[go: up one dir, main page]

WO2020175630A1 - Batterie secondaire à semi-conducteurs - Google Patents

Batterie secondaire à semi-conducteurs Download PDF

Info

Publication number
WO2020175630A1
WO2020175630A1 PCT/JP2020/008067 JP2020008067W WO2020175630A1 WO 2020175630 A1 WO2020175630 A1 WO 2020175630A1 JP 2020008067 W JP2020008067 W JP 2020008067W WO 2020175630 A1 WO2020175630 A1 WO 2020175630A1
Authority
WO
WIPO (PCT)
Prior art keywords
current collector
layer
positive electrode
negative electrode
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/008067
Other languages
English (en)
Japanese (ja)
Inventor
泰輔 益子
田中　一正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Corp
Original Assignee
TDK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TDK Corp filed Critical TDK Corp
Publication of WO2020175630A1 publication Critical patent/WO2020175630A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M10/058—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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of 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
    • 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 all solid state secondary battery.
  • Lithium ion secondary batteries which are currently used for general purposes, have conventionally used an electrolyte (electrolyte solution) such as an organic solvent as a medium for moving ions.
  • electrolyte electrolyte solution
  • organic solvent organic solvent
  • Patent Document 1 discloses that a positive electrode current collector, a negative electrode current collector, a positive electrode active material, a negative electrode active material, a solid electrode which form an all-solid secondary battery by using an oxide-based solid electrolyte stable in air. It describes an all-solid-state secondary battery manufactured by a manufacturing method in which each of the densities is formed into a sheet, laminated to form a laminated body, and then fired simultaneously. At this time, 89, 01, 8, 8 and 1: are used as current collector elements.
  • Patent Document 2 describes an all-solid-state secondary battery in which, as a current collector element, O, R, or the like is used and fired in a low oxygen atmosphere. ⁇ 02020/175630 2 (: 17 2020/008067 Prior art documents)
  • Patent Document 1 International Publication No. 2007/1 35790
  • Patent Document 2 JP 2007-227362 A
  • An object of the present invention is to provide an all solid state secondary battery having good cycle characteristics.
  • the present invention provides the following means in order to solve the above problems.
  • the all-solid secondary battery according to the first aspect of the present invention includes a positive electrode layer including a positive electrode current collector and a positive electrode active material layer, a negative electrode current collector and a negative electrode active material layer.
  • a negative electrode layer including a solid electrolyte layer, and a solid electrolyte layer including a solid electrolyte, and the positive electrode layer and the negative electrode layer are alternately laminated with the solid electrolyte layer interposed therebetween to form a positive electrode current collector and the negative electrode.
  • the current collector includes a main part containing a first element as a main component and a sub-part containing a second element which is an element different from the first element.
  • 6, 8 9, 8 li, and I are elements selected from the group consisting of I, wherein the second element is 0, 1 ⁇ 1 and 8 9 , 8 li, It may be one or more elements selected from the group consisting of V, only IV!, ⁇ , “, 3 I, 06, 1_ ⁇ , and 8 ⁇ .
  • the weight ratio of the second element to the first element is in the range of 0.0002% or more and 20% or less. It may be inside. ⁇ 2020/175 630 3 (:171? 2020/008067
  • the sub-area may have a circle area conversion diameter of 0.5 or less.
  • the sub-portion may be obtained by segregating an element containing the second element in the main portion.
  • FIG. 1 is a schematic sectional view of an all solid state secondary battery according to the present embodiment.
  • Examples of the all-solid-state secondary battery include an all-solid-state lithium-ion secondary battery, an all-solid-state sodium ion secondary battery, and an all-solid magnesium-ion secondary battery.
  • an all-solid-state lithium ion secondary battery will be described as an example, but the present invention is applicable to all-solid-state secondary batteries in general.
  • Fig. 1 is an enlarged schematic cross-sectional view of a main part of the all-solid-state lithium-ion secondary battery according to the present embodiment.
  • the all-solid-state lithium-ion secondary battery shown in FIG. 1 includes a laminate having a first electrode layer, a second electrode layer, and a solid electrolyte layer.
  • one of the first electrode layer and the second electrode layer functions as a positive electrode and the other functions as a negative electrode.
  • the polarity of the electrode layer changes depending on which polarity is applied to the external terminal.
  • the first electrode layer will be described as a positive electrode layer and the second electrode layer will be described as a negative electrode layer.
  • the all-solid-state lithium-ion secondary battery 100 includes a positive electrode current collector 18 and a positive electrode active material layer.
  • Negative electrode layers 2 are provided with laminated bodies 20 that are alternately laminated with solid electrolyte layers 3 containing a solid electrolyte interposed therebetween.
  • the positive electrode layer 1 is connected to the first external terminal 6, and the negative electrode layer 2 is connected to the second external terminal 7, respectively.
  • the first external terminal 6 and the second external terminal 7 are electrical contacts with the outside.
  • the laminate 20 has a positive electrode layer 1, a negative electrode layer 2, and a solid electrolyte layer 3.
  • the positive electrode layer 1 and the negative electrode layer 2 are alternately laminated with the solid electrolyte layer 3 (more specifically, the interlayer solid electrolyte layer 38) interposed therebetween.
  • the solid electrolyte layer 3 more specifically, the interlayer solid electrolyte layer 38
  • the number of layers of the positive electrode layer 1 and the negative electrode layer 2 is not particularly limited, but the total number of the positive electrode layer 1 and the negative electrode layer 2 is generally in the range of 10 to 200 layers, and preferably 20 layers. The above is within the range of 100 layers or less.
  • the positive electrode layer 1 has a positive electrode current collector 1 and a positive electrode active material layer 1 containing a positive electrode active material.
  • the positive electrode current collector 18 includes, as main components, a main part 18 3 containing the first element and a sub part 18 s containing the second element which is an element different from the first element.
  • the negative electrode layer 2 has a negative electrode current collector 2 and a negative electrode active material layer 2 containing a negative electrode active material.
  • the negative electrode current collector 28 also has a main part that contains the first element as the main component, and a second part that contains the second element that is an element different from the first element. It consists of 2 heads.
  • the positive electrode current collector 18 and the negative electrode current collector 28 may be formed in layers. ⁇ 2020/175630 5 ⁇ (: 171-1?2020/008067
  • main portion 1 eight 3 and main portion 2 eight 3 of the negative electrode current collector 2 eight of the positive electrode current collector 1 eight includes high conductivity at least one element (first element).
  • first element for example, copper
  • copper examples include elements selected from the group consisting of nickel (1 ⁇ 11), iron (4, silver (89), gold (8), palladium (0000), and platinum ().
  • nickel are preferable in consideration of the manufacturing cost in addition to the high conductivity
  • copper is difficult to react with the positive electrode active material, the negative electrode active material and the solid electrolyte. substance may be the same or different have good.
  • main portion of the cathode current collector 1 eighth main portion 1 eight 3 and the negative electrode current collector 2 eight constituting the collector 1 eight and the anode current collector 2 eight 2 8 3 may further include metal oxides.
  • the metal oxides include: ⁇ ri ⁇ , ⁇ ri 2 ⁇ , 1 ⁇ 1 I ⁇ , 6 2 ⁇ 3 , 6 3 ⁇ 4 , 4 , etc. Is mentioned.
  • the sub-part 1 8 swatches of the positive electrode current collector 18 and the sub-part 2 8 swatches of the negative electrode current collector 2 8 are the second element which is an element different from the first element constituting the main part 18 3. including.
  • the second element is copper Nickel (1 ⁇ 1 ⁇ ), Iron (4, Silver (89), Gold (8), Palladium ( ⁇ , Platinum (), Vanadium (V), Titanium (Cho), Manganese (IV!n)) , Cobalt ( ⁇ ), zirconium ( ⁇ , silicon (3 ⁇ ), germanium ( ⁇ 6), lithium (1_ ⁇ ), and aluminum (8 ⁇ ), at least one element selected from the group consisting of
  • the “subpart” means that the concentration distribution of an element different from the first element contained as the main component of the current collector in the positive electrode current collector or the negative electrode current collector is high.
  • the positive electrode current collector 18 has a structure in which the sub-parts 18 13 are scattered, dispersed or mixed in the current collector composed of the main part 18 3 which is the main component.
  • the sub-portion 18 is generated by segregation of an element containing the second element in the current collector consisting of the main portion 18 3.
  • the negative electrode current collector 28 is the main component.
  • Sub-parts 2 8 13 are scattered, scattered, or mixed in the current collector consisting of parts 2 8 3.
  • the sub-part 2 8 s is the second part of the current collector consisting of the main part 2 8 3 . It is generated by the segregation of elements including elements
  • a part of the positive electrode current collector 18 and the negative electrode current collector 28 (the area indicated by the dotted circle) is expanded. In general, a configuration in which sub-parts are scattered, dispersed, or mixed in the current collector composed of the main part is shown.
  • the cycle characteristics of the all-solid secondary battery are improved.
  • the current collector has a sub-portion containing a second element different from the first element contained as the main component, a part having a different electron conductivity can be formed in the current collector.
  • the presence of a part with different electron conductivity in the current collector causes a difference in how the electrons are taken out, which improves the cycle characteristics of the all-solid-state secondary battery.
  • the weight ratio of the second element to the first element is preferably in the range of 0.0002 or more and 20% or less.
  • the cycle characteristics of the all-solid-state secondary battery become better. If the weight ratio of the second element to the first element is less than 0.0002%, the cycle characteristics are hardly affected. Also, if it exceeds 20%, there are too many prayers in the current collector, which may rather deteriorate the cycle characteristics.
  • the weight ratio of the second element to the first element is more preferably 15% or less, still more preferably 10% or less, and even more preferably 1% or less.
  • the weight ratio of the second element to the first element can be obtained by a known method.
  • LA- ICP-MS Spectrome try :LA- ICP-MS.
  • LA-CP-MS a single laser beam is focused and irradiated on the cross-section or surface of the current collector to evaporate/particulate, decompose and ionize in plasma, and generate ions in a mass spectrometer.
  • the first element and the second element ⁇ 2020/175 630 7 ⁇ (: 171-1? 2020/008067
  • the weight of the element can be obtained. Since the region irradiated with laser light is the target of analysis, it is possible to obtain local information from the current collector by narrowing down the spot diameter of laser light. Even when the spot diameter of the laser beam is larger than the thickness of the metal current collector, an accurate weight ratio can be obtained by comparing the weight ratios of the first metal element and the second metal element. it can.
  • the circle area calculated diameter ⁇ 1 of the sub-part 18 sq. of the positive electrode current collector 18 and the sub-part 28 sq. of the negative electrode current collector 28 is preferably 0.5 or less.
  • the maximum diameter is 0.5 or less among the “circular area conversion diameters” of the n cm sub parts thus obtained.
  • the thickness of the positive electrode current collector 18 and the negative electrode current collector 28 is not limited, but in the case of safety, it is in the range of 0.5 or more and 30 or less.
  • the positive electrode active material layer 1 is formed on one side or both sides of the positive electrode current collector 18.
  • the positive electrode layer 1, which is the uppermost layer in the stacking direction of the all-solid-state lithium-ion secondary battery 100 does not have the negative electrode layer 2 facing the stacking direction upper side. Therefore, the positive electrode active material layer 1 in the positive electrode layer 1, which is the uppermost layer of the all-solid-state lithium-ion secondary battery 100, need only be on one side on the lower side in the stacking direction. There is no.
  • the negative electrode active material layer 2 is also formed on one side or both sides of the negative electrode current collector 2, similarly to the positive electrode active material layer 1.
  • the thickness of the positive electrode active material layer 1 and the negative electrode active material layer 2 is preferably in the range of 0.5 or more and 5.0 or less. By increasing the thickness of the positive electrode active material layer 1 and the negative electrode active material layer 2 to 0.5 or more, the electric capacity of the all-solid-state lithium-ion secondary battery can be increased. ⁇ 2020/175630 8 ⁇ (: 171-1?2020/008067
  • the thickness is 5.0 or less, the diffusion distance of lithium ions is shortened, so that the internal resistance of the all-solid-state lithium-ion secondary battery can be further reduced.
  • the positive electrode active material layer 1 and the negative electrode active material layer 2 each include a positive electrode active material or a negative electrode active material that exchanges lithium ions and electrons.
  • a conductive auxiliary agent or the like may be included. It is preferable that the positive electrode active material and the negative electrode active material can efficiently insert and desorb lithium ions.
  • the active materials constituting the positive electrode active material layer 1 or the negative electrode active material layer 2 are compared, and the compound showing a more noble potential is determined as the positive electrode.
  • a compound showing a more base potential can be used as the negative electrode active material. Therefore, the active materials will be collectively described below.
  • a transition metal oxide, a transition metal composite oxide, or the like can be used as the active material.
  • Lithium cobaltate (1_ ⁇ thousand 2), lithium nickelate (1 - ⁇ 1 ⁇ 1 1 ⁇ 2), lithium manganese spinel (1 - ⁇ IV n 2 ⁇ 4), the general formula:! 1_ ⁇ 1 ⁇ 1 ⁇ ⁇ ⁇ 1 ⁇ /1 ⁇ 2 ⁇ 2 (X + V + 2 1 % 0 £ X £ 1 % 0 £ V £ 1 X 0 £ ⁇ £ 1) Lithium, a mixed metal oxide Vanadium compound (!_ ⁇ 2 0 5 ), olivine Tada Hachijo, “One or more elements selected from”, Lithium vanadium phosphate
  • the positive electrode current collector 1 and the negative electrode current collector 2 may include a positive electrode active material and a negative electrode active material, respectively.
  • the content ratio of the active material contained in each current collector is ⁇ 2020/175 639 9 (: 171-1? 2020 /008067
  • the volume ratio of the positive electrode current collector/positive electrode active material or the negative electrode current collector/negative electrode active material is preferably in the range of 90/10 to 60/40.
  • the positive electrode current collector 1 and the negative electrode current collector 2 include the positive electrode active material and the negative electrode active material, respectively, the positive electrode current collector 18 and the positive electrode active material layer 1 and the negative electrode current collector 28 and the negative electrode are formed. Adhesion with the active material layer 2 is improved.
  • solid electrolyte layer 3 has interlayer solid electrolyte layer 38 located between positive electrode active material layer 1 and negative electrode active material layer 2.
  • the solid electrolyte layer 3 is the outermost solid located outside either or both of the positive electrode layer 1 (positive electrode current collector 18) and the negative electrode layer 2 (negative electrode current collector 28) (both in FIG. 1).
  • the electrolyte layer 3 may be further provided.
  • the “outside” means a laminated body.
  • the solid electrolyte layer 3 may not have the outermost solid electrolyte layer 3, and in this case, the surfaces 58 and 5 of the laminate 20 are the positive electrode layer 1 or the negative electrode layer 2.
  • the solid electrolyte layer 3 it is preferable to use a substance having low electron conductivity and high lithium ion conductivity.
  • the solid electrolyte is, for example, ⁇ . 5 1_ ⁇ . Berobusukai preparative compounds such as 5 chome I ⁇ 3 and, 1_ ⁇ l4 Z n (060 4) 4 Rishi Con type compounds such as, G-type compound, 1_ ⁇ “ 2
  • I ⁇ 2 glass compounds such as 1-1 3 ⁇ 4 and 1_ I 3. 5 3 I_ ⁇ . 5 ⁇ . 5 ⁇ 4 and 1_ 1 2.9 ⁇ 3. 3 1 ⁇ 1 ⁇ .
  • Phosphorus, such as 46 Desirably it is at least a species selected from the group consisting of acid compounds.
  • the solid electrolyte layer 3 is preferably selected according to the active materials used for the positive electrode layer 1 and the negative electrode layer 2.
  • the solid electrolyte layer 3 is a component of the active material. ⁇ 2020/175 630 10 ⁇ (:171? 2020 /008067
  • the solid electrolyte layer 3 contains the same elements as the constituent elements of the active material, the bonding at the interface between the positive electrode active material layer 1 and the negative electrode active material layer 2 and the solid electrolyte layer 3 is strong. become. Further, the contact area at the interface between the positive electrode active material layer 1 and the negative electrode active material layer 2 and the solid electrolyte layer 3 can be widened.
  • the thickness of the inter-layer solid electrolyte layer 38 is preferably in the range of not less than 0.5 and not more than 20.
  • the thickness of the inter-layer solid electrolyte layer 38 is preferably in the range of not less than 0.5 and not more than 20.
  • the thickness of the outermost solid electrolyte layer 3 is not particularly limited, but, for example, as a guide, it is preferably 20 or more and 100 or less.
  • the thickness is 20 111 or more, the positive electrode layer 1 or the negative electrode layer 2 which is closest to the surfaces 58 and 5 of the laminate 20 is less likely to be oxidized due to the influence of the atmosphere in the firing process and has a high capacity. It becomes an all-solid-state lithium-ion secondary battery.
  • the thickness is 100 or less, the all-solid-state lithium-ion secondary battery will have sufficient moisture resistance even under the environment of high temperature and high humidity, high reliability, and high volume energy density.
  • the laminate 20 may include a solid electrolyte and may include a margin layer 4 arranged side by side with each of the positive electrode layer 1 and the negative electrode layer 2.
  • the margin layer 4 is preferably provided to eliminate the step between the inter-layer solid electrolyte layer 38 and the positive electrode layer 1, and the step between the inter-layer solid electrolyte layer 38 and the negative electrode layer 2. Therefore, the margin layer 4 has substantially the same height as the positive electrode layer 1 or the negative electrode layer 2 in the area other than the positive electrode layer 1 and the negative electrode layer 2 on the main surface of the solid electrolyte layer 3 (that is, the positive electrode layer 1 and the negative electrode layer 2). 2) to be placed side by side on each. Due to the presence of margin layer 4, solid electrolyte layer 3 and positive electrode layer 1 ⁇ 2020/175 630 1 1 ⁇ (:171? 2020 /008067
  • the solid electrolyte layer 3 and each electrode layer are highly dense, and delamination or warpage occurs due to firing of the all-solid-state battery. It gets harder.
  • the material forming the margin layer 4 is not particularly limited, but it is preferable to include a material having a heat shrinkage behavior similar to that of the solid electrolyte 3 in the firing step described later.
  • the margin layer 4 is also lithium aluminum lithium phosphate 1_ 1 1 +. ⁇ I ,7 I 2 _ ,( ⁇ 4 ) 3 (0 £ father £ 0 ⁇
  • the margin layer 4 may include a material other than the solid electrolyte, and as the material forming the margin layer 4, for example, the active material material forming the positive electrode active material 1 or the negative electrode active material layer 2 can be used. Glass material is effective in binding improvement (Snake ⁇ 2 0 3. 3 I ⁇ 2, including etc. Snake 2 ⁇ 3, Z N_ ⁇ ) and the like, such as.
  • the first external terminal 6 and the second external terminal 7 of the all-solid-state lithium ion secondary battery 100 it is preferable to use a material having high conductivity.
  • a material having high conductivity For example, silver (eight 9), gold (Hachiri), platinum (1 :), aluminum (eight ⁇ ), copper ( ⁇ Li), tin (3 n), nickel (1 ⁇ 1 ⁇ ), chromium (O O
  • the terminal may be a single layer or multiple layers.
  • the all-solid-state lithium-ion secondary battery 100 may have a protective layer (not shown) for electrically, physically and chemically protecting the laminated body 20 and terminals on the outer periphery of the laminated body 20. ..
  • the material forming the protective layer is preferably excellent in insulating property, durability, moisture resistance and environmentally safe. For example, it is preferable to use glass, ceramics, thermosetting resin, or photocurable resin.
  • the material of the protective layer may be only one kind or a combination of plural kinds.
  • the protective layer may be a single layer ⁇ 2020/175 630 12 boxes (:171? 2020 /008067
  • an organic-inorganic hybrid obtained by mixing a thermosetting resin and a ceramic powder is particularly preferable.
  • the all-solid-state lithium-ion secondary battery 100 may be manufactured by the simultaneous firing method or the sequential firing method.
  • the co-firing method is a method in which the materials forming the respective layers are laminated, and a laminated body is produced by simultaneous firing.
  • the sequential firing method is a method of sequentially producing each layer, and a firing step is performed each time each layer is produced.
  • the simultaneous baking method can reduce the work steps of the all-solid-state lithium-ion secondary battery 100. Further, when the co-firing method is used, the obtained laminated body 20 becomes denser.
  • the simultaneous firing method will be described as an example.
  • the co-firing method includes a step of forming a paste of each material constituting the laminated body 20, a step of applying a paste and drying the paste to produce a green sheet, and a step of laminating a green sheet And simultaneously firing the body.
  • the positive electrode current collector 18 constituting the laminate 20, the positive electrode active material layer 1 m, the solid electrolyte layer 3, the negative electrode active material layer 2 m, the negative electrode current collector 28, and the margin layer 4 Paste each material of.
  • the second element constituting the sub-parts 1 and 2 is the active material after firing.
  • the layer diffuses into the solid electrolyte layer and remains on the current collector, so that it cannot form a bias.
  • a current collector element powder with a large amount of segregating element for example, first, prepare a current collector element powder with a large amount of segregating element (thick coating), ⁇ 2020/175 630 13 ⁇ (:171? 2020/008067
  • the coated current collector element powder and the uncoated current collector element powder are mixed, and the coated current collector element powder and the uncoated current collector element powder are mixed depending on the size and amount of the sub-part.
  • a method of changing the ratio of the body element powder can be used.
  • the pasting method is not particularly limited.
  • a paste is obtained by mixing powder of each material with a vehicle.
  • the vehicle is a generic term for media in the liquid phase.
  • the vehicle includes a solvent and a binder.
  • the green sheet is obtained by applying the prepared paste onto a base material such as a knife (polyethylene terephthalate) in a desired order, drying it if necessary, and then peeling the base material.
  • a base material such as a knife (polyethylene terephthalate)
  • the method of applying the paste is not particularly limited. For example, known methods such as screen printing, coating, transfer, doctor blade, etc. can be used.
  • the positive electrode unit and the negative electrode unit described below can be prepared to produce the laminate.
  • a paste for solid electrolyte layer 3 is formed into a sheet shape on a knife film by a doctor blade method, and dried to form a solid electrolyte layer sheet.
  • a paste for a positive electrode active material layer 1 is printed by screen printing and dried to form a positive electrode active material layer 1.
  • the produced positive electrode active material layer 1 bottom is printed with a screen for a positive electrode current collector 18 by screen printing and dried to form a positive electrode current collector 18. Furthermore, a paste for the positive electrode active material layer 1 is printed again on the screen by screen printing and dried. Then, in the region of the solid electrolyte layer sheet other than the positive electrode layer 1, the margin layer 4 is screen-printed and dried to form the margin layer 4 having a height substantially equal to that of the positive electrode layer 1. Then, by peeling off the knife film, the positive electrode active material layer 1/positive electrode current collector 18/positive electrode active material layer is formed on the main surface of the solid electrolyte layer 3. ⁇ 2020/175 630 14 ⁇ (:171? 2020 /008067
  • a positive electrode unit is obtained in which the positive electrode layer 1 and the margin layer 4 in which the first layer is laminated in this order are formed.
  • the positive electrode unit and the negative electrode unit are alternately stacked and stacked so that one ends thereof do not coincide with each other, and a stacked body of an all-solid-state battery is manufactured.
  • the solid electrolyte layer 3 uses the outermost solid electrolyte layer 3 and the positive electrode unit or the negative electrode unit placed between them.
  • the solid electrolyte layer 3 uses the inter-layer solid electrolyte layer 38, respectively.
  • the manufacturing method is to manufacture a parallel type all-solid-state battery
  • the manufacturing method of the series-type all-solid-state battery is such that one end of the positive electrode layer 1 and one end of the negative electrode layer 2 are aligned. In other words, stacking may be performed without performing offset.
  • the produced laminates can be collectively pressed with a die press, a hot water isotropic press ⁇ ), a cold water isotropic press ( ⁇ I), a hydrostatic press, etc. to improve the adhesion. .. It is preferable to apply pressure while heating, and for example, it can be performed at 40 to 95°.
  • the produced laminated body is cut into chips using a dicing device, and then de-baked and fired to produce an all-solid-state battery laminated body.
  • the manufactured laminated body 20 is placed on a ceramic table, and, for example, in a nitrogen atmosphere.
  • a sintered body is obtained by heating to 600° to 1000° and firing.
  • the firing time is, for example, 0.1 to 3 hours. If it is a reducing atmosphere, firing may be performed in an argon atmosphere or a nitrogen-hydrogen mixed atmosphere instead of the nitrogen atmosphere.
  • a binder removal treatment can be performed as a step different from the firing step.
  • the debinding treatment is performed, for example, in a nitrogen atmosphere at a temperature in the range of 300° to 800°° for 0.1 to 10 hours. If it is a reducing atmosphere, the firing may be performed in an argon atmosphere or a nitrogen-hydrogen mixed atmosphere instead of the nitrogen atmosphere.
  • the sintered body may be placed in a cylindrical container together with an abrasive such as alumina and barrel-polished.
  • sandblast may be used for polishing. This method is preferable because only a specific portion can be removed.
  • the first external terminal 6 and the second external terminal 7 are formed so as to be in electrical contact with the positive electrode current collector 1 and the negative electrode current collector 28, respectively.
  • the positive electrode current collector 18 and the negative electrode current collector 28 exposed from the side surface of the sintered body can be formed by a known means such as a slaughter method, a diving method, or a spray coating method.
  • This paste for solid electrolyte layer was formed into a sheet by a doctor blade method using a knife film as a base material to obtain an outermost solid electrolyte layer sheet and an interlayer solid electrolyte layer sheet.
  • the outermost solid electrolyte layer sheet and the interlayer solid electrolyte layer sheet each had a thickness of 15.
  • the positive electrode active material layer paste and the negative electrode active material layer paste for a the active material 1- 1 3 2 ( ⁇ 4) 3 powder 1 0 0 parts ethylcellulose as a binder - a scan 1 5 parts solvent 6 parts by weight of dihydroterpineol was added and mixed-dispersed to prepare a positive electrode active material layer paste and a negative electrode active material layer paste.
  • V resinate which is a coating agent
  • ⁇ powder was added, followed by thorough stirring. This mixed solution was dried to remove volatile components, and further heat-treated at 200° ⁇ to obtain ⁇ powder having V coated on the surface of ⁇ powder. ⁇ The amount of V coating the surface of the powder is
  • ⁇ It was set to be 0.0001 parts by weight in terms of metal with respect to 100 parts by weight.
  • the coating powder obtained in this way and !_ ⁇ 3 ⁇ 2 ( ⁇ 4 ) 3 powder were mixed in a volume ratio of 60:40, and then 100 parts by weight of this mixed powder.
  • 10 parts by weight of ethyl cellulose as a binder and 50 parts by weight of dihydroterpineol as a solvent were added, and the mixture was kneaded and dispersed in a three-necked mixture to prepare a current collector paste.
  • a positive electrode unit and a negative electrode unit were produced as follows.
  • a screen for active material was printed with a thickness of 5 by screen printing.
  • the printed paste for active material was dried at 80 ° ⁇ for 5 minutes, and the paste for current collector was printed thereon with a thickness of 5 by screen printing.
  • the printed current collector paste was dried at 80 ° for 5 minutes, and the active material paste was again printed thereon with a thickness of 5 by screen printing.
  • the printed active material paste was dried at 80 ° for 5 minutes, and then a margin layer paste was screen-printed on the area of the solid electrolyte sheet other than the electrode layer.
  • the printed margin layer paste was dried at 80 ° for 5 minutes to form a margin layer having almost the same height as the electrode layer, and then the Mending film was peeled off.
  • an electrode in which an electrode layer (a positive electrode layer or a negative electrode layer) in which an active material layer/a current collector/an active material layer are stacked in this order and a margin layer are formed on a solid electrolyte layer sheet are formed.
  • a positive electrode layer or a negative electrode layer in which an active material layer/a current collector/an active material layer are stacked in this order and a margin layer are formed on a solid electrolyte layer sheet are formed.
  • the laminated chips were simultaneously fired to obtain a laminated body 20.
  • the co-firing is carried out in a nitrogen atmosphere rather than in an air atmosphere so that the current collector metal is less than 3 and the active material !_ ⁇ 3 2 (90 4 ) 3 is not oxidized or decomposed.
  • the firing temperature was raised to 840 °C at ⁇ /hour, the temperature was maintained for 2 hours, and after cooling, it was naturally cooled.
  • a first external terminal and a second external terminal were attached to the sintered laminated body (sintered body) to fabricate an all solid state secondary battery.
  • the lead wire is attached to each of the first external terminal and the second external terminal, and the charge/discharge test is performed to measure the initial discharge capacity of the all-solid-state secondary battery and the cycle characteristics (capacity retention rate) after 100 cycles. did.
  • the measurement conditions were 20 for both the current during charging and discharging, and 1.6 V and 0 V for the final voltages during charging and discharging, respectively.
  • the results are shown in Table 1.
  • the capacity at the first discharge was defined as the initial discharge capacity.
  • the cycle characteristics (capacity retention rate) were calculated by dividing the discharge capacity at the 100th cycle by the initial discharge capacity.
  • the base material for the current collector was manufactured as follows.
  • An all-solid secondary battery was produced in the same manner as in Example 1 except that the production of the current collector base was performed as described above.
  • Table 1 shows the cycle characteristics (capacity retention rate) obtained using the all-solid-state secondary battery thus manufactured.
  • Example 1 in which the current collector had a sub portion, the cycle characteristics were significantly improved as compared with Comparative Example 1 in which the current collector had no sub portion.
  • Basts for current collectors were produced in the same manner as in Example 1 except that 9, 8, and I resinates were used. Further, an all-solid secondary battery was produced in the same manner as in Example 1 by using this current collector paste.
  • Table 2 shows the cycle characteristics (capacity retention rate) obtained using each all-solid-state secondary battery prepared in this way.
  • Example 2 V resin and a resin resinate were used as the coating agent, and the amount of V and powder coated on the surface of the powder was adjusted to 3 (100 parts by weight).
  • a current collector base was prepared in the same manner as in Example 1 except that the total metal content was adjusted to 0.0001 parts by weight. Then, in the same manner as in Example 1, an all-solid-state secondary battery ⁇ 2020/175 630 20 boxes (: 171-1?2020/008067
  • the secondary parts of the positive electrode current collector and the negative electrode current collector in the laminated body were analyzed by a 3-cylinder 1 ⁇ /1 (scanning transmission electron microscope), and the secondary parts were It has been confirmed that it includes the following.
  • Table 2 shows the cycle characteristics (capacity retention rate) obtained using the all-solid-state secondary battery manufactured in this way.
  • V resinate and IV! n resinate were used as the coating agent, and the amount of V and IV! coated on the surface of the powder was 3 (100 parts by weight).
  • a current collector paste was produced in the same manner as in Example 1 except that the total amount was 0.001 parts by weight in terms of metal. Then, an all-solid-state secondary battery was manufactured in the same manner as in Example 1. Regarding the sub-portions of the positive electrode current collector and the negative electrode current collector in the laminated body (sintered body), 3 pcs. 0 3 Analysis was performed and it was confirmed that the sub-part contained V and IV! n.
  • Table 2 shows the cycle characteristics (capacity retention rate) obtained using the all-solid-state secondary battery manufactured in this way.
  • each sub-portion is formed of two kinds of elements, V and T, whereas in Example 2-17, a sub-portion consisting of V in the current collector is used. This is an example in which sub-parts made up of gadgets are scattered, dispersed, or mixed.
  • V coating ⁇ powder uses V resinate as a resinate, and the amount of V coated on the surface of powder powder is 3 (100 parts by weight relative to 3 parts by weight).
  • the coating powder was prepared so that the amount of the coating powder was 1 part by weight, and the coating resin was a resinate, which was a resinate. It was prepared so that it would be 0.0001 parts by weight in terms of metal with respect to 100 parts by weight. ⁇ 2020/175 630 21 ⁇ (: 171-1? 2020 /008067
  • Parts and parts coating 0 powder 50 parts by weight are weighed and mixed ⁇ 3 powder! -After mixing with 3 2 ( ⁇ 4 ) 3 powder in a volume ratio of 60: 40, 100 parts by weight of this mixed powder was mixed with 10 parts by weight of ethyl cellulose as a binder. Then, 50 parts by weight of dihydroterpineol was added as a solvent, and the mixture was kneaded and dispersed in a three-necked mixture to prepare a current collector paste. Further, an all-solid-state secondary battery was manufactured in the same manner as in Example 1 using this current collector base material.
  • Table 2 shows the cycle characteristics (capacity retention rate) obtained using the all-solid-state secondary battery manufactured in this way.
  • each sub-portion is formed by two elements of V and 1 ⁇ /1 n , whereas in Example 2-18, V is contained in the current collector.
  • sub-parts and sub-parts consisting of IV! n are scattered, dispersed, or mixed.
  • V coating ⁇ powder uses V resinate as a resinate, and the amount of V coated on the surface of powder powder is 3 (100 parts by weight relative to 3 parts by weight). It was prepared so that the amount would be 1 part by weight IV!n coating ⁇ powder was used as the coating agent resinate. Using resinate, it was prepared so that the amount of IV! coated on the surface of the powder was (0.01 parts by weight in terms of metal with respect to 100 parts by weight of V. V! coating) 50 parts by weight of the re-powder and 50 parts by weight of the IV!
  • An all-solid secondary battery was prepared in the same manner as in Example 1 using the body paste.
  • _ 3 analysis of the sub-portions of the positive electrode current collector and the negative electrode current collector in the laminate (sintered body) was performed, and the sub-portion consisting of V and the sub-portion consisting of IV! It was confirmed that they were scattered or dispersed or mixed.
  • Table 2 shows the cycle characteristics (capacity retention rate) obtained using the all-solid-state secondary battery manufactured in this way.
  • V and IV! n mixed with V and G, and mixed V and IV! n have high cycle characteristics of 90% or more.
  • the secondary element is Mn, 1 ⁇ 1 and V and D! In the case of V and IV! n, it was found that the cycle characteristics were particularly high at 92% or more.
  • Example 3 _ 1 to Example 3 _ 10 the amount of V coated on the surface of powder was 0.0002, 0. 01, 0. 1 in terms of metal with respect to 100 parts by weight of 0. , 0.4, 0.8, 1, 5, 10, 10, 15 and 20 parts by weight were prepared in the same manner as in Example 1 to prepare a base current collector. Further, an all-solid secondary battery was manufactured in the same manner as in Example 1 by using this current collector paste.
  • Table 3 shows the cycle characteristics (capacity retention rate) obtained using each all-solid-state secondary battery.
  • the cycle characteristic is 92%, and the weight ratio of the secondary part is 0.001%. It was found that the cycle characteristics were high when the weight ratio of the above was 0.002% or more and 20% or less, especially when it was 0.001% or more and 0.01% or less. It was found that when the weight ratio of the auxiliary part is 15% or less, the cycle characteristics are as high as 75% or more, and when the weight ratio of the auxiliary part is 1% or less, the cycle characteristics are as high as 80% or more.
  • the circle area conversion diameter of the sub-part can be adjusted by adjusting the amount of the sub-part element (second element) coated on the powder surface.
  • the amount of V coated on the surface of the powder was (1% by weight in terms of metal, based on 3 parts by 100 parts by weight, in the same manner as in Example 1). I obtained the powder coated with V on the surface of /.
  • Table 4 shows the cycle characteristics (capacity retention rate) obtained using the fabricated all-solid-state secondary battery.
  • Example 4 — 1 uncoated ⁇ 2020/175 630 25 ⁇ (:171? 2020 /008067
  • Table 4 shows the cycle characteristics (capacity maintenance rate) obtained using each of the fabricated all-solid-state secondary batteries.
  • Example 4_2 to 4_6 the positive electrode current collector and the negative electrode current collector each in the sintered laminate (sintered body) were processed in the same manner as in Example 1. Then, we obtained 3M 1 ⁇ /1 images of each cross section and calculated the circle-area conversion diameter of each sub-part image. The maximum circle-area conversion diameter of each sub-part image was 0. 05 (50 nm), ⁇ . (
  • Example 5_1 to Example 5-6 ⁇ 2020/175 630 26 ⁇ (:171? 2020 /008067
  • Example 5 _ 1 to Example 5 _ 6 are the same as Example 1 except that the current collector metal (the main part of the current collector) was 1 ⁇ 1 and was 6, 8, 9 , 8 and 1, respectively.
  • a current collector base was prepared.
  • an all-solid secondary battery was manufactured in the same manner as in Example 1 using this current collector paste.
  • Table 5 shows the cycle characteristics (capacity retention rate) obtained using the fabricated all-solid-state secondary battery.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

Batterie secondaire à semi-conducteurs (100) possédant une couche d'électrode positive (1) comprenant un collecteur de courant d'électrode positive (1A) et une couche de matériau actif d'électrode positive (1B), une couche d'électrode négative (2) comprenant un collecteur de courant d'électrode négative (2A) et une couche de matériau actif d'électrode négative (2B), et une couche d'électrolyte solide (3) contenant un électrolyte solide, un stratifié (20) étant formé par la stratification en alternance de la couche d'électrode positive (1) et de la couche d'électrode négative (2) avec la couche d'électrolyte solide (3) entre celles-ci, et le collecteur de courant d'électrode positive (1A) et le collecteur de courant d'électrode négative (2A) étant chacun formés d'une partie principale (1Aa, 2Aa) comprenant un premier élément en tant que composant principal, et d'une sous-partie (1Ab, 2Ab) comprenant un second élément qui est un élément différent du premier élément.
PCT/JP2020/008067 2019-02-27 2020-02-27 Batterie secondaire à semi-conducteurs Ceased WO2020175630A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-034332 2019-02-27
JP2019034332 2019-02-27

Publications (1)

Publication Number Publication Date
WO2020175630A1 true WO2020175630A1 (fr) 2020-09-03

Family

ID=72239695

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/008067 Ceased WO2020175630A1 (fr) 2019-02-27 2020-02-27 Batterie secondaire à semi-conducteurs

Country Status (1)

Country Link
WO (1) WO2020175630A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014156638A1 (fr) * 2013-03-26 2014-10-02 古河電気工業株式会社 Accumulateur entièrement solide
JP2015220110A (ja) * 2014-05-19 2015-12-07 Tdk株式会社 蓄電装置
WO2018181576A1 (fr) * 2017-03-30 2018-10-04 Tdk株式会社 Batterie totalement solide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014156638A1 (fr) * 2013-03-26 2014-10-02 古河電気工業株式会社 Accumulateur entièrement solide
JP2015220110A (ja) * 2014-05-19 2015-12-07 Tdk株式会社 蓄電装置
WO2018181576A1 (fr) * 2017-03-30 2018-10-04 Tdk株式会社 Batterie totalement solide

Similar Documents

Publication Publication Date Title
JP4728385B2 (ja) リチウムイオン二次電池、及び、その製造方法
JP6927289B2 (ja) 全固体二次電池
KR101757017B1 (ko) 리튬 이온 이차 전지 및 그 제조 방법
JP6651708B2 (ja) リチウムイオン二次電池
JP6492958B2 (ja) 固体電池及びそれを用いた組電池。
US12080847B2 (en) All-solid-state battery
JP6992803B2 (ja) 全固体リチウムイオン二次電池
US12002925B2 (en) Solid-state secondary battery
CN101663788A (zh) 锂离子二次电池以及其制造方法
US11532812B2 (en) All-solid lithium ion secondary battery
JP6623542B2 (ja) リチウムイオン二次電池
JP2016001595A (ja) リチウムイオン二次電池
US10854917B2 (en) All solid-state lithium ion secondary battery
US11349146B2 (en) All-solid lithium ion secondary battery
JP6992802B2 (ja) 全固体リチウムイオン二次電池
JP2021027044A (ja) 全固体電池
WO2018181575A1 (fr) Batterie rechargeable lithium-ion tout solide
CN113169372B (zh) 全固体二次电池
CN114616697B (zh) 全固体电池
JPWO2018181545A1 (ja) 全固体リチウムイオン二次電池
JP7509748B2 (ja) 全固体二次電池
JP6777181B2 (ja) リチウムイオン二次電池
WO2020175630A1 (fr) Batterie secondaire à semi-conducteurs
WO2023188470A1 (fr) Batterie secondaire entièrement solide
CN114982031A (zh) 层叠型全固体电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20762201

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20762201

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP