CN104313652A - Preparation method of aluminum-based multiphase inert composite anode material - Google Patents
Preparation method of aluminum-based multiphase inert composite anode material Download PDFInfo
- Publication number
- CN104313652A CN104313652A CN201410496658.6A CN201410496658A CN104313652A CN 104313652 A CN104313652 A CN 104313652A CN 201410496658 A CN201410496658 A CN 201410496658A CN 104313652 A CN104313652 A CN 104313652A
- Authority
- CN
- China
- Prior art keywords
- composite anode
- anode
- preparation
- heterogeneous
- anode materials
- 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.)
- Granted
Links
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000007747 plating Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000000243 solution Substances 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 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- 229910001316 Ag alloy Inorganic materials 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000005363 electrowinning Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 abstract 3
- 230000000694 effects Effects 0.000 abstract 2
- 229910000978 Pb alloy Inorganic materials 0.000 abstract 1
- 238000002048 anodisation reaction Methods 0.000 abstract 1
- 229910000420 cerium oxide Inorganic materials 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000013527 degreasing agent Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 239000012669 liquid formulation Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- STDOKXGTOHCKPX-UHFFFAOYSA-N O.[Na].[Na].[Na].C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound O.[Na].[Na].[Na].C(CC(O)(C(=O)O)CC(=O)O)(=O)O STDOKXGTOHCKPX-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 229940001516 sodium nitrate Drugs 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a preparation method of an aluminum-based multiphase inert composite anode material, and belongs to the technical field of metal surface treatment. The aluminum-based PbO2-MnO2-CeO2-WC multiphase inert composite anode material doped by nanometer cerium oxide and micrometer tungsten carbide is prepared through an anodization technology, a coating layer of the material has a dark-black compact crystallization surface, has a thickness of 90-180[mu]m, and has good adhesion with a substrate. When the composite anode material is used as an anode in zinc electrowinning, the surface of the anode is in a non-soluble state as a conductive multiphase composite material, so the pollution of the dissolving of traditional lead and a lead-based alloy anode to a cathode zinc is avoided, and the quality of the cathode product is improved; the addition of tungsten carbide (WC) with good electrocatalytic activity and electrical conductivity enhances the electrocatalytic activity of electrode materials, and the bath voltage of the anode of the invention is 0.2-0.5V lower than that of traditional lead and silver alloy anodes, and is stable, so the power consumption is effectively reduced; and the addition of a rare earth oxide CeO2 makes the grains of the coating refined and the coating compact and flattened, so the corrosion resistance of the material is effectively improved.
Description
Technical field
The present invention relates to a kind of preparation method of heterogeneous inertia composite anode materials, belong to field of metal surface treatment technology.
Background technology
In Zinc hydrometallurgy process, Pb-Ag alloy anode is widely used, such anode material can meet the basic need that electrowinning zinc is produced, but also there is many inherent defects being difficult to improve, as: easily bending distortion causes that short circuit, weight cause greatly assembling difficulty, electrolytic deposition process energy consumption is high, anode electro catalytic activity is lower.Meanwhile, anode lead is easily with Pb
2+ionic species dissolves and enters solution, and in cathodic deposition, cathode zinc product hierarchy is declined.In order to solve the problem, scientific worker carries out modification to conventional P b base alloy anode on the one hand, continues on the one hand to explore the novel inertia energy-conserving anode of research and development, as PbO
2and MnO
2anode etc.For the research of Pb base alloy anode, mainly concentrating on the research and development of the alloy materials such as Pb-Ag, Pb-Ca, Pb-Ag-Ti, Pb-Ca-Sn, in the research of novel inertia energy-conserving anode, is mainly the PbO of matrix with Ti
2or MnO
2deng metal oxide as outer field anode material, though the latter has lower overpotential for oxygen evolution, its defect such as high cost and low life-span makes it be difficult to replace traditional lead based alloy anodes.Therefore, the important topic that novel inertia energy-conserving anode material is still zinc hydrometallurgy field is is at present researched and developed.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of heterogeneous inertia composite anode materials, specifically comprise the following steps:
(1) aluminum substrate is carried out the pre-treatment of physics polishing and oil removing;
(2) aluminum substrate processed step (1) carries out two step leaching zinc successively;
(3) aluminum substrate after two step leaching zinc process is carried out quick electronickelling;
(4) aluminum substrate obtained in step (3) being made anode, is that negative electrode is at temperature 60 ~ 80 DEG C, anodic current density 20-40mA/cm with stainless steel plate
2, mechanical stirring 200-250r/min condition under plating 1 ~ 2 hour, the anode after plating through washing, dry up after aluminium base PbO
2-MnO
2-CeO
2-WC inertia composite anode materials.
The described physics polishing of step (1) can adopt 120 order sand paper to polish, with industrial alkaline degreaser oil removing.
Step (1) described polishing and oil removal treatment are conventional treatment process, specifically comprise the following steps: polishing → washing → oil removing (Na
3pO
440g/L, Na
2siO
315g/L, 1-3min) leaching of → washing → alkali (NaOH 20 g/L, Na
2cO
32 g/L, 1min) → washing → acidleach (HF 10mlL
-1, HNO
3250 mlL
-1, H
3pO
4250 mlL
-1, 3min) and → washing.
Two steps leaching zinc described in step (2) are conventional method: and the Al matrix → washing after pre-treatment → once zinc-plated (60 seconds) → wash → move back zinc (20 seconds, with the HNO of 1:1
3solubilize moves back zinc) → secondary galvanization (40 seconds), temperature controls at normal temperature; Wherein, galvanizing flux formula is: sodium hydroxide 500g/L, Seignette salt 50g/L, zinc oxide 50g/L, iron trichloride 3g/L, SODIUMNITRATE 2g/L.
Quick electronickelling described in step of the present invention (3): the Al matrix after twice electroless zinc plating is after washing, and the Al matrix after twice electroless zinc plating is done negative electrode, and graphite cake of the same area makes anode, is 50 DEG C in temperature, and current density is 1.5Adm
-2, electroplating time is carry out quick electronickelling under the condition of 5 minutes; Wherein, nickel-plating liquid formula: NiSO
480 gL
-1, two citric acid monohydrate trisodium (Na
3c
6h
5o
72H
2o) 90 gL
-1, H
3bO
310gL
-1, NaCl10 gL
-1, Na
2sO
4.10H
2o 35gL
-1, additive (gelatin) 0.4 gL
-1.
In step of the present invention (4), the area of cathode material is 1.5 ~ 2 times of sheet material area to be plated.
Adopt ultrasonic wave by mixed electrolytic solution dispersion 30 ~ 40 minutes in step of the present invention (4) before plating.
In electroplating process described in step of the present invention (4), the composition of electroplate liquid is lead nitrate 190-250g/L, manganese nitrate solution 40-70g/L, Sodium Fluoride 1-2g/L, cerium dioxide 10-20g/L, wolfram varbide 20-50g/L.
In step of the present invention (4), the granularity of cerium dioxide is 10 ~ 30nm, and the granularity of wolfram varbide is 1 ~ 3 μm, and the particle diameter of cerium dioxide is 10 ~ 30nm, and the particle diameter of wolfram varbide is 1 ~ 3 μm.
This composite anode materials surface is in furvous, and surface crystallization is fine and close, and thickness of coating is 90-180 μm, coating and substrate caking power excellent.
The present invention adopts anonizing to prepare doped micron-size wolfram varbide (WC) and nano level cerium dioxide (CeO
2) aluminium base β-PbO
2-MnO
2-CeO
2the heterogeneous inertia composite anode materials of-WC, when making anode in Zinc electrolysis, as conduction heterogeneous composite material, its surface is in non-molten state, avoids the pollution of tradition lead and lead based alloy anodes dissolving anticathode zinc, improves cathode product quality; What have wolfram varbide (WC) particle of satisfactory electrical conductivity adds the electro catalytic activity and erosion resistance that improve electrode materials, reduces overpotential for oxygen evolution, bath voltage can be made to reduce 0.2-0.5V, and bath voltage is stablized, and effectively reduces power consumption; Rare earth oxide CeO
2add, can crystal grain thinning, make coating more fine and close smooth, effectively can improve the erosion resistance of anode material.
Beneficial effect of the present invention is:
(1) the heterogeneous inertia composite anode materials of the Zinc electrolysis prepared by, avoids the pollution of tradition lead and lead based alloy anodes dissolving anticathode zinc, effectively can improve the grade of cathode zinc product;
(2) this anode material has good electro catalytic activity, effectively can reduce oxygen overpotential on anode, thus reduces bath voltage, reaches energy-saving and cost-reducing object;
(3) the adding of rare earth oxide, make electrode surface more fine and close smooth, can effectively improve its erosion resistance, increase the service life.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1
(1) aluminum substrate is carried out the pre-treatment of physics polishing and oil removing:
120 order sand paper are adopted to polish, with industrial alkaline degreaser oil removing.Concrete steps are: (degreaser consists of: Na in polishing → washing → oil removing
3pO
440g/L, Na
2siO
315g/L, 1-3min) leaching of → washing → alkali (NaOH 20 g/L, Na
2cO
32 g/L, 1min) → washing → acidleach (HF 10mlL
-1, HNO
3250 mlL
-1, H
3pO
4250 mlL
-1, 3min) and → washing.
(2) aluminum substrate processed step (1) carries out two step leaching zinc successively:
Two steps leaching zinc are carried out to the aluminum substrate of pre-treatment, two step dip galvanizing techniques formulas: the Al matrix → washing after pre-treatment → once zinc-plated (60 seconds) → wash → move back zinc (20 seconds, with the HNO of 1:1
3solubilize moves back zinc) → secondary galvanization (40 seconds), temperature controls at normal temperature; Wherein, galvanizing flux formula is: sodium hydroxide 500g/L, Seignette salt 50g/L, zinc oxide 50g/L, iron trichloride 3g/L, SODIUMNITRATE 2g/L.
(3) aluminum substrate after two step leaching zinc process is carried out quick electronickelling: the Al matrix after twice electroless zinc plating is after washing, Al matrix after twice electroless zinc plating is done negative electrode, graphite cake of the same area makes anode, is 50 DEG C in temperature, and current density is 1.5Adm
-2, electroplating time is carry out quick electronickelling under the condition of 5 minutes; Wherein, nickel-plating liquid formula: NiSO
480 gL
-1, two citric acid monohydrate trisodium (Na
3c
6h
5o
72H
2o) 90gL
-1, H
3bO
310gL
-1, NaCl10 gL
-1, Na
2sO
4.10H
2o 35gL
-1, additive (gelatin) 0.4 gL
-1.
(4) aluminium base β-PbO is prepared in galvanic deposit
2-MnO
2-CeO
2the heterogeneous inertia composite anode materials of-WC: be that negative electrode is at temperature 70 C, anodic current density 30mA/cm with stainless steel plate
2, mechanical stirring 230r/min condition under plating 1.5 hours, the anode after plating through washing, dry up after aluminium base PbO
2-MnO
2-CeO
2-WC inertia composite anode materials; Wherein, electroplate liquid formulation is: lead nitrate (Pb (NO
3)
2) 190g/L, 50% manganese nitrate solution (Mn (NO
3)
2) 40g/L, Sodium Fluoride (NaF) 1g/L, cerium dioxide (CeO
2granularity is: 15nm) 10g/L, wolfram varbide (wc grain size is 2 μm) 20g/L; Before plating, electroplate liquid is carried out ultrasonic wave and disperse 35 minutes.
The thickness of multiple plating that the present embodiment prepares is 90 ~ 120 μm, and in coating, Ce constituent content is 5.26 ~ 6.78%, and content of element W is 1.48 ~ 3.91%.
Embodiment 2
In the present embodiment, step (1) ~ (3) are identical with embodiment 1; Difference is to be that negative electrode is at temperature 80 DEG C, anodic current density 40mA/cm with stainless steel plate in step (4)
2, mechanical stirring 250r/min condition under plating 2 hours, the anode after plating through washing, dry up after aluminium base PbO
2-MnO
2-CeO
2-WC inertia composite anode materials; Wherein, electroplate liquid formulation is: lead nitrate (Pb (NO
3)
2) 220g/L, 50% manganese nitrate solution (Mn (NO
3)
2) 50g/L, Sodium Fluoride (NaF) 1.5g/L, cerium dioxide (CeO
2granularity is: 10 ~ 30nm) 15g/L, wolfram varbide (wc grain size is 3 μm) 30g/L; Before plating, electroplate liquid is carried out ultrasonic wave and disperse 40 minutes.
Aluminium base β-the PbO that the present embodiment prepares
2-MnO
2-CeO
2-WC thickness of multiple plating is 130 ~ 160 μm, and in coating, Ce constituent content is 8.75 ~ 9.67%, and content of element W is 3.61 ~ 4.59%.
Embodiment 3
In the present embodiment, step (1) ~ (3) are identical with embodiment 1; Difference is to be that negative electrode is at temperature 60 C, anodic current density 20mA/cm with stainless steel plate in step (4)
2, mechanical stirring 200r/min condition under plating 1 hour, the anode after plating through washing, dry up after aluminium base PbO
2-MnO
2-CeO
2-WC inertia composite anode materials; Wherein, electroplate liquid formulation is: lead nitrate (Pb (NO
3)
2) 250g/L, 50% manganese nitrate solution (Mn (NO
3)
2) 70g/L, Sodium Fluoride (NaF) 2g/L, cerium dioxide (CeO
2granularity is: 20 ~ 30nm) 20g/L, wolfram varbide (wc grain size is 1 μm) 40g/L; Before plating, electroplate liquid is carried out ultrasonic wave and disperse 30 minutes.
Aluminium base β-the PbO that the present embodiment prepares
2-MnO
2-CeO
2-WC thickness of multiple plating is 140 ~ 180 μm, and in coating, Ce constituent content is 9.01 ~ 12.38%, and content of element W is 5.64 ~ 7.89%.
Claims (5)
1. a preparation method for heterogeneous inertia composite anode materials, is characterized in that, specifically comprise the following steps:
(1) aluminum substrate is carried out the pre-treatment of physics polishing and oil removing;
(2) aluminum substrate processed step (1) carries out two step leaching zinc successively;
(3) aluminum substrate after two step leaching zinc process is carried out quick electronickelling;
(4) aluminum substrate obtained in step (3) being made anode, is that negative electrode is at temperature 60 ~ 80 DEG C, anodic current density 20-40mA/cm with stainless steel plate
2, mechanical stirring 200-250r/min condition under plating 1 ~ 2 hour, the anode after plating through washing, dry up after aluminium base PbO
2-MnO
2-CeO
2-WC inertia composite anode materials.
2. the preparation method of heterogeneous inertia composite anode materials according to claim 1, is characterized in that: the area of cathode material is 1.5 ~ 2 times of sheet material area to be plated.
3. the preparation method of heterogeneous inertia composite anode materials according to claim 1, is characterized in that: adopt ultrasonic wave by mixed electrolytic solution dispersion 30 ~ 40 minutes before plating.
4. the preparation method of heterogeneous inertia composite anode materials according to claim 1, it is characterized in that: in electroplating process described in step (4), the composition of electroplate liquid is lead nitrate 190-250g/L, manganese nitrate solution 40-70 g/L, Sodium Fluoride 1-2 g/L, cerium dioxide 10-20 g/L, wolfram varbide 20-50 g/L.
5. the preparation method of heterogeneous inertia composite anode materials according to claim 2, is characterized in that: the granularity of cerium dioxide is 10 ~ 30nm, and the granularity of wolfram varbide is 1 ~ 3 μm, and the particle diameter of cerium dioxide is 10 ~ 30nm, and the particle diameter of wolfram varbide is 1 ~ 3 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410496658.6A CN104313652B (en) | 2014-09-25 | 2014-09-25 | Preparation method of aluminum-based multiphase inert composite anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410496658.6A CN104313652B (en) | 2014-09-25 | 2014-09-25 | Preparation method of aluminum-based multiphase inert composite anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104313652A true CN104313652A (en) | 2015-01-28 |
| CN104313652B CN104313652B (en) | 2017-02-15 |
Family
ID=52368956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410496658.6A Active CN104313652B (en) | 2014-09-25 | 2014-09-25 | Preparation method of aluminum-based multiphase inert composite anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104313652B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762639A (en) * | 2015-03-09 | 2015-07-08 | 中南大学 | A porous aluminum-based composite anode used for a hydrometallurgy electrodeposition process and a preparing method |
| CN105568340A (en) * | 2015-12-30 | 2016-05-11 | 河北工业大学 | Preparation method for manganese-ion-doped lead dioxide anode material used for super capacitor |
| CN107841765A (en) * | 2017-09-29 | 2018-03-27 | 中南大学 | A kind of Zinc electrolysis anode material and preparation method thereof |
| CN108774737A (en) * | 2018-06-13 | 2018-11-09 | 昆明理工恒达科技股份有限公司 | A kind of preparation method of foam metal base metal composite anode materials |
| CN109537000A (en) * | 2018-11-27 | 2019-03-29 | 昆明理工大学 | A kind of stainless base steel β-PbO2-MnO2-CeO2-ZrO2The preparation method of inertia composite anode materials |
| CN110904463A (en) * | 2019-12-04 | 2020-03-24 | 安徽铜冠有色金属（池州）有限责任公司 | Cleaning method for removing oil stains on cathode and anode plate surfaces in zinc hydrometallurgy |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072586A (en) * | 1975-12-10 | 1978-02-07 | Diamond Shamrock Technologies S.A. | Manganese dioxide electrodes |
| US5632872A (en) * | 1995-06-21 | 1997-05-27 | Marion Dattilo | Composite electrical electrode and a method for forming the same |
| CN101736369A (en) * | 2009-12-29 | 2010-06-16 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102838191A (en) * | 2012-09-27 | 2012-12-26 | 昆明理工大学 | Method for preparing composite anode material |
| CN103060874A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of stainless steel-based beta-PbO2-SnO2-CeO2-ZrO2 inertia composite anode material |
| CN103060875A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of copper-based SnO2-Sb2O5-CeO2-TiO2 inert composite anode material |
-
2014
- 2014-09-25 CN CN201410496658.6A patent/CN104313652B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4072586A (en) * | 1975-12-10 | 1978-02-07 | Diamond Shamrock Technologies S.A. | Manganese dioxide electrodes |
| US5632872A (en) * | 1995-06-21 | 1997-05-27 | Marion Dattilo | Composite electrical electrode and a method for forming the same |
| CN101736369A (en) * | 2009-12-29 | 2010-06-16 | 昆明理工大学 | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition |
| CN102838191A (en) * | 2012-09-27 | 2012-12-26 | 昆明理工大学 | Method for preparing composite anode material |
| CN103060874A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of stainless steel-based beta-PbO2-SnO2-CeO2-ZrO2 inertia composite anode material |
| CN103060875A (en) * | 2013-01-30 | 2013-04-24 | 昆明理工大学 | Preparation method of copper-based SnO2-Sb2O5-CeO2-TiO2 inert composite anode material |
Non-Patent Citations (4)
| Title |
|---|
| 杨锐等: ""纳米CeO2对β-PbO2-ZrO2¬-CeO2复合电极耐蚀性的EIS分析"", 《化学研究与应用》 * |
| 杨锐等: ""纳米CeO2对β-PbO2-ZrO2¬-CeO2复合电极耐蚀性的EIS分析"", 《化学研究与应用》, vol. 25, no. 11, 15 November 2013 (2013-11-15), pages 1521 * |
| 陆丽芳: ""Al/Pb-WC-CeO2/PbO2/MnO2电极的制备及其电化学性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 陈步明: ""新型节能阳极材料制备技术及电化学性能研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762639A (en) * | 2015-03-09 | 2015-07-08 | 中南大学 | A porous aluminum-based composite anode used for a hydrometallurgy electrodeposition process and a preparing method |
| CN104762639B (en) * | 2015-03-09 | 2017-03-15 | 中南大学 | Hydrometallurgy electro-deposition operation porous aluminum based composite anode and preparation method |
| CN105568340A (en) * | 2015-12-30 | 2016-05-11 | 河北工业大学 | Preparation method for manganese-ion-doped lead dioxide anode material used for super capacitor |
| CN105568340B (en) * | 2015-12-30 | 2021-03-05 | 河北工业大学 | Preparation method of manganese ion-doped lead dioxide positive electrode material for supercapacitor |
| CN107841765A (en) * | 2017-09-29 | 2018-03-27 | 中南大学 | A kind of Zinc electrolysis anode material and preparation method thereof |
| CN107841765B (en) * | 2017-09-29 | 2019-08-16 | 中南大学 | A kind of Zinc electrolysis anode material and preparation method thereof |
| CN108774737A (en) * | 2018-06-13 | 2018-11-09 | 昆明理工恒达科技股份有限公司 | A kind of preparation method of foam metal base metal composite anode materials |
| CN108774737B (en) * | 2018-06-13 | 2020-02-14 | 昆明理工恒达科技股份有限公司 | Preparation method of foam metal-based lead alloy composite anode material |
| CN109537000A (en) * | 2018-11-27 | 2019-03-29 | 昆明理工大学 | A kind of stainless base steel β-PbO2-MnO2-CeO2-ZrO2The preparation method of inertia composite anode materials |
| CN109537000B (en) * | 2018-11-27 | 2020-12-08 | 昆明理工大学 | Stainless steel based beta-PbO2-MnO2-CeO2-ZrO2Preparation method of inert composite anode material |
| CN110904463A (en) * | 2019-12-04 | 2020-03-24 | 安徽铜冠有色金属（池州）有限责任公司 | Cleaning method for removing oil stains on cathode and anode plate surfaces in zinc hydrometallurgy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104313652B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103205780B (en) | Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode | |
| CN104313652B (en) | Preparation method of aluminum-based multiphase inert composite anode material | |
| CN101736369B (en) | Method for preparing novel aluminum-based composite lead dioxide-manganese dioxide anode for zinc electrodeposition | |
| CN101962788B (en) | Preparation method of Al-based Pb-WC-CeO2 inert composite anode material | |
| CN101343758B (en) | Method for preparing novel energy conservation inert anode material for zinc electrodeposition | |
| CN103060874B (en) | A kind of stainless steel-based β-PbO 2-SnO 2-CeO 2-ZrO 2the preparation method of inertia composite anode materials | |
| CN100580147C (en) | Method for manufacturing energy-saving inert anode material for non-ferro metals electrodeposition | |
| CN102888625B (en) | Non-ferrous metal electrodeposition palisading type positive plate | |
| CN101538724B (en) | Method for preparing energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning | |
| US10731266B2 (en) | Composite anode unit, anode plate and methods for preparing the same | |
| CN101922024B (en) | Light composite electro-catalysis energy-saving anode for non-ferrous metal electro-deposition and preparation method thereof | |
| CN103422123A (en) | Method for electro-deposition of magnesium nickel alloy in ionic liquid | |
| CN104962977B (en) | Preparation method of rod-shaped bimetallic-based composite anode material | |
| CN104611609A (en) | Low-silver lead alloy multi-element anode material for non-ferrous metal electrodeposition and preparation method thereof | |
| CN102433581B (en) | Method for preparing novel anode material for electro-deposition of nonferrous metals | |
| CN102051640B (en) | Preparation method of Al-based Pb-ZrO2-CeO2 composite anode material for zinc electrodepositing | |
| CN103060846B (en) | Method for preparing Zn-Pb-Bi-La alloy electrode material through pulse electrodeposition | |
| CN105132980B (en) | A kind of lead silver alloy anode surface recombination ceramic film film build method | |
| CN103060875B (en) | Preparation method of copper-based SnO2-Sb2O5-CeO2-TiO2 inert composite anode material | |
| CN103806054A (en) | Pulse plating method of Ag-Ni alloy for electric contact material | |
| CN109537000B (en) | Stainless steel based beta-PbO2-MnO2-CeO2-ZrO2Preparation method of inert composite anode material | |
| CN113293411B (en) | Gradient composite lead dioxide anode plate and preparation method and application thereof | |
| CN110484942A (en) | A kind of more first micron crystalline substance coating of Ni-P-C-Si-W, plating solution and preparation method thereof | |
| CN102443822A (en) | Gradient functional inert anode material used for zinc electrodeposition and its preparation method | |
| CN114808041A (en) | Preparation and activation regeneration method of Pb-based pseudomorphic stable anode for manganese electrodeposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210310 Address after: 650106, No. 1299 Chang Yuan North Road, Kunming hi tech Development Zone, Yunnan Patentee after: KUNMING HENDERA SCIENCE AND TECHNOLOGY Co.,Ltd. Address before: 650093 No. 253, Xuefu Road, Wuhua District, Yunnan, Kunming Patentee before: Kunming University of Science and Technology |