CN105032198A - Porous nickel flat sheet membrane preparation method and porous nickel flat sheet membrane prepared by using same - Google Patents
Porous nickel flat sheet membrane preparation method and porous nickel flat sheet membrane prepared by using same Download PDFInfo
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- CN105032198A CN105032198A CN201510404184.2A CN201510404184A CN105032198A CN 105032198 A CN105032198 A CN 105032198A CN 201510404184 A CN201510404184 A CN 201510404184A CN 105032198 A CN105032198 A CN 105032198A
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- flat membrane
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- nickel porous
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Abstract
The invention discloses a porous nickel flat sheet membrane preparation method and a porous nickel flat sheet membrane prepared by using same. The method comprises the following steps: 1) preparing a casting membrane solution, wherein a formula of the casting membrane solution comprises: 30-70% of nickel powder with a particle size range of 0.5-50 microns, 3-7% of a binder, 0-1% of a thickener and the balance of a solvent; and the binder is selected from one or more of polyacrylonitrile, polysulfone and polyether sulfone; 2) scraping the membrane, wherein a wet membrane is prepared from the casting membrane solution obtained in the step 1) by adopting a membrane scraping method, the prepared formed wet membrane is soaked into water until a solvent is sufficiently separated out, and the wet membrane is dried in air to obtain a to-be-sintered membrane; and 3), sintering, wherein the to-be-sintered membrane obtained in the step 2) is roasted, the temperature increasing rate is 1-10 DEG C/min during sintering, the highest sintering temperature is 700-1000 DEG C, and the porous nickel flat sheet membrane is obtained by naturally cooling after reaching the highest sintering temperature and preserving the temperature for 0-120 minutes.
Description
Technical field
The present invention relates in porous metal material field, particularly a kind of method of nickel porous film.
Background technology
Porous metal film is the material relying on the space between powder particle to be separated material, and common pore diameter range is between 0.1 μm-10 μm.Porous metal film originates from the forties in last century, in the stainless steel membrane development nineties rapidly, is used as diffusion barrier because of superior performance afterwards.
Porous metal film is integrated with the large porosity of porous metals and specific area, the characteristic of metal advantages such as ceramic membrane intensity is high, easy cleaning that make it both have thus be applied to UF membrane aspect, simultaneously the metal structure of porous makes metal film in electricity, magnetics, thermodynamics etc., have functional characteristic not available for ordinary metallic material or other diffusion barriers, has a extensive future.
At present about a variety of method has appearred in the preparation of porous metals, the Feng Wei of Chengdu University proposes a kind of method (Chengdu University preparing nickel porous, Feng Wei, the preparation method of nickel porous, publication number: CN104263989A), adopt pore creating material naphthalene powder to mix with nickel powder, sintering makes naphthalene distillation pore-forming.The Chen Gang of Jiangsu University by nickel zinc melting mixing then vacuum evaporation zinc removing is formed nickel porous (Jiangsu University, Chen Gang, a kind of preparation method of nickel porous, publication number: CN103627920).The preparation method of nickel porous is various, but all can not accomplish laminar nickel porous film.
Pin of the present invention have employed especially one very simple and easy and efficiently preparation method to prepare nickel porous Flat Membrane.Adopt and the most simply scrape membrane technology, by controlling knifing rod and the gap size of scraping between lamina membranacea can regulate and control arbitrarily the thickness of metal film, the thinlyyest reaching ten microns, can change porosity by changing composition parameter simultaneously.The nickel porous film of such preparation has the characteristic of porous metals, can be used as electrode material, separation membrane etc., has a extensive future.
Summary of the invention
The invention provides the very simple film technique of one and prepare porous metals Flat Membrane, simple to operate and cost is low, to realize industrial production, be applied to filtration system.Can accomplish very thin thickness, large porosity can be used for electrochemistry aspect simultaneously.
The invention provides a kind of nickel porous Flat Membrane preparation method, be characterised in that and said method comprising the steps of
Step 1) preparation casting solution
The formula of described casting solution is, particle size range is the nickel powder 30-70% of 0.5-50 μm, binding agent 3-7%, thickener 0-1%, and the solvent of surplus, and described percentage is all weight percentage; Said components mixes and obtains casting solution, and described binding agent is selected from one or more in polyacrylonitrile (PAN), polysulfones, polyether sulfone.
2) knifing
By step 1) casting solution that obtains adopts knifing legal system to obtain wet film, and obtained shaping wet film is dipped in water after solvent fully separates out, dry and obtain film to be sintered.
3) sinter
By step 2) film to be sintered that obtains sinters, when sintering, programming rate is at 1-10 DEG C/min, and sintering maximum temperature is 700 ~ 1000 DEG C, as sintering temperature T≤T
1time sintering atmosphere be argon gas and/or hydrogen, as sintering temperature T > T
1time sintering atmosphere be the gaseous mixture that hydrogen or hydrogen and argon gas form, in described gaseous mixture, the percent by volume of hydrogen is greater than 20%, 300 DEG C≤T
1≤ 400 DEG C, after reaching sintering maximum temperature, after insulation 0-120min, cooling obtains nickel porous Flat Membrane naturally.
Described nickel porous Flat Membrane preparation method, is characterized in that step 3) obtain the cleaning of nickel porous Flat Membrane to carbon-free residual.
Described nickel porous Flat Membrane preparation method, its feature is preferably polyacrylonitrile at described binding agent.
Described nickel porous Flat Membrane preparation method, is characterized in that the particle size range of described nickel powder is preferably 0.5-10 μm.
Described nickel porous Flat Membrane preparation method, is characterized in that the ratio of the maximum particle diameter of described nickel powder and the difference of minimum grain size and nickel powder meso-position radius D50 is less than 50%, is preferably less than 20%.
Described nickel porous Flat Membrane preparation method, it is characterized in that described solvent is can dissolve binding agent and can water-soluble organic solvent, be selected from 1-METHYLPYRROLIDONE (NMP), N, one or more in dinethylformamide (DMF), ethylene carbonate (EC), dimethylacetylamide (DMAc), preferred 1-METHYLPYRROLIDONE.
Described thickener is selected from one or more in polyvinylpyrrolidone (PVP), hydroxypropyl methylcellulose, hydroxyethylcellulose, preferably polyethylene pyrrolidones.
Described nickel porous Flat Membrane preparation method, is characterized in that described step 1) in component in formula of casting mixed the concrete grammar obtaining casting solution be: be heated to 40-80 DEG C and be stirred to mix after all components mixing by formula.Preferably adopt the method mixing 30-120min of sonic oscillation before heating.
Described nickel porous Flat Membrane preparation method, is characterized in that step 2) in the wet-film thickness that obtains be 10-200 μm, preferred 20-100 μm.
Described nickel porous Flat Membrane preparation method, is characterized in that preferred described step 3) in the hydrogen volume degree of gaseous mixture be greater than 30%.
Preferred described step 3) sintering maximum temperature be 800 ~ 950 DEG C.
Preferred described step 3) programming rate be 1-8 DEG C/min, be more preferably 2-5 DEG C/min.
Described nickel porous Flat Membrane preparation method, is characterized in that described step 4) in adopt ethanol and/or acetone as cleaning agent.
The present invention also provides a kind of nickel porous Flat Membrane, it is characterized in that described nickel porous Flat Membrane prepares with described arbitrary preparation method.The pore diameter range of preferred described nickel porous Flat Membrane is 0.5-20 μm.
Beneficial effect of the present invention is: the technology concrete grammar that the invention provides a kind of easy preparation nickel porous Flat Membrane.
Compared with prior art it has the following advantages:
1) film forming thickness can control arbitrarily and the thinlyyest reach less than 10 μm, and the space uniformity is high.
2) the nickel porous Flat Membrane intensity obtained is large, good toughness, has all advantages of porous metals, can be used for UF membrane etc. and require harsher workplace to film strength, toughness, temperature etc. when thickness is greater than 40 μm.
3) the nickel porous Flat Membrane porosity obtained is high, good conductivity, can be used for making the electrochemical applications such as collector, electrode material occasion.
Accompanying drawing explanation
Fig. 1 is the surface scan Electronic Speculum figure of the nickel porous Flat Membrane that embodiment 1 obtains
Fig. 2 is the cross-sectional scans Electronic Speculum figure of the nickel porous Flat Membrane that embodiment 2 obtains
Detailed description of the invention
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
The nickel porous Flat Membrane preparation method that this detailed description of the invention provides, comprises the following steps
A kind of nickel porous Flat Membrane preparation method, is characterised in that and said method comprising the steps of
1) casting solution is prepared
After in the formula of described casting solution, all components first mixes rear sonic oscillation 30min, then heating water bath to 50 DEG C be stirred to mix and obtain casting solution.
2) knifing
By step 1) casting solution that obtains adopts knifing legal system to obtain wet film, and obtained shaping wet film is dipped in water after solvent fully separates out, dry and obtain film to be sintered.
3) sinter
By step 2) film to be sintered that obtains carries out sintering and obtains film to be cleaned, and programming rate during sintering is V DEG C/min;
As sintering temperature T≤T
1dEG C time sintering atmosphere be argon gas and/or hydrogen, in sintering atmosphere, the volumn concentration of hydrogen is H
1%;
As sintering temperature T > T
1time sintering atmosphere be the gaseous mixture that hydrogen or hydrogen and argon gas form, the hydrogen volume in gaseous mixture is than being H
2%;
Sinter to maximum temperature T
maxafter insulation tmin, cooling obtains nickel porous Flat Membrane naturally.
Obtained nickel porous Flat Membrane is detected as film thickness with ethanol or acetone cleaning to carbon-free remaining.
The nickel powder particle size range adopted in this detailed description of the invention is 1 ~ 3 μm, and meso-position radius D50 is 2 μm.
Embodiment 1 ~ 6
Formula and the obtained wet-film thickness of embodiment 1 ~ 6 see the following form 1
The formula of table 1 embodiment 1 ~ 6 and obtained wet-film thickness
The step 3 of all embodiments 1 ~ 6) in concrete sintering process as following table 2:
The formula of table 2 embodiment 1 ~ 6, technique and obtained wet-film thickness
Note: embodiment 2 ~ 4 is in sintering process, and sintering temperature reaches T
1front and back all adopt same sintering atmosphere, wherein reach T in embodiment 4
1programming rate is before 2 DEG C/min, and programming rate is 5 DEG C/min afterwards.
When adopting the NMP in DMF, EC, DMAc alternative embodiment, also nickel porous Flat Membrane can be obtained.
The surface scan Electronic Speculum figure of the porous flat plate film that embodiment 1 obtains as shown in Figure 1.
The cross-sectional scans Electronic Speculum figure of the porous flat plate film that embodiment 2 obtains as shown in Figure 2.
As can be seen from Fig. 1,2, employing the invention provides the nickel porous Flat Membrane that preparation method obtains, and nickel powder material is complete at sintering film forming film structure, porous nickel.
Stretching experiment is carried out to the porous flat plate film that embodiment 4 obtains, sample film length 40mm, sectional area 0.4mm
2, draw speed 5mm/min, the following fracture strength 11.87MPa of average behavior data obtained, elongation at break 1.858%.
As can be seen from above-mentioned data, adopt the nickel porous Flat Membrane that the invention provides preparation method and obtain, very high fracture strength is shown when carrying out stretching experiment, and above-mentioned nickel porous Flat Membrane still can keep complete after carrying out repeatedly doubling, illustrates that film provided by the invention has higher intensity and toughness.
Claims (10)
1. a nickel porous Flat Membrane preparation method, is characterised in that and said method comprising the steps of
1) casting solution is prepared
The formula of described casting solution is, particle size range is the nickel powder 30-70% of 0.5-50 μm, binding agent 3-7%, thickener 0-1%, and the solvent of surplus, and described percentage is all weight percentage, and said components mixes and obtains casting solution; Described binding agent is selected from one or more in polyacrylonitrile, polysulfones, polyether sulfone;
2) knifing
By step 1) casting solution that obtains adopts knifing legal system to obtain wet film, and obtained shaping wet film is dipped in water after solvent fully separates out, dry and obtain film to be sintered;
3) sinter
By step 2) film to be sintered that obtains sinters, and when sintering, programming rate is at 1-10 DEG C/min, and sintering maximum temperature is 700 ~ 1000 DEG C, as sintering temperature T≤T
1time sintering atmosphere be argon gas and/or hydrogen, as sintering temperature T > T
1time sintering atmosphere be the gaseous mixture that hydrogen or hydrogen and argon gas form, in described gaseous mixture, the percent by volume of hydrogen is greater than 20%, 300 DEG C≤T
1≤ 400 DEG C, after reaching sintering maximum temperature, after insulation 0-120min, cooling obtains nickel porous Flat Membrane naturally.
2. nickel porous Flat Membrane preparation method as claimed in claim 1, is characterized in that described binding agent is polyacrylonitrile.
3. nickel porous Flat Membrane preparation method as claimed in claim 1, it is characterized in that described solvent be can dissolve binding agent and can be water-soluble organic solvent.
4. nickel porous Flat Membrane preparation method as claimed in claim 3, is characterized in that described solvent is selected from 1-METHYLPYRROLIDONE, one or more in DMF, ethylene carbonate, dimethylacetylamide.
5. nickel porous Flat Membrane preparation method as claimed in claim 1, is characterized in that one or more that described thickener is selected from polyvinylpyrrolidone, hydroxypropyl methylcellulose, hydroxyethylcellulose.
6. nickel porous Flat Membrane preparation method as claimed in claim 1, is characterized in that step 2) in the wet-film thickness that obtains be 10-200 μm.
7. nickel porous Flat Membrane preparation method as claimed in claim 1, is characterized in that described step 3) sintering maximum temperature be 800 ~ 950 DEG C.
8. nickel porous Flat Membrane preparation method as claimed in claim 1, is characterized in that described step 3) sintering time programming rate be 1-8 DEG C/min.
9. a nickel porous Flat Membrane, is characterized in that described nickel porous Flat Membrane obtains with the preparation method as described in as arbitrary in claim 1 ~ 8.
10. nickel porous Flat Membrane as claimed in claim 1, described in its feature, the pore diameter range of nickel porous Flat Membrane is 0.5-20 μm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854633A (en) * | 2016-05-27 | 2016-08-17 | 成都易态科技有限公司 | Porous film and preparation method thereof |
| CN108251881A (en) * | 2018-01-22 | 2018-07-06 | 天津工业大学 | A kind of POROUS TITANIUM/titania nanotube composite flat membrane and preparation method thereof |
| CN108365163A (en) * | 2017-12-29 | 2018-08-03 | 天津工业大学 | Continuous three-dimensional porous copper current collector and preparation method thereof |
| CN108365226A (en) * | 2017-12-29 | 2018-08-03 | 天津工业大学 | Copper-tin oxide porous alloy film and preparation method thereof for lithium cell negative pole |
| CN109589802A (en) * | 2018-11-06 | 2019-04-09 | 国电南瑞科技股份有限公司 | A kind of porous diffusion barrier and its preparation method utilize the made battery of the porous diffusion barrier |
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| CN101088595A (en) * | 2007-07-11 | 2007-12-19 | 湖北工业大学 | Process of preparing plate porous membrane with high permeating flux |
| CN103657435A (en) * | 2013-12-10 | 2014-03-26 | 南京工业大学 | Porous metal hollow fibrous membrane and preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088595A (en) * | 2007-07-11 | 2007-12-19 | 湖北工业大学 | Process of preparing plate porous membrane with high permeating flux |
| CN103657435A (en) * | 2013-12-10 | 2014-03-26 | 南京工业大学 | Porous metal hollow fibrous membrane and preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854633A (en) * | 2016-05-27 | 2016-08-17 | 成都易态科技有限公司 | Porous film and preparation method thereof |
| CN105854633B (en) * | 2016-05-27 | 2019-05-31 | 成都易态科技有限公司 | Porous membrane and preparation method thereof |
| CN108365163A (en) * | 2017-12-29 | 2018-08-03 | 天津工业大学 | Continuous three-dimensional porous copper current collector and preparation method thereof |
| CN108365226A (en) * | 2017-12-29 | 2018-08-03 | 天津工业大学 | Copper-tin oxide porous alloy film and preparation method thereof for lithium cell negative pole |
| CN108365226B (en) * | 2017-12-29 | 2021-01-26 | 天津工业大学 | Copper-tin oxide porous alloy film for lithium battery negative electrode and preparation method thereof |
| CN108251881A (en) * | 2018-01-22 | 2018-07-06 | 天津工业大学 | A kind of POROUS TITANIUM/titania nanotube composite flat membrane and preparation method thereof |
| CN109589802A (en) * | 2018-11-06 | 2019-04-09 | 国电南瑞科技股份有限公司 | A kind of porous diffusion barrier and its preparation method utilize the made battery of the porous diffusion barrier |
| CN109589802B (en) * | 2018-11-06 | 2021-08-24 | 国电南瑞科技股份有限公司 | Porous separation membrane for zinc-bromine flow battery and preparation method thereof |
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