CN1313246A - Process for preparing nm-class beta-phase spherical nickel hydroxide - Google Patents
Process for preparing nm-class beta-phase spherical nickel hydroxide Download PDFInfo
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- CN1313246A CN1313246A CN 01109695 CN01109695A CN1313246A CN 1313246 A CN1313246 A CN 1313246A CN 01109695 CN01109695 CN 01109695 CN 01109695 A CN01109695 A CN 01109695A CN 1313246 A CN1313246 A CN 1313246A
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Abstract
A process for preparing nm beta-phase spherical nickel hydroxide features that the surface tension coefficient of reaction liquid is controlled, the stability of nm particles in over-saturated reaction liquid is increased and proper disperser is chosen to obtain the powdered nickel hydroxide with high dispersity and 10 nm of average granularity. The resultant nickel hydroxide can be used to prepare Ni electrode for high compactness, high electrochemical capacity and excellent high-speed charge-discharge performance.
Description
The present invention relates to a kind of manufacture method of nm-class beta-phase spherical nickel hydroxide.Belong to chemical engineering and field of new.
Nickel metal hydride battery is one of most widely used reversible cell.The biggest obstacle of nickel metal hydride battery development at present is that electrochemistry capacitance is difficult to significantly improve, and basic reason is that the capacity of nickel electrode is near the limit by the preparation method and the technology of existing electrode materials.Nano-sized nickel hydroxide has big specific surface area, high diffusion of protons coefficient, low electrochemical impedance and new electron channel, is the hope of nickel electrode of new generation.But nano material is very easily reunited, and tap density is low, and microstructural defects is big, is difficult to reach practical requirement.Only Connecticut, USA founds university has announced a kind of nanostructured oxide and oxyhydroxide in 1999 synthetic method at present, and they prepare nanoparticle with spray method, make the micron-scale stores through Overheating Treatment again.This method requires height to the dispersity of nanoparticle, and technology is complicated.
Method of the present invention is different with aforesaid method.
The objective of the invention is to propose a kind of manufacture method of nm-class beta-phase spherical nickel hydroxide.By selecting the synthetic dispersion agent, reduce the surface tension of supersaturation mixed reaction solution, make nucleus form critical size and reduce significantly, nanophase small-particle stable existence in the reaction solution obtains small size (about 10 nanometers), β phase, ball-type nickel hydroxide that crystalline network is more complete.Compound with the nm-class beta-phase spherical nickel hydroxide that the present invention makes with micron ball-type nickel hydroxide, can obtain the good nano-electrode material of high compacted density, high electrochemistry capacitance and fast charging and discharging performance, have practical value.
The present invention is achieved in that
At first with deionized water with industrial nickel salt (single nickel salt, nickelous nitrate or hydrochloric acid nickel) dissolution filter, remove impurity, dispersion agent (tensio-active agent) is added filters in the clean nickel salt solution.Through sonic oscillation emulsification, make the nickel salt aqueous solution that contains dispersion agent; With industrial caustic alkali (sodium hydroxide or potassium hydroxide) dissolution precipitation, remove impurity with deionized water, with ammoniacal liquor or ammonium salt add that precipitation is clean, in the caustic-alkali aqueous solution behind the purifying, stirring and evenly mixing is made the caustic-alkali aqueous solution that contains ammonia or ammonium.To contain the nickel salt aqueous solution of dispersion agent respectively and contain the caustic-alkali aqueous solution of ammonia or ammonium and flow in the continuous injecting reactor, keep temperature, pH value and the stirring velocity certain value of reaction solution, in 1 hour～5 hours reaction times, constantly take out resultant of reaction.Resultant of reaction is cleaned up with deionized water, and through sonic oscillation and filtration, lyophilize then obtains that favorable dispersity, β phase crystalline network are more complete, particle is the nickel hydroxide powder about ball-type, median size 10 nanometers.Compound with the nm-class beta-phase spherical nickel hydroxide powder that the present invention makes with micron ball-type nickel hydroxide powder, can be made into have high compacted density, high electrochemistry capacitance and the good new nickel electrode material of fast charging and discharging performance.
Feature of the present invention just is choose reasonable and utilizes dispersion agent (tween 80 or OP-10) that the coefficient of surface tension of control reaction solution reduces the critical nucleation size greatly, makes nanophase small-particle energy stable existence in mixed reaction solution.
The processing parameter of the present invention's design is: the concentration of nickel salt aqueous solution is 0.3mol/l～0.8mol/l, wherein is optimum value about 0.5mol/l; The concentration of caustic-alkali aqueous solution is 0.08mol/l～1.5mol/l, wherein is optimum value about 1.0mol/l; The concentration that contains dispersion agent (tween 80 or OP-10) in the nickel salt aqueous solution is 0.05g/l～2.0g/l, wherein is optimum value about 1.0g/l; Concentration 0.05mol/l～the 1.6mol/l that contains ammonia or ammonium in the caustic-alkali aqueous solution wherein is optimum value about 0.26mol/l; The nickel salt aqueous solution sonic oscillation emulsification 3～5 minutes of dispersion agent will be contained, the caustic-alkali aqueous solution stirring and evenly mixing of ammonia or ammonium will be contained.Inject nickel salt aqueous solution that contains dispersion agent and the caustic-alkali aqueous solution that contains ammonia or ammonium simultaneously in reactor continuously, stirring velocity is 200 rev/mins～1000 rev/mins, wherein is optimum value about 500 rev/mins.The temperature of mixed reaction solution is 30～70 ℃, wherein is optimum value about 55 ℃.The pH value of mixed reaction solution is 9～12, and wherein 11 is optimum value.Reaction times is 1～5 hour, and wherein 2～3 hours is optimum value.Resultant cleans up with deionized water, disperses through sonic oscillation, and the nm-class beta-phase spherical nickel hydroxide sample is made in solid-liquid separation and lyophilize.Method of the present invention can linear amplification.
Example: with deionized water dissolving industrial sulphuric acid nickel, remove impurity after filtration and obtain nickel sulfate solution, making its concentration is 0.5mol/l.Tween 80 is added in the nickel sulfate solution, and the concentration of tween 80 is 1.0g/l.The nickel sulfate solution sonic oscillation emulsification of tween 80 5 minutes is standby; The sodium hydroxide alkali aqueous solution is precipitated through deionized water dissolving by industrial sodium hydroxide, removes impurity and obtains, and its concentration is joined and is 1.0mol/l, and the concentration of ammonia is 0.26mol/l in the aqueous sodium hydroxide solution, and ammoniated aqueous sodium hydroxide solution stirring and evenly mixing is standby; The useful volume of reactor is 600ml, the nickel sulfate solution 300ml of preparation, aqueous sodium hydroxide solution 300ml, with taking out press pump respectively with in nickel sulfate solution and the simultaneously continuous injecting reactor of aqueous sodium hydroxide solution, 500 rev/mins of reaction stirring velocitys, keeping the temperature of mixed reaction solution is 55 ℃, and the pH value is 11,1.5 hours reaction times.Throw out cleans up with deionized water, disperses through sonic oscillation, filters lyophilize then.The sample that obtains is the more complete β phase of crystalline network, the ball-type nickel hydroxide powder.The powder motility is good, and median size is about 10 nanometers.Compound with the nm-class beta-phase spherical nickel hydroxide that this example is made with the micron nickel hydroxide, make the volume electrochemistry capacitance of ball-type nickel hydroxide improve more than 20%.
Claims (19)
1, a kind of manufacture method of nm-class beta-phase spherical nickel hydroxide comprises:
Nickel salt aqueous solution and caustic-alkali aqueous solution;
From the mixture of nickel salt aqueous solution and caustic-alkali aqueous solution, be settled out nm-class beta-phase spherical nickel hydroxide;
Drying and supersound process nm-class beta-phase spherical nickel hydroxide.
2, the method for claim 1, wherein the nickel salt in the nickel salt aqueous solution comprises single nickel salt, nickelous nitrate, hydrochloric acid nickel.
3, the concentration of nickel salt aqueous solution as claimed in claim 2 is 0.3mol/l～0.8mol/l.
4, contain dispersion agent in the nickel salt aqueous solution as claimed in claim 3.
5, comprise tween 80 (Tween-80), OP-10 as dispersion agent in the nickel salt aqueous solution as described in the claim 4.
6, method as claimed in claim 5, wherein containing dispersion agent in every liter of nickel salt aqueous solution is 0.05g～2g.
7, contain the dispersion agent nickel salt aqueous solution as described in claim 6, sonic oscillation emulsification is 3 minutes-5 minutes before using.
8, the method for claim 1, wherein alkali comprises in the caustic-alkali aqueous solution: sodium hydroxide, potassium hydroxide.
9, the concentration of caustic-alkali aqueous solution as claimed in claim 8 is 0.5mol/l～1.6mol/l.
10, contain ammonia or ammonium in the caustic-alkali aqueous solution as claimed in claim 9.
11, the concentration of ammonia or ammonium is 0.08mol/l～1.5mol/l in the caustic-alkali aqueous solution as claimed in claim 10.
12, caustic-alkali aqueous solution as claimed in claim 11, stirring and evenly mixing before using.
13, the method for claim 1, nickel salt aqueous solution and caustic-alkali aqueous solution are and flow continuous injecting reactor.
14, method as claimed in claim 13 is equipped with agitator in the reactor, stirring velocity is 200 rev/mins～1000 rev/mins.
15, the hybrid reaction liquid temp is 30～70 ℃ in the reactor as claimed in claim 14.
16, the pH value of mixed reaction solution is 9～12 in the reactor as claimed in claim 15.
17, the mixed reaction solution reaction times as claimed in claim 16 is 1～5 hour.
18, the method for claim 1, wherein throw out is by ultra-sonic dispersion.
19, method as claimed in claim 18, the resultant lyophilize obtains nm-class beta-phase spherical nickel hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011096950A CN1176854C (en) | 2001-03-20 | 2001-03-20 | Process for preparing nm-class beta-phase spherical nickel hydroxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011096950A CN1176854C (en) | 2001-03-20 | 2001-03-20 | Process for preparing nm-class beta-phase spherical nickel hydroxide |
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| CN1313246A true CN1313246A (en) | 2001-09-19 |
| CN1176854C CN1176854C (en) | 2004-11-24 |
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| CNB011096950A Expired - Fee Related CN1176854C (en) | 2001-03-20 | 2001-03-20 | Process for preparing nm-class beta-phase spherical nickel hydroxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676441B (en) * | 2008-09-16 | 2013-11-13 | 中国科学院福建物质结构研究所 | Single-layer beta phase nickel hydroxide two dimensional nano single chip and synthesizing method thereof |
| CN104909415A (en) * | 2015-04-16 | 2015-09-16 | 桂林理工大学 | Preparation method of nickel hydroxide negative electrode material for lithium ion batteries |
-
2001
- 2001-03-20 CN CNB011096950A patent/CN1176854C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676441B (en) * | 2008-09-16 | 2013-11-13 | 中国科学院福建物质结构研究所 | Single-layer beta phase nickel hydroxide two dimensional nano single chip and synthesizing method thereof |
| CN104909415A (en) * | 2015-04-16 | 2015-09-16 | 桂林理工大学 | Preparation method of nickel hydroxide negative electrode material for lithium ion batteries |
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| Publication number | Publication date |
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| CN1176854C (en) | 2004-11-24 |
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