CN114940516A - Preparation method of multi-component cathode material precursor - Google Patents

Abstract

The disclosure provides a preparation method of a multi-element anode material precursor, which is based on solid metal nickel, solid metal cobalt, solid metal manganese or aluminum and other doped solid metals such as Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr and the like as raw materials, and comprises the steps of heating and melting the solid metals into liquid metal melts with uniform components; the melt and oxygen or air injected into the oxidation chamber at high speed are quickly oxidized to generate multi-element metal oxide powder; and cooling the multi-element metal oxide powder to obtain the sphere-like multi-element anode material precursor with particularly uniform components. The method disclosed by the invention has the characteristics of short process flow, environmental friendliness and lower cost.

Description

Preparation method of multi-component cathode material precursor

technical field

The present disclosure relates to a preparation method of a multi-component positive electrode material precursor, in particular to a method for preparing a multi-component positive electrode material precursor by a high-temperature oxidation method, and belongs to the field of secondary battery materials.

Background technique

Due to its advantages in specific energy, life, and specific power, lithium-ion batteries have been widely used in 3C equipment, pure electric vehicles, and electrochemical energy storage power stations and occupy a dominant position. However, further reducing the cost of lithium-ion batteries and further improving the performance of lithium-ion batteries are constrained by cathode materials. Among them, ternary cathode materials represented by nickel-cobalt lithium manganate and nickel-cobalt lithium aluminate have become the technical breakthroughs in the industry. the key of.

The performance and cost of ternary cathode materials largely depend on the precursor materials. At present, co-precipitation method is the main method to prepare ternary precursor materials. However, the preparation of ternary precursor materials by coprecipitation has the following problems.

First, the process flow is long and the preparation time period is long. The co-precipitation method includes processes such as salt dissolution, complexation, crystal nucleation, crystal growth, formation, filtration, washing, and drying. The preparation time period is long, which leads to many process parameters control requirements and difficulty in control. Wastewater and by-products.

Second, the requirements for raw materials are high and the selectivity is strong. In order to obtain an ideal ternary precursor material, the co-precipitation reaction has strict control requirements on the type, concentration and impurity content of the reactants, otherwise it may not be uniformly co-precipitated or the composition of the co-precipitated product may not be uniform; this aspect increases the number of raw materials. On the other hand, it is very difficult to prepare doped ternary precursor materials or multi-component precursor materials.

The third is higher cost. The long preparation period of the co-precipitation method, the high requirements and strong selectivity for raw materials, and the treatment of a large amount of wastewater are the main factors leading to high costs. Moreover, these high cost factors make it difficult to have a good solution under the technical route of co-precipitation.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present disclosure is to overcome the above-mentioned defects in the prior art, and to provide a low-cost, short production cycle and high uniformity multi-element cathode material precursor preparation method.

The present disclosure is achieved through the following schemes.

A method for preparing a multi-component positive electrode material precursor, the multi-component positive electrode material precursor includes a first type of multi-component positive electrode material precursor, a second type of multi-component positive electrode material precursor, and a third type of multi-component positive electrode material precursor.

The preparation steps of the first type of multi-element cathode material precursor are as follows:

(1) Weigh solid metal nickel, solid metal cobalt, solid metal manganese, and solid metal N1 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A1, wherein the solid metal N1 is Mg, Ca, Sc, One or more of Ti, Zn, Cr, Fe, Zr, Cu, Ru, Al;

(2) heating and melting A1 in step (1) to form a liquid metal melt B1 with uniform composition;

(3) The metal melt B1 is injected into the oxidation chamber, and it collides with the air or oxygen that the high-speed jet enters the oxidation chamber to form metal droplets C1, and the metal droplets C1 undergo rapid oxidation reaction to generate multi-component metal oxide powder D1;

(4) The multi-component metal oxide powder D1 is cooled to obtain the multi-component positive electrode material precursor T1.

The preparation steps of the second type of multi-component cathode material precursor are as follows:

(1) Weigh solid metal nickel, solid metal cobalt, solid metal aluminum, and solid metal N2 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A2, wherein the solid metal N2 is Mg, Ca, Sc, One or more of Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn;

(2) heating and melting A2 in step (1) to form a liquid metal melt B2 with uniform composition;

(3) The metal melt B2 is injected into the oxidation chamber, and it collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets C2. The metal droplets C2 undergo rapid oxidation reaction to generate multi-component metal oxide powder D2 ;

(4) The multi-component metal oxide powder D2 is cooled to obtain the multi-component positive electrode material precursor T2.

The preparation steps of the third type of multi-component cathode material precursor are as follows:

(1) Weigh solid metal nickel and solid metal N3 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A3, wherein the solid metal N3 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr , one or more of Cu, Ru, Mn, Al;

(2) heating and melting A3 in step (1) to form a liquid metal melt B3 with uniform composition;

(3) The metal melt B3 is injected into the oxidation chamber, and it collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets C3. The metal droplets C3 undergo rapid oxidation reaction to generate multi-component metal oxide powder D3 ;

(4) The multi-component metal oxide powder D3 is cooled to obtain the multi-component positive electrode material precursor T3.

The molecular formula of the multi-component metal oxide powder D1, that is, the multi-component positive electrode material precursor T1 is Ni _x Co _a M _b N _c O _d , wherein M is Mn, and N1 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, One or more of Zr, Cu, Ru, Al, 0<a<0.5, 0<b<0.4, 0≤c<0.2, 1<d<2, 0.4<x<1.

The molecular formula of the multi-element metal oxide powder D2, that is, the multi-element positive electrode material precursor T2 is Ni _x Co _a M _b N _c O _d , wherein M is Al, and N2 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, One or more of Zr, Cu, Ru and Mn, 0<a<0.5, 0<b<0.4, 0≤c<0.2, 1<d<2, 0.4<x<1.

The molecular formula of the multi-element metal oxide powder D3, that is, the multi-element positive electrode material precursor T3 is Ni _x N _c O _d , wherein N3 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn, One or more of Al, 0<c<0.55, 1<d<2, 0.4<x<1.

The solid metal nickel, solid metal cobalt, solid metal manganese (or solid metal aluminum), and solid metal N1, solid metal N2, and solid metal N3 can be any one of metal blocks, metal balls, metal powders, and metal rods or more.

Nickel, cobalt, manganese, and N1 in the solid metal mixture A1 can be in the form of metal elements, or can be in the form of any binary or more than binary alloys formed by nickel, cobalt, manganese, and N1; the solid metal Nickel, cobalt, aluminum, and N2 in the mixture A2 can be in the form of metal elements, or in the form of any binary or more than binary alloys formed by nickel, cobalt, aluminum, and N2; Nickel and N3 can be in the form of metal element, and can also be in the form of any binary or more than binary alloy formed by nickel and N3.

The multi-component metal oxide powder D1, the multi-component metal oxide powder D2, and the multi-component metal oxide powder D3 are all spherical, and the median particle size satisfies D ₅₀ =0.5 μm~15 μm.

The melting furnace may be an intermediate frequency induction furnace.

The multi-component positive electrode material precursor is mixed and sintered with lithium salt to obtain lithium ion multi-component positive electrode material; the multi-component positive electrode material precursor is mixed and sintered with sodium salt to obtain sodium ion multi-component positive electrode material.

The method for preparing a cathode material precursor by rapid oxidation of high temperature metal melt droplets of the present disclosure has the following beneficial effects.

(1) The process flow is short and the preparation time period is short. Since the method of the present disclosure has only three main steps of solid metal melting, atomization and oxidation, and cooling, the process flow is less than half of the co-precipitation method, and the preparation time period is less than one-third of the co-precipitation method.

(2) The raw materials are easy to obtain, and the product has good composition uniformity. The raw materials of the present disclosure are all solid metals, which are abundant and easy to obtain; each metal element of the present disclosure is in an atomic-level uniform subdivision state before the oxidation reaction, that is, a liquid metal melt, and the oxidation reaction speed is fast, and the generated multi-component metal oxide powder That is, the multi-element cathode material precursor has good composition uniformity, and the multi-element cathode material precursor with good homogeneity is beneficial to the preparation of high-performance multi-element cathode material; the present disclosure does not have the problem of multi-element uniform co-precipitation process, so the multi-element cathode material can be easily realized. Preparation of precursors (multi-component, that is, the types of metal elements in the cathode material precursor can be three or four or five or more than five).

(3) The cost is lower. The present disclosure uses solid metal as the raw material, which saves the cost of preparing salt from the metal; the present disclosure does not generate waste water and has no by-products; the present disclosure has a short process flow, a short time period, and high production efficiency; the above three aspects are very beneficial to The preparation cost of the multi-component cathode material precursor is reduced.

Description of drawings

FIG. 1 is a flow chart 1 of the preparation process of the first type of multi-component cathode material precursor according to the present disclosure.

FIG. 2 is a second flow chart of the preparation process of the second type of multi-component cathode material precursor according to the present disclosure.

FIG. 3 is a third process flow diagram of the preparation of a third type of multi-component cathode material precursor according to the present disclosure.

4 is a SEM picture of the Mg-doped nickel-cobalt-manganese quaternary cathode material precursor powder prepared according to Example 2 of the present disclosure.

Detailed ways

The technical solutions of the present disclosure will be further described below in conjunction with the accompanying drawings and embodiments of the description. It should be pointed out that for those skilled in the art, several improvements and modifications can be made without departing from the principles of the present disclosure. Improvements and modifications should also fall within the scope of the present disclosure.

First, as shown in FIG. 1 , the present disclosure provides a nickel-cobalt-manganese ternary cathode material precursor and doping with other metal elements (Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, One or more of Al) nickel-cobalt-manganese multi-element cathode material precursors, including:

(1) Weigh solid metal nickel, solid metal cobalt, solid metal manganese, and solid metal N1 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A1, wherein the solid metal N1 is Mg, Ca, Sc, One or more of Ti, Zn, Cr, Fe, Zr, Cu, Ru, Al;

(2) heating and melting A1 in step (1) to form a liquid metal melt B1 with uniform composition;

(3) The metal melt B1 is injected into the oxidation chamber, and it collides with the air or oxygen that the high-speed jet enters the oxidation chamber to form metal droplets C1, and the metal droplets C1 undergo rapid oxidation reaction to generate multi-component metal oxide powder D1;

(4) The multi-component metal oxide powder D1 is cooled to obtain the multi-component positive electrode material precursor T1.

Secondly, as shown in FIG. 2 , the present disclosure provides a nickel-cobalt-aluminum ternary cathode material precursor and doping with other metal elements (Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, One or more of Mn) nickel-cobalt-aluminum multi-component cathode material precursors, including:

(1) Weigh solid metal nickel, solid metal cobalt, solid metal aluminum, and solid metal N2 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A2, wherein the solid metal N2 is Mg, Ca, Sc, One or more of Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn;

(2) heating and melting A2 in step (1) to form a liquid metal melt B2 with uniform composition;

(3) The metal melt B2 is injected into the oxidation chamber, and it collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets C2. The metal droplets C2 undergo rapid oxidation reaction to generate multi-component metal oxide powder D2 ;

(4) The multi-component metal oxide powder D2 is cooled to obtain the multi-component positive electrode material precursor T2.

As shown in FIG. 3 , the present disclosure provides a cobalt-free nickel-based cathode material precursor and doping with other metal elements (Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn, One or more of Al) cobalt-free multicomponent cathode material precursor, including:

(1) Weigh solid metal nickel and solid metal N3 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A3, wherein the solid metal N3 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr , one or more of Cu, Ru, Mn, Al;

(2) heating and melting A3 in step (1) to form a liquid metal melt B3 with uniform composition;

(3) The metal melt B3 is injected into the oxidation chamber, and it collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets C3. The metal droplets C3 undergo rapid oxidation reaction to generate multi-component metal oxide powder D3 ;

(4) The multi-component metal oxide powder D3 is cooled to obtain the multi-component positive electrode material precursor T3.

In the present disclosure, the molecular formula of the multi-component metal oxide powder D1, that is, the multi-component cathode material precursor T1 is Ni _x Co _a M _b N _c O _d , wherein M is Mn, and N1 is Mg, Ca, Ti, Zn, Cr, Fe, One or more of Zr, Cu, Ru, Al, 0<a<0.5, 0<b<0.4, 0≤c<0.2, 1<d<2, 0.4<x<1.

In the present disclosure, the molecular formula of the multi-component metal oxide powder D2, that is, the multi-component positive electrode material precursor T2 is Ni _x Co _a M _b N _c O _d , wherein M is Al, and N2 is Mg, Ca, Ti, Zn, Cr, Fe, One or more of Zr, Cu, Ru and Mn, 0<a<0.5, 0<b<0.4, 0≤c<0.2, 1<d<2, 0.4<x<1.

In the present disclosure, the molecular formula of the multi-component metal oxide powder D3, that is, the multi-component cathode material precursor T3 is Ni _x N _c O _d , wherein N3 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, One or more of Mn and Al, 0<c<0.55, 1<d<2, 0.4<x<1.

In the present disclosure, solid metal nickel, solid metal cobalt, solid metal manganese (or solid metal aluminum), and solid metal N1, solid metal N2, and solid metal N3 may be any of metal blocks, metal balls, metal powders, and metal rods. one or more.

In the present disclosure, nickel, cobalt, manganese, and N1 in the solid metal mixture A1 can be in the form of metal elements, or can be in the form of any binary or more than binary alloys formed by nickel, cobalt, manganese, and N1; the The nickel, cobalt, aluminum, and N2 in the solid metal mixture A2 can be in the form of metal elements, or in the form of any binary or more than binary alloys formed by nickel, cobalt, aluminum, and N2; the solid metal mixture A3 The nickel and N3 in the compound can be in the form of a metal element, or in the form of any binary or more than binary alloy formed by nickel and N3.

In the present disclosure, the multi-component metal oxide powder D1, the multi-component metal oxide powder D2, and the multi-component metal oxide powder D3 are all spherical, and the median particle size satisfies D ₅₀ =0.5 μm~15 μm.

In the present disclosure, the melting furnace is an intermediate frequency induction furnace.

The multi-component positive electrode material precursor prepared in the present disclosure is mixed and sintered with lithium salt to obtain a lithium ion multi-component positive electrode material; the multi-component positive electrode material precursor prepared in the present disclosure is mixed and sintered with a sodium salt to obtain a sodium ion multi-component positive electrode material.

Example 1

A nickel-cobalt-manganese ternary cathode material precursor is prepared.

The bulk solid metal nickel, the bulk solid metal cobalt, and the bulk solid metal manganese are weighed according to the stoichiometric ratio, that is, the mol ratio of Ni:Co:Mn is 0.8:0.1:0.1, and put into an intermediate frequency induction furnace to form a solid metal mixture. The intermediate frequency induction furnace is heated to 1600°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a nickel-cobalt-manganese ternary positive electrode material precursor.

After testing, the median particle size of the precursor powder of the nickel-cobalt-manganese ternary positive electrode material prepared in this example is 10.5 μm, the shape is spherical, and the chemical composition is Ni _0.8 Co _0.1 Mn _0.1 O _1.35 .

Example 2

A Ti-doped nickel-cobalt-manganese quaternary cathode material precursor is prepared.

The bulk solid metallic nickel, bulk solid metallic cobalt, bulk solid metallic manganese, and bulk solid metallic titanium are weighed according to the stoichiometric ratio, that is, the mol ratio of Ni:Co:Mn:Ti is 0.78:0.1:0.1:0.02, Put into a medium frequency induction furnace to form a solid metal mixture. The intermediate frequency induction furnace is heated to 1710°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a titanium-doped nickel-cobalt-manganese quaternary positive electrode material precursor.

After testing, the median particle size of the Ti-doped nickel-cobalt-manganese quaternary cathode material precursor powder prepared in this example is 9.6 μm, the shape is spherical, and the chemical composition is Ni _0.78 Co _0.1 Mn _0.1 Ti _0.02 O _1.56 . FIG. 3 is a SEM picture of the Ti-doped nickel-cobalt-manganese quaternary cathode material precursor powder prepared in this example.

Example 3

A nickel-cobalt-manganese five-element cathode material precursor doped with Ti and Fe was prepared.

The bulk solid metallic nickel, bulk solid metallic cobalt, bulk solid metallic manganese, bulk solid metallic titanium, and flake metallic iron are in a stoichiometric ratio, that is, the mol ratio of Ni:Co:Mn:Ti:Fe is 0.80:0.06 :0.1:0.02:0.04 Weigh it, put it in an intermediate frequency induction furnace, and form a solid metal mixture. The intermediate frequency induction furnace is heated to 1720°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a nickel-cobalt-manganese five-element cathode material precursor doped with Ti and Fe.

After testing, the median particle size of the precursor powder of the nickel-cobalt-manganese pentagonal cathode material doped with Ti and Fe prepared in this example is 9.8 μm, the morphology is spherical, and the chemical composition is Ni _0.80 Co _0.06 Mn _0.1 Ti _0.02 Fe _0.04 O _1.59 ..

Example 4

A nickel-cobalt-aluminum ternary cathode material precursor is prepared.

The bulk solid metal nickel, the bulk solid metal cobalt, and the bulk solid metal aluminum are weighed according to the stoichiometric ratio, that is, the mol ratio of Ni:Co:Al is 0.8:0.15:0.05, and placed in an intermediate frequency induction furnace to form a solid metal mixture. The intermediate frequency induction furnace is heated to 1580°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a nickel-cobalt-aluminum ternary positive electrode material precursor.

After testing, the median particle size of the precursor powder of the nickel-cobalt-aluminum ternary positive electrode material prepared in this example is 11.6 μm, the shape is spherical, and the chemical composition is Ni _0.8 Co _0.15 Al _0.05 O _1.50 .

Example 5

A Zr-doped nickel-cobalt-aluminum quaternary cathode material precursor was prepared.

The bulk solid metal nickel, the bulk solid metal cobalt, the bulk solid metal aluminum, and the bulk solid metal zirconium are weighed according to the stoichiometric ratio, that is, the mol ratio of Ni:Co:Al:Zr is 0.78:0.15:0.05:0.02, Put into a medium frequency induction furnace to form a solid metal mixture. The intermediate frequency induction furnace is heated to 1900°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a Zr-doped nickel-cobalt-aluminum quaternary cathode material precursor.

After testing, the median particle size of the Zr-doped nickel-cobalt-aluminum quaternary cathode material precursor powder prepared in this example is 11.3 μm, the shape is spherical, and the chemical composition is Ni _0.78 Co _0.15 Al _0.05 Zr _0.02 O _1.51 ..

Example 6

A nickel-cobalt-aluminum five-element cathode material precursor doped with Ti and Zr was prepared.

The bulk solid metal nickel, bulk solid metal cobalt, bulk solid metal aluminum, bulk solid metal titanium, and flake metal zirconium are stoichiometrically, that is, the mol ratio of Ni:Co:Al:Ti:Zr is 0.76:0.1 :0.1:0.02:0.02 Weigh it, put it into an intermediate frequency induction furnace, and form a solid metal mixture. The intermediate frequency induction furnace is heated to 1910°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a nickel-cobalt-aluminum five-element cathode material precursor doped with Ti and Zr.

After testing, the median particle size of the precursor powder of the nickel-cobalt-aluminum pentagonal cathode material doped with Ti and Zr prepared in this example is 10.2 μm, the morphology is spherical, and the chemical composition is Ni _0.76 Co _0.1 Al _0.1 Ti _0.02 Zr _0.02 O _1.52 ..

Example 7

A cobalt-free nickel-manganese-aluminum ternary cathode material precursor is prepared.

The bulk solid metal nickel, the bulk solid metal manganese, and the bulk solid metal aluminum are weighed according to the stoichiometric ratio, that is, the mol ratio of Ni:Mn:Al is 0.8:0.15:0.05, and placed in an intermediate frequency induction furnace to form a solid metal mixture. The intermediate frequency induction furnace is heated to 1560°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a nickel-manganese-aluminum ternary positive electrode material precursor.

After testing, the median particle size of the precursor powder of the nickel-manganese-aluminum ternary cathode material prepared in this example is 10.7 μm, the shape is spherical, and the chemical composition is Ni _0.8 Mn _0.15 Al _0.05 O _1.57 .

Example 8

A cobalt-free nickel-manganese-aluminum-titanium quaternary cathode material precursor is prepared.

The bulk solid metal nickel, the bulk solid metal manganese, the bulk solid metal aluminum, and the bulk solid metal titanium are weighed according to the stoichiometric ratio, that is, the mol ratio of Ni:Mn:Al:Ti is 0.8:0.15:0.02:0.03, Put into a medium frequency induction furnace to form a solid metal mixture. The intermediate frequency induction furnace is heated to 1780°C, and the solid metal mixture is melted to form a liquid metal melt with uniform composition. The metal melt is injected into the oxidation chamber, and collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets. The metal droplets undergo rapid oxidation reaction to generate multi-component metal oxide powder. The multi-component metal oxide powder is cooled to obtain a nickel-manganese-aluminum-titanium quaternary positive electrode material precursor.

After testing, the median particle size of the precursor powder of the nickel-manganese-aluminum-titanium quaternary cathode material prepared in this example is 10.3 μm, the shape is spherical, and the chemical composition is Ni _0.8 Mn _0.15 Al _0.02 Ti _0.03 O _1.59 .

From the above embodiments, it can be found that the method for preparing a cathode material precursor by rapid oxidation of high temperature metal melt droplets of the present disclosure has the following beneficial effects.

(1) The process flow is short and the preparation time period is short. Since the method of the present disclosure has only three main steps of solid metal melting, atomization and oxidation, and cooling, the process flow is less than half of the co-precipitation method, and the preparation time period is less than one-third of the co-precipitation method.

(2) The raw materials are easy to obtain, and the product has good composition uniformity. The raw materials of the present disclosure are all solid metals, which are abundant and easy to obtain; each metal element of the present disclosure is in an atomic-level uniform subdivision state before the oxidation reaction, that is, a liquid metal melt, and the oxidation reaction speed is fast, and the generated multi-component metal oxide powder That is, the multi-element cathode material precursor has good composition uniformity, and the multi-element cathode material precursor with good homogeneity is beneficial to the preparation of high-performance multi-element cathode material; the present disclosure does not have the problem of multi-element uniform co-precipitation process, so the multi-element cathode material can be easily realized. Preparation of precursors (multi-component, that is, the types of metal elements in the cathode material precursor can be three or four or five or more than five).

(3) The cost is lower. The present disclosure uses solid metal as the raw material, which saves the cost of preparing salt from the metal; the present disclosure does not generate waste water and has no by-products; the present disclosure has a short process flow, a short time period, and high production efficiency; the above three aspects are very beneficial to The preparation cost of the multi-component cathode material precursor is reduced.

Claims (8)

1. a preparation method of multi-element positive electrode material precursor, is characterized in that: The multi-component positive electrode material precursor includes a first type of multi-component positive electrode material precursor, a second type of multi-component positive electrode material precursor, and a third type of multi-component positive electrode material precursor; The preparation steps of the first type of multi-element cathode material precursor are as follows: (1) Weigh solid metal nickel, solid metal cobalt, solid metal manganese, and solid metal N1 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A1, wherein the solid metal N1 is Mg, Ca, Sc, One or more of Ti, Zn, Cr, Fe, Zr, Cu, Ru, Al; (2) heating and melting A1 in step (1) to form a liquid metal melt B1 with uniform composition; (3) The metal melt B1 is injected into the oxidation chamber, and it collides with the air or oxygen that the high-speed jet enters the oxidation chamber to form metal droplets C1, and the metal droplets C1 undergo rapid oxidation reaction to generate multi-component metal oxide powder D1; (4) The multi-component metal oxide powder D1 is cooled to obtain the multi-component cathode material precursor T1; The preparation steps of the second type of multi-component cathode material precursor are as follows: (1) Weigh solid metal nickel, solid metal cobalt, solid metal aluminum, and solid metal N2 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A2, wherein the solid metal N2 is Mg, Ca, Sc, One or more of Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn; (2) heating and melting A2 in step (1) to form a liquid metal melt B2 with uniform composition; (3) The metal melt B2 is injected into the oxidation chamber, and it collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets C2. The metal droplets C2 undergo rapid oxidation reaction to generate multi-component metal oxide powder D2 ; (4) The multi-component metal oxide powder D2 is cooled to obtain the multi-component cathode material precursor T2; The preparation steps of the third type of multi-component cathode material precursor are as follows: (1) Weigh solid metal nickel and solid metal N3 according to the stoichiometric ratio, put them into a melting furnace, and form a solid metal mixture A3, wherein the solid metal N3 is Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr , one or more of Cu, Ru, Mn, Al; (2) heating and melting A3 in step (1) to form a liquid metal melt B3 with uniform composition; (3) The metal melt B3 is injected into the oxidation chamber, and it collides with the high-pressure air or high-pressure oxygen entering the oxidation chamber with a high-speed jet to form metal droplets C3. The metal droplets C3 undergo rapid oxidation reaction to generate multi-component metal oxide powder D3 ; (4) The multi-component metal oxide powder D3 is cooled to obtain the multi-component positive electrode material precursor T3. 2. The method for preparing a multi-element positive electrode material precursor according to claim 1, characterized in that: the multi-element metal oxide powder D1 is the molecular formula of the multi-element positive electrode material precursor T1 is Ni _x Co _a M _b N _c O _d , where M is Mn, N1 is one or more of Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, Al, 0<a<0.5, 0<b<0.4, 0 ≤c<0.2, 1<d<2, 0.4<x<1. 3. The method for preparing a multi-element positive electrode material precursor according to claim 1, wherein the multi-element metal oxide powder D2 is the molecular formula of the multi-element positive electrode material precursor T2 is Ni _x Co _a M _b N _c O _d , where M is Al, N2 is one or more of Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn, 0<a<0.5, 0<b<0.4, 0 ≤c<0.2, 1<d<2, 0.4<x<1. 4. The method for preparing a multi-component positive electrode material precursor according to claim 1, wherein the molecular formula of the multi-component metal oxide powder D3, that is, the multi-component positive electrode material precursor T3 is Ni _x N _c O _d , wherein N3 is One or more of Mg, Ca, Sc, Ti, Zn, Cr, Fe, Zr, Cu, Ru, Mn, Al, 0<c<0.55, 1<d<2, 0.4<x<1. 5. The method for preparing a multi-component positive electrode material precursor according to claim 1, wherein the solid metal nickel, solid metal cobalt, solid metal manganese (or solid metal aluminum), and solid metal N1, solid metal N2 , The solid metal N3 can be any one or more of metal blocks, metal balls, metal powders, and metal rods. 6. The preparation method of multi-component positive electrode material precursor according to claim 1, wherein: nickel, cobalt, manganese, N in the solid metal mixture A1 can be in the form of metal element, or can be nickel, cobalt , manganese, N1 form any binary or more than binary multi-alloy form; the nickel, cobalt, aluminum, N2 in the solid metal mixture A2 can be in the form of metal elements, or can be nickel, cobalt, aluminum, N2 Any binary or more than binary multi-alloy form formed; Nickel and N in the solid metal mixture A3 can be in the form of metal elements, or can be any binary or more than binary formed by nickel and N The multi-alloy form. 7 . The method for preparing a multi-element cathode material precursor according to claim 1 , wherein the melting furnace can be an intermediate frequency induction furnace. 8 . 8. The method for preparing a multi-component positive electrode material precursor according to claim 1, wherein the multi-component metal oxide powder D1, the multi-component metal oxide powder D2, and the multi-component metal oxide powder D3 are all spherical, and the middle The particle size satisfies D ₅₀ =0.5 μm~15 μm.

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