WO2021200444A1 - 二次電池システム - Google Patents
二次電池システム Download PDFInfo
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- WO2021200444A1 WO2021200444A1 PCT/JP2021/012183 JP2021012183W WO2021200444A1 WO 2021200444 A1 WO2021200444 A1 WO 2021200444A1 JP 2021012183 W JP2021012183 W JP 2021012183W WO 2021200444 A1 WO2021200444 A1 WO 2021200444A1
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- Prior art keywords
- secondary battery
- soc
- peak top
- charging
- discharging
- Prior art date
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Images
Classifications
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
- H02J7/00714—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery charging or discharging current
- H02J7/00718—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery charging or discharging current in response to charge current gradient
-
- 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
- H02J7/0047—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries with monitoring or indicating devices or circuits
- H02J7/0048—Detection of remaining charge capacity or state of charge [SOC]
-
- 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
-
- 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
- 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
- H01M10/448—End of discharge regulating measures
-
- 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
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
- H02J7/007182—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage
- H02J7/007184—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage in response to battery voltage gradient
-
- 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
- This disclosure relates to a secondary battery system.
- the Q-dV / dQ curve is a curve showing the relationship between dV / dQ, which is a differential value of the change amount dV of the voltage V of the secondary battery with respect to the change amount dQ of the capacity Q, and the value of the capacity Q.
- Patent Document 1 discloses a secondary battery system in which the charging state (hereinafter, SOC) at the start and end of a charge / discharge cycle is set in advance while avoiding the peak top.
- the SOCs at the start and end of the charge / discharge cycle are merely set. For example, when the user finishes charging / discharging at the peak top existing between the start end and the end end, the deterioration of the secondary battery is accelerated. Further, when the charge / discharge cycle is set so that the peak top does not exist between the SOC at the start end and the SOC at the end end, the battery capacity is greatly reduced.
- An object of the present disclosure is to provide a secondary battery system capable of controlling charging / discharging so as to avoid SOC in which the charging / discharging end position reaches the peak top.
- the secondary battery system includes an electrode body in which a positive electrode plate and a negative electrode plate are laminated via a separator, a secondary battery having a non-aqueous electrolyte, and electricity connected to the secondary battery.
- the dV / dQ which is the differential value of the load and the change in the voltage V of the secondary battery dV with respect to the change in the capacity Q of the secondary battery, is expressed as a percentage of the capacity Q with respect to the fully charged capacity of the secondary battery.
- SOC-dV / dQ curve plotted against the charged state (SOC) to be performed at least one peak top SOC range including the peak SOC is set, and charging or discharging is stopped in the peak top SOC range.
- a control device for terminating the charging or discharging of the secondary battery while avoiding the peak top SOC range by discharging the secondary battery by an electric load is provided.
- the secondary battery system includes an electrode body in which a positive electrode plate and a negative electrode plate are laminated via a separator, a secondary battery having a non-aqueous electrolyte, and an auxiliary battery connected to the secondary battery.
- the differential value of dV / dQ which is the differential value of the change in the voltage V of the secondary battery with respect to the change in the capacity Q of the battery and the secondary battery, is expressed as a percentage of the capacity Q with respect to the fully charged capacity of the secondary battery.
- At least one peak top SOC range including the peak SOC is set, and charging or discharging is stopped in the peak top SOC range.
- a control device for terminating the charging or discharging of the secondary battery while avoiding the peak top SOC range by charging the secondary battery with the auxiliary battery is provided.
- charging / discharging can be controlled so as to avoid SOC in which the charging / discharging end position reaches the peak top.
- FIG. 1 is a block diagram showing a secondary battery system which is an example of the embodiment.
- FIG. 2 is a cross-sectional view of a secondary battery which is an example of the embodiment.
- FIG. 3 is a graph showing a SOC-dV / dQ curve.
- FIG. 4 is a flow chart showing the flow of charge control.
- FIG. 5 is a flow chart showing the flow of discharge control.
- FIG. 6 is a block diagram showing a secondary battery system which is another example of the embodiment.
- FIG. 7 is a graph showing the charging cycle of the embodiment.
- FIG. 1 is a block diagram showing a secondary battery system 10.
- the secondary battery system 10 is a system that controls the charging and discharging of the secondary battery 20.
- the secondary battery system 10 includes a secondary battery 20, a control device 40 that controls charging / discharging of the secondary battery 20, a voltage measuring device 11 that measures the voltage of the secondary battery 20, and a charging current of the secondary battery 20.
- it includes a current measuring device 12 for measuring the discharge current, an electric load 13 connected to the secondary battery 20, and a changeover switch 14 for ON / ⁇ FF connection between the secondary battery 20 and the electric load 13.
- the electric load 13 discharges the secondary battery 20, and a resistor is preferably used. Further, the resistor preferably has a resistance value capable of discharging the secondary battery 20 at a current value within a range normally used.
- the secondary battery system 10 of the present embodiment is configured to include one secondary battery 20, but is not limited to this. It may be configured to include an assembled battery in which a plurality of secondary batteries 20 are combined.
- the control device 40 controls the charging / discharging of the assembled battery, and the electric load 13 is connected to the assembled battery.
- FIG. 2 is a cross-sectional view showing the secondary battery 20.
- the secondary battery 20 is, for example, a cylindrical battery, and closes an electrode body 24, an electrolyte, an outer can 25 containing the electrode body 24 and the electrolyte, and an opening of the outer can 25. It has a sealing body 30 and.
- the electrode body 24 includes a positive electrode plate 21, a negative electrode plate 22, and a separator 23, and has a structure in which the positive electrode plate 21 and the negative electrode plate 22 are spirally wound via the separator 23.
- the positive electrode plate 21 has a positive electrode core body and a positive electrode mixture layer formed on at least one surface of the core body.
- a metal foil stable in the potential range of the positive electrode plate 21, such as aluminum or an aluminum alloy, or a film in which the metal is arranged on the surface layer can be used.
- the positive electrode mixture layer contains a positive electrode active material, a conductive agent such as acetylene black, and a binder such as polyvinylidene fluoride, and is preferably formed on both sides of the positive electrode core body.
- a lithium transition metal composite oxide is used for example.
- a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, a binder, and the like is applied onto the positive electrode core, the coating film is dried, and then the coating film is compressed to form a positive electrode mixture layer.
- the negative electrode plate 22 has a negative electrode core body and a negative electrode mixture layer formed on at least one surface of the core body.
- a metal foil stable in the potential range of the negative electrode plate 22 such as copper or copper alloy, a film in which the metal is arranged on the surface layer, or the like can be used.
- the negative electrode mixture layer contains a negative electrode active material and a binder such as styrene-butadiene rubber (SBR), and is preferably formed on both sides of the negative electrode core body.
- SBR styrene-butadiene rubber
- the negative electrode active material for example, graphite, a silicon-containing compound or the like is used.
- a negative electrode mixture slurry containing a negative electrode active material, a binder, and the like is applied onto the negative electrode core body, the coating film is dried, and then the coating film is compressed to form a negative electrode mixture layer on the core body. It can be manufactured by forming it on both sides.
- a non-aqueous electrolyte for example, a non-aqueous electrolyte is used.
- the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
- the non-aqueous solvent esters, ethers, nitriles, amides, a mixed solvent of two or more of these, and the like can be used.
- the non-aqueous solvent may contain a halogen substituent in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
- the non-aqueous electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte.
- the electrolyte salt for example, a lithium salt such as LiPF 6 is used.
- the type of the electrolyte is not particularly limited, and may be an aqueous electrolyte.
- the secondary battery 20 has insulating plates 26 and 27 arranged above and below the electrode body 24, respectively.
- the positive electrode lead 28 connected to the positive electrode plate 21 extends toward the sealing body 30 through the through hole of the insulating plate 26, and the negative electrode lead 29 connected to the negative electrode plate 22 is outside the insulating plate 27. It extends to the bottom surface portion 25A side of the outer can 25 through the outer can 25.
- the positive electrode lead 28 is connected to the lower surface of the metal plate 31 which is the bottom plate of the sealing body 30 by welding or the like, and the rupture plate 32 of the sealing body 30 electrically connected to the metal plate 31 serves as the positive electrode external terminal.
- the negative electrode lead 29 is connected to the inner surface of the bottom surface portion 25A of the outer can 25 by welding or the like, and the outer can 25 serves as a negative electrode external terminal.
- the control device 40 is a device that executes charge control and discharge control, which will be described in detail later.
- the charge control is a control for ending the charging of the secondary battery 20 so as to avoid the peak top charge rate range described later.
- the discharge control is a control for ending the discharge of the secondary battery 20 so as to avoid the peak top charge rate range.
- the control device 40 is equipped with a CPU as an arithmetic processing unit that executes the above control, and a ROM, RAM, and a hard disk drive (HDD) as storage devices connected to the CPU.
- the charge / discharge stop detection unit 41 that detects the charge / discharge stop timing of the secondary battery 20 and the charge state (hereinafter, SOC) of the charge / discharge stop timing are in the peak top SOC range. It has a peak top determination unit 42 for determining whether or not there is a peak top determination unit 42. Further, the control device 40 is connected to the voltage measuring device 11, the current measuring device 12, and the changeover switch 14.
- the charge / discharge stop detection unit 41 has a function of detecting the timing at which charging of the secondary battery 20 is stopped.
- the timing at which charging of the secondary battery 20 is stopped includes a timing at which charging is stopped when the secondary battery 20 is determined to be fully charged, and a timing at which charging is stopped after a predetermined time has elapsed. Further, the charge / discharge stop detection unit 41 may detect the timing at which the connection between the secondary battery 20 and the charger is cut off as the timing at which the charging of the secondary battery 20 is stopped.
- the charge / discharge stop detection unit 41 has a function of detecting the timing at which the discharge of the secondary battery 20 is stopped.
- the timing at which the discharge of the secondary battery 20 is stopped includes the timing at which the discharge is stopped when the voltage of the secondary battery 20 drops to a predetermined value. Further, the charge / discharge stop detection unit 41 may detect the timing at which the connection between the secondary battery 20 and the battery load is cut off as the timing at which the discharge of the secondary battery 20 is stopped.
- the peak top determination unit 42 determines whether or not the SOC of the charge / discharge stop timing of the secondary battery 20 detected by the charge / discharge stop detection unit 41 is within the set peak top SOC range (hereinafter, peak top range). Has a function.
- the peak top range is a predetermined range of the SOC including the SOC which is the peak top of the SOC-dV / dQ curve, which will be described in detail later.
- FIG. 3 is a graph showing a SOC-dV / dQ curve.
- the horizontal axis is SOC (%) and the vertical axis is dV / dQ.
- SOC is expressed as a percentage of the capacity Q of the secondary battery 20 with respect to the fully charged capacity of the secondary battery 20.
- dV / dQ represents the differential value of the voltage V with respect to the change amount dQ of the capacity Q of the secondary battery 20.
- the dV / dQ can be calculated from, for example, the QV curve obtained by measuring the change in the voltage V with respect to the capacity Q during charging or discharging.
- the SOC-dV / dQ curve includes a plurality of peak tops.
- the peak top is the maximum point on the SOC-dV / dQ curve.
- the position and number of peak tops on the SOC-dV / dQ curve are determined according to the type of electrode material such as the active material of the secondary battery 20. If the charging or discharging of the secondary battery 20 is stopped and left in the SOC corresponding to the peak top, self-discharge is easily generated and the deterioration of the battery is accelerated. As shown in FIG. 3, in the secondary battery 20, the peak top of dV / dQ is confirmed at 10%, 25%, 45%, 60%, and 78% SOC (P in the figure).
- the peak top range is ⁇ 5% from the SOC corresponding to the peak top.
- the peak top range is preset in the RAM of the control device 40.
- the peak top range can be arbitrarily set according to the type of electrode material such as the active material of the secondary battery 20.
- FIG. 4 is a flow chart showing the flow of charge control.
- the charge control is a control for ending the charging of the secondary battery 20 so as to avoid the peak top range as described above. According to the charge control, when the charging of the secondary battery 20 is stopped in the peak top range, the secondary battery 20 can be discharged by the electric load 13 to avoid the peak top range and end the charging. ..
- step S11 when the charge / discharge stop detection unit 41 detects the charge stop timing, the process proceeds to step S12.
- step S12 the peak top determination unit 42 shifts to step S13 when the SOC of the charging stop timing of the secondary battery 20 is within the set peak top range.
- step S13 the control device 40 connects the secondary battery 20 and the electric load 13 with the changeover switch 14 set to ON, and discharges the secondary battery 20. Steps S12 and S13 are repeated until the SOC of the charge stop timing of the secondary battery 20 deviates from the peak top range.
- FIG. 5 is a flow chart showing the flow of discharge control.
- the discharge control is a control for ending the discharge of the secondary battery 20 so as to avoid the peak top range as described above. According to the discharge control, when the discharge of the secondary battery 20 is stopped in the peak top range, the secondary battery 20 can be discharged by the electric load 13 to avoid the peak top range and end the discharge. ..
- step S21 when the charge / discharge stop detection unit 41 detects the discharge stop timing, the process proceeds to step S22.
- the peak top determination unit 42 shifts to step S23 when the SOC of the discharge stop timing of the secondary battery 20 is within the set peak top range.
- step S23 the control device 40 connects the secondary battery 20 and the electric load 13 with the changeover switch 14 set to ON, and discharges the secondary battery 20. Steps S22 and S23 are repeated until the SOC of the discharge stop timing of the secondary battery 20 deviates from the peak top range.
- the secondary battery system 110 which is another example of the present embodiment, will be described with reference to FIG.
- FIG. 6 is a block diagram showing the secondary battery system 110.
- the secondary battery system 110 is a system that controls the charging and discharging of the secondary battery 20.
- the secondary battery system 110 includes a secondary battery 20, a control device 40 that controls charging / discharging of the secondary battery 20, a voltage measuring device 11 that measures the voltage of the secondary battery 20, and a charging current of the secondary battery 20.
- it has a current measuring device 12 for measuring the discharge current, an auxiliary battery 15 connected to the secondary battery 20, and a changeover switch 14 for ON / ⁇ FF connection between the secondary battery 20 and the auxiliary battery 15.
- the auxiliary battery 15 charges the secondary battery 20, and for example, a secondary battery is preferably used.
- the secondary battery constituting the auxiliary battery 15 has a smaller capacity than the secondary battery 20, and preferably has a capacity of about 20% of the capacity of the secondary battery 20.
- the auxiliary battery 15 may be configured to discharge the secondary battery 20. However, from the viewpoint of controlling the auxiliary battery 15, it is preferable that the auxiliary battery 15 charges the secondary battery 20.
- the control device 40 charges the secondary battery 20 with the auxiliary battery 15 to avoid the peak top range and finish charging / discharging the secondary battery 20. It is a device.
- the secondary battery 20 when the charging of the secondary battery 20 is stopped in the peak top range, the secondary battery 20 is charged by the auxiliary battery 15 to avoid the peak top range. Can be terminated. Further, according to the discharge control of the secondary battery system 110, when the discharge of the secondary battery 20 stops in the peak top range, the auxiliary battery 15 charges the secondary battery 20 to avoid the peak top range. The discharge can be terminated.
- Example 1 Aluminum-containing lithium nickel cobalt oxide (LiNi 0.88 Co 0.09 Al 0.03 O 2 ) was used as the positive electrode active material. 100 parts by mass of LiNi 0.88 Co 0.09 Al 0.03 O 2 (positive electrode active material), 1.0 part by mass of acetylene black, and 0.9 parts by mass of polyvinylidene fluoride (PVDF) (binding agent) ) was mixed in a solvent of N-methylpyrrolidone (NMP) to obtain a positive electrode slurry. This paste was uniformly applied to both sides of an aluminum foil having a thickness of 15 ⁇ m. Next, heat treatment was performed at a temperature of 100 to 150 ° C.
- PVDF polyvinylidene fluoride
- the compressed positive electrode plate was brought into contact with a roll heated to 200 ° C. for 5 seconds to perform heat treatment, and the positive electrode plate was cut into a thickness of 0.144 mm, a width of 62.6 mm, and a length of 861 mm to prepare a positive electrode plate.
- the negative electrode active material graphite powder was mixed in an amount of 95 parts by mass and Si oxide was mixed in an amount of 5 parts by mass. Then, 100 parts by mass of the negative electrode active material, 1 part by mass of CMC as a thickener, and 1 part by mass of styrene-butadiene rubber as a binder were dispersed in water to prepare a negative electrode slurry. This negative electrode slurry was applied to both sides of a negative electrode current collector of a copper foil having a thickness of 8 ⁇ m to form a negative electrode coated portion.
- the negative electrode was compressed with a compression roller so that the thickness of the negative electrode was 0.160 mm, the thickness of the negative electrode mixture layer was adjusted, and the negative electrode plate was cut into a width of 64.2 mm and a length of 959 mm to prepare a negative electrode plate.
- a non-aqueous electrolyte was prepared by dissolving 1.5 M of LiPF 6 in a mixed solvent in which ethylene carbonate (EC), dimethyl carbonate (DMC), and methyl acetate (MA) were mixed at a volume ratio of 20:75: 5. ..
- an aluminum positive electrode lead was attached to the positive electrode current collector, and a nickel-copper-nickel negative electrode lead was attached to the negative electrode current collector. Then, an electrode body was produced by winding it between the positive electrode current collector and the negative electrode current collector via a polyethylene separator. Next, insulating plates were placed above and below the electrode body, the negative electrode leads were welded to the battery case, and the positive electrode leads were welded to the sealing plate having an internal pressure actuated safety valve and stored inside the outer can. .. Then, a non-aqueous electrolyte was injected into the outer can by a pressure method. Finally, a secondary battery was manufactured by crimping the open end of the battery case to the sealing plate via a gasket. The capacity of the battery was 3400 mAh.
- Example 2 As shown in FIG. 7, a battery was produced in the same manner as in Example 1 except that the charge / discharge test was performed in the range of SOC 15% to SOC 65%, and the charge / discharge cycle electric test was performed.
- Table 1 shows the deterioration rates of Examples 1 and 2 and Comparative Example as a relative index with the deterioration rate of Comparative Example 1 as 1.
Abstract
Description
[正極極板の作製]
正極活物質としてアルミニウム含有ニッケルコバルト酸リチウム(LiNi0.88Co0.09Al0.03O2)を用いた。100質量部のLiNi0.88Co0.09Al0.03O2(正極活物質)と1.0質量部のアセチレンブラックと、0.9質量部のポリフッ化ビニリデン(PVDF)(結着剤)をN-メチルピロリドン(NMP)の溶剤中で混合して、正極スラリーを得た。このペーストを厚み15μmのアルミニウム箔の両面に均一に塗布した。次に、加熱した乾燥機中で100~150℃の温度で熱処理してNMPを除去後、圧縮ローラで圧縮した。さらに圧縮後の正極極板を、200℃に熱したロールに5秒間接触させることで、熱処理をおこない、厚み0.144mm、幅62.6mm、長さ861mmに裁断して正極板を作製した。
負極活物質として、黒鉛粉末を95質量部、Si酸化物を5質量部になるように混合した。その後、100質量部の負極活物質、増粘剤としての1質量部のCMC、結着剤としての1質量部のスチレンブタジエンゴムを水に分散させ、負極スラリーを調製した。この負極スラリーを、厚さ8μmの銅箔の負極集電体の両面に塗布して負極塗工部を形成した。次いで、乾燥した後、負極厚みが0.160mmになるように圧縮ローラで圧縮し負極合剤層の厚みを調整し、幅64.2mm、長さ959mmに裁断して負極板を作製した。
エチレンカーボネート(EC)、ジメチルカーボネート(DMC)、及び酢酸メチル(MA)を20:75:5の体積比で混合した混合溶媒に、1.5MのLiPF6を溶解して非水電解質を調製した。
まず、正極集電体にアルミニウム製の正極リードを取り付け、負極集電体にニッケル-銅-ニッケル製の負極リードを取り付けた。その後、正極集電体と負極集電体との間にポリエチレン製のセパレータを介して巻回して電極体を作製した。次に、電極体の上と下とに絶縁板をそれぞれ配置し、負極リードを電池ケースに溶接すると共に、正極リードを内圧作動型の安全弁を有する封口板に溶接して、外装缶の内部に収納した。その後、外装缶の内部に非水電解質を加圧方式により注入した。最後に、電池ケースの開口端部を、ガスケットを介して封口板にかしめることにより二次電池を作製した。電池の容量は3400mAhであった。
電池のSOC-dV/dQ曲線において、ピークトップとなるSOCから±5%の範囲をピークトップ範囲とした。
図7に示すように、SOC15%からSOC90%の範囲で、充電、放電のいずれも20時間率のレートで充放電サイクル試験を行った。このときの総放電容量を横軸に、容量維持率を縦軸にプロットして得られた容量維持率の傾きから劣化速度を評価した。
図7に示すように、SOC15%からSOC65%の範囲で充放電試験を行った以外は、実施例1と同様に電池を作製し、充放サイクル電試験を行った。
図7に示すように、SOC15%からSOC78%の範囲で充放電試験を行った以外は、実施例1と同様に電池を作製し、充放電サイクル試験を行った。
と状態が不安定になり、自己放電が容易に発生して劣化が促進することが考えられる。
Claims (2)
- 正極板と負極板とがセパレータを介して積層された電極体と、非水電解質とを有する二次電池と、
前記二次電池に接続される電気負荷と、
前記二次電池の容量Qの変化量dQに対する前記二次電池の電圧Vの変化量dVの微分値であるdV/dQが、前記二次電池の満充電状態の容量に対する前記容量Qの百分率で表される充電状態(SOC)に対してプロットされたSOC-dV/dQ曲線において、ピークトップとなるSOCを含むピークトップSOC範囲が少なくとも一つ設定され、前記ピークトップSOC範囲にて充電又は放電が停止する場合には、前記電気負荷によって前記二次電池を放電することによって前記ピークトップSOC範囲を避けて前記二次電池の充電又は放電を終了する制御装置と、
を備える、
二次電池システム。 - 正極板と負極板とがセパレータを介して積層された電極体と、非水電解質とを有する二次電池と、
前記二次電池に接続される補助電池と、
前記二次電池の容量Qの変化量dQに対する前記二次電池の電圧Vの変化量dVの微分値であるdV/dQが、前記二次電池の満充電状態の容量に対する前記容量Qの百分率で表される充電状態(SOC)に対してプロットされたSOC-dV/dQ曲線において、ピークトップとなるSOCを含むピークトップSOC範囲が少なくとも一つ設定され、前記ピークトップSOC範囲にて充電又は放電が停止する場合には、前記補助電池によって前記二次電池を充電することによって前記ピークトップSOC範囲を避けて前記二次電池の充電又は放電を終了する制御装置と、
を備える、
二次電池システム。
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WO2013157132A1 (ja) * | 2012-04-20 | 2013-10-24 | 日立ビークルエナジー株式会社 | 二次電池システム、二次電池の劣化状態判断方法 |
WO2015080285A1 (ja) * | 2013-11-29 | 2015-06-04 | 日立オートモティブシステムズ株式会社 | 電池モジュールおよび組電池 |
JP2018041529A (ja) * | 2015-01-29 | 2018-03-15 | 三洋電機株式会社 | 非水電解質二次電池の放電制御装置及び方法 |
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WO2013157132A1 (ja) * | 2012-04-20 | 2013-10-24 | 日立ビークルエナジー株式会社 | 二次電池システム、二次電池の劣化状態判断方法 |
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JP2018041529A (ja) * | 2015-01-29 | 2018-03-15 | 三洋電機株式会社 | 非水電解質二次電池の放電制御装置及び方法 |
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