WO2013035187A1 - リチウム二次電池の製造方法 - Google Patents
リチウム二次電池の製造方法 Download PDFInfo
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- WO2013035187A1 WO2013035187A1 PCT/JP2011/070511 JP2011070511W WO2013035187A1 WO 2013035187 A1 WO2013035187 A1 WO 2013035187A1 JP 2011070511 W JP2011070511 W JP 2011070511W WO 2013035187 A1 WO2013035187 A1 WO 2013035187A1
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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- 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
- H01M10/058—Construction or manufacture
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- 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
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- 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
- H01M10/446—Initial charging measures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to a method for manufacturing a lithium secondary battery.
- lithium secondary batteries typically lithium ion batteries
- the lithium secondary battery includes a positive electrode having a positive electrode active material made of a lithium-containing composite oxide, a negative electrode having a negative electrode active material capable of occluding and releasing lithium ions, a separator interposed between the positive electrode and the negative electrode, A positive electrode, a negative electrode, and a nonaqueous electrolyte impregnated in the separator.
- a positive electrode, a negative electrode, and a separator are assembled, and after impregnating them with a nonaqueous electrolyte, charging is performed.
- Patent Document 1 after injecting an electrolytic solution into the battery, the first charge / discharge is performed by alternating current having a frequency of 1 Hz to 1000 Hz, and further, a standing time of 1 hour to 48 hours after charge / discharge is provided. It is described to stabilize the properties.
- the technique disclosed in Patent Document 1 by repeatedly applying such an alternating voltage, the metal mixed as a foreign substance on the positive electrode when the voltage is increased is dissolved in the electrolytic solution. Further, when the voltage is lowered, the negative electrode potential is maintained at a level equal to or higher than the dissolution potential of the metal, and the metal ions diffuse in the electrolytic solution without being deposited on the negative electrode. It is described that, by providing a standing time, ions generated by dissolution diffuse in a wide range and do not concentrate in one place even when deposited on the negative electrode surface.
- Patent Document 2 after charging for one hour at least once, discharging is performed until the potential of the negative electrode becomes 2.0 V or more and 3.35 V or less with respect to the oxidation-reduction potential of lithium, and in that state, 3 It is described that it is left for more than a minute.
- Patent Document 3 describes that 0.01% to 0.1% of the battery capacity is charged at the time of the first charge, and then a standing time of 1 to 48 hours is provided.
- Patent Documents 1 to 3 are preferably applied to, for example, a positive electrode having, as an active material, a lithium nickel composite oxide (typically LiNiO 2 ) having a high capacity retention rate. It is considered possible. However, it has a high capacity such as a positive electrode (hereinafter, sometimes simply referred to as a ternary positive electrode) having an active material such as a ternary lithium-containing composite oxide containing cobalt, nickel, and manganese, which has recently attracted attention.
- a positive electrode having a slightly lower capacity retention rate than lithium nickel composite oxide or the like is used, the potential of the positive electrode drops greatly when left at the time of microcharging, and the above technique cannot be applied as it is.
- Patent Document 2 The technique described in Patent Document 2 is to discharge and leave after long-time charging, and since the negative electrode potential is increased by the discharge, dissolved metal ions are diffused, and concentrated precipitation on the negative electrode is suppressed. There is expected. However, at the time of long-time charging before the discharge, precipitation occurred in the negative electrode, and the precipitate might grow.
- Patent Document 3 is left for a long time after microcharging, and the negative electrode potential decreases during charging and is left in that state for a long time. Therefore, precipitation may occur in the negative electrode and the precipitate may grow. was there.
- the present invention has been created to solve the above-described conventional problems, and the object of the present invention is to suppress local precipitation of metallic foreign matter on the negative electrode regardless of the type of the positive electrode.
- An object of the present invention is to provide a method for manufacturing a lithium secondary battery.
- Another object of the present invention is to provide a highly reliable lithium secondary battery which is less likely to cause a short circuit obtained by this manufacturing method.
- a lithium secondary battery including a positive electrode having a positive electrode active material made of a lithium-containing composite oxide, a negative electrode having a negative electrode active material capable of occluding and releasing lithium ions, and a nonaqueous electrolyte is manufactured.
- a method is provided. Such a manufacturing method includes the following steps. (1) Assembling a cell including the positive electrode, the negative electrode, and the non-aqueous electrolyte. (2) Before the initial conditioning charge is performed on the assembled cell, dissolution of the mixed expected metal species (Me) in which the positive electrode potential with respect to the metal lithium (Li) reference electrode is set in advance is started. A microcharging process in which microcharging is performed until the potential exceeds the Me dissolution potential. Typically, a minute charge is performed for a charging time of 10 seconds or shorter (preferably 5 seconds or shorter). (3) A Me dissolution potential holding step of holding the positive electrode potential of the cell at a time equal to or higher than the Me dissolution potential after the micro charge.
- Me mixed expected
- the “lithium secondary battery” means a general battery that can be repeatedly charged using lithium ions as a charge carrier, and typically includes a lithium ion battery, a lithium polymer battery, and the like.
- active material can reversibly occlude and release (typically insertion and removal) chemical species (for example, lithium ions in a lithium ion battery) that serve as charge carriers in a secondary battery.
- chemical species for example, lithium ions in a lithium ion battery
- a metal species (Me) such as a mixed expected metal having the highest dissolution potential among the metal species expected to be mixed in the positive electrode or the like is predicted, and dissolution of the metal species (Me) is started.
- the Me dissolution potential is set in advance. Then, until the positive electrode potential of the cell with respect to the metal lithium (Li) reference electrode becomes a potential exceeding the Me dissolution potential, the micro charge is typically performed for a short time such that the charge time is 10 seconds or less.
- the expected mixed metal species (Me) is the metal species having the highest dissolution potential among the metal foreign materials that may be mixed in the manufacturing process of the lithium secondary battery, and the lithium secondary battery It is a metal species that has an oxidation-reduction potential within the operating voltage range of the battery and can become (dissolve) ions.
- the metal foreign matter is expected to be mixed in the positive electrode or the like, the metal that is not likely to be ionized (dissolved) within the operating voltage range of the lithium secondary battery, There is no need to consider it as a mixed expected metal species (Me).
- the charging time in microcharging can be extremely shortened (for example, 10 seconds or less), and therefore, metal ions can be prevented from reaching the negative electrode and being deposited within the charging time. be able to.
- the Me dissolution potential of the mixed expected metal species can be considered to correspond to the oxidation-reduction potential (Li standard) of the metal species.
- the actual Me dissolution potential may be higher than the oxidation-reduction potential of the metal species.
- the Me dissolution potential can be set to the actual Me dissolution potential, for example, higher than the oxidation-reduction potential of the metal species.
- the potential of the positive electrode is held for a predetermined time to be equal to or higher than the above Me melting potential.
- the expected mixed metal species and other metal species mixed on the surface of the positive electrode metal species having a lower melting potential than the expected mixed metal species, including these and the expected mixed metal species are referred to as “dissolved metals”).
- the potential of the positive electrode is maintained at a level equal to or higher than the Me dissolution potential, so that dissolution (ionization) of the metal species to be dissolved can be realized.
- the micro charge may be performed for a very short time (for example, 10 seconds or less, preferably 5 seconds or less) compared to the normal charge, the potential of the negative electrode can be kept relatively high, and therefore the metal charge is made of a metal species to be dissolved. Reduction and precipitation of metal ions concentrated on a specific negative electrode surface region is suppressed. Therefore, metal ions composed of the metal species to be dissolved are diffused and deposited on the negative electrode, and do not precipitate locally. Therefore, even if metal foreign matters (metal species to be dissolved such as expected mixed metal species) are mixed, they do not cause a short circuit, and the metal foreign matters are rendered harmless.
- metal foreign matters metal species to be dissolved such as expected mixed metal species
- the micro charge is performed such that the charge amount at the time of charge is less than 0.01% of the capacity of the cell.
- the microcharging step is performed once within the predetermined time period in order to hold the positive electrode potential of the cell at or above the Me melting potential. Or repeat it more than once. That is, before the positive electrode potential of the cell falls below the Me dissolution potential, the micro charge is performed to raise the positive electrode potential of the cell to a potential higher than the Me dissolution potential.
- various improvements have been made to lithium secondary batteries for the purpose of improving battery performance. Examples thereof include changes in the materials and compositions of the positive electrode and negative electrode active materials, changes in the size and surface coating of the negative electrode active material, and changes and additions of additives such as conductive materials and dispersants.
- the method of detoxifying the metal foreign matter in the future lithium secondary battery can positively control various positive electrode potential behaviors.
- the amount of charge in one micro charge is performed by a very small proportion of the capacity of the cell (for example, as described above, less than about 0.01% of the cell capacity).
- this micro charge can be performed as many times as necessary. That is, the positive electrode potential can be delicately and positively controlled according to the potential behavior of the target positive electrode.
- the positive electrode active material when a lithium nickel composite oxide having a high capacity retention rate is adopted as the positive electrode active material, or a positive electrode ternary active material or the like whose capacity maintenance rate is slightly inferior to lithium nickel composite oxide or the like is used as the active material. Even if it is adopted, the positive electrode potential can be maintained at or higher than the Me dissolution potential in an optimum state with less waste. Thereby, said effect can be acquired efficiently irrespective of the kind of positive electrode.
- the above minute charge can be repeated for each period set based on the rate of decrease of the positive electrode potential measured in advance. That is, for a lithium secondary battery manufactured in advance, the behavior of the positive electrode potential (the rate of decrease in the positive electrode potential) after performing a minute charge is examined. From this positive electrode potential behavior, a holding time such that the positive electrode potential does not fall below the Me dissolution potential can be obtained, and this can be set as a cycle for performing microcharging. Thereby, the optimal detoxification process can be simply performed according to the target lithium secondary battery.
- the micro charge is performed with a pulse current so that the charge time is 2 seconds or less.
- a current of 0.5 C or more for example, 1 C or more (typically 0.5 to 5 C, particularly 1 to 3 C).
- the metal ions can be sufficiently diffused while suppressing local precipitation of the metal species (ions) to be dissolved, such as expected mixed metal species, on the negative electrode.
- fine and positive control of the positive electrode potential behavior can be more effectively performed by the minute charge by the pulse current.
- the connection with an external power source is disconnected after the micro charge.
- the cell is left unattended.
- the positive electrode potential decreases due to self-discharge of the positive electrode. Therefore, after microcharging, for example, by removing the charging terminal and disconnecting from the external power supply, self-discharge can be suppressed. Thereby, the fall of the positive electrode potential in a Me melt
- the method further includes performing a micro discharge after the micro charge.
- a micro discharge since lithium ions as charge carriers move from the negative electrode side to the positive electrode side, an effect of preventing the movement of metal ions of the metal species to be dissolved to the negative electrode side is obtained.
- the potential of the positive electrode rises to some extent by the reaction of the discharge while the potential of the negative electrode is maintained. Thereby, not only the effect of maintaining the positive electrode at the target potential can be obtained by discharging other than charging, but also an effect of suppressing precipitation at the negative electrode can be obtained.
- the amount of discharge is smaller than the amount of charge charged by the minute charge.
- the positive electrode potential tends to continue to decrease when micro charge and discharge are repeated.
- the adjustment of the discharge amount and the charge amount can be realized by reducing (or increasing) the discharge current (or charge current) or shortening (or increasing) the discharge time (or charge time).
- the microdischarge is performed with a pulse current of 0.5 C or more. Since the potential of the positive electrode and the negative electrode can be adjusted in a short time by performing a small discharge for a short time with a relatively large current, local metal species to be dissolved such as expected mixed metals on the negative electrode Metal ions can be sufficiently diffused while suppressing precipitation. In addition, the dissolution target metal species such as mixed expected metals deposited on the negative electrode are suppressed from being dissolved again from the negative electrode.
- the discharge time is 10 seconds or shorter, and more preferably 2 seconds or shorter.
- copper (Cu) is set as the mixed expected metal species (Me), and the micro charge has a positive electrode potential with respect to a metal lithium (Li) reference electrode. It is performed so as to be a potential higher than the Cu dissolution potential at which the dissolution of Cu is started. That is, it is a metal foreign substance that is highly likely to be mixed in the manufacturing process of a lithium secondary battery, has a redox potential within the operating voltage range of the lithium secondary battery, and is a redox potential among metals that easily become ions The highest is copper (Cu), and its redox potential is about 3.2V.
- the Me dissolution potential can be set to 3.2 V or higher.
- the maximum potential of the negative electrode during micro discharge is set to less than 3.2V.
- the positive electrode active material is composed of a lithium-containing composite oxide containing at least manganese, cobalt, and nickel, and the nickel in the transition metal constituting the lithium-containing composite oxide. Is less than 50 mol%.
- This active material has a high capacity but a relatively low capacity retention rate.
- the type of the positive electrode active material is not limited. However, when a lithium secondary battery having such a positive electrode active material is targeted, the advantages of the present invention can be effectively utilized. it can.
- a method for manufacturing a lithium secondary battery even when a metal foreign object is mixed into the positive electrode surface, a short circuit due to the presence of the metal foreign object can be prevented. Thereby, it is possible to reliably detoxify the metal foreign matter. That is, a method for manufacturing a lithium secondary battery that does not cause a problem in battery performance even if foreign matter is mixed is provided. Therefore, a more reliable lithium secondary battery can be realized at a lower cost.
- FIG. 1 is a diagram showing an example of short-term potential behavior in the manufacturing method of the present invention.
- FIG. 2 is a diagram showing the long-term potential behavior of FIG.
- FIG. 3 is a process flow diagram according to one embodiment of the present invention.
- FIG. 4 is a diagram for explaining an example of a potential behavior when a minute charge and a minute discharge are combined.
- FIG. 5 is a cross-sectional view showing a part of a lithium secondary battery according to an embodiment.
- FIG. 6 is a diagram illustrating a vehicle including a lithium secondary battery according to an embodiment.
- FIG. 7 is a diagram showing another example of long-term potential behavior by the manufacturing method of the present invention.
- FIG. 8 is an observation image showing an example of metallic foreign matter mixed on the positive electrode surface.
- FIG. 8 is an observation image showing an example of metallic foreign matter mixed on the positive electrode surface.
- FIG. 9A is an observation image showing an example of the positive electrode surface after the preliminary charging according to the comparative example.
- FIG. 9B is an observation image showing an example of the surface on the positive electrode side of the separator after the preliminary charging according to the comparative example.
- FIG. 9C is an observation image showing an example of the negative electrode side surface of the separator after the preliminary charging according to the comparative example.
- FIG. 9D is an observation image showing an example of the negative electrode surface after the preliminary charging according to the comparative example.
- FIG. 10A is an observation image showing an example of the positive electrode surface after preliminary charging according to an embodiment.
- FIG. 10B is an observation image showing an example of the positive electrode side surface of the separator after preliminary charging according to an embodiment.
- FIG. 10C is an observation image showing an example of the negative electrode-side surface of the separator after preliminary charging according to an embodiment.
- FIG. 10D is an observation image showing an example of the negative electrode surface after preliminary charging according to an embodiment.
- the manufacturing method according to this embodiment is impregnated in a positive electrode having a positive electrode active material made of a lithium-containing composite oxide, a negative electrode having a negative electrode active material capable of occluding and releasing lithium ions, and the positive electrode and the negative electrode. And a non-aqueous electrolyte.
- a separator may be interposed between the positive electrode and the negative electrode.
- Such a lithium secondary battery includes a positive electrode (typically a separator) in a process of assembling a cell (that is, a structure constituting the lithium secondary battery and before performing initial conditioning charging). And) Assembling the negative electrode, housing them together with the nonaqueous electrolyte in a battery case, and sealing the battery case makes a cell.
- the positive electrode for example, the positive electrode active material layer formed on the positive electrode current collector
- the positive electrode may contain a metal species to be dissolved such as copper or iron.
- the metal foreign matter When a metal foreign matter is contained in the positive electrode, when the potential of the positive electrode becomes higher than the dissolution potential of the metal foreign matter during charging, the metal foreign matter (dissolving target metal species) is dissolved to generate metal ions. Conventionally, this metal ion has moved linearly between the positive and negative electrodes (typically in the separator) toward the negative electrode, so that the metal ion reaches the negative electrode when charging is continued and is locally located at a position opposite to the negative electrode. It was precipitated. As the charging progresses, the precipitate on the negative electrode gradually grows toward the positive electrode side.
- FIG. 1 is a diagram for explaining an example of preliminary charging. From the top of the graph, the positive electrode potential, the negative electrode potential, the potential difference between the positive electrode and the negative electrode (hereinafter simply referred to as potential difference), and the supplied current Represents time change.
- dissolution of the mixed expected metal species (Me) in which the positive electrode potential with respect to the metal lithium (Li) reference electrode is set in advance is started.
- the micro charge is performed for a short time (for example, a charge time of 10 seconds or less) until the potential exceeds the Me dissolution potential.
- This minute charge is set so that the maximum potential of the positive electrode with respect to the Li reference electrode exceeds the Me dissolution potential.
- this highest ultimate potential it can set suitably in the range which exceeds a Me melt
- the redox potential of various metal elements with respect to the redox potential of lithium can be determined in consideration of the redox potential of various metal elements with respect to the redox potential of lithium.
- the redox potential may be the same as the dissolution potential.
- copper (Cu) having a higher dissolution potential than iron (Fe) is assumed as a mixed expected metal species (Me), and the Me dissolution potential (Cu here) is 3.2 V (Li standard). It is.
- the actual maximum potential reached to the positive electrode by minute charging is about 3.9V.
- the maximum positive electrode potential can be set to 4.0 V or more, for example.
- the minute charge is continued for a minute time of 10 seconds or less.
- the positive electrode potential temporarily becomes higher than the dissolution potential of the mixed expected metal. Therefore, the mixed expected metal dissolves to generate metal ions, and these metal ions move between the positive and negative electrodes (typically in the separator) toward the negative electrode.
- this minute charge is preferably performed so that the amount of charge during charging is less than 0.01% of the capacity of the cell. By performing such a small charge amount, it is possible to control the positive electrode potential more effectively without waste.
- a Me dissolution potential holding step of holding the positive electrode potential of the cell at a predetermined time or more above the Me dissolution potential is included.
- This Me dissolution potential holding step is a time (predetermined time) during which it is determined that the metal species to be dissolved such as mixed expected metals are sufficiently dissolved and diffused and can be deposited on the negative electrode in a manner that does not affect battery performance. Will continue until.
- dissolution potential holding process (1) The magnitude
- the micro charge is repeated once or twice or more within a predetermined time in order to keep the positive electrode potential of the cell equal to or higher than the Me dissolution potential.
- the positive electrode potential of the cell is typically the highest ultimate potential that exceeds the Me dissolution potential (in this case, 3.2 V) by microcharging in the microcharging process. After that, it gradually drops in the range exceeding 3.2V. The degree of this drop depends on the characteristics of the positive electrode used in the cell.
- Such microcharging in the Me dissolution potential holding step can be repeated once or twice or more within a predetermined time.
- movement of metal ions composed of the metal species to be dissolved toward the negative electrode is relaxed, and the metal ions are sufficiently diffused between the positive and negative electrodes, typically in the separator.
- the said metal ion reaches
- the number of repetitions of microcharging is not particularly limited, but the effect of suppressing intensive precipitation of metal ions is expected as the number of repetitions increases.
- the number of repetitions can be appropriately determined according to characteristics such as capacity retention rate of the lithium secondary battery to be manufactured and a predetermined holding time. For example, it may be 10 times or more, or 100 times or more.
- FIG. 2 is a diagram showing an example in which the short-term (0 to 2500 seconds) potential behavior in the preliminary charging shown in FIG. 1 is performed in the long-term (0 to 20 hours). For example, in the manufacture of a lithium secondary battery using a ternary positive electrode, as shown in FIG.
- the micro charge is repeated for a predetermined time (20 hours) at intervals of about 10 minutes, for a total of about 120 times. It is what I did. Even when the positive electrode potential is left as it is, it becomes about 3.2 V or more (specifically, about 3.4 V or more), which indicates that the metal species to be dissolved are sufficiently dissolved and diffused. Conversely, when manufacturing a lithium secondary battery using a lithium nickel-based positive electrode with a high capacity retention rate, for example, a series of steps of a microcharging step and a holding step are repeated at intervals of about 120 minutes for about 20 hours, It may be repeated about 10 times.
- the micro charge in the above-described Me dissolution potential holding step can be repeated, for example, for each period set based on the rate of decrease of the positive electrode potential measured in advance. That is, the positive electrode potential behavior (the positive electrode potential decreasing rate) is examined in advance for a battery (cell) to be manufactured, a holding time is determined so that the positive electrode potential does not fall below the Me dissolution potential, and a cycle for performing microcharging is set. Can do. For example, in the case of the example shown in FIG. 2, the micro charge cycle is set to 10 minutes. Thereby, the detoxification process of the metal foreign material most suitable for the lithium secondary battery made into object can be performed simply.
- FIG. 3 is a flowchart showing an example of the present manufacturing method.
- step of assembling the cell S10
- preliminary charging is performed before performing initial conditioning charging (main charging).
- main charging The positive electrode potential behavior in the preliminary charging can be grasped by measuring in real time.
- Micro charging is performed in the micro charging step (S20), and the positive electrode potential of the cell is temporarily increased to a value exceeding the Me dissolution potential. Thereafter, the process proceeds to the Me dissolution potential holding step (S30).
- microcharging will be described in more detail.
- the current and time in microcharging are as described above, with a charging time of 10 seconds or less, preferably within a range where the charging amount is less than 0.01% of the cell capacity. Can be set.
- the charging time in the minute charging can be set to be extremely short compared to the conventional case. If the time for microcharging is too long, metal ions tend to be concentrated on the negative electrode. Therefore, as a preferred embodiment of the present invention, the micro charge is performed with a pulse current so that the charge time is 2 seconds or less. In this case, a pulsed voltage is applied between the positive electrode and the negative electrode.
- the pulse current in the micro charge is relatively sharp.
- Such a minute charging time is preferably 2 seconds or less, for example, 1 second or 0.5 seconds, for example.
- the current value is preferably 0.5C or more, for example, 1C, 2C, 3C, 5C, or the like.
- the charging time and current value of each time when performing micro charging a plurality of times may be the same or different.
- the charge amount is set to a small amount of less than 0.01% of the capacity of the cell. Therefore, in the Me melting potential holding step, for example, by removing the charging terminal and disconnecting from the external power source, for example, except at the time of minute charging, it is possible to suppress the decrease in the positive electrode potential due to self-discharge.
- the method further includes performing a micro discharge after the micro charge.
- FIG. 4 is a diagram for explaining an example of potential behavior when a minute discharge is performed after the minute charge.
- the potential of the positive electrode is temporarily increased to form a pulse, and the potential immediately after the minute charge is higher than the potential immediately before the minute charge.
- the negative electrode potential is temporarily lowered to form a pulse, and the potential immediately after the minute charge becomes lower than the potential immediately before the minute charge.
- lithium ions move from the positive electrode to the negative electrode, but since the potential gradient is small, the force acting on the lithium ions and metal ions is relatively weak.
- the charge amount of micro charge and the discharge amount of micro discharge may be the same, and one may be larger than the other. However, when the charge amount is equal to or less than the discharge amount, it is discharged as a whole including the influence of self-discharge, and therefore the positive electrode potential may continue to decrease, which is not preferable.
- the self-discharge amount is large, and the positive electrode potential continues to decrease. The tendency is strong. For this reason, it is preferable to make the micro charge capacity longer than the micro discharge capacity. By making the capacity of the micro charge larger than the capacity of the micro discharge, the decrease in the positive electrode potential can be suppressed and the dissolution can be continued until the metal species to be dissolved are sufficiently diffused.
- a pulsed voltage is applied between the positive electrode and the negative electrode so that the current waveform becomes a pulse shape even during a minute discharge.
- the current and time in the minute discharge can be appropriately set as in the case of the minute charge.
- the charging amount can be preferably set to be larger than the discharging capacity.
- the pulse time is preferably 10 seconds or less, more preferably 5 seconds or less. For example, it may be 2 seconds or less, and may be 1 second or 0.5 seconds.
- the current value in the micro discharge is preferably relatively high. This is because the potential of the positive electrode can be rapidly decreased and the potential of the negative electrode can be rapidly increased.
- the current value at the time of the minute discharge is not particularly limited, but is preferably 0.5 C or more, and more preferably 1 C or more, for example.
- a discharge of about 0.5 to 5C, particularly about 1 to 3C is preferable.
- the current value of the minute discharge and the current value of the minute charge may be the same or different.
- the micro discharge can be performed a plurality of times, and the current value of each time may be the same or different.
- the current value of the minute charge and minute discharge is about 5A.
- the current during charging is represented as a positive current
- the current during discharging is represented as a negative current.
- the micro discharge is performed following the micro charge, and an interval of about several seconds, for example, about 1 to 2 seconds may be provided between them.
- the main charging initial conditioning charging process
- this charge is performed over a time that greatly exceeds 10 seconds.
- the lithium secondary battery is charged to a predetermined battery capacity.
- the positive electrode potential is first increased to a value exceeding the Me dissolution potential of the mixed expected metal by performing microcharging, and the mixed predicted metal and the like are dissolved from the positive electrode.
- the target metal species is dissolved (ionized).
- the dissolved metal ions are diffused into the non-aqueous electrolyte by the Me dissolution potential holding step.
- a minute discharge is performed as necessary to raise the lowered positive electrode potential, to dissolve the metal species to be dissolved again from the positive electrode, and to suppress precipitation of metal ions on the negative electrode.
- diffusion of metal ions can be further promoted by accompanying micro discharge after micro charge.
- microcharging is repeated at appropriate times as necessary to sufficiently dissolve the metal species to be dissolved on the positive electrode and sufficiently diffuse the dissolved metal ions.
- the metal species to be dissolved are dispersed and deposited on the negative electrode without adversely affecting the battery performance.
- the form, capacity, usage, etc. of the lithium secondary battery manufactured by the manufacturing method according to the present embodiment are not particularly limited.
- a lithium ion battery 1 will be described as an example of a lithium secondary battery with reference to FIG.
- the lithium ion battery 1 includes a flat battery case 15 having a square shape.
- the electrode body 5 is accommodated in the battery case 15.
- the electrode body 5 includes a positive electrode 10, a negative electrode 20, and two separators 30 each formed in a sheet shape. These are overlapped with each other like a separator 30, a positive electrode 10, a separator 30, and a negative electrode 20, and are wound.
- the wound electrode body 5 is formed into a flat shape by being pressed from the side so as to match the shape of the battery case 15.
- the positive electrode 10 has a positive electrode current collector 11 and a positive electrode active material layer 12 containing a positive electrode active material and provided on the positive electrode current collector 11.
- the positive electrode active material layer 12 is formed on both surfaces of the positive electrode current collector 11.
- the negative electrode 20 includes a negative electrode current collector 21 and a negative electrode active material layer 22 including a negative electrode active material and provided on the negative electrode current collector 21.
- the positive electrode active material layer 12 is not formed at one end in the longitudinal direction of the positive electrode current collector 11.
- a positive electrode terminal 14 is connected to the exposed portion 11 ⁇ / b> A of the positive electrode current collector 11.
- the negative electrode active material layer 22 is not formed at one end in the longitudinal direction of the negative electrode current collector 21, and the negative electrode terminal 16 is connected to the exposed portion 21 ⁇ / b> A of the negative electrode current collector 21. .
- the battery case 15 After inserting the electrode body 5 to which the terminals 14 and 16 are connected into the battery case 15 and supplying a nonaqueous electrolyte (not shown) therein, the battery case 15 is sealed, so that the lithium ion battery 1 is Built.
- the positive electrode current collector 11 is preferably a conductive member made of a metal having good conductivity, like the current collector used for the positive electrode of a conventional lithium secondary battery (typically a lithium ion battery). It is done.
- a metal containing aluminum, nickel, titanium, iron, or the like as a main component or an alloy containing these as a main component can be used.
- limiting in particular about the shape of a positive electrode electrical power collector Various things can be considered according to the shape of a lithium secondary battery, etc. For example, it may be in various forms such as a bar shape, a plate shape, a sheet shape, a foil shape, and a mesh shape.
- a sheet-like positive electrode current collector made of aluminum is used.
- a lithium-containing transition metal oxide capable of occluding and releasing lithium is used, which is a kind of material conventionally used in lithium secondary batteries (for example, a layered oxide or a spinel oxide).
- two or more kinds can be used without any particular limitation.
- examples thereof include lithium-containing composite oxides such as lithium nickel composite oxides, lithium cobalt composite oxides, lithium manganese composite oxides, and lithium magnesium composite oxides.
- a ternary lithium-containing transition metal oxide containing manganese, nickel, and cobalt in particular, nickel in a transition metal constituting a lithium-containing composite oxide
- the content ratio is less than 50 mol%.
- the lithium nickel-based composite oxide is an ⁇ -NaFeO 2 type lithium nickelate (LiNiO 2 ) having lithium (Li) and nickel (Ni) as constituent metal elements, as well as this LiNiO 2 .
- the nickel site transition metal site
- the nickel ratio is maintained at 50% or more. It is the meaning which also includes the oxide containing.
- Examples of the metal element other than Li and Ni include, for example, cobalt (Co), aluminum (Al), manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium (Mg), and titanium (Ti ), Zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin (Sn), lanthanum (La) ), And one or more metal elements selected from the group consisting of cerium (Ce). The same meaning is applied to lithium cobalt complex oxides, lithium manganese complex oxides, and lithium magnesium complex oxides.
- a so-called ternary lithium-containing composite oxide (typically, LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) containing at least three kinds of transition metal elements such as manganese, cobalt, and nickel,
- So-called lithium-excess type lithium-containing composite oxide containing excessive lithium typically xLi [Li 1/3 Mn 2/3 ] O 2.
- LiMeO 2 where 0 ⁇ x ⁇ 1 and Me represents a transition metal element.
- an olivine type lithium phosphate represented by the general formula LiMPO 4 (M is at least one element of Co, Ni, Mn, Fe; for example, LiFeO 4 , LiMnPO 4 ) is used as the positive electrode active material. Also good.
- the compound constituting such a positive electrode active material can be prepared and provided by, for example, a known method.
- a desired lithium-containing composite oxide is prepared by mixing several raw material compounds appropriately selected according to the atomic composition at a predetermined molar ratio and firing the mixture at an appropriate means and at a predetermined temperature. Can do.
- the fired product is pulverized, granulated and classified by an appropriate means to obtain a granular positive electrode active material powder substantially composed of secondary particles having a desired average particle size and / or particle size distribution. be able to.
- the preparation method itself of a positive electrode active material does not characterize this invention at all.
- the positive electrode active material layer 12 may contain a conductive material, a binder, and the like as necessary in addition to the positive electrode active material.
- a conductive material for example, carbon materials such as carbon black (for example, acetylene black, furnace black, ketjen black) and graphite powder can be preferably used. Among these, you may use together 1 type, or 2 or more types.
- the binder a polymer material that dissolves or disperses in water can be preferably used. Cellulose polymers such as carboxymethylcellulose (CMC), methylcellulose (MC), cellulose acetate phthalate (CAP), hydroxypropylmethylcellulose (HPMC), etc .; polyvinyl alcohol (PVA) And the like are exemplified.
- polymer materials that are dispersed in water examples include vinyl polymers such as polyethylene (PE) and polypropylene (PP); polyethylene oxide (PEO), polytetrafluoroethylene (PTFE), and tetrafluoroethylene.
- vinyl polymers such as polyethylene (PE) and polypropylene (PP); polyethylene oxide (PEO), polytetrafluoroethylene (PTFE), and tetrafluoroethylene.
- -Fluorine resins such as perfluoroalkyl vinyl ether copolymer (PFA); vinyl acetate copolymer; rubbers such as styrene butadiene rubber (SBR).
- PFA perfluoroalkyl vinyl ether copolymer
- SBR styrene butadiene rubber
- the binder is not limited to a water-based one, and a solvent-based binder such as polyvinylidene fluoride (PVDF) can also be used.
- PVDF polyvinyliden
- a conductive member made of a metal having good conductivity is preferably used.
- a copper material, a nickel material, or an alloy material mainly composed of them is preferable to use.
- the shape of the negative electrode current collector can be the same as the shape of the positive electrode.
- a sheet-like copper negative electrode current collector is used.
- the negative electrode active material may be any material that can occlude and release lithium, and one or more negative electrode active materials conventionally used in lithium secondary batteries can be used without particular limitation.
- carbon materials such as graphite (graphite), oxide materials such as lithium titanium oxide (Li 4 Ti 5 O 12 ), metals such as tin, aluminum (Al), zinc (Zn), silicon (Si), or Examples thereof include metal materials composed of metal alloys mainly composed of these metal elements.
- a particulate carbon material (carbon particles) including a graphite structure (layer structure) at least partially is preferably used. Any carbon material of a so-called graphitic material (graphite), non-graphitizable carbon material (hard carbon), easily graphitized carbon material (soft carbon), or a combination of these materials is preferably used. can do.
- the negative electrode active material layer 22 formed on the negative electrode 20 can contain, in addition to the negative electrode active material, for example, one or two or more materials that can be blended in the positive electrode active material layer.
- various materials that can function as a binder, a dispersing agent, and the like as listed as constituent materials of the positive electrode active material layer 12 can be similarly used.
- the binder is not limited to a water-based one, and a solvent-based binder such as polyvinylidene fluoride (PVDF) can also be used.
- the positive electrode 10 and the negative electrode 20 according to the present embodiment can be manufactured by a conventional method. That is, a paste-like composition (hereinafter referred to as an active material layer forming paste) in which the above active material and a binder are dispersed in an appropriate solvent (water, organic solvent, etc.) similar to the conventional one is prepared. To do. The prepared active material layer forming paste is applied to the current collectors 11, 21, dried, and then compressed (pressed) to obtain an electrode in which the current material is provided with the active material layer.
- an active material layer forming paste in which the above active material and a binder are dispersed in an appropriate solvent (water, organic solvent, etc.) similar to the conventional one is prepared.
- an appropriate solvent water, organic solvent, etc.
- a non-aqueous electrolyte (not shown) contains a lithium salt as a supporting salt in an organic solvent (non-aqueous solvent).
- a nonaqueous electrolyte that is liquid at room temperature (that is, an electrolytic solution) can be preferably used.
- the lithium salt for example, a known lithium salt conventionally used as a supporting salt for a non-aqueous electrolyte of a lithium secondary battery can be appropriately selected and used. Examples of such lithium salts include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , Li (CF 3 SO 2 ) 2 N, LiCF 3 SO 3 and the like.
- These supporting salts can be used alone or in combination of two or more.
- a particularly preferred example is LiPF 6 .
- an organic solvent used for a general lithium secondary battery can be appropriately selected and used.
- Particularly preferred non-aqueous solvents include carbonates such as ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and propylene carbonate (PC). These organic solvents can be used alone or in combination of two or more.
- the same separator as the conventional one can be used.
- a porous sheet made of resin a microporous resin sheet
- polyolefin resins such as polyethylene (PE), polypropylene (PP), and polystyrene are preferable.
- a porous structure such as a PE sheet, a PP sheet, a two-layer structure sheet in which a PE layer and a PP layer are laminated, and a three-layer structure sheet in which one PE layer is sandwiched between two PP layers.
- a polyolefin sheet can be suitably used.
- a separator may not be necessary (that is, in this case, the electrolyte itself can function as a separator).
- the lithium secondary battery according to the present embodiment can be suitably used as a power source for a motor (electric motor) mounted on a vehicle such as an automobile.
- the lithium ion battery 1 can be suitably used as a power source for a vehicle driving motor (electric motor) mounted on a vehicle 50 such as an automobile.
- the type of the vehicle 50 is not particularly limited, but is typically a hybrid vehicle, an electric vehicle, a fuel cell vehicle, or the like.
- Such a lithium ion battery 1 may be used alone, or may be used in the form of an assembled battery that is connected in series and / or in parallel.
- a small laminate cell (lithium secondary battery) for testing was constructed as follows. First, in forming the positive electrode active material layer in the positive electrode, a positive electrode active material layer forming paste was prepared.
- the paste includes a ternary lithium transition metal oxide (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) as a positive electrode active material, acetylene black (AB) as a conductive material, and a binder. And polyvinylidene fluoride (PVDF) were mixed with ion-exchanged water so that the mass% ratio of these materials was 87: 10: 3.
- a ternary lithium transition metal oxide LiNi 1/3 Mn 1/3 Co 1/3 O 2
- AB acetylene black
- PVDF polyvinylidene fluoride
- the positive electrode active material layer forming paste is applied to the positive electrode current collector so that the coverage of the positive electrode active material per unit area is about 12 mg / cm 2 on the aluminum foil (thickness 15 ⁇ m) as the positive electrode current collector. It was applied to one side and dried. After drying, the sheet was stretched into a sheet shape with a roller press to form a thickness of about 90 ⁇ m, and slit so that the positive electrode active material layer had a predetermined width to produce a positive electrode (positive electrode sheet). Note that copper particles having a diameter of 100 ⁇ m and a thickness of 6 ⁇ m were adhered as metal foreign substances on the positive electrode active material layer.
- a negative electrode active material layer forming paste for preparing a negative electrode of a lithium secondary battery was prepared.
- the paste comprises graphite as a negative electrode active material, styrene butadiene block copolymer (SBR) as a binder, and carboxymethyl cellulose (CMC) in a mass% ratio of these materials of 98: 1: 1. It was prepared by mixing with ion exchange water. This paste is applied to one side of a negative electrode current collector so that the coating amount of the negative electrode active material per unit area is about 6.5 mg / cm 2 on a copper foil (thickness 10 ⁇ m) as the negative electrode current collector. I let you. After drying, the film was stretched into a sheet by a roller press to form a thickness of about 60 ⁇ m, and the negative electrode active material layer was slit so as to have a predetermined width, thereby preparing negative electrodes (negative electrode sheets).
- SBR styrene butadiene block copolymer
- CMC carboxymethyl cellulose
- a laminate cell (lithium secondary battery) for testing was constructed. That is, a positive electrode sheet (dimensions of about 23 mm ⁇ 23 mm) and a negative electrode sheet (dimensions of about 25 mm ⁇ 25 mm) are laminated with a separator interposed therebetween so that the active material layers of both electrode sheets face each other.
- a separator interposed therebetween so that the active material layers of both electrode sheets face each other.
- a reference electrode in which a lithium metal foil was attached to a nickel lead was placed apart from the negative electrode sheet.
- a three-layer film made of polypropylene / polyethylene / polypropylene was used.
- This electrode body was housed in a laminated bag-shaped battery container together with a non-aqueous electrolyte, and sealed to construct two test lithium secondary batteries (referred to as Sample 1 and Sample 2).
- a non-aqueous electrolyte a 1: 7 (volume ratio) mixed solvent of ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) was used, and 1 mol / L LiPF 6 (LPFO) as a lithium salt.
- EC ethylene carbonate
- DEC diethyl carbonate
- EMC ethyl methyl carbonate
- LPFO 1 mol / L LiPF 6
- FIG. 1 is graphs showing temporal changes in the positive electrode potential, the negative electrode potential, the potential difference, and the supply current.
- a pulsed current was supplied by applying a pulse voltage between the positive electrode and the negative electrode. That is, in Sample 1, after performing a minute charge for 0.5 seconds at a current of 2 C, the sample was left as it was to confirm the potential behavior.
- the maximum potential of the positive electrode at the time of the first micro charge was 4.0V.
- micro charge is performed at 1.25 C for 2 seconds, then discharge is performed at 1.25 C for 0.5 second with an interval of 1 second, and then every 600 seconds.
- the same micro charge and micro discharge were repeated 120 times.
- the maximum potential of the positive electrode during the first micro charge is 3.9 V, and the maximum potential of the positive electrode during the second and subsequent micro charges is about 3.7 V to about 3.9 V, both of which are above 3.2 V It was. Note that the maximum potential reached by the negative electrode during microdischarge was about 1.5 V to about 2.7 V, both of which were 3.2 V or less.
- FIG. 8 is an observation image of copper particles as a metal foreign matter adhered on the positive electrode.
- FIGS. 9A to 9D and FIGS. 10A to 10D are A: positive electrode of Sample 1 and Sample 2 after preliminary charging, respectively.
- FIG. 7 in Sample 1 in which the micro charge was performed only once, it was confirmed that the positive electrode potential fell below 3.2 V approximately 25 minutes after the micro charge.
- the lithium secondary battery obtained by the manufacturing method disclosed herein does not affect the battery performance even if metallic foreign matter is contained, and is provided at a lower cost and with higher reliability.
- this invention was demonstrated by suitable embodiment, such description is not a limitation matter and of course various modifications are possible.
- a method capable of manufacturing a lithium secondary battery without affecting the battery performance even when a metal foreign object is mixed According to this manufacturing method, it is possible to provide a lithium secondary battery with higher reliability at a lower cost. Therefore, according to the present invention, as shown in FIG. 6, a vehicle including such a lithium secondary battery 1 (which may be in the form of an assembled battery formed by connecting a plurality of such batteries 1 in series) as a power source. 50 (typically automobiles, in particular automobiles equipped with electric motors such as hybrid cars and electric cars) can be provided.
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Abstract
Description
特許文献3には、初回の充電時に電池容量の0.01%~0.1%充電し、その後に1時間~48時間の放置時間を設けることが記載されている。
例えば、特許文献1記載の技術によると、1時間以上48時間以内の放置時間には充放電を行わない。そのため、リチウムニッケル複合酸化物等に比べ容量維持率が若干劣る三元系正極等の電極材料を用いた場合には、微小充電時の放置における正極電位の降下が大きく、金属異物の溶解電位(とりわけCuの3.2V以上)を保持できないおそれがあった。この場合、正極電位が金属異物の溶解電位を下回ると正極からの金属異物の溶解反応が途中で止まり、溶解した金属イオンの拡散効果も得られず、その後負極の局所的表面に析出してしまう。
特許文献3記載の技術は、微小充電後に長時間放置するものであり、充電時に負極電位が低下してその状態で長時間放置されるため、負極において析出が生じ、その析出物が成長するおそれがあった。
(1)上記正極、上記負極および上記非水電解質を含むセルを組み立てる工程。
(2)上記組み立てられたセルに対して、初期コンディショニング充電を行う前に、金属リチウム(Li)基準極に対する正極電位が、予め設定されている混在予想金属種(Me)の溶解が開始されるMe溶解電位を上回る電位となるまで微小充電を行う微小充電工程。典型的には、充電時間10秒以下(好適には5秒以下)の微小充電を行う。
(3)上記微小充電後に、上記セルの正極電位を上記Me溶解電位以上に所定の時間保持するMe溶解電位保持工程。
また、本明細書において「活物質」は、二次電池において電荷担体となる化学種(例えば、リチウムイオン電池ではリチウムイオン)を可逆的に吸蔵および放出(典型的には挿入および脱離)可能な物質をいう。
かかる方法によると、まず、(1)セルを組み立てる工程において、正極、負極および非水電解質等を組み立ててセルを構築する。次いで、(2)微小充電工程において、上記の組み立てられたセルに対し、初期コンディショニング充電を行う前に、微小充電を行うようにする。
ここで、混在予想金属種(Me)は、リチウム二次電池の製造工程において混入する可能性のある金属異物金属異物のうちで最も溶解電位の高い金属種であって、かつ、該リチウム二次電池の作動電圧範囲内に酸化還元電位を有し、イオンになる(溶解する)可能性のある金属種である。ここに開示される製造方法では、正極等に混在すると予想される金属異物であっても、該リチウム二次電池の作動電圧範囲内でイオンになる(溶解する)可能性のない金属については、混在予想金属種(Me)として考慮する必要はない。
このような微小充電によると、正極の最高到達電位が混在予想金属種(Me)の溶解が開始されるMe溶解電位を超えているため、正極に混在する混在予想金属は溶解し、金属イオンとなって負極側へと移動する。金属イオンの拡散速度は比較的遅いため、従来の方法で充電を長時間継続した場合には、金属イオンが負極に達して負極上で局所的に析出してしまうおそれがある。しかし、ここに開示された製造方法によれば、微小充電における充電時間を極めて短くすることができる(例えば10秒以下)ので、充電時間内に金属イオンが負極に達して析出することを抑制することができる。
なお、混在予想金属種(Me)のMe溶解電位は、該金属種の酸化還元電位(Li基準)に相当すると考えることができる。しかしながら、電池の構成等によっては、該金属種の酸化還元電位よりも、実際のMe溶解電位の方が高くなる場合等も考えられる。そのような場合には、Me溶解電位を実際のMe溶解電位に設定して、たとえば該金属種の酸化還元電位より高い値に設定することができる。
なお、リチウム二次電池は、これまでに、電池性能の向上を目的として様々な改良がなされてきた。正極および負極の両極活物質の材料および組成の変更や、負極活物質の細粒化および表面被覆、導電材や分散剤等の添加材の変更や追加等、がその一例である。このような変更は、正極の電位挙動に大きな差異をもたらす。したがって、今後のリチウム二次電池における金属異物の無害化の手法は、多様な正極電位挙動に対して積極的なコントロールを行うものとなり得る。ここに開示された製造方法においては、上記のとおり、一回の微小充電における充電量を、当該セルの容量の極めて小さい割合(例えば上記のとおり、セル容量の0.01%未満程度)だけ行い、様々な正極電位挙動に応じて、この微小充電を必要な回数だけ行い得る。すなわち、対象とする正極の電位挙動に応じて、繊細かつ積極的に正極電位の制御を行い得る。したがって、例えば、正極活物質として、容量維持率の高いリチウムニッケル複合酸化物を採用した場合や、リチウムニッケル複合酸化物等に比べ容量維持率が若干劣る正極三元系活物質等を活物質として採用した場合であっても、より無駄のない、最適な状態で、正極電位をMe溶解電位以上に保持することが可能となる。これにより、正極の種類に因らず、上記の効果を効率的に得ることができる。
図1は、予備充電の一例を説明するための図であり、グラフの上から、正極電位、負極電位、正極と負極との間の電位差(以下、単に電位差という)、および供給される電流の時間変化を表す。
なお、この最高到達電位については、混在予想金属種の種類に応じ、Me溶解電位を上回る範囲で適宜設定することができる。例えば、具体的には、リチウムの酸化還元電位に対する各種金属元素の酸化還元電位を考慮して決定することができる。酸化還元電位は溶解電位と同じであってもよい。図1の例では、混在予想金属種(Me)として鉄(Fe)よりも溶解電位の高い銅(Cu)を想定しており、Me溶解電位(ここではCu)は3.2V(Li基準)である。これに対し、微小充電による実際の正極最高到達電位は約3.9Vである。またこれに限らず、正極最高到達電位を、例えば、4.0V以上に設定することなどもできる。
なお、この微小充電は、充電時の充電量がセルの容量の0.01%未満となるように行われるのが好ましい。このような微小な充電量の充電を行うことにより、無駄のない、より効果的な正極電位の制御が可能となる。
微小充電の繰り返し回数は特に限定されないが、繰り返し回数が多いほど、金属イオンの集中的な析出を抑制する効果が期待される。繰り返し回数は、製造するリチウム二次電池の容量維持率などの特性や、所定の保持時間に応じて適宜決定することができる。例えば10回以上としてもよく、100回以上としてもよい。例えば、図2は、図1に示した予備充電における短期的(0~2500秒)な電位挙動を、長期的(0~20時間)に行った例について示した図である。例えば、三元系正極を用いたリチウム二次電池の製造に際しては、図2に示したように、微小充電を、10分程度の間隔で、所定の時間(20時間)繰り返し、合計120回程度行ったものである。正極電位が放置中でも約3.2V以上(具体的には約3.4V以上)となり、溶解対象金属種が十分に溶解および拡散されていることが伺える。逆に、容量維持率の高いリチウムニッケル系正極を用いたリチウム二次電池の製造に際しては、例えば、微小充電工程および保持工程の一連の工程をおよそ120分程度の間隔で、20時間程度繰り返し、10回程度繰り返すようにしても良い。
さらに、一般式がLiMPO4(MはCo、Ni、Mn、Feのうちの少なくとも一種以上の元素;例えばLiFeO4、LiMnPO4)で表記されるオリビン型リン酸リチウムを上記正極活物質として用いてもよい。
負極活物質としては、リチウムを吸蔵および放出可能な材料であればよく、従来からリチウム二次電池に用いられる負極活物質の一種または二種以上を特に限定なく使用することができる。例えば、黒鉛(グラファイト)等の炭素材料、リチウム・チタン酸化物(Li4Ti5O12)等の酸化物材料、スズ、アルミニウム(Al)、亜鉛(Zn)、ケイ素(Si)等の金属若しくはこれらの金属元素を主体とする金属合金からなる金属材料、等が挙げられる。典型例として、少なくとも一部にグラファイト構造(層状構造)を含む粒子状の炭素材料(カーボン粒子)が好ましく用いられる。いわゆる黒鉛質のもの(グラファイト)、難黒鉛化炭素質のもの(ハードカーボン)、易黒鉛化炭素質のもの(ソフトカーボン)、これらを組み合わせた構造を有するもののいずれの炭素材料も、好適に使用することができる。
以下のようにして、試験用の小型のラミネートセル(リチウム二次電池)を構築した。
まず、正極における正極活物質層を形成するにあたり正極活物質層形成用ペーストを調製した。該ペーストは、正極活物質としての三元系のリチウム遷移金属酸化物(LiNi1/3Mn1/3Co1/3O2)と、導電材としてのアセチレンブラック(AB)と、結着剤としてのポリフッ化ビニリデン(PVDF)とを、これら材料の質量%比が87:10:3となるようにイオン交換水と混合することにより調製した。次いで、正極集電体としてのアルミニウム箔(厚さ15μm)に単位面積あたりの正極活物質の被覆量が凡そ12mg/cm2になるように該正極活物質層形成用ペーストを正極集電体の片面に塗布して乾燥させた。乾燥後、ローラプレス機にてシート状に引き伸ばすことにより厚さ凡そ90μmに成形し、正極活物質層が所定の幅を有するようにスリットして正極(正極シート)を作製した。なお、正極の活物質層上に金属異物として直径100μm、厚み6μmの銅粒子を付着させた。
次に、リチウム二次電池の負極を作製するための負極活物質層形成用ペーストを調製した。該ペーストは、負極活物質としてのグラファイトと、結着材としてのスチレンブタジエンブロック共重合体(SBR)と、カルボキシメチルセルロース(CMC)とを、これら材料の質量%比が98:1:1となるようにイオン交換水と混合することにより調製した。このペーストを、負極集電体としての銅箔(厚さ10μm)に単位面積あたりの負極活物質の被覆量が凡そ6.5mg/cm2になるように負極集電体の片面に塗布し乾燥させた。乾燥後、ローラプレス機にてシート状に引き伸ばすことにより厚さ凡そ60μmに成形し、負極活物質層が所定の幅を有するようにスリットして負極(負極シート)をそれぞれ作製した。
上記調製した正極シートと負極シートとを用いて試験用のラミネートセル(リチウム二次電池)を構築した。すなわち、セパレータを間に介して、正極シート(寸法約23mm×23mm)と負極シート(寸法約25mm×25mm)とを、両電極シートの互いの活物質層が対向するように積層して電極体を作製した。なお、セパレータの負極側面に、正極、負極それぞれのリチウム基準電位を計測するために、ニッケルリードにリチウム金属箔を貼り付けた参照極を、負極シートとは離して設置した。セパレータとしては、ポリプロピレン/ポリエチレン/ポリプロピレン製の三層フィルム(PP/PE/PPフィルム)を用いた。
この電極体を非水電解液とともにラミネート製の袋状電池容器に収容し、封口して試験用リチウム二次電池を2個(サンプル1およびサンプル2とする)構築した。非水電解液としては、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)およびエチルメチルカーボネート(EMC)の3:7(体積比)混合溶媒に、リチウム塩としての1mol/LのLiPF6(LPFO)と、添加剤としての0.05mol/LのLiPF2(C2O4)2を溶解させたものを用いた。
電極体を非水電解質に含浸させてから20時間後に、サンプル1に対して図7に示すような、サンプル2に対しては図1および図2に示すような予備充電を施した。なお、図1、図2および図7は、正極電位、負極電位、電位差、および供給電流の時間変化を示すグラフである。微小充電時および微小放電時には、正極と負極との間にパルス電圧を印加することにより、パルス状の電流を供給した。
すなわち、サンプル1では、電流2Cで0.5秒間の微小充電を行った後、そのまま放置して電位挙動を確認した。初回の微小充電時の正極の最高到達電位は4.0Vであった。
また、サンプル2では、微小充電工程で、1.25Cで2秒間の微小充電を行った後、1秒の間隔を持って、1.25Cで0.5秒間の放電を行い、次いで600秒毎に同様の微小充電および微小放電を120回繰り返し行った。初回の微小充電時の正極の最高到達電位は3.9V、2回目以降の微小充電時の正極の最高到達電位は約3.7V~約3.9Vであり、いずれも3.2V以上であった。なお、微小放電時の負極の最高到達電位は約1.5V~約2.7Vであり、いずれも3.2V以下であった。
予備充電後の各セルを分解し、光学顕微鏡を用いて正極シートおよび負極シートの表面を観察した。なお、図8は、正極上に付着させた金属異物としての銅粒子の観察像であり、図9A~9Dおよび図10A~10Dは、それぞれ予備充電後のサンプル1およびサンプル2の、A:正極の表面の観察画像、B:負極表面の観察画像、C:セパレータの正極側表面の観察画像、およびD:セパレータの負極側表面の観察画像である。微小充電を1回行っただけのサンプル1では、図7に示したように、微小充電の約25分後に正極電位が3.2Vを下回ってしまうことが確認された。また、微小充電後正極の表面は、図9Aに示すように、銅粒子の殆どが溶け残り、図9B~9Dに示すように、セパレータおよび負極への析出がみられないことが確認された。一方、ここに開示された製造方法により予備充電されたサンプル2は、図10Aに示すように、正極表面のほぼ全ての銅粒子が溶解し、溶け残りがないことが確認された。また、図10B~10Dからわかるとおり、セパレータの正極側、負極側、負極の表面へと進むにつれて銅が拡散してゆき、析出する様子が確認された。また、析出物の成長はセパレータの途中で止まっており、短絡を招くような析出物の成長は見られないことも確認された。
以上、本発明を好適な実施形態により説明してきたが、こうした記述は限定事項ではなく、勿論、種々の改変が可能である。
5 正極体
10 正極
11 正極集電体
11A 露出部分
12 正極活物質層
14 正極端子
15 電池ケース
16 負極端子
20 負極
21 負極集電体
21A 露出部分
22 負極活物質層
30 セパレータ
50 車両
Claims (14)
- リチウム含有複合酸化物からなる正極活物質を有する正極と、リチウムイオンの吸蔵および放出が可能な負極活物質を有する負極と、非水電解質とを備えるリチウム二次電池を製造する方法であって:
前記正極、前記負極および前記非水電解質を含むセルを組み立てる工程;
前記組み立てられたセルに対して、初期コンディショニング充電を行う前に、金属リチウム(Li)基準極に対する正極電位が、予め設定されている混在予想金属種(Me)の溶解が開始されるMe溶解電位を上回る電位となるまで微小充電を行う微小充電工程;および
前記微小充電後に、前記セルの正極電位を前記Me溶解電位以上に所定の時間保持するMe溶解電位保持工程;
を包含する、リチウム二次電池製造方法。 - 前記微小充電は、該充電時の充電量が前記セルの容量の0.01%未満となるように行われる、請求項1に記載の製造方法。
- 前記Me溶解電位保持工程において、前記セルの正極電位を前記Me溶解電位以上に保持するために、前記所定の時間内において前記微小充電工程を1回もしくは2回以上繰り返す、請求項1または2に記載の製造方法。
- 予め測定した正極電位の下降速度に基づき設定した周期ごとに前記微小充電を繰り返す、請求項1~3のいずれか一項に記載の製造方法。
- 前記微小充電は、充電時間が2秒以下となるように、パルス電流で行われる、請求項1~4のいずれか一項に記載の製造方法。
- 1C以上の電流を供給する、請求項5に記載の製造方法。
- 前記Me溶解電位保持工程において、前記セルの正極電位を前記Me溶解電位以上に保持するために、前記微小充電後に外部電源との接続を外して前記セルを放置する、請求項1~6のいずれか一項に記載の製造方法。
- 前記微小充電後に、微小放電を行うことを更に包含する、請求項1~7のいずれか一項に記載の製造方法。
- 前記微小放電は、放電容量が前記微小充電で充電される充電量よりも小さく設定されて行われる、請求項8に記載の製造方法。
- 前記微小放電は、電流0.5C以上のパルス電流で行われる、請求項8または9に記載の製造方法。
- 前記混在予想金属種(Me)として銅(Cu)が設定されており、
前記微小充電は、金属リチウム(Li)基準極に対する正極電位が、Cuの溶解が開始されるCu溶解電位を上回る電位となるように行われる、請求項1~10のいずれか一項に記載の製造方法。 - 前記正極活物質は、少なくともマンガン、コバルト、およびニッケルを含むリチウム含有複合酸化物からなり、
前記リチウム含有複合酸化物を構成する遷移金属における前記ニッケルの含有割合が50モル%未満である、請求項1~11のいずれか一項に記載の製造方法。 - 請求項1~12のいずれか一項に記載の製造方法で製造された、リチウム二次電池。
- 請求項13に記載のリチウム二次電池を備える、車両。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015025207A1 (en) * | 2013-08-22 | 2015-02-26 | Toyota Jidosha Kabushiki Kaisha | Manufacturing method of nonaqueous electrolytic solution secondary battery |
US10128547B2 (en) | 2012-02-16 | 2018-11-13 | Toyota Jidosha Kabushiki Kaisha | Method for producing secondary battery |
JP2019021510A (ja) * | 2017-07-18 | 2019-02-07 | トヨタ自動車株式会社 | リチウムイオン二次電池の製造方法 |
JP2022084169A (ja) * | 2020-11-26 | 2022-06-07 | プライムプラネットエナジー&ソリューションズ株式会社 | リチウムイオン電池の製造方法 |
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JP6382274B2 (ja) * | 2016-10-04 | 2018-08-29 | 本田技研工業株式会社 | ミクロショートを解消する方法 |
JP6965839B2 (ja) * | 2018-07-12 | 2021-11-10 | トヨタ自動車株式会社 | 二次電池の充電方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005235624A (ja) * | 2004-02-20 | 2005-09-02 | Japan Storage Battery Co Ltd | 非水電解液二次電池の製造方法 |
JP2007018963A (ja) * | 2005-07-11 | 2007-01-25 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池の製造方法とその製造方法で作製した非水電解液二次電池 |
JP2010244981A (ja) * | 2009-04-09 | 2010-10-28 | Toyota Motor Corp | リチウムイオン二次電池の製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3869775B2 (ja) * | 2002-08-26 | 2007-01-17 | 三洋電機株式会社 | リチウム二次電池 |
JP2005243537A (ja) | 2004-02-27 | 2005-09-08 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池の製造法 |
JP4639883B2 (ja) | 2005-03-24 | 2011-02-23 | パナソニック株式会社 | 非水電解液二次電池の製造方法 |
JP4784194B2 (ja) | 2005-08-04 | 2011-10-05 | パナソニック株式会社 | 非水電解液二次電池の製造法 |
JP2009072039A (ja) * | 2007-09-18 | 2009-04-02 | Panasonic Corp | 電源システム |
JP4771180B2 (ja) * | 2008-08-28 | 2011-09-14 | トヨタ自動車株式会社 | 組電池および組電池の制御システム |
US20100156357A1 (en) * | 2008-11-13 | 2010-06-24 | Ibrahim Abou Hamad | System and method for charging rechargeable batteries |
JP5331493B2 (ja) * | 2009-01-13 | 2013-10-30 | 日立ビークルエナジー株式会社 | 電池制御装置 |
WO2012081128A1 (ja) | 2010-12-17 | 2012-06-21 | トヨタ自動車株式会社 | リチウム二次電池の製造方法 |
-
2011
- 2011-09-08 KR KR1020147008857A patent/KR101571642B1/ko active IP Right Grant
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005235624A (ja) * | 2004-02-20 | 2005-09-02 | Japan Storage Battery Co Ltd | 非水電解液二次電池の製造方法 |
JP2007018963A (ja) * | 2005-07-11 | 2007-01-25 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池の製造方法とその製造方法で作製した非水電解液二次電池 |
JP2010244981A (ja) * | 2009-04-09 | 2010-10-28 | Toyota Motor Corp | リチウムイオン二次電池の製造方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10128547B2 (en) | 2012-02-16 | 2018-11-13 | Toyota Jidosha Kabushiki Kaisha | Method for producing secondary battery |
WO2015025207A1 (en) * | 2013-08-22 | 2015-02-26 | Toyota Jidosha Kabushiki Kaisha | Manufacturing method of nonaqueous electrolytic solution secondary battery |
JP2019021510A (ja) * | 2017-07-18 | 2019-02-07 | トヨタ自動車株式会社 | リチウムイオン二次電池の製造方法 |
JP2022084169A (ja) * | 2020-11-26 | 2022-06-07 | プライムプラネットエナジー&ソリューションズ株式会社 | リチウムイオン電池の製造方法 |
JP7182590B2 (ja) | 2020-11-26 | 2022-12-02 | プライムプラネットエナジー&ソリューションズ株式会社 | リチウムイオン電池の製造方法 |
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CN103782441A (zh) | 2014-05-07 |
US20150064566A1 (en) | 2015-03-05 |
US9385398B2 (en) | 2016-07-05 |
KR101571642B1 (ko) | 2015-11-24 |
JP5682801B2 (ja) | 2015-03-11 |
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