GB2101395A - Thermal electric cells - Google Patents
Thermal electric cells Download PDFInfo
- Publication number
- GB2101395A GB2101395A GB8216471A GB8216471A GB2101395A GB 2101395 A GB2101395 A GB 2101395A GB 8216471 A GB8216471 A GB 8216471A GB 8216471 A GB8216471 A GB 8216471A GB 2101395 A GB2101395 A GB 2101395A
- Authority
- GB
- United Kingdom
- Prior art keywords
- lithium
- thermal
- anode
- cell
- nickel
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 7
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000000374 eutectic mixture Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 5
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 239000001989 lithium alloy Substances 0.000 claims abstract description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 4
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000005496 eutectics Effects 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000001464 adherent effect Effects 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000008188 pellet Substances 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FUXWSNBUHAEWQU-UHFFFAOYSA-N [Li].[Li].[Li] Chemical compound [Li].[Li].[Li] FUXWSNBUHAEWQU-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Abstract
A thermal cell (10) comprises a layered stack composed of a cathode (11), an electrolyte (12) and an anode (13). The cathode (11) is formed by a pellet (2) of iron disulphide and/or calcium chromate. The electrolyte (12) is a compressed pellet (3) of active material together with an inert binder, the active material being a eutectic mixture of lithium and potassium chlorides or a mixture, which may be eutectic, of lithium bromide, chloride and fluoride, or a eutectic mixture of lithium bromide, chloride, fluoride and iodide. The anode is formed by a nickel or iron cup (5) containing a body (4) of sintered nickel plaque impregnated with an anode reactive material which may be lithium or lithium alloys which are molten at the cell operating temperature. The cell (10) may be one of a set housed together with a pellet of pyrotechnic material (26) within a thermally insulated container (21) and electrically interconnected to form a battery (20). <IMAGE>
Description
SPECIFICATION
Thermal cells
This invention relates to thermal cells and thermal batteries.
Thermal cells are well known and comprise an anode, a cathode and an electrolyte which at ambient and storage temperatures are inactive but which are activated by means of a pyrotechnic material. In a known form of thermal cell the anode comprises a reactive material contained in a porous conductive matrix which has the dual function of acting as a current collector and as a means or confining the reactive material which is relatively mobile during active operation of the cell. The anode reactive material is usually lithium which is highly mobile at the elevated temperatures prevailing when the cell is operational or certain lithium alloys which are also highly mobile at these temperatures.
According to the present invention there is provided a thermal cell comprising an anode, a cathode, and an electrolyte, wherein the anode comprises a reactive material contained in a porous
conductive matrix, characterised in that the matrix is principally sintered nickel plaque and the reactive
material is lithium or lithium alloys which are molten at the cell operating temperature.
Preferably the matrix comprises a perforated support sheet of nickel or nickel-plated steel to which
nickel sinter is adherent on both sides thereof. Conveniently this form of matrix material is supplied by
Berec (Special Batteries) limited.
By virtue of the present invention improved cell performance can easily be achieved because anode
capacity can be controlled to a noticeably greater degree using sintered nickel plaque than with other
known forms of conductive matrix partly because of the chemical purity of the plaque, partly because of the robust nature of the plaque which permits continuous lithium impregnation, and partly because of the consistency of porosity per unit volume of the plaque.
Conveniently the cathode of the cell, which may take any known physical room, comprises iron
disulphide or calcium chromate as the reactive material and the electrolyte is a eutectic mixture of
lithium and potassium chlorides or a eutectic mixture of lithium bromide, chloride and fluoride or a
mixture of lithium bromide, chloride, fluoride and iodide. Conveniently such mixtures are eutectic. The
electrolyte may also incorporate an inert binder material to provide bulk and increase the volume of the
electrolyte without increasing the active material content thereof whilst reducing mobility of the active
material content.
The present invention also provides a thermal battery comprising a plurality of thermal cells each
in accordance with the present invention together with a pyrotechnic material for activation of the
battery.
Embodiments of the present invention will now be described by way of example with reference to
the accompanying drawing in which:
Fig. 1 illustrates a thermal cell in exploded form together with a pyrotechnic material; and
Fig. 2 schematically illustrates a thermal battery.
As is shown in Fig. 1 a thermal cell 10 comprises a layered stack composed of a cathode 11, an
electrolyte 12, and an anode 13. Associated with the cell 10 is a layer 14 of pyrotechnic material for
thermal activation of the cell 10 in a manner known per se. The cathode 11 1 is formed by a pellet 2 of
iron disulphide as the reactive material together with an iron or nickel current collector 6 although this is
optional since in its operational state the iron disulphide pellet 2 is itself electrically conductive.The
electrolyte i 2 is in the form of a compressed pellet 3 of active material together with an inert binder, the
active material being a eutectic mixture of lithium and potassium chlorides or lithium bromide, lithium
chloride and lithium fluoride. If so desired the cathode pellet 2 may additionally incorporate a body of
the active electrolyte material in order to increase the surface area of the cathode reactive material.
The anode 13 is formed by a nickel or iron cup 5 containing a body 4 of sintered nickel plaque
impregnated with lithium as the anode reactive material.
As shown in Fig. 2 a thermal battery 20 comprises a hollow container 21 internally lined with thermal insulation material 22 and housing a plurality of thermal cells 10 of which only one is shown in its entirety in the interests of clarity. The cells 10 are of course electrically connected in series and the cathode current collector 6 of the uppermost cell is connected to one terminal 23A of the battery 20 whereas the anode of the lowermost cell is connected to the other terminal 233 of the battery. The
battery 20 also incorporates a fusible igniter assembly 24 which is connected to terminals 25A, 25B to
permit thermal activation of the various cells 10 in the battery.At strategic levels throughout the battery there are pellets 26 of pyrotechnic material corresponding to layer 14 of Fig. 1 and to sustain the necessary temperature level within the battery 20 there are 'end heat' pellets 27A, 27B of thermite
and asbestos.
The various anodes illustrated in the drawings incorporate sintered nickel plaque supplied by
Berec (Special Batteries) Limited and consist of a perforated support of nickel or nickel-plated steel
0.1 mm + 0.01 mm in thickness and being 48~49% 'open' with nickel sinter adherent to both sides of
the support. With this construction a range of anode thicknesses from 0.25 mm upwards can be
produced and stamped into circular anode discs. Table 1 lists various thicknesses and anode capacities
for a nominal 75 mm diameter disc.It will be observed that the nickel plaque thickness may be selected
in steps of about 0.20 mm below 1.00 mm in order to tailor the anode capacity to the desired level and this is a significant advantage over known matrix materials, particularly foam metal which has a
minimum thickness of 1.2 mm if easy handling is to be maintained. However, even if the delicate nature of foam metals could be overcome to enable anode thicknesses of less than 1.00 mm to be manufactured the variability of porosity in foam metals is so great as to prevent accurate anode capacities being manufactured consistently. Table 2 provides a comparison between nickel plaque and foam me-;al I for a nominal anode size of 0.5 mm thickness and 60 mm diameter.This highlights that the porosity of nickel plaque can be controlled during manufacture to within 3% by volume whereas foam metal can vary by as much as + 15%.
An additional advantage of nickel plaque over foam metal is that nickel plaque contains practical y no harmful chemical impurities whereas foam metal is known to contain significant proporticns of sulphur, carbon and nitrogen all of which are reactive with lithium and reduce the effective less of lithium as the anode reactive material.
TABLE 1
Anode Capacity and Material Thickness
Nominal Electrode ~ Theoretical Anode Material Thickness Diameter Capacity (mm) (mm) (Amp. Min.) 0.25 75 70 0.46 75 1 161 0.60 75 241 TABLE 2 Domparison of Variability of Lithium
In Nickel Plaque and Foam Metal (% by Weight)
Anode Average Maximum Minimum Thickness Diam. Lithium Lithium Lithium Material ' (mm) (mm) Ni Plaque 0.5 60 12.1 12.11 12.09 Foam Metal (Rectimet) 0.5 so r 14.5 16.7 12.3 Data based on 20 samples.
Claims (10)
1. A thermal cell comprising an anode, a cathode, and an electrolyte, said anode comprising a reactive material contained in a porous conductive matrix and characterised in that the matrix is pdncipalty sintered nickel plaque and the reactive material is lithium or lithium alloys which are molten at the cel operating temperature.
2. A thermal cell as claimed in claim 1, wherein said matrix comprises a perforated sheet of nickel or nickel plated steel to which nickel sinter is adherent on both sides thereof.
3. ""thermal cell as claimed in either preceding claim, wherein said cathode comprises a reactive material in the form of iron disulphide or calcium chromate.
4. A thermal cell as claimed in claim 3, wherein said electrolyte comprises an active material which is a eutectic mixture of lithium and potassium chlorides.
5. A thermal cell as claimed in claim 3, wherein said electrolyte comprises an active material which is a mixture of lithium bromide, chloride and fluoride.
6. A thermal cell as claimed in claim 5, wherein said mixture further includes lithium iodide and the mixture is eutectic.
7. A thermal cell as claimed in any one of claims 4 to 6, wherein said electrolyte comprises an inert binder material.
8. A thermal cell as claimed in claim 1 and substantially as hereinbefore described with reference to Fig. 1 of the drawings.
9. A thermal battery comprising a plurality of thermal cells and a pyrotechnic material housed within a thermally insulated container, characterised in that at least one of said thermal cells is as claimed in any preceding claim.
10. A thermal battery as claimed in claim 9 and substantially as hereinbefore described with reference to Fig. 2 of the drawings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8216471A GB2101395B (en) | 1981-06-26 | 1982-06-07 | Thermal electric cells |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8119806 | 1981-06-26 | ||
| GB8216471A GB2101395B (en) | 1981-06-26 | 1982-06-07 | Thermal electric cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2101395A true GB2101395A (en) | 1983-01-12 |
| GB2101395B GB2101395B (en) | 1984-07-04 |
Family
ID=26279931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8216471A Expired GB2101395B (en) | 1981-06-26 | 1982-06-07 | Thermal electric cells |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2101395B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2556886A1 (en) * | 1983-12-19 | 1985-06-21 | Aerospatiale | THERMAL BATTERIES WITH AN ALKALI OR ALKALI-METAL ANODE OF THE IMPROVED CALCIUM TYPE AND THERMAL BATTERIES MADE BY SUCH BATTERIES |
| GB2363898A (en) * | 2000-06-20 | 2002-01-09 | Secr Defence | Rapidly activated thermal battery |
| WO2006046245A1 (en) * | 2004-10-28 | 2006-05-04 | Rafael-Armament Development Authority Ltd. | Heat sources for thermal batteries |
| CN114122510A (en) * | 2021-11-25 | 2022-03-01 | 华北电力大学 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
-
1982
- 1982-06-07 GB GB8216471A patent/GB2101395B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2556886A1 (en) * | 1983-12-19 | 1985-06-21 | Aerospatiale | THERMAL BATTERIES WITH AN ALKALI OR ALKALI-METAL ANODE OF THE IMPROVED CALCIUM TYPE AND THERMAL BATTERIES MADE BY SUCH BATTERIES |
| EP0147309A2 (en) * | 1983-12-19 | 1985-07-03 | AEROSPATIALE Société Nationale Industrielle | Thermal cells with an anode of an alkali metal or an alkaline earth metal of the calcium type and thermal batteries composed of said cells |
| EP0147309A3 (en) * | 1983-12-19 | 1985-08-14 | AEROSPATIALE Société Nationale Industrielle | Thermal cells with an anode of an alkali metal or an alkaline earth metal of the calcium type and thermal batteries composed of said cells |
| GB2363898A (en) * | 2000-06-20 | 2002-01-09 | Secr Defence | Rapidly activated thermal battery |
| WO2006046245A1 (en) * | 2004-10-28 | 2006-05-04 | Rafael-Armament Development Authority Ltd. | Heat sources for thermal batteries |
| CN114122510A (en) * | 2021-11-25 | 2022-03-01 | 华北电力大学 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
| CN114122510B (en) * | 2021-11-25 | 2024-03-19 | 华北电力大学 | Four-component inorganic molten salt electrolyte for lithium-based liquid metal battery |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2101395B (en) | 1984-07-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20010607 |