JPWO2014030230A1 - 電力貯蔵電池 - Google Patents
電力貯蔵電池 Download PDFInfo
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- negative electrode
- electrode electrolyte
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- 238000003860 storage Methods 0.000 title claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 35
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 abstract description 18
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 6
- 239000008151 electrolyte solution Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000011261 inert gas Substances 0.000 description 14
- 239000011149 active material Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 230000005865 ionizing radiation Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 231100000987 absorbed dose Toxicity 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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Abstract
Description
図1に示すように、レドックスフロー型電池は、充放電セル11を備える。充放電セル11の内部は、隔膜12によって正極側セル21と負極側セル31とに仕切られている。レドックスフロー型電池は、正極側セル21に用いられる正極電解液22を貯蔵する正極電解液タンク23と、負極側セル31に用いられる負極電解液32を貯蔵する負極電解液タンク33とを備える。レドックスフロー型電池には、充放電セル11周辺の温度を調節する温度調節装置が必要に応じて設けられる。
正極電解液22のpH及び負極電解液32のpHは、2以上、8以下の範囲内である。正極電解液22のpH及び負極電解液32のpHは、好ましくは4以上、7以下の範囲内である。すなわち、各電解液22,32として、上記pHの範囲内で酸化還元反応を行うことのできる活物質を含む水溶液が用いられる。正極電解液22のpH及び負極電解液32のpHが2以上であることで、耐食性が確保され易くなる。正極電解液22のpH及び負極電解液32のpHが8以下であることで、例えば、活物質の溶解性が確保され易くなる。
隔膜12は、正極側セル21と負極側セル31との間において活物質の透過を抑制する。隔膜12はイオン交換膜から構成されている。隔膜12は、充電時には、正極側セル21中の例えばナトリウムイオンを負極側セル31へ透過させるとともに、放電時には、負極側セル31中の例えばナトリウムイオンを正極側セル21へ透過させる。イオン交換膜は、エチレン−ビニルアルコール共重合体をマトリックスとする樹脂フィルム基材にスチレンスルホン酸塩をグラフト重合して得られる。このイオン交換膜は、グラフト鎖の有するスルホン酸塩構造が陽イオンの交換に寄与する。
<隔膜12(イオン交換膜)の製造>
隔膜12(イオン交換膜)は、重合工程を通じて製造される。
レドックスフロー型電池に用いられる電解液のpHは、2以上、8以下の範囲内である。こうした電解液は、エチレン−ビニルアルコール共重合体をマトリックスとする樹脂フィルム基材を有するイオン交換膜を劣化させ難い。
クーロン効率は、好ましくは80%以上である。
電圧効率は、好ましくは75%以上である。
エネルギー効率は、好ましくは60%以上である。
前記実施形態は以下のように変更されてもよい。
<イオン交換膜(隔膜)の製造>
エチレン−ビニルアルコール共重合体フィルム(商品名:エバールEF−F、厚み50μm、エチレン含量32mol%、株式会社クラレ製)を80×80mmの寸法に切断した樹脂フィルム基材を窒素置換したプラスチックバッグ中に密封した。これに電子線を加速電圧750kV、吸収線量50kGyの条件で照射した後、プラスチックバッグ中に10質量%のスチレンスルホン酸ナトリウム水溶液を20mL注入した。次に、プラスチックバッグを50℃の恒温槽中で2時間振とうすることで、樹脂フィルム基材にスチレンスルホン酸ナトリウムをグラフト重合させることで、イオン交換膜(隔膜)を得た。
正極電解液及び負極電解液として、一液式の電解液(プレミックス方式の電解液とも呼ばれる)となるように、次の方法によって水溶液を調製した。蒸留水40mLに、0.08モル(40g)のCrK(SO4)2・12H2Oを溶解させた。続いて、この水溶液に、0.09モル(26.3g)のEDTA4Hと、0.18モル(7.2g)のNaOHとを少量ずつ添加して溶解させた。得られた水溶液を加熱して4時間還流させた。還流中に、濃度が5.0モル/LのNaOH水溶液32mLを少量ずつ添加した。そして、水溶液を冷却した後、0.2モル(16.4g)の無水酢酸ナトリウムを溶解させた。
上述したレドックスフロー型電池に上記イオン交換膜を隔膜として装着するとともに上記電解液を用いて充放電試験を行った。
実施例2〜5では、表1に示すようにグラフト率が異なるイオン交換膜(隔膜)に変更した以外は、実施例1と同様に充放電試験を行った。その結果を表1に示す。
実施例6〜10では、表1に示すように樹脂フィルム基材の厚み及びグラフト率の異なるイオン交換膜(隔膜)に変更した以外は、実施例1と同様に充放電試験を行った。その結果を表1に示す。
樹脂フィルム基材として、ポリエチレンフィルムを用いて、そのフィルムにスチレンスルホン酸ナトリウムをグラフト重合することを試みたが、グラフト率は数%に留まった。得られたイオン交換膜は、隔膜としての性能が得られなかった。
樹脂フィルム基材として、ポリプロピレンフィルムを用いて、そのフィルムにスチレンスルホン酸ナトリウムをグラフト重合することを試みたが、グラフト率は数%に留まった。得られたイオン交換膜は、隔膜としての性能が得られなかった。
樹脂フィルム基材として、ポリアミドフィルムを用いて、そのフィルムにスチレンスルホン酸ナトリウムをグラフト重合することを試みたが、グラフト率は数%に留まった。得られたイオン交換膜は、隔膜としての性能が得られなかった。
Claims (3)
- pHが2以上、8以下の範囲内の正極電解液及び負極電解液が用いられる電力貯蔵電池であって、エチレン−ビニルアルコール共重合体をマトリックスとする樹脂フィルム基材にスチレンスルホン酸塩をグラフト重合してなるイオン交換膜を、正極電解液と負極電解液の隔膜として有することを特徴とする電力貯蔵電池。
- 前記樹脂フィルム基材の厚みは、50μm以上、100μm以下である、請求項1に記載の電力貯蔵電池。
- 前記イオン交換膜のグラフト率は、10%を超え、120%未満である、請求項1又は請求項2に記載の電力貯蔵電池。
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