WO2000042673A1 - Procede de charge d'une cellule secondaire et chargeur - Google Patents

Procede de charge d'une cellule secondaire et chargeur Download PDF

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Publication number
WO2000042673A1
WO2000042673A1 PCT/JP1999/000124 JP9900124W WO0042673A1 WO 2000042673 A1 WO2000042673 A1 WO 2000042673A1 JP 9900124 W JP9900124 W JP 9900124W WO 0042673 A1 WO0042673 A1 WO 0042673A1
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WIPO (PCT)
Prior art keywords
charging
current value
battery
charge
current
Prior art date
Application number
PCT/JP1999/000124
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English (en)
Japanese (ja)
Inventor
Tamotsu Yamamoto
Hiroshi Horiuchi
Kensuke Yoshida
Masami Tsutsumi
Tsutomu Miyashita
Original Assignee
Fujitsu Limited
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.)
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Application filed by Fujitsu Limited filed Critical Fujitsu Limited
Priority to PCT/JP1999/000124 priority Critical patent/WO2000042673A1/fr
Publication of WO2000042673A1 publication Critical patent/WO2000042673A1/fr

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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
    • H01M10/42—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
    • H02J7/0071—Regulation of charging or discharging current or voltage with a programmable schedule
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 relates to a method and a device for charging a secondary battery used as a power source for driving a notebook computer or portable electronic device.
  • non-aqueous electrolyte secondary batteries using lithium metal or lithium alloy for the negative electrode have an extremely high energy density, and are attracting attention as batteries suitable for miniaturization and weight reduction. Research is being done.
  • lithium on the negative electrode becomes lithium ions and moves to the positive electrode side in the electrolytic solution, and when charging, on the contrary, lithium escapes from the positive electrode and deposits on the negative electrode. Since lithium is very active, if lithium precipitates coarsely during charging and the surface area increases, it tends to react with the components in the electrolyte, and an irreversible film (called dead lithium; ), which leads to a reduction in the charge and discharge cycle life.
  • Japanese Patent Application Laid-Open No. 7-123604 discloses a charging method capable of shortening the charging time of a secondary battery. According to one embodiment of this charging method, the charging current at the initial stage of charging is increased, and the charging current is reduced as the charging end period is approached. ing. However, in such a charging method, since the current value at the initial stage of charging is high, lithium is coarsely precipitated, and there is a problem that the cycle life when charging and discharging are repeated is shortened. Disclosure of the invention
  • a main object of the present invention is to provide a method of charging a secondary battery capable of achieving a longer life or a shorter charging time when charging and discharging are repeated, or both. It is in.
  • Another object of the present invention is to provide a charging device suitable for performing such a charging method.
  • the charging process is divided into a plurality of stages having different charging current values, The charging current value at the charging stage at the start of charging is set relatively small, and the charging current value at each subsequent charging stage is set to be larger than the charging current value at the start of charging.
  • a method for charging a secondary battery is provided.
  • the present invention is based on the following operation principle.
  • the form of lithium deposition depends not only on the charging current but also on the amount of charge.
  • the charging current value at the start of charging i.e., the average current value in consideration of the duty ratio when charging is performed using the pulse current
  • the charging current value at the start of charging is set to be relatively small.
  • Japanese Patent Application Laid-Open No. 8-182152 discloses a method of charging a secondary battery using a pulse current in order to perform appropriate charging without overcharging or insufficient charging regardless of the battery history.
  • the difference between the pulse-on voltage and the pulse-off voltage (the internal resistance of the battery It is disclosed that the charging current is controlled so as to decrease the charging current value in inverse proportion to the charging current value. Therefore, because the history of the battery that happened to be charged happens to be special, if the differential voltage at the beginning of charging is high and the differential voltage at the end of charging is low, the charging current value at the beginning of charging is low, The charging current value of the battery may be high (page 8, right column, lines 29 to 47 of the same publication).
  • switching from a relatively low charging current value to a relatively high charging current value is performed by determining the amount of charge from the start of charging.
  • charging at a relatively low charging current value is preferably performed until the charged amount from the start of charging reaches 17 to 80% of the battery capacity. If the charge at a relatively low charge current value is smaller than 17% of the battery capacity, the tendency of the deposited lithium to become coarse increases, and the cycle life when repeating charge and discharge is shortened. Conversely, if the charge at a relatively low charge current value is greater than 80% of the battery capacity, the cycle life when repeating charge / discharge becomes longer, but the charge time for each charge / discharge cycle becomes longer.
  • the state of the battery differs depending on the depth of discharge at the start of charging.
  • the depth of discharge before the start of charging is shallow, the state where lithium on a smooth surface easily precipitates has already been completed, and when the depth of discharge is deep, lithium tends to precipitate coarsely. I have. Therefore, it is preferable to set the charge amount of charging performed at a relatively low charging current value according to the discharge depth at the start of charging.
  • the charging current value immediately after the start of charging is set to 0.4 mA (0.05 C: 1 C corresponds to 8 mA) or less.
  • 0.05 C: 1 C corresponds to 8 mA
  • the relatively high charging current value used in the subsequent charging phase is set to 2 to 5 times the charging current value at the start of charging to minimize the charging time. No.
  • the charging method of the present invention can be applied to a secondary battery typically using lithium metal or lithium alloy as a negative electrode active material.
  • a phenomenon similar to that of the lithium secondary battery is observed in the nickel-cadmium battery and the lead-acid battery, and therefore, the present invention may be used as a method for charging these batteries.
  • a charging device for a secondary battery wherein a metal is used as a negative electrode active material and the metal is precipitated during charging, a power supply circuit for supplying a direct current for charging the battery.
  • a current control circuit for controlling a charging current value; a timer for measuring a charging time; and a charging amount based on a charging current value from the current control circuit and a charging time from the timer.
  • a voltage measuring device for measuring the voltage of the battery, and supplying the battery to the battery via the current control circuit based on the charge amount from the computing device and the battery voltage from the voltage measuring device.
  • a current judging unit for judging a charging current value to be supplied and stopping supply of the charging current wherein the current judging unit sets the current until the charged amount from the start of charging reaches a predetermined value.
  • Control circuit The charging current value supplied to the battery is set relatively small, and after the charging amount from the start of charging reaches the predetermined value, the charging current value is set to be smaller than the charging current value at the start of charging.
  • a charging device for a secondary battery wherein the charging device is set to be large.
  • FIG. 1 is a cross-sectional view showing the structure of a coin-type lithium secondary battery as a typical example to which the charging method according to the present invention can be applied.
  • FIG. 2 is a half sectional view showing a configuration of a cylindrical lithium secondary battery as another typical example to which the charging method according to the present invention can be applied.
  • FIG. 3 is a fragmentary perspective view showing a positive electrode-negative electrode-separator laminate used for producing the cylindrical lithium secondary battery shown in FIG.
  • FIG. 4 is a process diagram showing a charging device used to carry out the charging method according to the present invention.
  • FIG. 5 is a graph showing a preferred embodiment of the charging method according to the present invention.
  • FIG. 6 is a graph showing another preferred embodiment of the charging method according to the present invention.
  • FIG. 7 is a graph showing still another preferred embodiment of the charging method according to the present invention.
  • FIG. 8 is a graph showing still another preferred embodiment of the charging method according to the present invention.
  • FIG. 9 is a graph showing still another preferred embodiment of the charging method according to the present invention.
  • FIG. 10 is a graph showing the relationship between the charging current and the charge / discharge cycle life of the battery.
  • FIG. 1 shows a so-called coin battery
  • FIG. 2 shows a cylindrical battery
  • FIG. 3 is a fragmentary view of the positive electrode-negative electrode-separate overnight laminate used to construct the cylindrical battery of FIG. 2 in a partially separated and developed state.
  • the coin-type lithium secondary battery shown in FIG. 1 has a positive electrode 1 made of, for example, LiCo 2 (lithium cobaltate) as an active material, a negative electrode 2 made of, for example, lithium foil, And a separator 3 made of, for example, a porous film made of polypropylene interposed between the negative electrodes 2.
  • the positive electrode 1 is formed on a positive electrode current collector 4 made of, for example, aluminum, and the positive electrode current collector 4 is fixed to an inner surface of a positive electrode can 5 made of, for example, stainless steel.
  • the negative electrode 2 is formed on a negative electrode current collector 6 made of, for example, nickel, and the negative electrode current collector 6 is fixed to an inner surface of a negative electrode can 7 made of, for example, stainless steel.
  • the space formed between the positive electrode can 5 and the negative electrode can 7 is filled with an electrolytic solution for allowing movement of lithium ions between the positive electrode 1 and the negative electrode 2. Then, the space between the positive electrode can 5 and the negative electrode can 7 is sealed with, for example, a packing 8 made of polypropylene to complete the battery.
  • the positive electrode 1 is a mixture including a positive electrode active material capable of inserting and extracting lithium ions, a conductive agent having a function of supplementing the conductivity of the positive electrode, and a binder for bonding the positive electrode active material and the conductive agent. is there.
  • L i N i 0 2 lithium nickel oxide
  • L i Mn0 2 lithium manganate
  • L i Mn 2 O 4 spinel
  • V 2 0 5 vanadium pentoxide
  • the conductive agent acetylene black or graphite can be used, but is not limited thereto.
  • the binder for example, polyvinylidene fluoride resin (PVDF), Teflon resin, ethylene-propylene-gene terpolymer, etc. can be used.
  • a lithium plate or a lithium alloy plate for example, a lithium-aluminum alloy, a lithium-tin alloy, a lithium-lead alloy) or the like may be used.
  • L i PF 6 lithium hexafluorophosphate
  • L i BF 4 lithium tetrafluoroborate
  • L i C 10 4 lithium perchlorate lithium ion conductivity
  • PC propylene carbonate
  • T HF tetrahydrofuran
  • EC ethylene carbonate
  • DME 1,2-dimethoxyethane
  • DEC dimethyl carbonate
  • a non-aqueous electrolyte prepared by dissolving in an organic solvent such as —Me THF) and dimethyl carbonate (DMC) can be used.
  • the cylindrical lithium secondary battery shown in FIG. 2 also includes, for example, a positive electrode 1 ′ using Li CoO 2 (lithium cobalt oxide) as an active material, a negative electrode 2 ′ including lithium foil, for example, and these positive electrodes 1 and And a separator 3 ′ made of, for example, a porous film made of polypropylene interposed between the negative electrodes 2 ′.
  • a positive electrode 1 ′ using Li CoO 2 (lithium cobalt oxide) as an active material
  • a negative electrode 2 ′ including lithium foil for example
  • a separator 3 ′ made of, for example, a porous film made of polypropylene interposed between the negative electrodes 2 ′.
  • the laminate of the positive electrode 1 ′, the negative electrode 2, and the separator 3 is formed by winding a long strip in a spiral around the center pin 9 ′ (FIG. 2).
  • the wound laminate is housed in a cylindrical negative electrode can 7 'made of, for example, stainless steel.
  • the positive electrode 1, for example, is formed by applying a positive electrode mixture to both surfaces of an aluminum foil as a positive electrode current collector and rolling.
  • the negative electrode 2 ′ is formed, for example, by sandwiching a copper foil as a negative electrode current collector from both sides with a lithium foil as a negative electrode active material. It has a configuration.
  • the negative electrode 1 ' has a negative electrode lead tab 10', which extends beyond the lower insulating plate 11 'and is welded to the inner bottom surface of the negative electrode can 7'.
  • the positive electrode 1 ' is electrically connected to the positive electrode lead tab 12'.
  • the positive electrode lead tab 12' extends through the upper insulating plate 13 'and is electrically connected to the positive electrode lid 5' via the positive electrode lead pin 14 '. .
  • the negative electrode can 7' electrode lid 5 into the space formed between the, for example if L i PF 6 a (lithium hexafluorophosphate) ethylene carbonate (EC) and Jefferies Chiruka one Poneto (DEC) A non-aqueous electrolyte prepared by dissolving in a mixed organic solvent is filled. Then, the space between the positive electrode lid 5 'and the negative electrode can 7, is sealed with, for example, a packing 8' made of polypropylene to complete the battery.
  • L i PF 6 a lithium hexafluorophosphate
  • EC ethylene ethylene carbonate
  • DEC Jefferies Chiruka one Poneto
  • FIG. 4 is a block diagram showing the configuration of the charging device according to the preferred embodiment.
  • the charging device includes a power supply circuit 20 for supplying a DC current capable of charging the battery B, a current control circuit 21 for controlling a charging current value, and an evening circuit for measuring a charging time.
  • a computing unit 23 for calculating the amount of charge based on the charging current value from the current control circuit 21 and the charging time from the evening control 22, and a voltage measuring device 24 for measuring the voltage of the battery B.
  • a current judging unit 25 To determine the value of the charging current to be supplied to the battery B via the current control circuit 21 based on the charge amount from the arithmetic unit 23 and the battery voltage from the voltage measuring device 24, or to stop the supply of the charging current.
  • a current judging unit 25 for supplying a DC current capable of charging the battery B, a current control circuit 21 for controlling
  • the computing unit 23 calculates a charge amount by adding a multiplying unit 23 a for integrating the charging time from the timer 22 and the charging current value from the current control circuit 21 and an output from the multiplying unit 23 a. And a storage unit 23c for storing the calculated charge amount and performing feedback for addition in the addition unit 23b.
  • charging when charging a lithium secondary battery as shown in FIG. 1 or FIG. 2, charging is divided into a plurality of stages, and a charging current value is relatively set in an initial stage after the start of charging. Set the charging current to a small value, and set the charging current value relatively high at the stage of charging near the end of charging, to extend the battery life or shorten the charging time or Both are achieved.
  • the number of steps for switching the charging current value is not particularly limited, but usually, two steps are sufficient.
  • FIG. 5 is a graph showing the switching state of the charging current value in one embodiment of the charging method according to the present invention.
  • the vertical axis shows the charging current value
  • the horizontal axis shows the ratio of the charged amount to the battery capacity.
  • a small first charging of 0.354 mA 0.044 C: 1 C is equivalent to 8 mA; the same applies hereinafter.
  • Charging is performed at the current value, and when the charged amount reaches 50% of the battery capacity, the charging current value rapidly increases to, for example, a second charging current value of 1.062 mA (0.133 C). After that, the second charge current value is maintained until charging is completed (full charge state).
  • the current control circuit 21 controls the charging current from the power supply circuit 20 to the first charging current value simultaneously with the start of charging, and Ima 2 2 starts timing.
  • the computing unit 23 calculates the amount of charge based on the timing information from the timer 22 and the current value from the current control circuit 21, and outputs it to the current determination unit 25.
  • a predetermined value for example, an amount corresponding to 50% of the initial battery capacity
  • An instruction is issued to the current control unit 21 to increase the charging current value to a second charging current value higher than the first charging current value. Thereby, the battery B is charged at the second charging current value until the charging ends.
  • the voltage measuring device 24 constantly monitors the voltage of the battery B and outputs it to the current judging unit 25.
  • the measured voltage is a predetermined charge cut-off voltage (a battery voltage at which charging should be terminated, for example, lithium
  • the current judging unit 25 issues a command to the current control unit 21 to stop supplying current to the battery B.
  • charging of the battery B is completed.
  • the determination of switching from the first charging current value to the second charging current value by the current determination unit 25 based on the charge amount by the computing unit 23 is based on the battery state at the start of charging. This is because it is difficult to determine the switching of the charging current value with the battery voltage because the voltage is different. Therefore, in the charging device according to the present embodiment, the measurement of the battery voltage by the voltage measuring device 24 is used only for determining the end of charging.
  • a coin-type lithium secondary battery having a configuration shown in FIG. 1 (diameter: 20 mm, thickness: 3.2 mm, capacity: using a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte specified below) 8 mAh) was prepared and a charge / discharge cycle test was performed under the conditions described below.
  • L i Co_ ⁇ 2 (lithium cobaltate) 90% as a positive electrode active material, ⁇ cetirizine Ren black as a conductive agent 2.5% and graphite 2.5%, 5% polyvinylidene fluoride resin (PVDF) as a binder
  • PVDF polyvinylidene fluoride resin
  • a lithium foil was used as the negative electrode.
  • a polyethylene porous film was used for the separation.
  • a charge / discharge cycle test was performed on the lithium secondary battery with the above configuration using a charging device with the configuration shown in Fig. 4 under the following conditions.
  • charging starts at the first charging current value of 0.354mA (0.044C), and when charging reaches 4mAh (equivalent to 50% of the initial battery capacity), 1 Switched to the second charge current value of 062mA (0.14C) and continued charging until the end of charging.
  • the charge cutoff voltage (the battery voltage at which charging is completed) was set to 4.2V.
  • the discharge cutoff voltage battery voltage at which discharge ends
  • the discharge depth discharge at each charge / discharge cycle 100% capacity when discharged to cut-off voltage Then, it was discharged to 100%.
  • the rest time after discharge was set to 1 minute after charge.
  • charging starts at the first charging current value of 0.354 mA (0.044 C), and when charging reaches 2.5 mAh, the second charging of 1.062 mA (0.14 C) starts. Switching to the charging current value, charging was continued until charging was completed. At this time, as in Example 1, the charge cutoff voltage was set to 4.2 V.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cutoff voltage of 3.0 V to a discharge depth of 100%.
  • the battery performance was evaluated in the same manner as in Example 1. As shown in Table 1, the cycle life was 59 times and the charging time (representative value) was 12.2 hours. Was.
  • charging starts at the first charging current value of 0.354 mA (0.044 C), and when the charging amount reaches 0.2 mAh, the second charging of 1.062 mA (0.14 C) Switching to the current value, charging was continued until charging was completed.
  • the charge cutoff voltage was set to 4.2 V.
  • the battery performance was evaluated in the same manner as in Example 1. As shown in Table 1, the cycle life was 215 times and the charging time (representative value) was 4.1 hours.
  • charging starts at the first charging current value of 0.354 mA (0.044C), and when the charging amount reaches 2.0 mAh, the second charging of 1.062 mA (0.14C) starts. Switching to the current value, charging was continued until charging was completed. At this time, as in Example 1, the charge cutoff voltage was set to 4.2 V.
  • the discharge was performed at a constant current of 1.77 mA (0.22 C) to a depth of discharge of 50%.
  • the battery performance was evaluated in the same manner as in Example 1. As shown in Table 1, the cycle life was 210 times and the charging time (representative value) was 7.5 hours.
  • Example 1 In order to compare the charging method of the present invention with the conventional charging method, the same configuration as in Example 1 was used. The following charge / discharge cycle test was performed using the coin-type lithium secondary battery.
  • charging was performed at a constant current of 0.531 mA (0.056 C) up to a charge cutoff voltage of 4.2 V.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cutoff voltage of 3.0 V to a discharge depth of 100%.
  • the battery performance was evaluated in the same manner as in Example 1. As shown in Table 1, the cycle life was 58 times and the charging time (representative value) was 15.1 hours. Was.
  • Example 1 When this comparative example is compared with Example 1, the charging time is the same at 15.1 hours in both cases, but the cycle life of Example 1 is approximately doubled. This confirms the life improvement effect of the present invention.
  • charging was performed at a constant current of 0.654 mA (0.082 C) up to a charge cutoff voltage of 4.2 V.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cutoff voltage of 3.0 V to a discharge depth of 100%.
  • the battery performance was evaluated in the same manner as in Example 1. As shown in Table 1, the cycle life was 45 times and the charging time (representative value) was 12.2 hours. Was.
  • Example 2 When this comparative example is compared with Example 2, the charging time is the same at 12.2 hours in both cases, but the cycle life of Example 2 is about 1.3 times longer than that of Example 2. From this Can also confirm the life improvement effect of the present invention ⁇ Table 1
  • FIG. 6 is a pulse characteristic graph showing a charging method according to another embodiment of the present invention, in which the vertical axis represents a current value and the horizontal axis represents time.
  • the minimum current value was 0 and the maximum current value was 0.708 mA (0.089 C), and the average current value was 0.354 mA. (0.044 C) at a duty ratio of 1/2, and when the charge reaches 4 mAh, the average current value is 1.062 mA (0.
  • the maximum pulse current was switched to 2.124 mA (0.27C) (the minimum current and the duty ratio were maintained) so that the charging was completed, and charging was continued until the end of charging.
  • the charge cutoff voltage was set to 4.2 V, as in the first embodiment.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cutoff voltage of 3.0 V to a discharge depth of 100%.
  • Example 3 Three In this example, the battery performance was evaluated in the same manner as in Example 1. As a result, the cycle life and the charging time were almost the same as those in Example 1.
  • FIG. 7 is a pulse characteristic graph showing a charging method according to still another embodiment of the present invention, wherein the vertical axis represents a current value and the horizontal axis represents time.
  • the pulse current having the minimum current value of 0 and the maximum current value of 2.124 mA (0.27 C) was converted to the average current value of 0.354 mA. (0.044 C) at a duty ratio of 1 Z6.
  • the average current value is 1.062 mA (0.14 C )
  • the duty ratio of the pulse current was switched to 1 to 2 so that the minimum current value and the maximum current value were maintained, and charging was continued until charging was completed.
  • the charge cutoff voltage was set to 4.2 V.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cut-off voltage of 3.0 V to a discharge depth of 100%. .
  • Example 1 the battery performance was evaluated in the same manner as in Example 1. As a result, the cycle life and the charging time were almost the same as those in Example 1.
  • FIG. 8 is a pulse characteristic graph showing a charging method according to still another embodiment of the present invention, in which the vertical axis represents a current value and the horizontal axis represents time.
  • Example 7 As shown in the graph of FIG. 8, in Example 7, as the first charging stage, a pulse current having a minimum current value of 0 and a maximum current value of 2.124 mA (0.27 C) was converted to an average current value of 0.354 mA. (0.044 C) at a duty ratio of 1/6 When the amount of charge reaches 4 mAh, as the second charging stage, the minimum current value of the pulse current is set to 1.264 mA (0.158 C) so that the average current value becomes 1.062 mA (0.14 C). ) (The maximum current value and duty ratio are maintained), and charging was continued until charging was completed. At this time, the charge cutoff voltage was set to 4.2 V, as in the first embodiment.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cutoff voltage of 3.0 V to a discharge depth of 100%.
  • Example 1 the battery performance was evaluated in the same manner as in Example 1. As a result, the cycle life and the charging time were almost the same as those in Example 1.
  • FIG. 9 is a graph showing a charging method according to still another embodiment of the present invention, in which the vertical axis indicates the charging current value, and the horizontal axis indicates the ratio of the charging amount to the battery capacity.
  • Example 8 As shown in the graph of FIG. 9, in Example 8, as the first charging stage, charging was performed at the first charging current value of 0.354 mA (0.044 C), and when the charged amount reached 4 mAh.
  • the battery voltage is switched to 4.2 V by switching to the second charging current value of 1.062 mA (0.14 C), and then, in the third charging stage, the 4.2 V Constant voltage charging was performed until the final current value decreased to 0.354 mA (0.044C). That is, this embodiment is the same as the first embodiment up to the second charging stage, but differs from the first embodiment in that a third charging stage is added.
  • the reason for adding the third charging stage in this way is that at the end of charging, the battery voltage is actually slightly lower than the charge cutoff voltage due to the voltage drop due to polarization. Charge it.
  • Example 1 the discharge was performed at a constant current of 1.77 mA (0.22 C) with a discharge cutoff voltage of 3.0 V to a discharge depth of 100%.
  • the battery performance was evaluated in the same manner as in Embodiment 1.
  • the charging time was about 3% longer than that in Embodiment 1 by the addition of the third charging stage, but the cycle life was longer.
  • the result was about 10% longer than that of Example 1, and more than the increase in the charging time was obtained.
  • the charging current value in the first charging stage In order to study how much it is preferable to set the average current value when using the luster current), the relationship between the charging current value and the cycle life of the lithium secondary battery was examined. The results are shown in the graph of FIG. In the graph, the vertical axis represents the cycle life of the battery, and the horizontal axis represents the charging current value.
  • the charge current value of the first charging stage is less than 0.4 mA (0.05 C).
  • the charging current in the first charging stage may be set slightly higher, and generally 0. If it is less than 8 mA (0.1 C), it is within the allowable range.
  • increasing the charging current value is for shortening the charging time, so it is necessary to increase the charging current value to a certain extent in order to achieve its purpose. It is preferable that the charge current value is 2 to 5 times the one-stage charge current value.
  • the use of the charging method and the charging device of the present invention makes it possible to extend the cycle life of the secondary battery and / or to increase the charging life compared to the conventional charging method and the charging device. Time can be reduced.
  • Examples 1 to 8 all relate to a coin-type lithium secondary battery, similar effects can be obtained by applying the present invention to a cylindrical battery (FIGS. 2 and 3) or a square battery. Further, the present invention is not limited to the lithium secondary battery, and the present invention can be applied to a secondary battery (for example, a nickel-cadmium battery or a lead-acid battery) using a metal as a negative electrode active material and depositing the metal during charging.
  • a secondary battery for example, a nickel-cadmium battery or a lead-acid battery

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Charge And Discharge Circuits For Batteries Or The Like (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de charge d'une cellule secondaire, plus particulièrement d'une cellule secondaire de lithium dont la matière active négative se compose d'un métal déposé en cours de charge. Selon ce procédé, la charge s'effectue en plusieurs étapes. La valeur du courant de charge est petite au départ et s'amplifie en cours de charge.
PCT/JP1999/000124 1999-01-14 1999-01-14 Procede de charge d'une cellule secondaire et chargeur WO2000042673A1 (fr)

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PCT/JP1999/000124 WO2000042673A1 (fr) 1999-01-14 1999-01-14 Procede de charge d'une cellule secondaire et chargeur

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7265520B2 (en) 2000-08-11 2007-09-04 Seiko Epson Corporation Electronic apparatus and method of controlling the electronic apparatus
JP2010034016A (ja) * 2008-06-24 2010-02-12 Ricoh Co Ltd 評価装置、評価方法および評価プログラム
JP2010158129A (ja) * 2008-12-28 2010-07-15 Starlite Co Ltd 二次電池の充電方法及び充電装置
US9520736B2 (en) 2011-07-27 2016-12-13 Mitsubishi Electric Corporation Charging control apparatus and charging control method for secondary battery
JP2020009724A (ja) * 2018-07-12 2020-01-16 トヨタ自動車株式会社 二次電池の充電方法
JP2020080603A (ja) * 2018-11-13 2020-05-28 株式会社Ｐｌａｎ Ｂｅ 鉛蓄電池の運転制御方法および微小容量充電装置
WO2022065088A1 (fr) * 2020-09-28 2022-03-31 パナソニックＩｐマネジメント株式会社 Procédé de charge de batterie rechargeable et système de charge
WO2023126674A1 (fr) * 2021-12-27 2023-07-06 日産自動車株式会社 Procédé de charge de batterie secondaire
WO2024018247A1 (fr) * 2022-07-20 2024-01-25 日産自動車株式会社 Procédé de fabrication de batterie secondaire au lithium

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JPS61290814A (ja) * 1985-06-18 1986-12-20 Sharp Corp Ｄ型フリツプ・フロツプ
JPH09283184A (ja) * 1996-04-12 1997-10-31 Fujitsu Ltd 非水電解液二次電池の充電法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61290814A (ja) * 1985-06-18 1986-12-20 Sharp Corp Ｄ型フリツプ・フロツプ
JPH09283184A (ja) * 1996-04-12 1997-10-31 Fujitsu Ltd 非水電解液二次電池の充電法

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7265520B2 (en) 2000-08-11 2007-09-04 Seiko Epson Corporation Electronic apparatus and method of controlling the electronic apparatus
JP2010034016A (ja) * 2008-06-24 2010-02-12 Ricoh Co Ltd 評価装置、評価方法および評価プログラム
JP2010158129A (ja) * 2008-12-28 2010-07-15 Starlite Co Ltd 二次電池の充電方法及び充電装置
US9520736B2 (en) 2011-07-27 2016-12-13 Mitsubishi Electric Corporation Charging control apparatus and charging control method for secondary battery
JP2020009724A (ja) * 2018-07-12 2020-01-16 トヨタ自動車株式会社 二次電池の充電方法
JP2020080603A (ja) * 2018-11-13 2020-05-28 株式会社Ｐｌａｎ Ｂｅ 鉛蓄電池の運転制御方法および微小容量充電装置
JP7213442B2 (ja) 2018-11-13 2023-01-27 株式会社Plan Be 鉛蓄電池の運転制御方法および微小容量充電装置
WO2022065088A1 (fr) * 2020-09-28 2022-03-31 パナソニックＩｐマネジメント株式会社 Procédé de charge de batterie rechargeable et système de charge
WO2023126674A1 (fr) * 2021-12-27 2023-07-06 日産自動車株式会社 Procédé de charge de batterie secondaire
WO2024018247A1 (fr) * 2022-07-20 2024-01-25 日産自動車株式会社 Procédé de fabrication de batterie secondaire au lithium

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