JP3041776B2 - Manufacturing method of gas diffusion electrode by self-organization - Google Patents
Manufacturing method of gas diffusion electrode by self-organizationInfo
- Publication number
- JP3041776B2 JP3041776B2 JP9245442A JP24544297A JP3041776B2 JP 3041776 B2 JP3041776 B2 JP 3041776B2 JP 9245442 A JP9245442 A JP 9245442A JP 24544297 A JP24544297 A JP 24544297A JP 3041776 B2 JP3041776 B2 JP 3041776B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- gas diffusion
- added
- diffusion electrode
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000009792 diffusion process Methods 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000010419 fine particle Substances 0.000 claims description 49
- 239000006185 dispersion Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000004094 surface-active agent Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 230000002209 hydrophobic effect Effects 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000000693 micelle Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 238000004220 aggregation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- 238000000527 sonication Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 239000006229 carbon black Substances 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- JMLBVODNHIWHAQ-UHFFFAOYSA-N C=C.FC(F)=C(F)F.F.F.F.F Chemical compound C=C.FC(F)=C(F)F.F.F.F.F JMLBVODNHIWHAQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 240000002609 Pyrus pyrifolia var. culta Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002481 ethanol extraction Methods 0.000 description 1
- MSKQYWJTFPOQAV-UHFFFAOYSA-N fluoroethene;prop-1-ene Chemical group CC=C.FC=C MSKQYWJTFPOQAV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、食塩電解の酸素陰
極、亡硝電解の電極等に用いることができる、酸素還元
性能の高いガス拡散電極の製造方法、特に自己組織化に
よる、電極の酸素還元性能の高いガス拡散電極の反応層
を形成するガス拡散電極の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a gas diffusion electrode having a high oxygen reduction performance which can be used for an oxygen cathode for salt electrolysis, an electrode for sodium nitrite electrolysis, and the like. The present invention relates to a method for manufacturing a gas diffusion electrode that forms a reaction layer of a gas diffusion electrode having high reduction performance.
【０００２】[0002]
【従来の技術】イオン交換膜法による塩化アルカリ溶液
の電解において、その陰極にガス拡散電極を酸素陰極と
して使用することが行われている。通常イオン交換膜法
電解は、陽イオン交換膜であるイオン交換膜により陽極
室と陰極室とに区画された電解槽で行われ、この電解槽
では陽極を有する陽極室には塩化ナトリウム水溶液が、
陰極を有する陰極部には苛性ソ−ダ水溶液が入ってい
る。この中、陰極としてガス拡散電極を用いる形式の電
解槽では、その陰極部は、イオン交換膜とガス拡散電極
との間の苛性ソ−ダ水溶液が入っている陰極液室、反応
層とガス供給層とからなるガス拡散電極、および酸素ガ
ス室からなる構造を有している。このような構成の電解
槽では、陽極と陰極部（ガス拡散電極および酸素ガス室
からなっている）のガス拡散電極の両電極間に通電して
電解する際に、ガス拡散電極上で酸素還元反応が起こ
り、陰極電位が上昇するため、電解電圧が著しく低減さ
れるという利点を有する。2. Description of the Related Art In electrolysis of an alkali chloride solution by an ion exchange membrane method, a gas diffusion electrode is used as an oxygen cathode as its cathode. Normally, ion exchange membrane electrolysis is performed in an electrolytic cell partitioned into an anode chamber and a cathode chamber by an ion exchange membrane which is a cation exchange membrane.In this electrolytic tank, an aqueous sodium chloride solution is placed in an anode chamber having an anode,
A cathode portion having a cathode contains an aqueous solution of caustic soda. Among these, in the electrolytic cell of the type using a gas diffusion electrode as a cathode, the cathode part is a catholyte chamber containing an aqueous solution of caustic soda between the ion exchange membrane and the gas diffusion electrode, a reaction layer and a gas supply. It has a structure composed of a gas diffusion electrode composed of layers and an oxygen gas chamber. In the electrolytic cell having such a configuration, when electricity is supplied between the anode and the cathode portion (consisting of a gas diffusion electrode and an oxygen gas chamber) to conduct electrolysis, oxygen reduction is performed on the gas diffusion electrode. Since the reaction takes place and the cathode potential increases, there is an advantage that the electrolytic voltage is significantly reduced.
【０００３】ところで、従来のガス拡散電極の反応層の
製造方法においては、親水性カ−ボンブラックに界面活
性剤を加え分散させ、ポリテトラフロロエチレン（ＰＴ
ＦＥ）ディスパ−ジョンを混合して凍結し、疎水性カ−
ボンブラックに界面活性剤を加え分散させ、ＰＴＦＥデ
ィスパ−ジョンを混合して凍結し、それぞれを解凍して
混合していた。これらの凍結、解凍の操作でカ−ボンブ
ラック、ＰＴＦＥディスパ−ジョンが凝集することで、
親水部、疎水部の凝集体を作り、これらを混合して反応
層として働く微細な親水部と疎水部との混合状態とし
た。In a conventional method for producing a reaction layer of a gas diffusion electrode, a surfactant is added to and dispersed in hydrophilic carbon black to form polytetrafluoroethylene (PT).
FE) The dispersion is mixed and frozen, and the hydrophobic
The surfactant was added to Bon Black, dispersed, mixed with PTFE dispersion, frozen, thawed and mixed. Carbon black and PTFE dispersion coagulate by these freezing and thawing operations,
Agglomerates of a hydrophilic part and a hydrophobic part were formed, and these were mixed to form a mixed state of fine hydrophilic parts and hydrophobic parts that function as a reaction layer.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな従来のガス拡散電極の反応層の製造方法において
は、ＰＴＦＥディスパ−ジョン等を凝集させる凍結、解
凍の操作は時間がかかるので電極製造コストが高価であ
る。しかも、親水部、疎水部の混合状態が性能の良いも
のを得る上では必ずしも望ましいものではなく、制御も
困難であるという問題点があった。本発明は、このよう
な従来の課題に鑑みてなされたものであり、製造工程が
簡素化され、製造時間も短縮され、かつ高い酸素還元性
能を有するガス拡散電極の反応層を製造することができ
るガス拡散電極の製造方法を提供することを目的とす
る。However, in such a conventional method for manufacturing a reaction layer of a gas diffusion electrode, the operation of freezing and thawing for aggregating a PTFE dispersion or the like takes a long time, so that the electrode manufacturing cost is reduced. Expensive. Moreover, there is a problem that the mixed state of the hydrophilic part and the hydrophobic part is not always desirable for obtaining a good performance, and the control is difficult. The present invention has been made in view of such conventional problems, and the manufacturing process is simplified, the manufacturing time is shortened, and it is possible to manufacture a reaction layer of a gas diffusion electrode having high oxygen reduction performance. It is an object of the present invention to provide a method for manufacturing a gas diffusion electrode that can be used.
【０００５】[0005]
【課題を解決するための手段】本発明者は、前記課題を
解決すべく鋭意検討した結果、反応層の構成材料の微粒
子を液中に安定に分散させている界面活性剤のミセル構
造をアルコ−ル等の高水溶性溶媒からなるミセル破壊剤
で凝集制御することにより前記構成材料微粒子とフッ素
樹脂微粒子を自己組織化させることによって上記目的を
達成できることを見い出して本発明を完成するに至っ
た。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the micelle structure of a surfactant in which fine particles of a constituent material of a reaction layer are stably dispersed in a liquid has been modified. It has been found that the above object can be achieved by self-assembling the constituent material fine particles and the fluororesin fine particles by controlling the aggregation with a micelle-disrupting agent comprising a highly water-soluble solvent such as- .
【０００６】すなわち、本発明は、次の構成からなるも
のである。 （１）水にガス拡散電極の反応層構成材料の１次粒子が
平均粒径１ミクロン以下の微粒子及び界面活性剤を撹拌
又は超音波照射下に添加して、高度の分散状態になるよ
うに分散させ、次いでフッ素樹脂微粒子を添加して上記
撹拌又は超音波照射を継続して分散混合した後、微粒子
を安定分散させている界面活性剤のミセル構造をミセル
破壊剤を添加して凝集制御することにより反応層構成材
料の微粒子とフッ素樹脂微粒子を自己組織化させ、それ
によりガス拡散電極の原料を製造することを特徴とする
ガス拡散電極の製造方法。 （２）触媒金属微粒子を界面活性剤溶液中に撹拌又は超
音波照射下に添加して高分散させ、次いでフッ素樹脂デ
ィスパ−ジョンを添加して分散混合した後、ミセル破壊
剤を添加して触媒金属微粒子とフッ素樹脂微粒子とを自
己組織化させることによりガス拡散電極の反応層を製造
することを特徴とするガス拡散電極の製造方法。That is, the present invention has the following configuration. (1) Fine particles having a primary particle of a reaction layer constituting material of a gas diffusion electrode having an average particle diameter of 1 μm or less and a surfactant are added to water under stirring or ultrasonic irradiation so that a highly dispersed state is obtained. After the dispersion and then the addition of the fluororesin fine particles, and the above-mentioned stirring or ultrasonic irradiation is continued to be dispersed and mixed, the micelle structure of the surfactant in which the fine particles are stably dispersed is subjected to aggregation control by adding a micelle breaking agent. A method for producing a gas diffusion electrode, wherein the fine particles of the material constituting the reaction layer and the fluororesin fine particles are self-assembled to thereby produce a raw material for the gas diffusion electrode. (2) Catalytic metal fine particles are added to a surfactant solution under stirring or ultrasonic irradiation to obtain a high dispersion, and then a fluororesin dispersion is added and dispersed and mixed. A method for producing a gas diffusion electrode, comprising producing a reaction layer of a gas diffusion electrode by self-assembling metal fine particles and fluororesin fine particles.
【０００７】（３）触媒担持親水性微粒子を界面活性剤
溶液中に撹拌又は超音波照射下に添加して高分散させ、
次いでフッ素樹脂ディスパ−ジョンを添加して分散混合
した後、ミセル破壊剤を添加して自己組織化させて親水
部を構成させ、更に、疎水性微粒子を界面活性剤溶液中
に撹拌又は超音波照射下に添加して高分散させ、次いで
フッ素樹脂ディスパ−ジョンを添加して分散混合した
後、ミセル破壊剤を添加して自己組織化させて疎水部を
構成させ、前記親水部と前記疎水部とを混合することに
よりガス拡散電極の反応層を製造することを特徴とする
ガス拡散電極の製造方法。 （４）前記ミセル破壊剤が、メチルアルコ−ル、エチル
アルコ−ル、１−プロピルアルコ−ル、２−ブチルアル
コ−ル、ｔｅｒｔ−ブチルアルコ−ルのような高水溶性
のアルコ−ル、及びアセトンのような高水溶性のケトン
からなる群から選ばれる前記（１）〜（３）のいずれか
１項記載のガス拡散電極の製造方法。(3) The catalyst-carrying hydrophilic fine particles are added to a surfactant solution under stirring or ultrasonic irradiation to be highly dispersed,
Next, after adding and dispersing and mixing a fluororesin dispersion, a micelle breaking agent is added to form a self-assembled self-assembly to form a hydrophilic portion. Further, hydrophobic fine particles are stirred or irradiated with ultrasonic waves in a surfactant solution. The mixture is dispersed under high-dispersion by adding it below, and then dispersed and mixed by adding a fluororesin dispersion.Then, a micelle-disintegrating agent is added and self-organized to form a hydrophobic portion, and the hydrophilic portion and the hydrophobic portion are formed. A method for producing a gas diffusion electrode, comprising producing a reaction layer of a gas diffusion electrode by mixing (4) The micelle-destroying agent is a highly water-soluble alcohol such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-butyl alcohol, tert-butyl alcohol, and acetone. The method for producing a gas diffusion electrode according to any one of the above (1) to (3), which is selected from the group consisting of such highly water-soluble ketones.
【０００８】[0008]
【発明の実施の形態】本発明のガス拡散電極の反応層の
製造方法においては、先ず、触媒である、例えば銀の微
粒子又は親水性カ−ボンブラックに界面活性剤を添加
し、超音波分散させた後、ＰＴＦＥディスパ−ジョンを
添加、混合して分散させる。その際得られる分散液は、
前記の銀又は親水性カ−ボンブラック及びＰＴＦＥの各
微粒子が界面活性剤の作用によりミセル構造を形成して
微粒子の状態で安定に高度の分散状態を維持しているも
のである。その分散状態は、分散中の一次粒子が集合し
た粒子の径が平均粒径５ミクロン以下となるようなもの
である。前記の触媒の微粒子や親水性カ−ボンブラック
の微粒子は一次粒子が平均粒径１ミクロン以下のもので
あることが好ましい。この分散液にアルコ−ルを徐々に
添加することにより、それぞれの微粒子の分散を可能に
しているミセル構造を破壊されて、微粒子が凝集され
る。その際、凝集はフラクタル状態となり、それにより
フラクタル状態の親水層が形成される。前記のアルコ−
ルはミセル破壊剤として作用するものである。同様に、
疎水性カ−ボンブラックなどを構成材料として分散し
て、疎水部も凝集させるが、この場合には親水部より小
さい凝集状態にする。このようにして得た親水層と疎水
部とを混合すると、５〜１００ミクロンの範囲のフラク
タル構造をした親水部凝集体の周りに５〜１００ミクロ
ンの範囲の疎水部凝集体が入り込み、疎水部、親水部の
界面部の面積が巨大となる。なお、通常の場合、親水部
凝集体の大きさは疎水部凝集体の大きさよりも大きい。
この結果性能が向上すると同時に電極寿命も増加する。BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a reaction layer of a gas diffusion electrode according to the present invention, first, a surfactant is added to a catalyst, for example, silver fine particles or hydrophilic carbon black, and ultrasonic dispersion is performed. After that, the PTFE dispersion is added, mixed and dispersed. The dispersion obtained at that time is:
The fine particles of silver or hydrophilic carbon black and PTFE form a micelle structure by the action of a surfactant, and maintain a highly dispersed state stably in the state of fine particles. The dispersion state is such that the diameter of the particles in which the primary particles are aggregated during the dispersion is 5 μm or less in average. The primary particles of the catalyst fine particles and hydrophilic carbon black fine particles preferably have an average particle diameter of 1 μm or less. By gradually adding alcohol to the dispersion, the micelle structure that enables the dispersion of the fine particles is broken, and the fine particles are aggregated. At that time, the aggregation becomes a fractal state, thereby forming a hydrophilic layer in a fractal state. The aforementioned alcohol
Lu acts as a micelle disrupter. Similarly,
Hydrophobic carbon black or the like is dispersed as a constituent material so that the hydrophobic portion is also aggregated. In this case, the aggregated state is smaller than the hydrophilic portion. When the thus obtained hydrophilic layer and the hydrophobic part are mixed, the hydrophobic part aggregates in the range of 5 to 100 microns enter around the hydrophilic part aggregates having a fractal structure in the range of 5 to 100 microns, In addition, the area of the interface of the hydrophilic portion becomes huge. In addition, in a normal case, the size of the hydrophilic part aggregate is larger than the size of the hydrophobic part aggregate.
As a result, the performance is improved and the electrode life is also increased.
【０００９】すなわち、親水性カ−ボンブラックと疎水
性カ−ボンブラックを水と界面活性剤に添加し、分散さ
せ、ＰＴＦＥ微粒子を混合した後、界面活性剤の能力を
制御し、それによって親水性カ−ボンブラックとＰＴＦ
Ｅ微粒子及び疎水性カ−ボンブラックとＰＴＦＥ微粒子
を自己組織化させることにより反応層原料を製造する。
また、銀微粒子とＰＴＦＥ微粒子の場合は界面活性剤、
例えばトライトンで分散し、エタノ−ルを添加すること
で銀微粒子とＰＴＦＥ微粒子がそれぞれ数ミクロン程度
のフラクタル状に凝集し、これらが二次凝集する。That is, after adding a hydrophilic carbon black and a hydrophobic carbon black to water and a surfactant, dispersing them and mixing PTFE fine particles, the ability of the surfactant is controlled, whereby Carbon black and PTF
A reaction layer raw material is produced by self-assembling E fine particles, hydrophobic carbon black and PTFE fine particles.
In the case of silver fine particles and PTFE fine particles, a surfactant,
For example, by dispersing with Triton and adding ethanol, the silver fine particles and the PTFE fine particles respectively aggregate in a fractal form of about several microns, and these are secondarily aggregated.
【００１０】反応層の主要構成素材としては、白金など
の貴金属系からなる触媒、親水性カ−ボンの微粒子と撥
水性カ−ボン微粒子の混合物、少量のフッ素樹脂微粒子
と必要ならばこれら微粒子を繋ぐ結着剤粒子である。ガ
ス供給層の主要構成素材としては、撥水性カ−ボン微粒
子、フッ素樹脂微粒子と必要ならばこれら微粒子を繋ぐ
結着剤粒子である。触媒としては、耐アルカリ性の貴金
属、例えば白金、その他の白金属金属、金、銀及びこれ
らの貴金属の合金が挙げられるが、これに限定されるも
のではない。しかし、性能とコストを併せ考えると銀が
好ましい触媒といえる。なお、これらの貴金属は微粒子
の形で使用される。The main constituent materials of the reaction layer are a catalyst made of a noble metal such as platinum, a mixture of hydrophilic carbon fine particles and water-repellent carbon fine particles, a small amount of fluororesin fine particles and, if necessary, these fine particles. These are the binder particles to be connected. The main constituent materials of the gas supply layer are water-repellent carbon fine particles and fluororesin fine particles and, if necessary, binder particles connecting these fine particles. Catalysts include, but are not limited to, alkali-resistant noble metals such as platinum, other white metal, gold, silver and alloys of these noble metals. However, considering performance and cost, silver can be said to be a preferable catalyst. These noble metals are used in the form of fine particles.
【００１１】本発明のガス拡散電極の反応層の製造に際
しては、分散のために使用する界面活性剤としては、陰
イオン界面活性剤、陽イオン界面活性剤、非イオン界面
活性剤、両性界面活性剤のどれもが使用できるが、塩類
やイオンの影響を受けることがない点で非イオン界面活
性剤が好ましい。フッ素樹脂としては、四フッ化エチレ
ン（テトラフロロエチレン）樹脂、三フッ化塩化エチレ
ン（クロロトリフロロエチレン）樹脂、四フッ化エチレ
ン・六フッ化プロピレン（フッ化エチレンプロピレン）
樹脂、フッ化ビニリデン樹脂が挙げられるが、テトラフ
ロロエチレン樹脂（ＰＴＦＥ）が特に好ましい。ＰＴＦ
Ｅディスパ−ジョンは、ＰＴＦＥ微粒子の水分散液であ
って、ディスパ−ジョンには分散用の界面活性剤が含ま
れているが、前述したように界面活性剤は非イオン界面
活性剤であることが望ましい。ミセル破壊剤は、高水溶
性の有機溶媒、例えばメチルアルコ−ル、エチルアルコ
−ル、イソフロピルアルコ−ル等のアルコ−ル類、及び
アセトン等のケトン類が挙げられる。これらのミセル破
壊剤の使用量は、界面活性剤分子の集合体のミセル構造
を破壊してフラクタル状態にする量であればよいが、通
常は分散液に大して１：１であるが、その前後の割合で
用いてもよい。In the production of the reaction layer of the gas diffusion electrode of the present invention, the surfactant used for dispersion includes an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Any of the agents can be used, but nonionic surfactants are preferred because they are not affected by salts or ions. As the fluororesin, ethylene tetrafluoride (tetrafluoroethylene) resin, ethylene trifluoride chloride (chlorotrifluoroethylene) resin, ethylene tetrafluoride / propylene hexafluoride (fluoroethylene propylene)
Resin and vinylidene fluoride resin are mentioned, and tetrafluoroethylene resin (PTFE) is particularly preferable. PTF
The E dispersion is an aqueous dispersion of PTFE fine particles, and the dispersion contains a surfactant for dispersion. As described above, the surfactant must be a nonionic surfactant. Is desirable. Examples of the micelle breaking agent include highly water-soluble organic solvents, for example, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, and ketones such as acetone. The amount of use of these micelle-disrupting agents may be any amount as long as the micelle structure of the aggregate of surfactant molecules is broken into a fractal state. May be used.
【００１２】[0012]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこの実施例により何等限定されるもので
ない。また、実施例及び比較例を通じて部及びパ−セン
トとも格別の指示なき限り、すべて重量表示による。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples. Also, throughout the examples and comparative examples, parts and percentages are all indicated by weight unless otherwise specified.
【００１３】実施例１ 平均粒径０．１１ミクロンの銀微粒子（三井金属鉱業社
製、Ａｇ−３０１０）５部（重量）に界面活性剤トライ
トン（ロ−ムアンドハ−ス社製）を１部、水９部を添加
し超音波分散機で分散させた。これにＰＴＦＥディスパ
−ジョンＤ−１（ダンキン工業社製）１部を加え、撹拌
混合して分散した後に、これにエチルアルコ−ルを２０
部加え、更に撹拌を継続して凝集させ自己組織化させ
た。この沈殿物を０．８ミクロンの濾紙で濾過し、得ら
れた泥奨を０．３ｍｍ厚に銀メッキ発泡ニッケル（１２
×２８センチ角）上に塗り込み、１０ｋｇ／ｃｍ2の圧
力でプレスして内部に押し込むことによって反応層を形
成した。さらに裏からルブロンにエタノ−ルを加え糊状
にしたものを押し込みガス供給層を形成した。８０℃で
３時間乾燥、常温プレス４０ｋｇ／ｃｍ2 、６０秒間、
２５０℃で１０分間熱処理、冷却することにより電極を
得た。この電極の酸素還元性能を測定したところ、３０
Ａ／ｄｍ2 で０．８１Ｖ（ｖｓ．ＲＨＥ）の高い性能が
得られた。電極背面とガス室の銀メッキ発泡ニッケルと
の接触抵抗は２ｍオーム／ｃｍ 2 以下と小さい値を示し
た。Example 1 Silver fine particles having an average particle size of 0.11 micron (Mitsui Metal Mining Co., Ltd.)
Ag-3010) 5 parts (weight) of surfactant
Ton (Rome and Haas) 1 part, water 9 parts
And dispersed with an ultrasonic dispersing machine. PTFE disperse to this
Add 1 part of John D-1 (manufactured by Dunkin Industries, Ltd.) and stir
After mixing and dispersion, 20 parts of ethyl alcohol was added thereto.
Parts, and further continue stirring to aggregate and self-organize.
Was. The precipitate was filtered through 0.8 micron filter paper to give
0.3 mm thick silver-plated foamed nickel (12
X 28 cm square) on top, 10 kg / cmTwoPressure
The reaction layer is formed by pressing with force and pushing it inside.
Done. Add ethanol to Lubron from the back and paste
This was pressed to form a gas supply layer. At 80 ° C
Dry for 3 hours, press at room temperature 40kg / cmTwoFor 60 seconds
Heat treatment at 250 ° C for 10 minutes
Obtained. When the oxygen reduction performance of this electrode was measured, 30
A / dmTwoHigh performance of 0.81V (vs. RHE)
Obtained. With silver plated nickel foam on the back of the electrode and gas chamber
Has a contact resistance of 2 mOhm / cm TwoShows the following small values
Was.
【００１４】比較例１ 平均粒径０．１１ミクロンの銀微粒子（三井金属鉱業社
製、３０１０）５部に界面活性剤トライトンを１部、水
９部を加え超音波分散機で分散させた。これにＰＴＦＥ
ディスパ−ジョンＤ−１（ダイキン工業社製）１部を加
え、撹拌混合した後に自己組織化させずに０．８ミクロ
ンの濾紙で濾過した。得られた泥奨を０．３ｍｍ厚に銀
メッキ発泡ニッケル（１２×２８センチ角）上に塗り込
み、１０ｋｇ／ｃｍ2 の圧力でプレスして内部に押し込
むことによって反応層を形成した。さらに裏からルブロ
ンにエタノ−ルを加え糊状にしたものを押し込みガス供
給層を形成した。８０℃で３時間乾燥、常温プレス４０
ｋｇ／ｃｍ2 、６０秒間、２５０℃で１０分間熱処理、
冷却することにより電極を得た。この電極の酸素還元性
能を測定したところ、３０Ａ／ｄｍ2 で０．５６Ｖ（ｖ
ｓ．ＲＨＥ）と著しく低い性能しか得られなかった。Comparative Example 1 One part of Triton surfactant and 9 parts of water were added to 5 parts of silver fine particles (3010, manufactured by Mitsui Mining & Smelting Co., Ltd.) having an average particle diameter of 0.11 μm, and dispersed by an ultrasonic dispersing machine. This is PTFE
One part of Dispersion D-1 (manufactured by Daikin Industries, Ltd.) was added, and the mixture was stirred and mixed, and then filtered through 0.8 micron filter paper without self-organization. The obtained slurry was applied on silver-plated nickel foam (12 × 28 cm square) to a thickness of 0.3 mm, and pressed at a pressure of 10 kg / cm 2 to form a reaction layer. Further, from the back side, ethanol was added to rublon to form a paste, which was then pressed to form a gas supply layer. Dry at 80 ° C for 3 hours, press at room temperature 40
kg / cm 2 , heat treatment for 60 seconds at 250 ° C. for 10 minutes,
An electrode was obtained by cooling. When the oxygen reduction performance of this electrode was measured, it was 0.56 V (v) at 30 A / dm 2.
s. RHE).
【００１５】実施例２ 銀を１０％担持した親水性カ−ボンブラック（ＡＢ−１
２、平均粒径４００オングストロ−ム、試作品、電気化
学工業社製）２．５部に２０％トライトンを２０部とＰ
ＴＦＥディスパ−ジョン（Ｄ−１、ダイキン工業社製）
１部を分散させた。この分散液にイソプロピルアルコ−
ルを５０部加え自己組織化させた。別に、疎水性カ−ボ
ンブラック（Ｎｏ．６、平均粒径５００オングストロ−
ム、試作品、電気化学工業社製）２部に２０％トライト
ンを２０部とＰＴＦＥディスパ−ジョン（Ｄ−１、ダイ
キン工業社製）１部を分散させた。この分散液にイソプ
ロピルアルコ−ルを５０部加え自己組織化させた。Example 2 A hydrophilic carbon black (AB-1) supporting 10% of silver.
2, average particle diameter 400 angstrom, prototype, manufactured by Denki Kagaku Kogyo KK) 2.5 parts and 20 parts 20% triton and P
TFE dispersion (D-1, manufactured by Daikin Industries, Ltd.)
One part was dispersed. Add isopropyl alcohol to this dispersion.
And 50 parts were added for self-organization. Separately, hydrophobic carbon black (No. 6, average particle size 500 Å-
2 parts of 20% Triton and 1 part of PTFE dispersion (D-1; manufactured by Daikin Industries, Ltd.) were dispersed in 2 parts of the same. 50 parts of isopropyl alcohol was added to this dispersion to allow self-organization.
【００１６】これらの親水部と疎水部の自己組織化させ
た液を撹拌混合して、濾過して反応層原料にした。これ
を５０ｐｐＩの銀メッキ発泡ニッケル体上から２００ミ
クロン厚に塗り込み、１ｍｍのシリコンシ−トと共にロ
−ルすることにより発泡体内部に反応層を押し込んだ。
発泡ニッケルの裏から疎水性カ−ボンブラック（Ｎｏ．
６、平均粒径５００オングストロ−ム、試作品、電気化
学工業社製）２部とＰＴＦＥディスパ−ジョン（Ｄ−
１、ダイキン工業社製）１部から製造したガス供給層原
料を同様に押し込みガス供給層を形成した。８０℃で３
時間乾燥、界面活性剤をエタノ−ル抽出装置により除去
した。乾燥後、５０ｋｇ／ｃｍ2 で３８０℃、６０秒間
プレスすることにより電極を得た。この電極の酸素還元
性能を測定したところ、３０Ａ／ｄｍ2 で０．８１Ｖ
（ｖｓ．ＲＨＥ）の高い性能が得られた。従来の方法で
ある凍結により分散液を凝集して作成した電極に比べ性
能は２０ｍＶ優れていた。The liquid in which the hydrophilic part and the hydrophobic part were self-assembled was stirred and mixed, and filtered to obtain a reaction layer material. This was applied to a thickness of 200 μm from a 50 ppI silver-plated nickel foam body and rolled with a 1 mm silicon sheet to push the reaction layer into the foam body.
Hydrophobic carbon black (No.
6, 2 parts of average particle size 500 angstrom, prototype, manufactured by Denki Kagaku Kogyo KK and PTFE dispersion (D-
1, manufactured by Daikin Industries, Ltd.) to form a gas supply layer. 3 at 80 ° C
After drying for an hour, the surfactant was removed with an ethanol extraction device. After drying, an electrode was obtained by pressing at 380 ° C. for 60 seconds at 50 kg / cm 2 . When the oxygen reduction performance of this electrode was measured, it was 0.81 V at 30 A / dm 2 .
(Vs. RHE). The performance was 20 mV better than an electrode prepared by coagulating a dispersion by freezing, which is a conventional method.
【００１７】[0017]
【発明の効果】本発明によれば、界面活性剤のミセル構
造をアルコ−ル等のミセル破壊剤で凝集制御することに
よりガス拡散電極の反応層の銀などの触媒やカ−ボンブ
ラックの微粒子とフッ素樹脂微粒子を自己組織化させる
ことができる。その結果反応層の製造行程が簡素化さ
れ、製造時間も短縮され、かつ高い酸素還元性能の電極
が安定して製造できる。特にその凝集状態を制御するこ
とによりその自己組織化の状態を変えることができる。According to the present invention, the micellar structure of a surfactant is controlled by agglomeration with a micelle-disintegrating agent such as alcohol, whereby a catalyst such as silver in the reaction layer of the gas diffusion electrode and carbon black fine particles are formed. And the fluororesin fine particles can be self-organized. As a result, the production process of the reaction layer is simplified, the production time is shortened, and an electrode having high oxygen reduction performance can be produced stably. In particular, the state of self-organization can be changed by controlling the state of aggregation.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 古屋 長一 山梨県甲府市中村町２−14 (56)参考文献 特開 昭57−104678（ＪＰ，Ａ) 特開 平６−316784（ＪＰ，Ａ) 特開 平６−57474（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25B 1/00 - 15/08 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Choichi Furuya 2-14 Nakamuracho, Kofu City, Yamanashi Prefecture (56) References JP-A-57-104678 (JP, A) JP-A-6-316784 (JP, A) JP-A-6-57474 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25B 1/00-15/08
Claims (4)
次粒子が平均粒径１ミクロン以下の微粒子及び界面活性
剤を撹拌又は超音波照射下に添加して、高度の分散状態
になるように分散させ、次いでフッ素樹脂微粒子を添加
して上記撹拌又は超音波照射を継続して分散混合した
後、微粒子を安定分散させている界面活性剤のミセル構
造をミセル破壊剤を添加して凝集制御することにより反
応層構成材料の微粒子とフッ素樹脂微粒子を自己組織化
させ、それによりガス拡散電極の原料を製造することを
特徴とするガス拡散電極の製造方法。1. A material for forming a reaction layer of a gas diffusion electrode in water.
The fine particles having an average particle diameter of 1 micron or less and a surfactant are added under stirring or ultrasonic irradiation to disperse them so as to be in a highly dispersed state. After continuously dispersing and mixing by sonication, the micelle structure of the surfactant that stably disperses the fine particles is controlled by aggregation by adding a micelle-disrupting agent, whereby the fine particles of the material constituting the reaction layer and the fluororesin fine particles are self-assembled. A method for producing a gas diffusion electrode, thereby producing a material for the gas diffusion electrode.
拌又は超音波照射下に添加して高分散させ、次いでフッ
素樹脂ディスパ−ジョンを添加して分散混合した後、ミ
セル破壊剤を添加して触媒金属微粒子とフッ素樹脂微粒
子とを自己組織化させることによりガス拡散電極の反応
層を製造することを特徴とするガス拡散電極の製造方
法。2. A catalyst metal fine particle is added to a surfactant solution under stirring or ultrasonic irradiation to obtain a high dispersion, then a fluororesin dispersion is added and dispersed and mixed, and then a micelle breaking agent is added. A method for producing a reaction layer of a gas diffusion electrode by self-organizing catalyst metal fine particles and fluororesin fine particles by self-assembly.
中に撹拌又は超音波照射下に添加して高分散させ、次い
でフッ素樹脂ディスパ−ジョンを添加して分散混合した
後、ミセル破壊剤を添加して自己組織化させて親水部を
構成させ、更に、疎水性微粒子を界面活性剤溶液中に撹
拌又は超音波照射下に添加して高分散させ、次いでフッ
素樹脂ディスパ−ジョンを添加して分散混合した後、ミ
セル破壊剤を添加して自己組織化させて疎水部を構成さ
せ、前記親水部と前記疎水部とを混合することによりガ
ス拡散電極の反応層を製造することを特徴とするガス拡
散電極の製造方法。3. The catalyst-carrying hydrophilic fine particles are added to a surfactant solution under stirring or ultrasonic irradiation to achieve high dispersion, and then a fluororesin dispersion is added and dispersed and mixed. It is added and self-assembled to form a hydrophilic portion, and further, hydrophobic fine particles are added to a surfactant solution under stirring or ultrasonic irradiation to be highly dispersed, and then a fluororesin dispersion is added. After dispersing and mixing, a hydrophobic layer is formed by adding a micelle-disrupting agent and self-organizing, and a reaction layer of a gas diffusion electrode is manufactured by mixing the hydrophilic part and the hydrophobic part. Manufacturing method of gas diffusion electrode.
ル、エチルアルコ−ル、１−プロピルアルコ−ル、２−
ブチルアルコ−ル、ｔｅｒｔ−ブチルアルコ−ルのよう
な高水溶性のアルコ−ル、及びアセトンのような高水溶
性のケトンからなる群から選ばれる請求項１〜３のいず
れか１項記載のガス拡散電極の製造方法。4. The method according to claim 1, wherein the micelle-destroying agent is methyl alcohol-
, Ethyl alcohol, 1-propyl alcohol, 2-
The gas diffusion according to any one of claims 1 to 3, wherein the gas diffusion is selected from the group consisting of a highly water-soluble alcohol such as butyl alcohol, tert-butyl alcohol, and a highly water-soluble ketone such as acetone. Manufacturing method of electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9245442A JP3041776B2 (en) | 1997-09-10 | 1997-09-10 | Manufacturing method of gas diffusion electrode by self-organization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9245442A JP3041776B2 (en) | 1997-09-10 | 1997-09-10 | Manufacturing method of gas diffusion electrode by self-organization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1180985A JPH1180985A (en) | 1999-03-26 |
| JP3041776B2 true JP3041776B2 (en) | 2000-05-15 |
Family
ID=17133732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9245442A Expired - Fee Related JP3041776B2 (en) | 1997-09-10 | 1997-09-10 | Manufacturing method of gas diffusion electrode by self-organization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3041776B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6630081B1 (en) | 1999-06-30 | 2003-10-07 | Nagakazu Furuya | Process for producing gas diffusion electrode material |
| JP4262190B2 (en) | 2003-12-26 | 2009-05-13 | キヤノン株式会社 | Resistive film forming method and image display apparatus and television apparatus formed by using the film forming method |
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1997
- 1997-09-10 JP JP9245442A patent/JP3041776B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1180985A (en) | 1999-03-26 |
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