CN115020694A - Anion-cation co-modified tunnel oxide material and preparation method and application thereof - Google Patents

Anion-cation co-modified tunnel oxide material and preparation method and application thereof Download PDF

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CN115020694A
CN115020694A CN202210579568.8A CN202210579568A CN115020694A CN 115020694 A CN115020694 A CN 115020694A CN 202210579568 A CN202210579568 A CN 202210579568A CN 115020694 A CN115020694 A CN 115020694A
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sodium
cation
anion
tunnel oxide
oxide material
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龚华旭
王庆渊
陈永珍
程思源
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Jiangsu University of Technology
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Abstract

The invention discloses a cation and anion co-modified tunnel type oxide material and a preparation method and application thereof; the chemical formula of the cation and anion co-modified tunnel oxide material is represented as Na 0.44 Mn 1‑x A x O 2‑y B y . Preparation: (1) according to Na 0.44 Mn 1‑x A x O 2‑y B y According to the stoichiometric ratio of each element in the material, a sodium source, a manganese source, an A source, a B source and a solvent are mixed and stirred uniformly to form mixed slurry; (2) adjusting the mixed slurry to acidity, and ball-milling to obtain a precursor materialFeeding; (3) and (3) drying the precursor material in vacuum, grinding, calcining and cooling to obtain the cation and anion co-modified tunnel oxide material. The application comprises the following steps: the material is used as a positive electrode material of a sodium ion battery to assemble the sodium ion battery. The prepared material is used as the anode material of the sodium ion battery to assemble the sodium ion battery, so that the problems of large capacity attenuation, insufficient initial capacity and the like in the circulating process can be solved, and the assembled sodium ion battery has high specific capacity and excellent circulating stability.

Description

Anion-cation co-modified tunnel oxide material and preparation method and application thereof
Technical Field
The invention relates to the technical field of material preparation, in particular to a cation and anion co-modified tunnel type oxide material and a preparation method and application thereof.
Background
Due to the fact that the resource reserves of China are gradually exhausted due to the large use and consumption of traditional fossil energy, a series of environmental problems caused in the combustion process of fossil fuels are difficult to solve, and the appearance of renewable clean energy is considered as an important basis for sustainable development of human beings. In addition, in recent years, with the requirements of energy conservation and emission reduction, carbon neutralization and carbon peak-reaching, which are provided by the nation, a power grid scale Energy Storage System (ESS) of new energy is developed vigorously. In addition, in order to release the dependence of future transportation systems on traditional energy sources such as fossil fuels, batteries with high energy and high power density are urgently needed to be designed for Electric Vehicles (EVs). Therefore, researchers have focused on designing clean energy storage devices, including batteries, fuel cells, and supercapacitors. Among the various available energy storage technologies, batteries have been widely used and concerned with the advantages of providing stored chemical energy and providing it in the form of electrical energy, high conversion efficiency, no gas emission, etc.
In recent years, lithium ion batteries have been widely used in portable electronic devices such as mobile phones and computers due to their advantages of high energy density and long cycle life, and are gradually used in electric vehicles and some energy storage power stations, which greatly increases the demand for lithium resources. However, lithium is limited in the reserve of resources and is unevenly distributed, and therefore, it is widely used in industrial applications and expensive when used as a battery material. Sodium and lithium are in the I main group, the electrochemical properties are similar, sodium resources in the earth crust are rich, the price is low, and the earth crust is nontoxic, besides, the half potential of the sodium-ion battery is about 0.3V higher than that of the lithium-ion battery, which shows that the sodium-ion battery can utilize electrolyte solvent and electrolyte salt with lower decomposition potential, and the sodium-ion battery has relatively stable electrochemical performance and is safer to use, so the sodium-ion battery can be used for replacing the lithium-ion battery to meet the requirements of large-scale and sustainable development.
The positive electrode material is one of the important components of the sodium ion battery and mainly comprises metal oxides, polyanion compounds, Prussian blue and the like, wherein the related research of the metal oxides is derived from the research of manganese oxides with various structures, such as layered NaMnO 2 、Na 0.67 MnO 2 And Na of tunnel structure 0.44 MnO 2 And the like. The biggest problem in most manganese oxide application processes is that the great capacity attenuation exists in the circulation process, and the main reason of the problem is the dissolution of manganese; (2) the Jahn-Teller effect. Therefore, the research on a suitable manganese oxide modification method applied to the sodium ion battery has urgent significance.
Disclosure of Invention
The invention aims to provide an anion-cation co-modified tunnel oxide material (Na) with excellent performance, low cost and simple preparation process 0.44 Mn 1-x A x O 2-y B y ) And a preparation method and application thereof.
The invention is realized by the following technical scheme:
the cation and anion co-modified tunnel oxide material is characterized in that the chemical formula of the cation and anion co-modified tunnel oxide material is represented as Na 0.44 Mn 1-x A x O 2-y B y (ii) a In the formula: a is selected from any one of Zn, Y, Zr, Mg, Ti, Cu, Ni, Co and Fe; b is selected from any one of Br, Cl, I and F; x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.05.
Specifically, the prepared cation and anion co-modified tunnel oxide material (Na) is adopted in the invention 0.44 Mn 1-x A x O 2- y B y ) The sodium-ion battery assembled by using the positive electrode material as the sodium-ion battery can be used for improving the problems of large capacity attenuation, insufficient initial capacity and the like in the circulation process, and the assembled sodium-ion battery has the advantages ofHigher specific capacity and excellent cycling stability.
A preparation method of a cation and anion co-modified tunnel oxide material is characterized by comprising the following steps:
(1) according to Na 0.44 Mn 1-x A x O 2-y B y The stoichiometric ratio of each element in the material is that the sodium source, the manganese source, the A source, the B source and the solvent are mixed and stirred evenly to form mixed slurry;
(2) adjusting the mixed slurry to be acidic, and then carrying out ball milling to obtain a precursor material;
(3) vacuum drying the precursor material, grinding, calcining and cooling to obtain the anion and cation co-modified tunnel oxide material (Na) 0.44 Mn 1-x A x O 2-y B y )。
Further, a preparation method of the anion-cation co-modified tunnel oxide material comprises the following steps: the sodium source in the step (1) is selected from any one of sodium nitrate, sodium acetate, sodium hydroxide and sodium carbonate; the manganese source is selected from one or more of manganese acetate tetrahydrate, manganese sulfate, manganese carbonate, manganese nitrate and manganese sesquioxide.
Further, a preparation method of the anion-cation co-modified tunnel oxide material comprises the following steps: the source A in the step (1) is any one selected from titanium dioxide, tetrabutyl titanate, copper chloride, copper nitrate, copper sulfate, copper oxide, cobalt acetate, cobalt nitrate, cobaltosic oxide, cobalt chloride, cobalt sulfate, zinc nitrate, zinc sulfate, zinc acetate, zinc chloride, basic zinc carbonate, zinc oxide, magnesium chloride, magnesium acetate, magnesium nitrate, magnesium carbonate, zirconium chloride, zirconium nitrate, zirconium acetate, zirconium sulfate, ferric oxide, ferric chloride, ferric nitrate and yttrium oxide; the source B is selected from any one of sodium bromide, sodium fluoride, sodium chloride and sodium iodide; the solvent is selected from one or more of acetone, ethanol, ethylene glycol, isopropanol and N, N-dimethylformamide.
Further, a preparation method of the anion-cation co-modified tunnel oxide material comprises the following steps: and (2) adjusting the pH value of the mixed slurry to 4-6, and then putting the mixed slurry into a planetary ball mill for ball milling to obtain a precursor material.
Further, a preparation method of the anion-cation co-modified tunnel oxide material comprises the following steps: the ball material ratio is (10-50): 1, the ball milling speed is 300-.
Further, a preparation method of the anion-cation co-modified tunnel oxide material comprises the following steps: and (3) drying the precursor material in vacuum, fully grinding the precursor material by using an agate mortar, then putting the ground precursor material into a muffle furnace to heat and calcine the ground precursor material, and cooling the calcined precursor material to room temperature to obtain the anion-cation co-modified tunnel oxide material Na 0.44 Mn 1-x A x O 2-y B y (ii) a Wherein: the temperature of vacuum drying is 60-90 ℃, and the drying time is 8-12 hours; the grinding time is 10-30 minutes; the heating rate is 2-5 ℃/min, the temperature is increased to 750 ℃ and 950 ℃, and the heat preservation and calcination are carried out for 9-15 hours after the temperature is increased.
The preparation method of the cation and anion co-modified tunnel oxide material is based on a high-temperature solid-phase sintering method, and co-doping is carried out on cation transition metal elements such as zinc, yttrium, zirconium and magnesium and anion halogen elements such as bromine, chlorine and fluorine. The cation replaces partial manganese position to stabilize the material structure and inhibit the polarization of the electrode, thereby reducing the dissolution of manganese and the generation of Jahn-Teller effect and further improving the cycle stability and rate capability of the tunnel structure oxide. The doping of anions can enlarge the lattice parameter of the material, effectively increase the initial capacity, inhibit the capacity attenuation, improve the conductivity of the material and improve the intercalation and deintercalation rate of sodium ions.
The application of the cation and anion co-modified tunnel oxide material is characterized in that the cation and anion co-modified tunnel oxide material or the cation and anion co-modified tunnel oxide material prepared by the preparation method is used as a positive electrode material of a sodium ion battery and is used for assembling the sodium ion battery.
The sodium ion battery assembled by the invention has higher specific capacity, excellent cycling stability and rate capability, and provides reference for the commercial application of the sodium ion battery in the future.
The invention has the beneficial effects that:
(1) anion-cation co-modified tunnel oxide material (Na) prepared by using method of the invention 0.44 Mn 1-x A x O 2-y B y ) The material has the advantages of low cost, simple preparation process, stable existence in air, stable performance in the charge and discharge process and the like.
(2) According to the invention, cations such as titanium, zinc, zirconium, cobalt, nickel and the like are doped in the material, so that the structural stability of the material is improved, and the polarization of an electrode is inhibited, thereby reducing the dissolution of manganese and the generation of Jahn-Teller effect, improving the cycle performance of the battery and reducing the irreversible capacity loss in the cycle process, so that the assembled sodium-ion battery has good cycle performance and rate capability, and the capacity retention rate is high.
(3) According to the invention, the material is doped with anions such as bromine, chlorine, fluorine, iodine and the like, and a small amount of the anions is doped, so that the initial capacity of the material can be effectively improved, the cycle performance of the material is greatly facilitated, the material can be better crystallized, the material is more stable, and the conductivity of the anode material and the intercalation and deintercalation of sodium ions are improved. The anion and cation co-doping can play a complementary role, and provides great help for the future development of the sodium ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows Na obtained in example 1 of the present invention 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 XRD pattern of the material;
FIG. 2 shows Na obtained in example 1 of the present invention 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 SEM images of the material;
FIG. 3 is an impedance plot of a sodium ion battery assembled according to example 1 of the present invention and comparative example 1;
fig. 4 is a graph of rate performance of the sodium ion battery assembled in application example 4 of the present invention at 0.2C, 0.4C, 0.6C, 0.8C, 1C, and finally returning to 0.2C;
fig. 5 is a graph comparing the cycle performance at a current density of 0.1C for sodium ion batteries assembled according to application example 1 and comparative example 2 of the present invention;
fig. 6 is a graph comparing the cycle performance at a current density of 0.5C for sodium ion batteries assembled according to application example 1 and comparative example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An anion-cation co-modified tunnel oxide material with a chemical formula of Na 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 ；
The cation and anion co-modified tunnel oxide material (Na) 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 ) The preparation method comprises the following steps:
(1) according to Na 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 According to the stoichiometric ratio of each element in the material, 0.4g of sodium hydroxide (sodium source), 2.4818g of manganese carbonate (manganese source), 0.0928g of zinc oxide (A source) and 0.1403g of sodium bromide (B source) are weighed by an analytical balance and placed in a beaker, and then 10mL of acetone is added and stirred uniformly to obtain mixed slurry;
(2) adjusting the mixed slurry to an acidic pH value of 6 by using 1mol/L hydrochloric acid solution, then pouring the slurry into a planetary ball mill, and controlling the ball-to-material ratio to be 20: 1, ball-milling for 12 hours on a planetary ball mill at the rotating speed of 500rpm to obtain a precursor material;
(3) putting the obtained precursor material into a vacuum drying oven, drying for 12 hours at 80 ℃, fully grinding the vacuum-dried material for 30 minutes by using an agate mortar, putting the material into a muffle furnace, calcining for 12 hours at 850 ℃ under the air atmosphere (the heating rate is 5 ℃/min), and cooling to room temperature after calcining is finished to obtain Na 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 A material.
For Na obtained in example 1 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 XRD testing and SEM testing are carried out on the material, the obtained XRD testing pattern is shown in figure 1, and the obtained SEM testing is shown in figure 2; it can be seen from FIG. 1 that the material prepared in example 1 of the present invention has a peak pattern in accordance with that of the standard card; as can be seen from FIG. 2, Na was produced 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 The material is a three-dimensional tunnel rod-shaped structure, the particle size of the material is 0.5-1 μm in width, 3-7 μm in length and 0.1-0.3 μm in thickness, and the distribution is uniform.
Example 2
An anion-cation co-modified tunnel oxide material with a chemical formula of Na 0.44 Mn 0.98 Y 0.02 O 1.98 Cl 0.02 ；
The cation and anion co-modified tunnel oxide material (Na) 0.44 Mn 0.98 Y 0.02 O 1.98 Cl 0.02 ) The preparation method comprises the following steps:
(1) according to Na 0.44 Mn 0.98 Y 0.02 O 1.98 Cl 0.02 According to the stoichiometric ratio of each element in the material, 1.0599g of sodium carbonate, 5.4606g of manganese acetate tetrahydrate, 0.1027g of yttrium oxide and 0.0531g of sodium chloride are weighed by an analytical balance and placed in a beaker, and then 10mL of isopropanol is added and stirred uniformly to obtain mixed slurry;
(2) adjusting the mixed slurry to an acidic pH value of 5.5 by using 1mol/L hydrochloric acid solution, then pouring the slurry into a ball milling tank, and controlling the ball-to-material ratio to be 15: 1, ball-milling for 10 hours on a planetary ball mill at the rotating speed of 400rpm to obtain a precursor material;
(3) drying the obtained precursor material in a vacuum drying oven at 70 ℃ for 9 hours, fully grinding the vacuum-dried material by using an agate mortar for 20 minutes, putting the material into a muffle furnace, calcining the material at the high temperature of 800 ℃ for 9 hours in the air atmosphere (the heating rate is 3 ℃/min), and cooling the calcined material to room temperature to obtain Na 0.44 Mn 0.98 Y 0.02 O 1.98 Cl 0.02 A material.
Example 3
An anion-cation co-modified tunnel oxide material with a chemical formula of Na 0.44 Mn 0.99 Zr 0.01 O 1.99 I 0.01 ；
The cation and anion co-modified tunnel oxide material (Na) 0.44 Mn 0.99 Zr 0.01 O 1.99 I 0.01 ) The preparation method comprises the following steps:
(1) according to Na 0.44 Mn 0.99 Zr 0.01 O 1.99 I 0.01 According to the stoichiometric ratio of each element in the material, 0.8401g of sodium bicarbonate, 3.5525g of manganese oxide, 0.028g of zirconium dioxide and 0.0681g of sodium iodide are weighed by an analytical balance and put into a beaker, and then 10mL of ethylene glycol is added and stirred uniformly to obtain mixed slurry;
(2) the mixture slurry was adjusted to acidic pH 5 with 1mol/L HCl solution, and then the slurry was poured into a ball mill pot with a ball-to-feed ratio of 10: 1, ball-milling for 8 hours on a planetary ball mill at the rotating speed of 300rpm to obtain a precursor material;
(3) drying the obtained precursor material in a vacuum drying oven at 60 ℃ for 12 hours, fully grinding the vacuum-dried material by using an agate mortar for 15 minutes, putting the material into a muffle furnace, calcining the material at 900 ℃ for 10 hours under the air atmosphere (the heating rate is 4 ℃/min), and cooling the calcined material to room temperature to obtain Na 0.44 Mn 0.99 Zr 0.01 O 1.99 I 0.01 A material.
Example 4
An anion-cation co-modified tunnel oxide material with a chemical formula of Na 0.44 Mn 0.9 Ti 0.1 O 1.95 F 0.05 ；
The cation and anion co-modified tunnel oxide material (Na) 0.44 Mn 0.9 Ti 0.1 O 1.95 F 0.05 ) The preparation method comprises the following steps:
(1) according to Na 0.44 Mn 0.9 Ti 0.1 O 1.95 F 0.05 According to the stoichiometric ratio of each element in the material, 0.8203g of sodium acetate, 1.7785g of manganese dioxide, 0.1815g of titanium dioxide and 0.0954g of sodium fluoride are weighed by an analytical balance and put into a beaker, then 10mL of N, N-dimethylformamide is added and stirred uniformly to obtain mixed slurry;
(2) adjusting the mixed slurry to acidic pH value of 4.5 by using 1mol/L HCl solution, then pouring the slurry into a ball milling tank, and controlling the ball-to-material ratio to be 25: 1, ball-milling for 6 hours on a planetary ball mill at the rotating speed of 350rpm to obtain a precursor material;
(3) drying the obtained precursor material in a vacuum drying oven at 90 ℃ for 12 hours, fully grinding the vacuum-dried material with an agate mortar for 25 minutes, putting the material into a muffle furnace, calcining the material at 900 ℃ for 15 hours in an air atmosphere (the heating rate is 2 ℃/min), and cooling the calcined material to room temperature to obtain Na 0.44 Mn 0.9 Ti 0.1 O 1.95 F 0.05 A material.
Application example 1
Na prepared in example 1 above 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 The material is used as a positive electrode material of a sodium ion battery to assemble the sodium ion battery, and the method comprises the following specific steps:
(1) preparing a positive pole piece: 80mg of Na 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 Adding the material, 10mg of conductive carbon black and 10mg of polyvinylidene fluoride into 1.5ml of N-methyl pyrrolidone, uniformly stirring to form a dispersion liquid, then completely coating the dispersion liquid on an aluminum foil,coating with a 100-micron draw mill, and then vacuum drying at 80 ℃ for 6 hours to obtain a positive pole piece;
(2) assembling the sodium-ion battery: assembling the prepared positive pole piece and a sodium sheet formed by punching a sodium block into a sodium ion battery, taking a metal sodium sheet as a counter electrode, and manufacturing a 2016 type button battery in a glove box filled with argon, wherein the diaphragm adopts a GF/D glass fiber diaphragm, and the electrolyte adopts 1.0M NaClO 4 in EC:PC＝1:1Vol％with 5.0％FEC。
Application example 2
Na obtained in example 2 above 0.44 Mn 0.98 Y 0.02 O 1.98 Cl 0.02 The material is used as a positive electrode material of a sodium ion battery to assemble the sodium ion battery, and the method comprises the following specific steps:
(1) preparing a positive pole piece: 70mg of Na 0.44 Mn 0.98 Y 0.02 O 1.98 Cl 0.02 Adding the material, 20mg of Ketjen black and 10mg of sodium alginate into 1ml of N-methylpyrrolidone, uniformly stirring to form a dispersion solution, then completely coating the dispersion solution on an aluminum foil, coating by using a 100-micrometer draw mill, and then carrying out vacuum drying for 5 hours at 90 ℃ to obtain a positive pole piece;
(2) assembling the sodium-ion battery: assembling the prepared positive pole piece and a sodium sheet formed by punching a sodium block into a sodium ion battery, taking a metal sodium sheet as a counter electrode, and manufacturing a 2016 type button battery in a glove box filled with argon, wherein the diaphragm adopts a GF/D glass fiber diaphragm, and the electrolyte adopts 1.0M NaClO 4 in EC:PC＝1:1Vol％with 5.0％FEC。
Example 3
Na obtained in example 3 above 0.44 Mn 0.99 Zr 0.01 O 1.99 I 0.01 The material is used as a positive electrode material of a sodium ion battery to assemble the sodium ion battery, and the method comprises the following specific steps:
(1) preparing a positive pole piece: 70mg of Na 0.44 Mn 0.99 Zr 0.01 O 1.99 I 0.01 The material, 20mg of acetylene black and 10mg of sodium carboxymethylcellulose were added to 1ml of N-methylpyrrolidone and stirred well to form a dispersionCoating the dispersion liquid on an aluminum foil, coating by using a 100-micron draw mill, and then drying in vacuum at 70 ℃ for 4 hours to obtain a positive pole piece;
(2) assembling the sodium-ion battery: assembling the prepared positive pole piece and a sodium sheet formed by punching a sodium block into a sodium ion battery, taking a metal sodium sheet as a counter electrode, and manufacturing a 2016 type button battery in a glove box filled with argon, wherein the diaphragm adopts a GF/D glass fiber diaphragm, and the electrolyte adopts 1.0M NaClO 4 in EC:PC＝1:1Vol％with 5.0％FEC。
Application example 4
Na obtained in example 4 above 0.44 Mn 0.9 Ti 0.1 O 1.95 F 0.05 The material is used as a positive electrode material of a sodium ion battery to assemble the sodium ion battery, and the method comprises the following specific steps:
(1) preparing a positive pole piece: 80mg of Na 0.44 Mn 0.9 Ti 0.1 O 1.95 F 0.05 Adding the material, 10mg of conductive carbon black and 10mg of cyclodextrin into 1.5mL of N-methyl pyrrolidone, uniformly stirring to form a dispersion liquid, then completely coating the dispersion liquid on an aluminum foil, coating by using a 100-micrometer draw mill, and then drying in vacuum at 60 ℃ for 8 hours to obtain a positive pole piece;
(2) assembling the sodium-ion battery: assembling the prepared positive pole piece and a sodium sheet formed by punching a sodium block into a sodium ion battery, taking a metal sodium sheet as a counter electrode, and manufacturing a 2016 type button battery in a glove box filled with argon, wherein the diaphragm adopts a GF/D glass fiber diaphragm, and the electrolyte adopts 1.0M NaClO 4 in EC:PC＝1:1Vol％with 5.0％FEC。
Comparative example 1
Comparative example 1 is prepared in the same manner as in example 1 except that in comparative example 1, the transition metal cation (zinc ion) and the halogen anion (bromide ion) are not doped and modified, and the other conditions are the same; comparative example 1 the material prepared was Na 0.44 MnO 2 。
Comparative example 2
Comparative example 2 the same preparation method as in example 1 was conducted except that comparative example 2 was doped onlyTransition metal cation zinc ion, undoped halide anion bromide; comparative example 2 the material prepared was Na 0.44 Mn 0.95 Zn 0.05 O 2 . The material of comparative example 2 was assembled into a sodium ion battery under the conditions of application example 1.
Comparative example 3
Comparative example 3 is prepared in the same manner as in example 1 except that comparative example 3 is doped with only halide anion bromide ion and is not doped with transition metal cation zinc ion; comparative example 3 the material prepared was Na 0.44 MnO 1.97 Br 0.03 . The material of comparative example 3 was assembled into a sodium ion battery under the conditions of application example 1.
And (3) testing:
(1) FIG. 3 is an impedance diagram of a sodium ion battery assembled by using the products of example 1 and comparative example 1 as electrode materials, and it can be seen from FIG. 3 that Na prepared in example 1 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 Na prepared by using material as electrode material and assembling sodium-ion battery with impedance ratio compared with that of Na prepared by using comparative example 1 0.44 MnO 2 The material impedance is small; this illustrates the Na produced in example 1 of the invention 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 The material has higher conductivity, and can improve the transmission efficiency between the electrode and the electrolyte.
(2) The 2016 type button cell assembled in the application example 4 is placed in a blue test system, the cell performance is tested, the result is shown in fig. 4, the multiplying power performance is under the current density of 0.2C, 0.4C, 0.6C, 0.8C, 1C and 0.2C, one program is circulated, 10 circles of 0.2C circulation, 10 circles of 0.4C circulation, 10 circles of 0.6C circulation, 10 circles of 0.8C circulation, 10 circles of 1C circulation and finally 10 circles of 0.2C circulation are returned; the sodium ion battery assembled in the application example 4 can respectively maintain the specific discharge capacities of 91mAh/g, 85mAh/g, 83mAh/g, 79mAh/g, 76mAh/g and 89mAh/g, and the battery capacity is slightly reduced after multiple cycles, which shows that the assembled battery has good cycle performance and rate capability. It can be seen from fig. 4 that the charge and discharge specific capacity curves are almost overlapped and kept consistent.
(3) Example 1 and comparative aboveThe 2016 type button cell assembled in example 2 was placed in a blue test system and the cell performance was tested, and the results are shown in fig. 5, which was charged and discharged at a current density of 0.1C, and doped with Na of zinc oxide and sodium bromide 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 The specific discharge capacity of the material (the material of the embodiment 1) in the first circle is about 112mAh/g, the specific discharge capacity of about 100mAh/g is kept after 100 circles of circulation, the capacity retention rate is calculated to be about 90%, and only Na doped with zinc oxide and not doped with sodium bromide is used 0.44 Mn 0.95 Zn 0.05 O 2 The specific discharge capacity of the first circle of the material (the material of the comparative example 2) is about 108mAh/g, the specific discharge capacity of about 61mAh/g is kept after 100 circles of circulation, the capacity retention rate is calculated to be about 56%, and the coulomb efficiency of the assembled sodium-ion battery is close to 100% as can be seen from fig. 5. It can be seen from fig. 5 that the charge and discharge curves of the materials obtained in comparative example 2 and example 1 almost overlap.
(4) The 2016 type button cell prepared in example 1 and comparative example 3 was placed in a blue test system to test the cell performance, and the results are shown in FIG. 6, wherein the cell was charged and discharged at a current density of 0.5C, and the cell was doped with Na containing zinc oxide and sodium bromide 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 The specific discharge capacity of the material at the first circle is about 105mAh/g, the specific discharge capacity of the material still remains about 94mAh/g after 200 cycles, the capacity retention rate is calculated to be about 89%, and only Na which is doped with sodium bromide and not doped with zinc oxide is used 0.44 MnO 1.97 Br 0.03 The specific discharge capacity of the first circle of the material is about 102mAh/g, the specific discharge capacity of about 74mAh/g is kept after 200 circles of circulation, the capacity retention rate is calculated to be about 73%, and the coulomb efficiency of the assembled sodium-ion battery is close to 100% as can be seen from fig. 6. It can be seen from fig. 6 that the charge and discharge curves of the materials obtained in comparative example 3 and example 1 almost overlap.
Specific surface area tests and conductivity tests were performed on the products obtained in examples 1 to 4 and comparative examples 1 to 3, and the specific test results are shown in table 1 below.
Table 1 shows the performance parameters of the products obtained in examples 1 to 4 and comparative examples 1 to 3
Figure BDA0003661819610000141
Figure BDA0003661819610000151
As can be seen from Table 1, the product of comparative example 1 was lower in conductivity than the product of example 1 compared to the product of comparative example 1, which was not doped with elemental zinc and elemental bromine, as compared to example 1, and it can be seen that the incorporation of zinc oxide and sodium bromide was for Na 0.44 MnO 2 The specific surface area, the conductivity and the electrochemical performance of the material are improved, so that the material has a beneficial effect. Compared with example 1, comparative example 2 is only doped with zinc element and is not doped with bromine element, and the data in the table shows that the conductivity of the material prepared in comparative example 2 is lower, and the charge and discharge cycle stability of the battery is influenced. Compared with the embodiment 1, the comparative example 3 is only doped with bromine and is not doped with zinc, and the specific surface area of the material prepared by the comparative example 3 is smaller, the microstructure is irregular, and the electrochemical performance of the battery is influenced.
Product Na prepared by the process of the invention 0.44 Mn 0.95 Zn 0.05 O 1.97 Br 0.03 As a sodium ion battery anode material, the material structure stability is improved and the polarization of an electrode is inhibited through a co-doping technology of a transition metal element and a halogen element in a certain proportion, so that the dissolution of manganese and the generation of Jahn-Teller effect are reduced, the lattice parameter of the material is increased, the initial capacity is effectively increased, the capacity attenuation is inhibited, the conductivity of the material is improved, the sodium ion embedding and releasing rate is improved, the synthesized material has the advantages of regular appearance, large specific surface area, good conductivity and the like, and the cycle stability and the multiplying power performance of the tunnel structure oxide are further improved. The cost is greatly reduced by applying the material to the positive electrode material of the sodium-ion battery, and the application of the material to industrialization is facilitated.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.

Claims (8)

1. The cation and anion co-modified tunnel oxide material is characterized in that the chemical formula of the cation and anion co-modified tunnel oxide material is Na 0.44 Mn 1-x A x O 2-y B y (ii) a In the formula: a is selected from any one of Zn, Y, Zr, Mg, Ti, Cu, Ni, Co and Fe; b is selected from any one of Br, Cl, I and F; x is more than or equal to 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.05.
2. The method for preparing the anion-cation co-modified tunnel oxide material according to claim 1, wherein the method comprises the following steps:
(1) according to Na 0.44 Mn 1-x A x O 2-y B y According to the stoichiometric ratio of each element in the material, a sodium source, a manganese source, an A source, a B source and a solvent are mixed and stirred uniformly to form mixed slurry;
(2) adjusting the mixed slurry to be acidic, and then carrying out ball milling to obtain a precursor material;
(3) and (3) drying the precursor material in vacuum, grinding, calcining and cooling to obtain the cation and anion co-modified tunnel oxide material.
3. The method for preparing the anion-cation co-modified tunnel oxide material according to claim 2, wherein the sodium source in the step (1) is selected from any one of sodium nitrate, sodium acetate, sodium hydroxide and sodium carbonate;
the manganese source is selected from one or more of manganese acetate tetrahydrate, manganese sulfate, manganese carbonate, manganese nitrate and manganese sesquioxide.
4. The method according to claim 2, wherein the source A in step (1) is selected from any one of titanium dioxide, tetrabutyl titanate, copper chloride, copper nitrate, copper sulfate, copper oxide, cobalt acetate, cobalt nitrate, cobaltosic oxide, cobalt chloride, cobalt sulfate, zinc nitrate, zinc sulfate, zinc acetate, zinc chloride, zinc hydroxycarbonate, zinc oxide, magnesium chloride, magnesium acetate, magnesium nitrate, magnesium carbonate, zirconium chloride, zirconium nitrate, zirconium acetate, zirconium sulfate, ferric oxide, ferric chloride, ferric nitrate, and yttrium oxide;
the source B is selected from any one of sodium bromide, sodium fluoride, sodium chloride and sodium iodide;
the solvent is selected from one or more of acetone, ethanol, ethylene glycol, isopropanol and N, N-dimethylformamide.
5. The method for preparing an anion-cation co-modified tunnel oxide material according to claim 2, wherein in the step (2), the pH of the mixed slurry is adjusted to 4-6, and then the mixed slurry is put into a planetary ball mill for ball milling to obtain a precursor material.
6. The method for preparing the anion-cation co-modified tunnel oxide material according to claim 5, wherein the ball-to-feed ratio is (10-50): 1, the ball milling speed is 300-.
7. The method for preparing the anion and cation co-modified tunnel oxide material according to claim 2, wherein the precursor material is dried in vacuum in the step (3), then fully ground by an agate mortar, then placed in a muffle furnace for heating and calcining, and cooled to room temperature to obtain the anion and cation co-modified tunnel oxide material Na 0.44 Mn 1-x A x O 2-y B y (ii) a Wherein: the temperature of vacuum drying is 60-90 ℃, and the drying time is 8-12 hours; the grinding time is 10-30 minutes; the heating rate is 2-5 ℃/min, the temperature is increased to 750 ℃ and 950 ℃, and the heat preservation and calcination are carried out for 9-15 hours after the temperature is increased.
8. The application of the anion and cation co-modified tunnel oxide material is characterized in that the anion and cation co-modified tunnel oxide material in claim 1 or the anion and cation co-modified tunnel oxide material prepared by the preparation method in any one of claims 2 to 7 is used as a positive electrode material of a sodium ion battery and is used for assembling the sodium ion battery.
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