 are suitable as cathode material in lithium/iodine or silver/iodine solid electrolyte cells.
(I) IMAGE
in which M represents a divalent metal atom, R1 to R6 represent a range of hydrocarbon groups, and x represents a number from 1 to 300 are suitable as cathode material in lithium/iodine or silver/iodine solid electrolyte cells.
Description
~lX~Q~7~
6-14715/+
Solid electrolyte cell and iodine-doped metal complexes as the cathode material The present invention relates to a solid electrolyte cell having solid lithium or silver as the anode, a solid lithium iodide or silver ode as the electrolyte and an iodine-doped dibenzotetraaza[14]annulene metal complex as the cathode material and to metal complexes of this type and a process for their preparation.
The use of organic charge-transfer complexes as the cathode material in solid electrolyte cells is known. Iodine-doped polymers, for example polyvinylpyridine (PUP) and polyp vinylquinol;ne ~PVQ), have proved to be complexes of ;ndus-trial interest. Over and above the iodine attached as a come pled, these materials can additionally contain molecular iodine up to a total content of 124 moles of It per mole of monomer (cf. US Patent Specification 4,340,651).
It is mentioned in Japanese Patent Publication So 56-30,261 that these materials are semi-solid to pasty and can therefore only be processed with difficulty. The tab-letting of the materials in particular poses difficulties.
As a rule, cathodes of PVP-I2 are cast at an elevated tempera-I lure. Only at iodine contents up to not more than 30 moles of It per mole of vinylpyridine is it possible to mix the material in the solid state and to tablet it without deli-quiescence. However, these materials which have been mixed in the solid state from PUP and It, have high initial resistance values which take months to decrease again (cf. US Patent Specification 4,148,975). The cons-quince of this is that solid electrolyte cells containing these cathode materials have very high initial resistance values, and only maintain a usable potential at a slow disk charge in the region of a few PA Avery high Load resistance values).
In the Japanese Patent Publication So 56-30,261 already mentioned, charge-transfer complexes of iodine or brow mine and phthalocyanine petal complexes are suggested as cathode material for lithium cells. The doping with iodine takes place very slowly ether in organic solvents or using gaseous iodine, and can take up to a month. The amounts of iodine taken up are relatively small, which leads to a short working life for the batteries, which also only have a low energy density.
It has now been found that iodine-doped dibenzotetra-azaC14]annuLene metal complexes are excellently suitable as cathode material in lithium/iodine solid electrolyte cells.
The complexes can be prepared easily, can be doped with iodine within short periods and have a high conductivity even at high iodine contents. In add ton higher energy dens;-toes are achieved, on comparison with the phthalocyanine come plexus. The complexes are also observed to have, as soon as they have been prepared, only a low initial resistance value, Z5 which decreases even further on the course of short periods of time in the case of charge-transfer complexes prepared by mixing or grounding the solid reactants, thus decrease having, however, no appreciable effect on the internal resistance of a battery The present invention relates to a solid electrolyte cell containing a solid anode made of lithium or silver, a solid lithium iodide or solver iodide electrolyte and a charge-transfer complex consisting of a metal complex, and iodine as the cathode, wherein the cathode consists of an iodine-doped complex or a mixture thereof with iodine having the formula I
~l;23~
/-~
R \ A., x 12 tip 5/ /- y of I
I./
in which M is a diva lent metal atom belonging to the group consisting of Fe, Co, Nix Cut Zen, Pod and Pi, R1 and R2 independently of one another are a hydrogen atom or alkyd, cycloalkyl, aureole, aralkyl, alkaralkyl or azalea each of which is unsubstituted or substituted, R3, R4, R5 anrJ R6 index pendently of one another are a hydrogen atom, alkyd, alkoxy, alkylthio and alkoxycarbonyl having 1 to 8 C atoms in the allele cur ~lkoxy group, airlocks or halogen, or R end R and also R5.llll I to-getter arc -~C112 in which no 4 or I -O Clue O- in which m = 1-4, or a radical of the formula -CH=CH-CH=CH- and x is a rational number from 1 to 30û.
The complex of the formula I expresses the fact that a partial, non-integral charge transfer has taken place bet-teen the metal complex and part of the iodine and that fur-then excess iodine can be present in a molecular form.
In formula I, M is preferably Fe and especially Cut or Nix R1 and R2 are preferably identical substituents and the same is true for R3 to R6.
As alkyd, R1 and R2 can be linear or branched and preferably contain 1 to 6, especially 1 to 4, C atoms.
Examples are Huxley, ponytail, t-butyl, sec.-butyl, n-butyl, n-propyl, i-propyl and especially ethyl and methyl.
As cycloalkyl, R1 and RZ preferably contain 5 or o ring carbon atoms and can be, for example, Cyclopentyl or cyclohexyl.
As azalea, R1 and R2 preferably contain 2 to 6, en-specially 2 to 4, C atoms and can be, for example, acutely, propionyl or Ben owl. Examples of suitable substations for ~3~87~
R1 and R2 are halogen, such as Bra Of and F, or alkoxy which preferably has 1 to 4 C atoms.
As aureole, R1 and R2 are preferably phenol which can be substituted, for example, by halogen, especially Of and F, or alkoxy having 1 to 4 C atoms, especially methoxy.
The substituents are preferably located in the para-position.
As alkaryl, R1 and R2 are preferably alkylphenyl, especially p-alkylphenyl which preferably has 1 to 4 C atoms in the alkyd group. Examples are p-butylphenyl, p-propylphe-nil, p-ethylphenyl and especially p-methylphenyl.
As alkaralkyl, R1 and R2 are preferably alkylbenzyl which preferably has 1 to 4 C atoms in the alkyd group, en-specially p-alkylbenzyl, for example p-methylben~yl.
A preferred subgroup of the complexes of the formula I is formed by those in which R3 to R6 are a hydrogen atom and R1 and R2 are a hydrogen atom or alkyd, cycloalkyl, aureole, aralkyl, alkaralkyl or azalea.
As alkyd, alkoxy, alkylthio and alkoxycarbonyl, R3 to R6 preferably contain 1 to 4 C atoms and can be linear or branched. Examples are n-butyl, sec.-butyl, t-but~l, n-propel, propel, buttocks, propoxy, ethics, butylthio, propel-trio, ethylth;o, methoxycarbonyl, ethoxycarbonyl and en-specially methyl, ethyl, methoxy and methylthio. R3 and R4 and also R5 and R6 together are preferably -SHEA, -OUCH-, -OCH2CH20- or -CH=CH-CH=CH-. As airlocks, R3 to R6 are preferably phonics, and as halogen, they are pro-fireball Of and especially F.
In a preferred embodiment, R1 to R6 independently of one another are a hydrogen atom or one of the hydrocarbon groups previously defined, especially alkyd.
In formula I, x can preferably be a number from 1 to 200, especially 1 to 100 and particularly 2 to 50.
In a preferred embodiment, the cathode material con-sits of complexes of the formula I in which R1 to R6 index pendently of one another are a hydrogen atom or methyl Andy is Cut or Nix Complexes of the formula I in which x is a number not ~;~3~B~4 less than 5, preferably not less than 10, are novel. In these complexes, where is an excess of iodine, so that the charge-transfer complexes are distributed within a matrix of iodine. These mixtures surprisingly also have a high conduct S tivity and are distinguished by a low resistance value winced as cathode material in batteries.
The present invention also relates to an iod;ne-doped complex or a mixture thereof with iodine which has the for-mute II
R ~R3 I /! y My I! ! Y 2 IT
~.~
in which M us a diva lent metal atom belonging to the group consisting of Fe, Co, Nix Cut Zen, Pod and Pi, R1 and R2 independently of one another are a hydrogen atom or alkyd, cycloalkyl, aureole, aralkyl, alkaralkyl or azalea each of which is unsubstituted or substituted, R3, R4, R5 and R6 index pendently of one another are a hydrogen atom, alkyd, alkoxy, alkylth;o and alkoxycàrbonyl having 1 to 8 C atoms airlocks or halogen, or R3 and R4 and also R5 and R6 together are -SHEA- in which n = 3, 4 or 5, -SHEA 0- in which m = 1 to 4, or a radical of the formula -CH=CH-CH=CH-, and y is a rational number from 5 to 300.
The same preferences as for the complexes of the for-mute I apply to the complexes of the formula II. The number y is preferably S to 200, especially 5 to 100 and portico-laxly 5 to 50. The number y was also the number x in formula) indicates the molar ratio of metal complex to molecular iodine.
The preparation of the iodine-doped complexes or mix-lures thereof with iodine having the formulae I and II i s I effected in a manner known per so by oxidizing a metal come pled of the formula III
37~
R
,!~
R ~R3 I.
in which M and R1 to R6 are as defined above, by means of x or y moles ox molecular iodine and, if appropriate, sub-sequently mixing the resulting charge-transfér complexes with iodine.
S The metal complexes of the formula Ill are known Helvetica Comic Act, Volume 64, Issue 8, pages 2544-2554 (1981)] or can be prepared by analogous processes. Charge-transfer complexes having up to 4 moles of molecular iodine are also described therein.
The oxidation is preferably carried out under an atmosphere of a protective gas and with the exclusion of moisture. Various embodiments are possible for the ox-ration by means of iodine. Iodine vapor can be alloyed to act at room temperature on a solid metal complex of the for-mute III until no further absorption of iodine takes place, or the two components can be reacted with one another in the gaseous state at an elevated temperature in a co-sublimation process. It is more advantageous to carry out the oxidation in suitable inert solvents, preferably in polar, aprotic or-I genie solvents. In general, this process gives charge-trans-for complexes which have a definite stoichiometry and a cry-Tulane to pulverulent form and which can have a molar ratio of metal complex to molecular iodine of up to about 1:8.
In order to achieve higher iodine contents, the charye-transfer complexes thus obtained can be mixed with iodine in the desired ratio, for example in customary mixers equipped with high-speed stirring equipment, and advantage-ouzel in the melt at high iodine contents. In the case of dry powders, preparation by intensive grinding is also ~3q~37~
possible.
It is simpler to mix the metal complexes of the for mute III directly with iodine in the desired ratio; this is preferably carried out under an atmosphere of a protective gas and with the exclusion of moisture. Up to an iodine con-tent of about 2û moles of molecular iodine per mole of metal complex of the formula III, mixing by, for example, intensive grinding is possible, since solid, pulverulent products are formed. At higher iodine contents, the behavior of the so-lid is increasingly determined by the soft, plastic iodine and the mixing is more advantageously carried out in the melt.
The reaction times required for the formation of the charge-transfer complexes are within the range from minutes to a few hours, which is very efficient from the economic point of view.
The charge-transfer complexes or mixtures thereof with iodine having the formulae I and II are black solids which have an electrical conductivity within the range from 1û 1 to about 10 4 S cm 1. They can be processed easily and are excellently suitable for use as cathode material in l;th;um/;odine or silver/iodine solid electrolyte cells batteries).
The batteries can be constructed in various shapes, for example as button cells, as flat foil batteries or Solon-Dracula batteries or in the form of fairly large batteries which can also contain several cells. The batteries consist of a can of electrically conducting material which is inert towards the cathode material. This can be metals or metal alloys, for example stainless steel or chrome-nickel steel.
The lid of the battery also consists of such materials. The anode, consisting of lithium or silver, and the cathode, con-sting of the complexes of the formula I, are located bet-wren the lid and the can. The solid electrolyte layer, con-sting of HI or Ago, develops of itself into an inter-mediate layer as a result of connecting the anode and cathode The lid and can are sealed by means of a suitable sealing composition, for example a composition made of plastics, ~3~3~37~
such as polypropylene.
Figure 1 shows a partial view of a battery construe-ted in the form of a button cell.
Figure 2 shows the discharge curves of 3 button cells at different rates of current supply; (dbtaa) represents dip benzotetraazaannulene.
The batteries are prepared in a known manner by as-symboling the individual constituents with the application of pressure under an atmosphere of a protective gas and with the exclusion of moisture.
The cathodes can be prepared in a known manner, for example by compressing the iodine-doped complexes or mixtures thereof with iodine having the formula I to give, for example, tablets or other shapes. Dry powders are particularly suit-able for this process. It is therefore preferable to usecharge-transfer complexes having an iodine content of 2 to 50, especially 2 to 20, moles of molecular iodine per mole of metal complex of the formula III. Conductive materials which improve the electrical contact between the can and the cathode, for example wire netting made of metals, can be con-comitantly incorporated into the cathode and can also be spot-welded to the can. The charge-transfer complexes of the formula I and mixtures thereof with iodine can also be em-plowed as a casting composition for the production of various shapes of cathode.
The batteries according to the invention are destiny-gushed by a relatively long working life. A conceivable destruction caused by iodine, observable by exudation of iodine, is not found over a prolonged period of time. The potential achievable (open-circuit voltage, OCV) is I V and the internal resistance values for button cells of size 2016 in the non-discharged state are approximately between 0.2 and 1.2 kilo ohms.
The batteries according to the invention can be used for the operation of electrical equipment having a lo cur-rent consumption. In the form of button batteries they can be employed in electronic clocks or electronic calculators, I
for example as a memory back-up.
The following examples illustrate the invention in greater detail.
A) Preparation Examples 1-15:
The charge-transfer complexes described in Table 1 below are prepared by the following methods a) Preparation by mixing in an iodine melt 1.7 9 of metal complex of the formula III and iodine corresponding to the molar ratios indicated in Table 1 are put into a 0.3 lithe glass insert in an autoclave, with the exclusion of moisture and under argon, and the autoclave is closed. Stirring is then carried out for 1 hour and the melt is then cooled.
b) Preparation by mixing the components in prouder f_ 5 9 of metal complex of the formula III and iodine corresponding to the molar ratios in Table 1 are mixed, with the exclusion of water, in a laboratory mixer for 2 minutes at full revolution. The conductivity values after storage Z0 for 3 days are shown in Table 1.
- 1 0 - ~30~374 ..
Jo Tao i to I to N
owe_ Oily Jo E X X X X X X X X X X X X X x O I I) i cry Jo a 1` I kiwi .. . _.
O N N Us . or) CO (I
I N Us i I N i it N N N
I
. JO .
Jo MY X X
W
_ _ __ .. _ ___ I . _ _ O to u I: o X X Jo X I C7 I X X X O
o ' _ .. I .
QJ I _ I
E - _ .-._ --- - -- I - -- - I--O I X X X Z X I X 3: Z Z
_ _ _ _ . _ . .
S 'I; 'Z 'Z Z 'Z 'Z 'Z 'Z I 'Z 'Z 'Z 'Z
_ . _ . .__ _ L
o I pa I I it I Jo or I on Jo I I
D ¦ E O
__ 12~0~74 B) Use Examples 16-Z5:
The complexes of the formula I or mixtures with iodine listed on Table 2 below are prepared by method a (Examples 16 and 17) and by method b examples 14, 15 and 18-23) and are compressed under a pressure of 147 Ma to give pellets of diameter 15.9 mm and thickness 0.8 mm. A grid of stain-less steel is then pressed into place under the same pros-sure. Button cells of thickness 1.6 mm and diameter 20 mm are then prepared in accordance with the design of Figure 1 attached.
The cathode can and the anode lid each consist of stainless steel 0.2 mm thick. The lithium anode is punched out of foil û.45 mm thick. The button cell us sealed by means of a seal composed of polypropylene. The preparation of the button cell is carried out under argon as a protective gas.
Table 2 shows the potential and the internal nests-lance value Rj of the cell in the non-discharged state, as well as the composition of the cathode material.
3~)8~4 Jo X I I
v us It O I an I
I_ o' ox o o o o o o o' I !
Jo I I I o o o o Us o o O 0, I Cub US CO CO I
(I N
, , X o O O Us Us O O O
ED
X X S S
._ I S X
E
I S S X X S X X S
_ _ _ . _, X X 5: X
ox _ _ .. ___ E to X X I: 5: Ox I 3 S X
_ -IVY S X OX I I I COCK
_ Jo 'Z Z 'Z Z Z Z Z Z Z Z
__., . ._ __ .._.._ .
N
_ . E Z ,, _, _, NO N N us .
6-14715/+
Solid electrolyte cell and iodine-doped metal complexes as the cathode material The present invention relates to a solid electrolyte cell having solid lithium or silver as the anode, a solid lithium iodide or silver ode as the electrolyte and an iodine-doped dibenzotetraaza[14]annulene metal complex as the cathode material and to metal complexes of this type and a process for their preparation.
The use of organic charge-transfer complexes as the cathode material in solid electrolyte cells is known. Iodine-doped polymers, for example polyvinylpyridine (PUP) and polyp vinylquinol;ne ~PVQ), have proved to be complexes of ;ndus-trial interest. Over and above the iodine attached as a come pled, these materials can additionally contain molecular iodine up to a total content of 124 moles of It per mole of monomer (cf. US Patent Specification 4,340,651).
It is mentioned in Japanese Patent Publication So 56-30,261 that these materials are semi-solid to pasty and can therefore only be processed with difficulty. The tab-letting of the materials in particular poses difficulties.
As a rule, cathodes of PVP-I2 are cast at an elevated tempera-I lure. Only at iodine contents up to not more than 30 moles of It per mole of vinylpyridine is it possible to mix the material in the solid state and to tablet it without deli-quiescence. However, these materials which have been mixed in the solid state from PUP and It, have high initial resistance values which take months to decrease again (cf. US Patent Specification 4,148,975). The cons-quince of this is that solid electrolyte cells containing these cathode materials have very high initial resistance values, and only maintain a usable potential at a slow disk charge in the region of a few PA Avery high Load resistance values).
In the Japanese Patent Publication So 56-30,261 already mentioned, charge-transfer complexes of iodine or brow mine and phthalocyanine petal complexes are suggested as cathode material for lithium cells. The doping with iodine takes place very slowly ether in organic solvents or using gaseous iodine, and can take up to a month. The amounts of iodine taken up are relatively small, which leads to a short working life for the batteries, which also only have a low energy density.
It has now been found that iodine-doped dibenzotetra-azaC14]annuLene metal complexes are excellently suitable as cathode material in lithium/iodine solid electrolyte cells.
The complexes can be prepared easily, can be doped with iodine within short periods and have a high conductivity even at high iodine contents. In add ton higher energy dens;-toes are achieved, on comparison with the phthalocyanine come plexus. The complexes are also observed to have, as soon as they have been prepared, only a low initial resistance value, Z5 which decreases even further on the course of short periods of time in the case of charge-transfer complexes prepared by mixing or grounding the solid reactants, thus decrease having, however, no appreciable effect on the internal resistance of a battery The present invention relates to a solid electrolyte cell containing a solid anode made of lithium or silver, a solid lithium iodide or solver iodide electrolyte and a charge-transfer complex consisting of a metal complex, and iodine as the cathode, wherein the cathode consists of an iodine-doped complex or a mixture thereof with iodine having the formula I
~l;23~
/-~
R \ A., x 12 tip 5/ /- y of I
I./
in which M is a diva lent metal atom belonging to the group consisting of Fe, Co, Nix Cut Zen, Pod and Pi, R1 and R2 independently of one another are a hydrogen atom or alkyd, cycloalkyl, aureole, aralkyl, alkaralkyl or azalea each of which is unsubstituted or substituted, R3, R4, R5 anrJ R6 index pendently of one another are a hydrogen atom, alkyd, alkoxy, alkylthio and alkoxycarbonyl having 1 to 8 C atoms in the allele cur ~lkoxy group, airlocks or halogen, or R end R and also R5.llll I to-getter arc -~C112 in which no 4 or I -O Clue O- in which m = 1-4, or a radical of the formula -CH=CH-CH=CH- and x is a rational number from 1 to 30û.
The complex of the formula I expresses the fact that a partial, non-integral charge transfer has taken place bet-teen the metal complex and part of the iodine and that fur-then excess iodine can be present in a molecular form.
In formula I, M is preferably Fe and especially Cut or Nix R1 and R2 are preferably identical substituents and the same is true for R3 to R6.
As alkyd, R1 and R2 can be linear or branched and preferably contain 1 to 6, especially 1 to 4, C atoms.
Examples are Huxley, ponytail, t-butyl, sec.-butyl, n-butyl, n-propyl, i-propyl and especially ethyl and methyl.
As cycloalkyl, R1 and RZ preferably contain 5 or o ring carbon atoms and can be, for example, Cyclopentyl or cyclohexyl.
As azalea, R1 and R2 preferably contain 2 to 6, en-specially 2 to 4, C atoms and can be, for example, acutely, propionyl or Ben owl. Examples of suitable substations for ~3~87~
R1 and R2 are halogen, such as Bra Of and F, or alkoxy which preferably has 1 to 4 C atoms.
As aureole, R1 and R2 are preferably phenol which can be substituted, for example, by halogen, especially Of and F, or alkoxy having 1 to 4 C atoms, especially methoxy.
The substituents are preferably located in the para-position.
As alkaryl, R1 and R2 are preferably alkylphenyl, especially p-alkylphenyl which preferably has 1 to 4 C atoms in the alkyd group. Examples are p-butylphenyl, p-propylphe-nil, p-ethylphenyl and especially p-methylphenyl.
As alkaralkyl, R1 and R2 are preferably alkylbenzyl which preferably has 1 to 4 C atoms in the alkyd group, en-specially p-alkylbenzyl, for example p-methylben~yl.
A preferred subgroup of the complexes of the formula I is formed by those in which R3 to R6 are a hydrogen atom and R1 and R2 are a hydrogen atom or alkyd, cycloalkyl, aureole, aralkyl, alkaralkyl or azalea.
As alkyd, alkoxy, alkylthio and alkoxycarbonyl, R3 to R6 preferably contain 1 to 4 C atoms and can be linear or branched. Examples are n-butyl, sec.-butyl, t-but~l, n-propel, propel, buttocks, propoxy, ethics, butylthio, propel-trio, ethylth;o, methoxycarbonyl, ethoxycarbonyl and en-specially methyl, ethyl, methoxy and methylthio. R3 and R4 and also R5 and R6 together are preferably -SHEA, -OUCH-, -OCH2CH20- or -CH=CH-CH=CH-. As airlocks, R3 to R6 are preferably phonics, and as halogen, they are pro-fireball Of and especially F.
In a preferred embodiment, R1 to R6 independently of one another are a hydrogen atom or one of the hydrocarbon groups previously defined, especially alkyd.
In formula I, x can preferably be a number from 1 to 200, especially 1 to 100 and particularly 2 to 50.
In a preferred embodiment, the cathode material con-sits of complexes of the formula I in which R1 to R6 index pendently of one another are a hydrogen atom or methyl Andy is Cut or Nix Complexes of the formula I in which x is a number not ~;~3~B~4 less than 5, preferably not less than 10, are novel. In these complexes, where is an excess of iodine, so that the charge-transfer complexes are distributed within a matrix of iodine. These mixtures surprisingly also have a high conduct S tivity and are distinguished by a low resistance value winced as cathode material in batteries.
The present invention also relates to an iod;ne-doped complex or a mixture thereof with iodine which has the for-mute II
R ~R3 I /! y My I! ! Y 2 IT
~.~
in which M us a diva lent metal atom belonging to the group consisting of Fe, Co, Nix Cut Zen, Pod and Pi, R1 and R2 independently of one another are a hydrogen atom or alkyd, cycloalkyl, aureole, aralkyl, alkaralkyl or azalea each of which is unsubstituted or substituted, R3, R4, R5 and R6 index pendently of one another are a hydrogen atom, alkyd, alkoxy, alkylth;o and alkoxycàrbonyl having 1 to 8 C atoms airlocks or halogen, or R3 and R4 and also R5 and R6 together are -SHEA- in which n = 3, 4 or 5, -SHEA 0- in which m = 1 to 4, or a radical of the formula -CH=CH-CH=CH-, and y is a rational number from 5 to 300.
The same preferences as for the complexes of the for-mute I apply to the complexes of the formula II. The number y is preferably S to 200, especially 5 to 100 and portico-laxly 5 to 50. The number y was also the number x in formula) indicates the molar ratio of metal complex to molecular iodine.
The preparation of the iodine-doped complexes or mix-lures thereof with iodine having the formulae I and II i s I effected in a manner known per so by oxidizing a metal come pled of the formula III
37~
R
,!~
R ~R3 I.
in which M and R1 to R6 are as defined above, by means of x or y moles ox molecular iodine and, if appropriate, sub-sequently mixing the resulting charge-transfér complexes with iodine.
S The metal complexes of the formula Ill are known Helvetica Comic Act, Volume 64, Issue 8, pages 2544-2554 (1981)] or can be prepared by analogous processes. Charge-transfer complexes having up to 4 moles of molecular iodine are also described therein.
The oxidation is preferably carried out under an atmosphere of a protective gas and with the exclusion of moisture. Various embodiments are possible for the ox-ration by means of iodine. Iodine vapor can be alloyed to act at room temperature on a solid metal complex of the for-mute III until no further absorption of iodine takes place, or the two components can be reacted with one another in the gaseous state at an elevated temperature in a co-sublimation process. It is more advantageous to carry out the oxidation in suitable inert solvents, preferably in polar, aprotic or-I genie solvents. In general, this process gives charge-trans-for complexes which have a definite stoichiometry and a cry-Tulane to pulverulent form and which can have a molar ratio of metal complex to molecular iodine of up to about 1:8.
In order to achieve higher iodine contents, the charye-transfer complexes thus obtained can be mixed with iodine in the desired ratio, for example in customary mixers equipped with high-speed stirring equipment, and advantage-ouzel in the melt at high iodine contents. In the case of dry powders, preparation by intensive grinding is also ~3q~37~
possible.
It is simpler to mix the metal complexes of the for mute III directly with iodine in the desired ratio; this is preferably carried out under an atmosphere of a protective gas and with the exclusion of moisture. Up to an iodine con-tent of about 2û moles of molecular iodine per mole of metal complex of the formula III, mixing by, for example, intensive grinding is possible, since solid, pulverulent products are formed. At higher iodine contents, the behavior of the so-lid is increasingly determined by the soft, plastic iodine and the mixing is more advantageously carried out in the melt.
The reaction times required for the formation of the charge-transfer complexes are within the range from minutes to a few hours, which is very efficient from the economic point of view.
The charge-transfer complexes or mixtures thereof with iodine having the formulae I and II are black solids which have an electrical conductivity within the range from 1û 1 to about 10 4 S cm 1. They can be processed easily and are excellently suitable for use as cathode material in l;th;um/;odine or silver/iodine solid electrolyte cells batteries).
The batteries can be constructed in various shapes, for example as button cells, as flat foil batteries or Solon-Dracula batteries or in the form of fairly large batteries which can also contain several cells. The batteries consist of a can of electrically conducting material which is inert towards the cathode material. This can be metals or metal alloys, for example stainless steel or chrome-nickel steel.
The lid of the battery also consists of such materials. The anode, consisting of lithium or silver, and the cathode, con-sting of the complexes of the formula I, are located bet-wren the lid and the can. The solid electrolyte layer, con-sting of HI or Ago, develops of itself into an inter-mediate layer as a result of connecting the anode and cathode The lid and can are sealed by means of a suitable sealing composition, for example a composition made of plastics, ~3~3~37~
such as polypropylene.
Figure 1 shows a partial view of a battery construe-ted in the form of a button cell.
Figure 2 shows the discharge curves of 3 button cells at different rates of current supply; (dbtaa) represents dip benzotetraazaannulene.
The batteries are prepared in a known manner by as-symboling the individual constituents with the application of pressure under an atmosphere of a protective gas and with the exclusion of moisture.
The cathodes can be prepared in a known manner, for example by compressing the iodine-doped complexes or mixtures thereof with iodine having the formula I to give, for example, tablets or other shapes. Dry powders are particularly suit-able for this process. It is therefore preferable to usecharge-transfer complexes having an iodine content of 2 to 50, especially 2 to 20, moles of molecular iodine per mole of metal complex of the formula III. Conductive materials which improve the electrical contact between the can and the cathode, for example wire netting made of metals, can be con-comitantly incorporated into the cathode and can also be spot-welded to the can. The charge-transfer complexes of the formula I and mixtures thereof with iodine can also be em-plowed as a casting composition for the production of various shapes of cathode.
The batteries according to the invention are destiny-gushed by a relatively long working life. A conceivable destruction caused by iodine, observable by exudation of iodine, is not found over a prolonged period of time. The potential achievable (open-circuit voltage, OCV) is I V and the internal resistance values for button cells of size 2016 in the non-discharged state are approximately between 0.2 and 1.2 kilo ohms.
The batteries according to the invention can be used for the operation of electrical equipment having a lo cur-rent consumption. In the form of button batteries they can be employed in electronic clocks or electronic calculators, I
for example as a memory back-up.
The following examples illustrate the invention in greater detail.
A) Preparation Examples 1-15:
The charge-transfer complexes described in Table 1 below are prepared by the following methods a) Preparation by mixing in an iodine melt 1.7 9 of metal complex of the formula III and iodine corresponding to the molar ratios indicated in Table 1 are put into a 0.3 lithe glass insert in an autoclave, with the exclusion of moisture and under argon, and the autoclave is closed. Stirring is then carried out for 1 hour and the melt is then cooled.
b) Preparation by mixing the components in prouder f_ 5 9 of metal complex of the formula III and iodine corresponding to the molar ratios in Table 1 are mixed, with the exclusion of water, in a laboratory mixer for 2 minutes at full revolution. The conductivity values after storage Z0 for 3 days are shown in Table 1.
- 1 0 - ~30~374 ..
Jo Tao i to I to N
owe_ Oily Jo E X X X X X X X X X X X X X x O I I) i cry Jo a 1` I kiwi .. . _.
O N N Us . or) CO (I
I N Us i I N i it N N N
I
. JO .
Jo MY X X
W
_ _ __ .. _ ___ I . _ _ O to u I: o X X Jo X I C7 I X X X O
o ' _ .. I .
QJ I _ I
E - _ .-._ --- - -- I - -- - I--O I X X X Z X I X 3: Z Z
_ _ _ _ . _ . .
S 'I; 'Z 'Z Z 'Z 'Z 'Z 'Z I 'Z 'Z 'Z 'Z
_ . _ . .__ _ L
o I pa I I it I Jo or I on Jo I I
D ¦ E O
__ 12~0~74 B) Use Examples 16-Z5:
The complexes of the formula I or mixtures with iodine listed on Table 2 below are prepared by method a (Examples 16 and 17) and by method b examples 14, 15 and 18-23) and are compressed under a pressure of 147 Ma to give pellets of diameter 15.9 mm and thickness 0.8 mm. A grid of stain-less steel is then pressed into place under the same pros-sure. Button cells of thickness 1.6 mm and diameter 20 mm are then prepared in accordance with the design of Figure 1 attached.
The cathode can and the anode lid each consist of stainless steel 0.2 mm thick. The lithium anode is punched out of foil û.45 mm thick. The button cell us sealed by means of a seal composed of polypropylene. The preparation of the button cell is carried out under argon as a protective gas.
Table 2 shows the potential and the internal nests-lance value Rj of the cell in the non-discharged state, as well as the composition of the cathode material.
3~)8~4 Jo X I I
v us It O I an I
I_ o' ox o o o o o o o' I !
Jo I I I o o o o Us o o O 0, I Cub US CO CO I
(I N
, , X o O O Us Us O O O
ED
X X S S
._ I S X
E
I S S X X S X X S
_ _ _ . _, X X 5: X
ox _ _ .. ___ E to X X I: 5: Ox I 3 S X
_ -IVY S X OX I I I COCK
_ Jo 'Z Z 'Z Z Z Z Z Z Z Z
__., . ._ __ .._.._ .
N
_ . E Z ,, _, _, NO N N us .
Claims (9)
1. A solid electrolyte cell containing a solid anode made of lithium or silver, a solid lithium iodide or silver iodide electrolyte and a charge-transfer complex consisting of a metal complex, and iodine as the cathode, wherein the cathode consists of an iodine-doped complex or a mixture thereof with iodine having the formula I
(I) in which M is a divalent metal atom belonging to the group consisting of Fe, Co, Ni, Cu, Zn, Pd and Pt, R1 and R2 in-dependently of one another are a hydrogen atom or C1-C6-alkyl, C5-C6 cycloalkyl, phenyl, (C1-C4 alkyl)-benzyl, (C1-C4-alkyl)-phenyl, C1-C6 acyl or benzoyl each of which is unsub-stituted or substituted by halogen or C1-C4 alkoxy, R3, R4, R5 and R6 independently of one another are a hydrogen atom, alkyl, alkoxy, alkylthio and alkoxycarbonyl having 1 to 8 C atoms in the alkyl or alkoxy group, phenoxy or halogen, or R3 and R4 and also R5 and R6 together are in which n=3, 4 or 5, in which m = 1 to 4 or a radical of the formula -CH=CH-CH=CH-, and x is a rational number from 1 to 300.
(I) in which M is a divalent metal atom belonging to the group consisting of Fe, Co, Ni, Cu, Zn, Pd and Pt, R1 and R2 in-dependently of one another are a hydrogen atom or C1-C6-alkyl, C5-C6 cycloalkyl, phenyl, (C1-C4 alkyl)-benzyl, (C1-C4-alkyl)-phenyl, C1-C6 acyl or benzoyl each of which is unsub-stituted or substituted by halogen or C1-C4 alkoxy, R3, R4, R5 and R6 independently of one another are a hydrogen atom, alkyl, alkoxy, alkylthio and alkoxycarbonyl having 1 to 8 C atoms in the alkyl or alkoxy group, phenoxy or halogen, or R3 and R4 and also R5 and R6 together are in which n=3, 4 or 5, in which m = 1 to 4 or a radical of the formula -CH=CH-CH=CH-, and x is a rational number from 1 to 300.
2. A solid electrolyte cell according to claim 1, wherein M in formula I is Fe, Cu or Ni.
3. A solid electrolyte cell according to claim 1, wherein R1 and R2 are a hydrogen atom, methyl, ethyl, phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl or p-fluorophenyl and R3, R4, R5 and R6 are a hydrogen atom, methyl, ethyl, methoxy, methylthio or fluorine or R3 and R4 and also R5 and R6 together are , , -OCH2CH20- or -CH=CH-CH=CH-.
4. A solid electrolyte cell according to claim 1, wherein x in formula I is a number from 1 to 200.
5. A solid electrolyte cell according to claim 4, wherein x in formula I is a number from 1 to 100.
6. A solid electrolyte cell according to claim 4, wherein x in formula I is a number from 2 to 50.
7. A solid electrolyte cell according to claim 1, wherein R1 to R6 in formula I are a hydrogen atom or methyl and M is Cu or Ni.
8. An iodine-doped complex or mixtures thereof with iodine havinq the formula II
(II) in which M, R1, R2, R3, R4, R5 and R6 are as defined in claim 1 and y is a rational number from 5 to 300.
(II) in which M, R1, R2, R3, R4, R5 and R6 are as defined in claim 1 and y is a rational number from 5 to 300.
9. A process for the preparation of complexes or mix-tures thereof with iodine having the formula II according to claim 8, which comprises oxidising a metal complex of the formula III
(III) in which M and R1 to R6 have the meaning indicated in claim 1, by means of y moles of iodine, y being a rational number from 5 to 300.
(III) in which M and R1 to R6 have the meaning indicated in claim 1, by means of y moles of iodine, y being a rational number from 5 to 300.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6884/83-0 | 1983-12-23 | ||
| CH688483 | 1983-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1230874A true CA1230874A (en) | 1987-12-29 |
Family
ID=4316585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000470805A Expired CA1230874A (en) | 1983-12-23 | 1984-12-21 | Solid electrolyte cell and iodine-doped metal complexes as the cathode material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4584251A (en) |
| EP (1) | EP0150673B1 (en) |
| JP (1) | JPS60157162A (en) |
| CA (1) | CA1230874A (en) |
| DE (1) | DE3472503D1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4921586A (en) * | 1989-03-31 | 1990-05-01 | United Technologies Corporation | Electrolysis cell and method of use |
| US4824745A (en) * | 1987-02-25 | 1989-04-25 | Bridgestone Corporation | Electric cell comprising a polymeric material film electrode having a collection integrated therewith |
| EP0341201A3 (en) * | 1988-04-21 | 1991-03-20 | Ciba-Geigy Ag | Ultrathin layers from dibenzotetraazo-[14]-annulene derivatives |
| IT1218084B (en) * | 1988-06-16 | 1990-04-12 | Consiglio Nazionale Ricerche | CONDUCTIVE POLYMERS THAT CAN BE USED FOR THE REALIZATION OF COMPLETELY DRY BATTERIES |
| US4921585A (en) * | 1989-03-31 | 1990-05-01 | United Technologies Corporation | Electrolysis cell and method of use |
| US4952469A (en) * | 1990-01-03 | 1990-08-28 | Mine Safety Appliances Company | Lithium-iodine depolarizer |
| FR2675507A1 (en) * | 1991-04-19 | 1992-10-23 | Centre Nat Rech Scient | Process for the preparation of organoinorganic materials by an electron transfer reaction in the solid state between two organic versus inorganic redox antagonists |
| DE4445584A1 (en) * | 1994-12-20 | 1996-06-27 | Basf Ag | Use of organic materials of high nonionic charge carrier mobility |
| US10790534B2 (en) | 2018-05-17 | 2020-09-29 | Vissers Battery Corporation | Methods, devices and systems to isolate solid products in molten fluid electrode apparatus |
| US11056680B2 (en) | 2018-05-17 | 2021-07-06 | Vissers Battery Corporation | Molten fluid electrode apparatus |
| US10601080B2 (en) | 2018-05-17 | 2020-03-24 | Vissers Battery Corporation | Devices, systems, and methods to mitigate thermal runaway conditions in molten fluid electrode apparatus |
| US11264603B2 (en) | 2018-05-17 | 2022-03-01 | Vissers Battery Corporation | Molten fluid apparatus with solid non-brittle electrolyte |
| US10673064B2 (en) | 2018-05-17 | 2020-06-02 | Vissers Battery Corporation | Molten fluid electrode apparatus with solid lithium iodide electrolyte having improved lithium ion transport characteristics |
| US10461311B1 (en) | 2018-05-17 | 2019-10-29 | Vissers Battery Corporation | Devices, systems, and methods for molten fluid electrode apparatus management |
| CN118919724B (en) * | 2024-07-22 | 2025-12-26 | 北京化工大学 | A molecular catalyst/activated carbon composite material, its preparation method and applications |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660163A (en) * | 1970-06-01 | 1972-05-02 | Catalyst Research Corp | Solid state lithium-iodine primary battery |
| DE2046354C3 (en) * | 1970-09-19 | 1979-11-08 | Robert Bosch Gmbh, 7000 Stuttgart | Electrocatalyst for the oxygen cathode in electrochemical cells |
| DE2128842C3 (en) * | 1971-06-11 | 1980-12-18 | Robert Bosch Gmbh, 7000 Stuttgart | Fuel electrode for electrochemical fuel elements |
| US3773557A (en) * | 1972-03-01 | 1973-11-20 | Wurlitzer Co | Solid state battery |
| DE2326667C3 (en) * | 1973-05-25 | 1982-01-14 | Robert Bosch Gmbh, 7000 Stuttgart | Process for activating catalysts for electrodes in electrochemical cells |
| US4049890A (en) * | 1975-04-03 | 1977-09-20 | Catalyst Research Corporation | Lithium-iodine cells and method for making same |
| JPS5630261A (en) * | 1979-08-17 | 1981-03-26 | Matsushita Electric Ind Co Ltd | Battery and its manufacturing method |
| US4340651A (en) * | 1980-11-12 | 1982-07-20 | Medtronic, Inc. | Cathode material and high capacity lithium-iodine cells |
| US4469763A (en) * | 1983-10-21 | 1984-09-04 | Tracer Technologies, Inc. | Lithium oxyhalide battery with cathode catalyst |
-
1984
- 1984-12-12 US US06/680,682 patent/US4584251A/en not_active Expired - Fee Related
- 1984-12-17 EP EP84810634A patent/EP0150673B1/en not_active Expired
- 1984-12-17 DE DE8484810634T patent/DE3472503D1/en not_active Expired
- 1984-12-21 CA CA000470805A patent/CA1230874A/en not_active Expired
- 1984-12-21 JP JP59268771A patent/JPS60157162A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0150673B1 (en) | 1988-06-29 |
| US4584251A (en) | 1986-04-22 |
| EP0150673A2 (en) | 1985-08-07 |
| DE3472503D1 (en) | 1988-08-04 |
| JPS60157162A (en) | 1985-08-17 |
| EP0150673A3 (en) | 1986-05-21 |
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