CN102392270A - Method for preparing dendritic Ni nanocrystalline - Google Patents

Method for preparing dendritic Ni nanocrystalline Download PDF

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Publication number
CN102392270A
CN102392270A CN2011103442077A CN201110344207A CN102392270A CN 102392270 A CN102392270 A CN 102392270A CN 2011103442077 A CN2011103442077 A CN 2011103442077A CN 201110344207 A CN201110344207 A CN 201110344207A CN 102392270 A CN102392270 A CN 102392270A
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dendroid
nanocrystalline
nickel salt
preparing
organic solvent
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CN102392270B (en
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张亚非
王剑
魏浩
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The invention relates to a method for preparing Ni nanocrystalline, in particular to a method for preparing dendritic Ni nanocrystalline. The method for preparing dendritic Ni nanocrystalline comprises the step of electrolyzing an organic solvent solution of anhydrous nickel salt. The method provided by the invention has the advantages that not only a large amount of dendritic magnetic nickel nanocrystalline with stable quality can be prepared, but also the technology is simple, the cost is low, and the operability is strong; what's more, the effect of environmental protection is achieved, materials such as acidic materials, alkali materials, additives and the like are not introduced in an entire reaction, and no poisonous or harmful gas is discharged. The method provided by the invention solves the technical problems of complex technology, high cost, serious environment pollution and long technological production period of the dendritic Ni nanocrystalline preparation method in the prior art.

Description

A kind of nanocrystalline method of dendroid Ni for preparing
Technical field
The present invention relates to prepare the nanocrystalline method of Ni, relate in particular to a kind of nanocrystalline method of dendroid Ni for preparing.
Background technology
Nickel (Ni) nano material is a kind of ferromagnetic metal material, has good magnetic, hydrogen storage property, katalysis, is with a wide range of applications in fields such as aerospace, electronic information, national defense industry, environment protection, chemical industry, catalysis.In recent years, the Ni of different shape is nanocrystalline to be synthesized, as: Ni nano particle, Ni nano core-shell structure, Ni nanometer rod, Ni nano belt, Ni nano wire, Ni nano chain, Ni nanometer sheet and dendroid Ni are nanocrystalline etc.Wherein dendroid Ni is nanocrystalline, has unique three-dimensional structure, size, chemical functional, aspect the manufacturing and designing of research crystalline growth mechanism and advanced function material, has very important meaning.Yet, because the nanocrystalline complicated process of preparation of dendroid Ni, with high costs, mass production environment is seriously polluted, and makes its superior three-dimensional structure characteristic obtain well not bringing into play and utilizing.Therefore, develop that a kind of technology is simple, with low cost, the nanocrystalline method of dendroid Ni for preparing of environmental protection has very big realistic meaning.
Through being retrieved, existing literature finds; Application number is 200510007316.4, publication number is the one Chinese patent application of CN1651584A; Put down in writing a kind of " a kind of working method of dentritic morphology nickel powder ", wherein disclose a kind of method of utilizing hydrometallurgy to produce the dendritic crystal state metal nickel powder.The preparation process of this method comprises that the extraction of solution containing nickel, preparation nickel ammino close solution, nickelous oxalate deposition, filtration, washing, drying, reduction, fragmentation, obtain the dentritic morphology nickel powder product at last.Need use acidic substance (as: nitric acid, hydrochloric acid, oxalic acid), additive Vinylpyrrolidone polymer (PVP) or Trisodium Citrate etc. in the whole process flow to environmentally hazardous substance; If want mass industrialized production, then the waste liquid of discharging will cause very big influence to environment.If will these materials be carried out recycle or neutralizing treatment,, then need additional huge in addition recycle unit and high fund so that environment is not had influence or influences lessly.And this kind preparation method technology is numerous and diverse, cost is higher, take time and effort.Therefore, for this complex process, with high costs, preparation method that environmental pollution is serious, need further to improve and improve.
Further retrieval is found; X.Zhang, W.M.Liu, Controllable synthesis of nickel dendritic crystals induced by magnetic field; (induced by magnetic field is the synthetic nickel dentrite of control down for Mater.Res.Bull.34 (2008) 2100-2104; (U.S.) investigation of materials communique), disclosed and under induced by magnetic field, prepared the nickel dentrite, what article adopted is that nickelous acetate is dissolved in the terepthaloyl moietie; (PVP) makees stablizer with Vinylpyrrolidone polymer, and 197 ℃ of insulations made the nickel dentrite in 15 minutes.The nickel dentrite surface of this method preparation is closely coating one deck PVP, makes product in practical application, can't give play to the characteristic of nickel dentrite.J.Ye; Q.W.Chen; H.P.Qi et al.; Formation of nickel dendritic with peculiar orientations by magnetic-induced aggregation and limited diffusion, Crystal Growth & Design 8 (2008) 2464-2468 (through the nickel dentrite that induced by magnetic field is assembled and the Diffusion Limited preparation has unique orientation, (U.S.) crystal growth and design); Disclosed under induced by magnetic field; Adopt nickelous chloride, sodium hypophosphite, ammoniacal liquor compound in zero(ppm) water, mixing solutions is positioned in the Teflon-stainless steel autoclave of sealing, it is nanocrystalline that 160 ℃ of insulations can make dendroid Ni in 24 hours.Sodium hypophosphite that uses in this method and ammoniacal liquor compound, last discharging meeting causes very big pollution to environment; And this explained hereafter cycle long (needing 24 hours ability to prepare a stove sample).
Summary of the invention
The objective of the invention is to propose a kind of nanocrystalline method of dendroid Ni for preparing; This preparing method's technology is simple, with low cost, but the environmental protection industriallization is worked continuously; And the nanocrystalline steady quality of the dendroid Ni for preparing; Dendroid Ni preparation of nano crystal complex process, the technical problem that with high costs, environmental pollution is serious, the explained hereafter cycle is long have been solved in the prior art.
The present invention solves the problems of the technologies described above through following technical scheme, reaches the object of the invention.
A kind of nanocrystalline method of dendroid Ni for preparing may further comprise the steps:
A), get anhydrous nickel salt, said anhydrous nickel salt is dissolved in the organic solvent, dissolving evenly obtains the organic solvent solution of anhydrous nickel salt;
B), the organic solvent solution of said anhydrous nickel salt is placed electrolytic vessel, get the organic solvent solution that the yin, yang electrode places said anhydrous nickel salt, the organic solvent solution of the said anhydrous nickel salt of energising electrolysis produces atrament near the said negative electrode;
C), after said electrolysis finishes, from said electrolytic vessel, take out said yin, yang electrode, isolate said atrament, it is nanocrystalline promptly get said dendroid Ni, is left the surplus liquid of electrolysis; Preferably, isolating the method for said atrament, is to draw said atrament with magnet in said electrolytic vessel bottom.
When practical implementation of the present invention, preferably, saidly prepare the preparation process that the nanocrystalline method of dendroid Ni also comprises said anhydrous nickel salt, the preparation process of said anhydrous nickel salt is nickel salt to be heated to lose crystal water fully.Further, said nickel salt is NiCl 26H 2O, NiSO 46H 2O, Ni (NO 3) 26H 2O and Ni (CH 3COO) 24H 2A kind of among the O.
When practical implementation of the present invention, preferably, in the said step a), said anhydrous nickel salt is NiCl 2, NiSO 4, Ni (NO 3) 2And Ni (CH 3COO) 2In a kind of.
When practical implementation of the present invention, preferably, in the said step a), said organic solvent is a terepthaloyl moietie.
When practical implementation of the present invention, preferably, in the said step a), the method that said dissolving is adopted is a ultrasonic agitation.
When practical implementation of the present invention, preferably, in the said step a), in the organic solvent solution of said anhydrous nickel salt, Ni 2+The molecular volume ratio of amount of substance and said volume of organic solvent be 0.001～1.500mol/L.
When practical implementation of the present invention, preferably, in the said step b), said electrolytic voltage is 10～180V, and the electrolytic time is 1～10 hour.
When practical implementation of the present invention; Preferably; Saidly prepare the recycle operation that the nanocrystalline method of dendroid Ni also comprises the surplus liquid of said electrolysis, the recycle operation of the surplus liquid of said electrolysis is with the surplus liquid of said electrolysis in the said step c), as organic solvent; Carry out said step a) to step c), so circulation.
When practical implementation of the present invention, preferably, said electrolytic vessel is a glassware, and said yin, yang electrode all is graphite cakes.
When practical implementation of the present invention, preferably, in the said step a), said anhydrous nickel salt is NiCl 2, NiSO 4, Ni (NO 3) 2And Ni (CH 3COO) 2In a kind of, said organic solvent is a terepthaloyl moietie, the method that said dissolving is adopted is a ultrasonic agitation, in the organic solvent solution of said anhydrous nickel salt, Ni 2+The molecular volume ratio of amount of substance and said volume of organic solvent be 0.001～1.500mol/L; In the said step b), said electrolytic voltage is 10～180V, and the electrolytic time is 1～10 hour; Saidly prepare the recycle operation that the nanocrystalline method of dendroid Ni also comprises the surplus liquid of said electrolysis; The recycle operation of the surplus liquid of said electrolysis is with the surplus liquid of said electrolysis in the said step c); As organic solvent, carry out said step a) to step c), so circulation; Said electrolytic vessel is a glassware, and said yin, yang electrode all is graphite cakes.
Remarkable advantage of the present invention is:
1, preparing method's technology of the present invention simple, with low cost, workable, can realize that industriallization works continuously;
2, preparing method's environmental protection of the present invention, the surplus liquid reusable edible of electrolysis; Materials such as no acidic, alkaline in the surplus liquid of electrolysis, additive; No poisonous, obnoxious flavour is emitted in the whole process of preparation.
3, the trunk and the component of the dendroid magnetic nickel nano crystalline substance of the present invention's preparation are controlled, can control effectively through nickel ion concentration, electrolysis time, electrolysis voltage in the organic solvent solution of anhydrous nickel salt; Experiment finds that nickel ion concentration increases, and bifurcated can appear in trunk, and component increases; Electrolysis time increases, and trunk and branch all increase; Electrolysis voltage increases, the trunk chap, and interconnected phenomenon appears in branch's thickening.
Below will combine accompanying drawing that the technique effect of design of the present invention, concrete steps and generation is described further, so that those skilled in the art understands the object of the invention, characteristic and effect fully.
Description of drawings
Fig. 1 is the nanocrystalline SEM figure of dendroid Ni for preparing among the embodiment 1;
Fig. 2 is the nanocrystalline XRD figure of dendroid Ni for preparing among the embodiment 1;
Fig. 3 is the nanocrystalline SEM figure of dendroid Ni for preparing among the embodiment 2;
Fig. 4 is the nanocrystalline XRD figure of dendroid Ni for preparing among the embodiment 2;
Fig. 5 is the nanocrystalline SEM figure of dendroid Ni for preparing among the embodiment 3;
Fig. 6 is the nanocrystalline XRD figure of dendroid Ni for preparing among the embodiment 3;
Fig. 7 is the nanocrystalline SEM figure of dendroid Ni for preparing among the embodiment 4;
Fig. 8 is the nanocrystalline XRD figure of dendroid Ni for preparing among the embodiment 4;
Fig. 9 is the nanocrystalline SEM figure of dendroid Ni for preparing among the embodiment 5;
Figure 10 is the nanocrystalline XRD figure of dendroid Ni for preparing among the embodiment 5.
Embodiment
A kind of nanocrystalline method of dendroid Ni for preparing, this method is the organic solvent solution of the anhydrous nickel salt of electrolysis.Particularly, this prepares the nanocrystalline method of dendroid Ni and may further comprise the steps or operation:
1) preparation of anhydrous nickel salt:
Get nickel salt, nickel salt is heated to loses crystal water fully, but do not make nickel salt decomposition or rotten, obtain anhydrous nickel salt; Nickel salt is NiCl 26H 2O, NiSO 46H 2O, Ni (NO 3) 26H 2O and Ni (CH 3COO) 24H 2A kind of among the O, Heating temperature is respectively: NiCl 26H 2O is heated to more than 140 ℃, below 973 ℃ (decomposition temperature), NiSO 46H 2O is heated to more than 103 ℃, below 840 ℃ (decomposition temperature), Ni (NO 3) 26H 2O is heated to more than 100 ℃, below 110 ℃ (decomposition temperature), Ni (CH 3COO) 24H 2O is heated to more than 115 ℃, (decomposition temperature) below 240 ℃; Confirm according to practical situation by those skilled in the art heat-up time.
2) configuration of the organic solvent solution of anhydrous nickel salt:
Get anhydrous nickel salt, anhydrous nickel salt is dissolved in the organic solvent, dissolving evenly obtains the organic solvent solution of anhydrous nickel salt; Anhydrous nickel salt is the NiCl that step 1) prepares 2, NiSO 4, Ni (NO 3) 2Or Ni (CH 3COO) 2Organic solvent is a terepthaloyl moietie; The method that dissolving is adopted is a ultrasonic agitation, ultrasonic frequency scope: 20-25kHz, power range: 50-800W; In the organic solvent solution of anhydrous nickel salt, Ni 2+The molecular volume ratio of amount of substance and volume of organic solvent be 0.001～1.500mol/L.
3) electrolysis:
The organic solvent solution of anhydrous nickel salt is placed the glassware as electrolytic vessel; Get graphite cake places anhydrous nickel salt with aspectant mode as the yin, yang electrode organic solvent solution; The organic solvent solution of the anhydrous nickel salt of energising electrolysis; Produce atrament near the negative electrode, electrolytic voltage is 10～180V, and the electrolytic time is 1～10 hour.
What 4) dendroid Ni was nanocrystalline obtains:
After electrolysis finishes, from electrolytic vessel, take out the yin, yang electrode, draw atrament with magnet in the electrolytic vessel bottom, it is nanocrystalline promptly to get dendroid Ni, the remaining surplus liquid of electrolysis.
5) recycle of the surplus liquid of electrolysis:
With the surplus liquid of the electrolysis in the step 4),, step of replacing 2) to 4 as organic solvent) in terepthaloyl moietie, carry out step 2) to step 4), so circulation.
In an embodiment of the present invention, carrying out equipment and correlation parameter that SEM characterize to adopt is: the model of Zeiss, Germany company is the sem of Ultra 55, and acceleration voltage is 5kV during test; Carrying out the equipment that XRD characterize to adopt is: the model of German Brooker company is the X-ray diffractometer of D8ADVANCE.
Embodiment 1
1) preparation of anhydrous nickel salt:
With 0.238g (0.001mol) NiCl 26H 2O is heated to 160 ℃, is incubated 0.5 hour, NiCl 26H 2O loses crystal water fully, obtains anhydrous NiCl 2
2) configuration of the organic solvent solution of anhydrous nickel salt:
Anhydrous NiCl with the step 1) preparation 2Be dissolved in the terepthaloyl moietie of 0.1L, after under the condition of ultrasonic frequency 20kHz, power 50W ultrasonic 0.5 hour, anhydrous NiCl 2Fully be dissolved in the terepthaloyl moietie, make anhydrous NiCl 2Ethylene glycol solution.
3) electrolysis:
With step 2) the anhydrous NiCl that configures 2Ethylene glycol solution to place capacity be the glassware of 1L, and (two graphite cake sizes are: 50mm*50mm*10mm) be positioned over anhydrous NiCl with aspectant mode with two graphite cakes 2Ethylene glycol solution in respectively as the yin, yang electrode, between two graphite cakes, add the voltage of 50V, electrolysis 3 hours, as there being a large amount of atraments to form around the graphite cake of negative electrode, it is nanocrystalline to be dendroid Ni.
What 4) dendroid Ni was nanocrystalline obtains:
After electrolysis finishes, take out two graphite cakes as the yin, yang electrode, hold atrament with magnet in the bottom of glassware, it is nanocrystalline to obtain dendroid Ni, then the surplus liquid of electrolysis is poured in another glassware, in order to recycle.
5) recycle of the surplus liquid of electrolysis:
With the surplus liquid of the electrolysis in the step 4) as solvent, step of replacing 2) to 4) in terepthaloyl moietie, repeating step 2 then) to 4), it is capable of circulation that to prepare dendroid Ni nanocrystalline.
SEM photo such as Fig. 1 of the atrament that present embodiment makes, the XRD figure of atrament such as Fig. 2 can confirm that by Fig. 1 and Fig. 2 the atrament that present embodiment prepares is that dendroid Ni is nanocrystalline.
Embodiment 2
1) preparation of anhydrous nickel salt:
With 48.5g (0.184mol) NiSO 46H 2O is heated to 120 ℃ of insulations 1 hour, NiSO 46H 2O loses crystal water fully, obtains anhydrous NiSO 4
2) configuration of the organic solvent solution of anhydrous nickel salt:
Anhydrous NiSO with the step 1) preparation 4Be dissolved in the terepthaloyl moietie of 1L, after under the condition of ultrasonic frequency 22kHz, power 200W ultrasonic 1 hour, anhydrous NiSO 4Fully be dissolved in the terepthaloyl moietie, make anhydrous NiSO 4Ethylene glycol solution.
3) electrolysis:
With step 2) the anhydrous NiSO that configures 4Ethylene glycol solution to place capacity be the glassware of 2L, and (two graphite cake sizes are: 70mm*70mm*30mm) be positioned over anhydrous NiSO with aspectant mode with two graphite cakes 4Ethylene glycol solution in respectively as the yin, yang electrode, between two graphite cakes, add the voltage of 70V, electrolysis 5 hours, as there being a large amount of atraments to form around the graphite cake of negative electrode, it is nanocrystalline to be dendroid Ni.
What 4) dendroid Ni was nanocrystalline obtains:
After electrolysis finishes, take out two graphite cakes as the yin, yang electrode, hold atrament with magnet in the bottom of glassware, it is nanocrystalline to obtain dendroid Ni, then the surplus liquid of electrolysis is poured in another glassware, in order to recycle.
5) recycle of the surplus liquid of electrolysis:
With the surplus liquid of the electrolysis in the step 4) as solvent, step of replacing 2) to 4) in terepthaloyl moietie, repeating step 2 then) to 4), it is capable of circulation that to prepare dendroid Ni nanocrystalline.
SEM photo such as Fig. 3 of the atrament that present embodiment makes, the XRD figure of atrament such as Fig. 4 can confirm that by Fig. 3 and Fig. 4 the atrament that present embodiment prepares is that dendroid Ni is nanocrystalline.
Embodiment 3
1) preparation of anhydrous nickel salt:
With 135.5g (0.466mol) Ni (NO 3) 26H 2O is heated to 105 ℃ of insulations 2 hours, Ni (NO 3) 26H 2O loses crystal water fully, obtains anhydrous Ni (NO 3) 2
2) configuration of the organic solvent solution of anhydrous nickel salt:
Anhydrous Ni (NO with the step 1) preparation 3) 2Be dissolved in the terepthaloyl moietie of 3L, after under the condition of ultrasonic frequency 23kHz, power 500W ultrasonic 2 hours, anhydrous Ni (NO 3) 2Fully be dissolved in the terepthaloyl moietie, make anhydrous Ni (NO 3) 2Ethylene glycol solution.
3) electrolysis:
With step 2) the anhydrous Ni (NO that configures 3) 2Ethylene glycol solution to place capacity be the glassware of 5L, and (two graphite cake sizes are: 150mm*150mm*20mm) be positioned over anhydrous Ni (NO with aspectant mode with two graphite cakes 3) 2Ethylene glycol solution in respectively as the yin, yang electrode, between two graphite cakes, add the voltage of 180V, as there being a large amount of atraments to form around the graphite cake of negative electrode, it is nanocrystalline to be dendroid Ni after 1 hour in electrolysis.
What 4) dendroid Ni was nanocrystalline obtains:
After electrolysis finishes, take out two graphite cakes as the yin, yang electrode, hold atrament with magnet in the bottom of glassware, it is nanocrystalline to obtain dendroid Ni, then the surplus liquid of electrolysis is poured in another glassware, in order to recycle.
5) recycle of the surplus liquid of electrolysis:
With the surplus liquid of the electrolysis in the step 4) as solvent, step of replacing 2) to 4) in terepthaloyl moietie, repeating step 2 then) to 4), it is capable of circulation that to prepare dendroid Ni nanocrystalline.
SEM photo such as Fig. 5 of the atrament that present embodiment makes, the XRD figure of atrament such as Fig. 6 can confirm that by Fig. 5 and Fig. 6 the atrament that present embodiment prepares is that dendroid Ni is nanocrystalline.
Embodiment 4
1) preparation of anhydrous nickel salt:
With 1.30g (0.005mol) Ni (CH 3COO) 24H 2O is heated to 125 ℃ of insulations 1 hour, Ni (CH 3COO) 24H 2O loses crystal water fully, obtains anhydrous Ni (CH 3COO) 2
2) configuration of the organic solvent solution of anhydrous nickel salt:
Anhydrous Ni (CH with the step 1) preparation 3COO) 2Be dissolved in the terepthaloyl moietie of 0.5L, after under the condition of ultrasonic frequency 20kHz, power 150W ultrasonic 1 hour, anhydrous Ni (CH 3COO) 2Fully be dissolved in the terepthaloyl moietie, make anhydrous Ni (CH 3COO) 2Ethylene glycol solution.
3) the nanocrystalline preparation of dendroid nickel:
With step 2) the anhydrous Ni (CH that configures 3COO) 2Ethylene glycol solution to place capacity be the glassware of 1L, and (two graphite cake sizes are: 50mm*50mm*10mm) be positioned over anhydrous Ni (CH with aspectant mode with two graphite cakes 3COO) 2Ethylene glycol solution in as the yin, yang electrode, between two graphite cakes, add the voltage of 50V, electrolysis 4 hours, as there being a large amount of atraments to form around the graphite cake of negative electrode, it is nanocrystalline to be dendroid Ni.
What 4) dendroid Ni was nanocrystalline obtains:
After electrolysis finishes, take out two graphite cakes as the yin, yang electrode, hold atrament with magnet in the bottom of glassware, it is nanocrystalline to obtain dendroid Ni, then the surplus liquid of electrolysis is poured in another glassware, in order to recycle.
5) recycle of the surplus liquid of electrolysis:
With the surplus liquid of the electrolysis in the step 4) as solvent, step of replacing 2) to 4) in terepthaloyl moietie, repeating step 2 then) to 4), it is capable of circulation that to prepare dendroid Ni nanocrystalline.
SEM photo such as Fig. 7 of the atrament that present embodiment makes, the XRD figure of atrament such as Fig. 8 can confirm that by Fig. 7 and Fig. 8 the atrament that present embodiment prepares is that dendroid Ni is nanocrystalline.
Embodiment 5
1) preparation of anhydrous nickel salt:
With 357g (1.500mol) NiCl 26H 2O is heated to 190 ℃ of insulations 0.5 hour, NiCl 26H 2O loses crystal water fully, obtains anhydrous NiCl 2
2) configuration of the organic solvent solution of anhydrous nickel salt:
Anhydrous NiCl with the step 1) preparation 2Be dissolved in the terepthaloyl moietie of 1L, after under the condition of ultrasonic frequency 25kHz, power 800W ultrasonic 3 hours, anhydrous NiCl 2Fully be dissolved in the terepthaloyl moietie, make anhydrous NiCl 2Ethylene glycol solution.
3) the nanocrystalline preparation of dendroid nickel:
With step 2) the anhydrous NiCl that configures 2Ethylene glycol solution to place capacity be the glassware of 20L, and (two graphite cake sizes are: 300mm*300mm*50mm) be positioned over anhydrous NiCl with aspectant mode with two graphite cakes 2Ethylene glycol solution in as the yin, yang electrode, between two graphite cakes, add the voltage of 10V, electrolysis 10 hours, as there being a large amount of atraments to form around the graphite cake of negative electrode, it is nanocrystalline to be dendroid Ni.
What 4) dendroid Ni was nanocrystalline obtains:
After electrolysis finishes, take out two graphite cakes as the yin, yang electrode, hold atrament with magnet in the bottom of glassware, it is nanocrystalline to obtain dendroid Ni, then the surplus liquid of electrolysis is poured in another glassware, in order to recycle.
5) recycle of the surplus liquid of electrolysis:
With the surplus liquid of the electrolysis in the step 3) as solvent, step of replacing 1) to 3) in terepthaloyl moietie, repeating step 1 then) to 3), it is capable of circulation that to prepare dendroid Ni nanocrystalline.
SEM photo such as Fig. 9 of the atrament that present embodiment makes, the XRD figure of atrament such as Figure 10 can confirm that by Fig. 9 and Figure 10 the atrament that present embodiment prepares is that dendroid Ni is nanocrystalline.
In the XRD figure (Fig. 2,4,6,8,10) of embodiment 1-5; Near these peaks, peak (perhaps 44.34 °, 51.67 °, 76.09 ° positions, the peak occurring) corresponding successively (111), (200), (220), (311) peak are appearring near 44.34 °, 51.67 °, 76.09 °, the 92.55 ° positions; And other position Wu Feng shows that atrament is pure Ni crystal.SEM figure (Fig. 1,3,5,7,9) by embodiment 1-5 can find out that atrament is that dendroid is nanocrystalline.Can conclude that by XRD and SEM figure the prepared atrament that goes out of embodiment 1-5 is that dendroid Ni is nanocrystalline.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variation.Therefore, all technician in the art all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology through the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (10)

1. one kind prepares the nanocrystalline method of dendroid Ni, it is characterized in that, may further comprise the steps:
A), get anhydrous nickel salt, said anhydrous nickel salt is dissolved in the organic solvent, dissolving evenly obtains the organic solvent solution of anhydrous nickel salt;
B), the organic solvent solution of said anhydrous nickel salt is placed electrolytic vessel, get the organic solvent solution that the yin, yang electrode places said anhydrous nickel salt, the organic solvent solution of the said anhydrous nickel salt of energising electrolysis produces atrament near the said negative electrode;
C), after said electrolysis finishes, from said electrolytic vessel, take out said yin, yang electrode, isolate said atrament, it is nanocrystalline promptly get said dendroid Ni, is left the surplus liquid of electrolysis.
2. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1; It is characterized in that; Saidly prepare the preparation process that the nanocrystalline method of dendroid Ni also comprises said anhydrous nickel salt, the preparation process of said anhydrous nickel salt is nickel salt to be heated to lose crystal water fully.
3. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 2 is characterized in that said nickel salt is NiCl 26H 2O, NiSO 46H 2O, Ni (NO 3) 26H 2O and Ni (CH 3COO) 24H 2A kind of among the O.
4. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1 is characterized in that in the said step a), said anhydrous nickel salt is NiCl 2, NiSO 4, Ni (NO 3) 2And Ni (CH 3COO) 2In a kind of.
5. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1 is characterized in that in the said step a), said organic solvent is a terepthaloyl moietie.
6. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1 is characterized in that in the said step a), the method that said dissolving is adopted is a ultrasonic agitation.
7. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1 is characterized in that, in the said step a), and in the organic solvent solution of said anhydrous nickel salt, Ni 2+The molecular volume ratio of amount of substance and said volume of organic solvent be 0.001～1.500mol/L.
8. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1 is characterized in that in the said step b), said electrolytic voltage is 10～180V, and the electrolytic time is 1～10 hour.
9. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1; It is characterized in that; Saidly prepare the recycle operation that the nanocrystalline method of dendroid Ni also comprises the surplus liquid of said electrolysis, the recycle operation of the surplus liquid of said electrolysis is with the surplus liquid of said electrolysis in the said step c), as organic solvent; Carry out said step a) to step c), so circulation.
10. the nanocrystalline method of dendroid Ni for preparing as claimed in claim 1 is characterized in that said electrolytic vessel is a glassware, and said yin, yang electrode all is graphite cakes.
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CN103722167A (en) * 2013-12-10 2014-04-16 大连理工大学 Method for preparing nano nickel powder through electrolytic deposition in ethanol solution of nickel chloride hexahydrate
CN111705334A (en) * 2020-05-27 2020-09-25 金川集团股份有限公司 Method for improving physical appearance quality of electrodeposited nickel in pure sulfate system
JP2020204052A (en) * 2019-06-14 2020-12-24 清川メッキ工業株式会社 Dendritic nickel crystal particle, and method of producing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1651584A (en) * 2005-02-06 2005-08-10 金川集团有限公司 Production method of dentritic morphology nickel powder
US7635518B1 (en) * 2005-02-04 2009-12-22 University Of Louisiana At Lafayette Dendritic magnetic nanostructures and method for making same
CN102010015A (en) * 2010-10-15 2011-04-13 哈尔滨工业大学 Preparation method of magnetic manometer wire through magnetic field induction
CN102181891A (en) * 2011-04-08 2011-09-14 温州大学 Silver nanodendrite surface enhanced Raman scattering (SERS) substrate, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7635518B1 (en) * 2005-02-04 2009-12-22 University Of Louisiana At Lafayette Dendritic magnetic nanostructures and method for making same
CN1651584A (en) * 2005-02-06 2005-08-10 金川集团有限公司 Production method of dentritic morphology nickel powder
CN102010015A (en) * 2010-10-15 2011-04-13 哈尔滨工业大学 Preparation method of magnetic manometer wire through magnetic field induction
CN102181891A (en) * 2011-04-08 2011-09-14 温州大学 Silver nanodendrite surface enhanced Raman scattering (SERS) substrate, and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103722167A (en) * 2013-12-10 2014-04-16 大连理工大学 Method for preparing nano nickel powder through electrolytic deposition in ethanol solution of nickel chloride hexahydrate
JP2020204052A (en) * 2019-06-14 2020-12-24 清川メッキ工業株式会社 Dendritic nickel crystal particle, and method of producing the same
JP6990437B2 (en) 2019-06-14 2022-01-12 清川メッキ工業株式会社 Dendrite nickel crystal particles and their manufacturing method
JP7349747B2 (en) 2019-06-14 2023-09-25 清川メッキ工業株式会社 Dendritic nickel crystal particles and method for producing the same
CN111705334A (en) * 2020-05-27 2020-09-25 金川集团股份有限公司 Method for improving physical appearance quality of electrodeposited nickel in pure sulfate system
CN111705334B (en) * 2020-05-27 2022-04-08 金川集团股份有限公司 Method for improving physical appearance quality of electrodeposited nickel in pure sulfate system

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