CA1067144A - Anion conductive solid electrolytes and solid state battery systems - Google Patents
Anion conductive solid electrolytes and solid state battery systemsInfo
- Publication number
- CA1067144A CA1067144A CA252,219A CA252219A CA1067144A CA 1067144 A CA1067144 A CA 1067144A CA 252219 A CA252219 A CA 252219A CA 1067144 A CA1067144 A CA 1067144A
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- CA
- Canada
- Prior art keywords
- pbf2
- electrochemical cell
- alkali metal
- electrolyte
- solid
- 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
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
-
- 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)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
ABSTRACT
A solid electrolyte including PbF2 and an alkali metal halide dopant is described. Methods of preparing the solid electrolyte are disclosed as well as electro-chemical cells using such a solid electrolyte.
A solid electrolyte including PbF2 and an alkali metal halide dopant is described. Methods of preparing the solid electrolyte are disclosed as well as electro-chemical cells using such a solid electrolyte.
Description
This invention relates to electrochemical cells and more particularly to such cells utilizing solid electrolytes.
Until recently electrolytes of electrochemical cells have been based upon liquid systems with all of the attendant drawbacks of li~uids. Such drawbacks indlude leakage of the low surface tension liquids, need for electrolyte separators and electrolyte absorbers to confine the electrolyte and its ionic components to the desired portions of the cells. To - overcome these drawbacks it has been proposed to utilize solid electrolytes. However, most proposed solid electrolytes have insufficient ionic conductivity for general use.
It is an object of this invention to provide a solid electrolyte for use in electrochemical cells.
It is another object of this invention to provide a solid electrolyte having relatively high ionic conductivity.
, " It is another object of this invention to provide ... . .
electrochemical cells utilizing the solid electrolytes of this invention.
It is still another object of this invention to ;
provide solid electrolyte cells which can be operated as primary or secondary cells.
According to the above objects, from a broad -aspect, the present invention provides an electrochemical cell comprising an anode, a cathode and a solid electrolyte ; which comprises an alkali metal halide and lead fluoride.
The halide and lead fluoride are in solid solution form and ; in a molar proportion of halide to lead fluoride in the range of 1:1000 to 1:1.
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; We have discovered that incorporation of alkali :-metal halides such as halides of K, Na and Li, and preferably alkali metal fluorides such as KF, NaF and LiF as dopants , into lead fluoride (PbF2) increases the ionic conductivity of the resultant PbF2 composition solids. The PbF2., without the inclusion of the alkali metal halide dopant, `
has a room temperature (25C) conductivity of about .'' .'' ~ .
, ',.
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` 106'7~44 7 (+1) x 10-8 ohm~l -cm~l . The solid electrolytes of this invention are conductors having a conductivity in the range --of about 10-7 to about 10-2 ohm~l-cm~l and, preferably in the range of about 10-3 to about 10-6 ohm~l-cm~l at about 25C.
The inclusion of alkali metal halide dopant causes an increase in the concentration of the mobile or conducting species in PbF2 , Such species may be either the interstitial - ~
ions or ion vacancies regardless of the alkali metal halide -used : ., .
~ 10 As a result of the improved conductivity resulting ?~
~......................................................................... . .
from the addition of the alkali metal halide to the PbF2 , ' of which an alkali metal fluoride is the preferred species -with potassium fluoride (KF) being the presently most preferred species, it is possible to prepare solid electrolytes for use in electrochemical cells operative over a broad range of temperatures.
Moreover the PbF2 -alkali metal fluoride solids have sufficiently high ionic conductivity with very low electronic conductivity and, consequently, they can be used as solid electrolyte materials in both primary and secondary electro-chemical systems.
In general we found that the incorporation of - an alkali metal halide such as potassium fluoride in amounts . wherein the molar proportions of KF to PbF2 ranges from 1:1000 to 1:1 provides a sufficient increase in ionic con-ductivity to furnish a useful solid electrolyte. Within this range we prefer the concentration of the KF within the range of 0.5 to 25 mole percent.
Lead fluoride can exist at room temperature in both orthorhombic (~ -PbF2 ) and cubic (~ -PbF2 ) forms.
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, ~' , ' ' .~
Until recently electrolytes of electrochemical cells have been based upon liquid systems with all of the attendant drawbacks of li~uids. Such drawbacks indlude leakage of the low surface tension liquids, need for electrolyte separators and electrolyte absorbers to confine the electrolyte and its ionic components to the desired portions of the cells. To - overcome these drawbacks it has been proposed to utilize solid electrolytes. However, most proposed solid electrolytes have insufficient ionic conductivity for general use.
It is an object of this invention to provide a solid electrolyte for use in electrochemical cells.
It is another object of this invention to provide a solid electrolyte having relatively high ionic conductivity.
, " It is another object of this invention to provide ... . .
electrochemical cells utilizing the solid electrolytes of this invention.
It is still another object of this invention to ;
provide solid electrolyte cells which can be operated as primary or secondary cells.
According to the above objects, from a broad -aspect, the present invention provides an electrochemical cell comprising an anode, a cathode and a solid electrolyte ; which comprises an alkali metal halide and lead fluoride.
The halide and lead fluoride are in solid solution form and ; in a molar proportion of halide to lead fluoride in the range of 1:1000 to 1:1.
.
.
~ .
B~
; We have discovered that incorporation of alkali :-metal halides such as halides of K, Na and Li, and preferably alkali metal fluorides such as KF, NaF and LiF as dopants , into lead fluoride (PbF2) increases the ionic conductivity of the resultant PbF2 composition solids. The PbF2., without the inclusion of the alkali metal halide dopant, `
has a room temperature (25C) conductivity of about .'' .'' ~ .
, ',.
:, ~
i ~, ,,~., .
, , ;
, '.''", . .
,~
~ - la -. ' , .
` 106'7~44 7 (+1) x 10-8 ohm~l -cm~l . The solid electrolytes of this invention are conductors having a conductivity in the range --of about 10-7 to about 10-2 ohm~l-cm~l and, preferably in the range of about 10-3 to about 10-6 ohm~l-cm~l at about 25C.
The inclusion of alkali metal halide dopant causes an increase in the concentration of the mobile or conducting species in PbF2 , Such species may be either the interstitial - ~
ions or ion vacancies regardless of the alkali metal halide -used : ., .
~ 10 As a result of the improved conductivity resulting ?~
~......................................................................... . .
from the addition of the alkali metal halide to the PbF2 , ' of which an alkali metal fluoride is the preferred species -with potassium fluoride (KF) being the presently most preferred species, it is possible to prepare solid electrolytes for use in electrochemical cells operative over a broad range of temperatures.
Moreover the PbF2 -alkali metal fluoride solids have sufficiently high ionic conductivity with very low electronic conductivity and, consequently, they can be used as solid electrolyte materials in both primary and secondary electro-chemical systems.
In general we found that the incorporation of - an alkali metal halide such as potassium fluoride in amounts . wherein the molar proportions of KF to PbF2 ranges from 1:1000 to 1:1 provides a sufficient increase in ionic con-ductivity to furnish a useful solid electrolyte. Within this range we prefer the concentration of the KF within the range of 0.5 to 25 mole percent.
Lead fluoride can exist at room temperature in both orthorhombic (~ -PbF2 ) and cubic (~ -PbF2 ) forms.
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-2-1067~44 . . ~
The incorporation of the alkali metal fluoride dopant such as KF, substantially increases the ionic conductivity of both ~ -PbF2 and ~-PbF2 . Such a conductivity increase is caused by the fact that the concentration of the mobile (or conductive)species (interstitial fluoride ions or fluoride ion vacancies) is increased by the incorporation of KF in the PbF2 lattice.
, . . .
The KF doped PbF2 obtained by quenching the melt -, . ,:. , to room temperature is in the cubic form. However, the !`
orthorhombic o:form PbF2 can be obtained by prolonged grinding of the cubic form ~ -PbF2 . Furthermore, when ~-PbF2 powder '~
is pressed under a pressure of 30,000 psi or higher, a -pellet of orthorhombicoc-PbF2 is formed. In order to obtain ;~ a cubic p-PbF2 pellet, the orthorhombic PbF2 pellet is slowly : - heated to 300-350C where aC-PbF2 transforms into~-PbF2 .
, Once the ~ -PbF2 pellet is formed, the temperature may be lowered to room temperature or below and the PbF2 pellet will remain in the cubic form (~ -PbF2 ) without transforming back to the orthorhombic form. Therefore, both KF doped oc -PbF2 and KF doped ~-PbF2 pellets suitable for solid A'',electrolyte use can be made and maintained at temperatures below 300C.
Figure 3 shows the conductivity of the KF doped oc -PbF2 as a function of KF concentration up to one mole --- percent (1 m/o) at room temper-ature ~25~2C~.
Figure 4 shows the conductivity of the KF doped -PbF2 as a function of KF concentration at room temperature ` (25+2C).
Figure 5 shows the conductivity of the KF doped ~-PbF2 as a function of temperature.
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Figure 6 shows the conductivity of the KF doped -PbF2 as a function of temperature.
As can be seen from the above, while the ~ form ~cubic) of doped PbF2 has slightly higher conductivity, and / is preferred, either the ocor ~ form can be used in this invention. `~
; The method of preparincJ the ionic conducting solids suitable for the solid electrolyte of this invention - includes mixing proper amounts of the alkali metal halide ~ 10 with PbF2 . The mixture is treated such-as by heating at - -- a temperature where sufficient diffusion of the mixture components " occùr to provide possible solution and intercrystaIlization ;
; of the alkali metal halide in the PbF2 . The treating step .; . . ... .
- is preexably continued until such diffusion and/or solution or intercrystallization is substantially c~mplete. At higher temperatures the reaction is completed within minutes and depending upon the composition of the mixture with the ;
formation of a liquiduus. At the lower temperatures the .;
;~ desired lead fluoride solid electrolyte formation is usually -~
completed within several hours but a liquid state is not always achieved as an alkali metal halide such as KF and PbF2 (in pure form) melt at about 800C.
Upon completion Of the treatment formation of the ~ ~ solid electrolyte intercrystalline composition, it is rapidly ; cooled (quenched) to room temperature and ground to a powder.
As set forth above the solid electrolyte of this ; invention can be used in either primary or secondary cells.
PRIMARY CELLS
The lead fluoride-alkali metal halide electrolyte of this invention may be used in various solid state electro- ~
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.
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~ - 1067144 .
chemical systems wherein the anode actlve ma~erials are those ' ' which will not reduce ionic lead (Pb++ ) to metallic lead (viz: , , Handbood of Cllemistry and Physics-Potentials of Electrochemical ~, Reactions). Useful cathode active materials are preferably the ' , heavy metal fluorides such as AgF, AgF2 , PbF4 , CuF2 ,1~gF2 , , ~
, intercalated fluorides such as SbF5 in graphite, fluorine and ~, fluorine based materials including carbon with absorbed '~ fluorine. ' ' SECONDARY SOLID STATE ELECTROLYTE CELLS :~
, 10 Useful rechargeable solid state cells can be con-', structed using the PbF2 -alkali metal halide solid electrolytes.
, Such different solid electrolyte cells in the discharged ~' state have the following postulated compositions: ' , ; a) C/PbF~ (KF doped) /Ag b) Pb/PbF2 ~KF doped) /Ag c) Pb/PbF2 (KF doped) /Cu d) C/PbF 2 (KF doped) /Cu ;, , e) C/PbF 2 ' (KF doped) /C ' , ' ' These cells can be charged to the active states '' ~' having the following postulated compositions: ;
f) Pb/PbF2 (KF doped) /Ac~F/Ag -' g) Pb/PbF2 (KF doped) /Cuf2 /Cu '20 h) Pb/PbF2 (KF doped) /PbF4 /C
,' The invention will be more fully described by reference to the following examples showing procedures for preparing the composition for the solid electrolyte of this " ~ invention and'construction of primary and secondary batteries utilizing'such solid electrolytes. The procedures disclosed are exemplary of modes for practice of this invention. All ' art recognized equivalent procedures and'materials of those herein disclosed are intended. For example, the electrolyte can '', be used in forms other than the pellet form of the Examples.
,' 30 . . .
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; ~067 ~4 , '' ' , . .
A mixture of PbF2 (75 mole percent) and KF (25~
~ . .
; mole percent) is heated to a temperature of about 600~C for a `
period of about 6 hours. After heating, the material is quenched by pouring it in thin layers upon a cooled metallic -. ' surface. When the poured material reaches room temperature it is pulverized. A conductivity cell of this PbF2 -KF
composition is made by pressing a weighed amount of the electrolyte powder between two Pb discs in a steel die at 100,000 psi. The resistance of a Pb/PbF2 -KF/Pb conductivity cell is measured by a conductance bridge at 1,000 Hz. The conductivity of the electrolyte pellet determined from these ;
measurements was 3 (+1~ x 10-5 ohm~~l -cm~l at room temperature.
The conductivity of PbF2 without the alkali metal fluoride dopant is 7 (+~) x 10-8 ohm~1-cm~1 at room temperature.
EXAMPLE 2 ,~
, A mixture of a composition similar to that of - Example 1 is heated to a temperature of about 850C, Within several minutes a liquiduus is noted. The liquiduus is poured upon a cooled metal sheet and thus quenched rapidly to room temperature. The resultant solid material is pulverized .. . ..
- and a conductivity cell is prepared-therewith in the same manner as in Example 1. The conductivity of the thus obtained electrolyte pellet is substantially the same as that obtained in with the pellet of Example 1.
; ~ A Pb/pbF2~75 mole percent) KF (25]mole percent) /AgF, Ag solid electrolyte cell is made by pressing the components as powders in a steel die. The anode,is a mixture ~, . . .
of Pb and the electrolyte. The cathode is a mixture of . . ,' ' :' .: . .
.
~ ~7r ~ . ., "
f~' ~gF, Ag and the electrolyte. The solid electrolyte is ' PbF2 containing 25 mole percent KF. The procedures for the abrication of the test cells are as follows: a weighe~ a~ount o solid elec~rolyte'powder is pre-pressed in '~
a 0.6" diameter die at about 3000 psi. The anode mixture and the cathode mixture are then placed on either side of , , the pre-pressed solid electrolyte pellet in the steel die and the total assembly is pressed at lO0,000 psi. The resultant solid electrolyte cell has a geometric area of about 1.8 cm 2 and the thickness of the electrolyte layer is determined to be about 0.5 mm. The cell exhibits an open circuit voltage of 1.26 volts at room temperature and is ~ , discharged at a discharge rate of 22 micro-amperes at room , ,temperature. The discharge curve of this cell is shown in Fig~
, ' , EXAMPLE 4 ` .
~ solid electrolyte cell is madé by compressing a mixture of powdered Pb and 5% powdered electrolyte, (PbF2 and 25 mole percent of KF as dopant) as the anode. A mixture of 20 powdered Ag and 5% electrolyte is used as the cathode. The solid electrolyte is 75 mole percent of PbF2 doped with 25 ' ~, , mole percent of K~. The test cell is prepared according to the procedure set forth Ln Example 3. The geometric area of , .' ' the cell is about 1.8 cm 2 and the thickness of the electrolyte :'' ' . -' layer is approximately 1 millimeter. The cell assembled as ' in Example 3 is charged and discharged at approximately 50 4 micro-amperes. The charge and discharge phases are accom'plished at about 25C. Fig. 2 shows the charge and -discharge curves of the rechargea~le 'cell according to this 30 example.
~.
1067~44 The substitution of PbBr2 , or PbC12 , or PbI2 for PbF2 in a solid electrolyte system that includes an `
alkali metal halide does not appear to result in the high level o conductivity as does the PbF2 -alkali metal halide containing solid electrolyte.
"Alkali metals" as used herein means and includes -, metals of Group IA of the periodic system such as lithium (Li), sodium (Na), and potassium (K). "Halide" as used herein with alkali metals means and includes binary compounds of fluorine, chlorine, bromine, and iodine, and also astatine wherein the compound when mixed with PbF2 forms a r ' I
! solid eléctrolyte that has a conductivity in the range of about 10 7to 10 2 ohm l-cm l with high ion conductivity which can be used in electrochemical cells.
( Thé presence of small amounts of impurity elements is not believed to play a critical role in the invention.
It should be understood, however, that we contemplate the -possibility of other elements with PbF2 and the alkali . . . ;
metal halide to produce a solid electrolyte that do not affect the desired properties of the electrolyte.
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The incorporation of the alkali metal fluoride dopant such as KF, substantially increases the ionic conductivity of both ~ -PbF2 and ~-PbF2 . Such a conductivity increase is caused by the fact that the concentration of the mobile (or conductive)species (interstitial fluoride ions or fluoride ion vacancies) is increased by the incorporation of KF in the PbF2 lattice.
, . . .
The KF doped PbF2 obtained by quenching the melt -, . ,:. , to room temperature is in the cubic form. However, the !`
orthorhombic o:form PbF2 can be obtained by prolonged grinding of the cubic form ~ -PbF2 . Furthermore, when ~-PbF2 powder '~
is pressed under a pressure of 30,000 psi or higher, a -pellet of orthorhombicoc-PbF2 is formed. In order to obtain ;~ a cubic p-PbF2 pellet, the orthorhombic PbF2 pellet is slowly : - heated to 300-350C where aC-PbF2 transforms into~-PbF2 .
, Once the ~ -PbF2 pellet is formed, the temperature may be lowered to room temperature or below and the PbF2 pellet will remain in the cubic form (~ -PbF2 ) without transforming back to the orthorhombic form. Therefore, both KF doped oc -PbF2 and KF doped ~-PbF2 pellets suitable for solid A'',electrolyte use can be made and maintained at temperatures below 300C.
Figure 3 shows the conductivity of the KF doped oc -PbF2 as a function of KF concentration up to one mole --- percent (1 m/o) at room temper-ature ~25~2C~.
Figure 4 shows the conductivity of the KF doped -PbF2 as a function of KF concentration at room temperature ` (25+2C).
Figure 5 shows the conductivity of the KF doped ~-PbF2 as a function of temperature.
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_3_ . ; ~067144 ` - -- ,:
Figure 6 shows the conductivity of the KF doped -PbF2 as a function of temperature.
As can be seen from the above, while the ~ form ~cubic) of doped PbF2 has slightly higher conductivity, and / is preferred, either the ocor ~ form can be used in this invention. `~
; The method of preparincJ the ionic conducting solids suitable for the solid electrolyte of this invention - includes mixing proper amounts of the alkali metal halide ~ 10 with PbF2 . The mixture is treated such-as by heating at - -- a temperature where sufficient diffusion of the mixture components " occùr to provide possible solution and intercrystaIlization ;
; of the alkali metal halide in the PbF2 . The treating step .; . . ... .
- is preexably continued until such diffusion and/or solution or intercrystallization is substantially c~mplete. At higher temperatures the reaction is completed within minutes and depending upon the composition of the mixture with the ;
formation of a liquiduus. At the lower temperatures the .;
;~ desired lead fluoride solid electrolyte formation is usually -~
completed within several hours but a liquid state is not always achieved as an alkali metal halide such as KF and PbF2 (in pure form) melt at about 800C.
Upon completion Of the treatment formation of the ~ ~ solid electrolyte intercrystalline composition, it is rapidly ; cooled (quenched) to room temperature and ground to a powder.
As set forth above the solid electrolyte of this ; invention can be used in either primary or secondary cells.
PRIMARY CELLS
The lead fluoride-alkali metal halide electrolyte of this invention may be used in various solid state electro- ~
. .
.
: ~ r .
~ - 1067144 .
chemical systems wherein the anode actlve ma~erials are those ' ' which will not reduce ionic lead (Pb++ ) to metallic lead (viz: , , Handbood of Cllemistry and Physics-Potentials of Electrochemical ~, Reactions). Useful cathode active materials are preferably the ' , heavy metal fluorides such as AgF, AgF2 , PbF4 , CuF2 ,1~gF2 , , ~
, intercalated fluorides such as SbF5 in graphite, fluorine and ~, fluorine based materials including carbon with absorbed '~ fluorine. ' ' SECONDARY SOLID STATE ELECTROLYTE CELLS :~
, 10 Useful rechargeable solid state cells can be con-', structed using the PbF2 -alkali metal halide solid electrolytes.
, Such different solid electrolyte cells in the discharged ~' state have the following postulated compositions: ' , ; a) C/PbF~ (KF doped) /Ag b) Pb/PbF2 ~KF doped) /Ag c) Pb/PbF2 (KF doped) /Cu d) C/PbF 2 (KF doped) /Cu ;, , e) C/PbF 2 ' (KF doped) /C ' , ' ' These cells can be charged to the active states '' ~' having the following postulated compositions: ;
f) Pb/PbF2 (KF doped) /Ac~F/Ag -' g) Pb/PbF2 (KF doped) /Cuf2 /Cu '20 h) Pb/PbF2 (KF doped) /PbF4 /C
,' The invention will be more fully described by reference to the following examples showing procedures for preparing the composition for the solid electrolyte of this " ~ invention and'construction of primary and secondary batteries utilizing'such solid electrolytes. The procedures disclosed are exemplary of modes for practice of this invention. All ' art recognized equivalent procedures and'materials of those herein disclosed are intended. For example, the electrolyte can '', be used in forms other than the pellet form of the Examples.
,' 30 . . .
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; ~067 ~4 , '' ' , . .
A mixture of PbF2 (75 mole percent) and KF (25~
~ . .
; mole percent) is heated to a temperature of about 600~C for a `
period of about 6 hours. After heating, the material is quenched by pouring it in thin layers upon a cooled metallic -. ' surface. When the poured material reaches room temperature it is pulverized. A conductivity cell of this PbF2 -KF
composition is made by pressing a weighed amount of the electrolyte powder between two Pb discs in a steel die at 100,000 psi. The resistance of a Pb/PbF2 -KF/Pb conductivity cell is measured by a conductance bridge at 1,000 Hz. The conductivity of the electrolyte pellet determined from these ;
measurements was 3 (+1~ x 10-5 ohm~~l -cm~l at room temperature.
The conductivity of PbF2 without the alkali metal fluoride dopant is 7 (+~) x 10-8 ohm~1-cm~1 at room temperature.
EXAMPLE 2 ,~
, A mixture of a composition similar to that of - Example 1 is heated to a temperature of about 850C, Within several minutes a liquiduus is noted. The liquiduus is poured upon a cooled metal sheet and thus quenched rapidly to room temperature. The resultant solid material is pulverized .. . ..
- and a conductivity cell is prepared-therewith in the same manner as in Example 1. The conductivity of the thus obtained electrolyte pellet is substantially the same as that obtained in with the pellet of Example 1.
; ~ A Pb/pbF2~75 mole percent) KF (25]mole percent) /AgF, Ag solid electrolyte cell is made by pressing the components as powders in a steel die. The anode,is a mixture ~, . . .
of Pb and the electrolyte. The cathode is a mixture of . . ,' ' :' .: . .
.
~ ~7r ~ . ., "
f~' ~gF, Ag and the electrolyte. The solid electrolyte is ' PbF2 containing 25 mole percent KF. The procedures for the abrication of the test cells are as follows: a weighe~ a~ount o solid elec~rolyte'powder is pre-pressed in '~
a 0.6" diameter die at about 3000 psi. The anode mixture and the cathode mixture are then placed on either side of , , the pre-pressed solid electrolyte pellet in the steel die and the total assembly is pressed at lO0,000 psi. The resultant solid electrolyte cell has a geometric area of about 1.8 cm 2 and the thickness of the electrolyte layer is determined to be about 0.5 mm. The cell exhibits an open circuit voltage of 1.26 volts at room temperature and is ~ , discharged at a discharge rate of 22 micro-amperes at room , ,temperature. The discharge curve of this cell is shown in Fig~
, ' , EXAMPLE 4 ` .
~ solid electrolyte cell is madé by compressing a mixture of powdered Pb and 5% powdered electrolyte, (PbF2 and 25 mole percent of KF as dopant) as the anode. A mixture of 20 powdered Ag and 5% electrolyte is used as the cathode. The solid electrolyte is 75 mole percent of PbF2 doped with 25 ' ~, , mole percent of K~. The test cell is prepared according to the procedure set forth Ln Example 3. The geometric area of , .' ' the cell is about 1.8 cm 2 and the thickness of the electrolyte :'' ' . -' layer is approximately 1 millimeter. The cell assembled as ' in Example 3 is charged and discharged at approximately 50 4 micro-amperes. The charge and discharge phases are accom'plished at about 25C. Fig. 2 shows the charge and -discharge curves of the rechargea~le 'cell according to this 30 example.
~.
1067~44 The substitution of PbBr2 , or PbC12 , or PbI2 for PbF2 in a solid electrolyte system that includes an `
alkali metal halide does not appear to result in the high level o conductivity as does the PbF2 -alkali metal halide containing solid electrolyte.
"Alkali metals" as used herein means and includes -, metals of Group IA of the periodic system such as lithium (Li), sodium (Na), and potassium (K). "Halide" as used herein with alkali metals means and includes binary compounds of fluorine, chlorine, bromine, and iodine, and also astatine wherein the compound when mixed with PbF2 forms a r ' I
! solid eléctrolyte that has a conductivity in the range of about 10 7to 10 2 ohm l-cm l with high ion conductivity which can be used in electrochemical cells.
( Thé presence of small amounts of impurity elements is not believed to play a critical role in the invention.
It should be understood, however, that we contemplate the -possibility of other elements with PbF2 and the alkali . . . ;
metal halide to produce a solid electrolyte that do not affect the desired properties of the electrolyte.
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Claims (9)
1. An electrochemical cell comprising an anode, a cathode and a solid electrolyte which comprises an alkali metal halide and lead fluoride, with said halide and lead fluoride being in solid solution form and in a molar proportion of halide to lead fluoride in the range of 1:1000 to 1:1.
2. The electrochemical cell according to claim 1 wherein said alkali metal halide is selected from halides of K, Na and Li.
3. The electrochemical cell according to claim 2 wherein the alkali metal halide is KF.
4. The electrochemical cell according to claim 2 wherein the alkali metal halide is KF in a molar proportion of KF to PbF2 in the electrolyte composition in the range of 1 to 25 mole percent.
5. The electrochemical cell of claim 1 wherein said anode comprises an anode active material of lead, or a metal below lead in the EMF series or mixtures thereof; said cathode comprises as cathode active materials heavy metal fluorides, intercalated fluorides, fluorine or mixtures thereof; with said solid electrolyte being between the cathode and the anode.
6. The electrochemical cell according to claim 2 wherein the alkali metal is potassium.
7. The electrochemical cell according to claim 5 wherein the anode is lead, said cathode active material is AgF
and said solid electrolyte is a solid composition essentially consisting of 25 mole percent of KF in PbF2.
and said solid electrolyte is a solid composition essentially consisting of 25 mole percent of KF in PbF2.
8. The electrochemical cell according to claim 5 wherein the electrolyte has a conductivity in the range of about 10-2 to about 10-7 ohm-l-cm-1 at about room temperature.
9. The electrochemical cell according to claim 5 wherein the active cathode material is selected from the group consisting of AgF, AgF2, PbF4, CuF2, HgF2, and SbF5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58594975A | 1975-06-11 | 1975-06-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067144A true CA1067144A (en) | 1979-11-27 |
Family
ID=24343671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA252,219A Expired CA1067144A (en) | 1975-06-11 | 1976-05-11 | Anion conductive solid electrolytes and solid state battery systems |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5231332A (en) |
| AU (1) | AU496776B2 (en) |
| BE (1) | BE842829A (en) |
| CA (1) | CA1067144A (en) |
| DE (1) | DE2624941A1 (en) |
| DK (1) | DK257376A (en) |
| FR (1) | FR2314589A1 (en) |
| GB (1) | GB1524126A (en) |
| IL (1) | IL49482A (en) |
| IT (1) | IT1064028B (en) |
| NL (1) | NL7606259A (en) |
| SE (1) | SE7606557L (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4186249A (en) * | 1978-12-27 | 1980-01-29 | Union Carbide Corporation | Solid state electrolytes |
| USRE31365E (en) | 1978-12-27 | 1983-08-30 | Union Carbide Corporation | Solid state electrolytes |
| US4186248A (en) * | 1978-12-27 | 1980-01-29 | Union Carbide Corporation | Solid state electrolytes |
| RU2295177C2 (en) | 2005-04-21 | 2007-03-10 | Общество с ограниченной ответственностью "Высокоэнергетические батарейные системы" (ООО "ВЭБС") | Solid-state secondary power supply manufacturing method |
| RU2295178C2 (en) * | 2005-04-21 | 2007-03-10 | Общество с ограниченной ответственностью "Высокоэнергетические батарейные системы" (ООО "ВЭБС") | Solid-state secondary power supply |
| RU2313158C2 (en) * | 2006-01-10 | 2007-12-20 | Общество С Ограниченной Ответственностью "Высокоэнергетические Батарейные Системы" | Solid-state chemical current supply and method for raising discharge capacity/ |
| RU2413340C1 (en) * | 2009-08-10 | 2011-02-27 | ООО "Высокоэнергетические Батарейные Системы" ("High Power Battery Systems Ltd.", HPBS) | Chemical source of current |
| DE102013106998A1 (en) | 2013-07-03 | 2015-01-08 | Thyssenkrupp Industrial Solutions Ag | Method and device for producing a tablet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2258011A1 (en) * | 1974-01-12 | 1975-08-08 | Varta Batterie |
-
1976
- 1976-04-27 IL IL49482A patent/IL49482A/en unknown
- 1976-04-30 AU AU13532/76A patent/AU496776B2/en not_active Expired
- 1976-05-11 CA CA252,219A patent/CA1067144A/en not_active Expired
- 1976-05-24 GB GB21383/76A patent/GB1524126A/en not_active Expired
- 1976-06-03 DE DE19762624941 patent/DE2624941A1/en not_active Withdrawn
- 1976-06-10 SE SE7606557A patent/SE7606557L/en unknown
- 1976-06-10 IT IT24151/76A patent/IT1064028B/en active
- 1976-06-10 NL NL7606259A patent/NL7606259A/en not_active Application Discontinuation
- 1976-06-10 DK DK257376A patent/DK257376A/en unknown
- 1976-06-10 FR FR7617607A patent/FR2314589A1/en not_active Withdrawn
- 1976-06-11 JP JP51068637A patent/JPS5231332A/en active Pending
- 1976-06-11 BE BE2055107A patent/BE842829A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IT1064028B (en) | 1985-02-18 |
| IL49482A0 (en) | 1976-06-30 |
| NL7606259A (en) | 1976-12-14 |
| DE2624941A1 (en) | 1976-12-23 |
| AU1353276A (en) | 1977-11-03 |
| FR2314589A1 (en) | 1977-01-07 |
| GB1524126A (en) | 1978-09-06 |
| JPS5231332A (en) | 1977-03-09 |
| BE842829A (en) | 1976-10-01 |
| DK257376A (en) | 1976-12-12 |
| SE7606557L (en) | 1976-12-12 |
| IL49482A (en) | 1978-12-17 |
| AU496776B2 (en) | 1978-10-26 |
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