WO2021100272A1 - Batterie secondaire et son procédé de production - Google Patents

Batterie secondaire et son procédé de production Download PDF

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Publication number
WO2021100272A1
WO2021100272A1 PCT/JP2020/031525 JP2020031525W WO2021100272A1 WO 2021100272 A1 WO2021100272 A1 WO 2021100272A1 JP 2020031525 W JP2020031525 W JP 2020031525W WO 2021100272 A1 WO2021100272 A1 WO 2021100272A1
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WIPO (PCT)
Prior art keywords
electrode
positive electrode
negative electrode
secondary battery
pole
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PCT/JP2020/031525
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English (en)
Japanese (ja)
Inventor
栄二 關
耕平 本蔵
杉政　昌俊
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株式会社日立製作所
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Publication of WO2021100272A1 publication Critical patent/WO2021100272A1/fr

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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
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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 a secondary battery and a method for manufacturing the secondary battery.
  • Lithium-ion batteries are one of the non-aqueous electrolyte secondary batteries, and because of their high energy density, they are also used as batteries for portable devices and, in recent years, as batteries for electric vehicles. However, it is known that a lithium ion battery deteriorates with use and the battery capacity decreases.
  • a carbon material such as lithium metal oxide is generally used as the active material for the positive electrode, and graphite is used as the active material for the negative electrode.
  • the positive electrode and the negative electrode of a lithium ion battery are produced by adding a binder, a conductive agent, or the like to a group of minute active material particles to form a slurry, and then applying the mixture to a metal foil.
  • the lithium ions released from the active material of the positive electrode are occluded in the active material of the negative electrode, and at the time of discharging, the lithium ions stored in the active material of the negative electrode are occluded and stored in the active material of the positive electrode. As the lithium ions move between the electrodes in this way, a current flows between the electrodes.
  • the capacity is reduced due to the electrical isolation of the positive electrode active material, the electrical isolation of the negative electrode active material, the immobilization of lithium ions, and the like.
  • lithium ion immobilization includes immobilization in the initial charge / discharge and immobilization by repeating the charge / discharge cycle.
  • a third electrode containing a lithium metal or a lithium metal is arranged inside the exterior body for the purpose of compensating for the decrease in battery capacity caused by the irreversible capacity of the negative electrode generated in a normal lithium secondary battery.
  • the positive electrode is charged to the negative electrode with a lithium amount or more corresponding to the irreversible capacity of the negative electrode, and then a discharge is performed between the third electrode and the positive electrode to make the positive electrode.
  • a method for manufacturing a lithium secondary battery, which carries lithium ions and then removes a third electrode, is disclosed.
  • Patent Document 1 In the lithium ion secondary battery described in Patent Document 1, the irreversible capacity (about 7%) of the negative electrode generated by the initial charging is replenished. However, Patent Document 1 does not describe the immobilization of lithium ions by repeating the charge / discharge cycle.
  • An object of the present invention is to suppress the immobilization of lithium ions and the excessive replenishment of lithium ions due to repeated charge / discharge cycles.
  • the method for manufacturing a secondary battery of the present invention includes a step of providing a third pole on an electrode body including a positive electrode and a negative electrode constituting the secondary battery, and a step of changing the potential difference between the negative electrode and the positive electrode using the third pole.
  • the potential difference is changed by charging only the negative electrode using the third electrode or by discharging the positive electrode using the third electrode after charging the positive electrode and the negative electrode.
  • the amount of change in the potential difference is 25% to 100% based on the difference between the capacity of the negative electrode and the capacity of the positive electrode.
  • FIG. 1 is a schematic cross-sectional view showing a state in which a third pole is provided in the manufacturing process of a lithium ion battery.
  • the electrode portion 1 is installed in the container 10, and the periphery of the electrode portion 1 is filled with the electrolytic solution 3.
  • the upper part of the container 10 is opened, and a metal positive electrode tab 5, a negative electrode tab 7, and a third electrode tab 6 project.
  • a positive electrode, a negative electrode, and a separator 2 are laminated on the electrode portion 1, and a third electrode is provided.
  • the discharge capacity of the negative electrode is larger than the discharge capacity of the positive electrode.
  • FIG. 2 is a schematic cross-sectional view showing the electrode portion of FIG. 1, and is shown so that the laminated state can be understood.
  • the electrode portion has a configuration in which the positive electrode 21 and the negative electrode 22 are alternately arranged via the separator 25.
  • the third pole 23 is arranged on the left side in the figure. The left and right ends in the drawing are covered with a separator 25.
  • the electrode portion is formed by winding or laminating.
  • the third pole 23 is installed near the winding shaft of the wound body, the outermost peripheral portion thereof, or as a part of the laminated body.
  • the positive electrode 21, the negative electrode 22, and the third pole 23 are each manufactured by applying a mixture of a predetermined electrode active material, a conductive agent, a binder, and the like to a predetermined metal current collecting foil.
  • the active material of the third pole 23 is preferably a material containing a reactive species inside.
  • LiCoO 2, LiNi x Mn y Co z O 2 positive active material, such as, a Li metal as the active material of the third pole 23.
  • the arrangement of the third pole 23 is not limited to this figure, and may be charged or discharged from the positive electrode 21 or the negative electrode 22.
  • the potential difference between the negative electrode and the positive electrode is changed using the third electrode.
  • the negative electrode is open-charged by a predetermined amount using the third electrode to add lithium ions to the negative electrode, or the positive electrode and the negative electrode are open-charged and then the third electrode is used.
  • FIG. 3 is a schematic cross-sectional view showing the completed lithium ion battery.
  • the lithium ion battery 300 shown in this figure is obtained by adjusting the potential difference between the negative electrode and the positive electrode by the above method, removing the third pole, and covering the electrode portion 31 and the separator 32 with a laminate film 39 (exterior body). is there.
  • the positive electrode tab 35 and the negative electrode tab 37 project to the outside of the laminated film 39.
  • the present invention is not limited to this, and the present invention can be applied to an all-solid-state battery, a semi-solid-state battery, etc. without a separator. Is.
  • FIG. 4 is a flow chart showing an example of the method for manufacturing the secondary battery of the present invention.
  • a third pole is provided on the electrode body including the positive electrode and the negative electrode so that charging and discharging are possible (S110). Then, the potential difference between the negative electrode and the positive electrode is changed by using the third electrode (S120). Then, the electrode body is sealed with the outer body (S130).
  • the third pole may be removed before the step S130.
  • the positive electrode mixture layer LiNi 0.5 Mn 0.2 Co 0.3 was used as the positive electrode active material, a carbon material was used as the positive electrode conductive agent, and polyvinylidene fluoride (PVDF) was used as the positive electrode binder.
  • the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is 93: 4: 3, and the positive electrode mixture layer slurry in which these are mixed is adjusted in viscosity with N-methyl-2-pyrrolidone as a dispersion solvent.
  • a 15 ⁇ m aluminum foil (positive electrode current collector) was coated to prepare a positive electrode mixture layer.
  • the coating amount of the positive electrode mixture layer was set to 300 g / m 2 .
  • the density was adjusted by a roll press to adjust the density of the positive electrode mixture layer to 3.0 g / cm 3 .
  • the negative electrode mixture layer graphite was used as the negative electrode active material, a carbon material was used as the negative electrode conductive agent, and styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) were used as the negative electrode binder.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • the mass ratio of the negative electrode active material, SBR, and CMC is 98: 1: 1, and the negative electrode mixture layer slurry in which these are mixed is applied to a 10 ⁇ m copper foil (negative electrode current collector) while adjusting the viscosity with water.
  • the work was carried out to prepare a negative electrode mixture layer.
  • the coating amount of the negative electrode mixture layer was 190 g / m 2 .
  • the density was adjusted by a roll press to adjust the density of the negative electrode mixture layer to 1.5 g / cm 3 .
  • the positive electrode, negative electrode and third electrode were cut to the specified size. At the time of cutting, the electrode tab portion where the electrode mixture layer was not applied to a part of the electrode current collector was left on the positive electrode, the negative electrode and the third electrode.
  • the cut positive electrode and the negative electrode were alternately laminated with a separator sandwiched between them, the third pole was attached to the outermost side, and the separator was further placed on the outer side to form an electrode body.
  • the plurality of positive electrode tabs, the plurality of negative electrode tabs, and the plurality of third electrode tabs of the electrode body are bundled, and the positive electrode terminal, the negative electrode terminal, and the third electrode terminal that electrically connect the inside and outside of the secondary battery are connected to each other.
  • the bundled electrode tabs were ultrasonically welded.
  • the capacity of the produced positive electrode is 300 mAh, and the capacity of the negative electrode opposite the positive electrode is 460 mAh.
  • the prepared electrode body was immersed in an electrolytic solution, the positive electrode and the negative electrode were connected to a charging / discharging device, and charged with a constant current of 4.2 V and a current of 0.05 CA. Then, constant voltage charging was carried out for 20 hours. Then, the battery was discharged at a constant current of 2.7 V and a current of 0.05 CA. Then, it was charged again with a constant current of 4.2 V and a current of 0.05 CA. Further, after that, constant voltage charging was performed for 20 hours.
  • the positive electrode and the third electrode were connected to a charging / discharging device (positive electrode is +, third electrode is-), and 40 mAh constant current discharge was performed with a current value of 1/100 CA. Then, a constant current of 2.7 V and a current of 0.05 CA was discharged between the positive and negative electrodes.
  • the constant current discharge of 40 mAh performed between the positive electrode and the third pole corresponds to the discharge capacity between the positive electrode and the third pole, and is the amount of change in the potential difference in the present invention.
  • the third electrode is removed from the electrode body, placed inside the exterior body, the edge of the exterior body is heat-welded and sealed at 175 ° C. for 10 seconds, and the positive electrode terminal and the negative electrode terminal are electrically insulated from the secondary battery. I made it protrude to the outside.
  • sealing is performed by heat welding except for one side of the edge of the exterior body, injecting the electrolytic solution into the voids of the electrode group, and vacuum pressurizing the remaining side. It was. As a result, the lithium-ion battery was completed.
  • the lithium ion secondary battery was continuously charged and discharged at 4.2-3.0 V and 1 C in an environment of 50 ° C. for 200 cycles, and the capacity retention rate was evaluated.
  • the ratio is 25% based on the difference between the capacity of the negative electrode of 460 mAh and the capacity of the positive electrode of 300 mAh (denominator). In the following examples, the same ratio is also described.
  • the positive electrode and the third electrode were connected to a charging / discharging device (positive electrode is +, third electrode is-), and 80 mAh (50%) constant current discharge was performed with a current value of 1/100 CA. Other than this, the same as in Example 1.
  • the positive electrode and the third electrode were connected to a charging / discharging device (positive electrode is +, third electrode is-), and 120 mAh (75%) constant current discharge was performed with a current value of 1/100 CA. Other than this, the same as in Example 1.
  • the positive electrode and the third electrode were connected to a charging / discharging device (positive electrode is +, third electrode is-), and 160 mAh (100%) constant current discharge was performed with a current value of 1/100 CA. Other than this, the same as in Example 1.
  • Example 1 The same procedure as in Example 1 was carried out except that the third pole was not used (the discharge capacity between the positive electrode and the third pole was 0 mAh) and the cell was prepared.
  • Examples 1 to 4 have improved cycle characteristics (capacity retention rate) as compared with Comparative Example 1.
  • Examples 1 to 4 since a large amount of lithium ions are supplied in advance using the third pole, it is considered that the capacity retention rate is high even if the lithium ions are immobilized in the continuous charge / discharge cycle.
  • the reversible capacity of the negative electrode when the reversible capacity of the negative electrode is smaller than the reversible capacity of the positive electrode, the amount of lithium ions replenished becomes excessive, and lithium ions that cannot be stored in the negative electrode active material during charging are precipitated as lithium metal. It is possible to avoid the problem that the concentration of lithium ions in the positive electrode active material becomes excessive at the time of discharge and promote the deterioration of the characteristics of the battery, and it is possible to suppress the immobilization of lithium ions due to the repetition of the charge / discharge cycle.
  • Electrode part 2 25, 32: Separator 3: Electrolyte solution 5, 35: Positive electrode tab, 6: Third electrode tab, 7, 37: Negative electrode tab, 10: Container, 21: Positive electrode, 22 : Negative electrode, 23: Third electrode, 39: Laminated film, 100: Cell, 300: Lithium ion battery.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

Procédé de production d'une batterie secondaire, ledit procédé comprenant : une étape consistant à fournir une troisième électrode sur un corps d'électrode contenant une électrode positive et une électrode négative d'une batterie secondaire ; une étape consistant à modifier la différence de potentiel entre l'électrode négative et l'électrode positive à l'aide de la troisième électrode ; et une étape consistant à sceller le corps d'électrode au moyen d'un boîtier externe. Par rapport à ce procédé de fabrication d'une batterie secondaire, la différence de potentiel est modifiée en chargeant uniquement l'électrode négative avec l'utilisation de la troisième électrode ou en déchargeant l'électrode positive avec l'utilisation de la troisième électrode après chargement de l'électrode positive et de l'électrode négative ; et la quantité de changement de la différence de potentiel est de 25 % à 100 % sur la base de la différence entre la capacité de l'électrode négative et la capacité de l'électrode positive. Par conséquent, la présente invention est capable de supprimer un remplissage excessif d'ions lithium et d'immobiliser des ions lithium en raison de la répétition du cycle de charge et de décharge.
PCT/JP2020/031525 2019-11-21 2020-08-20 Batterie secondaire et son procédé de production WO2021100272A1 (fr)

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Application Number Priority Date Filing Date Title
JP2019210292A JP2021082519A (ja) 2019-11-21 2019-11-21 二次電池及びその製造方法
JP2019-210292 2019-11-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583179A (zh) * 2022-03-04 2022-06-03 远景动力技术(江苏)有限公司 一种柔性锂离子电池及其制作方法

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CN107979402A (zh) * 2016-10-25 2018-05-01 华为技术有限公司 一种信道状态信息测量方法及装置
WO2018128580A1 (fr) * 2017-01-09 2018-07-12 Telefonaktiebolaget Lm Ericsson (Publ) Systèmes et procédés d'indication dynamique fiable pour csi-rs semi-persistants
WO2019130556A1 (fr) * 2017-12-28 2019-07-04 株式会社Ｎｔｔドコモ Dispositif utilisateur et procédé de sélection de ressource

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CN107979402A (zh) * 2016-10-25 2018-05-01 华为技术有限公司 一种信道状态信息测量方法及装置
WO2018128580A1 (fr) * 2017-01-09 2018-07-12 Telefonaktiebolaget Lm Ericsson (Publ) Systèmes et procédés d'indication dynamique fiable pour csi-rs semi-persistants
WO2019130556A1 (fr) * 2017-12-28 2019-07-04 株式会社Ｎｔｔドコモ Dispositif utilisateur et procédé de sélection de ressource

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583179A (zh) * 2022-03-04 2022-06-03 远景动力技术(江苏)有限公司 一种柔性锂离子电池及其制作方法
CN114583179B (zh) * 2022-03-04 2024-04-26 远景动力技术(江苏)有限公司 一种柔性锂离子电池及其制作方法

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