CN103101981A - Method for preparing Ni(OH)2 nanosheet array film by hydrothermal method - Google Patents
Method for preparing Ni(OH)2 nanosheet array film by hydrothermal method Download PDFInfo
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- CN103101981A CN103101981A CN2013100407653A CN201310040765A CN103101981A CN 103101981 A CN103101981 A CN 103101981A CN 2013100407653 A CN2013100407653 A CN 2013100407653A CN 201310040765 A CN201310040765 A CN 201310040765A CN 103101981 A CN103101981 A CN 103101981A
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Abstract
The invention provides a method for preparing a Ni(OH)2 nanosheet array film by a hydrothermal method. The method comprises the following steps: (1) placing a substrate with a clean surface into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and boiling till no bubble generates; (2) placing the substrate in pure oleic acid, soaking for 2-4 hours in a water bath kettle of 70 DEG C, then taking out the substrate, removing excessive oleic acid, and then placing the substrate in a potassium permanganate solution to be soaked for 4-8 hours to complete carboxylation of the substrate; (3) dropwise adding ammonium water into a nickelous acetate and ethanol solution till the pH value of the mixed solution is 8-9, and stirring to prepare a Ni(OH)2 sol; (4) dipping the carboxylated substrate in the Ni(OH)2 sol, and lifting twice to three times, and pre-growing a Ni(OH)2 crystal seed on the substrate; and (5) uniformly mixing a nickel salt solution and a hexamethylenetetramine solution in equimolar ratio to prepare a Ni(OH)2 growth solution, then pouring into a hydrothermal reaction kettle, and simultaneously placing the substrate, on which the Ni(OH)2 crystal seed is pre-grown, into the growth solution, warming for 2-4 hours at 70-80 DEG C, then heating to 160-180 DEG C, warming for 6-10 hours, naturally cooling, taking out the substrate, and washing and drying the substrate to obtain the Ni(OH)2 nanosheet array film.
Description
Technical field
The present invention relates to a kind of hydrothermal method and prepare Ni (OH)
2The method of nano-chip arrays film belongs to the film material with function technical field.
Background technology
Preparing in recent years heavy body, highly active nickel hydroxide active material of cathode becomes the focus of domestic and international research.With common micron spherical Ni (OH)
2Compare nanometer Ni (OH)
2Particle has higher proton shifting speed, less grain resistance, activating velocity faster.Nanometer Ni (OH)
2The research of powder body material is a lot, but directly prepares nanometer Ni (OH)
2The characteristics such as the research of film is relatively less, and thin-film microbattery is high due to energy density, has extended cycle life, and security is good, and operating temperature range is large are considered to the main trend of the development of battery from now on.Therefore study a kind of simple and practical Ni (OH)
2Method for manufacturing thin film is one of gordian technique that promotes the thin-film microbattery development.
Summary of the invention
Problem to be solved by this invention is to provide and a kind ofly can satisfies above-mentioned needs, workable, favorable reproducibility, the simple a kind of hydrothermal method of technique and prepare Ni (OH)
2The method of nano-chip arrays film.Its technical scheme is:
A kind of hydrothermal method prepares Ni (OH)
2The method of nano-chip arrays film, it is characterized in that adopting following steps: (1) substrate is simple glass, silica glass or ITO conductive glass, the substrate of surface clean is placed in the vitriol oil and hydrogen peroxide mixed solution, in mixed solution, the vitriol oil and hydrogen peroxide volume ratio are 7:3, boil to without Bubble formation, complete the hydroxylation of substrate; (2) substrate after hydroxylation is placed in pure oleic acid, soak 2 ~ 4h in the water-bath of 70 ℃ after, clean to remove again the unnecessary oleic acid of surface attachment with dehydrated alcohol, and then to be placed in concentration be that the potassium permanganate solution of 10mg/ml soaks 4 ~ 8h, complete the carboxylated of substrate; (3) ammoniacal liquor slowly is added drop-wise in the nickel acetate ethanolic soln that volumetric molar concentration is 0.01 ~ 0.2M in stirring, until the pH value of mixing solutions is 8 ~ 9, continues to stir 0.5 ~ 2h at 20 ~ 40 ℃, be mixed with Ni (OH)
2Colloidal sol; (4) with the substrate after carboxylated at Ni (OH)
2Flood 5 ~ 10min in colloidal sol, after taking out, at 100 ~ 120 ℃ of drying 10 ~ 20min, dipping lifts 2 ~ 3 times repeatedly, presets Ni (OH) on substrate
2Crystal seed; (5) nickel salt solution and the hexamethylenetetramine solution that volumetric molar concentration are 1～25mM evenly are mixed and made into Ni (OH) by equimolar ratio
2Then growth media is poured in hydrothermal reaction kettle, will preset simultaneously Ni (OH)
2The substrate of crystal seed is put into growth media, together is placed in baking oven, after 70 ~ 80 ℃ of insulation 2 ~ 4h, then is warming up to 160 ~ 180 ℃ of insulation 6 ~ 10h, takes out the substrate repetitive scrubbing after naturally cooling dry, can obtain Ni (OH)
2The nano-chip arrays film, wherein nickel salt solution is any in nickelous nitrate, single nickel salt or nickelous chloride.
Described hydrothermal method prepares Ni (OH)
2The method of nano-chip arrays film in step (1), successively with washings, acetone, ethanol and deionized water difference ultrasonic cleaning 15 ~ 20min, makes it surface cleaning clean with substrate.
The present invention compared with prior art, its advantage is:
1, adopt hydrothermal method directly to prepare Ni (OH) on glass substrate
2The nano-chip arrays film, Ni (OH)
2Nanometer sheet crystal size is controlled, and is workable, and favorable reproducibility is suitable for mass-producing, suitability for industrialized production.
2, in step (5), hydro-thermal reaction is carried out in two steps, and at first the purpose at 70 ~ 80 ℃ of insulation 2 ~ 4h is for the homogenous nucleation speed that slows down, and hexamethylenetetramine slowly is hydrolyzed discharges OH
-, guarantee Ni (OH)
2Nucleus forms evenly continuous Ni (OH) at Grown
2The nano-chip arrays film, then being warming up to 160 ~ 180 ℃ of insulation 6 ~ 10h increases Ni (OH) again
2The degree of crystallinity of crystal.
3, low to substrate specifications, shape need, aspect the film growth on large area film growth and irregular substrate material, have outstanding advantage.
Description of drawings
Fig. 1 is the embodiment of the present invention 1 gained Ni (OH)
2The XRD figure of nano-chip arrays film;
Fig. 2 is the embodiment of the present invention 1 gained Ni (OH)
2The SEM figure of nano-chip arrays film.
Embodiment
Embodiment 1, adopts following steps:
(1) the simple glass substrate is used successively washings, acetone, ethanol and deionized water ultrasonic cleaning 15min respectively, then the substrate with surface clean is placed in the vitriol oil and hydrogen peroxide mixed solution, in mixed solution, the vitriol oil and hydrogen peroxide volume ratio are 7:3, boil to without Bubble formation, complete the hydroxylation of substrate;
(2) substrate after hydroxylation is placed in pure oleic acid, soak 4h in the water-bath of 70 ℃ after, clean to remove again the unnecessary oleic acid of surface attachment with dehydrated alcohol, and then to be placed in concentration be that the potassium permanganate solution of 10mg/ml soaks 8h, complete the carboxylated of substrate;
(3) ammoniacal liquor slowly is added drop-wise in the nickel acetate ethanolic soln that volumetric molar concentration is 0.01M in stirring, until the pH value of mixing solutions is 8, continues to stir 0.5h at 40 ℃, be mixed with Ni (OH)
2Colloidal sol;
(4) with the substrate after carboxylated at Ni (OH)
2Flood 10min in colloidal sol, taking-up is rear at 120 ℃ of dry 10min, then dipping lifts 2 times repeatedly, presets Ni (OH) on substrate
2Crystal seed;
(5) nickel nitrate solution and the hexamethylenetetramine solution that volumetric molar concentration are 12.5mM evenly are mixed and made into Ni (OH) by equimolar ratio
2Then growth media is poured in hydrothermal reaction kettle, will preset simultaneously Ni (OH)
2The substrate of crystal seed is put into growth media, together is placed in baking oven, and after 70 ℃ of insulation 2h, then to be warming up to 180 ℃ of insulations be 6h, takes out the substrate repetitive scrubbing after naturally cooling dry, can obtain Ni (OH)
2The nano-chip arrays film.
Can be found out by Fig. 1 and Fig. 2, film is warming up to 180 ℃ after 70 ℃ of insulation 2h, after hydro-thermal reaction 6h, generated the good β-Ni (OH) of degree of crystallinity
2Phase, and β-Ni (OH)
2Crystal grain is structure in the form of sheets, and vertical-growth is in substrate surface, and nanometer sheet overlaps mutually, and the opening hole is left in the centre, presents Ni (OH)
2The nano-chip arrays membrane structure.
Embodiment 2:
(1) the silica glass substrate is used successively washings, acetone, ethanol and deionized water ultrasonic cleaning 20min respectively, then the substrate with surface clean is placed in the vitriol oil and hydrogen peroxide mixed solution, in mixed solution, the vitriol oil and hydrogen peroxide volume ratio are 7:3, boil to without Bubble formation, complete the hydroxylation of substrate;
(2) substrate after hydroxylation is placed in pure oleic acid, soak 2h in the water-bath of 70 ℃ after, clean to remove again the unnecessary oleic acid of surface attachment with dehydrated alcohol, and then to be placed in concentration be that the potassium permanganate solution of 10mg/ml soaks 4h, complete the carboxylated of substrate;
(3) ammoniacal liquor slowly is added drop-wise in the nickel acetate ethanolic soln that volumetric molar concentration is 0.1M in stirring, until the pH value of mixing solutions is 9, continues to stir 2h at 20 ℃, be mixed with Ni (OH)
2Colloidal sol;
(4) with the substrate after carboxylated at Ni (OH)
2Flood 5min in colloidal sol, taking-up is rear at 100 ℃ of dry 20min, then dipping lifts 2 times repeatedly, presets Ni (OH) on substrate
2Crystal seed;
(5) nickel sulfate solution and the hexamethylenetetramine solution that volumetric molar concentration are 25mM evenly are mixed and made into Ni (OH) by equimolar ratio
2Then growth media is poured in hydrothermal reaction kettle, will preset simultaneously Ni (OH)
2The substrate of crystal seed is put into growth media, together is placed in baking oven, and after 80 ℃ of insulation 2h, then to be warming up to 160 ℃ of insulations be 10h, takes out the substrate repetitive scrubbing after naturally cooling dry, can obtain Ni (OH)
2The nano-chip arrays film.
Embodiment 3:
(1) the ITO Conducting Glass is used successively washings, acetone, ethanol and deionized water ultrasonic cleaning 15min respectively, then the substrate with surface clean is placed in the vitriol oil and hydrogen peroxide mixed solution, in mixed solution, the vitriol oil and hydrogen peroxide volume ratio are 7:3, boil to without Bubble formation, complete the hydroxylation of substrate;
(2) substrate after hydroxylation is placed in pure oleic acid, soak 3h in the water-bath of 70 ℃ after, clean to remove again the unnecessary oleic acid of surface attachment with dehydrated alcohol, and then to be placed in concentration be that the potassium permanganate solution of 10mg/ml soaks 6h, complete the carboxylated of substrate;
(3) ammoniacal liquor slowly is added drop-wise in the nickel acetate ethanolic soln that volumetric molar concentration is 0.2M in stirring, until the pH value of mixing solutions is 8, continues to stir 1h at 30 ℃, be mixed with Ni (OH)
2Colloidal sol;
(4) with the substrate after carboxylated at Ni (OH)
2Flood 8min in colloidal sol, after taking out, at 110 ℃ of dry 15min, then dipping lifts 1 time, presets Ni (OH) on substrate
2Crystal seed;
(5) nickel chloride solution and the hexamethylenetetramine solution that volumetric molar concentration are 1mM evenly are mixed and made into Ni (OH) by equimolar ratio
2Then growth media is poured in hydrothermal reaction kettle, will preset simultaneously Ni (OH)
2The substrate of crystal seed is put into growth media, together is placed in baking oven, and after 75 ℃ of insulation 3h, then to be warming up to 170 ℃ of insulations be 8h, takes out the substrate repetitive scrubbing after naturally cooling dry, can obtain Ni (OH)
2The nano-chip arrays film.
Claims (2)
1. a hydrothermal method prepares Ni (OH)
2The method of nano-chip arrays film, it is characterized in that adopting following steps: (1) substrate is simple glass, silica glass or ITO conductive glass, the substrate of surface clean is placed in the vitriol oil and hydrogen peroxide mixed solution, in mixed solution, the vitriol oil and hydrogen peroxide volume ratio are 7:3, boil to without Bubble formation, complete the hydroxylation of substrate; (2) substrate after hydroxylation is placed in pure oleic acid, soak 2 ~ 4h in the water-bath of 70 ℃ after, clean to remove again the unnecessary oleic acid of surface attachment with dehydrated alcohol, and then to be placed in concentration be that the potassium permanganate solution of 10mg/ml soaks 4 ~ 8h, complete the carboxylated of substrate; (3) ammoniacal liquor slowly is added drop-wise in the nickel acetate ethanolic soln that volumetric molar concentration is 0.01 ~ 0.2M in stirring, until the pH value of mixing solutions is 8 ~ 9, continues to stir 0.5 ~ 2h at 20 ~ 40 ℃, be mixed with Ni (OH)
2Colloidal sol; (4) with the substrate after carboxylated at Ni (OH)
2Flood 5 ~ 10min in colloidal sol, after taking out, at 100 ~ 120 ℃ of drying 10 ~ 20min, dipping lifts 2 ~ 3 times repeatedly, presets Ni (OH) on substrate
2Crystal seed; (5) nickel salt solution and the hexamethylenetetramine solution that volumetric molar concentration are 1～25mM evenly are mixed and made into Ni (OH) by equimolar ratio
2Then growth media is poured in hydrothermal reaction kettle, will preset simultaneously Ni (OH)
2The substrate of crystal seed is put into growth media, together is placed in baking oven, and after 70 ~ 80 ℃ of insulation 2 ~ 4h, then to be warming up to 160 ~ 180 ℃ of insulations be 6 ~ 10h, takes out the substrate repetitive scrubbing after naturally cooling dry, can obtain Ni (OH)
2The nano-chip arrays film, wherein nickel salt solution is any in nickelous nitrate, single nickel salt or nickelous chloride.
2. hydrothermal method as claimed in claim 1 prepares Ni (OH)
2The method of nano-chip arrays film is characterized in that: in step (1), substrate successively with washings, acetone, ethanol and deionized water difference ultrasonic cleaning 15 ~ 20min, is made it surface cleaning clean.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482712A (en) * | 2013-09-06 | 2014-01-01 | 浙江大学 | Method for preparing beta-Ni(OH)2 flower-like microsphere |
| CN103588253A (en) * | 2013-10-08 | 2014-02-19 | 浙江大学 | Method for preparing alpha-phase porous flaky nickel hydroxide microspheres |
| CN104291386A (en) * | 2014-10-10 | 2015-01-21 | 九江学院 | Preparation method of two-dimensional nickel hydroxide ultrathin nano-film |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN108597879A (en) * | 2018-03-19 | 2018-09-28 | 西北师范大学 | A kind of TiO2The preparation method of nano wire/NiO nanometer sheets/porphyrin composite material |
| CN113716601A (en) * | 2021-09-08 | 2021-11-30 | 吉林大学 | Hydroxyl cadmium chloride crystal and preparation method thereof |
| CN114933420A (en) * | 2022-05-31 | 2022-08-23 | 中国人民解放***箭军工程大学 | Gradient temperature-based hydrothermal preparation method of multilayer nano-sheet NiO electrochromic film |
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| JP2010037163A (en) * | 2008-08-06 | 2010-02-18 | Univ Of Miyazaki | Nickel hydroxide hexagonal plate and its manufacturing method |
| JP2012176888A (en) * | 2012-04-23 | 2012-09-13 | Univ Of Miyazaki | Nickel hydroxide nanosheet and manufacturing method thereof |
| CN102891008A (en) * | 2011-07-21 | 2013-01-23 | 北京化工大学 | Nickel hydroxide nanosheet thin-film material as well as preparation method and application thereof |
| CN102897852A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for hydrothermal synthesis of nickel hydroxide hierarchical structure microspheres assembled by nano-sheets |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482712A (en) * | 2013-09-06 | 2014-01-01 | 浙江大学 | Method for preparing beta-Ni(OH)2 flower-like microsphere |
| CN103588253A (en) * | 2013-10-08 | 2014-02-19 | 浙江大学 | Method for preparing alpha-phase porous flaky nickel hydroxide microspheres |
| CN104291386A (en) * | 2014-10-10 | 2015-01-21 | 九江学院 | Preparation method of two-dimensional nickel hydroxide ultrathin nano-film |
| CN104291386B (en) * | 2014-10-10 | 2016-04-06 | 九江学院 | A kind of preparation method of two-dimentional nickel hydroxide ultrathin nanometer film |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN106745133B (en) * | 2017-01-24 | 2018-03-20 | 武汉工程大学 | A kind of preparation method of hydroxide not soluble in water |
| CN108597879A (en) * | 2018-03-19 | 2018-09-28 | 西北师范大学 | A kind of TiO2The preparation method of nano wire/NiO nanometer sheets/porphyrin composite material |
| CN108597879B (en) * | 2018-03-19 | 2020-09-22 | 西北师范大学 | TiO 22Preparation method of nanowire/NiO nanosheet/porphyrin composite material |
| CN113716601A (en) * | 2021-09-08 | 2021-11-30 | 吉林大学 | Hydroxyl cadmium chloride crystal and preparation method thereof |
| CN114933420A (en) * | 2022-05-31 | 2022-08-23 | 中国人民解放***箭军工程大学 | Gradient temperature-based hydrothermal preparation method of multilayer nano-sheet NiO electrochromic film |
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| CN103101981B (en) | 2016-06-15 |
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