CN115425210A - Binary high-nickel sodium-ion battery positive electrode material, preparation method and application - Google Patents

Binary high-nickel sodium-ion battery positive electrode material, preparation method and application Download PDF

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CN115425210A
CN115425210A CN202211188488.6A CN202211188488A CN115425210A CN 115425210 A CN115425210 A CN 115425210A CN 202211188488 A CN202211188488 A CN 202211188488A CN 115425210 A CN115425210 A CN 115425210A
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sodium
nickel
ion battery
positive electrode
solution
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冯茂华
阮丁山
张静静
吴星宇
刘宝烨
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to PCT/CN2023/078164 priority patent/WO2024066186A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention provides a binary high-nickel sodium-ion battery positive electrode material, a preparation method and application, wherein the binary high-nickel sodium-ion battery positive electrode material comprises a sodium-ion battery positive electrode particle material and a Ni-NaP layer coated on the surface of the positive electrode particle material; and mixing and sintering the sodium ion battery positive electrode particle material, phosphate and organic glue to obtain the binary high-nickel sodium ion battery positive electrode material, which can be applied to a sodium ion battery positive plate and a sodium ion battery. The Ni-NaP layer in the binary high-nickel sodium ion battery positive electrode material prepared by the invention has stronger conductive capability, is beneficial to improving the surface conductive performance of particles, can improve the conductivity of the positive electrode material, and promotes the transmission of ions among positive electrode particles.

Description

Binary high-nickel sodium-ion battery positive electrode material, preparation method and application
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a binary high-nickel sodium ion battery positive electrode material, a preparation method and application.
Background
Among the various electrochemical energy storage technologies studied, lithium ion batteries have achieved widespread commercial use due to their advantages of higher energy density, high safety, and low maintenance cost. However, when large-scale energy storage such as national power grid and communication base station is considered, the rising of lithium price and the uneven distribution force people to find other low-cost candidate systems. Under the background, the sodium ion battery is widely concerned by researchers at home and abroad, and also becomes an important substitute of the lithium ion battery in certain application fields, particularly in the fields of large-scale energy storage application and low-speed electric automobile application.
Sodium and lithium are in the same group in the periodic table, and the working principles of the sodium and lithium are very similar to each other, so that the lithium ion battery can be referred to in the research and development of the sodium ion battery. In addition, some materials that are not active in lithium ion batteries may be more suitable for sodium ion batteries, and new higher performance materials may be developed.
However, compared with metallic lithium, the dynamic performance of sodium ions is poorer, the de-intercalation process is accompanied with a more complex phase change process, the specific capacity is limited to be lower, and the application field is greatly reduced. Therefore, how to develop a high-conductivity sodium-electrode cathode material is one of the key issues in the development of sodium-ion batteries.
Disclosure of Invention
The invention aims to provide a binary high-nickel sodium-ion battery positive electrode material, a preparation method and an application of a sodium-ion battery positive electrode, and the conductivity of the sodium-ion battery positive electrode material is improved.
In a first aspect, the invention provides a binary high-nickel sodium-ion battery positive electrode material, which comprises a sodium-ion battery positive electrode particle material and a Ni-NaP layer coated on the surface of the positive electrode particle material, wherein the Ni-NaP layer is obtained by mixing and sintering organic glue and phosphate containing nickel and sodium.
In alternative embodiments, compound Na x Ni e M f O 2 @ C | Ni-NaP; m is at least one of titanium, zirconium, chromium, yttrium, manganese, cobalt, zinc and scandium; wherein x is more than or equal to 0.5 and less than or equal to 1.2, e is more than or equal to 0.6<1, e + f =1; wherein the positive electrode particle material of the sodium ion battery has a core-shell structure, wherein the core layer is Na x Ni e M f O 2 The shell layer is a C, ni-NaP layer coated on the shell layer;
preferably, wherein 0.6. Ltoreq. X. Ltoreq.0.9; e is more than or equal to 0.6 and less than 0.9;
preferably, the binary high nickel sodium ion battery positive electrode material is Na 0.64 Ni 0.65 M 0.35 O 2 @C|Ni-NaP、Na 0.71 Ni 0.65 M 0.35 @C|Ni-NaP、Na 0.78 Ni 0.68 M 0.32 O 2 @C|Ni-NaP、Na 0.86 Ni 0.78 M 0.22 O 2 @C|Ni-NaP、Na 0.88 Ni 0.84 M 0.16 O 2 @C|Ni-NaP、Na 0.81 Ni 0.89 M 0.11 @ C | Ni-NaP.
In a second aspect, the invention provides a preparation method of a binary high nickel sodium ion battery anode material, which comprises the steps of mixing a sodium ion battery anode particle material, phosphate and organic glue, and sintering to obtain the binary high nickel sodium ion battery anode material; the phosphate is one, two or three of sodium phosphate, nickel phosphate and nickel sodium phosphate.
In an alternative embodiment, the mass ratio of the sodium-ion battery positive electrode particle material to the phosphate to the organic glue is 100: (0.05-20): (0.05-5);
preferably, the mass ratio of the sodium-ion battery positive electrode particle material to the phosphate to the organic glue is 100: (2-5): (0.05-0.5);
preferably, the sintering temperature is 500-1000 ℃, and the sintering time is 4-24 h;
preferably, the sintering is performed in an inert gas atmosphere;
preferably, the sintering atmosphere is one of neon, argon and nitrogen;
preferably, the organic gum is at least one of guar gum, gum arabic, carrageenan, styrene butadiene rubber;
preferably, after sintering, ball milling, water washing, drying, sieving and demagnetizing are carried out, thus obtaining the binary high nickel sodium ion battery anode material.
In an alternative embodiment, a method for preparing a positive electrode particulate material for a sodium-ion battery includes:
mixing polyvinyl alcohol, water, a nickel source solution, a solution containing M and a sodium source solution, and reacting to obtain a mixed jelly;
evaporating, extruding, swelling, heating and post-treating the mixed jelly to obtain Na x Ni e M f O 2 @ C particles.
In an optional embodiment, polyvinyl alcohol and water are mixed and heated to 60-110 ℃, a nickel source solution, a M-containing solution and a sodium source solution are added for mixing and reaction to obtain a mixed jelly;
preferably, the polyvinyl alcohol content is 15-90% after mixing the polyvinyl alcohol and water;
preferably, the nickel source solution is obtained by mixing a nickel source and a citric acid solution or a citric acid solution;
preferably, the concentration of the citric acid solution is 0.05-1.8 mol/L;
preferably, the nickel source is at least one of nickel oxalate, nickel formate, nickel nitrate, nickel sulfate or nickel chloride;
preferably, the M-containing solution is obtained by mixing a source of M and a citric acid solution;
preferably, the M source is at least one of sulfate, chloride and nitrate of titanium, zirconium, chromium, yttrium, manganese, cobalt, zinc and scandium;
preferably, the sodium source solution is at least one of a sodium carbonate solution, a sodium acetate solution, a sodium oxalate solution or a sodium citrate solution.
In an alternative embodiment, the swelling treatment comprises the following specific steps: evaporating and extruding the mixed jelly, and then soaking the mixed jelly in a protonation solution and taking out the mixture;
preferably, the protonating solution is a sodium chloride solution;
preferably, the mass concentration of the protonation solution is 0.1-2%;
preferably, the temperature of the protonation solution is 30-60 ℃;
preferably, the soaking time is 20-60h;
preferably, the swollen mixed jelly is washed and dried after being taken out.
In an optional embodiment, the evaporation temperature is 80-110 ℃, and the evaporation is stopped until the water content of the mixed jelly is less than or equal to 18%;
preferably, a filiform mixed jelly is obtained after extrusion;
preferably, the temperature of the temperature-rising heat treatment is 500-1000 ℃, the atmosphere is oxygen-containing gas or oxygen, and the time is 0.5-2h; preferably: the atmosphere for heating heat treatment is oxygen or air;
preferably, the post-treatment comprises annealing, ball milling, sieving.
In a third aspect, the invention provides an application of a binary high-nickel sodium-ion battery positive electrode material in a sodium-ion battery positive electrode plate.
In a fourth aspect, the invention provides a processing method of a positive plate of a sodium-ion battery, which comprises the steps of mixing a binary high-nickel sodium-ion battery positive material, a binder, a conductive agent and a solvent, coating the mixture on a current collector, and processing to obtain the positive plate of the sodium-ion battery;
preferably, the binder comprises one or more of polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene butadiene latex (SBR);
preferably, the conductive agent comprises one or more of acetylene black, ketjen black, super-P, carbon nanotubes, carbon nanofibers, activated carbon, and graphene;
preferably, the solvent comprises N-methylpyrrolidone (NMP);
preferably, the mass ratio of the positive electrode material to the binder to the conductive agent is (80-110): (0.2 to 8): (1-5);
preferably, the mass ratio of the cathode material to the binder to the conductive agent is 90-96: 0.5 to 2:1 to 3;
preferably, the processing comprises drying and cold pressing.
The beneficial effects of the embodiment of the invention include, for example:
the Ni-NaP layer in the binary high-nickel sodium ion battery anode material prepared by the invention has stronger conductive capability, is beneficial to improving the surface conductivity of particles, can improve the conductivity of the anode material, and promotes the transmission of ions among anode particles; in addition, the compact coating formed by the Ni-NaP layer has structural stability, and can reduce the direct contact of electrolyte with nickel and M to the maximum extent on the premise of improving the nickel content in the anode material, thereby inhibiting the electrolyte decomposition on the surface of the anode particle material, stabilizing the internal structure of the multilayer anode particle, and improving intercrystalline cracks caused by long-period circulation under severe conditions.
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 embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows Na in example 3 0.78 Ni 0.68 M 0.32 TEM image of @ C | Ni-NaP cathode material;
FIG. 2 shows Na in comparative example 2 0.86 Ni 0.78 M 0.22 O 2 TEM image of @ C cathode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 some, but not all embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
It should be noted that the features of the embodiments of the present invention may be combined with each other without conflict.
The embodiment of the invention provides a binary high-nickel sodium-ion battery positive electrode material, which comprises a sodium-ion battery positive electrode particle material and a Ni-NaP layer coated on the surface of the positive electrode particle material, wherein the Ni-NaP layer is obtained by mixing and sintering organic glue and phosphate containing nickel and sodium.
The Ni-NaP layer in the binary high-nickel sodium ion battery positive electrode material prepared by the embodiment has stronger conductive capability, is beneficial to improving the surface conductivity of particles, can improve the conductivity of the positive electrode material, and promotes the transmission of ions among positive electrode particles; in addition, the compact coating formed by the Ni-NaP layer has structural stability, and can reduce the direct contact of electrolyte with nickel and M to the maximum extent on the premise of improving the nickel content in the anode material, thereby inhibiting the electrolyte decomposition on the surface of the anode particle material, stabilizing the internal structure of the multilayer anode particles, and improving intercrystalline cracks caused by long-period circulation under severe conditions.
Further, the chemical formula is Na x Ni e M f O 2 @ C | Ni-NaP; m is at least one of titanium, zirconium, chromium, yttrium, manganese, cobalt, zinc and scandium; wherein x is more than or equal to 0.5 and less than or equal to 1.2, e is more than or equal to 0.6<1, e + f =1; the positive electrode particle material of the sodium ion battery has a core-shell structure, wherein a core layer is Na x Ni e M f O 2 The shell layer is a C, ni-NaP layer and is coated on the shell layer;
preferably, wherein 0.6. Ltoreq. X. Ltoreq.0.9; e is more than or equal to 0.6 and less than 0.9.
Preferably, the binary high-nickel sodium-ion battery positive electrode material is Na 0.64 Ni 0.65 M 0.35 O 2 @C|Ni-NaP、Na 0.71 Ni 0.65 M 0.35 @C|Ni-NaP、Na 0.78 Ni 0.68 M 0.32 O 2 @C|Ni-NaP、Na 0.86 Ni 0.78 M 0.22 O 2 @C|Ni-NaP、Na 0.88 Ni 0.84 M 0.16 O 2 @C|Ni-NaP、Na 0.81 Ni 0.89 M 0.11 @ C | Ni-NaP.
The Ni-NaP layer is coated on the shell layer, so that the decomposition of electrolyte on the surface of the anode particle carbon is improved, the internal structure of the multi-layer lithium anode particle is stabilized, and intergranular cracks caused by long-period circulation under severe conditions can be improved. The binary high nickel sodium ion anode material is also double-layer coated, and the C layer and the Ni-NaP layer jointly stabilize Na x Ni e M f O 2 The internal structure of the particle.
The second aspect of the embodiment of the invention provides a preparation method of a binary high nickel sodium ion battery anode material, which comprises the steps of mixing a sodium ion battery anode particle material, phosphate and organic glue, and sintering to obtain the binary high nickel sodium ion battery anode material.
Further, the mass ratio of the positive electrode particle material of the sodium-ion battery, phosphate and organic glue is 100: (0.05-20): (0.05-5);
preferably, the mass ratio of the positive electrode particle material of the sodium-ion battery, the phosphate and the organic glue is 100: (2-5): (0.05-0.5);
specifically, it may be 100:0.05: 5. 100:10: 5. 100:20: 5. 100:5:0.05, 100: 5;
preferably, the phosphate is at least two of sodium phosphate, nickel phosphate and nickel sodium phosphate;
preferably, the sintering temperature is 500-1000 ℃, specifically 500 ℃, 700 ℃, 900 ℃, 1000 ℃, and the sintering time is 4-24 hours, specifically 4 hours, 8 hours, 12 hours, 18 hours, 24 hours;
preferably, the sintering is performed in an inert gas atmosphere;
preferably, the sintering atmosphere is one of neon, argon and nitrogen;
preferably, the organic gum is at least one of guar gum, gum arabic, carrageenan, styrene butadiene rubber;
preferably, after sintering, ball milling, water washing, drying, sieving and demagnetizing are carried out, so as to obtain the binary high-nickel sodium-ion battery positive electrode material.
High-temperature sintering enables phosphate and organic glue to form a compact Ni-NaP layer on the surface of the battery anode particle material, and the structural stability and the conductivity of the composite anode material are improved, so that the electrochemical performance of the battery is improved.
Further, the preparation method of the positive electrode particle material of the sodium-ion battery comprises the following steps:
mixing polyvinyl alcohol, water, a nickel source solution, a solution containing M and a sodium source solution, and reacting to obtain a mixed jelly;
evaporating the mixed jelly, extruding, swelling, heating for heat treatment, and post-treating to obtain Na x Ni e M f O 2 @ C particles.
Further, mixing polyvinyl alcohol and water, heating to 60-110 ℃, specifically 60 ℃, 80 ℃, 100 ℃ and 110 ℃, adding a nickel source solution, an M-containing solution and a sodium source solution, mixing, and reacting to obtain a mixed jelly;
preferably, the polyvinyl alcohol content after mixing the polyvinyl alcohol and water is 15-90%, and specifically 15%, 30%, 60%, 90%;
preferably, the nickel source solution is obtained by mixing a nickel source and a citric acid solution or a citric acid solution;
preferably, the concentration of the citric acid solution is 0.05-1.8 mol/L, and specifically can be 0.05mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L, 1.8mol/L;
preferably, the nickel source is at least one of nickel oxalate, nickel formate, nickel nitrate, nickel sulfate or nickel chloride;
preferably, the M-containing solution is obtained by mixing a source of M and a citric acid solution;
preferably, the M source is at least one of sulfate, chloride and nitrate of titanium, zirconium, chromium, yttrium, manganese, cobalt, zinc and scandium;
preferably, the sodium source solution is at least one of a sodium carbonate solution, a sodium acetate solution, a sodium oxalate solution or a sodium citrate solution.
Polyvinyl alcohol is one of carbon sources of the anode particle material, and the increase of the dosage of the polyvinyl alcohol in the solution increases the viscosity of the solution, which is not beneficial to obtaining uniform mixed jelly, and increases the thickness of the C layer, thereby hindering the diffusion of sodium ions to a certain extent.
Further, the swelling treatment comprises the following specific steps: evaporating and extruding the mixed jelly, and then soaking in a protonized solution and taking out;
preferably, the protonating solution is a sodium chloride solution;
preferably, the protonation solution has a mass concentration of 0.1 to 2%, in particular 0.1%, 0.5%, 1.0%, 2.0%;
preferably, the protonation solution temperature is 30-60 deg.C, specifically 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C;
preferably, the soaking time is 20-60h, specifically 20h, 40h and 60h;
preferably, the swollen mixed jelly is washed and dried after being taken out.
In order to ensure that the mixed jelly can be fully and uniformly calcined, firstly, the mixed jelly is changed into sericite, which is different from the mixed jelly stacked together, the heat absorption orientation degree of the section of the sericite is more consistent, and secondly, the sericite can be swelled in a sodium chloride protonation solution to be in a loose structure, so that oxygen is promoted to diffuse into the sericite in the temperature rise process, oxidation reaction is carried out, and the sericite is fully calcined.
Further, the evaporation temperature is 80-110 ℃, specifically 80 ℃, 90 ℃, 100 ℃ and 110 ℃, and the evaporation is stopped until the water content of the mixed jelly is less than or equal to 18 percent, and the evaporation degree is controlled, so that the filamentous mixed jelly is favorably formed;
preferably, a filiform mixed jelly is obtained after extrusion;
preferably, the temperature of the temperature-raising heat treatment is 500-1000 ℃, specifically 500 ℃, 700 ℃, 900 ℃, 1000 ℃, and the atmosphere is air or oxygen for 0.5-2 hours, specifically 0.5 hour, 1 hour, 2 hours;
preferably, the post-treatment comprises annealing, ball milling, sieving.
The third aspect of the embodiment of the invention provides an application of a binary high-nickel sodium-ion battery positive electrode material in a sodium-ion battery positive electrode plate.
The fourth aspect of the embodiment of the invention provides a processing method of a positive plate of a sodium-ion battery, which comprises the steps of mixing a binary high-nickel sodium-ion battery positive material, a binder, a conductive agent and a solvent, coating the mixture on a current collector, and processing to obtain the positive plate of the sodium-ion battery;
preferably, the binder comprises one or more of polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene butadiene latex (SBR);
preferably, the conductive agent comprises one or more of acetylene black, ketjen black, super-P, carbon nanotubes, carbon nanofibers, activated carbon, and graphene;
preferably, the solvent comprises NMP;
preferably, the mass ratio of the positive electrode material to the binder to the conductive agent is (80-110): (0.2-8): (1-5);
preferably, the mass ratio of the cathode material to the binder to the conductive agent is 90-96: 0.5 to 2:1 to 3; specifically, 93:0.5: 1. 93:0.5: 3. 93:0.5: 2. 92:1: 2. 92:2: 2. 90:2: 2. 96:2:2.
preferably, the processing includes drying and cold pressing.
To achieve the above objects, the features and properties of the present invention will be described in further detail with reference to embodiments.
Example of the implementation
Example 1
The chemical formula of the binary high nickel sodium ion cathode material of the embodiment is Na 0.64 Ni 0.65 Mn 0.35 O 2 @C|Ni-NaP。
The preparation method of the binary high nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 65 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3mol/L of citric acid, then adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.64;
(2) Continuously heating the mixed jelly at 95 ℃ until the water content in the mixed jelly is less than or equal to 18%, sending the mixed jelly into a temperature-resistant and pressure-resistant silk maker, extruding to obtain silk jelly with the diameter of about 7mm, performing swelling treatment (soaking in 0.55% sodium chloride protonation solution at 55 ℃, stirring for 24h, taking out the silk jelly, washing with distilled water, airing in a ventilated place), sending the silk jelly into a heating furnace, heating to 755 ℃ under the atmosphere of 21% oxygen for heat treatment for 45min, annealing to room temperature, drying, ball-milling, and sieving to obtain Na 0.64 Ni 0.65 M 0.35 O 2 Particles of @ C;
(3) 500g of Na 0.64 Ni 0.65 M 0.35 O 2 @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1)Heating for 10h in atmosphere, annealing to room temperature, ball milling, washing with water, drying, sieving, and removing magnetism to obtain Na 0.64 Ni 0.65 M 0.35 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.64 Ni 0.65 M 0.35 O 2 The material is prepared from @ C | Ni-NaP positive electrode material, polyvinylidene fluoride (PVDF) as a binder and carbon nanofiber as a conductive agent according to a mass ratio of 95:1:1.5 mixing, stirring, adding solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Example 2
The chemical formula of the binary high-nickel sodium ion cathode material of the embodiment is Na 0.71 Ni 0.65 Mn 0.35 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 65 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3mol/L citric acid, adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.71;
(2) Heating the mixed jelly at 95 deg.C until water content in the mixed jelly is less than or equal to 18%, extruding in a temperature-resistant silk pressing device to obtain 7mm silk jelly, swelling (soaking in 0.55% sodium chloride protonized solution at 55 deg.C, stirring for 24 hr, taking out the silk jelly, washing with distilled water, air drying in ventilation place), heating to 755 deg.C under 21% oxygen atmosphere in a heating furnace, annealing to room temperature, drying, ball milling, and sieving to obtain Na 0.71 Ni 0.65 Mn 0.35 O 2 Particles of @ C;
(3) 500g of Na 0.71 Ni 0.65 Mn 0.35 O 2 Mixing and stirring the @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1) and 0.9g of styrene butadiene rubber, heating for 10 hours at 640 ℃ under argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.71 Ni 0.65 Mn 0.35 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
mixing Na 0.71 Ni 0.65 Mn 0.35 O 2 The material is prepared from @ C | Ni-NaP positive electrode material, polyvinylidene fluoride (PVDF) as a binder and carbon nanofiber as a conductive agent according to a mass ratio of 95:1:1.5 mixing, stirring, adding solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Example 3
The chemical formula of the binary high nickel sodium ion cathode material of the embodiment is Na 0.78 Ni 0.68 Mn 0.32 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 87 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3Mol/L citric acid, adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.78;
(2) Heating the mixed jelly at 95 deg.C until water content is less than 18%, extruding to obtain 7mm sericin, soaking in 1.0% sodium chloride protonation solution at 50 deg.C, stirring for 36 hr, taking out sericin, washing with distilled water, and putting into a containerAir drying), transferring sericin into a heating furnace, heating to 840 deg.C under 21% oxygen atmosphere, heat treating for 40min, annealing to room temperature, drying, ball milling, and sieving to obtain Na 0.78 Ni 0.68 Mn 0.32 O 2 Particles of @ C;
(3) 500g of Na 0.78 Ni 0.68 Mn 0.32 O 2 Mixing and stirring the @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1) and 0.9g of styrene butadiene rubber, heating at 640 ℃ for 10 hours in an argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.78 Ni 0.68 Mn 0.32 O 2 The @ C | Ni-NaP cathode material, TEM image is shown in FIG. 1.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.78 Ni 0.68 Mn 0.32 O 2 The material is prepared from @ C | Ni-NaP positive electrode material, polyvinylidene fluoride (PVDF) as a binder and carbon nanofiber as a conductive agent according to a mass ratio of 93:1.5:2, mixing, stirring, adding a solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Example 4
The chemical formula of the binary high nickel sodium ion cathode material of the embodiment is Na 0.86 Ni 0.78 Mn 0.22 O 2 @C|Ni-NaP。
The preparation method of the binary high nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 82 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3mol/L of citric acid, then adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.86;
(2) Heating the mixed jelly at 95 deg.C continuously until mixedThe water content in the combined jelly is less than or equal to 18 percent, the combined jelly is sent to a temperature-resistant silk pressing device, silk jelly with the diameter of about 7mm is extruded and subjected to swelling treatment (1.0 percent sodium chloride protonation solution is soaked at 50 ℃, stirred for 36 hours, the silk jelly is taken out, washed clean by distilled water and dried in a ventilated place), the silk jelly is sent to a heating furnace, the temperature is raised to 840 ℃ under the atmosphere of 21 percent oxygen, the silk jelly is annealed to room temperature, dried, ball-milled and sieved to obtain Na 0.86 Ni 0.78 Mn 0.22 O 2 Particles of @ C;
(3) 500g of Na 0.86 Ni 0.78 Mn 0.22 O 2 Mixing and stirring the @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1) and 0.9g of styrene butadiene rubber, heating for 10 hours at 640 ℃ under argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.86 Ni 0.78 Mn 0.22 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.86 Ni 0.78 Mn 0.22 O 2 The material is prepared from @ C | Ni-NaP positive electrode material, polyvinylidene fluoride (PVDF) as a binder and carbon nanofiber as a conductive agent in a mass ratio of 94:1:2, mixing, stirring, adding a solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Example 5
The chemical formula of the binary high nickel sodium ion cathode material of the embodiment is Na 0.88 Ni 0.84 Mn 0.16 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 82 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3mol/L citric acid, adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.88;
(2) Continuously heating the mixed jelly at 96 deg.C until water content in the mixed jelly is less than or equal to 18%, extruding in a temperature-pressure resistant silk extruder to obtain 7mm silk jelly, swelling (soaking in 1.0% sodium chloride protonation solution at 50 deg.C, stirring for 36 hr, taking out the silk jelly, washing with distilled water, air drying in ventilation place), heating to 840 deg.C under 21% oxygen atmosphere in a heating furnace for 40min, annealing to room temperature, drying, ball milling, and sieving to obtain Na 0.88 Ni 0.84 Mn 0.16 O 2 Particles of @ C;
(3) 500g of Na 0.88 Ni 0.84 Mn 0.16 O 2 Mixing and stirring the @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1) and 0.9g of styrene butadiene rubber, heating for 10 hours at 640 ℃ under argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.88 Ni 0.84 Mn 0.16 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.88 Ni 0.84 Mn 0.16 O 2 The composite material is characterized by comprising the following components in parts by mass, of @ C | Ni-NaP positive electrode material, binder polyvinylidene fluoride (PVDF), and conductive agent carbon nanofiber, wherein the mass ratio of the @ C | Ni-NaP positive electrode material to the conductive agent carbon nanofiber is 96:1.2:2.5 mixing, stirring, adding solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Example 6
The chemical formula of the binary high-nickel sodium ion cathode material of the embodiment is Na 0.81 Ni 0.89 Mn 0.11 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 94 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.66mol/L citric acid, adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.81;
(2) Heating the mixed jelly at 96 deg.C until water content is less than 18%, extruding in a temperature-resistant silk press to obtain 7mm silk jelly, soaking in 1.3% sodium chloride protonation solution at 35 deg.C, stirring for 48 hr, taking out silk jelly, washing with distilled water, air drying, heating to 840 deg.C under 21% oxygen atmosphere, annealing to room temperature, drying, ball milling, and sieving to obtain Na 0.81 Ni 0.89 Mn 0.11 O 2 Particles of @ C;
(3) 500g of Na 0.81 Ni 0.89 Mn 0.11 O 2 Mixing and stirring the @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1) and 0.9g of styrene butadiene rubber, heating at 640 ℃ for 10 hours in an argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.81 Ni 0.89 Mn 0.11 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.81 Ni 0.89 Mn 0.11 O 2 The material is prepared from @ C | Ni-NaP positive electrode material, polyvinylidene fluoride (PVDF) as a binder and carbon nanofiber as a conductive agent in a mass ratio of 96:2:2, mixing, stirring, adding a solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Example 7
The chemical formula of the binary high nickel sodium ion cathode material of the embodiment is Na 0.81 Ni 0.89 C O0.11 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 60 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 90% of polyvinyl alcohol, dissolving nickel oxalate and cobalt chloride in the solution containing 1.8mol/L of citric acid, then adding a sodium source (the molar ratio of sodium to nickel to cobalt is 0.81;
(2) Continuously heating the mixed jelly at 80 deg.C until water content in the mixed jelly is less than or equal to 18%, extruding in a temperature-resistant and pressure-resistant silk extruder to obtain 7mm silk jelly, swelling (soaking in 0.13% sodium chloride protonation solution at 60 deg.C, stirring for 20 hr, taking out the silk jelly, washing with distilled water, air drying in ventilation place), heating to 1000 deg.C under 21% oxygen atmosphere in a heating furnace for 30min, annealing to room temperature, drying, ball-milling, and sieving to obtain Na 0.81 Ni 0.89 C O0.11 O 2 Particles of @ C;
(3) 500g of Na 0.81 Ni 0.89 C O0.11 O 2 Mixing and stirring the @ C particles, 50g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 2) 0.81 Ni 0.89 C O0.11 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.81 Ni 0.89 Mn 0.11 O 2 The material is prepared from @ C | Ni-NaP positive electrode material, polyvinylidene fluoride (PVDF) as a binder and carbon nanofiber as a conductive agent in a mass ratio of 80:0.5:5 mixing, stirring, adding solvent NMP, coating on a current collector to obtain a pole piece, drying, cold-pressing to obtain the sodium anodeAnd (3) slicing.
Example 8
The chemical formula of the binary high-nickel sodium ion cathode material of the embodiment is Na 0.81 Ni 0.89 Ti 0.11 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 110 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 15% of polyvinyl alcohol, dissolving nickel oxalate and titanium nitrate in the solution containing 0.05mol/L citric acid, then adding a sodium source (the molar ratio of sodium to nickel to titanium is 0.81;
(2) Continuously heating the mixed jelly at 110 deg.C until water content in the mixed jelly is less than or equal to 18%, extruding in a temperature-resistant and pressure-resistant silk extruder to obtain 7mm silk jelly, swelling (soaking in 2.0% sodium chloride protonation solution at 30 deg.C, stirring for 60 hr, taking out the silk jelly, washing with distilled water, air drying in ventilation place), heating to 500 deg.C in 21% oxygen atmosphere, heating for 120min, annealing to room temperature, drying, ball milling, and sieving to obtain Na 0.81 Ni 0.89 Ti 0.11 O 2 Particles of @ C;
(3) 500g of Na 0.81 Ni 0.89 Ti 0.11 O 2 Mixing and stirring the @ C particles, 0.25g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1, 2) and 0.25g of styrene butadiene rubber, heating for 24 hours at the controlled temperature of 500 ℃ under the argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.81 Ni 0.89 Ti 0.11 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
mixing Na 0.81 Ni 0.89 Ti 0.11 O 2 The composite material comprises the following components in parts by mass, wherein @ C | Ni-NaP positive electrode material, a binder polyvinylidene fluoride (PVDF), and a conductive agent carbon nanofiber are mixed according to the mass ratio of 110:8:1, mixing, stirring, adding a solvent NMP, coating on a current collector to obtain a pole piece, drying, and carrying out cold pressing to obtain the sodium positive pole piece.
Comparative example 1
The chemical formula of the binary high-nickel sodium ion cathode material of the comparative example is Na 0.64 Ni 0.65 Mn 0.35 O 2 @C|Ni-NaP。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 65 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3mol/L citric acid, adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.64);
(2) Continuously heating the mixed jelly at 95 ℃ until the water content in the mixed jelly is less than or equal to 18%, then sending the mixed jelly into a temperature-resistant wire pressing device, extruding to obtain a sericin substance with the diameter of about 7mm, sending the sericin substance into a heating furnace, heating to 755 ℃ under the atmosphere of 21% oxygen for heat treatment for 45min, annealing to room temperature, drying, ball-milling and sieving to obtain Na 0.64 Ni 0.65 M 0.35 O 2 Particles of @ C;
(3) 500g of Na 0.64 Ni 0.65 M 0.35 O 2 Mixing and stirring the @ C particles, 17.6g of phosphate (obtained by mixing sodium phosphate and nickel phosphate 1) and 0.9g of styrene butadiene rubber, heating for 10 hours at 640 ℃ under argon inert atmosphere, annealing to room temperature, ball-milling, washing with water, drying, sieving and demagnetizing to obtain Na 0.64 Ni 0.65 M 0.35 O 2 @ C | Ni-NaP cathode material.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
mixing Na 0.64 Ni 0.65 M 0.35 O 2 The material is characterized by comprising the following components in parts by mass: 1:1.5 mixing, stirring, adding solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Comparative example 2
The chemical formula of the binary high-nickel sodium ion cathode material of the comparative example is Na 0.86 Ni 0.78 Mn 0.22 O 2 @C。
The preparation method of the binary high-nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 82 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.3mol/L of citric acid, then adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.86;
(2) Continuously heating the mixed jelly at 95 ℃ until the water content in the mixed jelly is less than or equal to 18%, sending the mixed jelly into a temperature-pressure-resistant silk maker, extruding to obtain silk jelly with the diameter of about 7mm, performing swelling treatment (soaking in 1.0% sodium chloride protonation solution at 50 ℃, stirring for 36h, taking out the silk jelly, washing with distilled water, airing in a ventilated place), sending the silk jelly into a heating furnace, heating to 840 ℃ under the atmosphere of 21% oxygen for heat treatment for 40min, annealing to room temperature, drying, ball-milling and sieving to obtain Na 0.86 Ni 0.78 Mn 0.22 O 2 The @ C particles, TEM image are shown in FIG. 2.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
na is mixed with 0.86 Ni 0.78 Mn 0.22 O 2 The @ C positive electrode material, the binder polyvinylidene fluoride (PVDF), and the conductive agent carbon nanofiber are mixed according to the mass ratio of 94:1:2 mixingStirring, adding solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Comparative example 3
The chemical formula of the binary high-nickel sodium ion cathode material of the comparative example is Na 0.81 Ni 0.89 Mn 0.11 O 2 @C。
The preparation method of the binary high nickel sodium ion cathode material comprises the following steps:
(1) Placing polyvinyl alcohol in a heating reaction kettle, injecting deionized water, heating at 94 ℃ until the polyvinyl alcohol is dissolved to obtain a solution containing 64.7% of polyvinyl alcohol, dissolving nickel oxalate and manganese sulfate in the solution containing 0.66mol/L citric acid, adding a sodium source (the molar ratio of sodium to nickel to manganese is 0.81;
(2) Continuously heating the mixed jelly at 96 deg.C until water content in the mixed jelly is less than or equal to 18%, extruding in a temperature-pressure-resistant silk extruder to obtain 7mm silk jelly, swelling (soaking in 1.3% sodium chloride protonation solution at 35 deg.C, stirring for 48 hr, taking out the silk jelly, washing with distilled water, air drying in ventilation place), heating to 840 deg.C under 21% oxygen atmosphere in a heating furnace for 40min, annealing to room temperature, drying, ball milling, and sieving to obtain Na 0.81 Ni 0.89 Mn 0.11 O 2 @ C particles.
A preparation method of a positive plate of a sodium-ion battery comprises the following steps:
mixing Na 0.88 Ni 0.84 Mn 0.16 O 2 The @ C positive electrode material, the binder polyvinylidene fluoride (PVDF), and the conductive agent carbon nanofiber are mixed according to the mass ratio of 96:2:2, mixing, stirring, adding a solvent NMP, coating on a current collector to obtain a pole piece, drying, and cold-pressing to obtain the sodium positive pole piece.
Examples and comparative examples testing of negative electrode materials, pole pieces and batteries:
1. and (3) determining the specific surface area of the anode material by using a specific surface area tester, determining the median particle size D50 of the anode material by using a laser particle sizer, and measuring tap density by using a densimeter.
2. The positive pole pieces prepared in the examples and the comparative examples are placed in a vacuum oven for drying (80 ℃,3 h); and die cut into disks 12mm in diameter. In the half-cell, the positive electrode uses dry electrode slice, the positive electrode uses sodium slice as the counter electrode, the diaphragm is PP and PE composite diaphragm, electrolyte: 1M NaPF 6 EC, DMC, DEC (volume ratio of 1.
3. The cut-off voltage of the prepared half cell is 2.8-4.1V by utilizing a CT2001A type cell detection system. The discharge performance test is carried out at 0.1 ℃ after constant current charging to 4.1V at 0.1 ℃ and constant voltage charging to current less than or equal to 0.05V at 4.1V.
Table 1 specific surface area, particle size, tap density of positive electrode material of examples and comparative examples
Figure BDA0003865898510000231
Specific surface areas of the binary high nickel sodium ion positive electrode materials prepared in examples 1 to 6 are shown in table 1. The D50 of the binary high nickel sodium ion positive electrode material is 3.45-3.58 mu m, and the specific surface area is 2.28-2.54m 2 The tap density is 3.13-3.55g/cm 3 。
TABLE 2 Electrical Properties of the cell preparations of the examples and comparative examples 1-3
Figure BDA0003865898510000241
From the test results in Table 2, it can be seen that the first discharge specific capacities of the half-cells prepared in the embodiments 1 to 6 and the comparative examples 1 to 3 were respectively between 132.2 and 149.3 mAh/g. The discharge specific capacities of the embodiment 1 and the embodiment 1 are not greatly different, but the first coulombic efficiency and the capacity retention rates at 150 th circle and 500 th circle of the embodiment 1 are lower than those of the embodiment 1, the capacity retention rates at 150 th circle and 500 th circle, which shows that the swelling treatment is beneficial to improving the performance of the anode material, and the first coulombic efficiency and the capacity retention rates at 150 th circle and 500 th circle of the embodiment 2 and 3 are lower than those of the embodiment 1-6, the capacity retention rates at 150 th circle and 500 th circle, which shows that the Ni-NaP layer structure obtained by adding the modified coating in the embodiment 1-6 improves the surface conductivity of the anode particles and has strong structural stability.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The binary high-nickel sodium-ion battery positive electrode material is characterized by comprising a sodium-ion battery positive electrode particle material and a Ni-NaP layer coated on the surface of the positive electrode particle material, wherein the Ni-NaP layer is obtained by mixing and sintering organic glue and phosphate containing nickel and sodium.
2. The positive electrode material for binary high nickel sodium ion battery according to claim 1, wherein the chemical formula is Na x Ni e M f O 2 @ C | Ni-NaP; m is at least one of titanium, zirconium, chromium, yttrium, manganese, cobalt, zinc and scandium; wherein x is more than or equal to 0.5 and less than or equal to 1.2, e is more than or equal to 0.6<1, e + f=1; the positive electrode particle material of the sodium ion battery has a core-shell structure, wherein a core layer is Na x Ni e M f O 2 The shell layer is a C, ni-NaP layer coated on the shell layer;
preferably, wherein 0.6. Ltoreq. X. Ltoreq.0.9; e is more than or equal to 0.6 and less than 0.9.
3. The preparation method of the binary high nickel sodium ion battery anode material according to claim 1 or 2, characterized by mixing and sintering the sodium ion battery anode particle material, phosphate and organic glue to obtain the binary high nickel sodium ion battery anode material; the phosphate comprises nickel salt and sodium salt.
4. The preparation method of the binary high-nickel sodium-ion battery positive electrode material according to claim 3, wherein the mass ratio of the sodium-ion battery positive electrode particle material to the phosphate to the organic glue is 100: (0.05-20): (0.05-5);
preferably, the mass ratio of the sodium-ion battery positive electrode particle material to the phosphate to the organic glue is 100: (2-5): (0.05-0.5);
preferably, the sintering temperature is 500-1000 ℃, and the sintering time is 4-24 h;
preferably, the phosphate comprises at least two of sodium phosphate, nickel phosphate and nickel sodium phosphate;
preferably, the sintering is performed in an inert gas atmosphere;
preferably, the sintering atmosphere is one of neon, argon and nitrogen;
preferably, the organic gum is at least one of guar gum, gum arabic, carrageenan, styrene butadiene rubber;
preferably, after sintering, performing ball milling, water washing, drying, sieving and demagnetizing to obtain the binary high-nickel sodium-ion battery positive electrode material.
5. The method for preparing the cathode material of the binary high-nickel sodium-ion battery as claimed in claim 3, wherein the method for preparing the cathode particle material of the sodium-ion battery comprises the following steps:
mixing polyvinyl alcohol, water, a nickel source solution, a solution containing M and a sodium source solution, and reacting to obtain a mixed jelly;
evaporating, extruding, swelling, heating and post-treating the mixed jelly to obtain Na x Ni e M f O 2 @ C particles.
6. The preparation method of the binary high-nickel sodium-ion battery positive electrode material according to claim 5, characterized in that polyvinyl alcohol and water are mixed and heated to 60-110 ℃, and a nickel source solution, a M-containing solution and a sodium source solution are added for mixing and reacting to obtain a mixed jelly;
preferably, the polyvinyl alcohol content is 15-90% after the polyvinyl alcohol and the water are mixed;
preferably, the nickel source solution is obtained by mixing a nickel source and a citric acid solution or a citric acid solution;
preferably, the concentration of the citric acid solution is 0.05-1.8 mol/L;
preferably, the nickel source is at least one of nickel oxalate, nickel formate, nickel nitrate, nickel sulfate or nickel chloride;
preferably, the M-containing solution is obtained by mixing a M source and a citric acid solution;
preferably, the M source is at least one of sulfate, chloride and nitrate of titanium, zirconium, chromium, yttrium, manganese, cobalt, zinc and scandium;
preferably, the sodium source solution is at least one of a sodium carbonate solution, a sodium acetate solution, a sodium oxalate solution or a sodium citrate solution.
7. The preparation method of the binary high nickel sodium ion battery positive electrode material as claimed in claim 5, wherein the swelling treatment comprises the following specific steps: evaporating and extruding the mixed jelly, and then soaking the mixed jelly in a protonation solution and taking out the mixture;
preferably, the protonating solution is a sodium chloride solution;
preferably, the mass concentration of the protonation solution is 0.1-2%;
preferably, the temperature of the protonation solution is 30-60 ℃;
preferably, the soaking time is 20-60h;
preferably, the swollen mixed jelly is washed and dried after being taken out.
8. The method for preparing the cathode material of the binary high-nickel sodium-ion battery according to claim 5, wherein the evaporation temperature is 80-110 ℃, and the evaporation is stopped until the water content of the mixed jelly is less than or equal to 18%;
preferably, a filiform mixed jelly is obtained after extrusion;
preferably, the temperature of the temperature-rising heat treatment is 500-1000 ℃, the atmosphere is oxygen-containing gas or oxygen, and the time is 0.5-2h; preferably: the atmosphere for heating heat treatment is oxygen or air;
preferably, the post-treatment comprises annealing, ball milling and sieving.
9. A positive plate of a sodium-ion battery, which is characterized by comprising the positive electrode material of the binary high nickel sodium-ion battery as defined in any one of claims 1 to 8.
10. The preparation method of the positive plate of the sodium-ion battery of claim 9, characterized by mixing the binary high-nickel sodium-ion battery positive material, the binder, the conductive agent and the solvent, coating the mixture on a current collector, and processing the mixture to obtain the positive plate of the sodium-ion battery;
preferably, the binder comprises one or more of polyacrylic acid, polyvinylidene fluoride, carboxymethyl cellulose, and styrene-butadiene latex;
preferably, the conductive agent comprises one or more of acetylene black, ketjen black, super-P, carbon nanotubes, carbon nanofibers, activated carbon, and graphene;
preferably, the solvent comprises N-methylpyrrolidone;
preferably, the mass ratio of the positive electrode material to the binder to the conductive agent is (80-110): (0.2-8): (1-5);
preferably, the mass ratio of the positive electrode material, the binder and the conductive agent is (90-96): (0.5-2): (1-3);
preferably, the processing comprises drying and cold pressing.
CN202211188488.6A 2022-09-27 2022-09-27 Binary high-nickel sodium-ion battery positive electrode material, preparation method and application Pending CN115425210A (en)

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WO2024066186A1 (en) * 2022-09-27 2024-04-04 广东邦普循环科技有限公司 Binary high-nickel sodium ion battery positive electrode material, preparation method, and application

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CN115425210A (en) * 2022-09-27 2022-12-02 广东邦普循环科技有限公司 Binary high-nickel sodium-ion battery positive electrode material, preparation method and application

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