CN111924899B - Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application - Google Patents

Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application Download PDF

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CN111924899B
CN111924899B CN202010800396.3A CN202010800396A CN111924899B CN 111924899 B CN111924899 B CN 111924899B CN 202010800396 A CN202010800396 A CN 202010800396A CN 111924899 B CN111924899 B CN 111924899B
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aluminum
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CN111924899A (en
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李晓祥
裴晓东
骆艳华
鲍维东
刘晨
钱有军
张倩倩
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Sinosteel Nanjing New Material Research Institute Co Ltd
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    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • HELECTRICITY
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a method for preparing a nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, a product and application, wherein the method comprises the following steps: (1) Sequentially adding soluble nickel salt, soluble cobalt salt and soluble magnesium salt into a container a, and adding water to dissolve the soluble nickel salt, the soluble cobalt salt and the soluble magnesium salt into a transparent solution; (2) Sequentially adding soluble aluminum salt and soluble ferric salt into the container b, adding water to dissolve the soluble aluminum salt and the soluble ferric salt into a transparent solution, adding a certain amount of composite complexing agent, fully stirring, and standing; (3) Adding four materials of the container a, the container b, ammonia water and alkali liquor into a reaction container in a parallel flow manner, stirring, controlling the reaction pH, generating slurry at a certain reaction temperature, filtering, washing, drying and crushing to obtain powder C; (4) And (3) obtaining the high-entropy material from the powder C at a certain roasting temperature. After the high-entropy material is added with lithium, the battery has good cycling stability, greatly improved safety and higher discharge capacity.

Description

Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application
Technical Field
The invention belongs to the field of high-entropy battery materials, and particularly relates to a method for preparing a nickel-cobalt-iron-aluminum-magnesium quinary high-entropy material, a product and application.
Background
The high-entropy material is a novel multi-principal-element material consisting of multiple elements in an equimolar ratio or a nearly equimolar ratio, and breaks through the traditional material design concept. High entropy materials exhibit many structural and performance characteristics that are different from conventional materials due to their unique crystal structure characteristics.
In 2019, the nanometer technical expert, the Host-Hahn (Horst Hahn) team of Karl Schluur technical institute (KIT), germany, found that: high Entropy Oxide (HEO) materials can significantly improve the storage capacity and cycling stability of batteries. The material has high stability due to the disordered distribution of atoms. The special property of HEO is a result of entropy stabilization, which is a composite oxide containing 5 or more different metal ions in different amounts and having a single-phase crystal structure. Although the typical crystal structures of these elements vary widely, they form a united lattice and there is no apparent ordering of the sites in the crystal. This disorder, also called high entropy, is probably because it hinders the migration of defects in the crystal lattice and therefore enables a high stability of the material to be maintained.
The existing method for preparing the high-entropy oxide is generally a solid-phase sintering method, the application of a chemical precipitation method is few, and the high-entropy powder prepared by the chemical precipitation method is fine in particle size, uniform in particle size distribution, good in activity and uniform in distribution of elements compared with a solid-phase method.
The current chemical precipitation method for preparing high entropy oxides has some drawbacks. For example, application publication No. CN110845237A La (NO) 3 ) 3 、Co(NO 3 ) 2 、Cr(NO 3 ) 3 、Fe(NO 3 ) 3 、Mn(NO 3 ) 2 And Ni (NO) 3 ) 2 The mixed solution is mixed with ammonia water for coprecipitation reaction, high-entropy ceramic precursor powder is obtained after solid-liquid separation, the pH value of the coprecipitation reaction is 9-10, and obviously the pH value of iron ion precipitation is much different from that of other cation precipitation, so that the coprecipitation effect is difficult to achieve; niSO for application publication No. CN111302781A 4 ·6H 2 O,CoSO 4 ·7H 2 O,TiOSO 4 Solution, mnSO 4 ·H 2 O,FeSO 4 Using citric acid or oxalic acid as a complexing agent as a raw material to prepare the high-entropy oxide, but adding the five salt solutions together (adding an alkaline solution, the complexing agent and a Fe-Ti-Ni-Co-Mn transparent solution into a reactor to carry out stirring mixing reaction, controlling the pH value of the solution to generate a five-membered coprecipitate),citric acid or oxalic acid has no selectivity to the complexation of nickel, cobalt, titanium, manganese and iron elements, so that the iron and titanium precipitation speed is high, and the coprecipitation effect is difficult to achieve. The document "Nanocrystalline multicomponent elementary transfer metal oxides" is to continuously add ammonia water dropwise to a mixed nitrate solution to maintain the solution pH at about 10, to cause the solution to precipitate, then to dry at 120 ℃ for 4 hours, and to calcine at 1000 ℃ for 1 hour to obtain a high-entropy oxide (Co) 0.2 Cu 0.2 Mg 0.2 Ni 0.2 Zn 0.2 ) O ceramic powder. The pH value of the precipitation reaction in the elements of the high-entropy oxide is relatively close, but the precipitation reaction is not suitable for the coprecipitation containing Fe element.
In addition, the high-entropy oxide can be obtained in a gel manner. For example, CN110600703A uses equimolar amount of metal nitrate, then glycine, ethylene diamine tetraacetic acid, hexamethylene tetramine, hexamethylene diisocyanate, citric acid or oxalic acid are added, and the temperature is kept at high temperature to obtain the pentabasic spinel type oxide high-entropy material with the chemical formula of (Cr) 0.2 Fe 0.2 Mn 0.2 Zn 0.2 M 0.2 ) 3 O 4 Wherein M is a divalent metal cation Co 2+ Or Ni 2+ . The publication No. CN110818430A is a uniform high-entropy oxide ceramic nano-powder and a preparation method thereof, and CoCl with equal molar ratio is added 2 、CuCl 2 、MgCl 2 、NiCl 2 And ZnCl 2 Blending in absolute ethyl alcohol until the mixture is completely dissolved to obtain a mixed solution, adding urea into the mixed solution, fully mixing to enable the metal chloride and the urea to generate a crosslinking reaction to form gel, and performing high-temperature pyrolysis treatment on the dried gel to obtain uniform high-entropy oxide (Co, cu, mg, ni, zn) O ceramic submicron spherical powder. It can be easily found that the performance of the high-entropy oxides disclosed in these patents is still to be improved when applied to lithium ion batteries.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems, the invention provides a method for preparing a nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, which improves Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 The performance of the O high-entropy material meets the use requirement.
The invention also provides Ni obtained by the method 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 And O is a high-entropy material.
The invention also provides an application of the high-entropy material in a lithium ion battery.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the method for preparing the nickel-cobalt-iron-aluminum-magnesium quinary high-entropy material comprises the following steps of:
(1) Sequentially adding a battery-grade soluble nickel salt, a soluble cobalt salt and a soluble magnesium salt into a container a, and adding water to dissolve the materials into a transparent solution;
(2) Sequentially adding a battery-grade soluble aluminum salt and a battery-grade soluble iron salt into the container b, adding water to dissolve the aluminum salt and the soluble iron salt into a transparent solution, adding a certain amount of composite complexing agent, fully stirring, and standing;
(3) Adding four materials of the container a, the container b, ammonia water and alkali liquor into the reaction container in a parallel flow manner, stirring to control the reaction pH, generating slurry at a certain reaction temperature, filtering, washing, drying and crushing to obtain powder C;
(4) The powder C is roasted at a certain temperature to obtain Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material.
In one possible embodiment of the present invention, the soluble nickel salt in step (1) is nickel sulfate or nickel nitrate, the soluble cobalt salt is cobalt sulfate or cobalt nitrate, and the soluble magnesium salt is magnesium sulfate or magnesium nitrate; the concentration of the soluble nickel salt, the soluble cobalt salt and the soluble magnesium salt is 0.4-6 mol/L, preferably 2-4 mol/L.
In one possible embodiment of the present invention, the molar ratio of the soluble nickel salt, the soluble cobalt salt, the soluble magnesium salt, the soluble aluminum salt and the soluble iron salt in step (1) and step (2) is 1:1:1:1:1.
in one possible embodiment of the present invention, the concentration of the aluminum salt and the iron salt in step (2) is 0.4 to 6mol/L, preferably 2 to 4mol/L; the soluble aluminum salt and the soluble ferric salt are sodium metaaluminate, aluminum sulfate and ferric sulfate or aluminum nitrate and ferric nitrate;
the composite complexing agent is obtained by dissolving citric acid, ethylene diamine tetraacetic acid and glycol with pure water, wherein the molar ratio of the citric acid to the ethylene diamine tetraacetic acid to the glycol is 0.75-0.85: 0.1 to 0.2: 0.02-0.08;
the concentration of citric acid in the composite complexing agent is 0.3-5 mol/L, preferably 0.5-2 mol/L;
the molar weight of the complex complexing agent is 0.5 to 1.5 times, preferably 0.5 to 1 time of the total molar weight of the soluble aluminum salt and the soluble ferric salt.
In one possible embodiment of the invention, the adding amount of the ammonia water in the step (3) is 3-10 times of the molar amount of the composite complexing agent, and the concentration is 1.0-10.0 mol/L;
the adding speed of the ammonia water is that the amount of the added ammonia water in unit time is 1 to 5 times, preferably 2 to 3 times of the molar weight of the composite complexing agent;
the molar concentrations of the soluble nickel salt, the soluble cobalt salt, the soluble magnesium salt, the soluble aluminum salt and the soluble iron salt which are added into the reactor in unit time are the same when the container a and the container b are added into the reactor;
the alkali liquor is at least one of liquid alkali, sodium carbonate and sodium bicarbonate, and the molar concentration is 1.5-10.0 mol/L, preferably 4-8 mol/L; the rate of addition of the lye is determined by the pH of the system.
The pH is 10.0 to 11.5, preferably 10.5 to 11.0; the reaction temperature is 40 to 95 ℃, preferably 50 to 75 ℃.
In one possible embodiment of the invention, the roasting temperature in the step (4) is 600-1200 ℃, preferably 700-1000 ℃;
in one possible embodiment of the present invention, the Ni in the step (4) 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 Ni in O: co: fe: al: mg molar ratio of 1 +/-0.1: 1 ± 0.1:1 ± 0.1:1 ± 0.1:1 + -0.1.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts a chemical precipitation method and a composite complexing agent to prepare a high-entropy oxide battery material, and dissolves nickel salt, cobalt salt and magnesium salt which have high and similar precipitation pH values together, and dissolves ferric salt and aluminum salt which have low precipitation pH values together and adds the composite complexing agent for complexing first, the invention can realize quinary coprecipitation of the nickel salt, the cobalt salt, the magnesium salt, the ferric salt and the aluminum salt by controlling the proportion of citric acid, ethylene diamine tetraacetic acid and ethylene glycol in the composite complexing agent and the adding speed of ammonia water, and the obtained high-entropy material has small granularity, high activity and uniform granularity distribution, as can be seen in figures 1 to 3, the high-entropy oxide battery material prepared by reaction examples 1 to 3 has small granularity and uniform size;
(2) The high-entropy oxide battery material Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 After the O lithium is added, the battery has good cycling stability, greatly improved safety and higher discharge gram capacity; the technical scheme uses most metal elements with low price, and is convenient for industrial production.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an SEM image of a quinary high-entropy oxide cell material in example 1 of the present invention;
FIG. 2 is an SEM image of a quinary high-entropy oxide cell material in example 2 of the invention;
FIG. 3 is an SEM image of a quinary high-entropy oxide cell material in example 3 of the invention.
Detailed Description
Exemplary embodiments of the present invention are described in detail below. Although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it should be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the present invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
The experimental procedures used in the following examples are conventional unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The method for preparing the nickel-cobalt-iron-aluminum-magnesium quinary high-entropy material comprises the following steps of:
(1) Sequentially adding a battery-grade soluble nickel salt, a soluble cobalt salt and a soluble magnesium salt into a container a, wherein the container a can be selected from test equipment such as a beaker, and adding water to dissolve the materials into a transparent solution;
the soluble nickel salt is nickel sulfate or nickel nitrate, the soluble cobalt salt is cobalt sulfate or cobalt nitrate, and the soluble magnesium salt is magnesium sulfate or magnesium nitrate; the concentration of the soluble nickel salt, the soluble cobalt salt and the soluble magnesium salt is 0.4-6 mol/L, preferably 2-4 mol/L.
(2) Sequentially adding battery-grade soluble aluminum salt and soluble ferric salt into a container b, wherein the container b can be selected from test equipment such as a beaker and the like, adding water to dissolve the materials into a transparent solution, adding a certain amount of composite complexing agent, fully stirring and standing;
the concentrations of the aluminum salt and the ferric salt are 0.4-6 mol/L, preferably 2-4 mol/L; the soluble aluminum salt and the soluble ferric salt are sodium metaaluminate, aluminum sulfate and ferric sulfate or aluminum nitrate and ferric nitrate; the composite complexing agent is obtained by dissolving citric acid, ethylene diamine tetraacetic acid and glycol with pure water, wherein the molar ratio of the citric acid to the ethylene diamine tetraacetic acid to the glycol is 0.75-0.85: 0.1 to 0.2: 0.02-0.08; the concentration of citric acid in the composite complexing agent is 0.3-5 mol/L, preferably 0.5-2 mol/L; the molar weight of the composite complexing agent is 0.5 to 1.5 times, preferably 0.5 to 1 time of the total molar weight of the soluble aluminum salt and the soluble iron salt.
The mol ratio of the soluble nickel salt to the soluble cobalt salt to the soluble magnesium salt to the soluble aluminum salt to the soluble iron salt is 1:1:1:1:1.
(3) Adding four materials of the container a, the container b, ammonia water and alkali liquor into a reaction container in a parallel flow manner, wherein the reaction container can select sample equipment such as a reaction kettle and the like, stirring to control the reaction pH, generating slurry at a certain reaction temperature, filtering, washing, drying and crushing to obtain powder C;
the adding amount of the ammonia water is 3-10 times of the molar amount of the composite complexing agent, and the concentration is 1.0-10.0 mol/L; the adding speed of the ammonia water is that the amount of the added ammonia water in unit time is 1 to 5 times, preferably 2 to 3 times of the molar weight of the composite complexing agent; the molar concentrations of the soluble nickel salt, the soluble cobalt salt, the soluble magnesium salt, the soluble aluminum salt and the soluble iron salt which are added into the reactor in unit time are the same when the container a and the container b are added into the reactor; the alkali liquor is at least one of liquid alkali, sodium carbonate and sodium bicarbonate, and the molar concentration is 1.5-10.0 mol/L, preferably 4-8 mol/L; the rate of addition of the lye is determined by the pH of the system. The pH is 10.0 to 11.5, preferably 10.5 to 11.0; the reaction temperature is 40 to 95 ℃, preferably 50 to 75 ℃.
(4) The powder C is roasted at a certain temperature to obtain Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material. The roasting temperature is 600-1200 ℃, preferably 700-1000 ℃; the Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 Ni in O: co: fe: al: mg molar ratio of 1 +/-0.1: 1 ± 0.1:1 ± 0.1:1 ± 0.1:1 + -0.1.
Example 1
(1) Weighing a certain amount of battery-grade nickel sulfate, cobalt sulfate and magnesium sulfate, adding into a beaker a, and dissolving in pure water, wherein the molar concentrations of nickel, cobalt and magnesium are all 6mol/L, and the total volume is 500mL;
(2) Weighing a certain amount of battery-grade aluminum sulfate and ferric sulfate, adding the battery-grade aluminum sulfate and ferric sulfate into a beaker b, dissolving the beaker b in pure water, adding 4.8mol of citric acid, 0.9mol of ethylene diamine tetraacetic acid and 0.3mol of ethylene glycol, stirring and dissolving, wherein the molar concentrations of aluminum and iron are both 3mol/L, and the total volume is 1000mL;
(3) Adding a beaker a, a beaker b and 9mol/L ammonia water 2L,8mol/L sodium hydroxide solution into a reaction kettle (with heating and stirring) in a concurrent flow manner, wherein the adding speeds of the beaker a, the beaker b and the ammonia water are respectively 5ml/min, 10ml/min and 20ml/min; the reaction temperature is 40 ℃, the reaction pH is controlled at 10, and after the reaction is finished, the powder C is obtained by filtering, washing, drying and crushing at 100 ℃;
(4) The powder C is roasted at 1200 ℃ in a rotary kiln to obtain Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material.
The high-entropy material has small particle size and uniform particle size distribution (as shown in figure 1).
Example 2
(1) Weighing a certain amount of battery-grade nickel nitrate, cobalt nitrate and magnesium nitrate, adding the nickel nitrate, the cobalt nitrate and the magnesium nitrate into a beaker a, dissolving the mixture in pure water, wherein the molar concentrations of the nickel, the cobalt and the magnesium are all 3mol/L, and the total volume is 1000mL;
(2) Weighing a certain amount of battery-grade aluminum nitrate and ferric nitrate, adding the battery-grade aluminum nitrate and ferric nitrate into a beaker b, dissolving the beaker b in pure water, adding 2.25mol of citric acid, 0.6mol of ethylene diamine tetraacetic acid and 0.15mol of ethylene glycol, stirring and dissolving, wherein the molar concentrations of aluminum and iron are both 3mol/L, and the total volume is 1000mL;
(3) Adding a beaker a, a beaker b and 6mol/L ammonia water 2L,6mol/L sodium hydroxide solution into a reaction kettle in parallel, wherein the adding speeds of the beaker a, the beaker b and the ammonia water are respectively 10ml/min, 10ml/min and 20ml/min; the reaction temperature is 60 ℃, the reaction pH is controlled at 10.8, and after the reaction is finished, the powder C is obtained by filtering, washing, drying and crushing at 100 ℃;
(4) The powder C is roasted in a rotary kiln at the temperature of 900 ℃ to obtain Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material.
The high-entropy material has small particle size and uniform particle size distribution (as shown in figure 2).
Example 3
(1) Weighing a certain amount of battery-grade nickel sulfate, cobalt sulfate and magnesium sulfate, adding into a beaker a, and dissolving in pure water, wherein the molar concentrations of nickel, cobalt and magnesium are all 1mol/L, and the total volume is 3L;
(2) Weighing a certain amount of battery-grade aluminum sulfate and ferric sulfate, adding the battery-grade aluminum sulfate and ferric sulfate into a beaker b, dissolving the beaker b in pure water, adding 7.65mol of citric acid, 0.9mol of ethylene diamine tetraacetic acid and 0.45mol of ethylene glycol, stirring and dissolving, wherein the molar concentrations of aluminum and iron are both 1mol/L, and the total volume is 3L;
(3) Adding a beaker a, a beaker b, 9mol/L ammonia water 3L and 2mol/L sodium hydroxide solution into a reaction kettle in a concurrent flow manner, wherein the adding speeds of the beaker a, the beaker b and the ammonia water are respectively 30ml/min, 30ml/min and 30ml/min; the reaction temperature is 90 ℃, the reaction pH is controlled to be 11.2, and after the reaction is finished, the powder C is obtained by filtering, washing, drying and crushing at 100 ℃;
(4) The powder C is roasted at 600 ℃ in a rotary kiln to obtain Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material.
The high-entropy material has small particle size and uniform particle size distribution (as shown in figure 3).
Comparative example 1
The step (2) of the embodiment 1 is changed into the step of weighing a certain amount of battery-grade aluminum sulfate and ferric sulfate, adding the battery-grade aluminum sulfate and ferric sulfate into a beaker b, dissolving the beaker b in pure water, adding 4.8mol of citric acid and 0.3mol of ethylene glycol, stirring and dissolving, wherein the molar concentrations of aluminum and iron are both 3mol/L, and the total volume is 1000mL; others remain unchanged.
Comparative example 2
The step (2) of the embodiment 2 is changed into the step of weighing a certain amount of battery-grade aluminum nitrate and ferric nitrate, adding the battery-grade aluminum nitrate and ferric nitrate into a beaker b, dissolving the beaker b in pure water, adding 0.6mol of ethylene diamine tetraacetic acid and 0.15mol of ethylene glycol, stirring and dissolving, wherein the molar concentrations of aluminum and iron are both 3mol/L, and the total volume is 1000mL; others remain unchanged.
Comparative example 3
Changing the step (3) of the example 2 into a beaker a, a beaker b and 6mol/L sodium hydroxide solution, and adding the mixture into the reactor in a parallel flow manner, wherein the adding speeds of the beaker a and the beaker b are respectively 10ml/min and 10ml/min; the reaction temperature is 60 ℃, the reaction pH is controlled at 10.8, and after the reaction is finished, the powder C is obtained by filtering, washing, drying and crushing at 100 ℃.
Comparative example 4
The citric acid, the ethylene diamine tetraacetic acid and the ethylene glycol in the step (2) of the example 2 are not added, and other conditions are not changed.
The gram discharge capacity after addition of lithium carbonate for the examples and comparative examples is shown in Table 1 below.
TABLE 1 gram Capacity after lithium carbonate discharge
Figure BDA0002627169410000061
Figure BDA0002627169410000071
As can be seen from the data in Table 1, ni prepared using the complex complexing agent 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 The electrical property of the O high-entropy quinary battery material added with lithium is obviously higher.
It should be noted that: ni of the invention 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 The preparation method of the O high-entropy material comprises the steps of mixing soluble nickel salt, soluble cobalt salt and soluble magnesium salt into a transparent solution, forming a complex by soluble aluminum salt and soluble ferric salt, and then mixing the transparent solution with the complex, ammonia water and alkali liquor, wherein citric acid in a complex complexing agent can complex iron and aluminum, ethylenediaminetetraacetic acid can chelate iron and aluminum, both of which have a complexing effect, but the complexing ability of the ethylenediaminetetraacetic acid is stronger, and the decomplexing speed can be better controlled by the combination of the two so as to prevent the iron and the aluminum from being precipitated too fast; the ethylene glycol reacts with citric acid and ethylene diamine tetraacetic acid to generate corresponding ester, so that the ability of the composite complexing agent for complexing iron and aluminum is reduced, the corresponding ester is hydrolyzed when the ethylene glycol is added into a reactor for reaction, the complexing ability of the composite complexing agent can be improved, the precipitation speed is convenient to control, and the ethylene glycol has the effect of refining grains. The invention can realize the coprecipitation of five metal ions by controlling the proportion of citric acid, ethylene diamine tetraacetic acid and glycol and the dropping rate of ammonia water. In addition, the purpose of adding ammonia water is to generate ammonium citrate and ethylenediamine tetraacetic acid diamine with citric acid and ethylenediamine tetraacetic acid diamine in reaction, so that the decomplexing rate of aluminum and iron can be adjusted, and the metal elements can be completely and easily precipitated; the alkali liquor mainly adjusts the pH value of the system.
Under the combined action of the factors, the Ni prepared by the invention 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material, battery after adding lithiumThe high-entropy material has good cycling stability, greatly improved safety, higher discharge capacity and larger progress compared with the high-entropy material in the prior art.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and it should be noted that, for those skilled in the art, several modifications or equivalent substitutions can be made without departing from the principle of the present invention, and the spirit and scope of the technical solutions should be covered by the claims of the present invention.

Claims (9)

1. A method for preparing a nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material is characterized by comprising the following steps of:
(1) Sequentially adding soluble nickel salt, soluble cobalt salt and soluble magnesium salt into a container a, and adding water to dissolve the soluble nickel salt, the soluble cobalt salt and the soluble magnesium salt into a transparent solution;
(2) Sequentially adding soluble aluminum salt and soluble ferric salt into the container b, adding water to dissolve the soluble aluminum salt and the soluble ferric salt into a transparent solution, adding a certain amount of composite complexing agent, fully stirring, and standing;
(3) Adding four materials of the container a, the container b, ammonia water and alkali liquor into a reaction container in a parallel flow manner, stirring to control the reaction pH, generating slurry at a certain reaction temperature, filtering, washing, drying and crushing to obtain powder C;
(4) The powder C is roasted at a certain temperature to obtain Ni 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 O high entropy material;
the composite complexing agent is obtained by dissolving citric acid, ethylene diamine tetraacetic acid and glycol with pure water, wherein the molar ratio of the citric acid to the ethylene diamine tetraacetic acid to the glycol is 0.75-0.85: 0.1 to 0.2: 0.02-0.08; the concentration of citric acid in the composite complexing agent is 0.3-5 mol/L;
adding ammonia water in an amount which is 3 times of the molar weight of the composite complexing agent and is 1.0-10.0 mol/L;
the adding speed of the ammonia water is 3 times of the molar weight of the composite complexing agent added in unit time;
the molar concentrations of the soluble nickel salt, the soluble cobalt salt, the soluble magnesium salt, the soluble aluminum salt and the soluble iron salt which are added into the reactor in unit time are the same when the container a and the container b are added into the reactor;
the molar weight of the composite complexing agent is 0.5-1.5 times of the sum of the molar weights of the soluble aluminum salt and the soluble ferric salt;
the pH value is 10.0-11.5.
2. The method for preparing the five-element high-entropy material of nickel, cobalt, iron, aluminum and magnesium, according to claim 1, wherein the soluble nickel salt in the step (1) is nickel sulfate or nickel nitrate, the soluble cobalt salt is cobalt sulfate or cobalt nitrate, and the soluble magnesium salt is magnesium sulfate or magnesium nitrate; the concentration of the soluble nickel salt, the soluble cobalt salt and the soluble magnesium salt is 0.4-6 mol/L.
3. The method for preparing the five-element high-entropy material of nickel-cobalt-iron-aluminum-magnesium as claimed in claim 1, wherein the soluble aluminum salt in the step (2) is sodium metaaluminate, aluminum sulfate or aluminum nitrate, and the soluble iron salt is ferric sulfate or ferric nitrate; the concentration of the soluble aluminum salt and the soluble iron salt is 0.4-6 mol/L.
4. The method for preparing the five-element high-entropy material of nickel, cobalt, iron, aluminum and magnesium as claimed in claim 1, wherein the concentration of citric acid in the composite complexing agent is 0.5-2 mol/L.
5. The method for preparing the five-element high-entropy material of nickel, cobalt, iron, aluminum and magnesium as claimed in claim 1, wherein the adding speed of the ammonia water in the step (3) is 2-3 times of the molar quantity of the composite complexing agent added in unit time.
6. The method for preparing the quinary high-entropy material of nickel, cobalt, iron, aluminum and magnesium according to claim 1, wherein the alkali liquor is at least one of liquid alkali, sodium carbonate and sodium bicarbonate, and the molar concentration is 1.5-10.0 mol/L; the reaction temperature is 40-95 ℃.
7. The method for preparing the nickel-cobalt-iron-aluminum-magnesium quinary high-entropy material as claimed in claim 1, wherein the roasting temperature in the step (4) is 600-1200 ℃.
8. A product obtained by the method for preparing a nickel-cobalt-iron-aluminum-magnesium pentabasic high-entropy material according to any one of claims 1 to 7.
9. The Ni of claim 8 0.2 Co 0.2 Fe 0.2 Al 0.2 Mg 0.2 The application of the O high-entropy material in the lithium ion battery.
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