CN116177556B - Sodium-electricity positive electrode material, precursor thereof, preparation method and application - Google Patents

Sodium-electricity positive electrode material, precursor thereof, preparation method and application Download PDF

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CN116177556B
CN116177556B CN202310442746.7A CN202310442746A CN116177556B CN 116177556 B CN116177556 B CN 116177556B CN 202310442746 A CN202310442746 A CN 202310442746A CN 116177556 B CN116177556 B CN 116177556B
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sodium
sintering
sio
salt
citric acid
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CN116177556A (en
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张宝
程磊
邓鹏�
丁瑶
邓梦轩
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Zhejiang Power New Energy Co Ltd
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    • H—ELECTRICITY
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    • 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
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    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
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    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • H—ELECTRICITY
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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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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/00—Electrodes
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of sodium ion battery materials, and discloses a sodium ion positive electrode material, a precursor thereof, a preparation method and application thereof. The invention prepares SiO by adopting a gel sol method 2 /SiM 2 O 4 And (3) further compounding the composite nano material with a ternary precursor to finally prepare the ternary sodium-electricity precursor modified by compounding the silicon oxide/silicate composite nano material. The invention has the advantages of easily available raw materials, simple process and SiO prepared by the method 2 /SiM 2 O 4 The composite material has complete structure and uniform size, and provides a good raw material basis for further compounding with the ternary precursor; the battery using the composite modified cathode material has good capacity retention.

Description

Sodium-electricity positive electrode material, precursor thereof, preparation method and application
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a sodium-electricity material and a preparation method thereof, and more particularly relates to composite modification of the sodium-electricity material.
Background
Sodium-electric positive electrode materials have received extensive attention and research in recent years. Due to different effects of the multi-metal elements in the material structure, the stability and specific capacity of the sodium-electricity positive electrode material are relatively high. But the long cycle performance needs to be further improved by doping modification or cladding modification of the host material.
Surface coating, especially surface composite coating, will improve the overall structural stability of the material in many ways. Patent document with publication number of CN105655566A discloses a synthesis method of a silicon dioxide coated lithium-rich manganese-based positive electrode material, wherein a coating layer with controllable thickness, uniformity and compactness is formed on the surface of the material, an electrode is isolated from electrolyte, decomposition of the electrolyte is inhibited, and electrochemical performance of the lithium-rich manganese-based positive electrode material is improved. However, in the sodium-electricity field, sodium-electricity anode materials are protected, and sodium storage efficiency of the materials is improved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a composite modified sodium-electricity precursor material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following specific technical solutions.
A sodium electric precursor material comprises a composite material modified matrix material, wherein the molecular formula of the matrix material is NaMn (1-x) N x Cit, wherein Cit is citrate, N is at least one of Fe, ni, co, cu, zn, al, mg, ti, x is more than or equal to 0.1 and less than or equal to 0.5; the molecular formula of the composite material is SiO 2 /SiM 2 O 4 Wherein M is at least one of Ni, zn and Mg.
Based on the same inventive concept, the invention provides a preparation method of the sodium electric precursor material, which comprises the following steps:
step S1, dispersing metal salts of tetraethoxysilane and M in ethanolThen adding citric acid, stirring, dropwise adding ammonia water, and regulating the pH value; continuously reacting the reaction materials to sol state under the heating state; drying and sintering the sol-like product to obtain SiO 2 /SiM 2 O 4 A composite material;
s2, dissolving manganese salt, sodium salt and N salt in deionized water, adding citric acid, and reacting to form a gel-like mixture; siO is made of 2 /SiM 2 O 4 And adding the composite material into the gel-like mixture, stirring, and drying to obtain the sodium-electricity precursor material.
Further, as a preferable scheme, the metal salt of M is at least one of nitrate, acetate and oxalate.
Further, in the step S1, the molar ratio of the metal salts of ethyl orthosilicate and M to the citric acid is preferably 1:1: (5-10).
Further, in the step S1, the pH is adjusted to 8 to 9.
Further, in a preferred embodiment, in step S1, the temperature in the heating state is 60 to 90 ℃.
Further, in the step S1, the sintering temperature is 500-800 ℃ and the sintering time is 2-10 hours.
Further, as a preferable scheme, the manganese salt, sodium salt and N salt are one or two of acetate and nitrate.
Further, as a preferable scheme, in the step S2, the ratio of the sum of the molar amounts of the manganese salt, the sodium salt and the salt of N to the molar amount of the citric acid is 1 to 2:1.
further, in the step S2, the reaction temperature is preferably 60 to 100 ℃.
Further, in step S2, preferably, siO 2 /SiM 2 O 4 The molar ratio of the composite material to the sodium-electricity precursor material is 1-10: 100.
in addition, the invention also provides a sodium electric positive electrode material which is obtained by sintering the sodium electric precursor material.
Further, as a preferable scheme, the sintering is divided into two sections of sintering, wherein the sintering temperature of one section is 300-600 ℃ and the sintering time is 1-8 hours; the temperature of the two-stage sintering is 800-1100 ℃, and the sintering time is 2-20 h.
The invention also provides a sodium ion battery which comprises the sodium-electricity positive electrode material.
Compared with the prior art, the invention has the following obvious beneficial technical effects:
preparation of SiO by sol gel method 2 /SiM 2 O 4 Composite material, easily obtained raw materials, simple process and prepared SiO 2 /SiM 2 O 4 The composite material has complete structure and uniform size, and provides a good raw material basis for further compounding with the ternary precursor. SiM in composite material 2 O 4 The structural stability is strong, the ionic conductivity is high, and the multiplying power capacity of the material can be effectively improved; siO in composite material 2 The physical and chemical properties are stable, and the corrosion of the electrolyte can be effectively avoided. SiO (SiO) 2 And SiM 2 O 4 Can further improve the electrical property of sodium electricity.
SiO is made of 2 /SiM 2 O 4 The composite material is uniformly compounded on the surface of the sodium electric precursor, so that the comprehensive protection of the main body material can be realized.
The invention has simple process, short flow, easily obtained raw materials, no generation of toxic and harmful substances in the preparation process and easy realization of large-scale production.
Drawings
Fig. 1 is an SEM image of the sodium-electricity positive electrode material prepared in example 1.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
(1) 5 mmol of ethyl orthosilicate and 5 mmol of Zn (NO 3 ) 2 Dissolved in 50ml of ethanol, 5g of citric acid was added thereto, and the mixture was stirred continuously to effect a reaction. Then ammonia water is added dropwise, the pH value is regulated to 8.5, and the reaction is continued for 4 hours. It was then placed in an oil bath to react to sol by heating at 80 ℃. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 600 ℃ for 4 hours to obtain SiO 2 /SiZn 2 O 4 A composite material.
(2) 0.0167 mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、0.0167 mol Ni(CH 3 COO) 2 ·4H 2 O、0.0166 mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.1 mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, siO in (1) 2 /SiZn 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing the mixture in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 10h at 950 ℃ to obtain SiO 2 /SiZn 2 O 4 Modified spherical ternary sodium electric material Na 0.67 Mn 1/3 Ni 1/3 Fe 1/3 O 2 As shown in fig. 1.
Comparative example 1
0.0167 mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05mol CH 3 COONa、0.0167 mol Ni(CH 3 COO) 2 ·4H 2 O、0.0166 mol Fe(CH 3 COO) 2 ·4H 2 Dissolving O in 100 ml deionized water, adding 0.1 mol of citric acid, stirring at 80deg.C for reacting, and mixing to form gel-like mixtureAnd (3) a compound. After gel is formed, 5 mmol of tetraethoxysilane is added into the gel-like mixture, stirring reaction is continued for 1h, then the mixture is dried for 12h at 120 ℃, then the mixture is placed into a muffle furnace for high-temperature sintering, after presintering for 2h at 300 ℃, the mixture is further sintered for 10h at 950 ℃ to obtain SiO 2 Modified ternary sodium-electric material Na 0.67 Mn 1/3 Ni 1/3 Fe 1/3 O 2 。
Comparative example 2
(1) 2.5 mmol of ethyl orthosilicate and 5 mmol of Zn (NO 3 ) 2 Dissolved in 50ml of ethanol, 5g of citric acid was added thereto, and the mixture was stirred continuously to effect a reaction. Then ammonia water is added dropwise, the pH value is regulated to 8.5, and the reaction is continued for 4 hours. It was then placed in an oil bath to react to sol by heating at 80 ℃. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 600 ℃ for 4 hours to obtain SiZn 2 O 4 A composite material.
(2) 0.0167 mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、0.0167 mol Ni(CH 3 COO) 2 ·4H 2 O、0.0166 mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.1 mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, siZn in (1) 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing the mixture in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 10h at 950 ℃ to obtain SiZn 2 O 4 Modified ternary sodium-electric material Na 0.67 Mn 1/3 Ni 1/3 Fe 1/3 O 2 。
Example 2
(1) 5 mmol of ethyl orthosilicate and 5 mmol of Ni (NO 3 ) 2 Dissolved in 50ml of ethanol, and after adding 8g of citric acid, the reaction was carried out with stirring. Then ammonia water is added dropwise, the pH value is adjusted to 8, and the reaction is continued for 4 hours. Then placing it in an oil bath pan to heat at 60 deg.C for reactionIs applied to sol. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 500 ℃ for 4 hours to obtain SiO 2 /SiNi 2 O 4 A composite material.
(2) 0.0167 mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、0.0167 mol Ni(CH 3 COO) 2 ·4H 2 O、0.0166 mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.05mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, siO in (1) 2 /SiNi 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 10h at 800 ℃ to obtain SiO 2 /SiNi 2 O 4 Modified ternary sodium-electric material Na 0.67 Mn 1/3 Ni 1/3 Fe 1/3 O 2 And uses this as the positive electrode material active material.
Example 3
(1) 5 mmol of ethyl orthosilicate and 5 mmol of Mg (NO 3 ) 2 Dissolved in 50ml of ethanol, 5g of citric acid was added thereto, and the mixture was stirred continuously to effect a reaction. Then ammonia water is added dropwise, the pH value is regulated to 8.5, and the reaction is continued for 4 hours. Then it was put in an oil bath to heat and react at 90 ℃ to sol state. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 800 ℃ for 20 hours to obtain SiO 2 /SiMg 2 O 4 A composite material.
(2) 0.0167 mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、0.0167 mol Ni(CH 3 COO) 2 ·4H 2 O、0.0166 mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.1 mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, siO in (1) 2 /SiMg 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 2h at 1100 ℃ to obtain SiO 2 /SiMg 2 O 4 Modified ternary sodium-electric material Na 0.67 Mn 1/3 Ni 1/3 Fe 1/3 O 2 。
Example 4
(1) 2.5 mmol of ethyl orthosilicate and 2.5 mmol of Ni (NO 3 ) 2 Dissolved in 50ml of ethanol, 5g of citric acid was added thereto, and the mixture was stirred continuously to effect a reaction. Then ammonia water is added dropwise, the pH value is regulated to 8.5, and the reaction is continued for 4 hours. It was then placed in an oil bath to react to sol by heating at 80 ℃. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 600 ℃ for 4 hours to obtain SiO 2 /SiNi 2 O 4 A composite material.
(2) 0.0167 mol of Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、0.0167 mol Ni(CH 3 COO) 2 ·4H 2 O、0.0166 mol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.05mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, siO in (1) 2 /SiNi 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 10h at 1000 ℃ to obtain SiO 2 /SiNi 2 O 4 Modified ternary sodium-electric material Na 0.67 Mn 1/3 Ni 1/3 Fe 1/3 O 2 。
Example 5
(1) 5 mmol of ethyl orthosilicate and 5 mmol of Ni (NO 3 ) 2 Dissolved in 50ml of ethanol, and after adding 8g of citric acid, the reaction was carried out with stirring. Then dropwise adding ammonia water, adjusting the pH value to 8, and continuing the reaction4h. Then it was placed in an oil bath to perform a heating reaction at 60 ℃ to a sol state. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 500 ℃ for 4 hours to obtain SiO 2 /SiNi 2 O 4 A composite material.
(2) 0.0334 mol Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、8.35 mmol Ni(CH 3 COO) 2 ·4H 2 O、8.35 mmol Fe(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.05mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After gel formation, siO in (1) 2 /SiNi 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 10h at 800 ℃ to obtain SiO 2 /SiNi 2 O 4 Modified ternary sodium-electric material Na 0.67 Mn 2/3 Ni 1/6 Fe 1/6 O 2 And uses this as the positive electrode material active material.
Example 6
(1) 5 mmol of ethyl orthosilicate and 5 mmol of Ni (NO 3 ) 2 Dissolved in 50ml of ethanol, and after adding 8g of citric acid, the reaction was carried out with stirring. Then ammonia water is added dropwise, the pH value is adjusted to 8, and the reaction is continued for 4 hours. Then it was placed in an oil bath to perform a heating reaction at 60 ℃ to a sol state. The sol-like product was dried in a vacuum oven at 120℃for 12h. Sintering the dried gel at 500 ℃ for 4 hours to obtain SiO 2 /SiNi 2 O 4 A composite material.
(2) 0.0334 mol Mn (CH) 3 COO) 2 ·4H 2 O、0.05 mol CH 3 COONa、8.35 mmol Ni(CH 3 COO) 2 ·4H 2 O、8.35 mmol Co(CH 3 COO) 2 ·4H 2 O was dissolved in 100 ml deionized water, 0.05mol of citric acid was added, and the reaction was stirred well at 80℃until a gel-like mixture was formed. After forming gelSiO in (1) 2 /SiNi 2 O 4 Adding the composite material into the gel-like mixture, continuously stirring and reacting for 1h, drying for 12h at 120 ℃, placing in a muffle furnace for high-temperature sintering, presintering for 2h at 300 ℃, and further sintering for 10h at 800 ℃ to obtain SiO 2 /SiNi 2 O 4 Modified ternary sodium-electric material Na 0.67 Mn 2/3 Ni 1/6 Co 1/6 O 2 And uses this as the positive electrode material active material.
The battery assembly was completed by the following method:
the ternary sodium electromaterials obtained in examples 1-4 and comparative examples 1-2 are respectively used as positive electrode materials, mixed with conductive agent Acetylene Black (AB) and binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, and mixed with N-methylpyrrolidone (NMP) serving as a solvent in a small beaker at the speed of 800r/min for 2 hours to obtain slurry. Coating the slurry on a current collector aluminum foil by using an automatic coating machine, horizontally placing the current collector aluminum foil on toughened glass, transferring the toughened glass into a vacuum drying oven at 85 ℃ for drying for 4 hours, preparing a pole piece with the diameter of 12mm by using a punching sheet, then drying the pole piece at 105 ℃ for 4 hours in the vacuum drying oven, placing the pole piece in a glove box with the water content and the oxygen content being lower than 0.1ppm and filled with argon atmosphere for 4 hours to reduce the water absorbed by the pole piece in the transferring process, and then assembling the CR2032 button cell in the glove box. Rolling metal sodium into sheet, blanking into 14mm round sodium sheet to serve as anode, and adding NaClO of 1mol/L 4 The solution was used as an electrolyte and a glass fiber membrane having a diameter of 16mm was used as a separator. The battery assembly was completed with aging for 12 hours.
The specific discharge capacity of the cells after 100 cycles at a current density of 1C at a voltage of 2-4V was measured and the results are shown in table 1.
TABLE 1
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. A sodium electric precursor material is characterized by comprising a composite material modified matrix material, wherein the molecular formula of the matrix material is NaMn (1-x) N x Cit, wherein Cit is citrate, N is at least one of Fe, ni, co, cu, zn, al, mg, ti, x is more than or equal to 0.1 and less than or equal to 0.5; the molecular formula of the composite material is SiO 2 /M 2 SiO 4 Wherein M is at least one of Ni, zn and Mg; the composite material is prepared by the following steps: dispersing metal salts of tetraethoxysilane and M in ethanol, then adding citric acid, stirring, dropwise adding ammonia water, and regulating the pH value; continuously reacting the reaction materials to sol state under the heating state; drying and sintering the sol-like product to obtain SiO 2 /M 2 SiO 4 A composite material; the molar ratio of the added metal salt of the tetraethoxysilane to the metal salt of the M to the citric acid is 1:1: 5-10.
2. The method of preparing a sodium electric precursor material according to claim 1, comprising the steps of:
step S1, dispersing metal salts of tetraethoxysilane and M in ethanol, then adding citric acid, stirring, dropwise adding ammonia water, and regulating the pH value; continuously reacting the reaction materials to sol state under the heating state; drying and sintering the sol-like product to obtain SiO 2 /M 2 SiO 4 A composite material; the molar ratio of the added metal salt of the tetraethoxysilane to the metal salt of the M to the citric acid is 1:1: 5-10;
s2, dissolving manganese salt, sodium salt and N salt in deionized water, adding citric acid, and reacting to form a gel-like mixture; siO is made of 2 /M 2 SiO 4 And adding the composite material into the gel-like mixture, stirring, and drying to obtain the sodium-electricity precursor material.
3. The method of claim 2, wherein the metal salt of M is at least one of nitrate, acetate, and oxalate.
4. The method according to claim 2 or 3, wherein in step S1, the pH is adjusted to 8 to 9; the temperature of the heating state is 60-90 ℃; the sintering temperature is 500-800 ℃, and the sintering time is 2-10 h.
5. The preparation method according to claim 2, wherein the manganese salt, sodium salt and N salt are one or two of acetate and nitrate.
6. The preparation method according to claim 2, wherein in step S2, the ratio of the sum of the molar amounts of the manganese salt, sodium salt and N salt to the molar amount of citric acid is 1 to 2:1, a step of; the reaction temperature is 60-100 ℃.
7. A sodium electric positive electrode material, characterized in that it is obtained by sintering the sodium electric precursor material according to claim 1 or by sintering the sodium electric precursor material prepared by the preparation method according to any one of claims 2 to 6.
8. The sodium electric positive electrode material of claim 7, wherein the sintering is divided into two segments of sintering: the sintering temperature of the first section is 300-600 ℃ and the sintering time is 1-8h; the temperature of the second-stage sintering is 800-1100 ℃, and the sintering time is 2-20 h.
9. A sodium ion battery comprising the sodium-electrical positive electrode material of claim 7 or 8.
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