CN107267891B - 一种钴基非晶合金催化电极及生产方法 - Google Patents
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 57
- 239000010941 cobalt Substances 0.000 title claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 230000003197 catalytic effect Effects 0.000 title abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004080 punching Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 43
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000005253 cladding Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000005452 bending Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000005476 soldering Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 238000005219 brazing Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 8
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- -1 neopelex Chemical compound 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C25B11/061—Metal or alloy
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- C25D3/00—Electroplating: Baths therefor
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- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D3/00—Electroplating: Baths therefor
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Abstract
一种钴基非晶合金催化电极，其特征在于，电极由槽型电极架和可抽插式催化电极板组成，可抽插式催化电极板由金属网包覆钴基非晶合金的片状颗粒制成，钴基非晶合金片状颗粒的具体成分为Fe35‑95 wt%，其余合金元素为可与铁一起电沉积的元素，如P、Fe、Ni、Cr、Mo、W、Re等中的一种或多种元素的组合；槽型电极架则由金属薄板冲压成型，在槽型电极架的两侧板均匀开设有长方形孔，由长方形孔位置的金属冲裁、弯曲制成催化电极的固定板。
Description
技术领域
本发明涉及到电化学领域的催化电极，特别涉及到一种钴基非晶合金复合催化电极及生产方法。
背景技术
非晶合金由于具有以下特点；①非晶态合金在很宽的范围内可以制成各种组成的样品，从而可以在较宽大范围内调变它们的电子性质；②催化活性中心可以以单一的形式均匀分布在化学均匀的环境中；③非晶态合金表面具有浓度较高的不饱和中心，且不饱和中心的配位数具有一定的范围，因而使其催化活性和选择性一般优于相应的晶态催化剂；④其表面的非多孔性是其摆脱了多项催化剂存在的反应物种的扩散影响表面反应的问题。
非晶态合金催化剂可以用于加氢、氧化、裂解、异构化等反应。目前，非晶态合金催化剂的制备方法有多种，一般来说可以将其分为两大类：液体骤冷法和原子（离子）沉积法。非晶合金催化电极以沉积薄膜或镀层的二维催化电极为主，但其反应器面积较小，导致产率较小。
发明内容
针对以上问题，本发明提出一种钴基非晶合金催化电极及生产方法。本发明的技术解决方案是提供一种钴基非晶合金催化电极，其特征在于，电极由槽型电极架和可抽插式催化电极板组成，可抽插式催化电极板由金属网包覆钴基非晶合金的片状颗粒制成，钴基非晶合金片状颗粒的具体成分为Co35-95 wt %，其余合金元素为可与钴一起电沉积的元素，如P、Fe、Ni、Cr、Mo、W、Re等中的一种或多种元素的组合。槽型电极架则由金属薄板冲压成型，在槽型电极架的两侧板均匀开设有长方形孔，由长方形孔位置的金属冲裁、弯曲制成催化电极固定板。
本发明的技术解决方案是再提供一种钴基非晶合金催化电极的制备方法，包括以下步骤：
（1）可抽插式催化电极板的制备工艺
1）钴基非晶合金镀层的生产
（a）金属基板被镀表面的脱脂及氧化膜去除，金属基板材料应适宜进行常温下的塑性加工；
（b）电镀液组成；硫酸钴0.5-4mol/L，酸0.2-1mol/L、络合剂0.5-5g/L、合金元素添加剂0.2-4mol/L，水余量；
以上所述合金元素添加剂中，铁以可溶性亚铁盐（配0.5-2g/L的还原剂）、镍以可溶性镍盐、铬以铬酐、钼以钼酸钠、钨以钨酸钠、磷以亚磷酸或可溶性次磷酸盐、Re以Re可溶盐的形式添加；
上述酸包括硼酸、磷酸等多元中强酸；
上述络合剂包括糖精、十二烷基苯磺酸钠、酒石酸、柠檬酸盐等有机络合剂；
（c）采用电镀或电刷镀制备钴基非晶合金镀层，阳极采用石墨或不锈钢，电解液温度为40-90℃，滴定强酸溶液使Ph值不大于1；
2）非晶合金镀层的剥离
采用机械或物理的方法，如拉伸、弯曲、轧制压延、刮擦等方法使非晶合金镀层与金属基板发生剥离；
3）颗粒的破碎
（a）采用球磨机、行星式球磨机等，将剥落的非晶颗粒在真空或气体保护条件下进行球磨，采用球磨（3-10min）、停转（3-10min）这种间隔循环的方式，或采用球磨同时可附加强制冷却的方式球磨，球磨总时间（包含球磨和停转的时间）为0.5-3h，球料比为2-8:1；
（b）筛分成不同粗细的钴基非晶合金颗粒；
4）可抽插式催化电极金属包覆网的成型
采用金属网，裁剪、弯曲、钎焊制备板状包覆金属网，
5）非晶合金颗粒的注入与封装
往板状包覆金属网中注入钴基非晶合金颗粒，然后采用钎焊等方式封闭板状包覆金属网。
（2）槽型电极架的制备工艺
采用铜或铜合金薄板，裁剪、冲孔、弯曲制备槽型电极架。
（3）装配成钴基非晶合金催化电极
把可抽插式催化电极板置于两催化电极固定板中，制成钴基非晶合金催化电极。
与现有技术相比，本发明的优点：
1. 由于采用钴基非晶合金颗粒作为催化剂，可提高电极的催化性能；
2. 由于采用电镀+剥离+破碎制备钴基非晶合金微粒，微粒基本形状为层片状，这提高了非晶合金催化剂反应的表面积；
3.由于采用槽型电极架，并在两侧板开设有长方形孔，端部也未封闭，最大限度提高了溶液在电极内部的可流动性，增大催化电极与溶液的相对流动，可提高催化电极的催化效率；
4. 由于采用抽插式结构，因此电极的反应器面积以及催化电极板的间距很容易调整，也便于更换与维修。
附图说明
图1为本发明设备示意图。其中，槽型电极架（1），可采用铜或铜合金薄板制成；可抽插式催化电极板（2），采用板状金属网包覆钴基非晶合金颗粒制成；催化电极固定板（3）；长方形孔（4）。
具体实施方式
以下结合实施例对本发明作进一步说明。
1.钴-镍非晶合金催化电极的生产
（1）可抽插式催化电极板的制备工艺
1）钴镍非晶合金镀层的生产
（a）金属基板采用黄铜板，黄铜板表面的脱脂及氧化膜去除；
（b）电镀液组成；硫酸钴2.5 mol/L，磷酸0.55 mol/L、糖精0.8 g/L、柠檬酸钠0.3g/L，硫酸镍0.7mol/L，氯化镍0.5mol/L，水余量；
（c）采用电镀法制备钴镍非晶合金镀层，阳极采用石墨，电解液温度为75℃，滴定硫酸溶液使Ph值为1；
2）非晶合金镀层的剥离
采用反复弯曲的方法使钴镍非晶合金镀层与黄铜板发生剥离；
3）颗粒的破碎
（a）利用行星式球磨机，采用球磨5 min、停转5 min这种间隔循环的方式，将剥落的非晶颗粒在真空条件下进行球磨，球磨总时间（包含球磨和停转的时间）为1 h，球料比为3:1；
（b）筛分成不同粗细的钴镍非晶合金颗粒；
4）可抽插式催化电极金属包覆网的成型
采用100目的不锈钢筛网，裁剪、弯曲、钎焊制备板状包覆金属网，
5）非晶合金颗粒的注入与封装
往板状包覆金属网中注入大于100目的钴镍非晶合金颗粒，然后采用钎焊等方式封闭成板状包覆金属网。
（2）槽型电极架的制备工艺
采用黄铜薄板裁剪、冲孔、弯曲制备槽型电极架。
（3）装配成钴镍非晶合金催化电极
把可抽插式催化电极板置于两催化电极固定板中，制成钴镍非晶合金催化电极。
2.钴-镍-磷非晶合金催化电极
（1）可抽插式催化电极板的制备工艺
1）钴-镍-磷非晶合金镀层的生产
（a）08F薄钢板表面的脱脂及氧化膜去除；
（b）电镀液组成；硫酸钴3.5mol/L，硼酸0.7 mol/L、糖精0.8g/L，酒石酸0.5 g/L、硫酸镍1.5mol/L，次磷酸钠0.75mol/L，水余量；
（c）采用电刷镀制备钴-镍-磷非晶合金镀层，阳极采用石墨板，电解液温度为70℃，滴定强酸溶液使Ph值为1，电极板的相对移动速度为80 mm/s，电极板的平均电流密度为15A/cm2；
2）非晶合金镀层的剥离
采用双向拉伸的方法使非晶合金镀层与08F薄钢板发生剥离；
3）颗粒的破碎
（a）利用行星式球磨机，采用球磨3min、停转5min这种间隔循环的方式，将剥落的非晶颗粒氮气保护条件下进行球磨，球磨总时间（包含球磨和停转的时间）为0.5 h，球料比为5:1；
（b）筛分成不同粗细的钴-镍-磷非晶合金颗粒；
4）可抽插式催化电极金属包覆网的成型
采用100目的金属网，裁剪、弯曲、钎焊制备板状包覆金属网，
5）非晶合金颗粒的注入与封装
往板状包覆金属网中注入大于100目的钴-镍-磷非晶合金颗粒，然后采用钎焊等方式封闭板状包覆金属网。
（2）槽型电极架的制备工艺
采用青铜薄板，裁剪、冲孔、弯曲制备槽型电极架。
（3）装配成钴-镍-磷非晶合金催化电极
把可抽插式催化电极板置于两催化电极固定板中，制成钴-镍-磷非晶合金催化电极。
Claims (2)
1.钴基非晶合金催化电极的生产方法，其特征在于，包括以下步骤：（1）可抽插式催化电极板的制备；（2）采用铜或铜合金薄板，裁剪、冲孔、弯曲制备槽型电极架，在所述槽型电极架的两侧板均匀开设有长方形孔，由所述长方形孔位置的金属冲裁、弯曲制成催化电极固定板；（3）把可抽插式催化电极板置于所述催化电极固定板中，制成钴基非晶合金催化电极；
所述可抽插式催化电极板的生产步骤为：1）钴基非晶合金镀层的生产；2）采用物理的方法使钴基非晶合金镀层与金属基板发生剥落；3）将剥落的钴基非晶合金片状颗粒在真空或气体保护条件下进行球磨，球磨工艺采用球磨3-10min、停转3-10min这种间隔循环的方式，或采用球磨同时附加强制冷却的方式，球磨总时间为0.5-3h，球料比为2：1-8：1，所述球磨总时间包含球磨和停转的时间；4）采用100目的金属网，裁剪、弯曲、钎焊制备板状包覆金属网；5）往板状包覆金属网中注入大于100目的钴基非晶合金片状颗粒，钴基非晶合金片状颗粒的具体成分为Co35-95wt%，其余为与Co一起电沉积的元素，为P、Fe、Ni、Cr、Mo、W、Re中的一种或多种元素的组合，采用钎焊方式封闭板状包覆金属网。
2.如权利要求1所述钴基非晶合金催化电极的生产方法，其特征在于，所述钴基非晶合金镀层采用电镀的方式制备，其中电镀液的组成为硫酸钴0.5-4mol/L，多元中强酸0.2-1mol/L、络合剂0.5-5g/L、合金元素添加剂0.2-4mol/L，水余量；阳极采用石墨或不锈钢，电解液温度为40-90℃，滴定强酸溶液使pH值不大于1；
所述合金元素添加剂中，铁以可溶性亚铁盐、镍以可溶性镍盐、铬以铬酐、钼以钼酸钠、钨以钨酸钠、磷以亚磷酸或可溶性次磷酸盐、Re以Re可溶盐的形式添加，所述可溶性亚铁盐需配有0.5-2g/L的还原剂。
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