JP2018190601A - 蓄電デバイス用部材及び蓄電デバイス - Google Patents
蓄電デバイス用部材及び蓄電デバイス Download PDFInfo
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- JP2018190601A JP2018190601A JP2017092311A JP2017092311A JP2018190601A JP 2018190601 A JP2018190601 A JP 2018190601A JP 2017092311 A JP2017092311 A JP 2017092311A JP 2017092311 A JP2017092311 A JP 2017092311A JP 2018190601 A JP2018190601 A JP 2018190601A
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- electrode layer
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- 238000003860 storage Methods 0.000 title claims abstract description 47
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 73
- 239000011734 sodium Substances 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 29
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000005611 electricity Effects 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002228 NASICON Substances 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 33
- 230000007423 decrease Effects 0.000 description 29
- 239000011149 active material Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 10
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- RPMPQTVHEJVLCR-UHFFFAOYSA-N pentaaluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3] RPMPQTVHEJVLCR-UHFFFAOYSA-N 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 229910018068 Li 2 O Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 polypropylene carbonate Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
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- 239000012808 vapor phase Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910020570 Na3.12Zr1.88Y0.12Si2PO12 Inorganic materials 0.000 description 1
- 229910020582 Na3.4Zr0.9Hf1.4Al0.6Si1.2P1.8O12 Inorganic materials 0.000 description 1
- 229910020583 Na3.6Ti0.2Y0.8Si2.8O9 Inorganic materials 0.000 description 1
- 229910020554 Na3.6Zr0.13Yb1.67Si0.11P2.9O12 Inorganic materials 0.000 description 1
- 229910020607 Na3Hf2Si2PO12 Inorganic materials 0.000 description 1
- 229910020699 Na3Zr1.7Nb0.24Si2PO12 Inorganic materials 0.000 description 1
- 229910020687 Na3Zr1.88Y0.12Si2PO12 Inorganic materials 0.000 description 1
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 description 1
- 229910021283 NaFe0.2Mn0.4Ni0.4O2 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 210000001787 dendrite Anatomy 0.000 description 1
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- 238000010828 elution Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum 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
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
-
- 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
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Conductive Materials (AREA)
Abstract
Description
<蓄電デバイス用部材の作製>
固体電解質として、厚み1mmのβ”−アルミナ(組成式:Na1.6Li0.34Al10.66O17のLi2O安定化β”−アルミナ、Ionotec社製)を12mm角に切断したものを用いた。
上記のようにして作製した蓄電デバイス用部材を用いて、負極特性を評価するための電池を、以下のようにして作製した。露点−70℃以下のアルゴン雰囲気中にて、対極となる金属ナトリウムを、蓄電デバイス用部材の負極層が形成された面と反対側の面に圧着した。得られた積層体をコインセルの下蓋の上に載置した後、上蓋を被せてCR2032型評価用電池を作製した。
作製した評価用電池について、60℃で開回路電圧から0.001Vまでの定電流充電を行い、初回の充電容量を求めた。次に、放電は0.001Vから、実施例1および2においては2.0Vまで、実施例3〜5においては2.5Vまで定電流放電を行い、初回の放電容量を求めた。なお、Cレートは0.1Cで行い、20サイクル目の放電容量から、初回の放電容量に対する20サイクル目の放電容量維持率を算出した。なお、この充放電試験において、充電は負極活物質へのナトリウムイオンの吸蔵であり、放電は負極活物質からのナトリウムイオンを放出である。
<負極の作製>
負極集電体として厚み20μmの銅箔を用いた。この銅箔の片側表面の上に、開口部10mm角のマスキングを施し、形成する金属膜の組成が表2に示す組成となるターゲット(フルウチ化学社製)を用い、マグネトロンスパッタ装置(JEOL社製、JEC−3000FC)を用いてスパッタリングを行った。これにより、銅箔の片側表面の上に金属膜からなる負極を形成した。なお、スパッタリングは真空中にアルゴン(Ar)ガスを導入し、電流30mAを印加しながら行った。
上記のようにして作製した負極を用いて、負極特性を評価するための電池を、以下のようにして作製した。負極を、銅箔の面を下に向けてコインセルの下蓋に載置し、その上に70℃で8時間減圧乾燥した直径16mmのポリプロピレン多孔質膜からなるセパレータと、対極である金属ナトリウムとを積層し、電解液を含浸させた後、上蓋を被せて評価用電池を作製した。電解液としては、EC:DEC=1:1の混合溶媒に、1M(モル/リットル)のNaPF6を溶解させた溶液を用いた。なお、評価用電池の組み立ては、露点温度−70℃以下の環境で行った。
作製した評価用電池について、実施例1〜5と同様にして充放電試験を行い、初回の充電容量、初回の放電容量、初回の充放電効率、及び20サイクル目の放電容量維持率を測定した。測定結果を表2に示す。
2…固体電解質
3…負極層
11…蓄電デバイス
12…固体電解質
13…負極層
14…正極層
Claims (7)
- ナトリウムイオン伝導性酸化物からなる固体電解質と、
ナトリウムを吸蔵・放出可能な金属または合金からなり、前記固体電解質の上に設けられる負極層と、
を備える、蓄電デバイス用部材。 - 前記金属または前記合金が、Sn、Bi、Sb、及びPbからなる群より選ばれる少なくとも1種の元素を含む、請求項1に記載の蓄電デバイス用部材。
- 前記負極層が、前記固体電解質の上に形成された金属膜または合金膜からなる、請求項1または2に記載の蓄電デバイス用部材。
- 前記固体電解質が、β−アルミナ、β”−アルミナまたはNASICON型結晶である、請求項1〜3のいずれか一項に記載の蓄電デバイス用部材。
- 請求項1〜4のいずれか一項に記載の蓄電デバイス用部材と、
正極層と、
を備える蓄電デバイス。 - ナトリウムイオン伝導性酸化物からなる固体電解質と、
ナトリウムを吸蔵・放出可能な金属または合金からなる負極層と、
正極層と、
を備える蓄電デバイス。 - 前記負極層が、金属膜または合金膜から形成されている、請求項6に記載の蓄電デバイス。
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JP2017092311A JP7052215B2 (ja) | 2017-05-08 | 2017-05-08 | 蓄電デバイス用部材及び蓄電デバイス |
CN201880015809.8A CN110383558B (zh) | 2017-05-08 | 2018-04-23 | 蓄电设备用部件和蓄电设备 |
PCT/JP2018/016393 WO2018207597A1 (ja) | 2017-05-08 | 2018-04-23 | 蓄電デバイス用部材及び蓄電デバイス |
US16/492,962 US20200067134A1 (en) | 2017-05-08 | 2018-04-23 | Member for power storage device, and power storage device |
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Cited By (1)
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WO2023248793A1 (ja) * | 2022-06-20 | 2023-12-28 | 日本電気硝子株式会社 | 全固体二次電池 |
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CN112259726B (zh) * | 2020-10-15 | 2022-01-18 | 湘潭大学 | 一种AlCuCo准晶材料的应用 |
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JP2006216508A (ja) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
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KR20110045666A (ko) * | 2009-10-27 | 2011-05-04 | 경상대학교산학협력단 | 고체 나트륨 전지 및 그의 제조 방법 |
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