CN116344798A - Positive electrode material of sodium ion battery and sodium ion battery - Google Patents

Positive electrode material of sodium ion battery and sodium ion battery Download PDF

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CN116344798A
CN116344798A CN202310248702.0A CN202310248702A CN116344798A CN 116344798 A CN116344798 A CN 116344798A CN 202310248702 A CN202310248702 A CN 202310248702A CN 116344798 A CN116344798 A CN 116344798A
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positive electrode
electrode material
sodium ion
ion battery
transition metal
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张津晶
何广
陈客举
姚秋实
周贤机
张欢
虞风杨
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Zhejiang Xinna New Material 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
    • H01M4/48—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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
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    • 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

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Abstract

The invention discloses a sodium ion battery anode material and a sodium ion battery, and relates to the field of sodium ion batteries. The positive electrode material can exist stably in the aqueous solution, effectively solves the inaccurate phenomenon of testing residual alkali on the surface of the sodium ion positive electrode material in the aqueous solution, provides technical support for the development of the water washing process of the sodium ion positive electrode material, and further improves the viscosity stability of the slurry stirring material in the air. The sodium ion battery assembled with the positive electrode material has higher discharge capacity, and lays a foundation for the application of the sodium ion battery in the field of energy storage.

Description

Positive electrode material of sodium ion battery and sodium ion battery
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a sodium ion battery anode material and a sodium ion battery.
Background
With the development of society, the problems of energy shortage and environmental pollution caused by excessive consumption of fossil energy are increasingly serious, and the sustainable development of human society is seriously affected. Therefore, the development of renewable energy sources such as solar energy, wind energy, tidal energy and the like is a necessary trend. However, renewable energy sources (wind energy, solar energy and the like) are discontinuous and unstable, and are difficult to be utilized in a grid connection mode. Therefore, the large-scale energy storage technology is a bottleneck technology for realizing popularization and application of renewable energy sources, and a low-cost and environment-friendly energy storage material and technology are needed to provide continuous and stable energy output. Among the energy storage modes, the lithium ion battery is widely applied to the fields of portable electronic equipment and electric automobiles due to the advantages of high charge and discharge voltage, no memory effect, high energy density, small self-discharge, long service life and the like. However, lithium resources are limited in reserves and are extremely unevenly distributed, severely limiting their application in the field of large-scale energy storage.
Sodium ion batteries are becoming research hot spots in the field of large-scale energy storage due to the fact that sodium reserves are abundant (the abundance of Na in the crust is 1000 times that of Li), uniform distribution and low cost. However, na has a larger ionic radius than Li, and has a similar structure with a different atomic occupation, and the Na cannot be directly used as a positive electrode material of a sodium ion battery by being hard-sleeved. The resurgence of suitable electrode materials for sodium-ion batteries is critical to the practical and industrial use of sodium-ion batteries. The layered transition metal oxide has the advantages of high reversible capacity, proper operation voltage, simple synthesis method and the like, and is a sodium ion battery anode material with great application potential. The layered sodium oxide currently faces three challenges of irreversible phase change during charge and discharge, unstable electrode-electrolyte interface under high voltage, and poor air stability during storage and preparation. For air stability problems, although a few documents mention mechanisms such as surface decomposition, oxygen oxidation, water intercalation, proton intercalation into sodium layer, etc.; researchers at scientific research institutes such as Xiamen university, chinese academy of chemistry, chinese academy of physics, dalhousie University, etc. have proposed layered oxide materials that are stable in air, respectively. However, up to now, scientific researchers lack deep and systematic knowledge of the reaction mechanism of layered sodium ion oxides in humid air, and the design principle of air-stable layered sodium ion oxides is still blank, which greatly hinders development and practical application of the materials.
And the general transition metal oxide sodium salt is unstable in aqueous solution, and the structure of the exposed layered oxide changes more severely along with the increase of relative humidity and the appearance of carbon dioxide, wherein sodium element in a bulk phase can be dissolved in water, so that the problems of reduced sodium content of the transition metal oxide sodium salt, increased pH value of the aqueous solution, incapability of accurately testing the residual alkali content on the surface of the positive electrode material in a water system and the like are caused, the possibility of reducing the residual alkali on the surface of the transition metal oxide sodium salt through a water washing process is further limited, and the problem of incapability of using the transition metal oxide sodium salt due to increased viscosity caused by contact with moisture in air after slurry mixing of the material is further caused.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a sodium ion battery positive electrode material and a sodium ion battery, wherein the sodium ion battery positive electrode material is a positive electrode material stably existing in an aqueous solution, and the specific sodium ion positive electrode material is transition metal oxide sodium salt and has a layered structure.
The technical scheme of the invention is as follows:
the invention provides a positive electrode material of a sodium ion battery, which has a layered structure and a molecular formula shown as a formula (1):
Na α A β Ni x Mn y Fe z O γ (1)
In the formula (1), the element A is at least one selected from Ca, ce, pr, la, nd, ni;
0＜α≤1，0＜β≤0.3，1.7＜γ＜3.5，x+y+z＝1，0≤x＜1、0＜y≤1/2、0＜z≤1/2。
in the embodiment of the present invention, when x=0, that is, the ferro-manganese composite hydroxide (Fe 0.5 Mn 0.5 (OH) 2 ) The sodium carbonate, the calcium oxalate and the nickel oxide are prepared according to the mol ratio (1:0.33:0.02:0.3) to obtain the anode material Na 0.66 Ca 0.02 Ni 0.3 Mn 0.5 Fe 0.5 O 2 。
Preferably, the element a is selected from at least one of Pr, ce, la, nd.
Preferably, alpha is more than 0.66 and less than or equal to 0.95,0.02, beta is more than or equal to 0.3, gamma=2, x+y+z=1, x is more than or equal to 1/4 and less than or equal to 1/3, y is more than or equal to 1/3 and z is more than or equal to 1/4 and less than or equal to 1/3.
The invention also provides a preparation method of the sodium ion battery anode material, which comprises the following steps: mixing sodium salt, a transition metal compound or a transition metal composite hydroxide and a structural stabilizer, and performing a heat treatment reaction to obtain the sodium ion battery anode material; the ratio of the ion radius of the element A to the sodium ion radius is 0.95-1.05, and the equivalent ion radius is easier to be embedded into a crystal lattice in the process of preparing the material, so that the local electron distribution is changed, and the crystal lattice energy is improved and is more stable.
The sodium salt is sodium carbonate;
the transition metal compound is at least one of ferric oxide, ferrous oxide and manganese oxide; and/or a transition metal composite hydroxide, wherein the transition metal composite hydroxide is obtained by dissolving water-soluble transition metal salt in water, adding alkali liquor, stirring and filtering; the water-soluble transition metal salt is at least two of water-soluble ferric salt, water-soluble manganese salt and water-soluble nickel salt;
the structural stabilizer is at least one of calcium carbonate, calcium oxalate, cerium carbonate, lanthanum oxalate, neodymium oxalate and praseodymium oxalate.
Preferably, the water-soluble ferric salt is at least one of ferric sulfate and ferric sulfate hydrate; the water-soluble manganese salt is at least one of manganese sulfate and manganese sulfate hydrate; the water-soluble nickel salt is at least one of nickel sulfate and nickel sulfate hydrate.
The metal element of the additive is introduced into the transition metal compound in situ by a coprecipitation method, and the steps are as follows: dissolving water-soluble nickel salt, water-soluble manganese salt, water-soluble ferric salt and deionized water, dissolving NaOH in deionized water, simultaneously dripping 3 solutions into a stirrer for reaction to obtain the iron-manganese-nickel composite hydroxide, and filtering, washing and drying the iron-manganese-nickel composite hydroxide for use.
The specific steps of the coprecipitation method and solid phase sintering are as follows:
dissolving water-soluble ferric salt and water-soluble manganese salt in deionized water, dissolving NaOH in the deionized water, simultaneously dropwise adding 2 solutions into a stirrer for reaction, filtering to obtain the ferro-manganese composite hydroxide, filtering, washing and drying the ferro-manganese composite hydroxide, mixing the ferro-manganese composite hydroxide with sodium salt, a structure stabilizer and an additive, and calcining to obtain the anode material.
The mixing mode is ball milling, sand milling or high mixing, and the mixing time is 5-20h.
Preferably, when a transition metal compound is used, the temperature of the heat treatment reaction is 800 to 900 ℃ and the reaction time is 15 to 25 hours;
preferably, the temperature of the heat treatment reaction is 840-870 ℃ and the reaction time is 18-20 hours
When the transition metal composite hydroxide is used, the heat treatment reaction mode is that pre-sintering is performed firstly, and then high-temperature sintering is performed; the presintering temperature is 400-600 ℃, the presintering time is 4-10 h, the high-temperature sintering temperature is 800-1000 ℃, and the high-temperature sintering time is 8-22 h;
preferably, the high-temperature sintering time is 15-20 hours.
Preferably, the mass ratio of the transition metal compound to the additive, the sodium salt and the structural stabilizer is 7-95: 3-60:1, wherein the mass ratio of the transition metal compound to the additive is 1:0 to 1;
the additive is nickel oxide.
The invention also provides a positive electrode, which comprises a positive electrode current collector and the positive electrode material of the sodium ion battery, wherein the positive electrode material is arranged on one side or two side surfaces of the positive electrode current collector.
The invention also provides a sodium ion battery which comprises the positive electrode.
The invention also provides a detection method which can rapidly judge whether the sodium element in the positive electrode material phase is stable in water, and comprises the following steps:
grinding and sieving the positive electrode material by 100-200 meshes to obtain a sieved positive electrode material sample; preparing slurry with a certain concentration by using deionized water, under the condition of constant temperature, stirring and ultrasonic for 30 seconds, then testing the pH value record value m1 of the slurry by using a pH meter, stirring and ultrasonic for 5 minutes, then testing the pH value record data m2 of the slurry again, ultrasonic for 5 minutes, then testing the pH value record data m3 of the slurry again, and calculating that the absolute value of m1-m2 is less than or equal to 0.2 and the absolute value of m2-m3 is less than or equal to 0.05, so that the anode material stably exists in the aqueous solution.
The slurry comprises a screened positive electrode, deionized water and a dispersing agent;
the mass fraction of the positive electrode material is 8-20%, preferably 10-15%;
the dispersing agent is one or more of sodium hexametaphosphate, sodium pyrophosphate and sodium tripolyphosphate;
the mass fraction of the dispersing agent is 1-5%, preferably 2-3%;
the stirring can be magnetic stirring and electric stirring, the speed is 100-300 r/min, and the preferable rotating speed is 150r/min;
the ultrasonic frequency is 10-30 KHz, preferably 20-25 KHz;
the constant temperature is 20-30 ℃, preferably 25 ℃.
The invention has the beneficial effects that: the method for introducing the structure stabilizer is simple and effectively improves the unstable phenomenon that the sodium element in the bulk phase of the transition metal oxide sodium salt in the aqueous solution gradually reacts and dissolves, provides technical support for the development of a method for testing the residual alkali content of the anode material by taking the aqueous solution as a solvent and a material washing process, has strong universality, and is applicable to both solid-phase method and liquid-phase method synthesis. The invention also provides a rapid detection method for judging the stability of bulk phase elements of the positive electrode material.
The positive electrode material can exist stably in the aqueous solution, so that the inaccurate phenomenon of testing residual alkali on the surface of the sodium ion positive electrode material in the aqueous solution is effectively solved, technical support is provided for the development of a water washing process of the sodium ion positive electrode material, and the viscosity stability of the slurry stirring material in the air is further improved. The sodium ion battery assembled with the positive electrode material has higher discharge capacity, and lays a foundation for the application of the sodium ion battery in the field of energy storage.
The above-mentioned advantages are achieved by the starting materials not shown in the examples and by the related derivatives.
Drawings
FIG. 1 is an electron microscopic view of the positive electrode material (D1-1) prepared in comparative example 1.
FIG. 2 is an electron microscopic view of the positive electrode material (D2-1) prepared in comparative example 2.
FIG. 3 is an XRD pattern of the positive electrode materials (D2-1, D2-2) in comparative example 2.
Fig. 4 is a graph showing the discharge capacity change of the positive electrode materials (D1-1 and D1-2) prepared in comparative example 1.
FIG. 5 is a graph showing the cycle performance of the positive electrode materials (D1-1 and D1-2) prepared in comparative example 1.
Fig. 6 is a graph showing the variation of discharge capacity of the positive electrode materials (S7-1 and S7-2) prepared in example 7.
FIG. 7 is a cycle performance chart of the positive electrode materials (S7-1 and S7-2) prepared in example 7.
Detailed Description
Comparative example 1
FeSO in a molar ratio of 1:1 4 ·7H 2 O、MnSO 4 ·H 2 Dissolving O in deionized water to prepare a metal salt solution with the concentration of 1.5mol/L, dissolving 90g of sodium hydroxide in 540g of deionized water to prepare an alkali solution with the concentration of 2mol/L, dripping the metal salt solution and the alkali solution into a reaction kettle together, stirring for reaction for 4 hours, rapidly filtering by suction filtration to form a filter cake, and continuously washing by using 0.5L of deionized water for three timesDrying the mixture by using a blast oven at 120 ℃ to obtain Fe-Mn composite hydroxide 1/ 2 Mn 1/2 (OH) 2 . Putting the iron-manganese composite hydroxide and sodium carbonate into a mixer according to the molar ratio (1:0.33), adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, mixing for 4 hours, taking out a sample, putting into a muffle furnace, setting 5 ℃/min, heating to 500 ℃, preserving heat for 5 hours, continuing 5 ℃/min, heating to 870 ℃ and preserving heat for 22 hours, thus obtaining the anode material Na 0.66 Mn 0.5 Fe 0.5 O 2 (D1-1)。
The positive electrode material was tested by using Shimadzu XRD-6000 model equipment, and a distinct 002 characteristic peak was observed, which was illustrated as a layered material.
Mixing the positive electrode material (D1-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity D1-1.
The testing method comprises the following steps: under the condition of constant temperature, stirring and ultrasonic treatment for 30 seconds, using a PH meter to test the PH value record value m1 of the slurry, stirring and ultrasonic treatment for 5 minutes, then testing the PH value record data m2 of the slurry again, ultrasonic treatment for 5 minutes, then testing the PH value record data m3 of the slurry again, and calculating that the absolute value of m1-m2 is less than or equal to 0.2 and the absolute value of m2-m3 is less than or equal to 0.05, so that the anode material stably exists in the aqueous solution.
The above positive electrode materials were mixed with deionized water at a mass ratio of 1:15 to prepare a slurry, which was tested using the above test method using a Kexing instrument model MSP-2C magnetic stirrer and a Metrele-tolidof FE-20 PH meter, and the results obtained are shown in Table 1.
TABLE 1
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 12.65 13.05 13.30
Drying, grinding and crushing the slurry in a blast oven at 120 ℃, performing heat treatment in a muffle furnace at 250 ℃ for 5 hours, and cooling to obtain the anode material (D1-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, and 002 characteristic peaks and obvious impurity peaks can be observed, which indicates that the material is unstable due to impurity phases.
Mixing the positive electrode material (D1-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity D1-2.
Comparative example 2
FeSO is added in a molar ratio of 1:2:1 4 ·7H 2 O、MnSO 4 ·H 2 O、NiSO 4 ·6H 2 O is dissolved in deionized water to prepare a metal salt solution with the concentration of 1.5mol/L, 90g of sodium hydroxide is dissolved in 540g of deionized water to prepare an alkali solution with the concentration of 2mol/L, the metal salt solution and the alkali solution are added into a reaction kettle together in a dropwise manner, stirred and reacted for 4 hours, filtered, washed and dried to obtain the Fe-Mn-Ni composite hydroxide Ni 0.25 Mn 0.5 Fe 0.25 (OH) 2 . Putting the iron-manganese-nickel composite hydroxide and sodium carbonate into a mixer according to the molar ratio of 1:0.4, adding zirconium balls for mixing, wherein the ball-material ratio is 3:1, mixing for 4 hours, taking out a sample, putting into a muffle furnace, setting 5 ℃/min, heating to 500 ℃, preserving heat for 6 hours, continuing 5 ℃/min, heating to 870 ℃ and preserving heat for 20 hours, thus obtaining the anode material Na 0.8 Mn 0.5 Fe 0.25 Ni 0.25 O 2 (D2-1)。
The positive electrode material was tested by using Shimadzu XRD-6000 model equipment, and a distinct 003 characteristic peak was observed, which was described as a layered material.
Mixing the positive electrode material (D2-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling measurement capacity D2-1 by taking metal sodium as a negative electrode.
The above positive electrode materials were mixed with deionized water at a mass ratio of 1:15 to prepare a slurry, which was tested using a Koxing instrument MSP-2C model magnetic stirrer and a Metrele-tolidof FE-20 model PH meter using the test method in comparative example 1, and the results obtained are shown in Table 2.
TABLE 2
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 12.85 13.15 13.25
Drying, grinding and crushing the slurry in a blast oven at 120 ℃, performing heat treatment in a muffle furnace at 250 ℃ for 5 hours, and cooling to obtain the anode material (D2-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, and a 003 characteristic peak and an obvious impurity peak can be observed, so that the material is unstable due to the occurrence of impurity phases.
Mixing the positive electrode material (D2-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity D2-2.
Comparative example 3
Putting ferrous oxide, manganese oxide, sodium carbonate and nickel oxide with the molar ratio of 1:1:1.5:1 into a mixer in proportion, adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, taking out a sample after mixing for 4 hours, putting into a muffle furnace, setting 5 ℃/min, heating to 870 ℃, and preserving heat for 18 hours to obtain a positive electrode material NaNi 1/3 Mn 1/3 Fe 1/3 O 2 (D3-1)，
The positive electrode material (D3-1) was tested using Shimadzu XRD-6000 model equipment, and a distinct 003 characteristic peak was observed, which was described as a layered material.
Mixing the positive electrode material (D3-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling measurement capacity D3-1 by taking metal sodium as a negative electrode.
The above cathode materials were mixed with deionized water at a mass ratio of 1:20 to prepare a slurry, which was tested using a magnetic stirrer and a PH meter using the test method of comparative example 1, and the results obtained are shown in table 3.
TABLE 3 Table 3
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 12.85 13.13 13.33
Drying, grinding and crushing the slurry in a blast oven at 120 ℃, performing heat treatment in a muffle furnace at 250 ℃ for 5 hours, and cooling to obtain the positive electrode material (D3-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, and a 003 characteristic peak and an obvious impurity peak can be observed, so that the material is unstable due to the occurrence of impurity phases.
Mixing the positive electrode material (D3-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity D3-2.
Example 1
The iron-manganese composite hydroxide (Fe 0.5 Mn 0.5 (OH) 2 ) Adding sodium carbonate and calcium oxalate into a mixer according to the molar ratio (1:0.33:0.02), adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, mixing for 4 hours, taking out a sample, placing the sample into a muffle furnace, heating to 500 ℃ at 5 ℃/min, preserving heat for 5 hours, and continuously heating to 870 ℃ at 5 ℃/min, preserving heat for 22 hours to obtain the anode material Na 0.66 Ca 0.02 Mn 0.5 Fe 0.5 O 2 (S1-1)。
Mixing the positive electrode material (S1-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S1-1.
The above positive electrode materials were mixed with deionized water at a mass ratio of 1:15 to prepare a slurry, which was tested using a test method of comparative example 1, using a Kexing instrument model MSP-2C magnetic stirrer and a Metrele-tolidoFE model FE-20 PH meter, and the results obtained are shown in Table 4.
TABLE 4 Table 4
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 10.85 10.85 10.84
Drying, grinding and crushing the slurry in a blast oven at 120 ℃, performing heat treatment in a muffle furnace at 250 ℃ for 5 hours, and cooling to obtain the positive electrode material (S1-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 002 characteristic peaks can be observed, and no impurity peak at angles indicates that the material has no impurity phase and has stable structure.
Mixing the positive electrode material (S1-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S1-2.
Example 2
The iron-manganese composite hydroxide (Fe 0.5 Mn 0.5 (OH) 2 ) Adding sodium carbonate, calcium oxalate and nickel oxide into a mixer according to the molar ratio (1:0.33:0.02:0.3), adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, taking out a sample after mixing for 4 hours, placing the sample into a muffle furnace, setting 5 ℃/min to be heated to 400 ℃ for 4 hours, continuing 5 ℃/min to be heated to 840 ℃ for 18 hours, and obtaining the anode material Na 0.66 Ca 0.02 Ni 0.3 Mn 0.5 Fe 0.5 O 2 (S2-1)。
The positive electrode material was tested by using Shimadzu XRD-6000 model equipment, and a distinct 003 characteristic peak was observed, which was described as a layered material.
Mixing the positive electrode material (S2-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S2-1.
The above positive electrode materials were mixed with deionized water at a mass ratio of 1:15 to prepare a slurry, which was tested using a test method of comparative example 1 using a Kexing instrument MSP-2C model magnetic stirrer and a Metrele-tolidoFE-20 model PH meter, and the results obtained are shown in Table 5.
TABLE 5
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 10.80 10.81 10.81
The slurry is dried, ground and crushed in a blast oven at 120 ℃ and then is heat treated in a muffle furnace at 250 ℃ for 5 hours, and the positive electrode material is obtained after cooling (S2-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
Mixing the positive electrode material (S2-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S2-2.
Example 3
The iron-manganese-nickel composite hydroxide Ni prepared in comparative example 2 0.25 Mn 0.5 Fe 0.25 (OH) 2 . Putting iron-manganese-nickel composite hydroxide, sodium carbonate and neodymium oxalate into a mixer according to the molar ratio (1:0.4:0.1), adding zirconium balls for mixing, wherein the ball-material ratio is 3:1, taking out a sample after mixing for 4 hours, putting into a muffle furnace, setting 5 ℃/min to rise to 400 ℃ for heat preservation for 6 hours, continuing 5 ℃/min to rise to 800 ℃ for heat preservation for 8 hours, and obtaining the anode material Na under pure oxygen atmosphere 0.8 Nd 0.2 Mn 0.5 Fe 0.25 Ni 0.25 O 2 (S3-1)。
The positive electrode material was tested by using Shimadzu XRD-6000 model equipment, and a distinct 003 characteristic peak was observed, which was described as a layered material.
Mixing the positive electrode material, the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring the slurry, tabletting, drying, manufacturing a positive electrode plate, and manufacturing the buckling test capacity S3-1 by taking metal sodium as a negative electrode.
The above positive electrode materials were mixed with deionized water at a mass ratio of 1:15 to prepare a slurry, which was tested using a test method of comparative example 1, using a Kexing instrument model MSP-2C magnetic stirrer and a Metrele-tolidoFE model FE-20 PH meter, and the results obtained are shown in Table 6.
TABLE 6
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 10.95 10.96 10.96
Drying, grinding and crushing the slurry in a blast oven at 120 ℃, performing heat treatment in a muffle furnace at 250 ℃ for 5 hours, and cooling to obtain the positive electrode material (S3-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
Mixing the positive electrode material (S3-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S3-2.
Example 4
The iron-manganese-nickel composite hydroxide Ni prepared in comparative example 2 0.25 Mn 0.5 Fe 0.25 (OH) 2 . Putting the iron-manganese-nickel composite hydroxide, sodium carbonate and lanthanum oxalate into a mixer according to the molar ratio (1:0.4:0.05), adding zirconium balls for mixing, wherein the ball-material ratio is 3:1, taking out a sample after mixing for 4 hours, putting into a muffle furnace, setting 5 ℃/min to rise to 500 ℃ for heat preservation for 6 hours, continuing 5 ℃/min to rise to 900 ℃ for heat preservation for 22 hours, and obtaining the anode material Na 0.8 La 0.1 Mn 0.5 Fe 0.25 Ni 0.25 O 2 (S4-1)。
The positive electrode material (S4-1) was tested using Shimadzu XRD-6000 model equipment, and a distinct 003 characteristic peak was observed, which was described as a layered material.
Mixing the positive electrode material (S4-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling test capacity S4-1 by taking metal sodium as a negative electrode.
The above positive electrode materials were mixed with deionized water at a mass ratio of 1:15 to prepare a slurry, which was tested using a test method of comparative example 1, using a Kexing instrument model MSP-2C magnetic stirrer and a Metrele-tolidoFE model FE-20 PH meter, and the results obtained are shown in Table 7.
TABLE 7
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 11.05 11.05 11.05
The slurry is dried, ground and crushed in a blast oven at 120 ℃ and then is heat treated in a muffle furnace at 250 ℃ for 5 hours, and the positive electrode material is obtained after cooling (S4-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
Mixing the positive electrode material (S4-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S4-2.
Example 5
FeO, mnO, na in a molar ratio of 1:1:1.475:0.075:1 2 CO 3 、CaCO 3 Mixing NiO and zirconium balls in the ratio of 2 to 1 in a mixer, taking out the sample after mixing for 4 hr, and putting into a muffle furnaceSetting 5 ℃/min to rise to 870 ℃ and preserving heat for 18 hours to obtain the anode material Na 0.95 Ca 0.025 Ni 1/3 Mn 1/3 Fe 1/3 O 2 (S5-1)，
Mixing the positive electrode material (S5-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling test capacity S5-1 by taking metal sodium as a negative electrode.
The positive electrode material (S5-1) is prepared by the following components in mass ratio 1:20 and deionized water were mixed and slurried using the test method of comparative example 1, using a Kexing instrument model MSP-2C magnetic stirrer and a Metrele-tolidof-20 model PH meter, and the results obtained are shown in Table 8.
TABLE 8
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 11.02 11.03 11.03
The slurry is dried, ground and crushed in a blast oven at 120 ℃ and then is heat treated in a muffle furnace at 250 ℃ for 5 hours, and the positive electrode material is obtained after cooling (S5-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
Mixing the positive electrode material (S5-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S5-2.
Example 6
FeO, mnO, na in a molar ratio of 1:1:1.41:0.03:1 2 CO 3 、Ce(CO 3 ) 2 Putting NiO and zirconium balls into a mixer according to a proportion, adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, taking out a sample after mixing for 4 hours, putting into a muffle furnace, setting 5 ℃/min, heating to 900 ℃, and preserving heat for 18 hours to obtain a positive electrode material Na 0.94 Ce 0.02 Ni 1/3 Mn 1/3 Fe 1/3 O 2 (S6-1)，
Mixing the positive electrode material (S6-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling test capacity S6-1 by taking metal sodium as a negative electrode.
The positive electrode material (S6-1) is prepared by the following components in mass ratio 1:20 and deionized water were mixed and slurried using the test method of comparative example 1, using a Kexing instrument model MSP-2C magnetic stirrer and a Metrele-tolidof-20 model PH meter, and the results obtained are shown in Table 9.
TABLE 9
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 10.93 10.93 10.93
The slurry is dried, ground and crushed in a blast oven at 120 ℃ and then is heat treated in a muffle furnace at 250 ℃ for 5 hours, and the positive electrode material is obtained after cooling (S6-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
Mixing the positive electrode material (S6-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S6-2.
Example 7
FeO, mnO, na in a molar ratio of 1:1:1.41:0.03:1 2 CO 3 、La 2 (C 2 O 4 ) 3 Putting NiO and zirconium balls into a mixer according to a proportion, adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, taking out a sample after mixing for 4 hours, putting into a muffle furnace, setting 5 ℃/min, heating to 800 ℃, and preserving heat for 18 hours to obtain a positive electrode material Na 0.94 La 0.02 Ni 1/3 Mn 1/3 Fe 1/3 O 2 (S7-1)，
Mixing the positive electrode material (S7-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling test capacity S7-1 by taking metal sodium as a negative electrode.
The above positive electrode material (S7-1) was mixed with deionized water at a mass ratio of 1:20 to prepare a slurry, which was tested using a test method of comparative example 1 using a Kexing apparatus MSP-2C model magnetic stirrer and a Metrele-tolidoFE-20 model PH meter, and the results obtained are shown in Table 10.
Table 10
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 11.00 11.01 11.01
The slurry is dried, ground and crushed in a blast oven at 120 ℃ and then is heat treated in a muffle furnace at 250 ℃ for 5 hours, and the positive electrode material is obtained after cooling (S7-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
The positive electrode material (S7-2) was tested using Shimadzu XRD-6000 model equipment, and a distinct 003 characteristic peak was observed, indicating that the layered material was not destroyed.
Mixing the positive electrode material (S7-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S7-2.
Example 8
FeO, mnO, na in a molar ratio of 1:1:1.41:0.03:1 2 CO 3 、Pr 2 (C 2 O 4 ) 3 Putting NiO and zirconium balls into a mixer according to a proportion, adding zirconium balls for mixing, wherein the ball-material ratio is 2:1, taking out a sample after mixing for 4 hours, putting into a muffle furnace, setting 5 ℃/min, heating to 870 ℃, and preserving heat for 15 hours to obtain a positive electrode material Na 0.94 Pr 0.02 Ni 1/3 Mn 1/3 Fe 1/3 O 2 (S8-1)，
Mixing the positive electrode material (S8-1), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, preparing a positive electrode plate, and preparing the buckling test capacity S8-1 by taking metal sodium as a negative electrode.
The above positive electrode material (S8-1) was mixed with deionized water at a mass ratio of 1:20 to prepare a slurry, which was tested using a test method in comparative example 1 using a Kexing apparatus MSP-2C model magnetic stirrer and a Metrele-tolidoFE-20 model PH meter, and the results obtained are shown in Table 11.
TABLE 11
Stirring time 30 seconds For 5 minutes For 10 minutes
pH value of slurry 11.00 11.01 11.01
The slurry is dried, ground and crushed in a blast oven at 120 ℃ and then is heat treated in a muffle furnace at 250 ℃ for 5 hours, and the positive electrode material is obtained after cooling (S8-2). The positive electrode material is tested by using Shimadzu XRD-6000 model equipment, obvious 003 characteristic peaks are observed, the angles are free from impurity peaks, and the materials are free from impurity phases and stable in structure.
Mixing the positive electrode material (S8-2), the conductive agent and the adhesive according to the mass ratio of 9:0.5:0.5, stirring, tabletting, drying, manufacturing a positive electrode plate, and manufacturing a buckling test by taking metal sodium as a negative electrode to obtain the capacity S8-2.
Table 12
Figure BDA0004126999420000141
In comparative examples 1 to 3 and examples 1 to 8, the capacity obtained by buckling test was 0.2C discharge capacity, and the data are shown in table 12, which shows that the positive electrode material can exist stably in an aqueous solution when a structural stabilizer is added, so that the inaccuracy phenomenon of the residual alkali on the surface of the sodium ion positive electrode material in the test in the aqueous solution is effectively solved, and the viscosity stability of the stirring slurry material in the air is further improved, so that the sodium ion battery assembled with the positive electrode material has higher discharge capacity.
As can be seen from fig. 1 to 3, the positive electrode materials prepared in the comparative examples were not stable in aqueous solutions, and the morphology of the positive electrode materials before and after the slurry preparation and the drying was significantly different. Meanwhile, as can be seen from fig. 4 to 7, the capacity and the cycle performance (about 83%) of the cathode material prepared in the comparative example after being dried after being prepared into a slurry were drastically reduced, while the capacity and the cycle performance (about 93%) of the cathode material prepared in the examples before and after being dried after being prepared into a slurry were not significantly changed.

Claims (10)

1. The positive electrode material of the sodium ion battery is characterized by being of a layered structure, and the molecular formula of the positive electrode material of the sodium ion battery is shown as formula (1):
Na α A β Ni x Mn y Fe z O γ (1),
in the formula (1), the element A is at least one selected from Ca, ce, pr, la, nd, ni;
0＜α≤1，0＜β≤0.3，1.7＜γ＜3.5，x+y+z＝1，0≤x＜1、0＜y≤1/2、0＜z≤1/2。
2. the positive electrode material for sodium ion battery according to claim 1, wherein the a element is at least one selected from Pr, ce, la, nd.
3. The positive electrode material for sodium ion battery according to claim 1, wherein 0.66 < α.ltoreq. 0.95,0.02 < β.ltoreq.0.3, γ=2, x+y+z=1, 1/4.ltoreq.x.ltoreq.1/3, 1/3.ltoreq.y.ltoreq.1/2, 1/4.ltoreq.z.ltoreq.1/3.
4. A method for preparing a positive electrode material for a sodium ion battery according to any one of claims 1 to 3, comprising the steps of: mixing sodium salt, a transition metal compound or a transition metal composite hydroxide and a structural stabilizer, and performing a heat treatment reaction to obtain the sodium ion battery anode material;
the sodium salt is sodium carbonate;
the transition metal compound is at least one of ferric oxide, ferrous oxide and manganese oxide; and/or a transition metal composite hydroxide, wherein the transition metal composite hydroxide is obtained by dissolving water-soluble transition metal salt in water, adding alkali liquor, stirring and filtering; the water-soluble transition metal salt is at least two of water-soluble ferric salt, water-soluble manganese salt and water-soluble nickel salt;
the structural stabilizer is at least one of calcium carbonate, calcium oxalate, cerium carbonate, lanthanum oxalate, neodymium oxalate and praseodymium oxalate.
5. The method according to claim 4, wherein the water-soluble ferric salt is at least one of ferric sulfate and ferric sulfate hydrate; the water-soluble manganese salt is at least one of manganese sulfate and manganese sulfate hydrate; the water-soluble nickel salt is at least one of nickel sulfate and nickel sulfate hydrate.
6. The method of claim 4, wherein the mixing is performed by ball milling or sand milling for a period of 5 to 20 hours.
7. The process according to claim 4, wherein when a transition metal compound is used, the temperature of the heat treatment reaction is 800 to 900℃and the reaction time is 15 to 25 hours;
preferably, the temperature of the heat treatment reaction is 840-870 ℃, and the reaction time is 18-20 hours;
when the transition metal composite hydroxide is used, the heat treatment reaction mode is that pre-sintering is performed firstly, and then high-temperature sintering is performed; the presintering temperature is 400-600 ℃, the presintering time is 4-10 h, the high-temperature sintering temperature is 800-1000 ℃, and the high-temperature sintering time is 8-22 h;
preferably, the high temperature sintering time is 15-20 hours.
8. The preparation method according to claim 4, wherein the mass ratio of the transition metal compound to the additive, the sodium salt and the structure stabilizer is 7-95: 3 to 60:1, the mass ratio of the transition metal compound and the additive is 1:0-1;
the additive is nickel oxide.
9. A positive electrode comprising a positive electrode current collector and the sodium ion battery positive electrode material according to any one of claims 1 to 3 provided on one or both side surfaces of the positive electrode current collector.
10. A sodium ion battery comprising the positive electrode of claim 9.
CN202310248702.0A 2023-03-10 2023-03-10 Positive electrode material of sodium ion battery and sodium ion battery Pending CN116344798A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117352743A (en) * 2023-12-01 2024-01-05 宁德时代新能源科技股份有限公司 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, battery and electricity utilization device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117352743A (en) * 2023-12-01 2024-01-05 宁德时代新能源科技股份有限公司 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, battery and electricity utilization device
CN117352743B (en) * 2023-12-01 2024-04-12 宁德时代新能源科技股份有限公司 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, battery and electricity utilization device

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