WO2013108795A1 - Matériau d'électrolyte solide, batterie totalement à l'état solide et procédé de fabrication de matériau d'électrolyte solide - Google Patents

Matériau d'électrolyte solide, batterie totalement à l'état solide et procédé de fabrication de matériau d'électrolyte solide Download PDF

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WO2013108795A1
WO2013108795A1 PCT/JP2013/050690 JP2013050690W WO2013108795A1 WO 2013108795 A1 WO2013108795 A1 WO 2013108795A1 JP 2013050690 W JP2013050690 W JP 2013050690W WO 2013108795 A1 WO2013108795 A1 WO 2013108795A1
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solid electrolyte
electrolyte material
electrode active
active material
solid
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Japanese (ja)
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ポポビッチ ダニエル
明渡　純
永井　秀幸
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トヨタ自動車株式会社
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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
    • H01M10/056—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
    • 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

  • the present invention relates to a solid electrolyte material having a Li element, a B element, and a PO 4 structure and high Li ion conductivity.
  • lithium-ion batteries use electrolytes containing flammable organic solvents, so safety devices that prevent temperature rise during short circuits and improvements in structure and materials to prevent short circuits Is required.
  • an all-solid-state lithium ion battery in which the electrolyte is changed to a solid electrolyte layer to make the battery all solid does not use a flammable organic solvent in the battery. And is considered to be highly productive.
  • Patent Document 1 discloses an all solid state secondary battery including an inorganic solid electrolyte that is sintered by applying a direct current pulse current under pressure, and LiBPO 4 is cited as an example of the inorganic solid electrolyte.
  • Non-Patent Documents 1 to 4 also disclose LBPO as a solid electrolyte material exhibiting Li ion conductivity.
  • LBPO exhibits Li ion conductivity.
  • LBPO is a material having lower Li ion conductivity than other high Li ion conductive solid electrolyte materials (for example, LATP). Recognized.
  • the solid electrolyte material is required to improve Li ion conductivity.
  • the present invention has been made in view of the above circumstances, and has as its main object to provide a solid electrolyte material having a Li element, a B element, and a PO 4 structure and high Li ion conductivity.
  • the present invention provides a solid electrolyte material having a Li element, a B element, and a PO 4 structure and having a crystallite size of 50 nm or less.
  • the crystallite size is a predetermined value or less, a solid electrolyte material having high Li ion conductivity can be obtained.
  • the relative density with respect to the theoretical density is preferably 80% or more. This is because the Li ion conductivity is further improved.
  • a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and a solid electrolyte formed between the positive electrode active material layer and the negative electrode active material layer An all-solid-state battery, wherein at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer contains the above-described solid electrolyte material. To do.
  • the present invention when at least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer contains the above-described solid electrolyte material, a high output battery can be obtained.
  • a method for producing a solid electrolyte material having a Li element, B element, and PO 4 structure, wherein the crystallite size is reduced to 50 nm or less by applying pressure to the raw material particles of the solid electrolyte material comprising a pressure applying step.
  • a solid electrolyte material having high Li ion conductivity can be obtained by setting the crystallite size to a predetermined value or less in the pressure applying step.
  • the solid electrolyte material of the present invention has an effect of high Li ion conductivity.
  • FIG. 3 is a result of XRD measurement on the solid electrolyte membranes produced in Examples 1 to 3.
  • FIG. 3 is a result of measuring Li ion conductivity with respect to the evaluation members obtained in Examples 1 to 3. It is a result of Li ion conductivity measurement with respect to the evaluation member obtained by the comparative example.
  • the solid electrolyte material of the present invention is a solid electrolyte material having a Li element, a B element, and a PO 4 structure, and has a crystallite size of 50 nm or less.
  • LATP is a solid electrolyte material having a Li, Al, Ti, PO 4 structure (for example, Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ).
  • G means the inside of a crystal grain
  • GB means a crystal grain boundary
  • ⁇ means Li ion conductivity.
  • the crystal grain boundary becomes the rate-determining factor for Li ion conduction, so to improve Li ion conductivity, it is necessary to increase the crystallite size (ultimately to be a single crystal). It is considered effective.
  • Kai-Yun Yang et al. “Roles of lithium ions and La / Li-site vacancies in sinterability and total ionic conduction properties of cyclic Li 3x La 2 / 3-x TiO 3 solid electrolytes (0.21 ⁇ 3x ⁇ 0.50) ”, Journal of Alloys and Compounds 458 (2008) 415-424 discloses that increasing the sintering temperature and increasing the crystallite size reduces the grain boundaries and lowers the grain boundary resistance. Yes.
  • LBPO as described in the examples described later, ⁇ A ⁇ ⁇ B unexpectedly.
  • LBPO is different from ordinary solid electrolyte materials because Li ion conductivity ⁇ GB at grain boundary GB is higher than Li ion conductivity ⁇ G at crystal grain G. It is believed that there is. That is, it is suggested that the crystal grain boundary, which has been conventionally considered to be the rate-determining mechanism of Li ion conduction, actually has higher Li ion conductivity than the crystal grains, and the Li ion conduction mechanism is completely different.
  • the solid electrolyte material of the present invention is considered to be a material having high Li ion conductivity.
  • Non-Patent Documents 1 to 4 disclose LBPO, there is no description or suggestion that the Li ion conductivity is improved by reducing the crystallite size. As a result of experiments using the AD method described later, the present inventors have found that LBPO has higher Li ion conductivity as the crystallite size is smaller.
  • the Li ion conductivity of the polycrystalline solid electrolyte material largely depends mainly on the density and the crystallite size, but it is difficult to change the crystallite size while keeping the density constant by the conventional method.
  • the solid electrolyte material of the present invention has a Li element, a B element, and a PO 4 structure.
  • the composition of the solid electrolyte material of the present invention include xLi 2 O—BPO 4 (0.5 ⁇ x ⁇ 1.5), Li x B 1-x / 3 PO 4 (0.75 ⁇ x ⁇ 3), and the like. Can be mentioned. Further, the ratio of Li to B (mol basis) is preferably 1 or more. Further, the solid electrolyte material of the present invention may be composed only of Li element, B element, and PO 4 structure, or composed only of Li element, B element, O element, and PO 4 structure. Alternatively, at least one element of Li, B, P, and O may be partially substituted with another element.
  • the present invention is greatly characterized in that the crystallite size of the solid electrolyte material is in a specific range.
  • the crystallite refers to the largest group that can be regarded as a single crystal, and as shown in FIG. 2, a plurality of crystallites constitute a particle (polycrystalline particle).
  • grains are illustrated in FIG. 2, the solid electrolyte material of this invention may be a film
  • the crystallite size of the solid electrolyte material is usually 50 nm or less, and is preferably smaller from the viewpoint of improving Li ion conductivity. Specifically, it is preferably 40 nm or less, and more preferably 30 nm or less.
  • FWHM full width at half maximum
  • the peak position may be back and forth within a range of ⁇ 0.5 °.
  • the relative density of the solid electrolyte material of the present invention is not particularly limited, but is preferably in the range of 80% to 99%, for example, and more preferably in the range of 90% to 99%. If the relative density of the solid electrolyte material is too high (for example, exceeding 100%), the solid electrolyte material may be distorted. If the solid electrolyte material is too low, the solid electrolyte material will not be dense and sufficient This is because ionic conductivity may not be obtained.
  • the relative density of the solid electrolyte material can be obtained by dividing the actual density of the solid electrolyte material by the theoretical density of the solid electrolyte material. The actual density of the solid electrolyte material can be obtained, for example, by obtaining the volume of the solid electrolyte material from the area and film thickness of the solid electrolyte material and dividing the weight of the solid electrolyte material by the volume.
  • the solid electrolyte material of the present invention preferably has a high Li ion conductivity at room temperature (25 ° C.).
  • the Li ion conductivity is, for example, preferably 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 1 ⁇ 10 ⁇ 5 S / cm or more, and 1 ⁇ 10 ⁇ 4 S / cm or more. Is more preferably 1 ⁇ 10 ⁇ 3 S / cm or more.
  • Li ion conductivity can be obtained by an AC impedance method.
  • the shape of the solid electrolyte material of the present invention is not particularly limited, and may be a film shape or a particle shape.
  • the membrane-like solid electrolyte material can be obtained by using, for example, an aerosol deposition method as described later.
  • the particulate solid electrolyte material can be obtained, for example, by pulverizing a membrane solid electrolyte material.
  • the all solid state battery of the present invention includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, and a solid formed between the positive electrode active material layer and the negative electrode active material layer.
  • FIG. 3 is a schematic cross-sectional view showing an example of the all solid state battery of the present invention.
  • 3 is formed between a positive electrode active material layer 1 containing a positive electrode active material, a negative electrode active material layer 2 containing a negative electrode active material, and between the positive electrode active material layer 1 and the negative electrode active material layer 2.
  • the present invention is characterized in that at least one of the positive electrode active material layer 1, the negative electrode active material layer 2, and the solid electrolyte layer 3 contains the solid electrolyte material described in "A. Solid electrolyte material".
  • At least one of the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer contains the above-described solid electrolyte material, whereby a high output battery can be obtained.
  • the all solid state battery of the present invention will be described for each configuration.
  • Positive electrode active material layer is a layer containing at least a positive electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good.
  • a positive electrode active material an oxide active material etc. can be mentioned, for example.
  • the oxide active material examples include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), LiNi 1/3 Mn 1/3 Co 1/3 O 2 , lithium manganate (LiMn 2 O 4 ), Li 1 + x Mn 2-xy M y O 4 (M is one or more selected from Al, Mg, Co, Fe, Ni, Zn, 0 ⁇ x + y ⁇ 2)
  • M is one or more selected from Al, Mg, Co, Fe, Ni, Zn, 0 ⁇ x + y ⁇ 2
  • Examples thereof include lithium titanate, lithium metal phosphate (LiMPO 4 , M is one or more selected from Fe, Mn, Co, and Ni), vanadium oxide (V 2 O 5 ), and molybdenum oxide (MoO 3 ).
  • the positive electrode active material layer in the present invention may contain a solid electrolyte material. By adding the solid electrolyte material, the Li ion conductivity of the positive electrode active material layer can be improved. Especially, it is preferable that the solid electrolyte material contained in a positive electrode active material layer is the solid electrolyte material described in said "A. Solid electrolyte material.” This is because a high output battery can be obtained.
  • the positive electrode electrolyte layer in the present invention preferably contains the particulate solid electrolyte material described above.
  • the positive electrode active material layer may contain a conductive material. By adding a conductive material, the conductivity of the positive electrode active material layer can be improved.
  • the conductive material examples include acetylene black, ketjen black, and carbon fiber.
  • the positive electrode active material layer may contain a binder.
  • a binder fluorine-containing binders, such as polyvinylidene fluoride (PVDF), etc. can be mentioned, for example.
  • the thickness of the positive electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
  • the negative electrode active material layer in the present invention is a layer containing at least a negative electrode active material, and may contain at least one of a solid electrolyte material, a conductive material and a binder, if necessary. good.
  • the negative electrode active material include a metal active material and a carbon active material.
  • the metal active material include In, Al, Si, and Sn.
  • examples of the carbon active material include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon.
  • An oxide active material may be used as the negative electrode active material. Examples of the oxide active material include compounds containing Li, Ti, and O (for example, Li 4 Ti 5 O 12 ).
  • the negative electrode active material layer in the present invention may contain a solid electrolyte material.
  • the addition of the solid electrolyte material can improve the Li ion conductivity of the negative electrode active material layer.
  • the solid electrolyte material contained in a negative electrode active material layer is the solid electrolyte material described in the said "A. solid electrolyte material". This is because a high output battery can be obtained.
  • the negative electrode electrolyte layer in the present invention preferably contains the above-described particulate solid electrolyte material.
  • the conductive material and the binder contained in the negative electrode active material layer are the same as those described in “1. Positive electrode active material layer”.
  • the thickness of the negative electrode active material layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
  • the solid electrolyte layer in this invention is a layer formed between a positive electrode active material layer and a negative electrode active material layer.
  • the solid electrolyte material constituting the solid electrolyte layer is not particularly limited as long as it has Li ion conductivity, but is preferably the solid electrolyte material described in the above “A. Solid electrolyte material”. . This is because a high output battery can be obtained.
  • the solid electrolyte layer in the present invention is preferably composed of the above-described membrane-shaped solid electrolyte material.
  • the thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, and more preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
  • the all solid state battery of the present invention has at least the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material.
  • the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon.
  • examples of the material for the negative electrode current collector include SUS, copper, nickel, and carbon.
  • the thickness and shape of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the battery.
  • the battery case of a general battery can be used for the battery case used for this invention. Examples of the battery case include a SUS battery case.
  • All-solid battery may be a primary battery or a secondary battery, but is preferably a secondary battery.
  • it is useful as a vehicle battery.
  • Examples of the shape of the all solid state battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type.
  • the method for producing a solid electrolyte material of the present invention is a method for producing a solid electrolyte material having a Li element, B element, and PO 4 structure, and by applying pressure to the raw material particles of the solid electrolyte material, the crystallite size Having a pressure applying step of adjusting the thickness to 50 nm or less.
  • a solid electrolyte material having high Li ion conductivity can be obtained by setting the crystallite size to a predetermined value or less in the pressure applying step.
  • the pressure applying step in the present invention is a step of applying pressure to the raw material particles of the solid electrolyte material having a Li element, a B element and a PO 4 structure.
  • the crystallite size is set to 50 nm or less.
  • the preferred range of the crystallite size is the same as that described in the above “A. Solid electrolyte material”, and the description is omitted here.
  • the raw material particles used in the present invention usually have a Li element, a B element, and a PO 4 structure.
  • the composition of the raw material particles is preferably the same as the composition of the solid electrolyte material described above. Further, in the raw material particles, the ratio of Li to B (mol basis) is preferably 1 or more. This is because even when Li is volatilized, a solid electrolyte material having good Li ion conductivity can be obtained.
  • the crystallinity of the raw material particles may be improved in advance by heat treatment. This is because by improving the crystallinity in advance, it becomes easier to produce a solid electrolyte material having a desired crystallite size.
  • the average particle diameter of the raw material particles may be refined in advance.
  • the average particle diameter D 50 of the raw material particles is not particularly limited, but is preferably in the range of 0.4 ⁇ m to 4 ⁇ m, for example, and more preferably in the range of 0.6 ⁇ m to 2 ⁇ m.
  • the crystallite size of the raw material particles is not particularly limited, but is preferably in the range of 10 nm to 80 nm, for example, and more preferably in the range of 10 nm to 50 nm.
  • pressure is applied to the raw material particles.
  • the pressure applied to the raw material particles is preferably high enough to obtain a desired crystallite size, specifically 500 MPa or more, more preferably 1 GPa or more, and 1.2 GPa or more. More preferably.
  • the pressure application method for applying pressure to the raw material particles is not particularly limited as long as a desired crystallite size can be obtained, but a method in which the raw material particles are not actively heated is preferable. This is because it is possible to prevent grain growth from occurring due to heating and increase in crystallite size. Further, the pressure applying method may be a method of applying pressure to the raw material particles by collision with the substrate, or a method of applying pressure to the raw material particles by a pressure medium.
  • An example of a method for applying pressure to the raw material particles by collision with the substrate is an aerosol deposition method (AD method).
  • the AD method uses a “normal temperature impact solidification phenomenon” (a phenomenon in which only mechanical impact force is applied to the raw material particles and solidifies at a normal temperature without heating) to obtain a dense and highly adhesive film. be able to.
  • a “normal temperature impact solidification phenomenon” a phenomenon in which only mechanical impact force is applied to the raw material particles and solidifies at a normal temperature without heating
  • the film forming speed is several tens of times that of conventional thin film forming techniques.
  • since a high pressure is applied only to a very limited area of the substrate there are advantages that damage to the substrate is small and mutual diffusion due to heat does not occur.
  • FIG. 4 is a schematic diagram for explaining the aerosol deposition method (AD method).
  • a pedestal 12 is installed inside the chamber 11, and a substrate 13 is disposed on the pedestal 12.
  • the pressure inside the chamber 11 can be controlled to an arbitrary reduced pressure state by the rotary pump 14.
  • the raw material particles 16 are aerosolized by the carry-in gas supplied from the gas cylinder 15 inside the aerosol generator 17. Further, the aerosolized raw material particles are sprayed toward the substrate 13 from the nozzle 18 disposed inside the chamber 11. On the surface of the substrate 13, deposition occurs along with destructive deformation (atomization) of particles, and a thin film is formed.
  • the pressure P in the chamber at the time of film formation by the AD method is not particularly limited as long as it can obtain a desired density.
  • it is preferably higher than 100 Pa, more preferably 120 Pa or higher. More preferably, it is 150 Pa or more. This is because if the pressure during film formation is too low, the density of the active material layer may become too large.
  • the pressure P is preferably 400 Pa or less, and more preferably 350 Pa or less, for example. This is because if the pressure during film formation is too high, it may be difficult to obtain a dense active material layer.
  • the type of carrier gas in the AD method but not limited, helium (He), argon (Ar), nitrogen (N 2) an inert gas, such as, and can include dry air, or the like.
  • the gas flow rate of the carrier gas is not particularly limited as long as it is a flow rate capable of maintaining a desired aerosol. For example, 3 L / min. ⁇ 8L / min. It is preferable to be within the range.
  • a cold spray method or the like can be given.
  • examples of the method of applying pressure to the raw material particles with a pressure medium include CIP (Cold Isostatic Pressing), CUP (Cold Uniaxial Pressing), and the like.
  • Another example of the pressure application method is magnetic pulse compression (Magnetic (Pulse Compaction).
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
  • a solid electrolyte membrane was prepared by AD method using the obtained raw material particles.
  • An Al alloy (A5052, thickness 0.5 mm) was used for the substrate.
  • the film forming conditions are as follows. ⁇ Film formation conditions> ⁇ Temperature Normal temperature ⁇ Pressure in the chamber 600Pa ⁇ Gas He ⁇ Gas flow rate 2L / min. (Assist gas 3L / min.) ⁇ Scanning speed 2.5mm / sec. ⁇ Distance between substrate nozzles 20mm In this way, a solid electrolyte membrane was obtained on the substrate. Further, an Au thin film (current collecting part) was formed on the solid electrolyte film by sputtering to obtain an evaluation member.
  • Example 2 An evaluation member was obtained in the same manner as in Example 1 except that the conditions for forming the solid electrolyte membrane were changed as follows. ⁇ Film formation conditions> ⁇ Temperature Normal temperature ⁇ Pressure in the chamber 200Pa ⁇ Gas He ⁇ Gas flow rate 1.5L / min. (Assist gas 3.5L / min.) ⁇ Scanning speed 2.5mm / sec. ⁇ Distance between substrate nozzles 15mm
  • Example 3 An evaluation member was obtained in the same manner as in Example 1 except that the conditions for forming the solid electrolyte membrane were changed as follows. ⁇ Film formation conditions> ⁇ Temperature Normal temperature ⁇ Pressure in the chamber 100Pa ⁇ Gas O 2 ⁇ Gas flow rate 1.5L / min. (Assist gas 7.0L / min.) ⁇ Scanning speed 2.5mm / sec. ⁇ Distance between substrate nozzles 15mm
  • Example 1 The raw material particles used in Example 1 and the solid electrolyte membrane (cross section) produced in Example 1 were observed using a scanning electron microscope. The result is shown in FIG. As shown in FIG. 5 (a), the raw material particles used in Example 1 are particles, and as shown in FIG. 5 (b), the solid electrolyte membrane produced in Example 1 has finely divided raw material particles. It was confirmed that the film was 15.9 ⁇ m thick.
  • the density of the solid electrolyte membrane prepared in Examples 1 to 3 was calculated. First, the volume of the solid electrolyte membrane was determined from the area and film thickness of the solid electrolyte membrane. Next, the density of the solid electrolyte membrane was determined by measuring the weight of the solid electrolyte membrane and dividing the weight by the volume of the solid electrolyte membrane. The relative density was determined by dividing this value by the theoretical density. The results are shown in Table 1.
  • Li ion conductivity measurement Li ion conductivity measurement was performed on the evaluation members obtained in Examples 1 to 3. The measurement was performed by the AC impedance method. The results are shown in FIG.
  • the film forming conditions are as follows. ⁇ Film formation conditions> ⁇ Temperature Normal temperature ⁇ Pressure in the chamber about 1 Torr ⁇ Gas He ⁇ Gas flow rate: 1L / min. To 10L / min ⁇ Scanning speed 0.1mm / sec. ⁇ 10mm / sec. In this way, a solid electrolyte membrane was obtained on the substrate. Further, an Au thin film (current collecting part) was formed on the solid electrolyte film by sputtering to obtain an evaluation member.

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Abstract

L'objectif principal de la présente invention est de fournir un matériau d'électrolyte solide au lithium-ion ayant une haute conductivité et ayant une structure de lithium (Li), de bore (B) et de PO4. La présente invention résout le problème susmentionné par la fourniture d'un matériau d'électrolyte solide ayant une structure de lithium, de bore et de PO4, ledit matériau d'électrolyte solide étant caractérisé en ce que la taille des cristallites est inférieure à 50 nm.
PCT/JP2013/050690 2012-01-17 2013-01-16 Matériau d'électrolyte solide, batterie totalement à l'état solide et procédé de fabrication de matériau d'électrolyte solide WO2013108795A1 (fr)

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JP2012007091A JP5930372B2 (ja) 2012-01-17 2012-01-17 固体電解質材料、全固体電池および固体電解質材料の製造方法
JP2012-007091 2012-01-17

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JP7346799B2 (ja) 2019-03-11 2023-09-20 三井化学株式会社 リン酸ホウ素リチウム化合物、リチウム二次電池用添加剤、リチウム二次電池用非水電解液、リチウム二次電池前駆体、リチウム二次電池の製造方法、及びリチウム二次電池

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US10886515B2 (en) 2017-05-30 2021-01-05 Samsung Electronics Co., Ltd. All-solid secondary battery and method of preparing the same
KR102566410B1 (ko) * 2017-05-30 2023-08-14 삼성전자주식회사 전고체 이차전지 및 전고체 이차전지의 제조 방법
WO2023234350A1 (fr) * 2022-06-01 2023-12-07 富士フイルム株式会社 Batterie secondaire au lithium-ion entièrement solide enroulée et procédé de production d'une batterie secondaire au lithium-ion entièrement solide enroulée
WO2023234349A1 (fr) * 2022-06-01 2023-12-07 富士フイルム株式会社 Batterie secondaire au lithium-ion entièrement solide et procédé de fabrication de batterie secondaire au lithium-ion entièrement solide

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