CN1257572C - Method for recovering and preparing nano-cobalt oxide from waste lithium ion battery - Google Patents

Abstract

The present invention discloses a method for recovering and preparing nano cobalt oxide from a waste lithium ion battery, which belongs to chemical separation and the preparation technique of inorganic nano powder. The method comprises the following steps that a battery is cut to separate an anode material, and the anode material is sheared into small fragments; Al foil is soaked by excess NaOH at room temperature, and filter residue which is obtained by reaction and filtration is a mixture containing LiCoO2; the mixture is dissolved by HNO3 at the room temperature and is filtered to obtain nitrate solution containing Co<2+> and Li<1+>; the nitrate solution drops into the NaOH solution and pH is regulated to 9 to 11 to obtain a blue minute Co (OH) 2 deposit; the blue minute Co (OH) 2 deposit is converted into hydration cobalt oxide, and impurity ion in the hydration cobalt oxide is removed by filtration and wash; CoO (OH) is dried by an infrared lamp, and then, is heated for 2h at the temperature of 400 to 600 DEG C so as to obtain average grains and the Co3O4 nano powder. The present invention has the advantages of simple preparation processes of the method, easy operation, easy processing of different waste liquid, high purity of the obtained Co3O4 nano powder, and high specific surface area.

Description

Reclaim the method for preparing nanometer cobalt oxide from waste and old lithium ion battery

Technical field

The present invention relates to a kind of method for preparing nanometer cobalt oxide that from the lithium ion battery of scrapping, reclaims, belong to the technology of preparing of Chemical Decomposition and inorganic nanometer powder.

Background technology

Anode material for lithium-ion batteries is by active material LiCoO ₂, carbon black and acetylene black, binding agent stick on the aluminium foil according to a certain percentage, the content of positive electrode each several part is as shown in table 1:

The composition of table 1 anode material for lithium-ion batteries

Material	LiCoO 2	Carbon black, acetylene black	Binding agent	Aluminium foil
					Content (wt.%)	76.80	9.03	4.52	9.65

The processing of the lithium ion battery of scrapping faces following problem usually: the one, can contain a spot of simple substance lithium usually on the surface of the both positive and negative polarity of the lithium ion battery of scrapping, because the lithium metal of simple substance state has very strong inflammable and explosive property, this is the safety problem that pays particular attention in the Battery disposal; In addition, cobalt is a heavy metal, will work the mischief to environment if deal with improperly.Therefore the reasonable disposal of the lithium ion battery of scrapping has great importance for the protection environment.

At present, the research work of reclaiming about lithium rechargeable battery has had important progress abroad, Sony corporation of Japan has been developed the technology that reclaims cobalt etc. from the applying waste lithium ionic secondary cell with mine company of Sumitomo Metal Industries joint study, its technology is for burning battery to remove organic substance earlier, screening again is behind de-iron and the copper, with the heating of remaining powder and be dissolved in the acid, just can propose cobalt oxide with organic solvent extraction, this product can be used as raw material and is used for pigment, coatings industry.Yet also there is certain deficiency in above method: at first, adopt burning to remove organic method, need supporting flue gas purifying equipment, otherwise easily cause air environmental pollution; In addition, under the condition of heating,, equipment anticorrosion is required very high, severe operational environment with dissolving with hydrochloric acid " remaining powder ".

Summary of the invention

The objective of the invention is from the lithium ion battery of scrapping, to reclaim the preparation nanometer cobalt oxide.This method technical process is simple, and prepared cobalt oxide powder purity height, particle mean size are big less than 100 nanometers, specific area.

The present invention realized by following technical proposals: a kind ofly reclaim the method for preparing nanometer cobalt oxide from waste and old lithium ion battery, its feature may further comprise the steps:

(1) cutting of battery

Battery is cut in water, make positive electrode and other isolation of components, and positive electrode is cut into fractionlet;

(2) under the room temperature, adopting mass concentration is that 20%～60% excessive NaOH alkali soaks described fractionlet, reaction is filtered till can't see the generation bubble, filtrate collecting is stayed use it for anything else, filter residue is dry under infrared lamp, pulverize then, cross 80 mesh sieves, the alkali lye with same concentration and ratio dissolves one time again, filter, the filter residue that obtains is for containing LiCoO ₂Mixture;

(3) at room temperature, the employing mass concentration is 10%～50% HNO ₃Remove to dissolve this mixture, filter, the solution that obtains is for containing Co ²⁺, Li ⁺Nitrate solution, the addition of nitric acid is more than according to Co (NO ₃) ₂+ LiNO ₃The HNO that calculates of chemical dosage ratio ₃Amount;

(4) above-mentioned nitrate solution being added drop-wise to mass concentration is that pH is adjusted to 9～11 in 10%～60% the NaOH solution, obtains blue tiny Co (OH) ₂Precipitation, Co (OH) ₂Be deposited in the air unstablely, be converted into the aqua oxidation cobalt CoO (OH) of brownish black immediately, filter,,, filtered fluid and cleaning fluid are preserved, give over to the usefulness of recovery elemental lithium wherein to eliminate foreign ion wherein with deionized water cleaning and filtering thing repeatedly;

(5) CoO (OH) is dried under infrared lamp, at 400～600 ℃ of following heat treatment 2h, obtain the Co of average grain diameter then less than 100nm ₃O ₄Superfine powder.

The invention has the advantages that preparation process is simple and feasible, the Co that makes ₃O ₄The specific area of powder is 90～110m ²/ g, the average grain diameter of powder is less than 100nm, and purity reaches more than 99.5%, and the rate of recovery is more than 85%.

Specific embodiments

Example 1.

The battery that to get 10 substances be 28g, in water, battery is cut, make positive electrode and other isolation of components, positive electrode cut be fragment less than 2cm * 2cm size, at room temperature, these fragments are put into 500ml, and mass concentration is in 40% the NaOH solution, reaction until can't see produce bubble till, filter, filtrate collecting stayed use it for anything else, filter residue is dry under infrared lamp, pulverize then, cross 80 mesh sieves, alkali lye with same concentration and ratio dissolves one time again, filters, and the filter residue that obtains is for containing LiCoO ₂Mixture; At room temperature, use 400ml, mass concentration is 30% HNO ₃Solution removes to dissolve this mixture, filters, and the solution that obtains is Co ²⁺, Li ⁺Nitrate solution; Above-mentioned nitrate solution is added drop-wise to 400ml, and mass concentration is that pH is adjusted to 9～11 in 30% the NaOH solution, obtains blue tiny Co (OH) ₂Precipitation, Co (OH) ₂Be deposited in the air unstablely, be converted into the aqua oxidation cobalt CoO (OH) of brownish black immediately, filter, with deionized water cleaning and filtering thing (needing to clean more than three times) repeatedly, to eliminate foreign ion wherein; CoO (OH) is dried under infrared lamp, at 500 ℃ of following heat treatment 2h, obtain Co then ₃O ₄Nano powder is weighed product, the Co of gained ₃O ₄The weight of nano powder is 41g, calculates as can be known according to the theoretical content of various compositions in the battery, and be in the battery of 28g at 10 substances, can be for the Co that reclaims ₃O ₄Theoretical weight be about 47.8g, hence one can see that, adopts this technology to reclaim Co ₃O ₄The rate of recovery be 85.8%.

Example 2

The battery that to get 10 substances be 28g, in water, battery is cut, make positive electrode and other isolation of components, positive electrode cut be fragment less than 2cm * 2cm size, at room temperature, these fragments are put into 800ml, and mass concentration is in 20% the NaOH solution, reaction until can't see produce bubble till, filter, filtrate collecting stayed use it for anything else, filter residue is dry under infrared lamp, pulverize then, cross 80 mesh sieves, alkali lye with same concentration and ratio dissolves one time again, filters, and the filter residue that obtains is for containing LiCoO ₂Mixture; At room temperature, use 800ml, mass concentration is 20% HNO ₃Solution removes to dissolve this mixture, filters, and the solution that obtains is Co ²⁺, Li ⁺Nitrate solution; Above-mentioned nitrate solution is added drop-wise to 500ml, and mass concentration is that pH is adjusted to 9～11 in 20% the NaOH solution, obtains blue tiny Co (OH) ₂Precipitation, Co (OH) ₂Be deposited in the air unstablely, be converted into the aqua oxidation cobalt CoO (OH) of brownish black immediately, filter, with deionized water cleaning and filtering thing (needing to clean more than three times) repeatedly, to eliminate foreign ion wherein; CoO (OH) is dried under infrared lamp, at 600 ℃ of following heat treatment 2h, obtain Co then ₃O ₄Nano powder is weighed product, the Co of gained ₃O ₄The weight of nano powder is 39.5g, calculates as can be known according to the theoretical content of various compositions in the battery, and be in the battery of 28g at 10 substances, can be for the Co that reclaims ₃O ₄Theoretical weight be about 47.8g, hence one can see that, adopts this technology to reclaim Co ₃O ₄The rate of recovery be 82.6%.

Claims (1)

1, a kind ofly reclaim the method for preparing nanometer cobalt oxide from waste and old lithium ion battery, its feature may further comprise the steps:

(1) cutting of battery

Battery is cut in water, make positive electrode and other isolation of components, and positive electrode is cut into fractionlet;

(2) under the room temperature, adopting mass concentration is that 20%～60% excessive NaOH alkali soaks described fractionlet, reaction is filtered till can't see the generation bubble, filtrate collecting is stayed use it for anything else, filter residue is dry under infrared lamp, pulverize then, cross 80 mesh sieves, the alkali lye with same concentration and ratio dissolves one time again, filter, the filter residue that obtains is for containing LiCoO ₂Mixture;

(3) at room temperature, the employing mass concentration is 10%～50% HNO ₃Remove to dissolve this mixture, filter, the solution that obtains is for containing Co ²⁺, Li ⁺Nitrate solution, the addition of nitric acid is more than according to Co (NO ₃) ₂+ LiNO ₃The HNO that calculates of chemical dosage ratio ₃Amount;

(4) above-mentioned nitrate solution being added drop-wise to mass concentration is that pH is adjusted to 9～11 in 10%～60% the NaOH solution, obtains blue tiny Co (OH) ₂Precipitation, Co (OH) ₂Be deposited in the air unstablely, be converted into the aqua oxidation cobalt CoO (OH) of brownish black immediately, filter,,, filtered fluid and cleaning fluid are preserved, give over to the usefulness of recovery elemental lithium wherein to eliminate foreign ion wherein with deionized water cleaning and filtering thing repeatedly;

(5) CoO (OH) is dried under infrared lamp, at 400～600 ℃ of following heat treatment 2h, obtain the Co of average grain diameter then less than 100nm ₃O ₄Superfine powder.