CN114784241B - Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery - Google Patents

Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery Download PDF

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CN114784241B
CN114784241B CN202210385588.1A CN202210385588A CN114784241B CN 114784241 B CN114784241 B CN 114784241B CN 202210385588 A CN202210385588 A CN 202210385588A CN 114784241 B CN114784241 B CN 114784241B
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positive electrode
electrode material
ion battery
sodium ion
formula
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CN114784241A (en
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李亚迪
胡恒广
闫冬成
张广涛
王博
刘文渊
王维
郝艺
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Hebei Guangxing Semiconductor Technology Co Ltd
Beijing Yuanda Xinda Technology Co Ltd
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Hebei Guangxing Semiconductor Technology Co Ltd
Beijing Yuanda Xinda Technology Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • 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
    • 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
    • H01M4/485—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of sodium ion battery manufacturing, and discloses a sodium ion battery anode material, a preparation method thereof and a sodium ion battery. The molecular formula of the positive electrode material is NaNi x Ti y M z O 2 Formula (1); in the formula (1), the M element is selected from one of Fe, V, sn, mo, cr, cu; the M element comprises a low-valence M element and a high-valence M element, and the content molar ratio of the low-valence M element to the high-valence M element is 1:0.1-10; x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98; and placing the positive electrode material in an environment with the humidity of 10-30wt% for 10 days, wherein the pH value change value of the surface of the positive electrode material is not more than 0.01. The sodium ion battery prepared by the positive electrode material provided by the invention has excellent cycle stability and storage performance.

Description

Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
Technical Field
The invention relates to the technical field of sodium ion battery manufacturing, in particular to a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery.
Background
Currently, with the continuous development of new energy industries, people are urgently required to reduce the cost of raw materials while paying attention to energy storage density; due to uneven distribution of global lithium resources, the prices of raw materials such as lithium-containing ores are continuously increased in recent years, so that the manufacturing cost of batteries is continuously increased, and the continuous development of new energy industry is seriously hindered.
Wherein, sodium and lithium are in the same main group, the resources are very rich, and the sodium and the lithium have similar physical and chemical characteristics; when prepared into corresponding electrode materials, the material shows the property consistent with that of the positive electrode material of the lithium ion battery, and becomes one of the first choice for replacing the lithium ion battery.
Sodium ion batteries have great potential advantages: the sodium salt has rich raw material reserves and low price; na (Na) + Can be transported and transported in low concentration electrolyte; na (Na) + The aluminum does not react with aluminum, and the anode can adopt cheap aluminum foil as an electrode material; because the sodium ion battery has the characteristic of no need of overdischarge, the sodium ion battery is allowed to discharge to zero volt, and the energy density of the sodium ion battery is greatly improved.
In the whole sodium ion battery, the capacity and voltage of the positive electrode material directly influence the energy density of the system, and the cost of the positive electrode material also dominates, so that the requirement of the positive electrode material with stable structure, excellent performance and low price is a key for developing the sodium ion battery.
The existing sodium ion batteries mainly have three types: layered oxides, polyanionic compounds, prussian blue-based compounds.
The polyanion compound has a three-dimensional framework structure and rich sodium ion deintercalation channels, and has the advantages of high working voltage (> 3.5V), good power performance and good cycle stability (more than ten thousand weeks). However, the vanadium-based raw materials are generally sintered at high temperature, so that the cost is high, the cost is required to be reduced through the simplification of a synthesis method, and the problem of poor material conductivity also needs a reasonable solution strategy.
The discharge capacity and the working voltage of the Prlulan compound are moderate and not outstanding enough, and the interlayer water occupies the potential of sodium ions, so that the electrochemical reaction is seriously affected.
The layered oxide material has higher reversible specific capacity and more ideal electron conductivity, and is mainly divided into two types according to structural characteristics: o3 and P2. The P2 type material has low capacity and good multiplying power performance, but the matching difficulty of the whole battery is higher due to the limitation of sodium content in a crystal structure. The O3 type material has higher capacity and good commercial application prospect.
CN109449418A discloses a composite sodium ion positive electrode material with a core-shell structure and a preparation method thereof, and the scheme adopts a secondary sintering method to construct the core-shell structure, so that the problem of poor storage stability is solved, but secondary sintering consumes large energy, and sodium ion loss is serious after multiple times of sintering, so that the problem of poor cycling stability of a sodium ion battery is caused.
CN112968165a discloses a modified sodium ion positive electrode material, a modified sodium ion electrode and a preparation method, the solution is to introduce fluorine ions to replace oxygen ions so as to perform the modification function, but the obtained positive electrode material still has the problems of poor storage stability and sodium ion loss, so that the obtained sodium ion battery has poor cycle performance.
Therefore, how to develop a positive electrode material of a sodium ion battery with good storage stability and good cycle performance in air has great significance for developing the sodium ion battery.
Disclosure of Invention
The invention aims to solve the problems of poor storage stability and poor cycle stability of a sodium ion positive electrode material in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material for a sodium ion battery, characterized in that,the molecular formula of the positive electrode material is NaNi x Ti y M z O 2 Formula (1);
in the formula (1), the M element is selected from one of Fe, V, sn, mo, cr, cu; the M element comprises a low-valence M element and a high-valence M element, and the content molar ratio of the low-valence M element to the high-valence M element is 1:0.1-10;
x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98;
and placing the positive electrode material in an environment with the humidity of 10-30wt% for 10 days, wherein the pH value change value of the surface of the positive electrode material is not more than 0.01.
Preferably, the molar ratio of the low-valence M element to the high-valence M element is 1:1-10.
Preferably, in formula (1), x is 0.15 to 0.3, y is 0.15 to 0.3, and z is 0.45 to 0.85.
In a second aspect, the present invention provides a method for preparing the sodium ion positive electrode material according to the first aspect, the method comprising the steps of:
(1) Mixing sodium carbonate, nickel oxide, titanium dioxide and oxide containing M element in a first contact manner to obtain a first mixture, and sintering the first mixture to obtain a first solid material; the total molar amount of sodium carbonate calculated as sodium element is the sum of the initial amount a and the supplementary amount k;
(2) In the presence of a solvent, carrying out second contact mixing on the first solid material and the A auxiliary agent to obtain a second solid material, and drying the second solid material; the A auxiliary agent is at least one selected from phosphoric acid, ammonium chloride and ammonium fluoride;
wherein a is greater than 0, and k is calculated according to the formula shown in formula (2);
k＝[(2.18T 1 ×t+(T 1 -T 0 ) 2 ]121680V, formula (2);
in formula (2), T 0 Indicating the initial temperature of the sintering process, DEG C;
T 1 the sintering treatment temperature, DEG C;
t represents the heat preservation time of sintering treatment, and h;
v represents the temperature rising rate of the sintering treatment, min.
Preferably, in the step (1), the nickel oxide is used in an amount of (0.01 to 0.3) a mole, the titanium dioxide is used in an amount of (0.01 to 0.3) a mole, and the oxide containing the M element is used in an amount of (0.4 to 0.98) a mole, relative to the initial amount of a mole of the sodium carbonate in terms of the sodium element.
Preferably, in step (1), the conditions of the sintering treatment include at least: the temperature rising rate is 2-5 ℃/min, the temperature is 800-950 ℃, and the heat preservation time is 2-30h.
Preferably, in step (2), the amount of the A auxiliary agent is 2-5wt% based on the total weight of the first solid material.
Preferably, in step (2), the conditions of the second contact mixing include at least: the temperature is 20-40 ℃ and the time is 2-6h.
Preferably, in step (2), the conditions of the drying treatment include at least: the temperature is 100-150 ℃ and the time is 2-4h.
The third aspect of the invention provides a sodium ion battery, wherein the positive electrode material in the sodium ion battery is the positive electrode material of the sodium ion battery in the first aspect.
The sodium ion battery prepared by the positive electrode material provided by the invention has excellent cycle stability and storage performance, and particularly, the capacity retention rate of the sodium ion battery obtained by the invention is improved, and the specific discharge capacity is still maintained above 92% after 100 cycles of cycle.
Drawings
Fig. 1 is a graph showing the cycle capacity of a battery formed of the positive electrode materials prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise stated, the room temperature or the normal temperature represents 25.+ -. 2 ℃.
The first aspect of the invention provides a positive electrode material of a sodium ion battery, which is characterized in that the molecular formula of the positive electrode material is NaNi x Ti y M z O 2 Formula (1);
in the formula (1), the M element is selected from one of Fe, V, sn, mo, cr, cu; the M element comprises a low-valence M element and a high-valence M element, and the content molar ratio of the low-valence M element to the high-valence M element is 1:0.1-10;
x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98;
and placing the positive electrode material in an environment with the humidity of 10-30wt% for 10 days, wherein the pH value change value of the surface of the positive electrode material is not more than 0.01.
In the invention, the low-valence M element and the high-valence M element refer to low-valence and high-valence of the same element contained in the positive electrode material, and when the M element is copper, the positive electrode material can contain +1-valence cuprous ions and +2-valence copper ions at the same time; when the M element is iron, the positive electrode material can contain ferrous ions with the valence of +2 and ferric ions with the valence of +3.
Preferably, the molar ratio of the low-valence M element to the high-valence M element is 1:1-10. The inventors found that in this preferred embodiment, a sodium ion battery having more excellent cycle stability and storage stability can be obtained.
Preferably, in formula (1), x is 0.15 to 0.3, y is 0.15 to 0.3, and z is 0.45 to 0.85. The inventors have found that in this preferred embodiment, a sodium ion battery is obtained that has more excellent electrochemical properties.
In a second aspect, the present invention provides a method for preparing the sodium ion positive electrode material according to the first aspect, the method comprising the steps of:
(1) Mixing sodium carbonate, nickel oxide, titanium dioxide and oxide containing M element in a first contact manner to obtain a first mixture, and sintering the first mixture to obtain a first solid material; the total molar amount of the sodium carbonate is the sum of the initial amount a and the supplementary amount k;
(2) In the presence of a solvent, carrying out second contact mixing on the first solid material and the A auxiliary agent to obtain a second solid material, and drying the second solid material; the A auxiliary agent is at least one selected from phosphoric acid, ammonium chloride and ammonium fluoride;
wherein a is greater than 0, and k is calculated according to the formula shown in formula (2);
k＝[(2.18T 1 ×t+(T 1 -T 0 ) 2 ]121680V, formula (2);
in formula (2), T 0 Indicating the initial temperature of the sintering process, DEG C;
T 1 the sintering treatment temperature, DEG C;
t represents the heat preservation time of sintering treatment, and h;
v represents the temperature rising rate of the sintering treatment, min.
The inventor finds that the preparation method provided by the invention can accurately supplement the dosage of sodium carbonate in the research process, and avoids the problem of poor battery cycle performance caused by sodium ion loss.
Preferably, in the step (1), the nickel oxide is used in an amount of (0.01 to 0.3) a mole, the titanium dioxide is used in an amount of (0.01 to 0.3) a mole, and the oxide containing the M element is used in an amount of (0.4 to 0.98) a mole, relative to the initial amount of a mole of the sodium carbonate in terms of the sodium element.
Preferably, in step (1), the conditions of the first contact mixing include at least: the temperature is 20-40 ℃ and the time is 2-6h.
Preferably, in step (1), the conditions of the sintering treatment include at least: the temperature rising rate is 2-5 ℃/min, the temperature is 800-950 ℃, and the heat preservation time is 2-30h. More preferably, in step (1), the conditions of the sintering treatment include at least: the temperature rising rate is 2-5 ℃/min, the temperature is 800-900 ℃, and the heat preservation time is 5-24h. The inventor finds that the specific embodiment in the preferred case can effectively reduce the energy consumption on the premise of ensuring the cycle stability of the sodium ion battery.
Preferably, in step (2), the amount of the A auxiliary agent is 2-5wt% based on the total weight of the first solid material. The inventors found that with this preferred embodiment, a sodium ion battery is obtained that has more excellent cycle stability and storage stability.
Preferably, in step (2), the conditions of the second contact mixing include at least: the temperature is 20-40 ℃ and the time is 2-3.5h.
Preferably, in step (2), the conditions of the drying treatment include at least: the temperature is 100-150 ℃ and the time is 2-4h.
The third aspect of the invention provides a sodium ion battery, wherein the positive electrode material in the sodium ion battery is the positive electrode material of the sodium ion battery in the first aspect.
The present invention will be described in detail by examples. In the following examples, all of the raw materials used were commercial products unless otherwise specified.
A auxiliary agent: ammonium fluoride, available from a company of ala Ding Yaopin;
in the examples below, sodium carbonate, nickel oxide, titanium dioxide, copper oxide, cuprous oxide, ferric oxide, ferrous oxide, and ethanol are all analytical and purification reagents.
Example 1
The embodiment provides a method for preparing a positive electrode material of a sodium ion battery, which comprises the following steps:
(1) Mixing sodium carbonate, nickel oxide, titanium dioxide, ferric oxide and ferrous oxide according to a molar ratio of 1.03:0.15:0.15:0.45:0.375 (wherein the initial amount of sodium carbonate calculated as sodium element is 1 mol and the supplementary amount is 0.03 mol) in a first contact manner to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein, the conditions of the first contact mixing are: the temperature is room temperature and the time is 4 hours;
the sintering treatment conditions are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 hours;
(2) Dissolving 3.51g of A auxiliary agent (accounting for 3wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material for second contact mixing to obtain a second solid material, and drying the second solid material to obtain the sodium ion battery anode material NaNi 0.15 Ti 0.15 Fe 0.825 O 2 ；
Wherein the conditions of the second contact mixing are: the temperature is room temperature and the time is 2 hours;
the conditions of the drying treatment are as follows: the temperature was 120℃and the time was 2 hours.
Example 2
The embodiment provides a method for preparing a positive electrode material of a sodium ion battery, which comprises the following steps:
(1) Mixing sodium carbonate, nickel oxide, titanium dioxide, ferric oxide and ferrous oxide according to a molar ratio of 1.03:0.3:0.3:0.25:0.225 (wherein the initial amount of sodium carbonate calculated as sodium element is 1 mol and the supplementary amount is 0.03 mol) in a first contact manner to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein, the conditions of the first contact mixing are: the temperature is room temperature and the time is 4 hours;
the sintering treatment conditions are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 hours;
(2) Dissolving 3.41g of A auxiliary agent (accounting for 3wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material for second contact mixing to obtain a second solid material, and drying the second solid material to obtain the sodium ion battery anode material NaNi 0.3 Ti 0.3 Fe 0.475 O 2 ；
Wherein the conditions of the second contact mixing are: the temperature is room temperature and the time is 2 hours;
the conditions of the drying treatment are as follows: the temperature was 120℃and the time was 2 hours.
Example 3
The embodiment provides a method for preparing a positive electrode material of a sodium ion battery, which comprises the following steps:
(1) Mixing sodium carbonate, nickel oxide, titanium dioxide, ferric oxide and ferrous oxide according to a molar ratio of 1.03:0.15:0.15:0.4:0.45 (wherein the initial use amount of sodium carbonate calculated as sodium element is 1 mol and the supplementary use amount is 0.03 mol) in a first contact manner to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein, the conditions of the first contact mixing are: the temperature is room temperature and the time is 4 hours;
the sintering treatment conditions are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 5 ℃/min, the sintering treatment temperature is 800 ℃, and the heat preservation time is 20h;
(2) Dissolving 5.92g of A auxiliary agent (accounting for 5wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material for second contact mixing to obtain a second solid material, and drying the second solid material to obtain the sodium ion battery anode material NaNi 0.15 Ti 0.15 Fe 0.85 O 2 ；
Wherein the conditions of the second contact mixing are: the temperature is room temperature and the time is 2 hours;
the conditions of the drying treatment are as follows: the temperature was 150℃and the time was 2 hours.
Example 4
A method for producing a sodium ion cathode material was conducted in accordance with the method of example 1, except that in step (1), sodium carbonate, nickel oxide, titanium oxide, iron oxide and ferrous oxide were used in a molar ratio of 1.03:0.1:0.1:0.5:0.45 (wherein the initial amount of sodium carbonate as elemental sodium was 1 mol, and the supplemental amount was 0.03 mol).
The other steps are the same as those of example 1 to obtain NaNi as the positive electrode material of the sodium ion battery 0.15 Ti 0.15 Fe 0.95 O 2 。
Comparative example 1
A method of preparing a sodium ion positive electrode material according to the method of example 1, except that step (2) is not performed;
the method specifically comprises the following steps:
sodium carbonate, nickel oxide, titanium dioxide, ferric oxide and ferrous oxide are subjected to first contact mixing according to the molar ratio of 1.03:0.15:0.15:0.45:0.375 (wherein the initial use amount of sodium carbonate calculated as sodium element is 1 mol and the supplementary use amount is 0.03 mol) to obtain a first mixture, and the first mixture is subjected to sintering treatment to obtain the sodium ion battery anode material NaNi 0.15 Ti 0.15 Fe 0.825 O 2 ；
Wherein, the conditions of the first contact mixing are: the temperature is room temperature and the time is 4 hours;
the sintering treatment conditions are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 hours.
Comparative example 2
A method for preparing a sodium ion cathode material according to the method of example 1, except that in step (1), iron oxide and ferrous oxide are not added;
the method specifically comprises the following steps:
(1) Mixing sodium carbonate, nickel oxide and titanium dioxide in a first contact mode according to a molar ratio of 1.03:0.5:0.5 (wherein the initial use amount of the sodium carbonate calculated as sodium element is 1 mol and the supplementary use amount is 0.03 mol) to obtain a first mixture, and sintering the first mixture to obtain a first solid material;
wherein, the conditions of the first contact mixing are: the temperature is room temperature and the time is 4 hours;
the sintering treatment conditions are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 hours;
(2) 3.25g of A auxiliary agent (3 wt% based on the total weight of the first solid material) was dissolved in 100mL of ethanol, and then the first solid material obtained above was added to carry out the secondContact mixing to obtain a second solid material, and drying the second solid material to obtain a sodium ion battery anode material NaNi 0.5 Ti 0.5 O 2 ；
Wherein the conditions of the second contact mixing are: the temperature is room temperature and the time is 4 hours;
the conditions of the drying treatment are as follows: the temperature was 120℃and the time was 2 hours.
Comparative example 3
A method for producing a sodium ion cathode material according to the method of example 1, except that in step (1), sodium carbonate, nickel oxide, titanium dioxide, iron oxide and ferrous oxide are mixed in a first contact at a molar ratio of 1.03:0.215:0.28:0.05:0.65 (wherein the initial amount of sodium carbonate as elemental sodium is 1 mole and the supplemental amount is 0.03 mole), to obtain a first mixture, and the first mixture is subjected to a sintering treatment to obtain a first solid material;
wherein, the conditions of the first contact mixing are: the temperature is room temperature and the time is 4 hours;
the sintering treatment conditions are as follows: the initial temperature of the sintering treatment is 20 ℃, the heating rate is 3 ℃/min, the sintering treatment temperature is 900 ℃, and the heat preservation time is 24 hours;
(2) Dissolving 3.60g of A auxiliary agent (accounting for 3wt% of the total weight of the first solid material) in 100mL of ethanol, adding the obtained first solid material for second contact mixing to obtain a second solid material, and drying the second solid material to obtain the sodium ion battery anode material NaNi 0.215 Ti 0.28 Fe 0.7 O 2 ；
Wherein the conditions of the second contact mixing are: the temperature is room temperature and the time is 4 hours;
the conditions of the drying treatment are as follows: the temperature was 120℃and the time was 2 hours.
Test example 1
The positive electrode materials (5 g) in examples and comparative examples were dissolved in 100g of deionized water, respectively, to obtain suspensions, and then the suspensions were tested using a pH meter (meltretolido S400-K), to obtain pH values; the positive electrode material was placed in a space having a humidity of 20%, and after 10 days, the pH was again measured by the aforementioned method, and the specific test results are shown in table 1.
TABLE 1
Examples numbering First day After 10 days
Example 1 10.32 10.33
Example 2 10.38 10.37
Example 3 10.35 10.36
Example 4 10.33 10.33
Comparative example 1 12.08 12.82
Comparative example 2 10.67 10.68
Comparative example 3 10.37 10.36
As can be seen from the results in Table 1, the pH value of the surface of the positive electrode material prepared by the method is reduced, and the pH value is changed by only 0.01 after ten days; whereas comparative example 1 changed by 0.74 after ten days, it was demonstrated that the surface of the positive electrode material prepared in comparative example 1 had undergone a chemical reaction with air.
Test example 2
The positive electrode materials prepared by the adhesive PTFE, the conductive carbon black, the examples and the comparative examples are fully mixed and coated on an aluminum foil according to the mass ratio of 1:2:7 to obtain a pole piece loaded with active substances, and the loading is controlled to be 6mg/cm 2 Vacuum (vacuum degree is 133 Pa) preserving the heat of the cut pole piece (with the diameter of 12 mm) for 6 hours at 120 ℃, cooling to room temperature, transferring into a glove box filled with argon (the content of water and oxygen is less than 0.01 ppm), sequentially assembling the CR2032 battery by taking a sodium piece as a half battery cathode, sodium perchlorate as electrolyte and glass fiber as a diaphragm.
The conditions of the charge and discharge test are as follows: the working voltage range is set to 2V-4.2V, circulation is carried out at the multiplying power of 1C, the discharge specific capacities of the 1 st round, the 10 th round, the 50 th round and the 100 th round are respectively recorded after one hundred circles are circulated, the capacity retention rate is calculated, and the specific test results are shown in Table 2.
Capacity retention ratio 1: (10 th-cycle specific discharge capacity/1 st-cycle specific discharge capacity) ×100%;
capacity retention ratio 2: (50 th-cycle specific discharge capacity/1 st-cycle specific discharge capacity) ×100%;
capacity retention ratio 3: (specific discharge capacity at 100 th turn/specific discharge capacity at 1 st turn) ×100%.
TABLE 2
As can be seen from the results of table 2, the sodium ion battery formed by the positive electrode material prepared by the method of the present invention has more excellent specific discharge capacity and capacity retention rate.
The present invention exemplarily provides a battery cycle capacity map formed using the positive electrode materials prepared in example 1 and comparative example 1, see fig. 1.
As can be seen from fig. 1, the battery prepared from the positive electrode material provided by the invention has more excellent specific discharge capacity and capacity retention rate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (10)

1. The positive electrode material of the sodium ion battery is characterized in that the molecular formula of the positive electrode material is shown as a formula (1);
NaNi x Ti y M z O 2 formula (1);
in the formula (1), M is Fe; the M element comprises a low-valence M element and a high-valence M element, and the content molar ratio of the low-valence M element to the high-valence M element is 1:0.1-10;
x is 0.01-0.3, y is 0.01-0.3, and z is 0.4-0.98;
and placing the positive electrode material in an environment with the humidity of 10-30wt% for 10 days, wherein the pH value change value of the surface of the positive electrode material is not more than 0.01.
2. The positive electrode material according to claim 1, wherein the molar ratio of the lower valence M element to the higher valence M element is 1:1 to 10.
3. The positive electrode material according to claim 1 or 2, wherein in the formula (1), x is 0.15 to 0.3, y is 0.15 to 0.3, and z is 0.45 to 0.85.
4. A method for preparing the positive electrode material of a sodium ion battery according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) Mixing sodium carbonate, nickel oxide, titanium dioxide and oxide containing M element in a first contact manner to obtain a first mixture, and sintering the first mixture to obtain a first solid material; the total molar amount of sodium carbonate calculated as sodium element is the sum of the initial amount a and the supplementary amount k;
(2) In the presence of a solvent, carrying out second contact mixing on the first solid material and the A auxiliary agent to obtain a second solid material, and drying the second solid material; the A auxiliary agent is at least one selected from phosphoric acid, ammonium chloride and ammonium fluoride;
wherein a is greater than 0, and k is calculated according to the formula shown in formula (2);
k＝[(2.18T 1 ×t+(T 1 -T 0 ) 2 ]121680V, formula (2);
in formula (2), T 0 Indicating the initial temperature of the sintering process, DEG C;
T 1 the sintering treatment temperature, DEG C;
t represents the heat preservation time of sintering treatment, and h;
v represents the temperature rising rate of the sintering treatment, min.
5. The method according to claim 4, wherein in the step (1), the nickel oxide is used in an amount of (0.01 to 0.3) a mole, the titanium dioxide is used in an amount of (0.01 to 0.3) a mole, and the oxide containing the M element is used in an amount of (0.4 to 0.98) a mole, relative to a mole of the sodium carbonate in terms of sodium element.
6. The method of claim 4, wherein in step (1), the sintering process conditions include at least: the temperature rising rate is 2-5 ℃/min, the temperature is 800-950 ℃, and the heat preservation time is 2-30h.
7. The method according to any one of claims 4 to 6, wherein in step (2) the a auxiliary is used in an amount of 2 to 5wt% based on the total weight of the first solid material.
8. The method according to any one of claims 4-6, wherein in step (2), the conditions of the second contact mixing include at least: the temperature is 20-40 ℃ and the time is 2-6h.
9. The method according to any one of claims 4 to 6, wherein in step (2), the conditions of the drying treatment include at least: the temperature is 100-150 ℃ and the time is 2-4h.
10. A sodium ion battery, wherein the positive electrode material in the sodium ion battery is the positive electrode material of the sodium ion battery described in any one of claims 1 to 3.
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