CN101629312A - Method for electrodepositing lead by ionic liquid system - Google Patents
Method for electrodepositing lead by ionic liquid system Download PDFInfo
- Publication number
- CN101629312A CN101629312A CN200910094836A CN200910094836A CN101629312A CN 101629312 A CN101629312 A CN 101629312A CN 200910094836 A CN200910094836 A CN 200910094836A CN 200910094836 A CN200910094836 A CN 200910094836A CN 101629312 A CN101629312 A CN 101629312A
- Authority
- CN
- China
- Prior art keywords
- lead
- ionic liquid
- metallic
- coat
- ionogen
- 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.)
- Pending
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002659 electrodeposit Substances 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- -1 hexafluoro phosphorus lead borate Chemical compound 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 4
- 238000005202 decontamination Methods 0.000 claims description 4
- 230000003588 decontaminative effect Effects 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- KNHTZPJKVPEFGY-UHFFFAOYSA-N decanoic acid;lead Chemical compound [Pb].CCCCCCCCCC(O)=O KNHTZPJKVPEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004663 powder metallurgy Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 10
- 238000009713 electroplating Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- YVWHMWGVWOQIFR-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O.CC(C)=O YVWHMWGVWOQIFR-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 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 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- VSQAMHLYSYQSBM-UHFFFAOYSA-N [F].OB(O)O Chemical compound [F].OB(O)O VSQAMHLYSYQSBM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000017854 proteolysis Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a technical method for electrodepositing metallic lead layers on metallic copper and an alloy thereof, metallic titanium and an alloy thereof as well as metallic aluminum and an alloy thereof by using an ionic liquid system as an electrolyte. Compared with an ordinary technology for electrodepositing metallic lead, the technical method has the advantages that the technical method can be carried out at room temperature, has no steam volatilization, no color or taste, no combustion, no hydrogen release, good thermal stability and chemical stability, wider electrochemical stability windows (3-5V), compact coated layers and small internal stress, and can achieve higher current efficiency (more than or equal to 90 percent). The technical method has the biggest advantage of acquiring lead coated layers which can not be acquired on the metallic aluminum and an alloy substrate material thereof in a conventional technology. The method has simple process, short flow, easy control and lower cost.
Description
Technical field
The present invention relates to obtain the fine and close evenly processing method of lead-coat in the galvanic deposit mode, particularly relating to a kind of ion liquid system metallic aluminium and alloy thereof of adopting is the galvanic deposit splicer skill of base material.
Background technology
Few or do not have hole when the lead-coat based on very high purity of galvanic deposit, thickness of coating are reached for 25～75 μ m with regard to hole, matrix is had the favorable protection performance.Usually lead-coat is mainly used to protect metal not to be subjected to the erosion of sulfuric acid, sulfurous gas and other sulfide and vitriol.The purposes of galvanic deposit splicer skill in chemical industry is wider, and for example the lining of the inwall of autoclave, crystallizer, vacuum-evaporator, freezing salt tank and gasbomb mostly is lead-coat.In recent years, people research is in the surface electrical deposit lead of materials such as copper coin and titanium plate, and utilizes the battery electrode of its making to alleviate the weight of lead storage battery, to improve specific energy, specific power.
Plumbous fluorborate solution, silicofluoride electrolytic solution, perchlorate electrolytic solution, thionamic acid salt electrolyte, the methylsulphonic acid electrolytic solution, and citric acid-electrochemical systems such as EDTA system of adopting usually of water solution system galvanic deposit.What wherein adopt the earliest is the fluoroborate system, but must adopt a kind of intermediate product of proteolysis as the auxiliary agent that improves quality of coating owing to can the dendrite phenomenon take place under the high current density condition.This kind auxiliary agent can cause the flavescence of tank liquor to become muddy in prolonged operation, serious organic contamination occurs, and every activated carbon treatment on a large scale of must doing through three months is once removed too much impurity and decomposed organism, and technology is complicated, not easy care.For important innovative approach of head it off is to increase the free fluorine boric acid content to 4 times of original persons, but also must constantly add simultaneously to reach makes " boric acid " saturated as far as possible, keeping normal operation, and the public hazards of the foul smell of tank liquor, fluorine and boron, Organic pollutants still can not solve.80 year later stage added some " nonionic interfacial agent " (Non-Iornic Surfactant) as substitute in the fluoroborate system, avoided organic contamination to keep the plating bath clarification.But because of its coating distributes inequality, formation is plumbous on the hole wall of being everlasting measures more epithelium and is difficult for shelling most.
Owing to be limited to 15ppm in the permission of the fluorochemical in the environmental regulation regulation discharge water, and the processing of fluorine has only the precipitator method by calcium, certainly will will make a large amount of mud.And the boron content that allows is reduced to 1ppm difficulty especially.Thereby Schlotter company developed in 1988 again and a kind of " alkylsulphonic acid " (Alkanolsulfonate) or be called " organic sulfonic acid " (Organic Sulfonic Acid, be methylsulphonic acid) tank liquor, abandon fluoroboric acid fully, can avoid " fluoride pollution " or " boron pollution " disaster of being brought and the trouble of processing.This method coating densification, solidity to corrosion are good, and organic contamination is greatly lowered etc.Yet also, be added on again in the tank liquor, cause tank liquor pollution and uneven coating even because its nonaqueous " additive " need be dissolved in solvent earlier.The zinc-plated lead of the methylsulphonic acid of this new-type free-floride, its flow process is almost completely identical with the plumbous series of traditional tin fluoborate, only will advance presoak before the groove and make 10% OSA into by 10% HBF3 and get final product.But its construction cost has improved a lot.
Simultaneously in the process of galvanic deposit lead, water solution system has specific requirement to base material, reports more copper and titanium at present, and the power on report of deposit lead of pair metallic aluminium and aluminium alloy is seldom arranged.Not only density is little, electric conductivity is high and consider aluminium and aluminium alloy, and better mechanical property, has reduced the loss of electric energy in internal resistance, has improved material use efficiency, and pole plate is not yielding, helps combining closely of active substance.In the aluminium sheet deposit lead that powers on, both can satisfy the requirement of corrosion resistance and good, overpotential of hydrogen evolution height and good conductivity, reduced the weight of pole plate again, can improve specific energy.
Ionic liquid (ionic liquid) is called room temperature fused salt again, is the organic liquid material of being made up of ion fully under room temperature and the adjacent temperature, and it is made up of organic cation and inorganic or organic anion.Ionic liquid has good solvability to organic, the organic and inorganic compound of metal, all is liquid in very big temperature range, has the electrochemical window (generally greater than 3V) of broad, high and stable ionic conductivity, the volatilization degree is low, does not burn advantages such as easy recovery.Show good prospects for application in fields such as secondary cell, electrochemical capacitor, metal electrodepositions.
Nineteen fifty-one, people such as Hurley and Wier have reported the room temperature alkyl pyridine class ionic liquid that is formed by aluminum chloride and bromination ethylpyridine (mol ratio is 1: 2), and utilize this ionic liquid to carry out the galvanic deposit of metal.
Nineteen eighty-two, J.S.wikes has reported by AlCl
3With a kind of ionic liquid at room temperature that chlorination 1-methyl-3-ethyl imidazol(e) (EMI) is made.It has similar character to alkyl pyridine class ionic liquid, but specific conductivity compares AlCl
3-BPC system is high 2～3 times, and viscosity is reduced to original half approximately, and electrochemical window obviously is better than the alkyl pyridine class.The minimum fusing point of this system is at AlCl
3With the mol ratio of EMIC be 2: 1 places, fusing point is-75 ℃.Such ionic liquid can dissolve ferrocene, CuCl
2, TiCl
4Etc. multiple material, also can be miscible with benzene, toluene, acetonitrile equal solvent.People bear coordination ion [AlCl to this type of by dialkylimidazolium positive ion [EMI+] and aluminum chloride
4 -] ionic liquid (AlCl that forms
3The type ionic liquid) furthers investigate, find that this class ionic liquid has many outstanding physicochemical property: high conductivity, still has only very low vapour pressure under the high temperature, high electrochemical stability, to the high resolution of organism and inorganics, high thermal stability and flame retardant resistance, adjustable acid-basicity or the like, and be applied to battery, photocell, fields such as metal electrodeposition and electrical condenser manufacturing.
Summary of the invention
The present invention proposes a kind of new with ionic liquid as ionogen, the compound of metallic lead is dissolved in the ionic liquid as source metal, and utilize metallic lead anode or metal platinum anode, and platinized and titanized anode, in certain temperature, stir speed (S.S.), metallic copper and alloy thereof under certain bath voltage and the current density condition, metal titanium and alloy thereof obtain metallic lead coating on metallic aluminium and the alloy thereof.
The present invention passes through the following steps specific implementation with ionic liquid as the technical scheme of the method for ionogen electrodeposit metals lead-coat: add the metallic lead compound in ionic liquid, get cleaner liquid as in the open type electrochemical cell, the galvanic deposit water-bath is also controlled room temperature, electrochemical cell is with machinery or induction stirring, control flume voltage and current density, anode adopts pure Plante type plate, metal platinum plate or platinized and titanized anode pole plate, obtains metallic lead coating on metallic copper or its alloy, metal titanium or its alloy or metallic aluminium or its alloy substrates.
Described ionic liquid is N
+] X
-, [N wherein
+] be [BMIM
+] (1-butyl-3-Methylimidazole), [EMIM
+One of] in (1-ethyl-3-Methylimidazole), X
-Be F
-, Cl
-, Br
-, I
-, NO
3 -, PF
6 -, BF
4 -One of them.
The compound of metallic lead is plumbous mineral compound or plumbous organic compound, and wherein Qian mineral compound is: plumbous halogenide (PbCl
2, PbBr
2, PbI
2, PbF
2), lead nitrate (PbNO
3), Tetrafluoroboric acid lead (Pb (BF
4)
2), hexafluoro phosphorus lead borate (Pb (PF
6)
2), lead metaborate (B
2O
4PbH
2O) one of them; Plumbous organic compound is: plumbic acetate ((CH3COO)
2Pb), tetraethyllead ((CH
3CH
2)
4Pb), lead formiate ((CH
2O
2)
2Pb), capric acid lead (Pb (C
10H
19O
2)
2), 2 methyl caproic acid lead, isocaprylic acid lead, 2 ethyl hexanoic acid lead (C
16H
30O
4Pb) one of them.
Described galvanic deposition cell voltage 0.5～3V, current density is 10～200A/m
2, metal base is controlled at 1～5cm as negative electrode and positive plate distance.
Described when in ionic liquid, adding the metallic lead compound, need in vacuum glove box, operate to finish, with 20～100 rev/mins of stirrings 1～5 hour.
6, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: the mol ratio of the compound of described ionic liquid and metallic lead is 5～100: 1.
Described plating tank water-bath is controlled at 80～100 ℃ of room temperatures, and stir speed (S.S.) is 20～200 rev/mins; The processing mode of positive plate is with sheet metal, metalwork, metal fragment, known any other form of powder metallurgy casting die or others skilled in the art.
Described plating tank galvanic deposition cell voltage 0.5～3V, current density is 10～200A/m
2
Described metallic aluminium and alloy substrates thereof also need handle in the metal activation agent 1～5 minute before going into groove except according to the conventional surface preparation step, and acetone cleans that the back is charged rapidly goes into groove.
Described base metal need carry out oil removing before going into groove, decontamination, and copper brush mechanical polishing, and chemistry and electrochemical etching, the dehydrated alcohol cleaning-drying is chargedly gone into groove.
Concrete steps are:
1. use ionic liquid [N
+] X
-
2. add the metallic lead compound in the ionic liquid in step 1, stir 20～100 rev/mins simultaneously, 1～5 hour time, cross the leaching cleaner liquid, this step is operated in vacuum glove box and is prevented that ionic liquid from absorbing moisture content.Step 1 and step 2 intermediate ion liquid and metallic lead compound mol ratio are 5～100: 1.
3. ionic liquid that proportioning is good and plumbous metallic compound thereof be as in the open type electrochemical cell usually, and the galvanic deposit water-bath is controlled at room temperature～100 ℃; Electrochemical cell is with machinery or induction stirring mode;
4. base metal need carry out oil removing before going into groove, decontamination, and copper brush mechanical polishing, and chemistry and electrochemical etching, the dehydrated alcohol cleaning-drying is chargedly gone into groove.
5. metallic aluminium and alloy thereof also must be handled in the metal activation agent 1～5 minute before going into groove except all programs of experience step 5, and acetone cleans that the back is charged rapidly goes into groove.
6. metal base is controlled at 1～5cm as negative electrode and positive plate distance.
7. electroplating time was controlled at 1～10 hour, and thickness of coating is 1～30 μ m.
After electroplating end, metal base material is taken out from coating bath, clean with acetone-water-acetone respectively, oven dry obtains fine and close black-lead coating.
The present invention be based on use ion liquid system as ionogen at metallic copper and alloy thereof, metal titanium and alloy thereof, the processing method of electrodeposit metals lead layer on metallic aluminium and the alloy thereof.Compare with the plumbous technology of common electrodeposit metals, the advantage of processing method of the present invention is: can carry out at ambient temperature, no steam volatilization, colorless and odorless does not burn, and no hydrogen discharges, thermally-stabilised good with chemical stability, can obtain higher current efficiency (〉=90%), (3～5V) coating densifications, internal stress is little to have the electrochemical stability window of broad.Maximum advantage is can obtain can't obtain lead-coat on metallic aluminium and alloy substrates material thereof in routine techniques.
Description of drawings
Fig. 1 is a lead plating SEM shape appearance figure on the aluminium,
Fig. 2 is a lead plating layer EDX collection of illustrative plates on the aluminium,
Fig. 3 is a lead plating SEM shape appearance figure on the copper,
Fig. 4 is a lead plating layer EDX collection of illustrative plates on the copper.
Embodiment
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.Technical scheme of the present invention is passed through the following steps specific implementation:
1, uses ionic liquid [N
+] X
-, [N wherein
+] be [BMIM
+] (1-butyl-3-Methylimidazole), [EMIM
+One of] in (1-ethyl-3-Methylimidazole), X
-Be F
-, Cl
-, Br
-, I
-, NO
3 -, PF
6 -, BF
4. -One of them.
2, the ionic liquid [N in step 1
+] X
-The middle metallic lead compound that adds stirs 20～100 rev/mins simultaneously, 1～5 hour time, cross the leaching cleaner liquid, and this step is operated in vacuum glove box and is prevented that ionic liquid from absorbing moisture content.The metallic lead compound comprises mineral compound and organic compound, and mineral compound is plumbous halogenide (PbCl
2, PbBr
2, PbI
2, PbF
2), lead nitrate (PbNO
3), Tetrafluoroboric acid lead (Pb (BF
4)
2), hexafluoro phosphorus lead borate (Pb (PF
6)
2), lead metaborate (B
2O
4PbH
2O) one of them; Organic compound comprises plumbic acetate ((CH3COO)
2Pb), tetraethyllead ((CH
3CH
2)
4Pb), lead formiate ((CH
2O
2)
2Pb), capric acid lead (Pb (C
10H
19O
2)
2), 2 methyl caproic acid lead, isocaprylic acid lead, 2 ethyl hexanoic acid lead (C
16H
30O
4Pb) one of them.
3, step 1 and step 2 intermediate ion liquid and metallic lead compound mol ratio are 5～100: 1.
4, ionic liquid that proportioning is good and plumbous metallic compound thereof be as in the open type electrochemical cell usually, and the galvanic deposit water-bath is controlled at room temperature～100 ℃; Electrochemical cell is with machinery or induction stirring mode, and stir speed (S.S.) is 20～200 rev/mins; Anode adopts pure Plante type plate, and it is with sheet metal, metalwork, metal fragment, known any other form of powder metallurgy casting die or others skilled in the art; Also can adopt the metal platinum plate, or the platinized and titanized anode pole plate.
5, galvanic deposition cell voltage 0.5～3V, current density is 10 ~ 200A/m
2
6, base metal need carry out oil removing before going into groove, decontamination, and copper brush mechanical polishing, and chemistry and electrochemical etching, the dehydrated alcohol cleaning-drying is chargedly gone into groove.
7, metallic aluminium and alloy thereof also must be handled in the metal activation agent 1～5 minute before going into groove except all programs of experience step 5, and acetone cleans that the back is charged rapidly goes into groove.
8, metal base is controlled at 1～5cm as negative electrode and positive plate distance.
9, electroplating time was controlled at 1～10 hour, and thickness of coating is 1～30 μ m.
Embodiment 1 adopts [BMIM] PF
6Ionic liquid is as in the vacuum glove box, adds lead nitrate in 50: 1 in molar ratio, 80 rev/mins of induction stirring speed, 2 hours time, filter cleaner liquid.Get cleaner liquid 200ml and place electroplating container, heating in water bath to 40 ℃, 120 rev/mins of induction stirring speed.Anode adopts pure Plante type plate, size 60mm * 20mm * 1mm, and negative electrode is a fine aluminium, is of a size of 60mm * 10mm * 1mm.Bath voltage is 1.5V, and current density is 15A/m
2, electroplating time 2 hours.After electroplating end, metal base material is taken out from coating bath, clean with acetone-water-acetone respectively, oven dry obtains fine and close black-lead coating.
Coating SEM microscopic appearance as shown in Figure 1, its composition is shown in Fig. 2 EDX result.
Embodiment 2: adopt [EMIM] BF
4Ionic liquid is as in the vacuum glove box, adds plumbic acetate in 60: 1 in molar ratio, 80 rev/mins of induction stirring speed, 2 hours time, filter cleaner liquid.Get cleaner liquid 200ml and place electroplating container, service temperature is a room temperature, 120 rev/mins of induction stirring speed.Anode adopts pure Plante type plate, size 60mm * 20mm * 1mm, and negative electrode is a red copper, is of a size of 60mm * 10mm * 1mm.Bath voltage is 1.0V, and current density is 10A/m
2, electroplating time 1 hour.After electroplating end, metal base material is taken out from coating bath, clean with acetone-water-acetone respectively, oven dry obtains fine and close black-lead coating.Coating SEM microscopic appearance as shown in Figure 3, its composition EDX result is as shown in Figure 4.
Embodiment 3: the present embodiment difference from Example 1 is, ionic liquid and lead nitrate mol ratio 23: 1, and anode adopts the metal platinum pole plate, and bath voltage is 2.2V, and current density is 20A/m
2, electroplating time 2 hours.Other steps are identical with embodiment 1.
Embodiment 4: the present embodiment difference from Example 2 is, ionic liquid and lead nitrate mol ratio 25: 1, and anode adopts the metal platinum pole plate.Other steps are identical with embodiment 1.
Claims (10)
1, a kind of with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: in ionic liquid, add the metallic lead compound, get cleaner liquid as in the open type electrochemical cell, the galvanic deposit water-bath is also controlled room temperature, electrochemical cell is with machinery or induction stirring, control flume voltage and current density, anode adopts pure Plante type plate, metal platinum plate or platinized and titanized anode pole plate, obtains metallic lead coating on metallic copper or its alloy, metal titanium or its alloy or metallic aluminium or its alloy substrates.
2, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described ionic liquid is N
+] X
-, [N wherein
+] be [BMIM
+] (1-butyl-3-Methylimidazole), [EMIM
+One of] in (1-ethyl-3-Methylimidazole), X
-Be F
-, Cl
-, Br
-, I
-, NO
3 -, PF
6 -, BF
4. -One of them.
3, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: the compound of metallic lead is plumbous mineral compound or plumbous organic compound, and wherein Qian mineral compound is: plumbous halogenide (PbCl
2, PbBr
2, PbI
2, PbF
2), lead nitrate (PbNO
3), Tetrafluoroboric acid lead (Pb (BF
4)
2), hexafluoro phosphorus lead borate (Pb (PF
6)
2), lead metaborate (B
2O
4PbH
2O) one of them; Plumbous organic compound is: plumbic acetate ((CH3COO)
2Pb), tetraethyllead ((CH
3CH
2)
4Pb), lead formiate ((CH
2O
2)
2Pb), capric acid lead (Pb (C
10H
19O
2)
2), 2 methyl caproic acid lead, isocaprylic acid lead, 2 ethyl hexanoic acid lead (C
16H
30O
4Pb) one of them.
4, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described galvanic deposition cell voltage 0.5～3V, current density is 10～200A/m
2, metal base is controlled at 1～5cm as negative electrode and positive plate distance.
5, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described when in ionic liquid, adding the metallic lead compound, need in vacuum glove box, to operate to finish, stirred 1～5 hour with 20～100 rev/mins.
6, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: the mol ratio of the compound of described ionic liquid and metallic lead is 5～100: 1.
7, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described plating tank water-bath is controlled at 80～100 ℃ of room temperatures, and stir speed (S.S.) is 20～200 rev/mins; The processing mode of positive plate is with sheet metal, metalwork, metal fragment, known any other form of powder metallurgy casting die or others skilled in the art.
8, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described plating tank galvanic deposition cell voltage 0.5～3V, current density is 10～200A/m
2
9, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described metallic aluminium and alloy substrates thereof are except according to the conventional surface preparation step, also need to handle in the metal activation agent 1～5 minute before going into groove, acetone cleans that the back is charged rapidly goes into groove.
10, according to claim 1 with the method for ionic liquid as ionogen electrodeposit metals lead-coat, it is characterized in that: described base metal need carry out oil removing, decontamination before going into groove, copper brush mechanical polishing, and chemistry and electrochemical etching, the dehydrated alcohol cleaning-drying is chargedly gone into groove.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910094836A CN101629312A (en) | 2009-08-14 | 2009-08-14 | Method for electrodepositing lead by ionic liquid system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910094836A CN101629312A (en) | 2009-08-14 | 2009-08-14 | Method for electrodepositing lead by ionic liquid system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101629312A true CN101629312A (en) | 2010-01-20 |
Family
ID=41574586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910094836A Pending CN101629312A (en) | 2009-08-14 | 2009-08-14 | Method for electrodepositing lead by ionic liquid system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101629312A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103643262A (en) * | 2013-12-10 | 2014-03-19 | 昆明理工大学 | Method for deep eutectic solvent electrodeposition of lead powder |
| CN104499013A (en) * | 2014-12-19 | 2015-04-08 | 中国工程物理研究院材料研究所 | Room temperature ionic liquids electroplating method for electroplating aluminum on RAFM (Reduced Activation Ferritic/martensitic) steel surface |
| CN105780060A (en) * | 2016-03-11 | 2016-07-20 | 昆明理工大学 | Method for electrolytic separation of lead-antimony alloy through deep-eutectic solvent |
| CN105908219A (en) * | 2016-04-27 | 2016-08-31 | 昆明理工大学 | Method for extracting metallic lead by electrolytically reducing galena with ionic liquid |
| CN105951136A (en) * | 2016-06-01 | 2016-09-21 | 淄博火炬能源有限责任公司 | Copper grid fluoride-free electrodepositing lead solution for storage battery and preparation method of copper grid fluoride-free electrodepositing lead solution |
| CN106661753A (en) * | 2014-04-15 | 2017-05-10 | 尼奥工业有限责任公司 | Ionic liquid electrolyte and method to electrodeposit metals |
| CN107820521A (en) * | 2015-06-12 | 2018-03-20 | 帝国革新有限公司 | The electrochemistry recycling of plumbum-based material |
| CN114032581A (en) * | 2021-08-31 | 2022-02-11 | 中国科学院过程工程研究所 | Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide |
-
2009
- 2009-08-14 CN CN200910094836A patent/CN101629312A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103643262B (en) * | 2013-12-10 | 2016-08-24 | 昆明理工大学 | A kind of method of deep eutectic solvent electrodeposition of lead powder |
| CN103643262A (en) * | 2013-12-10 | 2014-03-19 | 昆明理工大学 | Method for deep eutectic solvent electrodeposition of lead powder |
| CN106661753A (en) * | 2014-04-15 | 2017-05-10 | 尼奥工业有限责任公司 | Ionic liquid electrolyte and method to electrodeposit metals |
| US11105013B2 (en) | 2014-04-15 | 2021-08-31 | Neo Industries Llc | Ionic liquid electrolyte and method to electrodeposit metals |
| CN104499013A (en) * | 2014-12-19 | 2015-04-08 | 中国工程物理研究院材料研究所 | Room temperature ionic liquids electroplating method for electroplating aluminum on RAFM (Reduced Activation Ferritic/martensitic) steel surface |
| CN107820521A (en) * | 2015-06-12 | 2018-03-20 | 帝国革新有限公司 | The electrochemistry recycling of plumbum-based material |
| CN107820521B (en) * | 2015-06-12 | 2021-03-30 | 帝国大学创新有限公司 | Electrochemical recycling of lead-based materials |
| CN105780060A (en) * | 2016-03-11 | 2016-07-20 | 昆明理工大学 | Method for electrolytic separation of lead-antimony alloy through deep-eutectic solvent |
| CN105908219A (en) * | 2016-04-27 | 2016-08-31 | 昆明理工大学 | Method for extracting metallic lead by electrolytically reducing galena with ionic liquid |
| CN105951136A (en) * | 2016-06-01 | 2016-09-21 | 淄博火炬能源有限责任公司 | Copper grid fluoride-free electrodepositing lead solution for storage battery and preparation method of copper grid fluoride-free electrodepositing lead solution |
| CN105951136B (en) * | 2016-06-01 | 2018-03-09 | 淄博火炬能源有限责任公司 | Battery copper coin grid free-floride electro-deposition lead solution and preparation method thereof |
| CN114032581A (en) * | 2021-08-31 | 2022-02-11 | 中国科学院过程工程研究所 | Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide |
| CN114032581B (en) * | 2021-08-31 | 2023-03-07 | 中国科学院过程工程研究所 | Method for electrochemically reconstructing metal surface by ionic liquid medium to electro-catalytically reduce carbon dioxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101629312A (en) | Method for electrodepositing lead by ionic liquid system | |
| El Abedin et al. | Additive free electrodeposition of nanocrystalline aluminium in a water and air stable ionic liquid | |
| Zhao et al. | Electrodeposition of aluminium from nonaqueous organic electrolytic systems and room temperature molten salts | |
| CN103422123B (en) | A kind of method of electro-deposition of magnesium nickel alloy in ionic liquid | |
| Zhang et al. | Effects of 1-butyl-3-methylimidazolium hydrogen sulfate-[BMIM] HSO 4 on zinc electrodeposition from acidic sulfate electrolyte | |
| US20100252446A1 (en) | Method to Electrodeposit Metals Using Ionic Liquids in the Presence of an Additive | |
| CN102517608A (en) | Method for electrodepositing zinc and zinc alloy at low temperature by ionic liquor | |
| CN102888630A (en) | Method for preparing nanometer aluminum or nanometer aluminum coating in low-temperature electro-deposition form by using ion liquid/additive system | |
| Wang et al. | Influence of chloride ion on zinc electrodeposition from choline chloride based deep eutectic solvent | |
| CN102839391B (en) | High purity indium preparation method | |
| Hsiu et al. | Electrodeposition behaviour of cadmium telluride from 1-ethyl-3-methylimidazolium chloride tetrafluoroborate ionic liquid | |
| Chang et al. | Green hydrometallurgical extraction of metallic lead from spent lead paste in the methanesulfonic acid system | |
| CN102002594A (en) | Method for recycling tin | |
| CN108441886A (en) | A method of preparing metal using ionic liquid electrolytic metal oxide | |
| CN101265588B (en) | Method for low-temperature electrolysis of aluminum oxide for producing aluminum adopting ion liquid | |
| CN102154661A (en) | Method for preparing aluminum ingot by low-temperature electrolysis of metal monocrystal surface electrodes | |
| CN103820827A (en) | Method for electrodepositing palladium from ionic liquid | |
| KR20190117366A (en) | Method of manufacturing aluminum | |
| CN103031571A (en) | Method for electrodepositing gallium at low temperature by using ionic liquid | |
| JP5888403B2 (en) | Method for preparing plating solution for electroaluminum plating having low melting point, electroplating solution for electroaluminum plating, method for producing aluminum foil, and method for reducing melting point of electroplating solution for electroaluminum plating | |
| CN1737205A (en) | Surface treatment method for magnesium alloy | |
| CN105177623A (en) | Method for recovering tin from copper-tin waste | |
| CN105671598A (en) | Method for directly preparing aluminum foil through low temperature electrolysis | |
| KR101298056B1 (en) | The method collecting the pure zr from the off grade scrap by using the molten salt electrolytic refining method | |
| CN106544699A (en) | A kind of method that ionic liquid electrolytic recovery waste lead accumulator lead plaster carries lead |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100120 |