CN100404429C

CN100404429C - Method for manufacturing spherical nickel oxyhydroxide

Info

Publication number: CN100404429C
Application number: CNB2005100485588A
Authority: CN
Inventors: 徐拥军; 尹正中; 康保家
Original assignee: Henan Xinfei Kelong Power Source Co ltd
Current assignee: Henan Kelong New Energy Ltd By Share Ltd
Priority date: 2005-11-11
Filing date: 2005-11-11
Publication date: 2008-07-23
Anticipated expiration: 2025-11-11
Also published as: CN1765754A

Abstract

A method for preparing spherical nickel oxyhydroxide, 1-2.5 mol/l nickel sulfate, 0-1.2 mol/l cobalt sulfate and 0-0.8 mol/l zinc sulfate are compounded into a nickel sulfate mixed solution, 4-10 mol/l alkaline solution and 5-10 mol/l ammonia water are respectively pumped into a reactor by a metering pump, the flow rate of each material is 1-10 l/min of the nickel sulfate mixed solution, 0.2-15 l/min of the alkaline solution, 1.2, 1.9, 7 or 10 l/min of the ammonia water and 1-3.5 l/min of the oxidant solution, the flow rate of the alkaline solution is controlled, the pH value is stabilized at 11-13.4, the reaction temperature is 20-80 ℃, and then 1-3.5 mol/l oxidant solution is pumped into the reactor at the flow rate of 1-3.5 l/min within 20 hours; and washing the overflowed mixed solution with pure water until the pH value is less than 9, and drying the washed product to obtain the required spherical nickel oxyhydroxide. The invention has the advantages of short process flow, less consumption of oxidant and alkali and adjustable oxidation quality of products.

Description

Method for manufacturing spherical nickel oxyhydroxide

Technical Field

The invention relates to a device for directly converting chemical energy into electric energy, in particular to a method for manufacturing spherical nickel oxyhydroxide by a one-step method.

Background

Nickel oxyhydroxide is an electrode material widely used in batteries, and batteries manufactured using the material have excellent large-current discharge performance. Currently, the production of spherical nickel oxyhydroxide is carried out by first producing nickel hydroxide and then oxidizing it with an oxidizing agent. For example, the invention of Chinese patent No. 021119031 is made up by mixing spherical nickel hydroxide with water according to the ratio of 1: 4-10, making them implement oxidation reaction with alkaline liquor and oxidant solution in reactor, then washing and drying. Similar method also has the method disclosed in the Chinese patent 021347360. The above-described methods are all used to produce nickel oxyhydroxide in a two-step process. Has the disadvantages of long process flow, high requirements on equipment and sites, large consumption of oxidant and alkali, high cost, and low oxidation amount in the product, which affects the product quality.

Disclosure of Invention

The invention aims to provide a method for preparing spherical nickel oxyhydroxide, which has the advantages of short manufacturing process flow, low consumption of oxidant and alkali and controllable oxidation quality of products.

The technical scheme of the invention is completed in the following way, a method for manufacturing spherical nickel oxyhydroxide is characterized in that 1-2.5 mol/L nickel sulfate, 0-1.2 mol/L cobalt sulfate and 0-0.8 mol/L zinc sulfate are compounded into a nickel sulfate mixed solution, 4-10 mol/L sodium hydroxide or potassium hydroxide alkaline solution and 5-10 mol/L ammonia water are respectively pumped into a reactor by a metering pump, the flow rate of each material is 1-10L/min nickel sulfate mixed solution, 0.2-15L/min alkaline solution, 1.2, 1.9, 7 or 10L/min ammonia water and 1-3.5L/min oxidant solution or the combination of one or 1-3.5L/min oxidant solution, the flow rate of the alkaline solution is controlled, the PH value is stabilized at 11-13.4, the reaction temperature is 20-80 ℃, then the flow rate of 1-3.5L/min oxidant solution is adjusted into the reactor within 20 hours, and the required reaction time can be carried out according to the particle size of the oxidant; and washing the mixed solution overflowing from the reactor by pure water until the pH value is less than 9, and drying the washed product by drying equipment to obtain the required spherical nickel oxyhydroxide.

The invention adopts a one-step manufacturing process of firstly generating crystal nucleus in the reaction and then crystallizing on the surface of the crystal nucleus, and controls the oxidation quality of the product by adjusting the reaction time, so the invention has the advantages of short process flow, less consumption of oxidant and alkali and controllable oxidation quality of the product.

Detailed Description

The invention adopts a method that small crystal nucleus is firstly generated in the reaction generation, and then crystallization growth is carried out on the surface of the crystal nucleus to form a spherical shape, and the specific process flow is as follows: 1. preparing various raw material solutions, a, preparing a nickel sulfate mixed solution containing 1-2.5 mol/L of nickel sulfate, 0-1.2 mol/L of cobalt sulfate and 0-0.8 mol/L of zinc sulfate for later use, b, preparing an alkaline solution with the concentration of 4-10 mol/L for later use, wherein the alkaline solution can be sodium hydroxide or potassium hydroxide and the like, c, preparing ammonia water with the concentration of 5-10 mol/L for later use, d, preparing an oxidant solution with the concentration of 1-3.5 mol/L for later use, and the oxidant can be one or more of sodium hypochlorite, sodium persulfate, ammonium persulfate and potassium persulfate; 2. pumping the raw material solutions into a reactor by a metering pump according to a certain flow rate, wherein a nickel sulfate mixed solution is 1-10 liters/minute, an alkaline solution is 0.2-15 liters/minute, ammonia water is 1.2, 1.9, 7 or 10 liters/minute, an oxidant solution is 1-3.5 liters/minute, the proportion of the alkaline solution and the nickel sulfate mixed solution is mainly controlled, the PH value is stabilized at 11-13.4, the reaction temperature is 20-80 ℃, the nickel sulfate mixed solution, the alkaline solution and the ammonia water simultaneously enter the reactor, the oxidant is pumped into the reactor within 20 hours after the three liquid materials enter, and the reaction time can be adjusted according to the required particle size; 3. and (3) washing the mixed solution overflowing from the reactor with pure water until the pH value is less than 9, and drying the separated spherical nickel oxyhydroxide by using drying equipment.

Example 1:

the manufacturing method of the hydroxyl nickel oxide suitable for the zinc-nickel and zinc-manganese batteries comprises the following steps:

(1) Preparing a raw material liquid: preparing a nickel sulfate solution, wherein the nickel sulfate solution contains 1.5 mol/L of nickel sulfate and does not contain cobalt sulfate and zinc sulfate; preparing a sodium hydroxide alkaline solution with the concentration of 6 mol/L; preparing ammonia water with the concentration of 8 mol/L; the concentration of the prepared oxidant solution is 3.5 mol/L, and the oxidant is sodium hypochlorite.

(2) The reaction process is as follows: the above raw materials were pumped into a reactor with a metering pump, wherein the nickel sulfate mixed solution was 1.0 liter/min; sodium hydroxide alkaline solution 0.5 l/min; 7 liters/min of ammonia water; the sodium hypochlorite solution as an oxidant is 1.0 liter/minute, the proportion of the alkaline solution and the nickel sulfate mixed solution is controlled to enable the pH value to be stable at 11.8, the reaction temperature is 40 ℃, the nickel sulfate mixed solution, the alkaline solution and ammonia water simultaneously enter a reactor, the oxidant is pumped into the reactor 0.5 hour after the three liquid materials enter, and the reaction time is 100 hours.

(3) The mixed solution overflowed from the reactor was washed with pure water until the pH was less than 9.

(4) Drying the separated spherical nickel oxyhydroxide by drying equipment.

The nickel oxyhydroxide content of the tested product was 99%.

Example 2:

(1) Preparing a raw material liquid: preparing a nickel sulfate solution, wherein the nickel sulfate solution contains 0.05 mol/L of cobalt sulfate, 0.1 mol/L of zinc sulfate and 2.0 mol/L of nickel sulfate; an alkaline solution of potassium hydroxide at a concentration of 8 moles/liter; ammonia water with a concentration of 8 mol/l; the oxidant was a solution of ammonium persulfate at a concentration of 2.0 moles/liter.

(2) The reaction process is as follows: the above raw materials were pumped into a reactor with a metering pump, in which the nickel sulfate mixed solution was 2.0 liters/min; 1.1L/min of alkaline solution; 1.2L/min of ammonia water; 2.5 liters/minute of oxidant, controlling the proportion of the alkaline solution and the nickel sulfate mixed solution to stabilize the PH at 13.0, controlling the reaction temperature at 70 ℃, simultaneously feeding the nickel sulfate mixed solution, the alkaline solution and the ammonia water into the reactor, pumping the oxidant into the reactor 0.5 hour after the three materials are fed, and carrying out continuous reaction or discontinuous reaction for reaction time according to the required particle size.

(4) Drying the separated spherical nickel oxyhydroxide by drying equipment.

The tested product has a nickel oxyhydroxide content of 93%, and simultaneously contains 2.3% of cobalt oxyhydroxide and 4.7% of zinc hydroxide.

Implementation 3:

the method for manufacturing the nickel oxyhydroxide suitable for the secondary zinc-nickel battery and the secondary nickel-hydrogen battery comprises the following steps:

(1) Preparing a raw material liquid: preparing a nickel sulfate solution containing cobalt sulfate and zinc sulfate, wherein the nickel sulfate solution contains 0.05 mol/L of cobalt sulfate, 0.1 mol/L of zinc sulfate and 2.0 mol/L of nickel sulfate; an alkaline solution of sodium hydroxide at a concentration of 8 moles/liter; ammonia water with a concentration of 8 mol/l; the oxidizing agent was potassium persulfate solution having a concentration of 2.0 mol/l.

(2) The reaction process is as follows: the above raw materials were pumped into a reactor with a metering pump, in which the nickel sulfate mixed solution was 3 liters/min; alkaline solution 1.6 l/min; 1.9L/min of ammonia water; 3.2 liters/minute of oxidant, controlling the proportion of the alkaline solution and the nickel sulfate mixed solution to stabilize the PH at 13.0, controlling the reaction temperature at 70 ℃, simultaneously feeding the nickel sulfate mixed solution, the alkaline solution and the ammonia water into the reactor, and pumping the oxidant solution into the reactor for 10 hours after 0.5 hour after the three materials are fed, wherein the total reaction time is 50 hours.

(4) Drying the separated nickel oxyhydroxide by drying equipment.

The nickel oxyhydroxide content of the tested product was 18%.

Claims

1. A method of making spherical nickel oxyhydroxide, characterized by: compounding nickel sulfate of 1-2.5 mol/L, cobalt sulfate of 0-1.2 mol/L and zinc sulfate of 0-0.8 mol/L into a nickel sulfate mixed solution, sodium hydroxide or potassium hydroxide alkaline solution of 4-10 mol/L and ammonia water of 5-10 mol/L, respectively pumping the nickel sulfate mixed solution, the alkaline solution of 0.2-15L/L, the ammonia water of 1.2, 1.9, 7 or 10L/min, sodium hypochlorite, sodium persulfate, ammonium persulfate and potassium persulfate solution or a combined oxidant solution of 1-3.5L/min into a reactor by using a metering pump, controlling the flow rate of the alkaline solution to stabilize the pH value at 11-13.4, controlling the reaction temperature at 20-80 ℃, and then pumping the oxidant solution of 1-3.5 mol/L into the reactor within 20 hours at the flow rate of 1-3.5L/min, wherein the reaction time can be adjusted according to the required particle size; and (3) washing the mixed solution overflowing from the reactor by pure water until the pH value is less than 9, and drying the washed product by drying equipment to obtain the required spherical nickel oxyhydroxide.