CN116344775A - 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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CN116344775A
CN116344775A CN202310441268.8A CN202310441268A CN116344775A CN 116344775 A CN116344775 A CN 116344775A CN 202310441268 A CN202310441268 A CN 202310441268A CN 116344775 A CN116344775 A CN 116344775A
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phase
positive electrode
equal
sodium ion
ion battery
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何广
杨泽龙
周玲
邬财浩
姚秋实
周贤机
张欢
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • 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 first phase material prepared by the invention has a polycrystalline mechanism, and the particle size of primary particles can be adjusted, so that reversible deintercalation of sodium ions is facilitated, and the capacity and the multiplying power performance of the electrode material are improved; the structural stabilizer is added into the first phase, and the second phase sodium material with controllable thickness is generated through in-situ reaction on the surface of the first phase, so that the composite material has a high stable structure for water, and the stability of air and water of the composite material is fundamentally stabilized through coating the surface of the first phase, so that the storage property of the material is thoroughly solved; the interface problem between the composite material and the electrolyte under high charging voltage can be adapted, the structural stability of the composite material under high potential is improved, and side reactions are reduced; the composite material has higher reversible discharge capacity, and compared with other coating layers, the composite material has the advantages that the discharge capacity of the composite material is not sacrificed while the first phase material is protected.

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
In recent years, new energy lithium battery industry in China makes great progress, but lithium carbonate price surge caused by factors such as serious unbalance of lithium resource distribution, rapid development of lithium battery industry and the like is also required to be seen, and the lithium carbonate is gradually a new strategic material. The sodium electric technology has the advantages that the raw materials and the performances are equivalent to those of lithium electric, and the sodium reserves are extremely rich and are uniformly distributed in the crust. The strong development of sodium electricity accords with the energy safety strategy of China and can cater to the huge market space in the future such as energy storage.
The layered oxide cathode material in several technical routes of the sodium ion battery has the advantages of high theoretical specific capacity, large optimization space of component structures, reference to lithium battery materials in the industrialization process and the like, and is a key material for sodium ion battery industrialization. Meanwhile, the layered material also has the challenges of poor stability under air, poor processability, poor actual capacity, and the like. The components of the layered material have great influence on performance, and in general, the sodium-rich phase material has higher discharge capacity, but has poor stability under air, and is easy to absorb water, so that poor processability and cycle life are caused; the sodium-poor phase material has a low capacity, but some components have high interfacial stability. Aiming at the air stability problem, the Xiamen university research team system researches the water absorption mechanism of the materials, and finds that certain materials with high sodium removal potential have very good stability and can be decomposed even in water under humid air, but the comprehensive properties of the materials such as circulation capacity and the like cannot meet the actual requirements (Zuo, W., qiau, J., liu, X.et a1.The stability of P2-layered sodium transitionmetal oxides in ambient atm circuits. Nat Commun11, 3544 (2020)); for high capacity materials, the interface stability can be improved by doping, etc., but either complete avoidance of hydrolysis is difficult to achieve (Xie, wu Feng, huang Yongxin. Sodium ion battery advanced technology and application, national heavy duty publication engineering, 2020.), or large-scale mass production of the solution is difficult. Therefore, the reasonable design of the components and the structure of the layered material balances the critical performance parameters such as capacity, processability, service life and the like, plays a role in the rapid industrialization, and has no effective solution for comprehensively improving the performances such as water absorption, capacity and the like at present.
Disclosure of Invention
Based on the obvious defects of the prior art, the invention provides a preparation process of a sodium ion layered anode material and application of the sodium ion layered anode material in sodium ion batteries. The invention provides a preparation technology of a composite layered material, which realizes high discharge capacity, high rate performance, long cycle life, excellent processability and the like through double design of components and structures of an electrode material, and is applied to a sodium ion battery. The required raw materials of the invention, such as the transition metal oxide precursor, can be purchased from mature material enterprises or self-made without decisive influence on the technology of the invention. In addition, the preparation process is simple, the preparation of the finished product material can be realized only by two sintering processes, the processes such as extra water washing and presintering are not needed, and the preparation process is basically compatible with the equipment of the current lithium battery layered material, and is very suitable for large-scale mass production.
The technical scheme of the invention is as follows:
the invention provides a sodium ion battery anode material, which comprises a first phase structural material and a second phase structural material;
the molecular formula of the first phase structure material is as follows: na (Na) a M b Ni c Fe a Mn e O 2 ，
Wherein M is selected from at least one of Al, ti, ca, cu, K, sn, li, mg, co, ag, ce, ba; a is more than or equal to 1.0 and less than or equal to 1.1, b is more than or equal to 0 and less than or equal to 0.05,0.2, c is more than or equal to 0.5, d is more than or equal to 0.2 and less than or equal to 0.4,0.3 and e is more than or equal to 0.4;
the molecular formula of the second phase structural material is as follows: na (Na) x N w Ni y Mn z O 2 ，
Wherein N is at least one selected from Mn, ni, ca, al, mg, zn; x is more than or equal to 0.5 and less than or equal to 0.7,0.0, y is more than or equal to 0.33,0.62, z is more than or equal to 0.8, and w is more than or equal to 0.05 and less than or equal to 0.1;
the second phase structural material is coated on the first phase structural material, and the surface of the first phase structural material grows in situ to form the second phase structural material.
Preferably, the first phase structure material accounts for 81-99% of the mass of the positive electrode material of the sodium ion battery; the second phase structural material accounts for 1-20% of the mass of the sodium ion battery anode material. Wherein the optimum molar ratio of the first phase to the second phase is 90:10.
Specifically, the first phase structure material is a layered structure, and the second phase structure material is a layered structure or a three-dimensional structure.
Preferably, M is selected from at least one of Ti, sn, K, ca.
The first phase material of the positive electrode of the sodium ion battery has a polycrystalline morphology, and the primary nano particles have large specific surface area, so that active sites are increased, the electrode reaction activity is improved, and the discharge capacity of the electrode is improved; the phenomena of water absorption, deliquescence and the like of the material are relieved through micro doping in the structure, and certain stability is maintained; the second material phase is introduced on the basis, is formed on the surface of the first material phase in situ, has high stability, can stably exist in water and contributes to capacity in a battery, in the two-phase composite structure, the second phase serves as a protective layer to keep the structural stability of the first phase in the interior, the processing performance degradation caused by water absorption is avoided, the first phase serves as a main phase to exert high capacity characteristic, a stable sodium source is provided for the second phase material, the second phase is kept in a shallow-flushing shallow-discharging process all the time, and the structural stability of the first phase can be continuously protected.
The invention also provides a preparation method of the sodium ion battery anode material, which comprises the following steps:
(1) Mixing and sintering a nickel-iron-manganese hydroxide precursor and a sodium source to prepare a first phase structure material;
(2) Mixing and sintering the first phase structural material prepared in the step (1) and the nano precursor, and preparing a second phase structural material on the surface of the first phase structural material through in-situ reaction to obtain the sodium ion battery anode material;
the nanometer precursor is NiO, al 2 O 3 、ZnO、MgCO 3 、Ni 2 O 3 、Mn 2 O 3 、MnO 2 、CaCO 3 、CaO、MgO、TiO 2 At least one of them.
The precursor of the sintered first phase material is prepared by a coprecipitation process, is usually purchased or self-made, and has a molecular formula of: ni (Ni) c Fe d Mn e (OH) 2 Wherein, c is more than or equal to 0.2 and less than or equal to 0.5, d is more than or equal to 0.2 and less than or equal to 0.4,0.3, and e is more than or equal to 0.4;
the sodium source is Na 2 C 2 O 4 、Na 2 CO 3 、NaHCO 3 At least one of HCOONa and NaOH.
The first phase material is prepared by sintering a precursor and a sodium source, wherein the sintering atmosphere is air or oxygen, the sintering temperature of the first phase is 850-900 ℃, and the sintering time is 15-18 hours;
the second phase material is prepared by in-situ reaction on the surface of the first phase material, the sintering atmosphere is air or oxygen, the sintering temperature of the second phase is 850-950 ℃, and the sintering time is 5-15 hours.
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 the two side surfaces of the positive electrode current collector.
The invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and organic electrolyte, wherein the positive electrode is the positive electrode.
The invention has the beneficial effects that:
(1) The first phase material prepared by the invention has a polycrystalline mechanism, and the particle size of primary particles can be adjusted. The nano structure provides rich reaction sites at the electrode/electrolyte interface, which is favorable for reversible deintercalation of sodium ions, thereby improving the capacity and rate capability of the electrode material;
(2) By adding the structure stabilizer into the first phase, the reaction of sodium ions with moisture and carbon dioxide in the air in the structure is inhibited in an atomic layer, so that the stability of the electrode is improved, and the stability of the electrode material in a humid environment is improved;
(3) By in situ reaction at the surface of the first phase, a second phase sodium material of controllable thickness is produced, which has three main functions: the composite material has the advantages that (a) the composite material has a high-stability structure to water, the stability of air and water of the composite material is fundamentally stabilized through coating the surface of a first phase, the storage and processing performance of the material are thoroughly solved, (b) the interface problem between the composite material and electrolyte under high charging voltage can be adapted, the structural stability of the composite material under high potential is improved, the occurrence of side reactions is reduced, and (c) the composite material has higher reversible discharge capacity, compared with other coating layers, the discharge capacity of the composite material is not sacrificed while the first phase material is protected.
(4) The invention fully considers the design and optimization of factors such as components, morphology, structure and the like of the electrode material, can improve the comprehensive performances of material processing and storage, discharge energy/multiplying power/circulation and the like through a simple sintering process, and has outstanding advantages in sodium ion batteries for power and energy storage.
Drawings
Fig. 1 is an XRD pattern of the positive electrode materials prepared in example 1 and comparative example 1.
Fig. 2 is an SEM image of the positive electrode materials prepared in example 1 and comparative example 1; wherein a is an SEM image of the positive electrode material prepared in example 1, and B is an SEM image of the positive electrode material prepared in comparative example 1.
Fig. 3 is a graph of gram capacity data of the positive electrode materials prepared in example 1 and comparative example 1.
Fig. 4 is a slurry diagram of the positive electrode materials prepared in example 2 and comparative example 2; wherein the left graph is the slurry of the positive electrode material prepared in example 2, and the right graph is the slurry of the positive electrode material prepared in comparative example 2.
Fig. 5 is a discharge capacity graph of a full cell equipped with the positive electrode materials of example 5 (first phase/second phase) and comparative example 3 (first phase).
Fig. 6 is a cycle performance chart of a full cell equipped with the positive electrode material of example 5 (first phase/second phase) and comparative example 3 (first phase).
Fig. 7 is a graph showing the gassing of the pouch cells equipped with the positive electrode materials of example 5 (left) and comparative example 3 (right).
Detailed Description
Example 1
Nickel-iron-manganese composite hydroxide Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 And anhydrous sodium carbonate Na 2 CO 3 Mixing in a mixer with the molar ratio of X (Fe+Mn+Ni) to Na of 1:1.05, the ball-material ratio of 2.5:1, taking out the sample after mixing for 2 hours, sintering in a box furnace, keeping the temperature rising speed at 5 ℃/min, keeping the temperature at 500 ℃ for 5 hours, and keeping the temperature at 850 ℃ for 18 hours at 5 ℃/min to obtain the polycrystalline anode material NaNi 0.33 Fe 0.33 Mn 0.33 O 2 。
Comparative example 1
Nickel-iron-manganese composite hydroxide Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 And anhydrous sodium carbonate Na 2 CO 3 Mixing in a mixer with the molar ratio of X (Fe+Mn+Ni) to Na of 1:1.0, the ball-material ratio of 2.5:1, taking out the sample after mixing for 2 hours, sintering in a box furnace, keeping the temperature rising speed at 5 ℃/min, keeping the temperature at 500 ℃ for 5 hours, and keeping the temperature at 950 ℃ for 30 hours at 5 ℃/min to obtain the monocrystal positive electrode material NaNi 0.33 Fe 0.33 Mn 0.33 O 2 。
Example 1 and comparative example 1 are control of polycrystalline and monocrystalline morphology and effect on discharge capacity. XRD and SEM characterization were performed on the positive electrode materials prepared in example 1 and comparative example 1, as shown in FIGS. 1 and 2, XRD demonstrated that both types of materials were pure phase O3 type crystal structures, but SEM pictures showed that the morphology of both types of materials was significantly different, the material in example 1 had a typical polycrystalline morphology, the primary particle size was around 100nm, the secondary particle size was 4-6 μm, and the material in comparative example 1 had a single crystal morphology, and the particle size was around 5 μm.
And (5) assembling the button cell by using the two types of materials for electrical performance evaluation. The positive electrode formulations of the two batteries are the same, and are all active materials: super P: PVDF=96:2.5:1.5, sodium metal sheet was used for the negative electrode, and 1mol NaPF was used as electrolyte 6 Dissolved in ec+pc (v: v=1:1). FIG. 3 shows that the gram capacity of the material in example 1 is about 5mAh/g higher than that of the material in comparative example 1 under the same test condition, and the polycrystalline material has better reaction sites and can better exert the high specific capacity characteristic of the material.
Example 2
Nickel-iron-manganese composite hydroxide Ni 0.27 Fe 0.3 Cu 0.03 Ti 0.05 Mn 0.35 (OH) 2 And anhydrous sodium oxalate Na 2 C 2 O 4 Putting the materials into a mixer according to the molar ratio of X (Fe+Mn+Ni+Cu+Ti) to Na of 1:1.03, mixing the materials with a ball material ratio of 2.5:1, taking out the samples after mixing for 2 hours, putting the samples into a box-type furnace for sintering, keeping the heating speed at 5 ℃/min, keeping the temperature at 500 ℃ for 5 hours, keeping the temperature at 5 ℃/min to 900 ℃ for 18 hours, and keeping the temperature at 5 ℃/min for anode Cu and Ti doped anode material Na 0.95 Ni 0.27 Fe 0.3 Cu 0.03 Ti 0.05 Mn 0.35 O 2 。
Example 3
Nickel-iron-manganese composite hydroxide Ni 0.28 Fe 0.3 Ca 0.04 Sn 0.05 Mn 0.35 (OH) 2 And sodium bicarbonate NaHCO 3 According to X (Fe+Mn+Ni+Ca+Sn): putting Na with a mole ratio of 1:1.03 into a mixer for mixing, wherein the ball material ratio is 2.5:1, taking out a sample after mixing for 2 hours, putting into a box-type furnace for sintering, keeping the heating speed at 5 ℃/min, keeping the temperature for 5 hours after heating to 500 ℃, continuing to keep the temperature at 5 ℃/min to 900 ℃ for 18 hours, and adding the positive electrode material NaNi doped with positive electrode Ca and Sn into the mixture 0.28 Fe 0.3 Ca 0.04 Sn 0.05 Mn 0.35 O 2 。
Example 4
Nickel-iron-manganese composite hydroxide Ni 0.3 Fe 0.27 K 0.03 Ti 0.05 Mn 0.35 (OH) 2 Adding sodium acetate HCOONa into a mixer according to the molar ratio of X (Fe+Mn+Ni+K+Ti) to Na of 1:1 for mixing, wherein the ball material ratio is 2.5:1, taking out a sample after mixing for 2 hours, putting the sample into a box-type furnace for sintering, keeping the heating speed at 5 ℃/min, keeping the temperature at 500 ℃ for 5 hours, keeping the temperature at 900 ℃ for 18 hours after the temperature is raised to 500 ℃, and keeping the temperature at 5 ℃/min, wherein positive electrode materials doped with positive electrode K and Ti are Na 0.95 Ni 0.3 Fe 0.27 K 0.03 Ti 0.05 Mn 0.35 O 2 。
Comparative example 2
Nickel-iron-manganese composite hydroxide Ni 0.3 Fe 0.3 Mn 0.4 (OH) 2 And anhydrous sodium oxalate Na 2 C 2 O 4 Mixing in a mixer with the molar ratio of X (Fe+Mn+Ni) to Na of 1:1.02, the ball-material ratio of 2.5:1, taking out the sample after mixing for 2 hours, sintering in a box furnace, keeping the temperature rising speed at 5 ℃/min, keeping the temperature at 500 ℃ for 5 hours, and keeping the temperature at 900 ℃ for 18 hours at 5 ℃/min to obtain the anode material NaNi 0.3 Fe 0.3 Mn 0.4 O 2 。
The two materials prepared in the above example 2 and comparative example 2 were mixed with deionized water at a mass ratio of 1:20 after being left for 48 hours in an environment with a relative humidity of 70%, and were prepared into slurries for pH testing, and the results are shown in table 1.The results show that Cu and Ti can improve the sensitivity of the material to moisture after being used as stabilizers for doping the material. Further, studies on the two materials show that the material in example 2 can maintain better slurry fluidity and viscosity when pole pieces are prepared under the environment of 70% relative humidity, and jelly gel phenomenon is obvious in the comparative example (fig. 4). This comparison shows that a small amount of stabilizer can slow down the adsorption and reaction of the material to water and improve the processing performance of the material.
TABLE 1
Stirring time 30 seconds For 1 minute 3 minutes
The pH of the slurry in example 2 11.36 11.52 11.65
pH of slurry in comparative example 2 12.27 12.99 13.85
Example 5
Nickel-iron-manganese composite hydroxide Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 Mixing with NaOH at a molar ratio of X (Fe+Mn+Ni) to Na of 1:1.1 in a mixer, mixing with a ball material ratio of 2.5:1, taking out the sample after mixing for 2 hr, sintering in a box furnace, maintaining the temperature at 5 deg.C/min, maintaining the temperature at 500 deg.C for 5 hr, continuing to maintain the temperature at 5 deg.C/min to 850 deg.C for 15 hr, naturally cooling to room temperature, and collecting the first phase material (Na 1.07 Ni 0.33 Fe 0.33 Mn 0.33 O 2 ) And (3) using. Mixing the sintered first phase material with nano Mn 2 O 3 NiO and CaCO 3 (molar ratio Mn) 2 O 3 ∶NiO∶CaCO 3 =31:33:5) and the ball-to-material ratio is equal toMixing for 1 hour at the ratio of 2:1, taking out the sample, putting the sample into a box-type furnace, and sintering at the temperature of 900 ℃ for 12 hours. Wherein the first phase and the second phase (formula Na 0.67 Ca 0.05 Mn 0.62 Ni 0.33 O 2 ) The molar ratio of (2) is 90:10.
Example 6
Nickel-iron-manganese composite hydroxide Ni 0.2 Fe 0.4 Mn 0.35 Ti 0.05 (OH) 2 And sodium hydroxide Na 2 CO 3 Mixing with a molar ratio of X (Fe+Mn+Ni+Ti) to Na of 1:1.1 in a mixer, mixing with a ball-material ratio of 2.5:1, taking out the sample after mixing for 2 hours, sintering in a box furnace, maintaining a heating rate of 5 ℃/min, heating to 500 ℃ and then maintaining the temperature for 5 hours, continuing to maintain the temperature at 5 ℃/min to 850 ℃ and maintaining the temperature for 15 hours, naturally cooling to room temperature, and obtaining a first phase material (Na 1.08 Ni 0.2 Fe 0.4 Mn 0.35 Ti 0.05 O 2 ) And (3) using. Mixing the sintered first phase material with nano Mn 2 O 3 ZnO and MgCO 3 (molar ratio Mn) 2 O 3 ∶ZnO∶MgCO 3 =40:10:10) and the ball-to-material ratio was 2:1, and after mixing for 1 hour, the sample was taken out and put into a box furnace for sintering at 870 ℃ for 12 hours. Wherein the first phase and the second phase (Na 0.5 Mn 0.8 Zn 0.05 Mg 0.05 O 2 ) The molar ratio of (2) is 90:10.
Example 7
Nickel-iron-manganese composite hydroxide Ni 0.5 Fe 0.18 Al 0.02 Mn 0.3 (OH) 2 Mixing with NaOH at molar ratio of X (Fe+Mn+Ni+A1) to Na of 1:1.05 in a mixer, mixing with ball material of 2.5:1, taking out sample after mixing for 2 hr, sintering in a box furnace, heating at 5 deg.C/min, heating to 500 deg.C, maintaining for 5 hr, heating to 850 deg.C at 5 deg.C/min, maintaining for 15 hr, naturally cooling to room temperature, and collecting the first phase material (Na 1.03 Ni 0.5 Fe 0.18 Mn 0.3 Al 0.02 O 2 ) And (3) using. Mixing the sintered first phase material with nano Al 2 O 3 ，NiO，Mn 2 O 3 And CuO (molar ratio Al) 2 O 3 ∶NiO∶Mn 2 O 3 CuO=5:20:33.5:10), the ball-to-material ratio is 2:1, the sample is taken out after mixing for 1 hour and put into a box-type furnace for sintering at 900 ℃ for 12 hours. Wherein the first phase and the second phase (Na 0.7 Ni 0.2 Al 0.1 Cu 0.1 Mn 0.67 O 2 ) The molar ratio of (2) is 95:5.
Comparative example 3
The first phase material in example 5 was cooled and no further treatment was performed.
(1) Sensitivity to moisture
The sensitivity of the materials prepared in example 5 and comparative example 3 to moisture is shown in table 2. The results show that the pH value of the composite phase material in the examples is very stable in water, the test time of 3 minutes is basically kept at about 11.5-11.6, and the pH value in the comparative examples is gradually increased along with the time, and the hydrolysis reaction is obvious. This comparison demonstrates the specific improvement in the moisture sensitivity of the second phase material of the examples over the composite.
TABLE 2
Stirring time 30 seconds For 1 minute 3 minutes
The pH of the slurry in example 5 11.58 11.55 11.61
pH of slurry in comparative example 3 11.99 12.42 12.76
(2) Discharge capacity
The two materials prepared in example 5 and comparative example 3 were assembled into a cylindrical battery, and the discharge capacity of the assembled battery of the two materials was measured. The positive electrode formulations of the two batteries are the same, and are all active materials: super P: PVDF=96:2.5:1.5, sodium metal sheet was used for the negative electrode, and 1mol NaPF was used as electrolyte 6 Dissolved in ec+pc (v: v=1:1). The experimental results are shown in fig. 5, and it can be seen that the capacity of the coated material is basically stable, which proves that the second phase material has certain activity and the overall performance of the battery is not reduced while the stability is improved.
(3) Cycle performance
Fig. 6 shows the cycle performance of the two materials of comparative example 5 and comparative example 3.
Experimental results show that under the same electrochemical window (1.5-3.95V), the capacity retention rate of the battery core prepared by the material of the example 5 is 97.7% at 300 cycles, and the capacity retention rate of the battery core prepared by the material of the comparative example 3 is only 95.1% under the same conditions, so that the composite material coated by the second phase is proved to have higher stability.
(4) Gas production phenomenon
Fig. 7 shows the gassing of the two materials of comparative example 5 and comparative example 3 in a pouch cell.
Experimental results show that under the same circulating condition (multiplying power 0.5C, window 1.5-3.95V), the soft package battery core manufactured in the embodiment 5 does not generate obvious gas after 500 cycles, and the material in the comparative example 3 cannot be normally used due to serious gas generation after 420 cycles.

Claims (10)

1. A sodium ion battery positive electrode material, characterized in that the sodium ion battery positive electrode material comprises a first phase structural material and a second phase structural material;
the molecular formula of the first phase structure material is as follows: na (Na) a M b Ni c Fe d Mn e O 2 ，
Wherein M is selected from at least one of Ti, cu, ca, K, sn, li, al, mg, co, ag, ce, ba; a is more than or equal to 0.95 and less than or equal to 1.1, b is more than or equal to 0 and less than or equal to 0.05,0.2, c is more than or equal to 0.5, d is more than or equal to 0.2 and less than or equal to 0.4,0.3 and e is more than or equal to 0.4;
the molecular formula of the second phase structural material is as follows: na (Na) x N w Ni y Mn z O 2 ，
Wherein N is at least one selected from Mn, ni, ca, al, mg, zn; x is more than or equal to 0.5 and less than or equal to 0.7,0.0, y is more than or equal to 0.33,0.62, z is more than or equal to 0.8, and w is more than or equal to 0.05 and less than or equal to 0.1;
the second phase structural material is coated on the first phase structural material, and the surface of the first phase structural material grows in situ to form the second phase structural material.
2. The positive electrode material of the sodium ion battery according to claim 1, wherein the first phase structure material accounts for 81-99% of the positive electrode material of the sodium ion battery; the second phase structural material accounts for 1-20% of the mass of the sodium ion battery anode material.
3. The sodium ion battery positive electrode material of claim 1, wherein M is selected from at least one of Ti, cu, sn, K, ca.
4. The positive electrode material of a sodium ion battery of claim 1, wherein the first phase structure material is a layered structure and the second phase structure material is a layered structure or a three-dimensional structure.
5. The method for preparing the positive electrode material of the sodium ion battery as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Mixing and sintering a nickel-iron-manganese hydroxide precursor and a sodium source to prepare a first phase structure material;
(2) Mixing and sintering the first phase structural material prepared in the step (1) and the nano precursor, and preparing a second phase structural material on the surface of the first phase structural material through in-situ reaction to obtain the sodium ion battery anode material;
the nanometer precursor is NiO, al 2 O 3 、ZnO、MgCO 3 、Ni 2 O 3 、Mn 2 O 3 、MnO 2 、CaCO 3 、CaO、MgO、TiO 2 At least one of them.
6. The method of preparing a positive electrode material for sodium ion battery according to claim 5, wherein the molecular formula of the nickel-iron-manganese hydroxide precursor in step (1) is: ni (Ni) c Fe d Mn e (OH) 2 Wherein, c is more than or equal to 0.2 and less than or equal to 0.5, d is more than or equal to 0.2 and less than or equal to 0.4,0.3, and e is more than or equal to 0.4;
the sodium source is Na 2 C 2 O 4 、Na 2 CO 3 、NaHCO 3 At least one of HCOONa and NaOH.
7. The method for preparing a positive electrode material for a sodium ion battery according to claim 5, wherein in the step (1), the sintering atmosphere is air or oxygen, the sintering temperature is 850-900 ℃, and the sintering time is 15-18 hours.
8. The method for preparing a positive electrode material for a sodium ion battery according to claim 5, wherein in the step (2), the sintering atmosphere is air or oxygen, the sintering temperature is 850-950 ℃, and the sintering time is 5-15 hours.
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 4 disposed on both side surfaces of the positive electrode current collector.
10. A sodium ion battery comprising a positive electrode, a negative electrode and an organic electrolyte, wherein the positive electrode is the positive electrode of claim 9.
CN202310441268.8A 2023-04-18 2023-04-18 Positive electrode material of sodium ion battery and sodium ion battery Pending CN116344775A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116914126A (en) * 2023-09-13 2023-10-20 深圳华钠新材有限责任公司 Sodium ion positive electrode material and preparation method and application thereof
CN117542961A (en) * 2024-01-10 2024-02-09 宁德时代新能源科技股份有限公司 Battery monomer, battery and power consumption device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116914126A (en) * 2023-09-13 2023-10-20 深圳华钠新材有限责任公司 Sodium ion positive electrode material and preparation method and application thereof
CN116914126B (en) * 2023-09-13 2023-11-28 深圳华钠新材有限责任公司 Sodium ion positive electrode material and preparation method and application thereof
CN117542961A (en) * 2024-01-10 2024-02-09 宁德时代新能源科技股份有限公司 Battery monomer, battery and power consumption device

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