EP0406295A1 - Improvements in thermal batteries - Google Patents

Improvements in thermal batteries

Info

Publication number
EP0406295A1
EP0406295A1 EP89904166A EP89904166A EP0406295A1 EP 0406295 A1 EP0406295 A1 EP 0406295A1 EP 89904166 A EP89904166 A EP 89904166A EP 89904166 A EP89904166 A EP 89904166A EP 0406295 A1 EP0406295 A1 EP 0406295A1
Authority
EP
European Patent Office
Prior art keywords
battery
heater
thermal
electrolyte
battery according
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.)
Withdrawn
Application number
EP89904166A
Other languages
German (de)
French (fr)
Inventor
Austin Attewell
Ian Faul
John Knight
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UK Secretary of State for Defence
Original Assignee
UK Secretary of State for Defence
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by UK Secretary of State for Defence filed Critical UK Secretary of State for Defence
Publication of EP0406295A1 publication Critical patent/EP0406295A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/658Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/61Types of temperature control
    • H01M10/615Heating or keeping warm
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/63Control systems
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/64Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/643Cylindrical cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/654Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/657Means for temperature control structurally associated with the cells by electric or electromagnetic means
    • H01M10/6571Resistive heaters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • This invention relates to thermal batteries, and is aimed at providing a means capable in many applications of extending the useful life of the battery.
  • This invention seeks to provide a means by which a small portion of the electrical capacity of a thermal battery can be used, if need be, to supplement the internal resistive heating or counter it ⁇ natural cooling in order to maintain the electrolyte above its freezing point.
  • This invention therefore consists of a thermal battery comprising a sacrificial resistive heater connectable between the terminals of the battery and operable to maintain the temperature of the battery electrolyte above its freezing point for as long as useful electrical capacity remains in the battery.
  • the heater may be arranged to operate as soon as the battery has been initiated or it may be switched on by a timing device, for example after a given interval after initiation of the battery, and in either case it may be controlled by a thermostat.
  • the thermostat would be arranged to cut in when the temperature of the electrolyte was somewhat higher than the freezing point - perhaps by as much as 50°C - since the electrolyte will continue to cool until heat dissipates through the electrolyte at a sufficient rate to compensate for the rate of heat loss.
  • the heater may be in one of several forms - thus it may be a wire coil enclosed in an electrically-insulating material such as mica and supported around the periphery of the cell stack of the battery inside the battery thermal insulation layers or as a cartridge heater within a central hole in the cell stack, or the heater could be an electrically-conducting heat-resisting film formed or deposited on an insulating substrate at similar locations.
  • the heater could generate heat uniformly over its surface, but it could be designed to generate greater heat in those areas where more heat is lost or where the electrolyte tends to freeze the most rapidly.
  • Figure 1 is a schematic partly cut-away perspective view of one embodiment of a thermal battery incorporating the invention.
  • Figures 2 to 8 are graphs illustrating the effect of sacrificial heaters on the performance of thermal batteries of different sizes operated under various conditions.
  • a thermal battery consists of a stack of cells 1, each consisting of *t least an anode, electrolyte and cathode in disc form, and pressed, either Individually or in multiples, together with a similar disc 2 of pyrotechnic material between each cell, and mounted around a central hollow shaft (not shown) to provide space for ignition means.
  • the cells and pellets are contained inside a layer of thermal insulation 3 within a can 4. External terminals of the battery 5 and 6 on the upper face of the battery are connected to interior terminals at the top and bottom ends of the stack of cells respectively.
  • a cylindrical heater 7 Located adjacent to the inner fa_ze of the insulation layer 3 and in thermal contact with the sta-k of cells is a cylindrical heater 7 comprising a thin, insulating substrate on the inner face of which is formed a beating element consisting of an electrically-conductive heat-resistant film, the film being electrically insulated from the cell stack by a mica layer (not shown) and in electrical contact at its bottom end with the lower interior terminal of tie stack of cells and at its upper end with a third external terminal 8.
  • the pattern and/or thickness of the heating element is adapted to provide the necessary electrical resistance to generate the power required for the particular application.
  • the battery is initiated by firing the pyrotechnic material 2 raising the temperature of the electrolyte above its melting point, which in the typical case of a LiCl/KCl electrolyte is 352°C
  • the electrolyte becomes conductive and ezables the cells to supply a useful current.
  • the electrolyte will steadily cool down *t a rate dependent on the amount of insulation provided and the heat generated by current flow, a function of the external load, through the cell stack.
  • the electrolyte will begin to freeze just as the electrical capacity of the battery has exhausted, but in other conditions the electrolyte will freeze before this stage is reached.
  • the terminals 5 and 8 are interconnected by an external timing unit, and when the circuit is closed some time after initiation of the battery the heater operates, reducing slightly the output available between terminals 5 and 6 but extending the time elapse before the electrolyte freezes.
  • the upper end of the heating element is connected internally with the upper interior terminal of the cell stack, either via an integral timer or directly so that the heater operates immediately the battery is initiated.
  • a thermostatic element may be incorporated into the connections and in thermal contact with the electrolyte so that the heater only operates when the temperature of the electrolyte approaches its freezing point.
  • Figure 4 shows the effect on electrolyte temperature of a larger battery of various heaters switched on at 1100s in order to attempt to maintain output to 2000s, this not being possible without a heater due to electrolyte freezing at 352°C, which is seen to commence at about 1750s. It is seen that a 502 heater is sufficient to maintain the electrolyte above freezing, more powerful heaters causing unnecessary current drain and even overheating. The effect of this on output is seen in Figure 5, showing that heavy pulses can be obtained from the battery at high voltage up to 2000s with a 502 heater, and the effect of current drain with the other heaters is quite clear.
  • the heater need not be in the form of a conductor formed on a substrate; it may be in the form of a wire coil, enclosed for example in mica and supported on a heat-resistant former and it may be appropriate in some applications for the heater to be located along the central hole of the battery rather than surrounding the electrolyte.
  • Other variations in the form of the invention will be readily apparent to those skilled in the art.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Automation & Control Theory (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

La batterie thermique décrite contient une résistance chauffante sacrificielle (7) pouvant être reliée entre les bornes de la batterie et pouvant fonctionner de façon à maintenir l'électrolyte au-dessus de son point de congélation après la mise en marche de la batterie et aussi longtemps que la pile conserve sa capacité utile. La résistance chauffante peut se présenter sous la forme d'un film conducteur déposé sur un substrat thermorésistant ou sur une bobine de fil retenue sur un gabarit et peut être disposée soit à l'intérieur d'un arbre central de la batterie soit autour de la pile des éléments à l'intérieur de la couche d'isolation thermique (3) de la batterie. La résistance chauffante peut être connectée directement par voie électrique aux extrémités de la pile des éléments ou peut être connectée à elles indirectement via un appareil horaire interne ou externe destiné à être commuté en position de marche après l'écoulement d'une période prédéterminée à partir de la mise en fonctionnement et la résistance chauffante peut être régulée par thermostat.The thermal battery described contains a sacrificial heating resistor (7) which can be connected between the terminals of the battery and which can operate so as to keep the electrolyte above its freezing point after switching on the battery and for as long the battery retains its useful capacity. The heating resistor may be in the form of a conductive film deposited on a heat-resistant substrate or on a coil of wire retained on a template and may be arranged either inside a central shaft of the battery or around the stack of cells inside the thermal insulation layer (3) of the battery. The heating resistor can be directly connected electrically to the ends of the cell of the elements or can be connected to them indirectly via an internal or external time device intended to be switched to the on position after the expiration of a predetermined period from from start-up and the heating resistance can be regulated by thermostat.

Description

IMPROVEMENTS IN THERMAL BATTERIES
This invention relates to thermal batteries, and is aimed at providing a means capable in many applications of extending the useful life of the battery.
There are two main mechanisms by which the useful life of a thermal battery is terminated - exhaustion of electrical capacity or a rapid rise in its internal resistance caused by cooling below a certain temperature around the freezing point of the electrolyte. For particular battery designs, there is often a considerable imbalance between the life expectancies governed by the separate effects: ideally these should be equal since an excess of cell volume (governing electrical capacity) or thermal insulation represents a cost, size and/or weight penalty. However, due to the usually wide temperature range over which a battery is required to provide a minimum specified performance, its life can often be limited by electrolyte freezing towards the lower end of the temperature range, whilst being capacity-limited at the top end due not only to more extensive side reactions at a higher battery internal temperature but also to a longer time elapse before commencement of electrolyte freezing.
This invention seeks to provide a means by which a small portion of the electrical capacity of a thermal battery can be used, if need be, to supplement the internal resistive heating or counter itβ natural cooling in order to maintain the electrolyte above its freezing point. This invention therefore consists of a thermal battery comprising a sacrificial resistive heater connectable between the terminals of the battery and operable to maintain the temperature of the battery electrolyte above its freezing point for as long as useful electrical capacity remains in the battery.
The heater may be arranged to operate as soon as the battery has been initiated or it may be switched on by a timing device, for example after a given interval after initiation of the battery, and in either case it may be controlled by a thermostat. In the latter case, the thermostat would be arranged to cut in when the temperature of the electrolyte was somewhat higher than the freezing point - perhaps by as much as 50°C - since the electrolyte will continue to cool until heat dissipates through the electrolyte at a sufficient rate to compensate for the rate of heat loss.
The heater may be in one of several forms - thus it may be a wire coil enclosed in an electrically-insulating material such as mica and supported around the periphery of the cell stack of the battery inside the battery thermal insulation layers or as a cartridge heater within a central hole in the cell stack, or the heater could be an electrically-conducting heat-resisting film formed or deposited on an insulating substrate at similar locations. For simplicity the heater could generate heat uniformly over its surface, but it could be designed to generate greater heat in those areas where more heat is lost or where the electrolyte tends to freeze the most rapidly.
By way of example, the invention will now he described with reference to the drawings, of which
Figure 1 is a schematic partly cut-away perspective view of one embodiment of a thermal battery incorporating the invention, and
Figures 2 to 8 are graphs illustrating the effect of sacrificial heaters on the performance of thermal batteries of different sizes operated under various conditions.
Referring to Figure 1, a thermal battery consists of a stack of cells 1, each consisting of *t least an anode, electrolyte and cathode in disc form, and pressed, either Individually or in multiples, together with a similar disc 2 of pyrotechnic material between each cell, and mounted around a central hollow shaft (not shown) to provide space for ignition means.
The cells and pellets are contained inside a layer of thermal insulation 3 within a can 4. External terminals of the battery 5 and 6 on the upper face of the battery are connected to interior terminals at the top and bottom ends of the stack of cells respectively.
Located adjacent to the inner fa_ze of the insulation layer 3 and in thermal contact with the sta-k of cells is a cylindrical heater 7 comprising a thin, insulating substrate on the inner face of which is formed a beating element consisting of an electrically-conductive heat-resistant film, the film being electrically insulated from the cell stack by a mica layer (not shown) and in electrical contact at its bottom end with the lower interior terminal of tie stack of cells and at its upper end with a third external terminal 8. The pattern and/or thickness of the heating element is adapted to provide the necessary electrical resistance to generate the power required for the particular application.
In operation, the battery is initiated by firing the pyrotechnic material 2 raising the temperature of the electrolyte above its melting point, which in the typical case of a LiCl/KCl electrolyte is 352°C On melting, the electrolyte becomes conductive and ezables the cells to supply a useful current. In the absence of any heater, the electrolyte will steadily cool down *t a rate dependent on the amount of insulation provided and the heat generated by current flow, a function of the external load, through the cell stack. Under some conditions, the electrolyte will begin to freeze just as the electrical capacity of the battery has exhausted, but in other conditions the electrolyte will freeze before this stage is reached. As an alternative to providing greater insulation - to which there is in any case a practical limit - to utilise fully the capacity of the battery the terminals 5 and 8 are interconnected by an external timing unit, and when the circuit is closed some time after initiation of the battery the heater operates, reducing slightly the output available between terminals 5 and 6 but extending the time elapse before the electrolyte freezes.
In other embodiments of the invention, the upper end of the heating element is connected internally with the upper interior terminal of the cell stack, either via an integral timer or directly so that the heater operates immediately the battery is initiated. In any embodiment a thermostatic element may be incorporated into the connections and in thermal contact with the electrolyte so that the heater only operates when the temperature of the electrolyte approaches its freezing point.
The effect on the battery output of the incorporation of a heater of the kind described can be seen from the results, reproduced in Figures 2 to 8, of computer simulations of various heater dissipations (expressed as various electrical resistance values) incorporated in large, medium and small sizes of commercially available batteries, and at high and low ambient temperatures.
In Figure 2 output voltage/time curves have been plotted for a battery of medium size at an ambient temperature of -40°C, having no heater and with heaters of 102, 202, 502 and 100Ω (the lowest resistance heaters dissipating the most power) and connected to the same external load.
With no heater, the output from the battery declines only very slowly until about 900s from initiation: the firing of the pyrotechnic will have raised the electrolyte temperature to well above its freezing point but by 900s re-freezing starts to take place. The electrolyte steadily freezes thereafter causing a rapid fall in battery output to an unacceptable level after a total time elapse of 1200s or so.
The effect of a 1002 heater switched on after about 300s from battery initiation is seen to prolong an essentially constant battery output at least until about 1500s, by which time the electrical capacity of the battery may be close to exhaustion. The effect of even a 1002 heater has therefore been sufficient in this case to maintain the electrolyte above its freezing point and therefore in a fully conducting condition. Little further benefit can be gained from the use of more powerful heaters, as the other curves show: a 502 heater does not drain the battery significantly but causes a slight reduction in battery output throughout its operation. Use of 202 and 102 heaters however exhaust the battery prematurely but in certain cases the use of a 202 heater would prolong slightly the useful life of the battery - at say 50% of maximum output level.
The above curves assume operation of the battery in an ambient temperature of -40°C. If the same battery is operated at rather higher ambient temperatures then the ignition of the pyrotechnic will raise the electrolyte temperature to a corresponding higher value, so that a longer time will elapse before the electrolyte freezing point is reached. Capacity exhaustion is thus more likely to occur first. This is illustrated by the curves in Figure 3, where no beneficial effect is apparently gained from the use of even a 1002 heater with the same battery as before but operated at +70°C. The effect on the output is indeed detrimental due to current drain through the heater. The incorporation of a heater in a battery for use at this temperature might however make it possible to employ considerably less insulation, and the resulting curves would then be more akin to those of Figure 2 even at the higher temperature - the use of, say, a 1002 heater would compensate for the decrease of insulation. Consistent results are found in simulations of larger and smaller batteries. Figure 4 shows the effect on electrolyte temperature of a larger battery of various heaters switched on at 1100s in order to attempt to maintain output to 2000s, this not being possible without a heater due to electrolyte freezing at 352°C, which is seen to commence at about 1750s. It is seen that a 502 heater is sufficient to maintain the electrolyte above freezing, more powerful heaters causing unnecessary current drain and even overheating. The effect of this on output is seen in Figure 5, showing that heavy pulses can be obtained from the battery at high voltage up to 2000s with a 502 heater, and the effect of current drain with the other heaters is quite clear.
With a small battery, the effect of heat loss through the insulation is more marked, especially at low temperatures. From Figure 6 it is seen that in spite of greater current drain 202 and 102 heaters are needed to maintain the electrolyte above freezing at 352°C in an ambient temperature of -40° . The corresponding output curves in Figure 7 confirm that a 202 heater is closer to optimum under these conditions, the similar electrolyte temperature maintained by a 102 heater being more than offset by its much higher current drain.
With the same battery used at +70βC though, the effects are very different. From Figure 8 it is seen that since the electrolyte does not freeze during its operation, no benefit appears to be gained from the use of a heater in these conditions. To use the same battery over a wide range of ambient temperatures, some kind of thermostatic control is needed.
The above examples illustrate that the degree of heating needed depends on all the variables βnder which the battery is used - its size, power requirement and ambient temperature range among others. The use of thermostatic control would reduce unnecessary heating and current drain, while the possibility of using less thermal insulation increases the efficiency of the battery in terms of energy per unit weight or volume. Overall it is possible to make the effective capacity of the battery to be less dependent on its operating variables.
Nevertheless, there are many instances - for example for some applications of smaller batteries such as that described with reference to Figure 8 - where a sacrificial heater would not only be unnecessary but would be detrimental by adding to the current drain of the battery, but by reference to all the examples described the extent of usefulness of this invention will be understood.
The heater need not be in the form of a conductor formed on a substrate; it may be in the form of a wire coil, enclosed for example in mica and supported on a heat-resistant former and it may be appropriate in some applications for the heater to be located along the central hole of the battery rather than surrounding the electrolyte. Other variations in the form of the invention will be readily apparent to those skilled in the art.

Claims

1. A thermal battery characterised by comprising a saσifidal resistive heater (7) connectable between the terminals of the battery (5, 6) and operable to maintain the temperature of the battery electrolyte above its freezing point for as long as useful electrical capadty remains in the battery.
2. A thermal battery according to Claim 1 in whidi the heater (7) comprises a layer of electrically-conducting material formed or deposited on an insulating substrate.
3. A thermal battery according to either preceding daim in which the heater is arranged to surround the stack of cells of the battery and in thermal contact therewith.
4. A thermal battery according to Claim 1 or Claim 2 in which the heater is located within an axial hole extending through the stack of cells of the battery.
5. A thermal battery according to any preceding daim induding a timing device arranged to actuate the heater after a pre-determined time lapse after initiation of the battery.
6. A thermal battery according to any preceding daim induding a thermostatic device to prevent operation of the heater under conditions where the electrolyte is not in danger of freezing within the required life of the battery.
7. A thermal battery according to any of Claims 1 to 4 in which the heater is connected internally and directly between the terminals of the battery so that heat is generated whenever the battery electrolyte is in a conducting state.
EP89904166A 1988-03-25 1989-03-23 Improvements in thermal batteries Withdrawn EP0406295A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8807217 1988-03-25
GB8807217A GB8807217D0 (en) 1988-03-25 1988-03-25 Improvements in thermal batteries

Publications (1)

Publication Number Publication Date
EP0406295A1 true EP0406295A1 (en) 1991-01-09

Family

ID=10634140

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89904166A Withdrawn EP0406295A1 (en) 1988-03-25 1989-03-23 Improvements in thermal batteries

Country Status (3)

Country Link
EP (1) EP0406295A1 (en)
GB (2) GB8807217D0 (en)
WO (1) WO1989009497A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9313437D0 (en) * 1993-06-30 1993-08-11 Smith Andrew W Pathogenicity sequences in helicobacter pylori
WO1996017397A1 (en) * 1994-11-28 1996-06-06 Chartec Laboratories A/S A method and an apparatus for controlling battery temperature during charging/discharging
GB2493511B (en) * 2011-07-29 2018-01-31 Sondex Wireline Ltd Downhole energy storage system
US20220247015A1 (en) * 2019-07-12 2022-08-04 Ampcera Inc. Interally heatable battery, internally heatable battery system, internally heatable battery method, and electric vehicle comprising the same

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Publication number Priority date Publication date Assignee Title
US3649366A (en) * 1970-02-19 1972-03-14 Esb Inc Storage battery and heater therefor
US3775181A (en) * 1971-08-12 1973-11-27 Broomfield Ryerson Res Corp Lithium storage cells with a fused electrolyte
US3823037A (en) * 1972-07-20 1974-07-09 Atomic Energy Commission Implantable battery
GB2094527B (en) * 1977-12-05 1982-11-24 Gearhart Ind Inc Power source used in making measurements in an earth borehole
GB2081000B (en) * 1980-07-23 1984-01-18 Chloride Silent Power Ltd Controlling the temperature of eg sodium-sulphur batteries
DE3340882C1 (en) * 1983-11-11 1985-06-27 Messerschmitt-Bölkow-Blohm GmbH, 8012 Ottobrunn Device for temperature monitoring and reconditioning of batteries consisting of electrochemical individual cells
DE3427028A1 (en) * 1984-07-21 1986-01-23 Eckhard 6800 Mannheim Wagner Accumulator

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Title
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Also Published As

Publication number Publication date
GB9020668D0 (en) 1990-11-21
WO1989009497A1 (en) 1989-10-05
GB8807217D0 (en) 1988-04-27
GB2234625A (en) 1991-02-06

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