WO2018181545A1 - Accumulateur lithium-ion totalement solide - Google Patents
Accumulateur lithium-ion totalement solide Download PDFInfo
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- WO2018181545A1 WO2018181545A1 PCT/JP2018/012921 JP2018012921W WO2018181545A1 WO 2018181545 A1 WO2018181545 A1 WO 2018181545A1 JP 2018012921 W JP2018012921 W JP 2018012921W WO 2018181545 A1 WO2018181545 A1 WO 2018181545A1
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- positive electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000011521 glass Substances 0.000 claims abstract description 189
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims description 25
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 239000010410 layer Substances 0.000 description 329
- 239000000463 material Substances 0.000 description 57
- 239000007774 positive electrode material Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 35
- 239000007773 negative electrode material Substances 0.000 description 35
- 239000002002 slurry Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011149 active material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 La 0.5 Li 0.5 TiO 3 Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010344 co-firing Methods 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 240000002329 Inga feuillei Species 0.000 description 1
- 229910018869 La0.5Li0.5TiO3 Inorganic materials 0.000 description 1
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 1
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 description 1
- 229910010500 Li2.9PO3.3N0.46 Inorganic materials 0.000 description 1
- 229910008918 Li2O—V2O5—SiO2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002223 garnet Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
-
- 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 lithium ion secondary battery. This application claims priority on March 29, 2017 based on Japanese Patent Application No. 2017-64399 filed in Japan, the contents of which are incorporated herein by reference.
- an all-solid-state lithium ion secondary battery for example, LiCoO 2 , LiMn 2 O 2 , LiFePO 4 , LiNiO 2 or the like is used as an active material. These active materials are likely to react with moisture. For this reason, in the conventional all-solid-state lithium ion secondary battery, the active material may react with moisture in the air to deteriorate the active material, resulting in a decrease in battery capacity.
- Patent Document 1 describes that the surface of a thin-film solid secondary battery is covered with a moisture prevention film.
- Patent Document 1 discloses that silicon oxide (SiO 2 ) or silicon nitride (SiN x ) is used as a moisture prevention film.
- Patent Document 2 describes that an all solid lithium ion secondary battery is coated with a resin.
- Patent Document 2 discloses that an all-solid lithium ion secondary battery is sealed with a glass layer.
- the conventional technology cannot sufficiently prevent moisture from entering the all-solid-state lithium ion secondary battery. For this reason, it has been required to more effectively prevent a decrease in battery capacity due to moisture intrusion into the all-solid-state lithium ion secondary battery.
- This invention is made
- the present inventor has made extensive studies.
- the first glass layer is provided with a low-melting glass material in contact with the laminate having the positive electrode layer, the negative electrode layer, and the solid electrolyte, and then the first glass layer has a higher melting point than the first glass layer.
- the second glass layer may be provided with a glass material. And it confirmed that the fall of the battery capacity resulting from the penetration
- An all-solid-state lithium ion secondary battery is in contact with the laminate including a positive electrode layer, a negative electrode layer, and a solid electrolyte sandwiched between the positive electrode layer and the negative electrode layer.
- a moisture-proof layer provided, and the moisture-proof layer comprises a first glass layer provided in contact with the laminate and a second glass layer provided on the first glass layer, The melting point of one glass layer is lower than the melting point of the second glass layer.
- the melting point of the first glass layer may be 465 to 565 ° C.
- the melting point of the second glass layer may be 550 to 730 ° C.
- the most contained component among the components contained in the first glass layer is selected from the group consisting of Bi 2 O 3 , V 2 O 5 , and B 2 O 3. It may be one kind.
- the most contained component among the components contained in the first glass layer may be Bi 2 O 3 .
- the first glass layer may contain 30 to 70% by weight of Bi 2 O 3 .
- the most contained component among the components contained in the second glass layer may be SiO 2 .
- the second glass layer may contain 20 to 70% by weight of SiO 2 .
- the positive electrode layer, the negative electrode layer, and the solid electrolyte sandwiched between the positive electrode layer and the negative electrode layer may have a relative density of 80% or more. Good.
- the all-solid-state lithium ion secondary battery according to one embodiment of the present invention is less likely to cause a reduction in battery capacity due to moisture intrusion, and has excellent reliability.
- FIG. 2 is an enlarged schematic cross-sectional view illustrating a part of FIG. 1 in an enlarged manner.
- 2 is a scanning electron microscope (SEM) photograph of the all solid state battery of Example 1.
- SEM scanning electron microscope
- the present inventor has obtained the following knowledge. That is, in order to form a glass layer having high moisture resistance on the surface of the laminate having the positive electrode layer, the negative electrode layer, and the solid electrolyte, a glass layer was formed using a glass material having a high melting point. In this case, sufficient adhesion between the glass layer and the laminate was not obtained, and moisture could not be sufficiently prevented from entering the laminate.
- a glass layer was formed using a method in which a slurry containing a glass material having a low melting point was applied to the surface of the laminate and the glass material was melted and fixed by heat treatment.
- the molten glass material that has entered the irregularities on the surface of the laminate works like a wedge (anchor effect) with respect to the laminate after curing (good effect between the glass layer and the laminate). Adhesion was obtained.
- the moisture resistance of the glass layer itself is insufficient, it was not possible to sufficiently prevent moisture from entering the laminate.
- the present inventor has focused on the melting point of the glass material to make the glass layer a two-layer structure, and formed the first glass layer in contact with the laminated body with a low melting point glass material with an emphasis on adhesion to the laminated body. did. And on the outer side of the first glass layer, a second glass layer made of a high-melting glass material, which has good adhesion to the first glass layer by intermixing at the time of manufacture and has high moisture resistance, was formed. . As a result, the inventors have found that a high effect of preventing the intrusion of moisture into the laminate can be obtained, and have arrived at the present invention.
- FIG. 1 is an enlarged schematic cross-sectional view of an all-solid-state lithium ion secondary battery according to the first embodiment.
- An all-solid-state lithium ion secondary battery (hereinafter sometimes abbreviated as “all-solid-state battery”) 10 shown in FIG. 1 includes a laminate 4, a first external terminal 5, a second external terminal 6, and a moisture proof. Layer 20.
- FIG. 2 is an enlarged schematic cross-sectional view showing a part of FIG. 1 in an enlarged manner.
- the laminate 4 is sandwiched between one or more first electrode layers 1, one or more second electrode layers 2, and the first electrode layer 1 and the second electrode layer 2. And a solid electrolyte 3.
- Each first electrode layer 1 is connected to a first external terminal 5.
- Each second electrode layer 2 is connected to a second external terminal 6.
- One of the first electrode layer 1 and the second electrode layer 2 functions as a positive electrode layer, and the other functions as a negative electrode layer.
- the polarity of the electrode layer varies depending on which polarity is connected to the external terminal.
- the first electrode layer 1 is referred to as a positive electrode layer 1
- the second electrode layer 2 is referred to as a negative electrode layer 2.
- the positive electrode layers 1 and the negative electrode layers 2 are alternately stacked via the solid electrolyte 3.
- the charging / discharging of the all-solid battery 10 is performed by the transfer of lithium ions between the positive electrode layer 1 and the negative electrode layer 2 through the solid electrolyte 3.
- the positive electrode layer 1 includes a positive electrode current collector layer 1A and a positive electrode active material layer 1B containing a positive electrode active material.
- the negative electrode layer 2 includes a negative electrode current collector layer 2A and a negative electrode active material layer 2B containing a negative electrode active material.
- the positive electrode current collector layer 1A and the negative electrode current collector layer 2A preferably have high electrical conductivity. Therefore, it is preferable to use, for example, silver, palladium, gold, platinum, aluminum, copper, nickel or the like for the positive electrode current collector layer 1A and the negative electrode current collector layer 2A.
- silver, palladium, gold, platinum, aluminum, copper, nickel or the like for the positive electrode current collector layer 1A and the negative electrode current collector layer 2A.
- copper hardly reacts with the positive electrode active material, the negative electrode active material, and the solid electrolyte. Therefore, when copper is used for the positive electrode current collector layer 1A and the negative electrode current collector layer 2A, the internal resistance of the all-solid battery 10 can be reduced.
- the materials constituting the positive electrode current collector layer 1A and the negative electrode current collector layer 2A may be the same or different.
- the positive electrode current collector layer 1A and the negative electrode current collector layer 2A may include a positive electrode active material and a negative electrode active material, respectively.
- the content ratio of the active material contained in each of the current collector layers 1A and 2A is not particularly limited as long as it functions as a current collector.
- the content ratio of the active material in each of the current collector layers 1A and 2A is preferably, for example, 10 to 30% by volume ratio.
- the adhesion between the positive electrode current collector layer 1A and the positive electrode active material layer 1B is improved. Further, when the negative electrode current collector layer 2A contains the negative electrode active material, the adhesion between the negative electrode current collector layer 2A and the negative electrode active material layer 2B is improved.
- the positive electrode active material layer 1B is formed on one side or both sides of the positive electrode current collector layer 1A.
- the positive electrode active material layer 1B is formed on one side or both sides of the positive electrode current collector layer 1A.
- the positive electrode active material layer 1B is formed on one or both surfaces of the negative electrode current collector layer 2A.
- the negative electrode active material layer 2B in the negative electrode layer 2 positioned in the lowermost layer is It only needs to be on one side.
- the positive electrode active material layer 1B includes a positive electrode active material that exchanges electrons, and may include a conductive additive and / or a binder.
- the negative electrode active material layer 2B includes a negative electrode active material that exchanges electrons, and may include a conductive additive and / or a binder. It is preferable that the positive electrode active material and the negative electrode active material can efficiently insert and desorb lithium ions.
- a transition metal oxide or a transition metal composite oxide is preferably used.
- Li 1 + n Al n Ti 2-n (PO 4 ) 3 (0 ⁇ n ⁇ 0.6) is used for the solid electrolyte 3
- LiVOPO 4 and Li 3 V 2 (PO 4 ) It is preferable to use one or both of 3 . Bonding at the interface between the positive electrode active material layer 1B and the negative electrode active material layer 2B and the solid electrolyte 3 becomes strong.
- the active materials constituting the positive electrode active material layer 1B or the negative electrode active material layer 2B there is no clear distinction between the active materials constituting the positive electrode active material layer 1B or the negative electrode active material layer 2B. By comparing the potentials of two kinds of compounds, a compound showing a more noble potential can be used as the positive electrode active material, and a compound showing a lower potential can be used as the negative electrode active material.
- Solid electrolyte 3 is preferably a phosphate solid electrolyte.
- the solid electrolyte 3 it is preferable to use a material having low electron conductivity and high lithium ion conductivity.
- perovskite type compounds such as La 0.5 Li 0.5 TiO 3
- riccon type compounds such as Li 14 Zn (GeO 4 ) 4
- garnet type compounds such as Li 7 La 3 Zr 2 O 12 NASICON type compounds such as Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 and Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , Li 3.25 Ge 0.25 2.
- Thiolisicon type compounds such as P 0.75 S 4 and Li 3 PS 4 , glass compounds such as Li 2 S—P 2 S 5 and Li 2 O—V 2 O 5 —SiO 2 , Li 3 PO 4 and Li 3. It is desirable to be at least one selected from the group consisting of phosphoric acid compounds such as 5 Si 0.5 P 0.5 O 4 and Li 2.9 PO 3.3 N 0.46 .
- the all-solid-state battery 10 includes a moisture-proof layer 20 that is provided in contact with the laminate 4 and prevents moisture from entering the laminate 4.
- the moisture-proof layer 20 is provided so as to cover all the areas of the surface of the multilayer body 4 that are not covered by the first external terminal 5 and the second external terminal 6.
- the moisture-proof layer 20 is provided so as to cover the outer surfaces of the first external terminal 5 and the second external terminal 6 within a range that does not hinder the electrical connection between the first external terminal 5 and the second external terminal 6 and the outside. It may be done.
- the moisture-proof layer 20 is composed of a first glass layer 21 and a second glass layer 22 as shown in FIG.
- the first glass layer 21 is provided in contact with the laminate 4.
- the second glass layer 22 is provided on the first glass layer 21.
- an intermediate composition between the composition of the first glass layer 21 and the composition of the second glass layer 22 is obtained by intermixing at the time of manufacturing the second glass layer 22. It is preferable that an intermixing layer is formed.
- the surface on the laminated body 4 side of the first glass layer 21 has a shape along the irregularities on the surface of the laminated body 4. In other words, a part of the first glass layer 21 enters the irregularities on the surface of the laminate 4.
- the melting point of the first glass layer 21 is lower than the melting point of the second glass layer 22.
- the low melting point glass material forming the first glass layer 21 is applied to the surface of the laminate 4 and then melted. It is easy to get into the irregularities on the surface of the laminate 4.
- the molten glass material that has entered the irregularities on the surface of the laminate 4 during the formation of the first glass layer 21 acts like a wedge on the laminate 4 after curing. For this reason, the 1st glass layer 21 is excellent in adhesiveness with the laminated body 4 (anchor effect of the 1st glass layer 21).
- the melting point of the first glass layer 21 is preferably 465 to 565 ° C., more preferably 540 to 565 ° C.
- the first glass layer 21 has a better moisture-proof function.
- the melting point of the first glass layer 21 is 565 ° C. or less, high fluidity can be obtained by melting.
- the glass material is melted and fixed by heat treatment to easily form the irregularities of the laminate 4.
- the 1st glass layer 21 with favorable adhesiveness which has the shape which follows is obtained.
- the material of the first glass layer 21 examples include Bi-based glass.
- Bi-based glass is a material that is excellent in adhesion to the laminate 4, and thus is preferable as a material for the first glass layer 21.
- the Bi-based glass most include the components of the components contained in the first glass layer 21 (hereinafter sometimes referred to as "main component".) Is a Bi 2 O 3, other Bi 2 O 3 ZnO, B 2 O 3 , SiO 2 , Al 2 O 3 , BaO, CaO, MgO, SrO, SO 3 , P 2 O 5 , K 2 O, ZrO 2 , Li 2 O, TiO 2 , CuO, SnO 2 and one containing at least one selected from the group consisting of V 2 O 5 .
- the first glass layer 21 is preferably one type selected from the group consisting of Bi 2 O 3 , V 2 O 5 , and B 2 O 3 as the main component, and in particular, the main component is Bi 2 O 3. It is preferable that If the first glass layer 21 containing Bi 2 O 3, preferably contains Bi 2 O 3 30 ⁇ 70 wt%. With such a first glass layer 21, it is easy to obtain the first glass layer 21 with better adhesion.
- the melting point of the second glass layer 22 is preferably 550 to 730 ° C., more preferably 550 to 610 ° C. When the melting point of the second glass layer 22 is 550 ° C. or higher, the second glass layer 22 has a better moisture-proof function. When the melting point of the second glass layer 22 is 730 ° C. or less, the glass material is melted by applying a heat treatment to the surface of the first glass layer 21 containing a slurry containing the glass material to be the second glass layer 22. The second glass layer 22 can be easily formed by the fixing method.
- Examples of the material of the second glass layer 22 include silica-based glass.
- Silica-based glass has good adhesion to Bi-based glass, which is preferable as a material for the first glass layer 21, and is a material having a good moisture-proof function and physical strength. preferable.
- the silica-based glass the most contained component among the components contained in the second glass layer 22 is SiO 2 , and besides SiO 2 , Bi 2 O 3 , ZnO, B 2 O 3 , Al 2 O 3 , BaO, CaO, MgO, SrO, SO 3 , Cl, P 2 O 5 , K 2 O, ZrO 2 , Na 2 O, Y 2 O 3 , PbO, Li 2 O The thing containing the above is mentioned.
- Second glass layer 22 the main component is preferably a SiO 2. If the second glass layer 22 comprising SiO 2, preferably contains SiO 2 20 ⁇ 70 wt%. With such a second glass layer 22, it is easy to obtain the second glass layer 22 having a better moisture-proof function and physical strength.
- the first external terminal 5 and the second external terminal 6 are electrically connected to the outside. As shown in FIG. 1, the first external terminal 5 is formed in contact with the side surface of the stacked body 4 (exposed surfaces of the end surfaces of the positive electrode layer 1 and the negative electrode layer 2). The second external terminal 6 is formed in contact with a side surface different from the side surface of the laminate 4 where the first external terminal 5 is formed.
- the first external terminal 5 and the second external terminal 6 are preferably made of a material having a high conductivity. For example, silver, gold, platinum, aluminum, copper, tin, nickel, gallium, indium, and alloys thereof can be used.
- the first external terminal 5 and the second external terminal 6 may be a single layer or a plurality of layers.
- a simultaneous firing method may be used, or a sequential firing method may be used.
- the co-firing method is a method in which a material for forming each layer is laminated and then a laminated body is produced by batch firing.
- the sequential firing method is a method for sequentially producing each layer, and is a method for performing a firing step every time each layer is produced.
- the laminate 4 can be formed with fewer work steps when the simultaneous firing method is used.
- the use of the co-firing method makes the resulting laminate 4 denser than the case of using the sequential firing method.
- the case where the laminated body 4 is manufactured using the simultaneous firing method will be described as an example.
- the simultaneous firing method includes a step of creating a paste of each material constituting the laminated body 4, a step of applying and drying the paste to produce a green sheet, and laminating the green sheets to form a laminated sheet, which are fired simultaneously.
- Process. each material of the positive electrode current collector layer 1A, the positive electrode active material layer 1B, the solid electrolyte 3, the negative electrode active material layer 2B, and the negative electrode current collector layer 2A constituting the laminate 4 is made into a paste.
- a method for pasting each material is not particularly limited.
- a paste can be obtained by mixing powder of each material in a vehicle.
- the vehicle is a general term for the medium in the liquid phase.
- the vehicle includes a solvent and a binder.
- a green sheet is created.
- the green sheet is obtained by applying the prepared paste onto a substrate such as a PET (polyethylene terephthalate) film and drying it as necessary, and then peeling the substrate.
- the method for applying the paste is not particularly limited. For example, known methods such as screen printing, coating, transfer, doctor blade, etc. can be employed.
- the produced green sheets are stacked in a desired order and the number of stacked layers to form a stacked sheet. When laminating green sheets, alignment, cutting, etc. are performed as necessary.
- the laminated sheet may be produced using a method in which a positive electrode active material layer unit and a negative electrode active material layer unit described below are produced and laminated.
- a solid electrolyte 3 paste is applied onto a substrate such as a PET film by a doctor blade method and dried to form a sheet-like solid electrolyte layer 3.
- the positive electrode active material layer 1B paste is printed on the solid electrolyte 3 by screen printing and dried to form the positive electrode active material layer 1B.
- the positive electrode current collector layer 1A paste is printed on the positive electrode active material layer 1B by screen printing and dried to form the positive electrode current collector layer 1A.
- the positive electrode active material layer 1B paste is printed on the positive electrode current collector layer 1A by screen printing and dried to form the positive electrode active material layer 1B.
- the positive electrode active material layer unit is a laminated sheet in which solid electrolyte layer 3 / positive electrode active material layer 1B / positive electrode current collector layer 1A / positive electrode active material layer 1B are laminated in this order.
- a negative electrode active material layer unit is prepared in the same procedure.
- the negative electrode active material layer unit is a laminated sheet in which solid electrolyte layer 3 / negative electrode active material layer 2B / negative electrode current collector layer 2A / negative electrode active material layer 2B are laminated in this order.
- one positive electrode active material layer unit and one negative electrode active material layer unit are laminated.
- the solid electrolyte layer 3 of the positive electrode active material layer unit and the negative electrode active material layer 2B of the negative electrode active material layer unit, or the positive electrode active material layer 1B of the positive electrode active material layer unit and the solid electrolyte layer 3 of the negative electrode active material layer unit Laminate so that
- positive electrode active material layer 1B / positive electrode current collector layer 1A / positive electrode active material layer 1B / solid electrolyte layer 3 / negative electrode active material layer 2B / negative electrode current collector layer 2A / negative electrode active material layer 2B / solid electrolyte layer 3 Is obtained in this order.
- the positive electrode current collector layer 1A of the positive electrode active material layer unit extends only to one end surface
- the negative electrode current collector layer of the negative electrode active material layer unit is The units are stacked while being shifted so that the electric conductor layer 2A extends only to the other surface.
- seat for solid electrolyte layers 3 of predetermined thickness is further stacked
- the produced laminated sheet is crimped together.
- the pressure bonding is preferably performed while heating.
- the heating temperature at the time of pressure bonding is, for example, 40 to 95 ° C.
- the pressure-bonded laminated sheet is simultaneously fired to obtain a laminated body 4 made of a sintered body.
- the laminated sheet is fired by heating to 600 ° C. to 1000 ° C. in a nitrogen atmosphere.
- the firing time is, for example, 0.1 to 3 hours.
- the obtained sintered body (laminated body 4) may be barrel-polished by putting it in a cylindrical container together with an abrasive such as alumina. Thereby, the corners of the laminate 4 can be chamfered.
- the laminate 4 may be polished by sandblasting. This method is preferable because only a specific portion can be removed.
- the relative density of the solid electrolyte sandwiched between the positive electrode layer, the negative electrode layer, and the positive electrode layer and the negative electrode layer may be 80% or more.
- the higher the relative density the easier it is for the mobile ion diffusion path in the crystal to be connected, and the ionic conductivity is improved.
- the laminated body 4 is obtained by the above process.
- the moisture-proof layer 20 is formed so as to cover the surface of the stacked body 4 excluding the region where the first external terminals 5 and the second external terminals 6 are formed.
- a tape or the like Mask using.
- a slurry containing a glass material to be the first glass layer 21 is applied to the surface of the sintered body 4.
- slurry containing the glass material used as the 1st glass layer 21 what disperse
- the slurry containing the glass material to be the first glass layer 21 may contain a binder as necessary.
- the slurry containing the glass material to be the first glass layer 21 can be applied by a known method such as a spray coating method or a dipping method, and the spray coating method is preferably used.
- the slurry containing the glass material to be the second glass layer 22 is applied on the coating film formed by applying the slurry containing the glass material to be the first glass layer 21.
- a slurry containing the glass material used as the 2nd glass layer 22 what disperse
- the slurry containing the glass material to be the second glass layer 22 may contain a binder as necessary.
- the same method as that for the slurry containing the glass material to be the first glass layer 21 can be used.
- a heat treatment is performed by heating to 500 ° C. to 800 ° C. in a nitrogen atmosphere to form the first glass layer 21.
- the glass material that becomes the glass material and the second glass layer 22 is melted.
- the glass material of the first glass layer 21 enters the irregularities on the surface of the laminate 4.
- good adhesion between the laminate 4 and the first glass layer 21 is obtained.
- by performing the heat treatment intermixing between the glass material of the first glass layer 21 and the glass material of the second glass layer 22 occurs. As a result, good adhesion between the first glass layer 21 and the second glass layer 22 is obtained.
- it cools and the glass material used as the 1st glass layer 21 and the 2nd glass layer 22 is hardened and fixed.
- the first external terminal 5 and the second external terminal are formed on the surface of the laminate 4 on the side surface where the moisture-proof layer 20 is not formed and the positive electrode current collector layer 1A and the negative electrode current collector layer 2A are exposed. 6 is formed.
- the first external terminal 5 and the second external terminal 6 are formed so as to be in electrical contact with the positive electrode current collector layer 1A and the negative electrode current collector layer 2A, respectively.
- the first external terminal 5 and the second external terminal 6 can be formed by a known method. Specifically, for example, a sputtering method, a spray coating method, a dipping method, or the like can be used.
- the first external terminal 5 and the second external terminal 6 are formed only on a predetermined portion of the surface of the laminate 4 where the positive electrode current collector layer 1A and the negative electrode current collector layer 2A are exposed. For this reason, when forming the 1st external terminal 5 and the 2nd external terminal 6, the area
- the all solid state battery 10 of the present embodiment thus obtained includes the moisture-proof layer 20 provided in contact with the laminate 4, so that the battery capacity is hardly reduced due to moisture intrusion, and is excellent. Reliable.
- Positive electrode current collector layer 1A and negative electrode current collector layer 2A Cu + Li 3 V 2 (PO 4 ) 3
- Positive electrode active material layer 1B and negative electrode active material layer 2B Li 3 V 2 (PO 4 ) 3
- Solid electrolyte 3 Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The temperature during simultaneous firing was 800 ° C., and the firing time was 1 hour.
- a slurry in which the glass material having the components shown in Table 1 serving as the first glass layer 21 is dispersed in water is prepared, and the first external terminal 5 and the second external terminal 6 are formed using a spray coating method. It apply
- distributed the glass material of the component shown in Table 2 used as the 2nd glass layer 22 in water was produced, and it apply
- Example 13 Example 13
- the glass material to be the first glass layer 21 and the glass material to be the second glass layer 22 are obtained. Melted. Then, it cooled and hardened and the 1st glass layer 21 and the 2nd glass layer 22 were formed. Through the above steps, the moisture-proof layer 20 composed of the first glass layer 21 and the second glass layer 22 was formed. Next, an InGa paste is applied to the opposing side surfaces where the positive electrode current collector layer 1A and the negative electrode current collector layer 2A are exposed, in which the moisture-proof layer 20 is not formed, on the surface of the laminate 4, respectively. The first external terminal 5 and the second external terminal 6 were formed, and an all-solid battery 10 was obtained.
- the all solid state batteries are taken out and left at room temperature for 8 hours or more.
- the discharge capacity after the moisture resistance test was measured in the same manner as the initial discharge capacity was measured.
- the discharge capacity of the all-solid-state secondary battery before the reliability test was set to 100%, and the time during which the discharge capacity of the all-solid-state battery after the reliability test was set to hold a capacity exceeding 80% was measured.
- the all solid state batteries of Examples 1 to 13 were Comparative Example 1 in which the second glass layer was not formed, Comparative Example 2 in which the first glass layer was not formed, and the melting point of the first glass layer. Compared with the all-solid-state battery of Comparative Example 3 whose melting point is higher than that of the second glass layer, the reliability test result was good.
- SYMBOLS 1 Positive electrode layer, 1A ... Positive electrode collector layer, 1B ... Positive electrode active material layer, 2 ... Negative electrode layer, 2A ... Negative electrode collector layer, 2B ... Negative electrode active material layer, 3 ... Solid electrolyte, 4 ... Laminate body, DESCRIPTION OF SYMBOLS 5 ... 1st external terminal, 6 ... 2nd external terminal, 10 ... All-solid-state lithium ion secondary battery (all-solid-state battery), 20 ... Dampproof layer, 21 ... 1st glass layer, 22 ... 2nd glass layer.
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Abstract
La présente invention concerne un accumulateur lithium-ion totalement solide qui comporte : un stratifié qui comprend une couche d'électrode positive, une couche d'électrode négative et un électrolyte solide qui est intercalé entre la couche d'électrode positive et la couche d'électrode négative ; et une couche de protection contre l'humidité qui est agencée pour être en contact avec le stratifié. La couche de protection contre l'humidité est composée d'une première couche de verre qui est agencée pour être en contact avec le stratifié et d'une deuxième couche de verre qui est agencée sur la première couche de verre ; et le point de fusion de la première couche de verre est inférieur au point de fusion de la deuxième couche de verre.
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JP2020155289A (ja) * | 2019-03-19 | 2020-09-24 | Tdk株式会社 | 積層型全固体電池の製造方法 |
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