WO1989012344A1 - Microprocessor based recharger for lithium secondary system - Google Patents

Microprocessor based recharger for lithium secondary system Download PDF

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Publication number
WO1989012344A1
WO1989012344A1 PCT/US1989/002441 US8902441W WO8912344A1 WO 1989012344 A1 WO1989012344 A1 WO 1989012344A1 US 8902441 W US8902441 W US 8902441W WO 8912344 A1 WO8912344 A1 WO 8912344A1
Authority
WO
WIPO (PCT)
Prior art keywords
cell
voltage
open circuit
circuit voltage
recharger
Prior art date
Application number
PCT/US1989/002441
Other languages
French (fr)
Inventor
On-Kok Chang
John C. Hall
Jeffrey Phillips
Lenard Frank Silvester
Original Assignee
Altus Corporation
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 Altus Corporation filed Critical Altus Corporation
Publication of WO1989012344A1 publication Critical patent/WO1989012344A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/3644—Constructional arrangements
    • G01R31/3648—Constructional arrangements comprising digital calculation means, e.g. for performing an algorithm
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
    • G01R31/3835—Arrangements for monitoring battery or accumulator variables, e.g. SoC involving only voltage measurements
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/007—Regulation of charging or discharging current or voltage
    • H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
    • H02J7/007182—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage
    • 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

Definitions

  • the present invention deals with a recharger for a non-aqueous secondary cell having an Li-CuCl2 couple.
  • Cells of this type exhibit a substantially constant open circuit voltage and it is this characteristic which provides the basis for the present recharger, which is capable of measuring the open circuit voltage and if the open circuit voltage is less than a predetermined lower set point voltage, recharging is terminated.
  • the present invention deals with a recharger for a non-aqueous electrochemical cell and, more particularly, with inorganic cells employing an alkaline metal, such as lithium, as the anode, with a cathode collector separated from the anode by a separator membrane.
  • an alkaline metal such as lithium
  • a cathode collector separated from the anode by a separator membrane.
  • the anode is generally lithium metal or alloys of lithium and the electrolyte solution is an ionically conductive solute dissolved in a solvent that is also the active cathode depolarizer.
  • the solute may be a simple or double salt which will produce an ionically conductive solution when dissolved in the solvent.
  • Preferred solutes are complexes of inorganic or organic Lewis acids and inorganic ionizable salts. The requirements for utility are that the salt, whether simple or complex, be compatible with the solvent being employed in that it yield a solution which is ionically conductive.
  • a typical Lewis acid suitable for incorporation in cells of the type contemplated herein is aluminum chloride which, when combined with a suitable ionizable salt such a lithium chloride, yields lithium aluminum chloride (LiAlCl. ) , which is maintained in a suitable solvent such as sulfur dioxide (SO2) .
  • a suitable ionizable salt such as lithium chloride
  • the cathode collector should preferably be inert under certain severe environmental conditions. These include a marked inertness toward the electrolyte solvent solution of, for example, lithium aluminum tetrachloride (LiAlCl. ) in sulfur dioxide (SO 2 ) . This inertness should evidence itself over the voltage range of 2.5-4.0V, while also exhibiting an inertness towards overcharge products. It is commonplace in non-aqueous secondary electrochemical cells to have cupric chloride present in the electrolyte solution. This is the result of the following reaction:
  • cathode collectors must also be inert towards cupric chloride and its reduced species, as well as display a low oh ic resistance.
  • Fig. l is a block diagram of the various component parts constituting the charger of the present invention
  • Fig. 2 is a logic diagram displaying the charger sequence as controlled by the microcomputer shown in Fig. 1
  • Fig. 3 is an Emf of a typical cell during the charging sequence
  • Fig. 4 is a current curve, again of a typical electrochemical cell subjected to the charger of the present invention.
  • the present invention deals with a recharger for a non-aqueous secondary cell having an Li-CuCl2 couple which exhibits a substantially constant open circuit voltage.
  • the recharger comprises a constant voltage limited- constant current power supply, a voltage sense circuit, and a microprocessor to control the recharging sequence.
  • the microprocessor is programmed such that the cell is not charged if the open circuit voltage is less than a lower set point voltage selected for a particular cell.
  • the present invention is based upon the recognition that the overall cell reaction for a non-aqueous electrochemical cell having an Li-CuCl2 couple is fixed irrespective of the cell's charge state. This is a result of the fact that the cells operate at a fixed chemical activity and, as a result, any abnormal decrease in open circuit voltage indicates a cell malfunction. By monitoring the open circuit voltage throughout the charging process charging may be terminated at the first sign of cell malfunction.
  • the recharger consists of a constant voltage limited- constant current power supply 12 which is coupled to a low voltage AC input via rectifier 11 and regulator 13.
  • the recharger sequence is controlled by microprocessor 16 which is coupled to the positive cell terminal 14 through the power supply 12 and cell voltage test circuit 17.
  • the charger operates by first checking the open circuit voltage and if the open circuit voltage is less than a lower predetermined set point, charging does not commence.
  • the state of the microprocessor can be deter ined by LED driver 19, whose output is visually perceived through LED indicators 20.
  • the cell is charged for a predetermined period of time. After charging, the cell is subjected to a preset dwell time, during which the open circuit voltage is again measured. If the open circuit voltage is less than the predetermined lower set point, charging is again terminated. If not, charging resumes, again for a predetermined period of time, followed by the mandatory preset dwell time and open circuit voltage measurement. This sequence is repeated over again until a preset total charge time is reached or until the open circuit voltage falls below the lower set point.
  • the flow diagram indicating the logic for controlling the charger is indicated in Fig. 2 and is quite self- explanatory. Microprocessor 16 can be programmed to carry out the logic steps of Fig. 2, said programming being well within the expertise of anyone of ordinary skill in this art.
  • the charger has set points for maximum allowed current and voltage, typically 40mA and 3.9V.
  • the charger will try to supply the maximum current consistent with the charger set points. For example, when a discharged cell is connected to the charger, if the charger can supply 40mA at an output voltage less than 3.9V, it will. That is, the charger will be current limited, and provide the maximum allowed current, 40mA. This is the constant current part of the charging cycle, and this mode remains until the cell nears recharge. The cell voltage then rises sharply, and the charger can no longer supply 40mA for to do so would require more voltage output than the maximum allowed of 3.9V. The charger is now voltage-limited, and will supply only 3.9V.
  • chargers of the present invention run at approximately 40mA current limit, 3.9V voltage limit, and at a lower set point limit of approximately 3.15V. All of these set points can be adjusted on the charger of the present invention to meet various design needs.
  • the dwell time is also adjustable and typically is approximately 5 minutes, with the charging time between dwell times typically being approximately 15 minutes, with the overall charge time being adjustable from 15 to 24 hours.
  • the charging current, lower set point, upper voltage limit, charge time, dwell time, and overall charge time are parameters which are set manually.
  • the microprocessor then "reads" this information as input and causes the recharger to operate within these preset parameters.
  • Figs. 3 and 4 display the Emf and charging current profiles for one charging of an AA secondary cell possessing an Li-CuCl2 couple. It is noted by viewing Fig. 3 that the Emf is basically stable and then drops off during dwell periods to the cell open circuit voltage.
  • Fig. 4 is a graph displaying the charging current profile of the AA secondary cell.
  • the current is basically steady during charging and drops to zero during the dwell period. Subsequently, there is a noted sharp rise in current when charging resumes.
  • the sloping shape of the curve near the end of the charging cycle indicates that the charger is going into the taper charge mode while still monitoring the cell open circuit voltage.
  • all of the component parts shown by block diagram Fig. 1 are readily available commercially. The commercial part numbers, where applicable, have been placed within each block of Fig. 1.

Abstract

A recharger for a non-aqueous secondary cell having an Li-CuCl2 couple. A constant voltage limited-constant current power supply (12), a voltage sense circuit (17) and a microprocessor (16) are employed to control the recharging sequence. Noting that a cell based upon an Li-CuCl2 couple exhibits a substantially constant open circuit voltage, the cell is not charged if the open circuit voltage is less than the lower set point voltage set for a particular cell.

Description

-]- MICROPROCESSOR BASED RECHARGER FOR LITHIUM SECONDARY SYSTEM
Technical Field of the Invention
The present invention deals with a recharger for a non-aqueous secondary cell having an Li-CuCl2 couple. Cells of this type exhibit a substantially constant open circuit voltage and it is this characteristic which provides the basis for the present recharger, which is capable of measuring the open circuit voltage and if the open circuit voltage is less than a predetermined lower set point voltage, recharging is terminated.
Background of the Invention
The present invention deals with a recharger for a non-aqueous electrochemical cell and, more particularly, with inorganic cells employing an alkaline metal, such as lithium, as the anode, with a cathode collector separated from the anode by a separator membrane. Among all the known combinations of lithium anodes with different cathodes and electrolytes, those believed to have among the highest energy density and lowest internal impedance use certain inorganic liquids as the active cathode depolarizer. This type of cell chemistry is commonly referred to as "liquid cathode" and it is with respect to this general chemistry that cells of the type disclosed herein are directed.
Liquid cathode cells using oxyhalides are described in U.S. Patent No. 3,926,669 issued to Auburn on
December 16, 1975. As described in Auburn, the anode is generally lithium metal or alloys of lithium and the electrolyte solution is an ionically conductive solute dissolved in a solvent that is also the active cathode depolarizer. The solute may be a simple or double salt which will produce an ionically conductive solution when dissolved in the solvent. Preferred solutes are complexes of inorganic or organic Lewis acids and inorganic ionizable salts. The requirements for utility are that the salt, whether simple or complex, be compatible with the solvent being employed in that it yield a solution which is ionically conductive. A typical Lewis acid suitable for incorporation in cells of the type contemplated herein is aluminum chloride which, when combined with a suitable ionizable salt such a lithium chloride, yields lithium aluminum chloride (LiAlCl. ) , which is maintained in a suitable solvent such as sulfur dioxide (SO2) .
In addition to an anode, an active cathode depolarizer and ionically-conductive electrolyte, cells of this type also require the use of a current or cathode collector. According to Bloomgren, as taught in British Patent No. 1,409,307, any compatible solid, which is substantially electrically conductive and inert in the cell, will be useful as a cathode collector since the function of the collector is to permit external electrical contact to be made with the active cathode material. It is taught to be desirable to have as much surface contact as possible between the liquid cathode and current collector and, as such, most teachings have focused upon the use of a porous material, such as graphite, as the current collector.
It has been recognized that for a non-aqueous secondary cell, the cathode collector should preferably be inert under certain severe environmental conditions. These include a marked inertness toward the electrolyte solvent solution of, for example, lithium aluminum tetrachloride (LiAlCl. ) in sulfur dioxide (SO2) . This inertness should evidence itself over the voltage range of 2.5-4.0V, while also exhibiting an inertness towards overcharge products. It is commonplace in non-aqueous secondary electrochemical cells to have cupric chloride present in the electrolyte solution. This is the result of the following reaction:
CuCl2 + AICI4 → CuCl2 + AICI3 + e"
As such, appropriate cathode collectors must also be inert towards cupric chloride and its reduced species, as well as display a low oh ic resistance.
In light of the fact that cells of the type discussed above permit high currents to be drawn and are characterized as exhibiting high power outputs, the cells can be rendered unsafe when subjected to abusive conditions. For example, it is recognized that such non- aqueous cells having an Li-CuCl2 couple have a lower cycle life than comparable aqueous systems, which employ cadmium or lead negative electrodes. A major cause of death of such lithium cells is the formation of dendrites which grow from the lithium electrode and make electronic contact with complementary positive electrodes. This can result in a catastrophic overheating of the cell and resultant venting of cell components. It is thus an object of the present invention to provide a recharger for a non-aqueous lithium based electrochemical cell.
It is a further object of the present invention to provide a recharger for such cells which is capable of detecting an unsafe cell condition and terminating the recharging operation if such an eventuality occurs.
These and further objects of the present invention will be more readily perceived when considering the following discussion and appended drawings wherein Fig. l is a block diagram of the various component parts constituting the charger of the present invention,
Fig. 2 is a logic diagram displaying the charger sequence as controlled by the microcomputer shown in Fig. 1, Fig. 3 is an Emf of a typical cell during the charging sequence, and Fig. 4 is a current curve, again of a typical electrochemical cell subjected to the charger of the present invention.
Summary of the Invention
The present invention deals with a recharger for a non-aqueous secondary cell having an Li-CuCl2 couple which exhibits a substantially constant open circuit voltage. The recharger comprises a constant voltage limited- constant current power supply, a voltage sense circuit, and a microprocessor to control the recharging sequence. The microprocessor is programmed such that the cell is not charged if the open circuit voltage is less than a lower set point voltage selected for a particular cell.
Detailed Description of the Invention
The present invention is based upon the recognition that the overall cell reaction for a non-aqueous electrochemical cell having an Li-CuCl2 couple is fixed irrespective of the cell's charge state. This is a result of the fact that the cells operate at a fixed chemical activity and, as a result, any abnormal decrease in open circuit voltage indicates a cell malfunction. By monitoring the open circuit voltage throughout the charging process charging may be terminated at the first sign of cell malfunction.
The recharger consists of a constant voltage limited- constant current power supply 12 which is coupled to a low voltage AC input via rectifier 11 and regulator 13. The recharger sequence is controlled by microprocessor 16 which is coupled to the positive cell terminal 14 through the power supply 12 and cell voltage test circuit 17.
In summary, the charger operates by first checking the open circuit voltage and if the open circuit voltage is less than a lower predetermined set point, charging does not commence. The state of the microprocessor can be deter ined by LED driver 19, whose output is visually perceived through LED indicators 20.
If the open circuit voltage is greater than the lower set point, the cell is charged for a predetermined period of time. After charging, the cell is subjected to a preset dwell time, during which the open circuit voltage is again measured. If the open circuit voltage is less than the predetermined lower set point, charging is again terminated. If not, charging resumes, again for a predetermined period of time, followed by the mandatory preset dwell time and open circuit voltage measurement. This sequence is repeated over again until a preset total charge time is reached or until the open circuit voltage falls below the lower set point. The flow diagram indicating the logic for controlling the charger is indicated in Fig. 2 and is quite self- explanatory. Microprocessor 16 can be programmed to carry out the logic steps of Fig. 2, said programming being well within the expertise of anyone of ordinary skill in this art.
Generally, the charger has set points for maximum allowed current and voltage, typically 40mA and 3.9V. The charger will try to supply the maximum current consistent with the charger set points. For example, when a discharged cell is connected to the charger, if the charger can supply 40mA at an output voltage less than 3.9V, it will. That is, the charger will be current limited, and provide the maximum allowed current, 40mA. This is the constant current part of the charging cycle, and this mode remains until the cell nears recharge. The cell voltage then rises sharply, and the charger can no longer supply 40mA for to do so would require more voltage output than the maximum allowed of 3.9V. The charger is now voltage-limited, and will supply only 3.9V. But at 3.9V the charger cannot supply 40mA so it supplies a lesser amount. As the cell voltage rises, the current tapers off as the charger continues to supply the maximum allowed voltage. The tapering charge method is a consequence of using a voltage-current limited power supply. There is no "switch" that changes the charger between constant current and constant voltage.
As a preferred embodiment, chargers of the present invention run at approximately 40mA current limit, 3.9V voltage limit, and at a lower set point limit of approximately 3.15V. All of these set points can be adjusted on the charger of the present invention to meet various design needs. The dwell time is also adjustable and typically is approximately 5 minutes, with the charging time between dwell times typically being approximately 15 minutes, with the overall charge time being adjustable from 15 to 24 hours.
The charging current, lower set point, upper voltage limit, charge time, dwell time, and overall charge time are parameters which are set manually. The microprocessor then "reads" this information as input and causes the recharger to operate within these preset parameters.
Figs. 3 and 4 display the Emf and charging current profiles for one charging of an AA secondary cell possessing an Li-CuCl2 couple. It is noted by viewing Fig. 3 that the Emf is basically stable and then drops off during dwell periods to the cell open circuit voltage.
Subsequently, there is a sharp rise in Emf to the charger voltage.
Fig. 4 is a graph displaying the charging current profile of the AA secondary cell. As would be expected, the current is basically steady during charging and drops to zero during the dwell period. Subsequently, there is a noted sharp rise in current when charging resumes. The sloping shape of the curve near the end of the charging cycle indicates that the charger is going into the taper charge mode while still monitoring the cell open circuit voltage. As will be readily appreciated, all of the component parts shown by block diagram Fig. 1 are readily available commercially. The commercial part numbers, where applicable, have been placed within each block of Fig. 1.

Claims

Claims
1. A recharger for a non-aqueous secondary cell having a Li-CuCl2 couple which exhibits a substantially constant open circuit voltage comprising power supply means for controllably applying a constant voltage limited-constant current to said cell; voltage sense means couplable to said cell for measuring the open circuit voltage thereof; and microprocessor means for controlling a recharging sequence of said cell in which the power supply means are controlled to alternately charge said cell and disconnected from said cell to permit the open circuit voltage thereof to be measured, wherein said cell is not charged if said open circuit voltage is less than a lower set point voltage selected for a particular cell.
2. The recharger of claim 1 wherein the power supply means has preset maximum allowed current and voltage values.
3. The recharger of claim 2 wherein said preset maximum allowed current value is approximately 40mA.
4. The recharger of claim 2 wherein said preset maximum allowed voltage value is approximately 3.9V.
5. The recharger of claim 1 wherein in the recharging sequence, if the open circuit voltage of said cell is at or greater than the lower set point, the cell is charged for a preset time period, after which charging ceases for a predetermined dwell time, and after which time, the open circuit voltage of said cell is again measured.
6. The recharger of claim 5 wherein in the recharging sequence, if the open circuit voltage of said cell is less than the lower set point, charging is stopped but if greater than the lower set point, charging continues for a predetermined period of time.
7. A recharger for a non-aqueous secondary cell having a Li-CuCl2 couple which exhibits a substantially constant open circuit voltage comprising a constant voltage limited-constant current power supply for controllably charging said cell; a voltage sense circuit connectible to said cell for measuring the voltage thereof; and microprocessor means communicating with said power supply and said voltage sense circuit for controlling a recharging sequence of said cell wherein the recharging sequence comprises
(a) measuring the open circuit voltage of said cell with said voltage sense circuit and if the open circuit voltage is less than a lower set point, withholding charging of said cell, but
(b) if the open circuit voltage is at or greater than the lower set point, charging the cell for a preset time period, charging is interrupted for a preset dwell time and thereafter measuring the open circuit voltage and (i) if the measured open circuit voltage is less than the lower set point, stopping charging of said cell, but
(ii) if greater than the lower set point, repeating step (b) until a preset total charge time has elapsed.
PCT/US1989/002441 1988-06-06 1989-06-05 Microprocessor based recharger for lithium secondary system WO1989012344A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20226388A 1988-06-06 1988-06-06
US202,263 1988-06-06

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Cited By (5)

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EP0583906A1 (en) * 1992-08-18 1994-02-23 Sony Corporation Battery unit and battery energy billing method
US6107802A (en) * 1992-07-08 2000-08-22 Matthews; Wallace Edward Battery pack with monitoring function utilizing association with a battery charging system
US6369576B1 (en) 1992-07-08 2002-04-09 Texas Instruments Incorporated Battery pack with monitoring function for use in a battery charging system
CN1325924C (en) * 2003-08-18 2007-07-11 旺宏电子股份有限公司 Monitoring circuit of generator battery charger
CN108808777A (en) * 2018-06-15 2018-11-13 西安微电子技术研究所 The charging circuit that one mode independently switches

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DE4027146A1 (en) * 1990-08-28 1992-03-05 Nortec Electronic Gmbh Battery esp. of nickel-cadmium type, charging circuit - has microprocessor control with initial test routine, main charging cycle and subsequent top up charging
DE4243710C2 (en) * 1992-12-23 1998-07-30 Telefunken Microelectron Charging process for accumulators and switching arrangement for carrying out the process
FR2733093B1 (en) * 1995-04-12 1997-07-04 Sgs Thomson Microelectronics BATTERY CHARGER

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US4467266A (en) * 1982-03-29 1984-08-21 Mcgraw-Edison Company Battery overcharge protection system
US4684871A (en) * 1985-12-18 1987-08-04 U.S. Philips Corporation Power supply circuit
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
US6107802A (en) * 1992-07-08 2000-08-22 Matthews; Wallace Edward Battery pack with monitoring function utilizing association with a battery charging system
US6369576B1 (en) 1992-07-08 2002-04-09 Texas Instruments Incorporated Battery pack with monitoring function for use in a battery charging system
EP0583906A1 (en) * 1992-08-18 1994-02-23 Sony Corporation Battery unit and battery energy billing method
US5525890A (en) * 1992-08-18 1996-06-11 Sony Corporation Battery unit and battery energy billing method
CN1325924C (en) * 2003-08-18 2007-07-11 旺宏电子股份有限公司 Monitoring circuit of generator battery charger
CN108808777A (en) * 2018-06-15 2018-11-13 西安微电子技术研究所 The charging circuit that one mode independently switches

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DE8906689U1 (en) 1989-08-24
DE3917795A1 (en) 1989-12-07

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