CN117069160A - High-entropy layered oxide composite material for strengthening electrochemical interface stability treatment and preparation method thereof - Google Patents

High-entropy layered oxide composite material for strengthening electrochemical interface stability treatment and preparation method thereof Download PDF

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CN117069160A
CN117069160A CN202311139389.3A CN202311139389A CN117069160A CN 117069160 A CN117069160 A CN 117069160A CN 202311139389 A CN202311139389 A CN 202311139389A CN 117069160 A CN117069160 A CN 117069160A
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entropy
layered oxide
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欧星
罗洁
明磊
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Central South University
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Abstract

The invention discloses a high-entropy layered oxide composite material for strengthening electrochemical interface stability treatment and a preparation method thereof. The chemical molecular formula of the high-entropy layered oxide positive electrode material is Na x (Ni 0.2 Mn 0.7 Mg 0.1 ) 1‑2y Ti y Me y O 2 Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0.05 and less than or equal to 0.2, me is one of metal entropy doping elements Cu, zn, ca, al, fe, and C 6 H 7 BO 2 Is a surface pretreatment agent; the metal elements Ni, mn and Mg are synthesized in situ through coprecipitation, and Ti and Me are doped into the phase through a high-temperature solid phase. And fully mixing phenylboronic acid with the synthesized material, and then sintering for the second time to remove residual alkali on the surface to construct a functional organic coating. The introduction of Ti and Me activates and promotes the oxidation-reduction of anions under high pressure, and inhibits the slippage of the transition metal layer. The multi-element functional organic coating layer is uniformly constructed on the surface of the synthetic material along the crystal lattice, so that the side reaction of the electrolyte and the anode material is relieved, and the stability of an electrochemical interface is enhanced. The high-entropy layered oxide composite material has higher specific capacity, excellent cycling stability and high toughness electrochemical interface.

Description

High-entropy layered oxide composite material for strengthening electrochemical interface stability treatment and preparation method thereof
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a high-entropy layered oxide composite material and a preparation method thereof.
Background
Sodium ion battery layered oxide Na x TMO 2 The raw materials are widely available, the specific capacity is high, and the preparation method is simple and has good development prospect. But the surface residual alkali generated in the preparation process severely loses the specific capacity of the material. Na (Na) x TMO 2 The service life of the material is greatly reduced by the generation of inter-crystal cracks in the process of irreversible phase change under high pressure and charge and discharge. In order to alleviate the problem of low specific capacity caused by surface residual alkali, researchers have proposed methods such as acid washing and alcohol washing to reduce the alkalinity of the cathode material, but such methods require multiple soaking and stirring to remove the surface residual alkali and simultaneously induce metal ions to be extracted from the crystal lattice, thereby damaging the crystal structure of the cathode material.
The doping and cladding modification strategies can effectively inhibit irreversible phase change and inter-crystal cracks under high pressure, and enhance the stability of a crystal structure. But inert ions are doped into the positive electrode material to occupy oxidation-reduction sites or sodium sites, so that the diffusion rate of sodium ions is slowed down, the charge compensation of metal elements is reduced, and the specific capacity of the material is obviously reduced. Common coating modification strategies, although effective in preventing CO 2 、H 2 Further contact of O with the surface of the positive electrode material to produce Na 2 CO 3 、NaHCO 3 The alkaline substance suppresses side reactions between the interface and the electrode, but does not eliminate surface residual alkali generated during sintering.
Therefore, a technology is needed to promote the circulation stability of the material by means of the incorporation of inert ions, and at the same time, the oxidation-reduction of anions can be activated and promoted, so that the cathode material has enough energy density. The coating layer grows along the crystal lattice to remove the original surface residual alkali while preventing the generation of new alkaline substances by virtue of the coating means, so that the ion conductivity and the structural stability of the material are enhanced.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a high-entropy layered oxide composite material and a preparation method thereof.
The aim of the invention can be achieved by the following technical proposal
A high-entropy layered oxide composite material and a preparation method thereof comprise the following steps:
s1, preparing a precursor material Ni by a coprecipitation method 0.2 Mn 0.7 Mg 0.1 (OH) 2 ；
S2, fully and uniformly mixing and sintering the precursor material, the doping agent titanium source, the Me source and the sodium source to obtain the high-entropy layered oxide anode material Na x (Ni 0.2 Mn 0.7 Mg 0.1 ) 1-2y Ti y Me y O 2 Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0.05 and less than or equal to 0.2;
s3, grinding and fully mixing the positive electrode material and phenylboronic acid in a dry environment, then placing the mixture in a tube furnace filled with inert gas, sintering at low temperature, and naturally cooling the mixture to obtain the Na with multi-element functional organic coating x (Ni 0.2 Mn 0.7 Mg 0.1 ) 1-2y Ti y Me y O 2 A composite material.
Further, preferably, the metal salt of nickel, manganese and magnesium is at least one of nitrate, chloride, sulfate, acetate and oxalate.
Further, as a preferred scheme, me is one of the entropy doping elements Cu, zn, ca, al, fe.
Further, as a preferable mode, the sodium source is at least one of sodium hydroxide, anhydrous sodium carbonate, sodium bicarbonate, sodium citrate, sodium acetate, sodium oxalate, sodium oxide, sodium peroxide, and sodium superoxide.
Further, as a preferable embodiment, the content of phenylboronic acid in the layered oxide positive electrode material is 4000ppm.
Further, as a preferable scheme, the precursor material Ni 0.2 Mn 0.7 Mg 0.1 (OH) 2 The particle size is 2-8 μm.
Further, as a preferable mode, the particle size of phenylboronic acid is not more than 3. Mu.m.
Further, as a preferable mode, phenylboronic acid is mixed with the positive electrode material in an environment with humidity lower than 20%.
Further, as a preferable scheme, the sintering is two-stage sintering, firstly, the sintering is carried out at 800-1000 ℃ for 10-24 hours, and after pretreatment, the sintering is carried out at 200-400 ℃ for 1-6 hours.
Compared with the prior art, the invention has the following obvious beneficial effects:
(1) According to the precursor material, metal elements Ni, mn and Mg are synthesized in situ through coprecipitation, and Ti and Me are doped into a bulk phase through a high-temperature solid phase. The synergistic effect of Ti and metal entropy Me is utilized to activate and promote the oxidation reduction of anions under high pressure, so that the average working potential of the battery is improved. Due to the doping of Ti and entropy increasing metal Me, the disorder degree of atoms in a crystal structure is increased, and the sliding of a transition metal layer in the process of deep sodium ion intercalation is effectively inhibited, so that the irreversible phase change of the anode material is relieved.
(2) According to the preparation method, phenylboronic acid and a precursor material are uniformly mixed, and a multi-element functional organic coating layer which is uniformly coated on the surface of the precursor along crystal lattices is constructed through low-temperature solid-phase sintering. The residual alkali on the surface is effectively removed, the electrochemical interface of the anode material is reinforced, and the long-cycle performance and the multiplying power performance of the material are improved.
(3) The layered oxide anode material provided by the invention has good air stability and high safety; the process flow for preparing the precursor and the positive electrode material is simple and controllable, and the cost is low.
Drawings
Fig. 1 is an SEM image of the positive electrode material prepared in example 1.
Fig. 2 is an XRD diffractogram of the positive electrode material prepared in example 1.
Fig. 3 is a graph showing the high-voltage cycle performance of the assembled button cell of the positive electrode material prepared in example 1 and comparative examples 1 to 4.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The preparation method of the high-entropy layered oxide composite material for strengthening the electrochemical interface stability comprises the following specific steps:
in the nickel-manganese-magnesium metal salt solution, the total molar concentration of nickel ions, manganese ions and magnesium ions is 1-4mol/L; the precipitant is sodium hydroxide; the complexing agent is ammonia water; the concentration of the precipitant solution is 1-4mol/L; the concentration of the complexing agent solution is 4-8mol/L.
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 4mol/L, wherein the mol ratio of manganese to nickel to magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with the concentration of 3 mol/L; preparing 3mol/L ammonia water solution to prepare a reaction kettle bottom solution, regulating the pH value of the reaction kettle bottom solution to 10, controlling the ammonia concentration to 6g/L, and introducing nitrogen; m1 was injected into the reaction vessel at a rate of 50ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH of the reaction system is regulated to 10, the ammonia concentration is 8g/L, and the stirring speeds are 300rpm.
(2) 8g of precursor powder is taken, and anhydrous sodium carbonate powder, copper acetate powder and nano titanium dioxide powder with certain mass are weighed according to the conditions that the molar ratio of sodium to entropy metal is 0.7:0.1:0.1 and the excessive sodium is 3 percent. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; and transferring the powder to a muffle furnace for sintering for 12 hours at 900 ℃, and naturally cooling to obtain the copper-titanium double-doped anode material.
(3) Ball milling the obtained material and 4000ppm phenylboronic acid in an environment of less than 20% for 1 hour at a rotating speed of 300rpm; then sintering for 3 hours in a muffle furnace at 300 ℃ to obtain the Na with the organic coating of the multielement 0.7 (Ni 0.2 Mn 0.7 Mg 0.1 ) 0.8 Ti 0.1 Cu 0.1 O 2 A composite material.
Comparative example 1
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 4mol/L, wherein the mol ratio of manganese to nickel to magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with the concentration of 3 mol/L; preparing 3mol/L ammonia water solution to prepare a reaction kettle bottom solution, regulating the pH value of the reaction kettle bottom solution to 10, controlling the ammonia concentration to 6g/L, and introducing nitrogen; m1 was injected into the reaction vessel at a rate of 50ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH of the reaction system is regulated to 10, the ammonia concentration is 8g/L, and the stirring speeds are 300rpm.
(2) 8g of precursor powder is taken, the proportion of sodium is 0.7, and the excessive sodium is 3 percent, and anhydrous sodium carbonate powder with a certain mass is weighed. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; transferring the powder to a muffle furnace for sintering at 900 ℃ for 12 hours, naturally cooling to obtain the anode material with the molecular formula of Na 0.7 Ni 0.2 Mn 0.7 Mg 0.1 O 2 。
Comparative example 2
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 4mol/L, wherein the mol ratio of manganese to nickel to magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with the concentration of 3 mol/L; preparing 3mol/L ammonia water solution to prepare a reaction kettle bottom solution, regulating the pH value of the reaction kettle bottom solution to 10, controlling the ammonia concentration to 6g/L, and introducing nitrogen; m1 was injected into the reaction vessel at a rate of 50ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH of the reaction system is regulated to 10, the ammonia concentration is 8g/L, and the stirring speeds are 300rpm.
(2) 8g of precursor powder is taken according to the condition that the molar ratio of sodium to titanium is 0.7:0.1, and the excess sodium is 3 percent, and anhydrous sodium carbonate powder and nano titanium dioxide powder with certain mass are weighed. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; transferring the powder to a muffle furnace for sintering at 900 ℃ for 12 hours, naturally cooling to obtain the titanium-doped positive electrode material, wherein the molecular formula is Na 0.7 (Ni 0.2 Mn 0.7 Mg 0.1 ) 0.9 Ti 0.1 O 2 。
Comparative example 3
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 4mol/L, wherein the mol ratio of manganese to nickel to magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with the concentration of 3 mol/L; preparing 3mol/L ammonia water solution to prepare a reaction kettle bottom solution, regulating the pH value of the reaction kettle bottom solution to 10, controlling the ammonia concentration to 6g/L, and introducing nitrogen; m1 was injected into the reaction vessel at a rate of 50ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH of the reaction system is regulated to 10, the ammonia concentration is 8g/L, and the stirring speeds are 300rpm.
(2) 8g of precursor powder is taken, and anhydrous sodium carbonate powder, copper acetate powder and nano titanium dioxide powder with certain mass are weighed according to the condition that the molar ratio of sodium to entropy metal, titanium and copper is 0.7:0.1:0.1 and the excess sodium is 3 percent. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; transferring the powder to a muffle furnace for sintering at 900 ℃ for 12 hours, naturally cooling to obtain the copper-titanium double-doped anode material with the molecular formula of Na 0.7 (Ni 0.2 Mn 0.7 Mg 0.1 ) 0.8 Ti 0.1 Cu 0.1 O 2 。
Comparative example 4
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 4mol/L, wherein the mol ratio of manganese to nickel to magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with the concentration of 3 mol/L; preparing 3mol/L ammonia water solution to prepare a reaction kettle bottom solution, regulating the pH value of the reaction kettle bottom solution to 10, controlling the ammonia concentration to 6g/L, and introducing nitrogen; m1 was injected into the reaction vessel at a rate of 50ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH of the reaction system is regulated to 10, the ammonia concentration is 8g/L, and the stirring speeds are 300rpm.
(2) 8g of precursor powder is taken, the proportion of sodium is 0.7, and the excessive sodium is 3 percent, and anhydrous sodium carbonate powder with a certain mass is weighed. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; and transferring the powder to a muffle furnace for sintering for 12 hours at 900 ℃, and naturally cooling to obtain the anode material.
(3) Ball milling the obtained material and 4000ppm phenylboronic acid in an environment of less than 20% for 1 hour at a rotating speed of 300rpm; then placing the mixture in a muffle furnace at 300 ℃ for sintering for 3 hours. To obtain Na with boron-rich organic coating 0.7 Ni 0.2 Mn 0.7 Mg 0.1 O 2 And a positive electrode material.
Example 2
The preparation method of the high-entropy layered oxide composite material for strengthening the electrochemical interface stability comprises the following specific steps:
in the nickel-manganese-magnesium metal salt solution, the total molar concentration of nickel ions, manganese ions and magnesium ions is 1-4mol/L; the precipitant is sodium hydroxide; the complexing agent is ammonia water; the concentration of the precipitant solution is 1-4mol/L; the concentration of the complexing agent solution is 4-8mol/L.
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 3mol/L, wherein the mol ratio of manganese to nickel to magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with concentration of 2 mol/L; preparing 2mol/L ammonia water solution, preparing reaction kettle bottom solution, adjusting the pH value of the reaction kettle bottom solution to 9, and introducing nitrogen gas, wherein the ammonia concentration is 5 g/L; m1 was injected into the reaction vessel at a rate of 40ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH value of the reaction system is adjusted to 11, the ammonia concentration is 8g/L, and the stirring speeds are all 250rpm.
(2) 8g of precursor powder is taken, and anhydrous sodium carbonate powder, zinc oxide powder and nano titanium dioxide powder with a certain mass are weighed according to the condition that the molar ratio of sodium to entropy metal, zinc and titanium is 0.7:0.18:0.18 and the excess sodium is 3 percent. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; and transferring the powder to a muffle furnace for sintering for 12 hours at 900 ℃, and naturally cooling to obtain the zinc-titanium double-doped anode material.
(3) Ball milling the obtained material and 4500ppm phenylboronic acid in an environment with the concentration lower than 20% for 1 hour at the rotating speed of 400rpm; then sintering for 3 hours in a muffle furnace at 300 ℃ to obtain the Na with the organic coating of the multielement 0.7 (Ni 0.2 Mn 0.7 Mg 0.1 ) 0.64 Ti 0.18 Zn 0.18 O 2 A composite material.
Example 3
The preparation method of the high-entropy layered oxide composite material for strengthening the electrochemical interface stability comprises the following specific steps:
in the nickel-manganese-magnesium metal salt solution, the total molar concentration of nickel ions, manganese ions and magnesium ions is 1-4mol/L; the precipitant is sodium hydroxide; the complexing agent is ammonia water; the concentration of the precipitant solution is 1-4mol/L; the concentration of the complexing agent solution is 4-8mol/L.
(1) Preparing sulfate solution M1 with total ion concentration of nickel, manganese and magnesium of 3.5mol/L, wherein the molar ratio of manganese, nickel and magnesium in the sulfate solution is 7:2:1, and preparing sodium hydroxide solution with the concentration of 2.5 mol/L; preparing 2.5mol/L ammonia water solution to prepare a reaction kettle bottom solution, regulating the pH value of the reaction kettle bottom solution to 10, controlling the ammonia concentration to 5g/L, and introducing nitrogen; m1 was injected into the reaction vessel at a rate of 45ml/min, and when the particle size of the reaction slurry reached 4. Mu.m, the reaction was stopped. Filtering, washing, drying the slurry, and grinding to obtain precursor powder. In the reaction process, the pH value of the reaction system is adjusted to 11, the ammonia concentration is 8g/L, and the stirring speeds are 300rpm.
(2) 8g of precursor powder is taken, and anhydrous sodium carbonate powder, calcium oxide powder and nano titanium dioxide powder with a certain mass are weighed according to the conditions that the molar ratio of sodium to entropy metal, calcium and titanium is 0.7:0.15:0.15 and the excessive sodium is 3 percent. Mixing in a ball mill for 1 hour at a rotational speed of 300rpm; and transferring the powder to a muffle furnace for sintering for 12 hours at 900 ℃, and naturally cooling to obtain the calcium-titanium double-doped anode material.
(3) Ball milling the obtained material and 3500ppm phenylboronic acid in an environment with the concentration lower than 20% for 1 hour at the rotating speed of 400rpm; then sintering for 3 hours in a muffle furnace at 400 ℃ to obtain the Na with the organic coating of the multielement 0.7 (Ni 0.2 Mn 0.7 Mg 0.1 ) 0.7 Ti 0.15 Ca 0.15 O 2 A composite material.

Claims (7)

1. The high-entropy layered oxide composite material and the preparation method thereof are characterized by comprising the following steps:
s1, preparing a precursor material Ni by a coprecipitation method 0.2 Mn 0.7 Mg 0.1 (OH) 2 ；
S2, fully and uniformly mixing and sintering the precursor material, the doping agent titanium source, the Me source and the sodium source to obtain the high-entropy layered oxide anode material Na x (Ni 0.2 Mn 0.7 Mg 0.1 ) 1-2y Ti y Me y O 2 Wherein x is more than or equal to 0.6 and less than or equal to 1, y is more than or equal to 0.05 and less than or equal to 0.2;
s3, grinding and fully mixing the positive electrode material and phenylboronic acid in a dry environment, then placing the mixture in a tube furnace filled with inert gas, sintering at low temperature, and naturally cooling the mixture to obtain the Na with multi-element functional organic coating x (Ni 0.2 Mn 0.7 Mg 0.1 ) 1-2y Ti y Me y O 2 A composite material.
2. The high-entropy layered oxide composite material and the preparation method thereof according to claim 1, wherein in the step S2, the titanium source is an oxide or a salt containing titanium, the Me source is an oxide or a salt containing Me, and the Ti and Me are incorporated into the bulk phase through a high-temperature solid phase.
3. The high-entropy layered oxide composite material and the preparation method thereof according to claim 1, wherein Me is one of metal entropy increasing doping elements Cu, zn, ca, al, fe.
4. The high-entropy layered oxide composite material and the preparation method thereof according to claim 1, wherein in the step S2, the high-entropy layered oxide positive electrode material has a chemical formula of Na x (Ni 0.2 Mn 0.7 Mg 0.1 ) 1-2y Ti y Me y O 2 Wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0.05 and less than or equal to 0.2.
5. The high-entropy layered oxide composite material and the preparation method thereof according to claim 1, wherein in the step S3, phenylboronic acid is used as a surface pretreatment agent, and the content of phenylboronic acid in the layered oxide positive electrode material is 1000-5000ppm.
6. The high-entropy layered oxide composite and the method for preparing the same according to claim 1, wherein in step S3, phenylboronic acid and the positive electrode material are mixed in an environment with humidity lower than 20%.
7. The high-entropy layered oxide composite and the method for preparing the same according to claim 1, wherein in step S3, the sintering is two-stage sintering, wherein the sintering is performed at 800-1000 ℃ for 10-24 hours, and the sintering is performed at 200-400 ℃ for 1-6 hours after the pretreatment.
CN202311139389.3A 2023-09-06 2023-09-06 High-entropy layered oxide composite material for strengthening electrochemical interface stability treatment and preparation method thereof Pending CN117069160A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117293302A (en) * 2023-11-24 2023-12-26 山东海化集团有限公司 Composite positive electrode material of sodium ion battery and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117293302A (en) * 2023-11-24 2023-12-26 山东海化集团有限公司 Composite positive electrode material of sodium ion battery and preparation method thereof
CN117293302B (en) * 2023-11-24 2024-06-07 山东海化集团有限公司 Composite positive electrode material of sodium ion battery and preparation method thereof

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