WO2017179541A1 - Dispositif de stockage d'électricité, et procédé de charge et son procédé de fabrication - Google Patents

Dispositif de stockage d'électricité, et procédé de charge et son procédé de fabrication Download PDF

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WO2017179541A1
WO2017179541A1 PCT/JP2017/014689 JP2017014689W WO2017179541A1 WO 2017179541 A1 WO2017179541 A1 WO 2017179541A1 JP 2017014689 W JP2017014689 W JP 2017014689W WO 2017179541 A1 WO2017179541 A1 WO 2017179541A1
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storage device
change point
electricity storage
small
voltage
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PCT/JP2017/014689
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English (en)
Japanese (ja)
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要 武谷
昌弘 外園
城戸　政美
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株式会社パワージャパンプリュス
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/42—Powders or particles, e.g. composition thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an electricity storage device. Specifically, the present invention relates to an electricity storage device that can improve cycle life.
  • a positive electrode containing a complex oxide of a metal such as cobalt, nickel, manganese and lithium, a negative electrode containing a carbonaceous material, a separator, and a lithium salt are included.
  • Many lithium ion secondary batteries equipped with a water electrolyte are used.
  • lithium ions are desorbed from the crystal structure of the positive electrode during charging and inserted between the carbonaceous material layers of the negative electrode and discharged from the carbonaceous material layer of the negative electrode during discharge. Is desorbed into the electrolyte and inserted into the crystal structure of the positive electrode.
  • an electricity storage device containing a carbonaceous material as an active material for both the positive electrode and the negative electrode is known.
  • Patent Document 1 discloses a power storage device including a positive electrode containing a graphite material and a negative electrode containing a carbonaceous material capable of occluding and releasing lithium ions.
  • a lithium salt-derived anion (PF 6 ⁇ etc.) such as LiPF 6 is inserted from a non-aqueous electrolyte into a carbonaceous material as a positive electrode active material during charging, and non-aqueous electrolysis Lithium ions are inserted from the liquid into the negative electrode active material.
  • anions such as PF 6- and the like from the positive electrode active material and lithium ions from the negative electrode active material are desorbed into the non-aqueous electrolyte.
  • This charge / discharge reaction is shown in the following reaction formulas 1 and 2 (the left side to the right side is a charge reaction, and the right side to the left side is a discharge reaction).
  • Patent Document 1 shows "a charging process at the positive electrode is a two-step sequential charging process of an anion adsorption process in the low voltage side region and an anion intercalation process in the high voltage side region", Furthermore, there is disclosed an electricity storage device that is characterized in that only a voltage region in which anions are intercalated is used as a charge / discharge region during use.
  • Patent Document 1 The contents of Patent Document 1 are summarized as follows.
  • the interlayer distance of the positive electrode material changes due to anion intercalation.
  • the fourth stage in which one layer of anion intercalates every four layers of graphite is the upper limit at which the cycle characteristics can be kept good. 3. Therefore, a device having good cycle characteristics can be designed by optimizing the charging voltage and adjusting the capacity balance between the positive electrode active material and the negative electrode active material.
  • Patent 5445556 Patent 554917 JP 2014-112524 A
  • Patent Document 1 states that “when the battery is charged until the positive electrode capacity is in the range of 47 mAh / g or less and 31 mAh / g or more, the voltage between the positive and negative terminals is 3.2 V. Although there is a description of “selecting the capacity of the active material”, this selection (determination of the capacity of the negative electrode active material) is not easy.
  • the present invention is more convenient in an electricity storage device containing a carbonaceous active material in both the positive electrode and the negative electrode (that is, “charging voltage optimization” and “capacity balance adjustment of positive electrode active material and negative electrode active material” as in the past).
  • Charging voltage optimization” and “capacity balance adjustment of positive electrode active material and negative electrode active material” as in the past Providing an electricity storage device that determines the use conditions with good cycle characteristics by a method that is not affected by selection of the positive electrode active material or positive electrode preparation conditions, etc. With the goal.
  • a positive electrode containing a carbonaceous positive electrode active material, a negative electrode containing a carbonaceous negative electrode active material, a nonaqueous electrolyte solution containing an electrolyte and a nonaqueous solvent, and a voltage profile during constant current charging is Five or more change points (change point A, change point B, change point C, change point D, change from small to large, large to small, small to large,... And the maximum voltage in the use of the storage device is in the vicinity of the voltage indicated by the point at which the slope on the highest potential side changes from small to large among the change points.
  • the present invention also includes a positive electrode containing a carbonaceous positive electrode active material, a negative electrode containing a carbonaceous negative electrode active material, a nonaqueous electrolyte solution containing an electrolyte and a nonaqueous solvent, and a voltage profile during constant current charging.
  • 5 or more change points (change point A, change point B, change point C, change point D) in which the slope changes from small to large, large to small, small to large,.
  • the maximum voltage at the time of charging the power storage device is the voltage indicated by the point at which the slope at the highest potential side changes from small to large among the change points.
  • the maximum voltage in the latter charging method is “the voltage indicated by the point at which the slope on the highest potential side changes from small to large”, and the maximum voltage in the use of the former storage device is set to “highest potential side”.
  • the reason for ⁇ near the voltage indicated by the point where the slope changes from small to large '' is that the maximum voltage when using the storage device is slightly higher than the maximum voltage when charging the storage device due to the presence of the internal resistance of the storage device. (See FIG. 6. Point X in FIG. 6 represents the maximum voltage during charging, and point Y represents the maximum voltage in use).
  • a voltage profile having a relatively flat region (a plateau-like region) sandwiched between a change point where the slope changes from small to large and a change point where the slope changes from large to small can be obtained.
  • the electricity storage device by using the voltage at the end position of the plateau-like region as the charging voltage, it is possible to provide an electricity storage device that has determined use conditions with good cycle characteristics, and a charging method and manufacturing method thereof.
  • FIG. 3 is a diagram showing cycle characteristics of a test cell 2 in Example 1.
  • 6 is a diagram showing cycle characteristics of a test cell 3 in Comparative Example 1.
  • FIG. 6 is a diagram showing cycle characteristics of a test cell 4 in Example 2.
  • FIG. It is a figure which shows the cycle characteristic of the test cell 5 in the comparative example 2.
  • FIG. 6 is a diagram showing cycle characteristics of a test cell 6 in Example 3.
  • 6 is a diagram showing cycle characteristics of a test cell 7 in Comparative Example 3.
  • FIG. 2 is a diagram illustrating a charge / discharge profile of a test cell 1 in Example 1.
  • FIG. It is a figure which shows the charging / discharging profile of the half cell in Example 1.
  • FIG. 6 is a table showing the oxidation resistance of a non-aqueous electrolyte described in Non-Patent Document 1.
  • the charging profile in FIG. 8 shows that the voltage rises almost linearly after showing one change point where the slope changes from large to small at about 1.9V.
  • the charging profile indicated by the dotted line as “Example 3” shows one change point where the slope changes from large to small at about 1.6V, and then slopes at about 3.2 to 3.3V. Indicates two change points from small to large and from large to small.
  • This flat region is generally called a plateau.
  • intercalation The insertion of another substance into a substance having a layer structure such as graphite is called intercalation, and the substance generated by the insertion is called an intercalation compound.
  • an intercalation compound generally, a substance inserted between layers has a regular laminated structure with several layers separated. This is called a stage (or the presence of a stage or a stage structure). 3.
  • nth stage or stage n when there is another substance for every n layers, it is called the nth stage or stage n.
  • the charging profile shows a flat region where the voltage is almost constant, and this is called a plateau.
  • the present inventors confirmed that the plateau-like region in the charge profile of the electricity storage device containing the carbonaceous active material for both the positive electrode and the negative electrode (which is considered to be a plateau on the charge profile, but in the present invention, the correlation with the above stage structure was confirmed. (It is described as a plateau-like region).
  • Patent Document 2 The reason why the plateau is confirmed (Patent Document 2) or not confirmed (Patent Document 1) is that the content of the layered material (graphite and / or graphite-like particles) contained in the carbonaceous positive electrode active material It seems to be due to the homogeneity and / or the charge profile of the negative electrode (for example, if the negative electrode charge profile has a steep slope, the plateau is difficult to see in the charge profile of the entire storage device), but it is not clear at this time .
  • the positive electrode active material in the present invention is a carbonaceous material capable of inserting and removing anions in the non-aqueous electrolyte (carbon positive electrode active material), for example, artificial graphite KS-6L, KS- 44, artificial graphite MCMB6-26 manufactured by Osaka Gas Co., Ltd.
  • a conductive agent composed of other carbonaceous material powders, or a binder for increasing the bonding property between the powders and / or increasing the adhesion to the positive electrode current collector is added as necessary.
  • a positive electrode slurry is prepared by mixing with an aqueous or organic solvent, and this positive electrode slurry is applied to a positive electrode current collector and dried to form a positive electrode active material layer, thereby producing a positive electrode.
  • a metal foil, mesh, or the like made of a metal such as stainless steel, aluminum, or titanium and having a thickness of about 10 to 100 microns is used.
  • the negative electrode active material in the present invention is a carbonaceous material capable of inserting and removing lithium ions in a non-aqueous electrolyte (carbonaceous negative electrode active material), and a carbonaceous material that can be used for a negative electrode of a lithium ion secondary battery.
  • Materials for example, hard carbon manufactured by Kureha Co., Ltd., MAG manufactured by Hitachi Chemical Co., Ltd.
  • a conductive agent made of another carbonaceous material powder or a binder for increasing the adhesion between the powders and / or increasing the adhesion to the negative electrode current collector is used for such a carbonaceous material.
  • a negative electrode slurry is prepared by mixing with an aqueous or organic solvent, and this negative electrode slurry is applied to a negative electrode current collector and dried to form a negative electrode active material layer, thereby producing a negative electrode.
  • a metal foil, mesh or the like made of a metal such as copper, stainless steel, titanium or nickel and having a thickness of about 10 to 100 microns is used.
  • the separator in the present invention is a porous film or thin plate having electronic insulation and ion permeability.
  • porous films that can be used for lithium ion secondary batteries such as polyolefin porous films manufactured by Asahi Kasei Chemicals Corporation and glass fiber filter paper, can be used as they are.
  • the non-aqueous electrolyte in the present invention includes an electrolyte (in this case, a lithium salt) such as LiBF 4 and LiPF 6 in a non-aqueous solvent such as diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (EMC). It is a solution containing anions such as PB 4 ⁇ and PF 6 ⁇ dissolved in about 1.0 mol / L to 4.0 mol / L.
  • a lithium salt such as LiBF 4 and LiPF 6
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC methyl ethyl carbonate
  • Example 1 Carbonaceous positive electrode active material (artificial graphite), conductive agent (acetylene black), and two kinds of binders (carboxymethylcellulose and acrylonitrile rubber) are mixed at a weight ratio of 90: 5: 3: 2, respectively, and kneaded with water to form a positive electrode A slurry was made.
  • artificial graphite artificial graphite
  • conductive agent acetylene black
  • binders carboxymethylcellulose and acrylonitrile rubber
  • This positive electrode slurry was applied to one surface of a 20 ⁇ m thick aluminum foil as a positive electrode current collector, dried at room temperature, and further dried at 120 ° C. for 5 minutes or more to form a positive electrode active material layer, thereby producing a positive electrode.
  • the carbonaceous negative electrode active material is Hitachi Chemical MAG-D, and conductive agent (acetylene black) and two kinds of binders (carboxymethylcellulose and acrylonitrile rubber) are mixed at a weight ratio of 90: 5: 3: 2, respectively, and kneaded with water. Thus, a negative electrode slurry was prepared.
  • This negative electrode slurry was applied to one side of a 15 ⁇ m-thick copper foil as a negative electrode current collector, dried at room temperature, and further dried at 120 ° C. for 5 minutes or more to form a positive electrode active material layer, thereby preparing a negative electrode.
  • test cell 1 An electricity storage device (test cell 1) was prepared using the positive electrode and the negative electrode.
  • a glass fiber filter paper was used for the separator, a 1.5 mol / L solution of LiPF 6 in dimethyl carbonate (DMC) was used as the non-aqueous electrolyte, and a CR2032 type stainless steel coin-type container was used as the container.
  • DMC dimethyl carbonate
  • FIG. 4 shows a charge / discharge profile (as an example, a profile with a repetition count of 5).
  • the reason why the maximum voltage during charging is set to 5.2 V is that, based on FIG. 10 (extracted from Non-Patent Document 1), the oxidation resistance (that is, oxidation potential) of the used non-aqueous solvent DMC is 5.3 V ( Li / Li + standard) and the potential of the carbonaceous negative electrode active material used in the following test cell 1 or the like is about 0.1 V (Li / Li + standard) (however, in the carbonaceous negative electrode active material) This is because, as Li + is intercalated, the potential approaches 0 V (Li / Li + reference)), so that the oxidation potential of DMC is considered to be 5.2 V at the minimum between the positive electrode and the negative electrode. .
  • the present inventors set the voltage at the change point E (the change point where the slope on the highest potential side of the change points changes from small to large and the end point of the plateau-like region on the highest potential side).
  • the deterioration state in the charge / discharge cycle was confirmed with 5.0V as the maximum charge value during constant current charging.
  • irreversible intercalation may occur each time the stage structure progresses, whereas first the plateau-like region end point on the high potential side (whether all the anions that can be inserted into a stage have entered, or another If charging / discharging is performed at the voltage of the point that the anion is no longer inserted into the stage for the reason, charging / discharging to the stage where irreversible intercalation occurs does not occur, and cycle characteristics may be improved.
  • iteratively reversible stages can be found by repeating the plateau-like region end point on the low voltage side.
  • substantially means that lowering the charging voltage also lowers the capacity of the electricity storage device, so the capacity of the electricity storage device is reduced even when the charge / discharge voltage has a certain degree of decrease in cycle characteristics. This means that it may be given priority.
  • test cell 2 an electricity storage device (test cell 2) similar to test cell 1 was produced, and charging / discharging was repeatedly performed in a voltage range of 3.0 V to 5.0 V at a charging / discharging current density of 0.5 mA / cm 2 . .
  • the capacity decrease is observed about 10 cycles after the start of charging / discharging, but the subsequent capacity decrease is gradual (compared to Comparative Example 1 described later), and the capacity is 50% or more of the initial capacity even after 300 cycles. Is maintained.
  • FIG. 6 shows a charge / discharge profile in the test cell 2 (as an example, a profile with the fifth repetition count).
  • Test cell 3 An electricity storage device (test cell 3) similar to test cell 1 was produced, and charged and discharged repeatedly at a charge / discharge current density of 0.5 mA / cm 2 in a voltage range of 3.0 V to 5.2 V.
  • the capacity drop increases after about 100 cycles, and after 300 cycles the result is lower than 50% of the initial capacity.
  • test cell 4 An electricity storage device (test cell 4) similar to test cell 1 was prepared, and charged and discharged repeatedly at a charge / discharge current density of 5.0 mA / cm 2 in a voltage range of 3.0 V to 5.0 V.
  • Test cell 5 An electricity storage device (test cell 5) similar to test cell 1 was produced, and charged and discharged repeatedly at a charge / discharge current density of 5.0 mA / cm 2 in a voltage range of 3.0 V to 5.2 V.
  • Example 3 An electricity storage device (test cell 6) similar to test cell 1 was prepared except that 1 wt% of tris (pentafluorophenyl) borane (hereinafter referred to as TPFPB) was added as an additive to the nonaqueous electrolytic solution.
  • TPFPB tris (pentafluorophenyl) borane
  • This additive TPFPB is a material described in, for example, Patent Document 3 as “it is repeatedly improved in durability (in an electricity storage device containing a carbonaceous material as an active material for both positive and negative electrodes)”. In addition to the result of Example 2, it was added with the aim of further improving the cycle performance.
  • test cell 6 was repeatedly charged / discharged at a charge / discharge current density of 5.0 mA / cm 2 in a voltage range of 3.0 V to 5.0 V.
  • Test cell 7 An electricity storage device (test cell 7) similar to the test cell 6 was produced, and charged and discharged repeatedly at a charge / discharge current density of 5.0 mA / cm 2 in a voltage range of 3.0 V to 5.2 V.

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  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

[Problème] Des dispositifs de stockage d'électricité dans lesquels un matériau actif carboné est utilisé dans les électrodes positive et négative sont connus pour présenter un problème en ce que la capacité de décharge diminue au fur et à mesure que le cycle de charge et de décharge est répété, c'est-à-dire, le problème de mauvaises caractéristiques de cycle. Une cause du problème est qu'une progression d'intercalation excessive dans le processus d'intercalation d'anions dans le matériau actif d'électrode positive (progression excessive de la structure d'étage) peut conduire à l'incapacité à effectuer une intercalation réversible, ou à la décomposition de l'électrolyte, par exemple. [Solution] La présente invention concerne un dispositif de stockage d'électricité dans lequel le profil de tension pendant une charge à courant constant comporte cinq points de changement ou plus au niveau desquels la pente change de faible à élevée, élevée à faible, faible à élevée, et ainsi de suite par rapport à une augmentation de capacité de charge, et dans lequel la tension maximale pendant l'utilisation du dispositif de stockage d'électricité est proche d'une tension indiquée par le point de changement le plus éloigné vers le côté de potentiel élevé, parmi les points de changement auxquels la pente change de faible à élevée. Le dispositif de stockage d'électricité empêche la charge ou la décharge dans un étage dans lequel une intercalation irréversible se produit et, par conséquent, améliore les caractéristiques de cycle.
PCT/JP2017/014689 2016-04-11 2017-04-10 Dispositif de stockage d'électricité, et procédé de charge et son procédé de fabrication WO2017179541A1 (fr)

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JP2016-089857 2016-04-11
JP2016089857A JP6832607B2 (ja) 2016-04-11 2016-04-11 蓄電デバイスと、その充電方法および製造方法

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Cited By (2)

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CN113097557A (zh) * 2021-03-05 2021-07-09 山东玉皇新能源科技有限公司 一种钠离子电池及其制备方法
CN117559017A (zh) * 2023-11-30 2024-02-13 江苏众钠能源科技有限公司 一种钠离子电池的化成方法、钠离子电池及电池模块

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CN112956053B (zh) * 2018-11-30 2024-04-16 株式会社村田制作所 二次电池

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CN113097557A (zh) * 2021-03-05 2021-07-09 山东玉皇新能源科技有限公司 一种钠离子电池及其制备方法
CN113097557B (zh) * 2021-03-05 2022-04-22 山东玉皇新能源科技有限公司 一种钠离子电池及其制备方法
CN117559017A (zh) * 2023-11-30 2024-02-13 江苏众钠能源科技有限公司 一种钠离子电池的化成方法、钠离子电池及电池模块

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