CN1891635A - Method for preparing nano cobaltous oxide - Google Patents

Abstract

This invention relates to a method for preparing nm Co2O including: dissolving dried Co salt in an organic solvent then adding suitable organic protection agent to be moved into a reaction kettle lined with PTFE and sealed then to be reacted under 160-200deg. C for 6-10 h to get the Co2O product, which is in particle state and the size of 50-90nm.

Description

A kind of method for preparing nano cobaltous oxide

Technical field the present invention relates to a kind of method for preparing nano cobaltous oxide (CoO).

The background technology cobaltous oxide is the important anode filler of Ni/Cd and N/NiH battery, also is good magneticsubstance, Co in battery ²⁺The layer that ion can enter nickel hydroxide improves the performance of oxyhydroxide in the lattice, obtains the high electrode materials of a kind of charging efficiency.But because cobaltous oxide is suboxide, chemical property is active, and deterioration by oxidation easily in air will successfully make cobaltous oxide and make its size reach nano level that then conditional request is very harsh.And the required CoO product of China's battery industry is mostly all by external import.

At present the method for preparing cobaltous oxide of report all is will be through just obtaining behind the salt of roasting cobalt under the condition of starvation such as cobaltous hydroxide, cobaltous carbonate, singly be the cost that this exacting terms has just increased preparation undoubtedly, and controlled atmosphere is improper will cause Co ₂O ₃Or Co ₃O ₄Generation, greatly reduce the using value of material; A. people [Chinese patent 1173855A] such as Ge Erre discloses the method that a kind of preparation contains the cobaltous oxide of cobalt metal simple-substance, and this method is to obtain CoO with thermolysis again after cobalt salt is made the uncertain subcarbonate of composition; Zhang Liying etc. [rare metal, 27 (2003) 547-551] have reported that this method need just can obtain in roasting with the method for the cobaltous oxide nano particle of sol-gel method preparation in protective atmosphere.[Chem.Phys.Letters, 366 (2002) 567-571] such as Congkang Xu have reported in fusion NaCl and have decomposed CoC ₂O ₄Method prepare the method for CoO nano wire, prepared the nano wire of long several micron, wide 10-80nm.Above-mentioned these methods all want multistep to finish, and all need calcination at high temperature, and complex process is unfavorable for large-scale industrialization production.

Summary of the invention the purpose of this invention is to provide the preparation method of a kind of nano cobaltous oxide (CoO), and this method steps is simple, easy to operate, production cost is low, be fit to suitability for industrialized production.

The preparation method of the nano cobaltous oxide that the present invention proposes is the hot method of liquid phase solvent, and concrete steps are as follows:

(1) cobalt compound is dried in air dry oven in air atmosphere until removing crystal water;

(2) cobalt compound and the organic protective agent that will remove crystal water joins in a certain proportion of organic solvent, stirs until dissolving fully;

(3) above-mentioned mixed solution is transferred in the reactor of inner liner polytetrafluoroethylene and good seal;

(4) reactor is put into 160～220 ℃ baking oven and is handled after 6～10 hours and take out, with deionized water wash get final product the nano cobaltous oxide powder.

Cobalt compound described in the step (1) is that cobalt chloride hexahydrate, 18 water close a kind of in rose vitriol, four hydration Cobaltous diacetates, the Cobaltous nitrate hexahydrate;

Organic solvent described in the step (2) is methyl alcohol, ethanol, quadrol, diethylamine, triethylamine, pyridine, benzene, dimethylbenzene, phenol, 1, a kind of in 2-dimethyl ethane, the tetracol phenixin;

Protective material in the step (2) is a kind of in cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, Trimethyllaurylammonium bromide, polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, CALCIUM ACRYLATE, the benzotriazole;

The ratio of cobalt compound described in the step (2) and organic solvent is to add 10～20 gram cobalt compounds in per 100 milliliters of solvents.

The ratio of organic protective agent described in the step (2) and organic solvent is to add 1～3 gram organic protective agent in per 100 milliliters of solvents.

Preferred 170～180 ℃ of oven temperature in the step (4), preferred 8～9 hours of heat treatment time.

The present invention has following distinguishing feature:

Preparation technology of the present invention is simple, only needs a step promptly to get material requested, and easy to operate, the recyclable utilization of solvent is suitable for suitability for industrialized production.The nano cobaltous oxide that the present invention obtains is a tawny, and particle mean size is 50 to 90 nanometers.

Description of drawings Fig. 1 is the XRD figure spectrum of the CoO of the embodiment of the invention 1 preparation;

Fig. 2 is the XRD figure spectrum of the CoO of the embodiment of the invention 2 preparations.

The invention will be further described by the following examples for embodiment.

Embodiment 1:

With 5g four hydration Cobaltous diacetates, oven dry is 4 hours in 60 ℃ of air dry ovens, with the 75ml dehydrated alcohol, the 1g polyvinyl alcohol mixes stirring until dissolving fully, then above-mentioned mixed solution is transferred in the reactor of inner liner polytetrafluoroethylene and good seal, the baking oven processing that reactor is put into 170 ℃ was taken out after 8 hours, and with deionized water wash gained precipitation, the XRD figure spectrum of product is seen accompanying drawing 1.

Embodiment 2:

With 5g four hydration Cobaltous diacetates, oven dry is 4 hours in 60 ℃ of air dry ovens, with the 75ml dehydrated alcohol, the 1g cetyl trimethylammonium bromide mixes stirring until dissolving fully, then above-mentioned mixed solution is transferred in the reactor of inner liner polytetrafluoroethylene and good seal, the baking oven processing that reactor is put into 220 ℃ was taken out after 8 hours, and with deionized water wash gained precipitation, the XRD figure spectrum of product is seen accompanying drawing 2.

Claims (2)

1. the preparation method of a nano cobaltous oxide is characterized in that:

(1) cobalt compound is dried in air dry oven in air atmosphere to removing crystal water;

(2) cobalt compound and the organic protective agent that will remove crystal water joins in a certain proportion of organic solvent, stirs until dissolving fully;

(3) above-mentioned mixed solution is transferred in the reactor of inner liner polytetrafluoroethylene and good seal;

(4) reactor is put into 160～220 ℃ baking oven and is handled after 6～10 hours and take out, with deionized water wash get final product the nano cobaltous oxide powder;

Cobalt compound described in the step (1) is that cobalt chloride hexahydrate, 18 water close a kind of in rose vitriol, four hydration Cobaltous diacetates, the Cobaltous nitrate hexahydrate;

Organic solvent described in the step (2) is methyl alcohol, ethanol, quadrol, diethylamine, triethylamine, pyridine, benzene, dimethylbenzene, phenol, 1, a kind of in 2-dimethyl ethane, the tetracol phenixin;

Protective material in the step (2) is a kind of in cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, Trimethyllaurylammonium bromide, polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, CALCIUM ACRYLATE, the benzotriazole;

The ratio of cobalt compound described in the step (2) and organic solvent is to add 10～20 gram cobalt compounds in per 100 milliliters of solvents;

The ratio of organic protective agent described in the step (2) and organic solvent is to add 1～3 gram organic protective agent in per 100 milliliters of solvents.

2. method according to claim 1 is characterized in that: preferred 170～180 ℃ of the oven temperature in the step (4), preferred 8～9 hours of heat treatment time.

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