WO2023105573A1 - リチウム二次電池、及び、リチウム二次電池の製造方法 - Google Patents

リチウム二次電池、及び、リチウム二次電池の製造方法 Download PDF

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WO2023105573A1
WO2023105573A1 PCT/JP2021/044721 JP2021044721W WO2023105573A1 WO 2023105573 A1 WO2023105573 A1 WO 2023105573A1 JP 2021044721 W JP2021044721 W JP 2021044721W WO 2023105573 A1 WO2023105573 A1 WO 2023105573A1
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Prior art keywords
electrode film
negative electrode
film
lithium
secondary battery
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PCT/JP2021/044721
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English (en)
French (fr)
Japanese (ja)
Inventor
浩伸 蓑輪
晃洋 鴻野
武志 小松
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NTT Inc
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Nippon Telegraph and Telephone Corp
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Priority to PCT/JP2021/044721 priority Critical patent/WO2023105573A1/ja
Priority to JP2023565681A priority patent/JPWO2023105573A1/ja
Priority to US18/714,023 priority patent/US20250174774A1/en
Publication of WO2023105573A1 publication Critical patent/WO2023105573A1/ja
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid 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
    • H01M10/056—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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 lithium secondary battery and a method for manufacturing a lithium secondary battery.
  • a lithium secondary battery is a battery that utilizes the intercalation and deintercalation reactions of lithium ions, and has a high energy density. Such lithium secondary batteries are used in various applications such as power sources for electronic devices, power sources for automobiles, and power storage sources. Even now, research and development of electrode materials and electrolyte materials are being advanced in order to improve the performance and reduce the cost of lithium secondary batteries.
  • lithium secondary batteries have attracted more attention as mobile power sources.
  • lithium secondary batteries are required to have flexibility and good design as power sources for transparent displays, ultra-thin displays, and the like.
  • Non-Patent Document 1 Japanese Patent Document 1
  • lithium secondary batteries are thin and can only be bent.
  • a lithium secondary battery that uses a material that has both thinness and transparency and a high energy density, it will increase the possibility that it can be used in a variety of devices that suit the design of the device. is expected to widen significantly.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lithium secondary battery that transmits visible light and has excellent charge-discharge cycle characteristics and a high energy density, and a lithium secondary battery. It is to provide a manufacturing method.
  • a lithium secondary battery of one embodiment of the present invention includes a positive electrode film into which lithium ions can be intercalated and deintercalated, a lithium negative electrode film, a negative electrode film formed of a material capable of forming an alloy with lithium, and lithium ions intercalated. and a detachable negative electrode film, a transparent and solid electrolyte film positioned between the positive electrode film and the negative electrode film and having lithium ion conductivity, and the electrolyte film and two transparent substrates sandwiching the positive electrode film and the negative electrode film between them with transparent conductive films formed on respective surfaces thereof.
  • a method for manufacturing a lithium secondary battery includes the steps of forming a transparent conductive film on the surface of a first transparent substrate and forming a transparent conductive film on the surface of a second transparent substrate; forming a positive electrode film capable of intercalating and deintercalating lithium ions on one surface of the electrolyte membrane; forming a positive electrode film on the other surface of the electrolyte membrane; a negative electrode film of lithium, a negative electrode film made of a material capable of forming an alloy with lithium, and a negative electrode film capable of intercalating and deintercalating lithium ions; a step of overlapping a transparent conductive film of the first transparent substrate on the surface of and overlapping a transparent conductive film of the second transparent substrate on the surface of the negative electrode film.
  • the present invention it is possible to provide a lithium secondary battery that transmits visible light, has excellent charge-discharge cycle characteristics, and has a high energy density, and a method for manufacturing the lithium secondary battery.
  • FIG. 1 is a cross-sectional view of a lithium secondary battery.
  • FIG. 2 is a top view of a lithium secondary battery.
  • FIG. 3 is a flowchart showing a method for manufacturing a lithium secondary battery.
  • FIG. 4 is a diagram showing measurement results of transmittance of a lithium secondary battery.
  • FIG. 5 is a diagram showing initial charge/discharge curves of a lithium secondary battery.
  • FIG. 1 is a cross-sectional view of a lithium secondary battery 1 according to this embodiment.
  • the lithium secondary battery 1 includes a positive electrode film 11, a negative electrode film 12, an electrolyte film 13, a first transparent substrate 14, a first transparent conductive film 15, a second transparent substrate 16, a second A transparent conductive film 17 and a sealant 18 are provided.
  • the positive electrode film 11 is a positive electrode film containing a substance capable of intercalating and deintercalating lithium ions. Such a positive electrode film 11 can be constructed using an existing material.
  • the negative electrode film 12 is any one of a negative electrode film containing metallic lithium, a negative electrode film composed of a metallic material capable of forming an alloy with lithium, and a negative electrode film containing a substance capable of intercalating and deintercalating lithium ions. is the negative electrode film of Such a negative electrode film 12 can also be constructed using existing materials.
  • the electrolyte membrane 13 is positioned between the positive electrode film 11 and the negative electrode film 12. One surface of the upper and lower surfaces contacts the positive electrode film 11 and the other surface contacts the negative electrode film 12, thereby providing lithium ion conductivity. It is a transparent and solid electrolyte membrane with The electrolyte membrane 13 may be a solid electrolyte membrane that is made of a material that has lithium ion conductivity, does not have electronic conductivity, and is transparent to visible light.
  • Such an electrolyte membrane 13 can be constructed, for example, by impregnating a separator with a predetermined electrolyte.
  • the separator is impregnated with a polymer electrolyte to which a polymer is added.
  • the polymer electrolyte may be further impregnated with an organic electrolyte or aqueous electrolyte, or may be further added with aluminum oxide or the like.
  • the first transparent substrate 14 is a transparent substrate such as glass having visible light transmittance.
  • the first transparent conductive film 15 is made of a material that transmits visible light, such as ITO (Indium Tin Oxide), and is formed on one of the upper and lower surfaces of the first transparent substrate 14. It is a transparent conductive film.
  • ITO Indium Tin Oxide
  • the second transparent substrate 16 is a transparent substrate such as glass having visible light transmittance.
  • the second transparent conductive film 17 is a transparent conductive film formed on one of the upper and lower surfaces of the second transparent substrate 16, which is made of a substance such as ITO that transmits visible light.
  • the first transparent substrate 14 and the second transparent substrate 16 are provided with a positive electrode film 11 and a negative electrode film 12 having an electrolyte film 13 therebetween, respectively. It is arranged so as to be sandwiched between the first transparent conductive film 15 and the second transparent conductive film 17 .
  • the sealant 18 covers the positive electrode film 11, the negative electrode film 12, the electrolyte film 13, the first transparent substrate 14, the first transparent conductive film 15, the second transparent substrate 16, and the second transparent conductive film 17. , and a sealing agent such as an adhesive or a sealing material that fixes the electrolyte membrane 13 and the like so as not to be displaced from each other and seals the contents such as the electrolyte membrane 13 from leaking to the outside.
  • a sealing agent such as an adhesive or a sealing material that fixes the electrolyte membrane 13 and the like so as not to be displaced from each other and seals the contents such as the electrolyte membrane 13 from leaking to the outside.
  • FIG. 2 is a top view of the lithium secondary battery 1 shown in FIG.
  • the first transparent substrate 14 and the first transparent conductive film 15 have exposed portions exposed from the main part of the battery with the electrolyte film 13 at the center. The exposed portion becomes the electrode terminal 21 of the positive electrode in the lithium secondary battery 1 .
  • the second transparent substrate 16 and the second transparent conductive film 17 also have exposed portions. The exposed portion becomes the electrode terminal 22 of the negative electrode.
  • Each edge of the first transparent substrate 14, the second transparent substrate 16, etc. is sealed with a sealant 18 so that the positive electrode terminal 21 and the negative electrode terminal 22 are exposed from the main part of the battery. be.
  • the positive electrode film 11 inside the battery can sufficiently transmit external visible light.
  • the negative electrode film 12 positioned on the back side can also sufficiently transmit external visible light.
  • the transparent electrolyte membrane 13 is also sufficiently permeable to external visible light.
  • a transparent conductive film such as ITO is formed on the entire surface of a transparent substrate that transmits visible light, such as glass.
  • Film formation methods include, for example, RF (Radio Frequency) sputtering and vapor deposition.
  • a positive electrode film capable of intercalating and deintercalating lithium ions is formed with a predetermined thickness on one surface (front surface) of the transparent and solid electrolyte film. Further, a negative electrode film capable of intercalating and deintercalating lithium ions is formed with a predetermined thickness on the other surface (back surface) of the electrolyte film.
  • the positive electrode film and the negative electrode film having the electrolyte film therebetween are sandwiched between the transparent conductive films of the two transparent substrates. Finally, the edges of each substrate are sealed with an adhesive so that only the positive electrode terminal portion and the negative electrode terminal portion are exposed to the outside from the battery main portion.
  • FIG. 3 is a flowchart showing a method for manufacturing the lithium secondary battery 1 according to Example 1.
  • FIG. 3 is a flowchart showing a method for manufacturing the lithium secondary battery 1 according to Example 1.
  • Step S1 First, the first transparent conductive film 15 is formed on the surface of the first transparent substrate 14 and the second transparent conductive film 17 is formed on the surface of the second transparent substrate 16 .
  • two glass substrates having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm were coated with ITO to a thickness of 150 nm by RF sputtering. Sputtering was performed using an ITO (5 wt % SnO 2 ) target under 50 W RF output conditions while allowing 1.0 Pa of argon to flow.
  • PVdF polyvinylidene fluoride
  • LiTFSI lithium bistrifluoromethanesulfonylimide
  • PC propylene carbonate
  • dispersion A solution was prepared by mixing tetrahydrofuran (THF) as a medium at a weight ratio of 4:6:10.
  • the solution was stirred at 60°C for 1 hour in dry air with a dew point of -50°C or less, poured into 200 ⁇ petri dishes in 50 ml portions, and vacuum-dried at 50°C for 12 hours to obtain a transparent film with a thickness of 0.1 mm.
  • a membrane a transparent polymer electrolyte with added polymer
  • the transparent film was formed into a length of 90 mm and a width of 100 mm.
  • a film of lithium cobaltate phosphate (LiCoPO 4 ) was formed to a thickness of 100 nm on one side of the electrolyte film produced in step S2 by RF sputtering. Sputtering was performed using a LiCoPO 4 ceramic target, a flow partial pressure ratio of argon and oxygen of 3:1, a total gas pressure of 3.7 Pa, and an RF output of 100 W.
  • Step S4 the negative electrode film 12 capable of intercalating and deintercalating lithium ions is formed on the other surface (back surface) of the electrolyte film 13 produced in step S2.
  • a film of lithium titanate Li 4 Ti 5 O 12
  • Sputtering was carried out using a Li 4 Ti 5 O 12 ceramic target, a flow partial pressure ratio of 3:1 between argon and oxygen, a total gas pressure of 4.0 Pa, and an RF output of 100 W.
  • Step S5 Finally, the first transparent conductive film 15 of the first transparent substrate 14 produced in step S1 is overlaid on the surface of the positive electrode film 11 formed in step S3. Also, the second transparent conductive film 17 of the second transparent substrate 16 produced in step S1 was overlaid on the surface of the negative electrode film 12 formed in step S4.
  • the two ITO-attached glass substrates prepared in step S1 were placed face to face so as to overlap each other with a length of 90 mm and a width of 100 mm.
  • the electrolyte membrane formed on the surface was sandwiched, and each edge of the two ITO-attached glass substrates was sealed with an adhesive.
  • the adhesive was placed in a vacuum dryer, and the adhesive was hardened after vacuum drying.
  • the remaining 10 mm long ⁇ 100 mm wide portions of the two ITO-attached glass substrates are used as a positive electrode terminal and a negative electrode terminal.
  • a commercially available charge-discharge measurement system was used to conduct a charge-discharge test on the lithium secondary battery 1 of Example 1 with a current density of 1 ⁇ A/cm 2 per effective area of the positive and negative electrodes. carried out.
  • a charging/discharging test was performed in a voltage range of 3.4V for the final charge voltage and 2.0V for the final discharge voltage.
  • the charging/discharging test of the battery was measured in a constant temperature chamber at 25°C (atmosphere is normal atmospheric environment).
  • step S4 a negative electrode film capable of intercalating and deintercalating lithium ions was formed.
  • a negative electrode film made of a metallic material may be formed.
  • the positive electrode was formed by forming a film of lithium cobaltate phosphate (LiCoPO 4 ) to a thickness of 100 nm on a 90 mm long ⁇ 100 mm wide region of one glass substrate with ITO by RF sputtering. Sputtering was performed using a LiCoPO 4 ceramic target, a flow partial pressure ratio of argon and oxygen of 3:1, a total gas pressure of 3.7 Pa, and an RF output of 100 W.
  • LiCoPO 4 lithium cobaltate phosphate
  • the negative electrode was formed by forming a film of lithium titanate (Li 4 Ti 5 O 12 ) to a thickness of 150 nm on the other ITO-attached glass substrate in a region of 90 mm long ⁇ 100 mm wide by RF sputtering. Sputtering was carried out using a Li 4 Ti 5 O 12 ceramic target, a flow partial pressure ratio of 3:1 between argon and oxygen, a total gas pressure of 4.0 Pa, and an RF output of 100 W.
  • Li 4 Ti 5 O 12 ceramic target Li 4 Ti 5 O 12 ceramic target, a flow partial pressure ratio of 3:1 between argon and oxygen, a total gas pressure of 4.0 Pa, and an RF output of 100 W.
  • the electrolyte was formed by forming a film of lithium phosphate (Li 3 PO 4 ) to a thickness of 100 nm on the entire surface of the positive electrode film of LiCoPO 4 by RF sputtering. Sputtering was performed using a Li 3 PO 4 ceramic target, a flow partial pressure ratio of argon and oxygen of 3:1, a total gas pressure of 3.7 Pa, and an RF output of 100 W.
  • 30 ⁇ L of an organic electrolyte prepared by dissolving 1 mol/L of lithium bistrifluoromethanesulfonylimide (LiTFSI) as a lithium salt in propylene carbonate (PC) was applied to the center of the glass substrate with ITO. After the ITO-attached glass substrate was fixed on a turntable, it was rotated at 50 rpm to cast the electrolytic solution.
  • the negative electrode prepared above was placed on top of the electrolyte so that the ITO was exposed from the main part of the battery. Sealed. Then, before the adhesive hardened, it was placed in a vacuum dryer, and the adhesive was hardened after vacuum drying.
  • FIG. 4 shows the measurement results of the transmittance of the lithium secondary battery 1 of Example 1 in the visible light region. It shows a transmittance of 60% or more in the visible light region with a wavelength of 400 nm or more, indicating that the lithium secondary battery 1 of Example 1 transmits visible light.
  • the initial charge/discharge curves of the lithium secondary batteries of Example 1 and Comparative Example are shown in FIG. It can be seen that the irreversible capacity, which is the difference between the charge capacity and the discharge capacity, of the lithium secondary battery of Example 1 is smaller than that of the comparative example. Also, the lithium secondary battery of Example 1 showed a charge/discharge capacity of about 0.199 mAh and an average discharge voltage of about 2.5V. This is probably because the permeation of the electrolyte membrane 13 facilitated the permeation of lithium ions in the electrolyte membrane 13, and the capacity was improved to increase the energy density per unit capacity.
  • the lithium secondary battery of the comparative example has a lower charge/discharge capacity and a lower discharge voltage and a higher charge voltage than the example. This is considered to be caused by the ionic conductivity of the electrolyte and the increase in resistance due to the contact at the interface between the electrolyte and the positive and negative electrodes.
  • Example 2 In Example 1, a polymer electrolyte was used as the electrolyte membrane 13 . In Example 2, a polymer electrolyte with added aluminum oxide is used. A lithium secondary battery 1 according to Example 2 was also produced in the same procedure as in Example 1.
  • the electrolyte consists of polyvinylidene fluoride (PVdF) powder as a binder, an organic electrolyte made by dissolving 1 mol/L of lithium bistrifluoromethanesulfonylimide (LiTFSI) as a lithium salt in propylene carbonate (PC), and a dispersing medium.
  • PVdF polyvinylidene fluoride
  • LiTFSI lithium bistrifluoromethanesulfonylimide
  • PC propylene carbonate
  • a solution was prepared by mixing tetrahydrofuran (THF) and aluminum oxide (Al 2 O 3 ) as a dispersion medium in a weight ratio of 4:6:10:0.3.
  • the above polymer electrolyte is molded to a size of 90 mm long x 100 mm wide, and a positive electrode capable of intercalating and deintercalating lithium ions is formed on one surface (front surface) of the polymer electrolyte, and the other surface (back surface) ), a negative electrode capable of intercalating and deintercalating lithium ions was formed. Then, it was sandwiched between two ITO-attached glass substrates so that the positive electrode and the negative electrode were all covered, respectively, and the edge of 90 mm long ⁇ 100 mm wide where the positive electrode, the electrolyte, and the negative electrode were overlapped was sealed with an adhesive. Then, before the adhesive hardened, it was placed in a vacuum dryer, and the adhesive was hardened after vacuum drying.
  • Example 2 After that, the lithium secondary battery of Example 2 was subjected to a charge/discharge test under the same conditions as in Example 1.
  • Example 2 Results of charge/discharge test of Example 2
  • the initial charge/discharge curve of the lithium secondary battery according to Example 2 is shown in FIG.
  • the lithium secondary battery according to Example 2 was chargeable and dischargeable, and exhibited a charge/discharge capacity of about 0.203 mAh and an average discharge voltage of about 2.7V.
  • the lithium secondary battery according to Example 2 has a higher charge/discharge capacity and a higher discharge voltage than those of Example 1, and a lower charge voltage. This is probably because the addition of aluminum oxide increased the ionic conductivity of the electrolyte and reduced the internal resistance.
  • the lithium secondary battery 1 includes a positive electrode film 11 capable of intercalating and deintercalating lithium ions, a negative electrode film of tium, a negative electrode film made of a material capable of forming an alloy with lithium, and a lithium A negative electrode film 12 among negative electrode films capable of intercalating and deintercalating ions, and a transparent and solid electrolyte film 13 positioned between the positive electrode film and the negative electrode film and having lithium ion conductivity. and two transparent substrates 14 and 16 sandwiching the positive electrode film and the negative electrode film having the electrolyte film between them with transparent conductive films 15 and 17 formed on the respective surfaces, so that visible light is transmitted. It is possible to provide a lithium secondary battery having excellent charge-discharge cycle characteristics and high energy density.
  • the lithium secondary battery 1 according to this embodiment can be used as a power drive source/power supply source for electronic devices and the like, and can be used in various industries that use batteries.
  • Lithium secondary battery 11 Positive electrode film 12: Negative electrode film 13: Electrolyte film 14: First transparent substrate 15: First transparent conductive film 16: Second transparent substrate 17: Second transparent conductive film 21: Positive electrode terminal 22: Negative electrode terminal

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PCT/JP2021/044721 2021-12-06 2021-12-06 リチウム二次電池、及び、リチウム二次電池の製造方法 Ceased WO2023105573A1 (ja)

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JP2023565681A JPWO2023105573A1 (https=) 2021-12-06 2021-12-06
US18/714,023 US20250174774A1 (en) 2021-12-06 2021-12-06 Lithium Secondary Battery and Manufacturing Method of Lithium Secondary Battery

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Citations (6)

* Cited by examiner, † Cited by third party
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