CN116354418A - Nickel-cobalt-manganese-aluminum quaternary precursor material, preparation method thereof and positive electrode material - Google Patents

Nickel-cobalt-manganese-aluminum quaternary precursor material, preparation method thereof and positive electrode material Download PDF

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CN116354418A
CN116354418A CN202310577692.5A CN202310577692A CN116354418A CN 116354418 A CN116354418 A CN 116354418A CN 202310577692 A CN202310577692 A CN 202310577692A CN 116354418 A CN116354418 A CN 116354418A
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nickel
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任香梦
江宏亮
李吉文
胡俊
岗俊格
曾旭
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Wuhu Jiana New Energy Materials Co ltd
Guangdong Jiana Energy Technology Co Ltd
Jiangxi Jiana Energy Technology Co Ltd
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Guangdong Jiana Energy Technology Co Ltd
Jiangxi Jiana Energy Technology Co Ltd
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Abstract

The invention relates to the technical field of lithium ion batteries, in particular to a nickel-cobalt-manganese-aluminum quaternary precursor material, a preparation method thereof and a positive electrode material. The nickel-cobalt-manganese-aluminum quaternary precursor material sequentially comprises an inner layer, an intermediate layer and an outer layer from inside to outside; the chemical formula of the inner layer is Ni a Co b Mn c Al 1‑a‑b‑c (OH) 2 0.94.gtoreq.a.gtoreq.0.8, b.gtoreq.c.gtoreq.1-a-b-c.gtoreq.0; the chemical formula of the intermediate layer is Ni l Co m Mn n Al 1‑l‑m‑n (OH) 2 0.9 is more than or equal to l is more than or equal to 0.8, n is more than or equal to m is more than 0, and 1-l-m-n is more than 0; the chemical formula of the outer layer is Ni w Co x Mn y Al z Nb 1‑w‑x‑y‑z (OH) 2 0.6 is more than or equal to w is more than or equal to 0.4,0.1 is more than or equal to x is more than 0,0.5 is more than or equal to y is more than or equal to 0.3,0.2 is more than or equal to z is more than or equal to 0.05, and 0.1 is more than or equal to 1-w-x-y-z is more than or equal to 0.01; has excellent multiplying power performance, cycle performance and safety performance.

Description

Nickel-cobalt-manganese-aluminum quaternary precursor material, preparation method thereof and positive electrode material
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nickel-cobalt-manganese-aluminum quaternary precursor material, a preparation method thereof and a positive electrode material.
Background
The lithium ion battery has the advantages of high energy density, long service life and the like, has become the main stream direction of research and development in the field of new energy batteries, has very rapid development, has higher and higher performance requirements on the lithium ion battery, such as higher and higher requirements on safety performance, multiplying power performance and the like of batteries and materials in various fields of aviation, military industry, electric vehicles and the like.
The ternary positive electrode material usually adopts a mode of increasing the proportion of nickel metal in the precursor material to increase the energy density of the material, but in the charge-discharge cycle process of the high-nickel ternary positive electrode material, the nickel is as follows 2+ Radius and Li + The radius is close, ni is easy to occur 2+ Occupying Li + In the case of sites, i.e. lithium nickel mixed rows, cation mixed rows lead to latticesThe space is reduced, the lithium ion channel is reduced, and free deintercalation of lithium ions is prevented, so that the cycle performance and the rate performance of the battery are reduced. The electrode material lithium removal is started from the surface layer, and the phenomenon of excessive lithium removal occurs in the surface layer structure along with the charging progress, and meanwhile, the layered structure of the high-nickel ternary material is converted into a spinel structure and an inert rock salt structure.
The transition of the structure and the unsmooth transfer path can also cause the phenomenon of lithium precipitation, in addition, the high-valence transition metal ions with strong oxidability on the surface layer and electrolyte have serious side reactions, gas is generated to cause the battery to be inflated, and the more serious the reaction is under the condition of excessive charge and discharge, the more serious the safety risk is caused.
The quaternary nickel-cobalt-manganese-aluminum positive electrode material is added with aluminum element on the basis of ternary materials, and is good in modification on high-nickel and ultrahigh-nickel positive electrode materials, and the performance of the quaternary nickel-cobalt-manganese-aluminum positive electrode material is superior to that of nickel-cobalt-manganese and nickel-cobalt-aluminum materials. The strength of the Al-O bond is stronger than that of Ni (Co, mn) -O bond, and the thermal stability of the material can be improved well. However, the problems of structural transformation caused by lithium nickel mixed discharge, battery inflation caused by side reaction and the like are not obviously improved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a nickel-cobalt-manganese-aluminum quaternary precursor material, which improves the crystal structure of a high-nickel positive electrode precursor material and improves the rate capability, the cycle performance and the safety performance.
The second aim of the invention is to provide a preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material, which can obtain the nickel-cobalt-manganese-aluminum quaternary precursor material with good sphericity, large specific surface area and consistent morphology.
A third object of the present invention is to provide a positive electrode material having excellent electrochemical properties and safety properties.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a nickel-cobalt-manganese-aluminum quaternary precursor material which sequentially comprises an inner layer, an intermediate layer and an outer layer from inside to outside;
the chemical formula of the inner layer is Ni a Co b Mn c Al 1-a-b-c (OH) 2 ，0.94≥a≥0.8，b≥c≥1-a-b-c＞0；
The chemical formula of the intermediate layer is Ni l Co m Mn n Al 1-l-m-n (OH) 2 ，0.9≥l≥0.8，n≥m＞0，1-l-m-n＞0；
The chemical formula of the outer layer is Ni w Co x Mn y Al z Nb 1-w-x-y-z (OH) 2 ，0.6≥w≥0.4，0.1＞x＞0，0.5≥y≥0.3，0.2≥z≥0.05，0.1≥1-w-x-y-z≥0.01。
Further, the thickness of the inner layer is 0.5-2 μm, the thickness of the intermediate layer is 3-12 μm, and the thickness of the outer layer is 1-4 μm.
Further, the specific surface area of the nickel-cobalt-manganese-aluminum quaternary precursor material is more than 50m 2 /g。
The invention also provides a preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material, which comprises the following steps:
s1, under inert atmosphere, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into a base solution to perform a first coprecipitation reaction to obtain a reaction solution I;
s2, under the atmosphere containing oxygen, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into the reaction solution I for a second coprecipitation reaction to obtain a reaction solution II;
and S3, under an inert atmosphere, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a solution containing an Nb source, a sodium hydroxide solution and ammonia water into the reaction solution II to perform a third coprecipitation reaction, and aging to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
Further, in step S1, the conditions of the first coprecipitation reaction are as follows: the pH value of the reaction system is 11.5-12.2, and NH in the reaction system 4 + The concentration of the catalyst is 6-8 g/L, the reaction temperature is 45-55 ℃, and the reaction time is 1-6 h.
Further, in the step S2, the volume percentage of oxygen in the atmosphere containing oxygen is 3% -8%.
Further, in step S2, the conditions of the second coprecipitation reaction are as follows: the pH value of the reaction system is 11-12.5, and NH in the reaction system 4 + The concentration of the catalyst is 5-10 g/L, the reaction temperature is 50-60 ℃, and the reaction time is 12-76 h.
Further, in step S3, the conditions of the third coprecipitation reaction are as follows: the pH of the reaction system is 10.8-12, NH in the reaction system 4 + The concentration of the catalyst is 4-7 g/L, the reaction temperature is 48-58 ℃, and the reaction time is 8-24 h.
Further, in step S1 and step S2, the sum of the metal concentration of the solution containing Ni salt, co salt and Mn salt and the metal concentration of the solution containing Al source is 1.5 to 2mol/L;
in step S3, the sum of the metal concentration of the solution containing Ni salt, co salt and Mn salt, the metal concentration of the solution containing Al source and the metal concentration of the solution containing Nb source is 1.5-2 mol/L.
Preferably, the concentration of the sodium hydroxide solution is 6-12 mol/L.
Preferably, the concentration of the ammonia water is 5-10 mol/L.
Preferably, the Nb source comprises Nb 2 O 5 、NbO 2 、Nb 2 O 3 And at least one of NbO.
The invention also provides a positive electrode material which is mainly prepared from the nickel-cobalt-manganese-aluminum quaternary precursor material.
Compared with the prior art, the invention has the beneficial effects that:
the nickel-cobalt-manganese-aluminum quaternary precursor material is a concentration gradient layered material with an inner layer of high/ultrahigh nickel, an intermediate layer of medium/high nickel and an outer layer of medium/low nickel; the Ni content gradually decreases from inside to outside, which is beneficial to improving the specific capacity of the precursor material, stabilizing the structure, and improving the multiplying power performance and the cycling stability of the material.
The outer layer of the nickel-cobalt-manganese-aluminum quaternary precursor material is a middle/low nickel material with Nb metal structural support, the doping of Nb metal can slow down the structure transformation and the occurrence of lithium precipitation phenomena in the charging and discharging process of crystals, the crystal structure of the high-nickel positive electrode precursor material is improved, and the purposes of improving the cycle performance and the multiplying power performance are achieved; in addition, the Nb-doped middle/low nickel outer layer structure isolates the internal high nickel material from being in direct contact with electrolyte, so that the safety problem caused by battery inflation due to side reaction of the battery is relieved, and the safety performance is improved.
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material can obtain the nickel-cobalt-manganese-aluminum quaternary precursor with good sphericity, consistent morphology and large specific surface area; in the process of generating the intermediate layer, a proper amount of oxygen is introduced, so that the specific surface area of the material is increased, and the rate capability of the material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation method of a nickel cobalt manganese aluminum quaternary precursor material in embodiment 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The nickel-cobalt-manganese-aluminum quaternary precursor material, the preparation method thereof and the positive electrode material are specifically described below.
In some embodiments of the invention, a nickel-cobalt-manganese-aluminum quaternary precursor material is provided, which comprises an inner layer, an intermediate layer and an outer layer from inside to outside in sequence;
the chemical formula of the inner layer is Ni a Co b Mn c Al 1-a-b-c (OH) 2 ，0.94≥a≥0.8，b≥c≥1-a-b-c＞0；
The chemical formula of the intermediate layer is Ni l Co m Mn n Al 1-l-m-n (OH) 2 ，0.9≥l≥0.8，n≥m＞0，1-l-m-n＞0；
The chemical formula of the outer layer is Ni w Co x Mn y Al z Nb 1-w-x-y-z (OH) 2 ，0.6≥w≥0.4，0.1＞x＞0，0.5≥y≥0.3，0.2≥z≥0.05，0.1≥1-w-x-y-z≥0.01。
The nickel-cobalt-manganese-aluminum quaternary precursor material is a concentration gradient layered material with high/ultrahigh nickel as an inner layer, medium/high nickel as an intermediate layer and medium/low nickel as an outer layer; the Ni-based alloy is of a three-layer core-shell structure, and the Ni content gradually decreases from inside to outside; the content of the internal nickel element is higher, so that high specific capacity is provided for the material; the nickel content is gradually reduced from inside to outside, the manganese content is gradually increased, and the structural stability of the material is improved; in addition, the doping of the niobium element at the outermost layer inhibits the phase change after lithium removal from outside to inside, so that the gradient material with excellent comprehensive performance is obtained.
The outer layer of the nickel-cobalt-manganese-aluminum quaternary precursor material is a middle/low nickel material with Nb metal structural support, the doping of Nb metal can slow down the structure transformation and the occurrence of lithium precipitation phenomena in the charging and discharging process of crystals, the crystal structure of the high-nickel positive electrode precursor material is improved, and the mixing discharge and excessive lithium removal of cations are inhibited from the surface layer, so that the layered structure transformation of the high-nickel positive electrode precursor material is inhibited, and the purposes of improving the cycle performance and the multiplying power performance are achieved. The Nb-doped middle/low nickel outer layer structure prevents the high nickel material (middle layer) in the material from being in direct contact with the electrolyte, improves the side reaction of the material and the electrolyte, relieves the safety problem caused by battery inflation due to the side reaction of the battery, and improves the safety performance.
In some embodiments of the invention, the inner layer has a thickness of 0.5 to 2 μm, the middle layer has a thickness of 3 to 12 μm, and the outer layer has a thickness of 1 to 4 μm; typical but non-limiting, for example, the thickness of the inner layer of nickel cobalt manganese aluminum quaternary precursor material may be in the range of 0.5 μm, 1 μm, 1.5 μm, 2 μm, or any two of these; the thickness of the intermediate layer of nickel cobalt manganese aluminum quaternary precursor material may be 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, or a range of any two of these; the thickness of the outer layer of the nickel cobalt manganese aluminum quaternary precursor material may be 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, or a range of any two of these.
The ultra-high nickel inner layer with the thickness of 0.5-2 mu m provides a growth point for the middle layer and simultaneously shows specific capacity superior to that of the middle layer material; meanwhile, the higher the nickel content is, the more serious the lithium nickel mixed discharge is, so that the smaller the thickness of the inner layer is, the more the lithium nickel mixed discharge degree under the ultrahigh nickel content can be slowed down.
The intermediate layer with the thickness of 3-12 μm is a structural position for mainly storing lithium ions and providing energy, so that the relatively thick intermediate layer can achieve the aim, and in addition, the intermediate layer plays a transition role in reducing the nickel content from high nickel/ultra-high nickel to medium nickel/medium low nickel.
The thickness of the outer layer, which is the key structural location for modification, is mostly dependent on the effect to be achieved, and the greater the doping layer thickness, the better the modification effect and the greater the specific capacity reduction.
In some embodiments of the invention, the nickel cobalt manganese aluminum quaternary precursor material has a (BET) specific surface area of > 50m 2 /g。
In some embodiments of the invention, the nickel cobalt manganese aluminum quaternary precursor material has a particle size of 4.5 to 18 μm.
The nickel-cobalt-manganese-aluminum quaternary precursor material has large specific surface area, and is beneficial to enhancing the multiplying power performance of the material.
In some embodiments of the present invention, a method for preparing the nickel-cobalt-manganese-aluminum quaternary precursor material is provided, including the following steps:
s1, under inert atmosphere, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into a base solution to perform a first coprecipitation reaction to obtain a reaction solution I;
s2, under the atmosphere containing oxygen, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into the reaction solution I for a second coprecipitation reaction to obtain a reaction solution II;
and S3, under an inert atmosphere, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a solution containing an Nb source, a sodium hydroxide solution and ammonia water into the reaction solution II to perform a third coprecipitation reaction, and aging to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
Firstly, adopting a salt solution, a complexing agent and a precipitator to generate an inner layer, then adopting the salt solution, the complexing agent and the precipitator to coat the inner layer to generate an intermediate layer, and then adopting the salt solution, a solution containing a Nb source, the complexing agent and the precipitator to coat the intermediate layer to obtain an outer layer; and the reaction process is precisely controlled, so that the nickel-cobalt-manganese-aluminum quaternary precursor with good sphericity, consistent morphology and large specific surface area can be obtained.
In the process of the second coprecipitation reaction, namely the generation of the intermediate layer, the invention increases the specific surface area of the material by introducing a proper amount of oxygen, thereby improving the multiplying power performance of the material.
In some embodiments of the invention, the base fluid comprises water, naOH, and NH 3 ·H 2 O. The base solution is mainly prepared by mixing water, ammonia water and liquid alkali.
In some embodiments of the invention, in step S1, the inert gas comprises nitrogen. Nitrogen is used as a shielding gas in the reaction process.
In some embodiments of the invention, in step S1, the conditions of the first coprecipitation reaction are: the pH of the reaction system is 11.5-12.2, and the reaction is reversedNH in reaction System 4 + The concentration of the catalyst is 6-8 g/L, the reaction temperature is 45-55 ℃, and the reaction time is 1-6 h.
In some embodiments of the invention, in step S1, the stirring rate of the first coprecipitation reaction is 400 to 600rmp.
In some embodiments of the invention, in step S1, the first coprecipitation reaction comprises: continuously introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into the base solution to react for 1-6 h, stopping feeding, and continuously stirring for 0.5-1 h.
In some embodiments of the present invention, in step S2, the volume percentage of oxygen in the atmosphere containing oxygen is 3% to 8%; preferably, the oxygen-containing atmosphere comprises nitrogen and oxygen.
In some embodiments of the invention, in step S2, the conditions of the second coprecipitation reaction are: the pH value of the reaction system is 11-12.5, and NH in the reaction system 4 + The concentration of the catalyst is 5-10 g/L, the reaction temperature is 50-60 ℃, and the reaction time is 12-76 h.
In some embodiments of the invention, in step S2, the stirring rate of the second coprecipitation reaction is 200 to 400rmp.
In some embodiments of the invention, in step S2, the second coprecipitation reaction comprises: continuously introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into the reaction solution I to react for 12-72 h, stopping feeding, and continuously stirring for 2-4 h.
In some embodiments of the invention, in step S3, the inert gas comprises nitrogen. Nitrogen is used as a shielding gas in the reaction process.
In some embodiments of the invention, in step S3, the conditions of the third coprecipitation reaction are: the pH of the reaction system is 10.8-12, NH in the reaction system 4 + The concentration of the catalyst is 4-7 g/L, the reaction temperature is 48-58 ℃, and the reaction time is 8-24 h.
In some embodiments of the invention, in step S3, the stirring rate of the third coprecipitation reaction is 50 to 120rmp.
In some specific embodiments of the present invention, in step S3, after continuously introducing a solution containing Ni salt, co salt and Mn salt, a solution containing Al source, a solution containing Nb source, a sodium hydroxide solution and ammonia water into the reaction solution II to react for 8-24 hours, stopping feeding, and sequentially aging, filtering, washing and drying to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
In some embodiments of the invention, in step S3, the aging time is 20 to 36 hours; the filtering mode comprises filter pressing and/or centrifugation; the drying temperature is 100-130 ℃, and the drying time is 10-24 hours.
In some embodiments of the present invention, in step S1 and step S2, the sum of the metal concentration of the solution containing the Ni salt, the Co salt, and the Mn salt and the metal concentration of the solution containing the Al source is 1.5 to 2mol/L.
In some embodiments of the invention, in step S1, the molar ratio of Ni, co and Mn in the solution containing Ni salt, co salt and Mn salt is a: b: c, performing operation; the molar ratio of Ni in the solution containing Ni salt, co salt and Mn salt to Al in the solution containing Al source is a:1-a-b-c.
In some embodiments of the invention, in step S2, the molar ratio of Ni, co and Mn in the solution containing Ni salt, co salt and Mn salt is l: m: n; the molar ratio of Ni in the solution containing Ni salt, co salt and Mn salt to Al in the solution containing Al source is l:1-l-m-n.
In some embodiments of the present invention, in step S3, the sum of the metal concentration of the solution containing the Ni salt, the Co salt, and the Mn salt, the metal concentration of the solution containing the Al source, and the metal concentration of the solution containing the Nb source is 1.5 to 2mol/L.
In some embodiments of the invention, in step S3, the molar ratio of Ni, co and Mn in the solution containing Ni salt, co salt and Mn salt is w: x: y; the molar ratio of Ni in the solution containing Ni salt, co salt and Mn salt to Al in the solution containing Al source is w: z; the molar ratio of Ni in the solution containing Ni salt, co salt and Mn salt to Nb in the solution containing Nb source is w:1-w-x-y-z.
In some embodiments of the invention, the Ni salt comprises at least one of nickel sulfate, nickel nitrate, and nickel chloride.
In some embodiments of the invention, the Co salt comprises at least one of cobalt sulfate, cobalt nitrate, and cobalt chloride.
In some embodiments of the invention, the Mn salt comprises at least one of manganese sulfate, manganese nitrate, and manganese chloride.
In some embodiments of the invention, the solution comprising the Al source comprises a sodium metaaluminate solution; preferably, the solution containing the Al source is mainly obtained by mixing at least one of aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum nitrate, and aluminum oxide with a sodium oxide solution.
In some embodiments of the invention, the solution containing the Nb source is mainly obtained by mixing an aqueous solution of at least one of carbonate and hydroxide with the Nb source; the Nb source includes Nb 2 O 5 、NbO 2 、Nb 2 O 3 And NbO; the carbonate comprises sodium carbonate and/or potassium carbonate, and the hydroxide comprises sodium hydroxide and/or potassium hydroxide
In some embodiments of the invention, in steps S1 to S3, the concentration of the sodium hydroxide solution is 6 to 12mol/L.
In some embodiments of the invention, in steps S1 to S3, the concentration of ammonia is 5 to 10mol/L.
In some embodiments of the invention, in steps S1-S3, the feed rate of the solution containing Ni salt, co salt and Mn salt is 200-500L/h; the feeding speed of the solution containing the Al source is 20-100L/h, and the feeding speed of the solution containing the Nb source is 20-100L/h; the feeding speed of the sodium hydroxide solution is 120-200L/h; the feeding speed of the ammonia water is 10-60L/h.
In some embodiments of the present invention, a positive electrode material is provided, which is mainly prepared from the nickel-cobalt-manganese-aluminum quaternary precursor material.
In some embodiments of the present invention, there is also provided a method for preparing a positive electrode material, including the steps of:
and sintering the nickel-cobalt-manganese-aluminum quaternary precursor material and lithium hydroxide.
In some embodiments of the invention, sintering comprises sintering at 680-900 ℃ for 15-24 hours after pre-sintering at 400-600 ℃ for 5-10 hours in an oxygen-rich environment (oxygen concentration ≡99.99%).
In some embodiments of the invention, typical but non-limiting, for example, the pre-sintering temperature is 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, or a range of any two of these; the pre-sintering time is 5h, 6h, 7h, 8h, 9h, 10h or a range formed by any two of the above; the sintering temperature is 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the range formed by any two of the above materials; the sintering time is 15h, 18h, 20h, 22h, 24h or a range of any two of the above.
In some embodiments of the present invention, a lithium ion battery is also provided, including the above-described positive electrode material.
Example 1
Solution a: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.94: 0.02: the mixture was weighed at a molar ratio of 0.02 and dissolved in pure water to prepare a 1.96mol/L solution.
Solution B: aluminum hydroxide was used in a molar ratio of Al to Ni in solution A of 0.02:0.94 mol/L sodium hydroxide solution is weighed and dissolved in 6mol/L sodium hydroxide solution, and a certain amount of pure water is added to prepare 0.24mol/L solution.
Solution C: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.89: 0.01: the mixture was weighed at a molar ratio of 0.08 and dissolved in pure water to prepare a 1.96mol/L solution.
Solution D: aluminum hydroxide was used in a molar ratio of Al to Ni in solution C of 0.02:0.89 is weighed, dissolved in 6mol/L sodium hydroxide solution, and added with a certain amount of pure water to prepare 0.24mol/L solution.
Solution E: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.6: 0.03:0.3 molar ratio, and 1.86mol/L solution is prepared by dissolving the mixture in pure water.
Solution F: aluminum hydroxide was used in a molar ratio of Al to Ni in solution E of 0.05:0.6 is weighed, dissolved in 6mol/L sodium hydroxide solution, and added with a certain amount of pure water to prepare 1.2mol/L solution.
Solution G: nb (Nb) 2 O 5 The molar ratio of Nb to Ni in solution E was 0.02:0.6 is weighed, dissolved in 6mol/L sodium hydroxide solution, and added with a certain amount of pure water to prepare 0.48mol/L solution.
Base solution: is prepared by mixing pure water, 8.3mol/L ammonia water and 10.8mol/L liquid alkali; the pH of the base solution was 12.1 and the ammonium concentration was 7g/L.
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material provided by the embodiment comprises the following steps:
s1, under the nitrogen atmosphere, introducing a solution A, a solution B, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into a reaction kettle containing base solution (the volume of the base solution accounts for 50% of the volume of the reaction kettle) at flow rates of 480L/h, 80L/h, 178L/h and 35L/h respectively to perform a first coprecipitation reaction (inner layer precipitation), wherein the first coprecipitation reaction conditions are as follows: the pH of the system is 12.1, NH in the system 4 + Is 7g/L; the temperature is 50 ℃, the stirring speed is 600rmp, and the reaction time is 6h; then closing the feeding, and continuing stirring for 1h to obtain a reaction liquid I;
s2, introducing compressed air and nitrogen, and introducing a solution C, a solution D, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into the reaction solution I at flow rates of 480L/h, 80L/h, 178L/h and 35L/h under the atmosphere with the oxygen volume fraction of 8% to perform a second coprecipitation reaction (intermediate layer precipitation), wherein the second coprecipitation reaction conditions are as follows: the pH of the system is 11.8, NH in the system 4 + Is 6g/L; the temperature is 50 ℃, the stirring speed is 400rmp, and the reaction time is 70h; then closing the feeding, and continuing stirring for 4 hours to obtain a reaction liquid II;
s3, introducing the solution E, the solution F, the solution G, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into the reaction solution II at flow rates of 480L/h, 40L/h, 178L/h and 35L/h respectively under the nitrogen atmosphere to perform a third coprecipitation reaction, wherein the third coprecipitation reaction conditions are as follows: the pH of the system is 10.8, NH in the system 4 + The concentration is 4g/L; the temperature is 55 ℃, the stirring speed is 50rmp, and the reaction time is 20h; then closing the feeding, transferring the feeding into an ageing tank, ageing for 24 hoursAnd after the formation, sequentially carrying out centrifugation, washing and drying at 125 ℃ for 20 hours to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
The preparation method of the positive electrode material provided by the embodiment comprises the following steps:
the molar ratio is 1.09:1 weighing the nickel-cobalt-manganese-aluminum quaternary precursor material and lithium hydroxide monohydrate, presintering for 8 hours at 400 ℃ and sintering for 24 hours at 700 ℃ in an oxygen-enriched environment to obtain the anode material.
A schematic flow chart of a preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material in the embodiment is shown in FIG. 1.
Example 2
Solution a: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.9: 0.04:0.04 mol ratio, and 1.96mol/L solution is prepared by dissolving the mixture in pure water.
Solution B: aluminum hydroxide was used in a molar ratio of Al to Ni in solution A of 0.02:0.9 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 0.24mol/L solution.
Solution C: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.82: 0.01: the mixture was weighed at a molar ratio of 0.12 and dissolved in pure water to prepare a 1.9mol/L solution.
Solution D: aluminum hydroxide was used in a molar ratio of Al to Ni in solution C of 0.01:0.82 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 0.6mol/L solution.
Solution E: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.5: 0.05:0.3 molar ratio, and is dissolved in pure water to prepare a solution of 1.7 mol/L.
Solution F: aluminum hydroxide was used in a molar ratio of Al to Ni in solution E of 0.1:0.5 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 2.4mol/L solution.
Solution G: nb (Nb) 2 O 5 The molar ratio of Nb to Ni in solution E was 0.05:0.5 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 1.2mol/L solution.
Base solution: is prepared by mixing pure water, 8.3mol/L ammonia water and 10.8mol/L liquid alkali; the pH of the base solution was 12.2 and the ammonium concentration was 8g/L.
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material provided by the embodiment comprises the following steps:
s1, under the nitrogen atmosphere, introducing a solution A, a solution B, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into a reaction kettle containing base solution at flow rates of 480L/h, 80L/h, 178L/h and 35L/h (the volume of the base solution is 50% of the volume of the reaction kettle) respectively to perform a first coprecipitation reaction, wherein the first coprecipitation reaction conditions are as follows: the pH of the system is 12.2, NH in the system 4 + Is 8g/L; the temperature is 54 ℃, the stirring speed is 600rmp, and the reaction time is 4 hours; then closing the feeding, and continuing stirring for 1h to obtain a reaction liquid I;
s2, introducing compressed air, and introducing a solution C, a solution D, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into the reaction solution I at flow rates of 480L/h, 80L/h, 178L/h and 35L/h under the atmosphere with the oxygen volume fraction of 6% to perform a second coprecipitation reaction, wherein the second coprecipitation reaction conditions are as follows: the pH of the system is 12.4, NH in the system 4 + Is 9g/L; the temperature is 58 ℃, the stirring speed is 300rmp, and the reaction time is 54h; then closing the feeding, and continuing stirring for 3 hours to obtain a reaction liquid II;
s3, introducing the solution E, the solution F, the solution G, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into the reaction solution II at flow rates of 480L/h, 40L/h, 178L/h and 35L/h respectively under the nitrogen atmosphere to perform a third coprecipitation reaction, wherein the third coprecipitation reaction conditions are as follows: the pH of the system is 11.5, NH in the system 4 + Is 7g/L; the temperature is 55 ℃, the stirring speed is 80rmp, and the reaction time is 15h; and then closing the feeding, transferring the material into an ageing tank for ageing for 20 hours, and after the ageing is finished, sequentially centrifuging, washing and drying at 125 ℃ for 20 hours to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
The preparation method of the positive electrode material provided by the embodiment comprises the following steps:
the molar ratio is 1.03:1 weighing the nickel-cobalt-manganese-aluminum quaternary precursor material and lithium hydroxide monohydrate, presintering for 6h at 600 ℃ in an oxygen-enriched environment, and sintering for 20h at 760 ℃ to obtain the anode material.
Example 3
Solution a: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.85: 0.06: the mixture was weighed at a molar ratio of 0.05 and dissolved in pure water to prepare a 1.92mol/L solution.
Solution B: aluminum hydroxide was used in a molar ratio of Al to Ni in solution A of 0.04:0.85 of the mixture is weighed, dissolved in 6mol/L sodium hydroxide solution, and added with a certain amount of pure water to prepare 0.48mol/L solution.
Solution C: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.8: 0.02: the mixture was weighed at a molar ratio of 0.12 and dissolved in pure water to prepare a 1.88mol/L solution.
Solution D: aluminum hydroxide was used in a molar ratio of Al to Ni in solution C of 0.06:0.8 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 0.72mol/L solution.
Solution E: nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.4: 0.03:0.4 molar ratio, and 1.66mol/L solution is prepared by dissolving the mixture in pure water.
Solution F: aluminum hydroxide was used in a molar ratio of Al to Ni in solution E of 0.1:0.4 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 2.4mol/L solution.
Solution G: nb (Nb) 2 O 5 The molar ratio of Nb to Ni in solution E was 0.07:0.4 weight, dissolve in 6mol/L sodium hydroxide solution, add a certain amount of pure water, prepare 1.68mol/L solution.
Base solution: is prepared by mixing pure water, 8.3mol/L ammonia water and 10.8mol/L liquid alkali; the pH of the base solution was 11.8 and the ammonium concentration was 6g/L.
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material provided by the embodiment comprises the following steps:
s1, under the nitrogen atmosphere, introducing the solution A, the solution B, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into a reaction kettle containing base solution (base solution) at flow rates of 480L/h, 80L/h, 178L/h and 35L/h respectively50% of the volume of the reaction kettle) for a first coprecipitation reaction, wherein the first coprecipitation reaction conditions are as follows: the pH of the system is 11.8, NH in the system 4 + Is 6g/L; the temperature is 48 ℃, the stirring speed is 400rmp, and the reaction time is 2h; then closing the feeding, and continuously stirring for 0.5h to obtain a reaction liquid I;
s2, introducing compressed air, and introducing a solution C, a solution D, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into the reaction solution I at flow rates of 480L/h, 80L/h, 178L/h and 35L/h under the atmosphere with the oxygen volume fraction of 4% to perform a second coprecipitation reaction, wherein the second coprecipitation reaction conditions are as follows: the pH of the system is 12, NH in the system 4 + Is 7g/L; the temperature is 52 ℃, the stirring speed is 200rmp, and the reaction time is 36h; then closing the feeding, and continuing stirring for 2 hours to obtain a reaction liquid II;
s3, introducing the solution E, the solution F, the solution G, 10.8mol/L sodium hydroxide solution and 8.3mol/L ammonia water into the reaction solution II at flow rates of 480L/h, 40L/h, 178L/h and 35L/h respectively under the nitrogen atmosphere to perform a third coprecipitation reaction, wherein the third coprecipitation reaction conditions are as follows: the pH of the system is 11.2, NH in the system 4 + Is 5g/L; the temperature is 48 ℃, the stirring speed is 100rmp, and the reaction time is 10 hours; and then closing the feeding, transferring the material into an ageing tank for ageing for 24 hours, and after the ageing is finished, sequentially centrifuging, washing and drying at 125 ℃ for 20 hours to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
The preparation method of the positive electrode material provided by the embodiment comprises the following steps:
the molar ratio is 1.06:1 weighing the nickel-cobalt-manganese-aluminum quaternary precursor material and lithium hydroxide monohydrate, presintering for 9 hours at 500 ℃ in an oxygen-enriched environment, and sintering for 20 hours at 850 ℃ to obtain the anode material.
Comparative example 1
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material provided in this comparative example is referred to example 3, and only differs in that in step S3, the solution G is not introduced.
The preparation method of the positive electrode material provided in this comparative example is different from that of example 3 only in that the nickel cobalt manganese aluminum quaternary precursor material of this comparative example is used.
Comparative example 2
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material provided in this comparative example is referred to in example 3, and is only different in that in the solution a, nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to Ni: co: mn=0.6: 0.5: weighing the mixture according to a molar ratio of 0.15; in solution B, the molar ratio of aluminum hydroxide to Ni in solution a was 0.2:0.6, weighing; in the solution C, nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.4: 0.15: weighing the mixture according to a molar ratio of 0.3; in solution D, the molar ratio of aluminum hydroxide to Ni in solution C was 0.15:0.4, weighing; in the solution E, nickel sulfate hexahydrate, cobalt sulfate heptahydrate and manganese sulfate monohydrate are prepared according to the following steps of Ni: co: mn=0.7: 0.05: weighing the mixture according to a molar ratio of 0.05; in solution F, the molar ratio of aluminum hydroxide to Ni in solution E was 0.15:0.7, weighing; in solution G, nb 2 O 5 The molar ratio of Nb to Ni in solution E was 0.05:0.7 weight.
The preparation method of the positive electrode material provided in this comparative example is different from that of example 3 only in that the nickel cobalt manganese aluminum quaternary precursor material of this comparative example is used.
Comparative example 3
The preparation method of the nickel-cobalt-manganese-aluminum quaternary precursor material provided in this comparative example is referred to example 3, except that in step S2, the atmosphere having an oxygen volume fraction of 8% is replaced with a nitrogen atmosphere.
The preparation method of the positive electrode material provided in this comparative example is different from that of example 3 only in that the nickel cobalt manganese aluminum quaternary precursor material of this comparative example is used.
Test example 1
The nickel cobalt manganese aluminum quaternary precursor materials of examples 1 to 3 and comparative examples 1 to 3 were characterized and the results are shown in table 1.
TABLE 1
Figure BDA0004240637330000171
As can be seen from Table 1, the nickel-cobalt-manganese-aluminum quaternary precursor material has the advantage of large specific surface area.
Test example 2
The electrochemical properties of the positive electrode materials of examples 1 to 3 and comparative examples 1 to 3 were measured, and the results are shown in table 2.
Positive electrode material, PVDF and acetylene black were mixed at 8:1:1 mass ratio, and pulping. Organic solvent and electrolyte LiPF 6 Additive at 0.85:0.1:0.05, wherein the organic solvent is methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate with the mass ratio of 0.5:0.3:0.2 mass ratio of the organic mixture. The negative electrode is graphite, and the diaphragm is polyethylene.
The above materials were assembled into 2032 button cells in a glove box and tested on a LAND cell test system.
TABLE 2
Figure BDA0004240637330000181
Figure BDA0004240637330000191
As can be seen from table 2, the positive electrode material of the present invention has excellent rate performance, cycle performance and safety performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. The nickel-cobalt-manganese-aluminum quaternary precursor material is characterized by sequentially comprising an inner layer, an intermediate layer and an outer layer from inside to outside;
the chemical formula of the inner layer is Ni a Co b Mn c Al 1-a-b-c (OH) 2 ，0.94≥a≥0.8，b≥c≥1-a-b-c＞0；
The chemical formula of the intermediate layer is Ni l Co m Mn n Al 1-l-m-n (OH) 2 ，0.9≥l≥0.8，n≥m＞0，1-l-m-n＞0；
The chemical formula of the outer layer is Ni w Co x Mn y Al z Nb 1-w-x-y-z (OH) 2 ，0.6≥w≥0.4，0.1＞x＞0，0.5≥y≥0.3，0.2≥z≥0.05，0.1≥1-w-x-y-z≥0.01。
2. The nickel cobalt manganese aluminum quaternary precursor material according to claim 1, wherein the thickness of the inner layer is 0.5-2 μιη, the thickness of the intermediate layer is 3-12 μιη, and the thickness of the outer layer is 1-4 μιη.
3. The nickel cobalt manganese aluminum quaternary precursor material according to claim 1, wherein the specific surface area of the nickel cobalt manganese aluminum quaternary precursor material is > 50m 2 /g。
4. A method for preparing a nickel-cobalt-manganese-aluminum quaternary precursor material according to any one of claims 1 to 3, comprising the steps of:
s1, under inert atmosphere, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into a base solution to perform a first coprecipitation reaction to obtain a reaction solution I;
s2, under the atmosphere containing oxygen, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a sodium hydroxide solution and ammonia water into the reaction solution I for a second coprecipitation reaction to obtain a reaction solution II;
and S3, under an inert atmosphere, introducing a solution containing Ni salt, co salt and Mn salt, a solution containing an Al source, a solution containing an Nb source, a sodium hydroxide solution and ammonia water into the reaction solution II to perform a third coprecipitation reaction, and aging to obtain the nickel-cobalt-manganese-aluminum quaternary precursor material.
5. The method of claim 4, wherein in step S1, the conditions of the first coprecipitation reaction are as follows: the pH value of the reaction system is 11.5-12.2, and NH in the reaction system 4 + The concentration of the catalyst is 6-8 g/L, the reaction temperature is 45-55 ℃, and the reaction time is 1-6 h.
6. The method of claim 4, wherein in step S2, the oxygen-containing atmosphere has a volume percentage of 3% -8%.
7. The method for preparing a nickel cobalt manganese aluminum quaternary precursor material according to claim 4, wherein in step S2, the conditions of the second coprecipitation reaction are: the pH value of the reaction system is 11-12.5, and NH in the reaction system 4 + The concentration of the catalyst is 5-10 g/L, the reaction temperature is 50-60 ℃, and the reaction time is 12-76 h.
8. The method for preparing a nickel cobalt manganese aluminum quaternary precursor material according to claim 4, wherein in step S3, the conditions of the third coprecipitation reaction are: the pH of the reaction system is 10.8-12, NH in the reaction system 4 + The concentration of the catalyst is 4-7 g/L, the reaction temperature is 48-58 ℃, and the reaction time is 8-24 h.
9. The method for producing a nickel cobalt manganese aluminum quaternary precursor material according to claim 4, wherein in step S1 and step S2, the sum of the metal concentration of the solution containing Ni salt, co salt and Mn salt and the metal concentration of the solution containing Al source is 1.5 to 2mol/L;
in the step S3, the sum of the metal concentration of the solution containing Ni salt, co salt and Mn salt, the metal concentration of the solution containing Al source and the metal concentration of the solution containing Nb source is 1.5-2 mol/L;
preferably, the concentration of the sodium hydroxide solution is 6-12 mol/L;
preferably, the concentration of the ammonia water is 5-10 mol/L;
preferably, the Nb source comprises Nb 2 O 5 、NbO 2 、Nb 2 O 3 And at least one of NbO.
10. A positive electrode material, characterized in that it is mainly prepared from the nickel-cobalt-manganese-aluminum quaternary precursor material according to any one of claims 1 to 3.
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CN115520904A (en) * 2022-09-26 2022-12-27 广东佳纳能源科技有限公司 Positive electrode material precursor, preparation method thereof and positive electrode material
CN116002774A (en) * 2022-12-21 2023-04-25 蜂巢能源科技(无锡)有限公司 Composite multielement precursor and preparation method and application thereof

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