CN101634037A - Polyaniline anode for electrochemical electrolysis and preparation method thereof - Google Patents
Polyaniline anode for electrochemical electrolysis and preparation method thereof Download PDFInfo
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- CN101634037A CN101634037A CN200910094858A CN200910094858A CN101634037A CN 101634037 A CN101634037 A CN 101634037A CN 200910094858 A CN200910094858 A CN 200910094858A CN 200910094858 A CN200910094858 A CN 200910094858A CN 101634037 A CN101634037 A CN 101634037A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 75
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 56
- 238000005469 granulation Methods 0.000 claims description 28
- 230000003179 granulation Effects 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 14
- 238000001238 wet grinding Methods 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 240000002791 Brassica napus Species 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910052580 B4C Inorganic materials 0.000 abstract description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 abstract 1
- 238000003701 mechanical milling Methods 0.000 description 6
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- 239000011248 coating agent Substances 0.000 description 4
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- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
The invention discloses an anode and a manufacture technology thereof. For obtaining the anode which can be manufactured at lower cost and used more economically, the invention provides a polyaniline anode for electrochemical electrolysis. The anode has two phases or a plurality of phases and comprises an anode matrix and a proper quantity of other mixed quadrivalent compounds such as titanium dioxide, zirconium dioxide, boron carbide, tungsten carbide and the like. The polyaniline anode is obtained by mixing and moulding polyaniline, a coupling agent, an adhesive and proper quantity of quadrivalent compounds. Moreover, in the forming process, a net is added as a framework of an anode plate. The obtained polyaniline anode has the characteristics of good product performance, high quality, simple operation, convenient operation, low pollution, higher conductivity, high intensity, good thermal stability, good chemical stability, good electric catalytic activity and the like.
Description
Technical field
The present invention relates to the electrochemical electrolysis technical field, particularly relate to polyaniline anode for electrochemical electrolysis and method of manufacturing technology.
Background technology
Electrochemical electrolysis is well known in the prior art with anode and insoluble anode, and electrochemical electrolysis is to be undertaken by soluble anode or insoluble anode as electrolytic copper, nickel, zinc or tin.Soluble anode is also referred to as the active anode system, enters electrolytic solution in electrolytic process; Insoluble anode is also referred to as inert anode system, does not enter electrolytic solution in electrolytic process.Insoluble anode is to be made of solid support material and the coating that is arranged on this solid support material, and described coating is called as active coating.Wherein, use titanium, niobium or other reaction carriers material to make solid support material usually, but using this material in any case, it becomes passive state under electrolytic condition.As active layer material, use electro-conductive material such as platinum, iridium or other precious metal usually, the compound of its mixed oxide or above-mentioned element.Wherein, the surface that active coating directly can be coated on solid support material maybe can be placed on the substrate that separates with solid support material.Substrate also can use above-mentioned material as solid support material, i.e. for example titanium, niobium etc., but the result is very expensive, so that be difficult to apply.
In conductive polymers, advantage such as polyaniline is good because of its conductivity, and environmental stability is good, and synthesis technique is simple, and raw materials cost is cheap all has been subjected to people at home and abroad to pay attention to greatly the conductive polymers of the most possible practical application of being known as.
Summary of the invention
The present invention is with reference to Germany Patent document DE 102 61 493A1, but manufacture method of the present invention is different from it.The purpose of this invention is to provide and cheap more mode to make and therefore to use more economical anode.The present invention seeks to so to realize: the present invention proposes a kind of polyaniline anode for electrochemical electrolysis, this anode is two-phase or multiphase, comprises anode substrate and skeleton, and wherein anode substrate is to be made by polyaniline and caking agent.
1. polyaniline anode for electrochemical electrolysis is characterized in that 4 valencys that mix or 5 divalent metal compounds and suppresses as skeleton with metallic mesh forming in the polyaniline matrix.
2. the manufacturing process of polyaniline anode for electrochemical electrolysis is characterized in that having following technological process and step:
(a) at first, all raw materials are dried, to guarantee the accurate of proportioning.Then, synthetic polyaniline, 4 valency compound nano particles and coupling agent are mixed by certain proportioning, wet-milling is 12～18 hours in ball mill, and ratio of grinding media to material is 2: 1, and wet grinding media is industrial alcohol (reducing the degree of oxidation of polyaniline in mechanical milling process).Slip is poured in the beaker, in baking oven, dried 8～10 hours for 50～60 ℃, remove ethanolic soln, the polyaniline raw material powder that obtains loosening.
(b) the polyaniline powder is carried out granulation, in the powder of oven dry, add a little concentration and be 1～5% polyvinyl alcohol solution, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose as caking agent.Raw material after the granulation was left standstill in encloses container 24～32 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture.
When (c) dry-pressing begins, be coated with skim oleic acid in advance at the inner side-wall of metal die, take by weighing quantitative granulation powder and pack in the die cavity, rap mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add reticulation as skeleton; In the pressure process, the pressing speed of held stationary keep-uped pressure after pressure reaches desired value 15～30 minutes, and then release, with the sample depanning.The forming pressure of compacting sample is 20～60Mpa in this experiment, and the sample after the moulding is put into loft drier, and drying is 3～8 hours under 40～50 ℃, and temperature rises to dry 3～4 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
The molar ratio of the add-on of 4 valencys or 5 divalent metal compound nanoparticles and polyaniline is 1: 5～20 among the present invention; Described nanoparticle can be any one in titanium dioxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, Vanadium Pentoxide in FLAKES, five oxidations, two thalliums, norbide and the wolfram varbide etc.
The scope of the mass ratio of coupling agent and polyaniline is 0.05～0.25 among the present invention: 1, and the coupling agent agent can be any in silane coupling agent, titanate coupling agent, aluminate coupling agent and the bimetal coupling agent.
The scope of the mass ratio of caking agent polyvinyl alcohol and polyaniline is 1～10 among the present invention: 100.
The skeleton of reticulation described in the present invention places between the described polyaniline anode substrate, can be by in iron net, copper mesh, titanium net and the carbon fibre web any, the net that preferred titanium is made.
The present invention obtains the anode of more cheap manufacture and more economical use, the polyaniline anode good product performance that the present invention obtains, quality height, simple, easy to operate and pollute characteristics such as little.This polyaniline anode has higher electroconductibility, the intensity height, and thermostability, chemical stability is good and electro catalytic activity is good.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Embodiment 1
Technological process and step in the present embodiment are as follows:
(a) at first, all raw materials are dried, to guarantee the accurate of proportioning.Then, synthetic polyaniline 100g, nano titanium oxide 20g and silane coupling agent 5g are mixed, wet-milling is 12 hours in ball mill, and ratio of grinding media to material is 2: 1, and wet grinding media is industrial alcohol (can reduce the degree of oxidation of polyaniline in mechanical milling process).Slip is poured in the beaker, in baking oven, dried 10 hours for 50 ℃, remove ethanolic soln, the polyaniline raw material powder that obtains loosening.
(b) the polyaniline powder is carried out granulation, in the powder of oven dry, add 1g concentration and be 5% polyvinyl alcohol solution, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose as caking agent.Raw material after the granulation was left standstill in encloses container 24 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture.
When (c) dry-pressing begins, be coated with skim oleic acid in advance at the inner side-wall of metal die, the granulation powder in (b) is packed in the die cavity, rap mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add the iron net as skeleton; In the pressure process, the pressing speed of held stationary keep-uped pressure after pressure reaches 20Mpa 15 minutes, and then release, with the sample depanning.Sample after the moulding is put into loft drier, and drying is 8 hours under 40 ℃, and temperature rises to dry 3 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
Embodiment 2
Technological process and step in the present embodiment are as follows:
(a) at first, all raw materials are dried, to guarantee the accurate of proportioning.Then, synthetic polyaniline 100g, nano titanium oxide 10g and titanate coupling agent 10g are mixed, wet-milling is 16 hours in ball mill, and ratio of grinding media to material is 2: 1, and wet grinding media is industrial alcohol (reducing the degree of oxidation of polyaniline in mechanical milling process).Slip is poured in the beaker, in baking oven, dried 9 hours for 60 ℃, remove ethanolic soln, the polyaniline raw material powder that obtains loosening.
(b) the polyaniline powder is carried out granulation, in the powder of oven dry, add 5g concentration and be 1% polyvinyl alcohol solution, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose as caking agent.Raw material after the granulation was left standstill in encloses container 28 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture.
When (c) dry-pressing begins, be coated with skim oleic acid in advance at the inner side-wall of metal die, the granulation powder in (b) is packed in the die cavity, rap mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add copper mesh as skeleton; In the pressure process, the pressing speed of held stationary keep-uped pressure after pressure reaches 40Mpa 25 minutes, and then release, with the sample depanning.Sample after the moulding is put into loft drier, and drying is 6 hours under 45 ℃, and temperature rises to dry 3.5 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
Embodiment 3
Technological process and step in the present embodiment are as follows:
(a) at first, all raw materials are dried, to guarantee the accurate of proportioning.Then, synthetic polyaniline 100g, nano zirconium dioxide 5g and aluminate coupling agent 25g are mixed, wet-milling is 18 hours in ball mill, and ratio of grinding media to material is 2: 1, and wet grinding media is industrial alcohol (reducing the degree of oxidation of polyaniline in mechanical milling process).Slip is poured in the beaker, in baking oven, dried 8 hours for 60 ℃, remove ethanolic soln, the polyaniline raw material powder that obtains loosening.
(b) the polyaniline powder is carried out granulation, in the powder of oven dry, add the 10g mass concentration and be 2.5% polyvinyl alcohol solution, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose as caking agent.Raw material after the granulation was left standstill in encloses container 32 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture.
When (c) dry-pressing begins, be coated with skim oleic acid in advance at the inner side-wall of metal die, the granulation powder in (b) is packed in the die cavity, rap mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add the titanium net as skeleton; In the pressure process, the pressing speed of held stationary keep-uped pressure after pressure reaches 60Mpa 30 minutes, and then release, with the sample depanning.Sample after the moulding is put into loft drier, and drying is 3 hours under 50 ℃, and temperature rises to dry 4 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
Embodiment 4
Technological process and step in the present embodiment are as follows:
(a) at first, all raw materials are dried, to guarantee the accurate of proportioning.Then, synthetic polyaniline 100g, nano boron carbide 15g and bimetal coupling agent 10g are mixed, wet-milling is 18 hours in ball mill, and ratio of grinding media to material is 2: 1, and wet grinding media is industrial alcohol (reducing the degree of oxidation of polyaniline in mechanical milling process).Slip is poured in the beaker, in baking oven, dried 8 hours for 60 ℃, remove ethanolic soln, the polyaniline raw material powder that obtains loosening.
(b) the polyaniline powder is carried out granulation, in the powder of oven dry, add the 8g mass concentration and be 2.5% polyvinyl alcohol solution, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose as caking agent.Raw material after the granulation was left standstill in encloses container 32 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture.
When (c) dry-pressing begins, be coated with skim oleic acid in advance at the inner side-wall of metal die, the granulation powder in (b) is packed in the die cavity, rap mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add carbon fiber as skeleton; In the pressure process, the pressing speed of held stationary keep-uped pressure after pressure reaches 45Mpa 30 minutes, and then release, with the sample depanning.Sample after the moulding is put into loft drier, and drying is 3 hours under 50 ℃, and temperature rises to dry 4 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
Embodiment 5
Technological process and step in the present embodiment are as follows:
(a) at first, all raw materials are dried, to guarantee the accurate of proportioning.Then, synthetic polyaniline 100g, nanometer Vanadium Pentoxide in FLAKES 20g and titanate coupling agent 15g are mixed, wet-milling is 18 hours in ball mill, and ratio of grinding media to material is 2: 1, and wet grinding media is industrial alcohol (reducing the degree of oxidation of polyaniline in mechanical milling process).Slip is poured in the beaker, in baking oven, dried 8 hours for 60 ℃, remove ethanolic soln, the polyaniline raw material powder that obtains loosening.
(b) the polyaniline powder is carried out granulation, in the powder of oven dry, add the 8g mass concentration and be 2.5% polyvinyl alcohol solution, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose as caking agent.Raw material after the granulation was left standstill in encloses container 32 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture.
When (c) dry-pressing begins, be coated with skim oleic acid in advance at the inner side-wall of metal die, the granulation powder in (b) is packed in the die cavity, rap mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add carbon fiber as skeleton; In the pressure process, the pressing speed of held stationary keep-uped pressure after pressure reaches 45Mpa 30 minutes, and then release, with the sample depanning.Sample after the moulding is put into loft drier, and drying is 3 hours under 50 ℃, and temperature rises to dry 4 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
Embodiment 6
Basic identical with the situation of embodiment 4, just changing nanoparticle is five oxidations, two thalliums, and other condition is identical with embodiment 4, and the sample that obtains is the polyaniline anode sample.
Embodiment 7
Basic identical with the situation of embodiment 5, just changing nanoparticle is Manganse Dioxide, and other condition is identical with embodiment 5, and the sample that obtains is the polyaniline anode sample.
Embodiment 8
Basic identical with the situation of embodiment 3, just changing nanoparticle is cerium dioxide, and other condition is identical with embodiment 3, and the sample that obtains is the polyaniline anode sample.
Claims (8)
1, a kind of polyaniline anode for electrochemical electrolysis, it is characterized in that this anode is two-phase or multiphase, comprise anode substrate and skeleton, wherein anode substrate is made up of polyaniline, coupling agent and caking agent, skeleton adopts metallic mesh, in anode substrate, mix 4 valencys or 5 divalent metal compound nanoparticles, whole polyaniline anode is formed by anode substrate and skeleton compacting, and the molar ratio of the add-on of 4 valencys or 5 divalent metal compound nanoparticles and polyaniline is 1: 5～20 in anode substrate; Described nanoparticle is any one in titanium dioxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, Vanadium Pentoxide in FLAKES, five oxidations, two thalliums, norbide and the wolfram varbide etc.
2, polyaniline anode for electrochemical electrolysis according to claim 1, it is characterized in that, the scope of the mass ratio of described coupling agent and polyaniline is 0.05～0.25: 1, the coupling agent agent can be any in silane coupling agent, titanate coupling agent, aluminate coupling agent and the bimetal coupling agent, and the scope of the mass ratio of caking agent polyvinyl alcohol and polyaniline is 1～10: 100.
3, polyaniline anode for electrochemical electrolysis according to claim 1 is characterized in that, described metallic mesh skeleton places between the polyaniline anode substrate, by in iron net, copper mesh, titanium net and the carbon fibre web any, and the net that preferred titanium is made.
4, a kind of preparation method of polyaniline anode for electrochemical electrolysis is characterized in that comprising following processing step:
(a) at first, all raw materials are dried, then, synthetic polyaniline, 4 valencys, 5 valency compound nano particles and coupling agent are mixed by proportioning, wet-milling is 12～18 hours in ball mill, ratio of grinding media to material is 2: 1, wet grinding media is an industrial alcohol, and slip is poured in the beaker, dries 8～10 hours for 50～60 ℃ in baking oven, remove ethanolic soln, the polyaniline powder that obtains loosening;
(b) the polyaniline powder that (a) obtained carries out granulation, in the anilino powder of oven dry, add a little concentration and be 1～5% polyvinyl alcohol solution as caking agent, in mortar, mix, again powder is sieved with 80 mesh sieve, to reach the granulation purpose, raw material after the granulation was left standstill in encloses container 24～32 hours,, moisture and binding agent in the powder are evenly distributed by the evaporation and the diffusion of moisture;
When (c) dry-pressing begins, inner side-wall at metal die is coated with skim oleic acid in advance, takes by weighing granulation powder that quantitative step (b) obtains and packs in the die cavity, raps mould side wall, suitably vibration makes each corner of the even loading mould cavity of powder, and guarantees the smooth of powder upper surface; In addition, in die cavity, add reticulation as skeleton; In the pressure process, the pressing speed of held stationary, after reaching desired value, pressure keep-uped pressure 15～30 minutes, and then release, with the sample depanning, the forming pressure of compacting sample is 20～60Mpa, sample after the moulding is put into loft drier, drying is 3～8 hours under 40～50 ℃, and temperature rises to dry 3～4 hours of 60 ℃ of continuation then, and the sample that obtains is the polyaniline anode sample.
5. the preparation method of polyaniline anode for electrochemical electrolysis according to claim 4,, it is characterized in that in the described polyaniline anode that the molar ratio of the add-on of 4 valencys or 5 divalent metal compound nanoparticles and polyaniline is 1: 5～20; Described nanoparticle can be any one in titanium dioxide, cerium dioxide, Manganse Dioxide, plumbic oxide, zirconium dioxide, Vanadium Pentoxide in FLAKES, five oxidations, two thalliums, norbide and the wolfram varbide etc.
6. the preparation method of polyaniline anode for electrochemical electrolysis according to claim 4, it is characterized in that, the scope of the mass ratio of coupling agent and polyaniline is 0.05～0.25: 1, and the coupling agent agent can be any in silane coupling agent, titanate coupling agent, aluminate coupling agent and the bimetal coupling agent.
7. the preparation method of polyaniline anode for electrochemical electrolysis according to claim 4 is characterized in that, the scope of the mass ratio of caking agent polyvinyl alcohol and polyaniline is 1～10: 100.
8. the preparation method of polyaniline anode for electrochemical electrolysis according to claim 4, it is characterized in that, described reticulation skeleton places between the described polyaniline anode substrate, can be by in iron net, copper mesh, titanium net and the carbon fibre web any, the net that preferred titanium is made.
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Cited By (5)
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| CN102409366A (en) * | 2011-12-05 | 2012-04-11 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| CN102505130A (en) * | 2011-12-01 | 2012-06-20 | 昆明理工大学 | Polyaniline-coated Al-based Pb-WC composite anode and preparation method thereof |
| CN105274557A (en) * | 2015-11-12 | 2016-01-27 | 厦门理工学院 | Electrode and preparation method thereof |
| CN105714329A (en) * | 2014-12-05 | 2016-06-29 | 上海奇谋能源技术开发有限公司 | Method for directly electrolyzing metal scraps |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4654104A (en) * | 1985-12-09 | 1987-03-31 | The Dow Chemical Company | Method for making an improved solid polymer electrolyte electrode using a fluorocarbon membrane in a thermoplastic state |
| CN1320171C (en) * | 2004-11-25 | 2007-06-06 | 复旦大学 | Lead dioxide electrode and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102505130A (en) * | 2011-12-01 | 2012-06-20 | 昆明理工大学 | Polyaniline-coated Al-based Pb-WC composite anode and preparation method thereof |
| CN102505130B (en) * | 2011-12-01 | 2015-08-12 | 昆明理工大学 | A kind of polyaniline-coated Al-based Pb-WC composite anode and preparation method thereof |
| CN102409366A (en) * | 2011-12-05 | 2012-04-11 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| CN102409366B (en) * | 2011-12-05 | 2015-05-20 | 昆明理工大学 | Lead aluminium-base composite inert anode material for Zn electrodeposition and preparation method thereof |
| CN105714329A (en) * | 2014-12-05 | 2016-06-29 | 上海奇谋能源技术开发有限公司 | Method for directly electrolyzing metal scraps |
| CN105714329B (en) * | 2014-12-05 | 2017-10-20 | 上海奇谋能源技术开发有限公司 | A kind of method of Direct Electrolysis scrap |
| CN106548877A (en) * | 2015-09-22 | 2017-03-29 | 南京绿索电子科技有限公司 | Carbon nano pipe array/polyaniline/ceria composite electrode and its preparation method and application |
| CN106548877B (en) * | 2015-09-22 | 2018-07-17 | 南京绿索电子科技有限公司 | Carbon nano pipe array/polyaniline/ceria composite electrode and its preparation method and application |
| CN105274557A (en) * | 2015-11-12 | 2016-01-27 | 厦门理工学院 | Electrode and preparation method thereof |
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