CN109524649B - Sodium-ion battery positive electrode material with coating structure and preparation method and application thereof - Google Patents
Sodium-ion battery positive electrode material with coating structure and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a sodium ion battery anode material with a coating structure and a preparation method and application thereof, wherein the method comprises the following steps: selecting/preparing a coating solution; the coating liquid comprises a coating precursor formed by metal salt and/or hydrate thereof; putting the anode material to be coated into a coating furnace, heating to 200-1000 ℃, carrying the coating liquid into the coating furnace by utilizing compressed air or nitrogen or argon, and uniformly coating the surface of the anode material with the oxide formed by the thermal decomposition of the coating precursor; and taking out the prepared cathode material with the oxide coating layer to obtain the cathode material of the sodium-ion battery with the coating structure.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a sodium ion battery anode material with a coating structure and a preparation method and application thereof.
Background
Energy is the basis of social development, secondary batteries play an important role in the development of human society, and lithium ion batteries are widely applied due to high energy density and high power density. Today, the large-scale application of lithium ion batteries reveals the problem of shortage of lithium resources and common transition metal resources thereof. Lithium resources belong to scarce resources, are distributed unevenly around the world, and are strategic resources like petroleum. Based on the characteristics of abundant sodium resources, consistent working principle and processing technology with the lithium ion battery and the like, the sodium ion battery is considered as beneficial supplement of the future lithium ion battery.
In recent years, sodium ion batteries have been studied more and more sufficiently, and they have also entered the initial stage of industrialization. The most approved anode materials are layered materials because of their high gram-capacity, high energy density and simple processing. However, the layered structure material has the defect of unstable circulation, so researchers have achieved certain results by improving the circulation performance of the layered structure material through a coating method.
The interface between the coated positive electrode material and the electrolyte is improved, and the structure is stabilized, so that the cycle performance can be improved. The existing material coating methods basically comprise a solid phase method and a liquid phase method. The solid phase method has the problem of uneven coating and is difficult to realize comprehensive coating; the liquid phase method causes waste liquid problem, and the material cost is increased by the difficulty of the drying process, so the coating method needs to be improved.
Disclosure of Invention
The invention provides a sodium ion battery anode material with a coating structure and a preparation method and application thereof. After coating, the interface of the anode material is optimized, and the cycling stability of the sodium-ion battery is improved.
In a first aspect, an embodiment of the present invention provides a method for preparing a positive electrode material of a sodium ion battery with a coating structure, including:
selecting/preparing a coating solution; the coating liquid comprises a coating precursor formed by metal salt and/or hydrate thereof;
putting the anode material to be coated into a coating furnace, heating to 200-1000 ℃, carrying the coating liquid into the coating furnace by utilizing compressed air or nitrogen or argon, and uniformly coating the surface of the anode material with the oxide formed by the thermal decomposition of the coating precursor;
and taking out the prepared cathode material with the oxide coating layer to obtain the cathode material of the sodium-ion battery with the coating structure.
Preferably, the coating furnace is a rotary atmosphere furnace.
Preferably, the positive electrode material to be coated is NaxM1aM2bO2；
Wherein, x is more than 0.6 and less than or equal to 1, a is more than 0, b is more than or equal to 0, a + b is 1, and the material is kept electrically neutral; m1 is a metal element, including one or more of Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn and Sn; m2 is nonmetal element, including one or more of B, F, Si.
Preferably, the preparing of the coating solution specifically comprises: dissolving a precursor solid raw material in a corresponding solvent to form the coating liquid;
wherein the solvent comprises: one or more of water, ethanol, N-methyl pyrrolidone and acetone.
Preferably, the selected coating solution specifically comprises: and taking the liquid coating precursor as the coating liquid.
Preferably, the step of taking out the prepared cathode material with the oxide coating layer to obtain the cathode material of the sodium-ion battery with the coating structure comprises the following steps:
and taking out the prepared cathode material with the oxide coating layer, and screening for removing iron to obtain the cathode material of the sodium-ion battery with the coating structure.
Preferably, the metal salt and/or hydrate thereof specifically includes:
nitrate of Al, Mg, Ti, Zn, Zr, Nb or La and one or more of hydrate, sulfate, hydrate and organic salt thereof.
In a second aspect, an embodiment of the present invention provides a positive electrode material of a sodium-ion battery, which is prepared by the preparation method in the first aspect, and the positive electrode material of the sodium-ion battery includes: a positive electrode material core with a layered structure and a coating layer;
the anode material with the layered structureThe nucleus is NaxM1aM2bO2，0.6<x≤1，a>0, b is more than or equal to 0, a + b is 1, and the material is kept electrically neutral; m1 is a metal element, including one or more of Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn and Sn; m2 is a nonmetal element, including one or more of B, F, Si;
the coating layer is an oxide shell of Al, Mg, Ti, Zn, Zr, Nb or La coated outside the core of the anode material with the laminated structure;
wherein, in the sodium ion battery anode material, the mass percentage of the coating layer is 0.05-20%.
In a third aspect, embodiments of the present invention provide a sodium-ion secondary battery, including the positive electrode material of the sodium-ion battery of the second aspect.
In a fourth aspect, embodiments of the present invention provide a use of the sodium ion secondary battery of the third aspect, where the secondary battery is used in electric tools, electric vehicles, and energy storage devices of solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power sources, or communication base stations.
According to the preparation method of the sodium-ion battery anode material with the coating structure, the anode material is coated by using a vapor deposition method, so that the coating process is simpler, the coating effect is better and more uniform, and the preparation method is more suitable for industrial production. After coating, the interface of the anode material is optimized, and the cycling stability of the sodium-ion battery is improved. The sodium ion battery made of the anode material by the method can be used for power supplies of electric tools and electric automobiles, and can also be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power supplies or communication base stations.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a schematic view of a preparation method of the coating structure cathode material in example 1;
FIG. 2 is a flow chart of a method for preparing the positive electrode material with the coating structure in example 1;
FIG. 3 is an SEM topography for raw material 1 of example 2;
FIG. 4 is an SEM topography of the cladding material 1 of example 2;
FIG. 5 is a charge-discharge cycle chart of raw material 1 in example 2;
FIG. 6 is a charge-discharge cycle chart of the clad material 1 in example 2;
FIG. 7 is an SEM topography for raw material 2 in example 3;
FIG. 8 is an SEM topography of the cladding material 2 of example 3;
FIG. 9 is a charge-discharge cycle chart of raw material 2 in example 3;
FIG. 10 is a charge-discharge cycle chart of the clad material 2 in example 3;
FIG. 11 is an SEM topography for raw material 3 in example 4;
FIG. 12 is an SEM topography of the cladding material 3 of example 4;
FIG. 13 is a charge-discharge cycle chart of raw material 3 in example 4;
fig. 14 is a charge-discharge cycle chart of the coating material 3 in example 4.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
The embodiment 1 of the invention provides a sodium ion battery anode material, which comprises: a positive electrode material core with a layered structure and a coating layer;
the core of the anode material with a layered structure is NaxM1aM2bO2，0.6<x≤1，a>0, b is more than or equal to 0, a + b is 1, and the material is kept electrically neutral; m1 is a metal element, including one or more of Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn and Sn; m2 is a nonmetal element, including one or more of B, F, Si;
the coating layer is an oxide shell of Al, Mg, Ti, Zn, Zr, Nb or La coated outside the core of the anode material with the laminated structure;
wherein, in the positive electrode material of the sodium-ion battery, the mass percentage of the coating layer is 0.05-20%.
The material can be prepared by the following method shown in figure 1, wherein gas is introduced into the coating liquid, and the coating liquid is carried into an atmosphere furnace, so that the coating precursor is heated and decomposed to coat the anode material. The specific preparation method can be shown as a flow chart shown in fig. 2, and specifically comprises the following steps:
specifically, the coating liquid comprises a coating precursor consisting of metal salt and/or hydrate thereof, wherein the metal salt and/or hydrate thereof is preferably one or more of nitrate, hydrate, sulfate and hydrate of nitrate, sulfate and organic salt of Al, Mg, Ti, Zn, Zr, Nb or La;
in this step, the liquid coating precursor may be directly used as the coating solution, or the precursor solid raw material may be dissolved in a corresponding solvent to form the coating solution. The solvent may include: one or more of water, ethanol, N-methyl pyrrolidone and acetone, preferably water.
specifically, the positive electrode material to be coated is NaxM1aM2bO2(ii) a Wherein, 0.6<x≤1，a>0, b is more than or equal to 0, a + b is 1, and the material is kept electrically neutral; m1 is a metal element, including one or more of Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn and Sn; m2 is nonmetal element, including one or more of B, F, Si.
The coating furnace preferably adopts an atmosphere furnace with a rotating function, namely a rotating atmosphere furnace.
And step 130, taking out the prepared cathode material with the oxide coating layer to obtain the cathode material of the sodium-ion battery with the coating structure.
Preferably, after the anode material coated with the oxide layer is taken out, screening is carried out to remove iron, so as to further improve the product quality.
The preparation method of the sodium-ion battery anode material with the coating structure coats the anode material by using a vapor deposition method. The coating method combines the traditional vapor deposition method, and achieves the effect of uniform coating on the surface of the material. Through simple thermal decomposition, an oxide coating is formed on the surface of the material, the coating amount is simple and controllable, the coating is uniform, and the method is very suitable for industrial production.
After coating, the interface of the anode material is optimized, and the cycling stability of the sodium-ion battery is improved. The sodium ion battery made of the anode material by the method can be used for power supplies of electric tools and electric automobiles, and can also be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power supplies or communication base stations.
The preparation process, material characteristics, properties and the like of the doped coated sodium-ion battery positive electrode material of the invention are described in detail by using some specific examples.
Example 2
Firstly, selecting Na as a positive electrode material0.9Cu0.22Fe0.30Mn0.48O2The particle size D50, designated as raw material 1, was 10 μm. The coating liquid consists of aluminum nitrate and water, the concentration of the coating liquid is 50g of aluminum nitrate per 100g of water, the gas is selected to be compressed air, and the furnace is selected to be a rotary furnace.
Then, 100kg of the positive electrode material was weighed and placed in a rotary furnace, and the rotary furnace was turned on to increase the contact area. And opening the furnace to raise the temperature, so that the temperature in the furnace reaches 700 ℃. Compressed air is opened, the compressed air carries the coating liquid into the furnace body, and the coating liquid is contacted with the material and is decomposed into Al at high temperature2O3And the coating is uniformly coated on the surface of the material. The 700 ℃ heat preservation time is set to 8 hours, and the ventilation is stopped after the time. Opening the cooling system, rapidly cooling the furnace body, and taking out to obtain Al2O3Coated Na0.9Cu0.22Fe0.30Mn0.48O2And is denoted as cladding material 1.
The scanning electron microscope test was performed on the raw material 1 and the clad material 1, and the results are shown in fig. 3 and 4. It can be seen that the surface of the raw material 1 is smooth and a uniform coating layer appears on the surface of the coating material 1, which coats the material throughout.
The raw material 1 and the coating material 1 prepared in the above way are respectively used as active substances of positive electrode materials of sodium-ion batteries and are used for preparing the sodium-ion batteries. The method comprises the following specific steps: mixing the prepared positive electrode material active substance of the sodium-ion battery with conductive carbon black and a binder polyvinylidene fluoride (PVDF) according to the weight ratio of 7: 2: 1, adding a proper amount of N-methyl pyrrolidone (NMP) solution, grinding in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying, and cutting into a circular pole piece with the diameter of 12 mm. The round pole piece is dried for 12 hours at 120 ℃ under the vacuum condition and then transferred to a glove box for later use. The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with metallic sodium as the counter electrode, glass fiber as the separator, and 1mol/L NaPF6The solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1: 1) is used as electrolyte to assemble the CR2032 button cell. The charge and discharge test was performed at a current density of 0.5C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.5V and the charge cutoff voltage was 4.05V.
The 0.5C cycle diagrams for the raw material 1 and the clad material 1 are shown in fig. 5 and 6, and comparing the cycle performance of the two materials, it can be seen that: the capacity retention ratio after 100-week cycle of raw material 1 was 91.6%, while Al2O3The capacity retention rate of the coated coating material 1 after 100 weeks is 97.2%, which is obviously improved. From the cycle results, it is clear that the coating effect of this example is good.
Example 3
Firstly, selecting Na as a positive electrode material1.0Ni0.22Cu0.11Fe0.33Mn0.33O2And is denoted as raw material 2, and has a particle size D50 of 10 μm. The coating liquid is tetrabutyl titanate, the gas is nitrogen, and the furnace is a rotary furnace.
Then, 100kg of the positive electrode material was weighed and placed in a rotary furnaceThe opening rotation increases its contact area. And opening the furnace to raise the temperature, so that the temperature in the furnace reaches 900 ℃. Opening compressed air to carry the coating liquid into the furnace body, and decomposing the coating liquid into TiO at high temperature2And the coating is uniformly coated on the surface of the material. The 900 ℃ heat preservation time is set to 4 hours, and the ventilation is stopped after the time. Opening a cooling system, rapidly cooling the furnace body, and taking out to obtain TiO2Coated Na1.0Ni0.22Cu0.11Fe0.33Mn0.33O2And is denoted as cladding material 2.
The scanning electron microscope test was performed on the raw material 2 and the clad material 2, and the results are shown in fig. 7 and 8. It can be seen that the surface of the coating material 2 also has a uniform coating.
The raw material 2 and the coating material 2 prepared in the above way are respectively used as active substances of the positive electrode material of the sodium-ion battery and are used for preparing the sodium-ion battery. Assembled into a CR2032 button cell, and a constant current charge-discharge mode is used for carrying out charge-discharge test at the current density of 0.5C. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The 0.5C cycle plots for the raw material 2 and clad material 2 are shown in fig. 9 and 10, comparing the cycle performance of the two materials, it can be seen that: the capacity retention after 100 cycles of raw material 2 was 92.3%, while TiO2The capacity retention rate of the coated material 2 after 100 weeks is 97.1%, and the cycle results show that the cycle performance of the coated material is improved, which indicates that the coating has a better effect.
Example 4
Firstly, selecting Na as a positive electrode material1.0Ni0.33Fe0.33Mn0.33O2The particle size D50, denoted as raw material 3, was 10 μm. The coating liquid consists of magnesium acetate and water, the solubility is 40g of magnesium acetate/100 g of water, the gas is argon, and the furnace is a rotary furnace.
Then, 100kg of the positive electrode material was weighed and placed in a rotary furnace, and the rotary furnace was turned on to increase the contact area. And opening the furnace to raise the temperature, so that the temperature in the furnace reaches 400 ℃. Argon gas is turned onThe coating liquid enters the furnace body, contacts with the material and is decomposed into MgO at high temperature, and the MgO is uniformly coated on the surface of the material. The 400 ℃ heat preservation time is set to 12 hours, and the ventilation is stopped after the time. Opening the cooling system, rapidly cooling the furnace body, and taking out to obtain MgO-coated Na1.0Ni0.33Fe0.33Mn0.33O2And is denoted as cladding material 3.
The scanning electron microscope test was performed on the raw material 3 and the clad material 3, and the results are shown in fig. 11 and 12. It can be seen that the surface of the raw material 3 is smooth and a uniform coating layer is present on the surface of the coating material 3.
The raw material 3 and the coating material 3 prepared in the above way are respectively used as active substances of the positive electrode material of the sodium-ion battery and are used for preparing the sodium-ion battery. Assembled into a CR2032 button cell, and a constant current charge-discharge mode is used for carrying out charge-discharge test at the current density of 0.5C. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The 0.5C cycle plots for the raw material 3 and the clad material 3 are shown in fig. 13 and 14, and comparing the cycle performance of the two materials, it can be seen that: the capacity retention rate of the raw material 3 after 100 cycles was 88.5%, while the capacity retention rate of the MgO-coated coating material 3 after 100 cycles was 95.0%, demonstrating the effectiveness of the coating and also demonstrating the feasibility of the coating method.
Example 5
Firstly, selecting NaNi as the anode material1/3Fe2/9B1/9Mn1/3O2And marked as raw material 4, the particle size D50 was 10 μm. The coating liquid consists of magnesium acetate and water, the solubility is 40g of magnesium acetate/100 g of water, the gas is argon, and the furnace is a rotary furnace.
Then, 100kg of the positive electrode material was weighed and placed in a rotary furnace, and the rotary furnace was turned on to increase the contact area. And opening the furnace to raise the temperature, so that the temperature in the furnace reaches 400 ℃. And opening argon, carrying the coating liquid into the furnace body, contacting the coating liquid with the material, decomposing the coating liquid into MgO at high temperature, and uniformly coating the MgO on the surface of the material. The 400-degree heat preservation time is set as 12 hours, and the ventilation is stopped after the time is up. Opening the cooling system, rapidly cooling the furnace body, and taking out to obtain MgO-coated NaNi1/3Fe2/9B1/9Mn1/3O2And is denoted as cladding material 4.
The raw material 4 and the coating material 4 prepared in the above way are respectively used as active substances of the positive electrode material of the sodium-ion battery and are used for preparing the sodium-ion battery. Assembled into a CR2032 button cell, and a constant current charge-discharge mode is used for carrying out charge-discharge test at the current density of 0.5C. The test conditions were: the discharge cutoff voltage was 2.0V and the charge cutoff voltage was 4.0V.
The cycling performance of the two materials was compared: the capacity retention rate of the raw material 4 after 100-week circulation is 90.7%, and the capacity retention rate of the MgO-coated coating material 2 after 100 weeks is 95.9%, and the circulation result shows that the circulation performance of the coated material is improved, which indicates that the coating has a better effect.
According to the preparation method of the sodium-ion battery cathode material with the coating structure, which is provided by the embodiment of the invention, the cathode material is coated by using a vapor deposition method, so that the coating process is simpler, the coating effect is better and more uniform, and the preparation method is more suitable for industrial production. After coating, the interface of the anode material is optimized, and the cycling stability of the sodium-ion battery is improved. The sodium ion battery can be applied to power batteries of low-speed electric vehicles or large-scale energy storage systems such as solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power supplies or communication base stations.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of a sodium-ion battery positive electrode material with a coating structure is characterized by comprising the following steps:
preparing a coating solution; the coating liquid comprises a coating precursor formed by metal salt and/or hydrate thereof;
putting the anode material to be coated into a coating furnace, heating to 200-1000 ℃, carrying the coating liquid into the coating furnace by utilizing compressed air or nitrogen or argon, and uniformly coating the surface of the anode material with the oxide formed by the thermal decomposition of the coating precursor;
taking out the prepared positive electrode material with the oxide coating layer to obtain the positive electrode material of the sodium-ion battery with the coating structure;
wherein the metal salt and/or hydrate thereof specifically includes: nitrate of Nb or La and one or more of hydrate, sulfate and hydrate thereof;
dissolving a precursor solid raw material in a corresponding solvent to form the coating liquid;
the coating furnace is a rotary atmosphere furnace;
the positive electrode material to be coated is NaxM1aM2bO2(ii) a Wherein, 0.6<x≤1，a>0, b is more than or equal to 0, a + b =1, and the material is kept electrically neutral; m1 is a metal element, including one or more of Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn and Sn; m2 is nonmetal element, including one or more of B, F, Si.
2. The method for preparing the positive electrode material of the sodium-ion battery with the coating structure according to claim 1, wherein the solvent comprises: one or more of water, ethanol, N-methyl pyrrolidone and acetone.
3. The method for preparing the positive electrode material of the sodium-ion battery with the coating structure according to claim 1, wherein the step of taking out the prepared positive electrode material with the oxide coating layer to obtain the positive electrode material of the sodium-ion battery with the coating structure comprises the following steps:
and taking out the prepared cathode material with the oxide coating layer, and screening for removing iron to obtain the cathode material of the sodium-ion battery with the coating structure.
4. The sodium-ion battery positive electrode material prepared according to the preparation method of any one of claims 1 to 3, wherein the sodium-ion battery positive electrode material comprises: a positive electrode material core with a layered structure and a coating layer;
the inner core of the anode material with the layered structure is NaxM1aM2bO2，0.6<x≤1，a>0, b is more than or equal to 0, a + b =1, and the material is kept electrically neutral; m1 is a metal element, including one or more of Li, Mg, Al, Ti, Mn, Fe, Co, Ni, Cu, Zn and Sn; m2 is a nonmetal element, including one or more of B, F, Si;
the coating layer is an oxide shell of Nb or La coated outside the core of the anode material with the laminated structure;
wherein, in the sodium ion battery anode material, the mass percentage of the coating layer is 0.05-20%.
5. A sodium-ion secondary battery characterized by comprising the sodium-ion battery positive electrode material according to claim 4.
6. Use of the sodium ion secondary battery according to claim 5, wherein the secondary battery is used for power tools, electric vehicles, and energy storage devices for solar power generation, wind power generation, smart grid peak shaving, distributed power plants, backup power sources, or communication base stations.
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| CN111082017A (en) * | 2019-12-25 | 2020-04-28 | 溧阳中科海钠科技有限责任公司 | Composite positive electrode material of sodium ion secondary battery, preparation method of composite positive electrode material and battery |
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