JP2013508930A - 固体アルカリイオン条件電解質及び水性電解質を有する電気化学装置 - Google Patents
固体アルカリイオン条件電解質及び水性電解質を有する電気化学装置 Download PDFInfo
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- 239000007787 solid Substances 0.000 title description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 47
- 239000012528 membrane Substances 0.000 claims abstract description 41
- 150000001768 cations Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
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- 229910052744 lithium Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910019385 NaPON Inorganic materials 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- FZRNJOXQNWVMIH-UHFFFAOYSA-N lithium;hydrate Chemical compound [Li].O FZRNJOXQNWVMIH-UHFFFAOYSA-N 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910005700 Ge 1-y Ti Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 102000005393 Sodium-Potassium-Exchanging ATPase Human genes 0.000 claims description 2
- 108010006431 Sodium-Potassium-Exchanging ATPase Proteins 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- -1 sodium phosphoric acid nitride Chemical class 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 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 description 9
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- 239000000243 solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
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- 125000002091 cationic group Chemical group 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 229920000557 Nafion® Polymers 0.000 description 3
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- AOPJVJYWEDDOBI-UHFFFAOYSA-N azanylidynephosphane Chemical compound P#N AOPJVJYWEDDOBI-UHFFFAOYSA-N 0.000 description 1
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- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
-
- 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
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/187—Solid electrolyte characterised by the form
-
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/24—Cells comprising two different electrolytes
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- 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
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- H01M6/188—Processes of manufacture
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- 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
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- 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
Abstract
Description
R=(r×e)/A
ここで、「r」は電解質の抵抗、「e」は電解質の厚さ、「A」は電解質の面積を示している。即ち、電解質の厚さeが小さくなればなるほど、装置のエネルギー効率が向上し得る。
− 固体電解質としての、アルカリカチオンを伝導することができ、上述したように塩基性のpHの水中で不溶性且つ化学的に安定であるカチオン伝導性有機ポリマーで被覆されたセラミックの膜、及び、
− 液体電解質としての、上記有機ポリマーと接触させるアルカリ金属水酸化物の水溶液。
− 金属リチウムを含む陰極の区画、
− 水酸化リチウム水溶液に浸された少なくとも一つの陽極としての空気電極を備える陽極の区画、
− 気密的且つ水密的に陽極の区画から陰極の区画を隔離する固体電解質であり、上記固体電解質は、本発明に係るセラミックの膜であり、一方の表面が、塩基性のpHの水中で不溶性且つ化学的に安定したカチオン伝導性有機ポリマーで被覆されており、そして、状況に応じて、必要であれば、他方の表面が、Li3N、Li3P、LiI、LiBr、LiF又はリチウムリン酸窒化物(LiPON)を主成分とする保護コーティングで被覆されており、他方の表面が、LiPONを主成分とする保護コーティングで被覆されていることが好ましい。
また、本発明に係る上記電気化学装置は、陰極の区画と陽極の区画とを備える電気分解セルであってもよく、上記二つの区画(陰極の区画と陽極の区画)(半セル)は、本発明の方法に基づいて、セラミックの膜により互いに分離しており、アルカリカチオンを伝導することができる。上記電気分解セルは、例えば、リチウム塩又はナトリウム塩から、水酸化リチウム又は水酸化ナトリウム、及び、上記塩のアニオンに相当する酸を再生するために用いられてもよい。上記再生を行うために、対象となる塩(例えばLi2SO4)の水溶液を陽極の区画に導入し、二つの電極間に電位を掛ける。電気分解反応の終わりに、陽極の区画には硫酸水溶液が含まれ、陰極の区画にはLiOH水溶液が含まれ、場合によりLiOHの沈殿物が含まれ得る。本発明に係る装置の本実施形態では、アルカリカチオンを伝導することができる膜は、少なくとも陰極の区画側の面が有機ポリマーで被覆されている。
図1は、本発明に係るリチウム−空気電池の構造を示している:
図2は、下記実施例で示された試験において、時間の経過に基づいて変化する2mAの電流を維持するためにどのくらいの電圧が必要かを示している。
セラミックの電解質の膜における表面上の疎水性且つカチオン伝導性の有機ポリマーの薄い層を形成することによる効果を実証するために、Li+イオンを伝導することができるセラミックの膜(LISICONの膜)(厚さ300μmであり、Oharaから市販されている膜)により互いに隔てられた二つの区画を備える電気化学装置を作製した。二つの区画を5MのLiOH水溶液で満たした。白金電極を両区画に挿入した。ポテンショスタット(potentiostat)を用いて2mAの電流を起こし、セルを介して二つの白金電極間で流した。そうすることで、Li+イオンを陽極の区画から陰極の区画に移動させた。Li+イオンの移動は、水又は酸素の還元による陽極の区画でのOH−イオンの形成と共に発生する。本装置の陽極の区画は、LISICONセラミックとLiOHを含む水性電解質との間の接触面での、リチウム−水電池又はリチウム−空気電池における陽極の区画の作用を模倣したものである。2mAの電流は、LiOHの飽和及び沈殿物が発生するまで維持され、2mAの電流を維持するために必要な電圧を、試験を通して測定した。
Claims (12)
- アルカリカチオンを伝導することができ、且つ、
表面の少なくとも一部が、カチオン伝導性有機多価電解質(organic cation-conductive polyelectrolyte)の層で被覆されており、
上記層は、塩基性のpHの水中において不溶性で且つ化学的に安定であるセラミックの膜。 - 下記化学式を有するセラミックの膜、
Li1+x(M,Ga,Al)x(Ge1−yTiy)2−x(PO4)3
(上記化学式において、Mは、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm及びYbから選ばれる一つ又はそれ以上の金属を表しており、0<x≦0.8、且つ、0≦y≦1.0である)
又は、
下記化学式を有するセラミックの膜、
Na1+xZr2SixP3−xO12
(上記化学式において、0≦x≦3)
である請求項1に記載のセラミックの膜。 - 厚さが、30μm〜500μmの範囲内であり、好ましくは50μm〜160μmの範囲内である請求項1又は2に記載のセラミックの膜。
- 上記有機ポリマーは、酸性基を備えるハロゲン系ポリマーであり、好ましくは酸性基を備えるフッ素系ポリマーである請求項1〜3のうち何れか一項に記載のセラミックの膜。
- 上記有機ポリマーは、テトラフルオロエチレン及び酸性基を備えるコモノマーの共重合体であり、好ましくはテトラフルオロエチレン及び−SO3 −M+基を有するコモノマーの共重合体である請求項4に記載のセラミックの膜。
- 上記有機ポリマーの層の厚さは、1μm〜50μmの範囲内であり、好ましくは2μm〜10μmの範囲内である請求項1〜5のうち何れか一項に記載のセラミックの膜。
- 何れか一方の表面が、カチオン伝導性有機多価電解質(organic cation-conductive polyelectrolyte)の層で被覆されており、
他方の表面が、Li3N、Li3P、LiI、LiBr、LiF若しくはリチウムリン酸窒化物(LiPON)を主成分とする保護コーティング、又は、ナトリウムリン酸窒化物(NaPON)を主成分とする保護コーティングで被覆されており、好ましくはLiPON又はNaPONを主成分とする保護コーティングで被覆されており、
上記層は、塩基性のpHの水中において不溶性で且つ化学的に安定である請求項1〜6のうち何れか一項に記載のセラミックの膜。 - 固体電解質としての、アルカリカチオンを伝導することができ、上記塩基性のpHの水中で不溶性且つ化学的に安定であるカチオン伝導性有機ポリマーで被覆された請求項1〜7のうち何れか一項に記載のセラミックの膜、及び、
液体電解質としての、上記有機ポリマーと接触させるアルカリ金属水酸化物の水溶液を備える電気化学装置。 - 金属−空気電池であり、好ましくはリチウム−空気電池である請求項8に記載の電気化学装置。
- 金属−水電池であり、好ましくはリチウム−水電池である請求項8に記載の電気化学装置。
- 電気分解セルである請求項8に記載の電気化学装置。
- リチウム・ポンプ又はナトリウム・ポンプである請求項8に記載の電気化学装置。
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