BE1029021B1 - Processes to synthesize NCA battery material by combustion or even deflagration - Google Patents

Abstract

The present invention relates to a method for synthesizing NCA battery material by combustion or even deflagration by preparing a first mixture material of selected nickel source, cobalt source and aluminum source according to a suitable mass, after which the combustion or even deflagration reaction is carried out under high temperature conditions, to obtain composite oxides, from which a composite oxide containing three elements of nickel, cobalt and aluminum in a molar ratio of 8:1.5:0.5 is selected, after adding a lithium source and the further combustion or even deflagration reaction under high temperature conditions, NCA battery material is obtained; the method of the present invention uses combustion or even deflagration reaction so that the added nitrate decomposes and fuses with the added metal powder in the course of the decomposition to finally produce the NCA battery material with molar ratio of lithium, nickel, cobalt and aluminum elements as 10 :8:1.5:0.5 wherein the particle size of the NCA battery material is 10-100 nm.

Description

Processes to synthesize NCA battery material by combustion or even deflagration

TECHNICAL FIELD The present invention relates to the field of battery material technology and relates in particular to a method for synthesizing NCA battery material by combustion or even deflagration.

BACKGROUND ART The battery accounts for almost half of the cost of the entire new energy vehicle, so whoever wins at power battery will win at new energy vehicle. Among the four main materials of batteries (cathode material, anode material, electrolyte and diaphragm), the cathode material not only accounts for 40% of the cost, but also directly determines the energy density of electric cells. In the technology direction of the cathode material, power batteries can be mainly divided into three categories, i. H. Divide lithium iron phosphate, ternary (NCA/NCM) and lithium manganese oxide batteries. The so-called ternary materials are mainly NCM and NCA, of which NCM materials can be divided into NCM111, NCMS23, NCM622, NCM811, etc. At present, the NCM materials are mainly applied domestically, especially NCM523, which accounts for 76% of the production of subordinate ternary materials in 2016, while NCMI111 and NCM622 account for 13% and 10%, respectively. With the increase in the element content of nickel, the specific capacity of the ternary cathode materials will gradually increase, and the energy density of the electric cells will also increase. Under the dual stimulus of improved range of new energy vehicles and rising cobalt prices, NCM811 and high nickel NCA materials have become the hotspot of market competition. Due to the high technical barrier for NCA materials, the production volume in China is relatively small, and the current main suppliers are Sumitomo Metal, Japan Chemical Industry Corporation and Toda Chemical. Among the domestic battery companies, there is no mass production of NCA battery, both the first-class manufacturer such as NCTL, BYD, Lixin, Guoxuan Hi-Tech, and the manufacturers such as BAK, Wal-Mart, Tianpeng Energy and Penghui Energy, which specialized in cylindrical batteries. China is the world's largest new-energy vehicle market, and China has achieved a breakthrough of installing NCA ternary batteries from zero for two consecutive years. After breaking from zero in 2016, the installed volume of 286.5 MWh in 2017 is more than three times that of 87 MWh in 2016, reaching a new level. The NCA material replaces manga, which modifies lithium nickel cobalt manga oxides through ion doping and surface plating, where ion doping can increase the stability and improve the cycling performance of the material. However, there is a barrier in the production of NCA materials since Al is an amphoteric metal that does not precipitate easily. Therefore, NCA battery cathode materials have become a research hotspot in recent years.

SUMMARY OF THE PRESENT INVENTION In order to solve the above problems of the prior art, the present invention provides an energy-efficient and simple method for synthesizing NCA battery material by combustion or even deflagration. The NCA battery material synthesized by the above production method has a particle size of 10-100 nm and a molar ratio of 8:1.5:0.5 for the three elements nickel, cobalt and aluminum. The technical solution of the present invention is: Method for synthesizing NCA battery material by combustion or even deflagration, comprising the following steps, (1) Taking respectively a source of nickel, a source of cobalt and a source of aluminum and mixing them thoroughly and uniformly to obtain a first to get mixture material,

(2) subjecting the first mixture material to a combustion or even deflagration reaction under high temperature conditions to obtain a composite oxide, (3) adding a lithium source to the composite oxide and mixing thoroughly and uniformly to obtain a second mixture material, (4) subjecting the second Mixture material undergoes a combustion or even a deflagration reaction under high temperature conditions to obtain the NCA battery material.

In step (1), the nickel source is nickel nitrate and/or nickel powder, the cobalt source is cobalt nitrate and/or cobalt powder, and the aluminum source is aluminum nitrate and/or aluminum powder.

In step (1), the mass ratio of the nickel source, the cobalt source and the aluminum source is 0.744-0.800:0.150-0.163:0.050-0.063. In step (2), a burn rate modifier is further added to the first mixture material.

The burn rate modifier is added at a mass of 3-8% of the mass of the first mixture material.

Said burn rate regulator is a mixture of one or more of melaninjin, thaumatin, picric acid, oxytocin and nitrate.

Said nitrate is a mixture of one or more of magnesium nitrate, cobalt nitrate, nickel nitrate, silver nitrate.

In step (2), the high temperature condition is at 500-1200°C and the time of combustion or even deflagration reaction is 3-4 hours.

In step (3), the lithium source is lithium nitrate and/or lithium powder; the mass ratio of the composite oxide and the lithium source is 0.636-0.660:0.340-0.364. In step (4), the high temperature condition is at 650-1000°C and the combustion or even deflagration reaction time is 4-6 hours.

In steps (2) and (4) the combustion or even deflagration reactions are carried out with the addition of a combustion aid; wherein the combustion aid is wood flour and/or carbon powder. The advantageous effect of the present invention are: The method described in the present invention for synthesizing NCA battery material by combustion or even deflagration by preparing a first mixture material of selected nickel source, cobalt source and aluminum source according to a suitable mass, after which the combustion or even deflagration reaction is carried out under high-temperature conditions to obtain composite oxides, from which a composite oxide containing three elements of nickel, cobalt and aluminum in a molar ratio of 8:1.5:0.5 is selected, after adding a lithium source and further combustion or even deflagration reaction under high temperature conditions, NCA battery material is obtained; the method of the present invention uses combustion or even deflagration reaction so that the added nitrate decomposes and fuses with the added metal powder in the course of the decomposition to finally form the NCA battery material with the required ratio of lithium, nickel, cobalt and aluminum elements to produce, and the data shows that the particle size of the NCA battery material is 10-100 nm, and the molar ratio of lithium, nickel, cobalt and aluminum is 10:8:1.5:0.5, so the NCA battery material as Cathode material is suitable for lithium batteries. The synthesis method by combustion or even deflagration described in the present invention is highly efficient and energy-saving, with simple process and high production efficiency, while it can also be realized on a large scale.

DETAILED DESCRIPTION The present invention is described in detail below in connection with certain exemplary embodiments.

example 1

This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps, (1) taking a nickel source (a mixture consisting of nickel nitrate and nickel powder 5 according to a 1:1 molar ratio), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a 1:1.5 molar ratio), an aluminum source (a mixture consisting of aluminum nitrate and aluminum powder in a 1:1.7 molar ratio) and a burn rate controller Black Soggin and controlling the mass ratio of the nickel source, the cobalt source, the aluminum source and the black soggin as 0.748:0.157:0.065:0.030, after thoroughly and uniformly mixing, obtaining a first mixture material, the first mixture material is fed into a small crucible for further use, (2) Weigh out wood powder and carbon powder as a combustion aid speaking a mass ratio of 1:1, mixing and placing in a large crucible, wherein the mass ratio of the combustion aid to the first mixture material is 3:1, (3) inserting the small crucible into the large crucible, then heating in a muffle furnace at 700°C for 4 hours.

After completion of the heating, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 10-50 nm. (4) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a 1:1 molar ratio) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.636:0.340 , thorough and uniform mixing to obtain a second mixture material, the second mixture material being fed into a small crucible for further use, (5) weighing wood powder and carbon powder as a combustion aid according to a mass ratio of 1:2, mixing and placing in one large crucible, with the mass ratio of the combustion aid to the second mixture material being 1:1,

(6) Inserting the small crucible into the large crucible, then heating in a muffle furnace at 680°C for 5 hours.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery material with a particle size of 10-50 nm.

example 2

This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps,

(1) Taking a nickel source (a mixture consisting of nickel nitrate and nickel powder in a 1:1 molar ratio), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a 1:1.5 molar ratio), an aluminum source (aluminum powder) and a burn rate controller octojin and controlling the mass ratio of the nickel source, the cobalt source, the alumina source and octojin to 0.763:0.153:0.050:0.034, wherein after thorough and uniform

mixing a first mixture material is obtained, the first mixture material being fed into a small crucible for further use,

(2) Weighing wood powder and carbon powder as a combustion aid in a mass ratio of 1:1.5, mixing and placing in a large crucible, the mass ratio of the combustion aid to the first mixture material being 2:1,

(3) Inserting the small crucible into the large crucible, then heating in a muffle furnace at 750°C for 4 hours.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain a composite oxide with a particle size of 55-75 nm,

(4) Sieving the resulting composite oxide, selecting the composite oxide with a

Molar ratio of nickel, cobalt and aluminum close to 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a molar ratio of 1:1.3) to the composite oxide and controlling the mass ratio the composite oxide and lithium source to 0.647:0.353, mixing thoroughly and uniformly to obtain a second mixture material,

whereby the second mixture material is fed into a small crucible for further use,

(5) Weigh out wood powder and carbon powder as a combustion aid in a mass ratio of 1:1.7, mix and place in a large crucible, wherein the mass ratio of the combustion aid to the second mixture material is 2.3:1, (6) Set the small crucible into the large crucible, then heating in a muffle furnace at 730°C for 4.7 h. After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery material with a particle size of 10-50 nm.

Example 3 This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps, (1) taking a nickel source (a mixture consisting of nickel nitrate and nickel powder according to a 1:1 molar ratio) , a source of cobalt (a mixture consisting of cobalt nitrate and cobalt powder in a molar ratio of 1:1.7), a source of aluminum (a mixture consisting of aluminum nitrate and aluminum powder in a molar ratio of 1:1.6) and a burn rate controller picric acid and controlling the mass ratio of the nickel source, the cobalt source, the aluminum source and the picric acid to 0.755:0.157:0.058:0.030, whereby after thorough and uniform mixing, a first mixture material is obtained, the first mixture material is fed into a small crucible for further use, (2) heating of the small crucible in a muffle furnace at 500°C for 3 H. After completion of the heating, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 75-100 nm. (3) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a 1:1.3 molar ratio) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.652 :0.348, mixing thoroughly and evenly to obtain a second mixture material,

wherein the second mixture material is fed into a small crucible for further use, (4) inserting the small crucible into the large crucible, then heating in a muffle furnace at 800°C for 4.3 hours.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery cathode material with a particle size of 75-100 nm.

The NCA battery cathode material is tested and contains lithium, nickel, cobalt and aluminum in a molar ratio of 10:8:1.5:0.5. Example 4 This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps, (1) taking a nickel source (a mixture consisting of nickel nitrate and nickel powder according to a 1:1 molar ratio, 6), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a 1:1.8 molar ratio), an aluminum source (a mixture consisting of aluminum nitrate and aluminum powder in a 1:1.3 molar ratio), and controlling the mass ratio of the nickel source , the source of cobalt, the source of aluminum to 0.782:0.156:0.062, after thorough and uniform mixing, obtaining a first mixture material, the first mixture material is fed into a small crucible for further use, (2) weighing wood powder and carbon powder as a combustion aid, respectively a mass ratio of 1:1.8, mixing and dumping n into a large crucible, the mass ratio of the combustion aid to the first mixture material being 4:2.5, (3) placing the small crucible in the large crucible, then heating in a muffle furnace at 1200°C for 2 hours.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 40-60 nm. (4) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, after

Adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a molar ratio of 1:1.3) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.658:0.342, mixing thoroughly and uniformly to obtain a second mixture material , the second mixture material being fed into a small crucible for further use, (5) weighing wood powder and carbon powder as a combustion aid according to a mass ratio of 1:1.7, mixing and placing in a large crucible, with the mass ratio of the combustion aid to the second mixture material is 3.4:1, (6) inserting the small crucible into the large crucible, then heating in a muffle furnace at 850°C for 5.2 h.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery material with a particle size of 10-50 nm.

The NCA battery cathode material is tested and contains lithium, nickel, cobalt and aluminum in a molar ratio of 10:8:1.5:0.5. Example 5 This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps, (1) taking a nickel source (a mixture consisting of nickel nitrate and nickel powder according to a 1:1 molar ratio, 2), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a 1:1.4 molar ratio), an aluminum source (a mixture consisting of aluminum nitrate and aluminum powder in a 1:1.3 molar ratio), and controlling the mass ratio of the nickel source , the cobalt source, the aluminum source to 0.800:0.150:0.050, after mixing thoroughly and uniformly, a first mixture material is obtained, the first mixture material is fed into a small crucible for further use,

(2) Weigh out 300 g of carbon powder as a combustion aid, put it in a large crucible, the mass ratio of the combustion aid to the first mixture material being 3:1, (3) Put the small crucible in the large crucible, then heat it in a muffle furnace at 1000° C for 5 h. After completion of the heating, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 60-90 nm. (4) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a molar ratio of 1:1.3) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.645 :0.355, thorough and uniform mixing to obtain a second mixture material, the second mixture material being fed into a small crucible for further use, (5) weighing wood powder and carbon powder as a combustion aid in a mass ratio of 1:1.6, mixing and placing in a large crucible wherein the mass ratio of the combustion aid to the second mixture material is 2.7:1 gt, (6) Inserting the small crucible into the large crucible, then heating in a muffle furnace at 880°C for 4 hours. After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery material with a particle size of 10-50 nm.

The NCA battery cathode material is tested and contains lithium, nickel, cobalt and aluminum in a molar ratio of 10:8:1.5:0.5.

Example 6 This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps,

(1) Take a nickel source (a mixture consisting of nickel nitrate and nickel powder in a molar ratio of 1:1), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a molar ratio of 1:1.7), an aluminum source (a mixture consisting of of aluminum nitrate and aluminum powder according to a molar ratio of 1:1.6) and a combustion rate controller Taian, and controlling the mass ratio of the nickel source, the cobalt source, the aluminum source and Taian to 0.755:0.157:0.058:0.030, after thoroughly and uniformly mixing, a first mixture material is obtained, with the first mixture material being fed into a small crucible for further use, (2) heating the small crucible in a muffle furnace at 500°C for 3 hours. After the completion of the heating, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 75-100 nm. (3) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a molar ratio of 1:1.3) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.660 :0.364, mixing thoroughly and uniformly to obtain a second mixture material, feeding the second mixture material into a small crucible for further use, (4) inserting the small crucible into the large crucible, then heating in a muffle furnace at 650°C for 6 hours. After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery cathode material with a particle size of 75-100 nm.

The NCA battery cathode material is tested and contains lithium, nickel, cobalt and aluminum in a molar ratio of 10:8:1.5:0.5.

Example 7 This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps,

(1) Take a nickel source (a mixture consisting of nickel nitrate and nickel powder in a molar ratio of 1:1), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a molar ratio of 1:1.7), an aluminum source (a mixture consisting of of aluminum nitrate and aluminum powder 5according to a molar ratio of 1:1.6) and a combustion rate controller magnesium nitrate and controlling the mass ratio of the nickel source, the cobalt source, the aluminum source and the magnesium nitrate to 0.755:0.157:0.058:0.030, after thorough and uniform mixing, a first mixture material is obtained, wherein the first mixture material is fed into a small crucible for further use, (2) heating the small crucible in a muffle furnace at 600°C for 3 hours.

After the completion of heating, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 85-100 nm. (3) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a 1:1.3 molar ratio) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.660 :0.364, mixing thoroughly and uniformly to obtain a second mixture material, feeding the second mixture material into a small crucible for further use, (4) inserting the small crucible into the large crucible, then heating in a muffle furnace at 750°C for 5 hours.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery cathode material with a particle size of 85-100 nm.

The NCA battery cathode material is tested and contains lithium, nickel, cobalt and aluminum in a molar ratio of 10:8:1.5:0.5. Example 8 This embodiment provides a method for synthesizing NCA battery material by combustion or even deflagration, the method comprising the following steps,

(1) Take a nickel source (a mixture consisting of nickel nitrate and nickel powder in a molar ratio of 1:1), a cobalt source (a mixture consisting of cobalt nitrate and cobalt powder in a molar ratio of 1:1.7), an aluminum source (a mixture consisting of of aluminum nitrate and aluminum powder according to a molar ratio of 1:1.6) and a combustion rate controller silver nitrate and controlling the mass ratio of the nickel source, the cobalt source, the aluminum source and the silver nitrate s to 0.763:0.153:0.050:0.034, wherein after thoroughly and uniformly mixing a obtaining the first mixture material, feeding the first mixture material into a small crucible for further use, (2) heating the small crucible in a muffle furnace at 600°C for 3 hours.

After the completion of heating, it is cooled for half an hour, removed and sieved to obtain a composite oxide having a particle size of 85-100 nm. (3) Sieving the resulting composite oxide, selecting the composite oxide having a molar ratio of nickel, cobalt and aluminum near 8:1.5:0.5 by XRD, then adding a lithium source (a mixture consisting of lithium nitrate and lithium powder according to a molar ratio of 1:1.3) to the composite oxide and controlling the mass ratio of the composite oxide and the lithium source to 0.660 :0.364, mixing thoroughly and uniformly to obtain a second mixture material, feeding the second mixture material into a small crucible for further use, (4) inserting the small crucible into the large crucible, then heating in a muffle furnace at 750°C for 5 hours.

After the heating is finished, it is cooled for half an hour, removed and sieved to obtain NCA battery cathode material with a particle size of 85-100 nm.

The NCA battery cathode material is tested and contains lithium, nickel, cobalt and aluminum in a molar ratio of 10:8:1.5:0.5. The present invention is not limited to the above optimal embodiment, and anyone can come to various other forms under the inspiration of the present invention, but regardless of any variation in its shape or structure, any technical solution having the same or similar technical features as contained in the present invention falls within the scope of the present invention.

Claims (10)

patent claims 1. Process for the synthesis of NCA battery material by combustion or even deflagration, characterized in that it comprises the following steps, (1) taking respectively a source of nickel, a source of cobalt and a source of aluminum and mixing them thoroughly and uniformly to obtain a first mixture material (2) subjecting the first mixture material to combustion or even deflagration reaction under high temperature conditions to obtain a composite oxide, (3) adding a lithium source to the composite oxide and mixing thoroughly and uniformly to obtain a second mixture material, (4) subjecting the second mixture material to a combustion or even a deflagration reaction under high temperature conditions to obtain the NCA battery material. 152. Process for the synthesis of NCA battery material by combustion or even deflagration according to claim 1, characterized in that in step (1) the nickel source is nickel nitrate and/or nickel powder, the cobalt source is cobalt nitrate and/or cobalt powder, and the aluminum source is aluminum nitrate and /or aluminum powder. 203. Process for the synthesis of NCA battery material by combustion or even deflagration according to claim 1, characterized in that in step (1) the mass ratio of the nickel source, the cobalt source and the aluminum source is 0.744-0.800:0.150-0.163:0.050 is -0.063. 4. Method for synthesizing NCA battery material by combustion or even deflagration according to claim 1, characterized in that in step (2) a combustion rate modifier is further added to the first mixture material. 5. Method for the synthesis of NCA battery material by combustion or even deflagration according to claim 4, characterized in that the combustion rate modifier is added with a mass of 3-8% of the mass of the first mixture material. 6. Process for the synthesis of NCA battery material by combustion or even deflagration according to claim 4 or 5, characterized in that the combustion rate regulator is a mixture of one or more of melaninjin, thaumatin, picric acid, oxytocin and nitrate. 57. Process for the synthesis of NCA battery material by combustion or even deflagration according to claim 1, characterized in that in step (2) the high temperature condition is at 500-1200°C and the time of the combustion or even the deflagration reaction is 2-4 Hours. amounts to 8. Process for the synthesis of NCA battery material by combustion or even deflagration according to claim 1, characterized in that in step (3) the lithium source is lithium nitrate and/or lithium powder; the mass ratio of the composite oxide to the lithium source is 0.636-0.660:0.340-0.364. 9. Process for synthesizing NCA battery material by combustion or even deflagration according to claim 1, characterized in that in step (4) the high temperature condition is at 650-1000°C and the combustion or even deflagration reaction time is 4-6 hours. 10. Process for the synthesis of NCA battery material by combustion or even deflagration according to claim 1, characterized in that in steps (2) and (4) the combustion or even deflagration reaction is carried out with the addition of a combustion aid, the combustion aid being wood powder and/or carbon powder.