CN117577826A - Oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, preparation method and application thereof - Google Patents

Oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, preparation method and application thereof Download PDF

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CN117577826A
CN117577826A CN202311640162.7A CN202311640162A CN117577826A CN 117577826 A CN117577826 A CN 117577826A CN 202311640162 A CN202311640162 A CN 202311640162A CN 117577826 A CN117577826 A CN 117577826A
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姜继成
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Yangtze River Delta Research Institute of UESTC Huzhou
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Abstract

The invention discloses oxide-coated multi-element co-doped layered oxidationSodium ion battery layered oxide positive electrode material, preparation method and application thereof, wherein the positive electrode material can be expressed as Na x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 @Mg e Al f Zn g Mn k Cu l O h . The oxide-coated multi-element co-doped layered oxide sodium ion battery anode material provided by the invention has significantly improved electrochemical performance; doping energy adjusting transition metal ion and O 2‑ Energy levels between anions, inhibiting O 2‑ Anions participate in electrochemical reaction, and the high voltage resistance and the cycle performance are improved. The invention also provides a method for simply and effectively doping and coating the layered oxide cathode material of the sodium ion battery by a one-step method, and the method can integrate the doping and coating steps into one coprecipitation reaction, has obvious effect of improving electrochemical performance and is suitable for large-scale production.

Description

Oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium battery materials, in particular to an oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, a preparation method and application thereof.
Background
The energy source is the basis of the social development, the secondary battery plays an important role in the development of the human society, and the lithium ion battery is widely applied due to the high energy density and the high power density. Today, the large-scale application of lithium ion batteries exposes the problem of lithium resource shortage. Lithium resources are scarce resources and are very unevenly distributed worldwide and are strategic resources like petroleum. Based on the characteristics of abundant sodium resources, consistent working principle and processing technology with the lithium ion battery, and the like, the sodium ion battery is considered as a beneficial supplement of the future lithium ion battery.
In recent years, research on sodium ion batteries has been increasingly carried out, and the early stages of industrialization have also been entered. The layered oxide anode material is a sodium ion battery anode material with a large industrialization prospect due to high specific capacity, high energy density and mature process conditions. But the layered oxide positive electrode material is due to O 2- Anions participate in redox reaction and dissolution of surface Mn element to cause poor cycle performance; [1-14] in addition, the surface of the material is unstable due to high content of residual alkali on the surface and sensitivity to air; more troublesome is that the cell assembled by the material can generate gas due to the catalysis of the surface transition metal element to the electrolyte, and the performance and the safety of the battery are affected. At present, since most techniques focus on only one aspect of cladding and doping. [4-14] However, to overcome the above-mentioned difficulties, it is necessary to use co-doping and cladding strategies simultaneously to effectively overcome the above-mentioned difficulties, so as to fully exert the positive oxide effectHigh specific energy potential of the polar materials.
Reference is made to:
[1]Yu,Y.；Ning,D.；Li,Q.；Franz,A.；Zheng,L.；Zhang,N.；Ren,G.；Schumacher,G.；Liu,X.,Revealing the anionic redox chemistry in O3-type layered oxide cathode for sodium-ion batteries,Energy Storage Materials 2021,38,130-140.
[2]Kong,W.；Wang,H.；Sun,L.；Su,C.；Liu,X.,Understanding the synergic roles of MgO coating on the cycling and rate performance of Na0.67Mn0.5Fe0.5O2 cathode,Applied Surface Science 2019,497.
[3]Kong,W.；Gao,R.；Li,Q.；Yang,W.；Yang,J.；Sun,L.；Liu,X.,Simultaneously tuning cationic and anionic redox in a P2-Na0.67Mn0.75Ni0.25O2 cathode material through synergic Cu/Mg co-doping,Journal of Materials Chemistry A 2019,7(15),9099-9109.
[4] xu Kaihua, jiang Zhenkang, zhang Kun, chen Kang, li Cong, li Jun, sun Haibo, fan Liangjiao a precursor for a doped lithium ion battery, a positive electrode material, and methods for preparing the precursor and the positive electrode material. 2019.08.27,2019.
[5] Tan Zhu, wang Chunfei, yang Guochao, teng Qin, li Dan e.g. Zhou Jianwen a process for preparing a magnesium doped modified nickel-iron-manganese based precursor material 2023.07.24,2023.
[6] Hu Zhanggui, stqing Su Dou, long Zhen, han Huawei, guo Shihong, guo Shuai, hong Ningyun, crowing, tong Liping, cao Yi, korean, chen Yimeng, jiang Xiubao, ma Xiaoru, hua Fang P2 type layered metal oxide sodium ion battery positive electrode material and a preparation method thereof. 2022.09.07,2022.
[7] Zhuang Zhi, deng Cheng, wu Huikang, yuan Yuan, zheng Tianrui, lu Peng, cui Ruyu, cheng Yue multi-element co-doped sodium ion positive electrode material, and preparation method and application thereof 2022.
[8] Zhang Genjiang and Mo Anlin are Cu, zn and Mg co-doped layered oxide sodium ion battery anode material, and preparation method and application thereof. 2022.07.07,2022.
[9] A layered cathode material in holy, dong Dong, pan, a method for preparing the same and use in sodium ion batteries, 2023.06.02,2023.
[10] Qi Hangtao, you Xiaorui, zhiyan and anion co-doped coated sodium ion battery anode material and a preparation method thereof. 2023.02.21,2023.
[11] Liu Zhongqing, cheng Yuan, tang Xuejian sodium ion battery positive electrode composite material, preparation method thereof and sodium ion battery. 2023.02.09,2023.
[12] Zhou Chaoyi to Qian, wu Yang, li Jinkai, wu Xingping, a sodium ion battery positive electrode material with a coating structure, a preparation method and application thereof, 2022.09.06,2022.
[13] Tang Yao, yang Xiaodong, marshal, li Xin, luo Tiwei, showa, yan Tiesheng, but one kind of alumina coated layered sodium ion positive electrode material and sodium ion battery 2023.06.09,2023.
[14] Hao Changwang, wang Jianxin, wang Weigang, to xiaoxia, li Shujun, tang sodium ion battery positive electrode precursor, sodium ion battery positive electrode material, method of preparing the same and sodium ion battery 2023.07.17,2023.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides an oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, a preparation method and application thereof, and doping can adjust transition metal element and O 2- Energy levels between anions, inhibiting O 2- Anions participate in electrochemical reaction, and the high-pressure resistance and the circulation performance are improved. The coating can prevent the transition metal element from being in direct contact with air and electrolyte, so that the interface stability is improved, and the gas production of the battery cell can be greatly reduced. The preparation method provided by the invention fuses the doping and coating steps in one coprecipitation reaction, has simple process and can uniformly coat the coating substance on the surface of the coated substance. The coating thickness can be accurately regulated and controlled, the improvement effect is obvious, and the method is suitable for industrial production.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, wherein the positive electrode material is expressed as Na x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 @Mg e Al f Zn g Mn k Cu l O h The inside of the positive electrode material particles is Na x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 Layered oxide positive electrode material with external oxide Mg e Al f Zn g Mn k Cu l O h External oxide Mg e Al f Zn g Mn k Cu l O h Densely covered with internal Na x Ni a Fe b Mn c Mg m Al n Zn p O 2 A surface of a layered oxide positive electrode material, wherein 0<x is less than or equal to 1, a+b+c+m+n+p+s=1, M is at least one of K, ca, sc, ti, V, cr, co, cu, ga, ge, mg e Al f Zn g Mn k Cu l O h MgO, znO, al of a shape of MgO, znO, al 2 O 3 、MnO 2 And one or more of CuO.
Further, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, p is more than or equal to 0 and less than or equal to 1, e is more than or equal to 1, f is more than or equal to 1, g is more than or equal to 0, k is more than or equal to 0,l is more than or equal to 0, and h is more than or equal to 0.
Preferably, x is more than or equal to 0.95 and less than or equal to 1,0.28, a is more than or equal to 0.33,0.28, b is more than or equal to 0.33,0.28, c is more than or equal to 0.33,0.002, m is more than or equal to 0.05,0.002, n is more than or equal to 0.05,0.002, p is more than or equal to 0.05, s is more than or equal to 0.01,0.5, e is more than or equal to 0.5 and less than or equal to 1, f is more than or equal to 0.5 and less than or equal to 1, g is more than or equal to 0.5 and less than or equal to 1, k is more than or equal to 0 and less than or equal to 0.02,0 and l is more than or equal to 0.05.
The invention also provides a preparation method of the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, which comprises the following steps:
the first step: according to the positive electrode material Na to be prepared x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 The corresponding metal sulfate or nitrate is weighed according to the mol ratio of Ni, fe, mn, mg, al, zn, M element in the water to be dissolved in deionized water to prepare an aqueous solution which is marked as solution A, and thenPreparing a certain volume of NaOH solution;
and a second step of: gradually adding the prepared sulfate or nitrate solution, naOH solution and ammonia water solution into a continuous stirring reaction kettle containing a certain base solution at a certain dropping speed through a peristaltic pump to react, and keeping the temperature, stirring speed, pH and ammonia water concentration constant in the reaction process;
and a third step of: after the sulfate solution is completely dripped, the substance Mg is coated according to oxide e Al f Zn g Mn k Cu l O h The metal element molar ratio and the corresponding coating amount are weighed, metal sulfate or nitrate is dissolved in deionized water to prepare an aqueous solution, the aqueous solution is marked as solution B, the solution B, naOH solution and the ammonia water solution are continuously and gradually added into a continuously stirred reaction kettle at a certain dropping speed for carrying out the reaction of the second stage, and the temperature, the stirring speed, the pH value and the ammonia water concentration are kept constant in the reaction process;
fourth step: after the reaction is completed and aged for a certain time, collecting a reaction product by a filter pressing method, washing the reaction product by pure water, drying the reaction product in an oven to obtain a precursor of the positive electrode material, mixing the precursor material with sodium carbonate according to a certain mass ratio, sintering the mixture for a certain time in an air atmosphere at a certain temperature after the precursor material is uniformly mixed to obtain the multi-element co-doped sodium ion battery layered oxide positive electrode material Na coated with oxide x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 @Mg e Al f Zn g Mn k Cu l O h The schematic diagram of the positive electrode material is shown in fig. 1.
Further, in the first step, an aqueous solution with a total molar concentration of metal elements of 2.0-3.0M is prepared and is denoted as solution A, and then a certain volume of 4.0-8.0M NaOH solution is prepared.
Further, in the reaction process of the second step, the temperature in the reaction kettle is constant between 50 and 64 ℃, the stirring speed is constant between 600 and 1000rmp, the pH value is constant between 10.6 and 11.2, the concentration of ammonia water is constant between 0.8 and 1.2M, the sulfate drop acceleration is 0.5 to 3000L/h (the drop acceleration can be larger or smaller according to the volume of the reaction kettle and the volume of the base solution), the base solution is an ammonia water solution with the concentration of 0.8 to 1.2M, and the volume of the base solution is 1.0 to 2000L.
Optimally, the temperature is 60-64 ℃, the pH value is 10.6-10.8, and the concentration of ammonia water is about 1.0M.
Further, in the third step, an aqueous solution with a total molar concentration of metal elements of 2.0-3.0M is prepared.
Further, the reaction time in the third step is 10-100h.
Further, in the fourth step, pure water is used for washing for 3 times, and then the positive electrode material precursor is obtained after the positive electrode material precursor is dried for 48 hours in an oven.
Further, in the fourth step, the aging time is 0-100h, and the mass ratio of sodium carbonate to precursor material is 0.57:1 to 0.62:1, the sintering temperature is 800-900 ℃ and the sintering time is 10-15h.
Optimally, the reaction time is 55-75h, the aging time is 12-16h, and the mass ratio of sodium carbonate to precursor material is 0.60:1, the sintering temperature is 850 ℃ and the sintering time is 15h.
Further, the particle size distribution of the positive electrode material prepared in the fourth step is 2-10um, D50 is 5-7um, tap density is 1.6-1.8g/ml, discharge specific capacity at 0.1C rate is 165-175 in a voltage interval of 2.0-4.2V, and capacity retention rate is more than 80% after 300 times of circulation in the button half cell.
The invention also provides application of the oxide-coated multi-element co-doped layered oxide sodium ion battery layered oxide positive electrode material in a sodium ion secondary battery.
The beneficial effects of the invention are as follows:
the invention provides a multi-element co-doped sodium ion battery layered oxide anode material coated by oxide with high stability, high capacity and high voltage; doping energy adjusting transition metal ion and O 2- Energy levels between anions, inhibiting O 2- Anions participate in electrochemical reaction, and the circulation performance is improved. The coating can prevent the transition metal element from being in direct contact with air and electrolyte, so that the interface stability is improved and the gas production is reduced. The invention also provides a stepThe method is simple and effective, the doping and coating steps can be fused in one coprecipitation reaction, the improvement effect on the electrochemical performance is obvious, and the method is suitable for large-scale production.
Drawings
FIG. 1 is a schematic view of a positive electrode material according to the present invention;
FIG. 2 is a drawing doped with 4% Mg, 1% Zn, 0.5% Al and 0.5% Cu element and coated with 2% Mg (OH) 2 、0.5％Al(OH) 3 And 1% Zn (OH) 2 Scanning electron microscope pictures of the precursor of the (c);
FIG. 3 is NaNi 0.313 Fe 0.313 Mn 0.313 Mg 0.04 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 2 Al 0.5 ZnO 3.75 ) 0.01 Scanning electron microscope pictures of the positive electrode material of the sodium ion battery;
FIG. 4 is NaNi 0.313 Fe 0.313 Mn 0.313 Mg 0.04 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 2 Al 0.5 ZnO 3.75 ) 0.01 The positive electrode material of the sodium ion battery was prepared at 0.1C (14 mA g -1 ) A first charge-discharge curve graph under multiplying power;
FIG. 5 is NaNi 0.313 Fe 0.313 Mn 0.313 Mg 0.04 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 2 Al 0.5 ZnO 3.75 ) 0.01 Sodium ion battery cathode material 1C rate (1C=140 mA g) -1 ) Is a cyclic performance graph of (2);
FIG. 6 is a graph doped with 3% Mg, 1% Zn, 0.5% Al, and 0.5% Cu element and coated with 3% Mg (OH) 2 、0.5％Al(OH) 3 0.5% MnOOH and 0.8% Zn (OH) 2 Scanning electron microscope pictures of the precursor of the (c);
FIG. 7 is NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 3 Al 0.5 Zn 0.5 Zn 0.8 O 5.05 ) 0.01 Scanning electron microscope pictures of the positive electrode material of the sodium ion battery;
FIG. 8 is a drawing doped with 3% Mg, 1% Zn, 0.5% Al and 0.5% Cu element and coated with 3% Mg (OH) 2 Scanning electron microscope pictures of the precursor of the (c);
FIG. 9 is NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(MgO) 0.03 Scanning electron microscope pictures of the positive electrode material of the sodium ion battery;
FIG. 10 is a drawing doped with 3% Mg, 1% Zn, 0.5% Al and 0.5% Cu element and coated with 4% Zn (OH) 2 Scanning electron microscope pictures of the precursor of the (c);
FIG. 11 is NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(ZnO) 0.04 Scanning electron microscope pictures of the positive electrode material of the sodium ion battery;
FIG. 12 is NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(ZnO) 0.04 The positive electrode material of the sodium ion battery was prepared at 0.1C (14 mA g -1 ) First charge-discharge curve graph at multiplying power.
Detailed Description
In the embodiment of the invention, the preparation method of the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material comprises the following steps:
the first step: according to the positive electrode material Na to be prepared x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 The corresponding metal sulfate or nitrate is weighed according to the mol ratio of the Ni, fe, mn, mg, al, zn, M element in the water, dissolved in deionized water to prepare an aqueous solution, marked as a solution A, and then a certain volume of NaOH solution is prepared;
and a second step of: gradually adding the prepared sulfate or nitrate solution, naOH solution and ammonia water solution into a continuous stirring reaction kettle containing a certain base solution at a certain dropping speed through a peristaltic pump to react, and keeping the temperature, stirring speed, pH and ammonia water concentration constant in the reaction process;
and a third step of: after the sulfate solution is completely dripped, the substance Mg is coated according to oxide e Al f Zn g Mn k Cu l O h The metal element molar ratio and the corresponding coating amount are weighed, metal sulfate or nitrate is dissolved in deionized water to prepare an aqueous solution, the aqueous solution is marked as solution B, the solution B, naOH solution and the ammonia water solution are continuously and gradually added into a continuously stirred reaction kettle at a certain dropping speed for carrying out the reaction of the second stage, and the temperature, the stirring speed, the pH value and the ammonia water concentration are kept constant in the reaction process;
fourth step: after the reaction is completed and aged for a certain time, collecting a reaction product by a filter pressing method, washing the reaction product by pure water, drying the reaction product in an oven to obtain a precursor of the positive electrode material, mixing the precursor material with sodium carbonate according to a certain mass ratio, sintering the mixture for a certain time in an air atmosphere at a certain temperature after the precursor material is uniformly mixed to obtain the multi-element co-doped sodium ion battery layered oxide positive electrode material Na coated with oxide x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 @Mg e Al f Zn g Mn k Cu l O h The schematic diagram of the positive electrode material is shown in fig. 1.
In order that the invention may be more fully disclosed, a more particular description of the invention will be rendered by the following examples.
Example 1
Synthesis of NaNi 0.313 Fe 0.313 Mn 0.313 Mg 0.04 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 2 Al 0.5 ZnO 3.75 ) 0.01 Experimental method of (2)
Weighing 9.873kg NiSO 4 ·6H 2 O、6.348kg MnSO 4 ·H 2 O、5.709kg FeSO 4 、1.183kg MgSO 4 ·7H 2 O、0.345kg ZnSO 4 ·7H 2 O、0.103kg Al 2 (SO 4 ) 3 And 0.15kg of CuSO 4 ·5H 2 O was dissolved in 60L deionized water and the solution was designated as solution A. Protective atmosphere of nitrogen is introduced in the dissolution process to prevent Fe 2+ Oxidized. 11.5472kg of NaOH was weighed and dissolved in 70L of deionized water.
The sulfate solution, naOH solution and ammonia water solution (obtained by direct purchase, 25 wt%) prepared above are gradually added into a 50L continuously stirred reaction kettle containing 32L base solution by a peristaltic pump at a certain dropping speed, the temperature is kept at 60 ℃ during the reaction, the stirring speed is 800rmp, the pH=10.8 and the ammonia water concentration is 1.0M, the dropping speed of sulfate is controlled to be 1.0L/h, after the solution A is consumed for 70 hours continuously, 0.592kg of MgSO is weighed again 4 ·7H 2 O、0.345kg ZnSO 4 ·7H 2 O、0.103kg Al 2 (SO 4 ) 3 Dissolving in 2.1L deionized water, denoted as solution B, continuously dropwise adding the solution B into a continuously stirred reaction kettle (NaOH solution and ammonia solution are also continuously dropwise added), and keeping the temperature, stirring speed, ammonia concentration and salt dropwise adding speed the same. And after the reaction is completed, collecting the obtained product by pressure filtration and drying, wherein the product is a precursor of the positive electrode material of the sodium ion battery. The morphology is shown in fig. 2, and the obtained precursor material can be seen to be in a spherical morphology.
Mixing the precursor material with Na 2 CO 3 According to the mass ratio of 1:0.6, and after being evenly mixed, the mixture is burned for 15 hours under the air atmosphere at 850 ℃ to obtain NaNi 0.313 Fe 0.313 Mn 0.313 Mg 0.04 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 2 Al 0.5 ZnO 3.75 ) 0.35 The morphology is shown in figure 3.
In this example, it was assembled into a CR2032 coin cell, and charge and discharge tests were performed at current densities of 0.1C and 1.0C using a constant current charge and discharge mode. The test conditions were: the discharge cutoff voltage was 2.0V, and the charge cutoff voltage was 4.0V. The charge and discharge properties and the cycle properties are shown in Table 1, FIG. 4 and FIG. 5, respectively. As can be seen from Table 1 and FIG. 4, the reversible specific capacity can reach 172mAh g at 0.1C multiplying power in the voltage range of 2.0-4.2V -1 Capacity retention of 80 for 300 cyclesPercent of the total weight of the composition. As can be seen from fig. 5, after 90 cycles, the capacity retention rate of 90% was still obtained, indicating excellent cycle performance.
Example 2
NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(Mg 3 Al 0.5 Zn 0.5 Zn 0.8 O 5.05 ) 0.01 Experimental method of (2)
Compared to example 1, only the solutions a and B were modified as follows:
solution a:5.772kg NiSO 4 ·6H 2 O、7.767kg MnSO 4 ·H 2 O、6.985kg FeSO 4 、0.887kg MgSO 4 ·7H 2 O、0.345kg ZnSO 4 ·7H 2 O、0.103kg Al 2 (SO 4 ) 3 And 0.15kg of CuSO 4 ·5H 2 O was dissolved in 60L deionized water.
Solution B:0.888kg MgSO 4 ·7H 2 O、0.276kg ZnSO 4 ·7H 2 O、0.103kg Al 2 (SO 4 ) 3 And 0.101kg MnSO 4 ·H 2 O was dissolved in 3.0L deionized water.
Other experimental steps and parameters are the same, and scanning electron microscope pictures of the precursor and the positive electrode material are shown in fig. 6 and 7. As can be seen from fig. 6 and 7, both the precursor and the cathode material are monodisperse spherical particles with a diameter of 6 μm, and maintain a complete spherical morphology after sintering.
The electrochemical properties are shown in Table 1, and the reversible specific capacity can reach 171mAh g under the 0.1C multiplying power in the voltage range of 2.0-4.2V according to the Table 1 -1 The 300-cycle capacity retention was 79.3%, indicating excellent cycle performance.
Example 3
NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(MgO) 0.03 Experimental method of (2)
In comparison to example 2, only solution B was modified as follows:
solution B:0.887kg MgSO 4 ·7H 2 O was dissolved in 2.0L deionized water.
The scanning electron microscope pictures of the precursor and the positive electrode material are shown in fig. 8 and 9, and referring to table 1, it can be seen from fig. 8 and 9 that the precursor and the positive electrode material are both monodisperse spherical particles with a diameter of 6 μm, and the complete spherical morphology is still maintained after sintering. As can be seen from Table 1, the reversible specific capacity can reach 170mAh g at 0.1C rate in the voltage range of 2.0-4.2V -1 The 300-cycle capacity retention rate was 82%, indicating excellent cycle performance.
Example 4
NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.03 Zn 0.01 Al 0.005 Cu 0.005 O 2 @(ZnO) 0.04 Experimental method of (2)
In comparison to example 2, only solution B was modified as follows:
solution B:1.38kg ZnSO 4 ·7H 2 O was dissolved in 3.0L deionized water.
The scanning electron microscope pictures of the precursor and the positive electrode material are shown in fig. 10 and 11, and the electrochemical properties are shown in table 1. The first charge-discharge curve is shown in fig. 12. As can be seen from fig. 10 and 11, both the precursor and the cathode material were monodisperse spherical particles with a diameter of 6 μm, and still maintain a complete spherical morphology after sintering. As can be seen from Table 1, the reversible specific capacity can reach 170mAh g at 0.1C rate in the voltage range of 2.0-4.2V -1 . As can be seen from FIG. 12, the reversible specific capacity can reach 172mAh g under the 0.1C multiplying power in the voltage range of 2.0-4.2V -1 The 300-cycle capacity retention was 81%, indicating excellent cycle performance.
Example 5
NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.02 Zn 0.01 Al 0.005 Cu 0.005 Cr 0.01 O 2 @(ZnO) 0.04 Experimental method of (2)
In comparison to example 4, only solution a was modified as follows:
solution a:5.772kg NiSO 4 ·6H 2 O、7.767kg MnSO 4 ·H 2 O、6.985kg FeSO 4 、0.592kg MgSO 4 ·7H 2 O、0.345kg ZnSO 4 ·7H 2 O、0.103kg Al 2 (SO 4 ) 3 、0.297kg CrSO 4 ·7H 2 O and 0.15kg CuSO 4 ·5H 2 O was dissolved in 60L deionized water.
Referring to Table 1, it is clear from Table 1 that the reversible specific capacity can reach 170mAh g at 0.1C rate in the voltage range of 2.0-4.2V -1 The 300-cycle capacity retention was 78%, indicating excellent cycle performance.
Example 6
NaNi 0.183 Fe 0.383 Mn 0.383 Mg 0.01 Zn 0.01 Al 0.005 Cu 0.005 Cr 0.01 Zr 0.01 O 2 @(ZnO) 0.04 Experimental method of (2)
In comparison to example 4, only solution a was modified as follows:
solution a:5.772kg NiSO 4 ·6H 2 O、7.767kg MnSO 4 ·H 2 O、6.985kg FeSO 4 、0.296kg MgSO 4 ·7H 2 O、0.345kg ZnSO 4 ·7H 2 O、0.103kg Al 2 (SO 4 ) 3 、0.297kg CrSO 4 ·7H 2 O、0.15kg CuSO 4 ·5H 2 O and 0.34kg Zr (SO) 4 ) 2 Dissolved in 60L deionized water.
Referring to Table 1, it is clear from Table 1 that the reversible specific capacity can reach 170mAh g at 0.1C rate in the voltage range of 2.0-4.2V -1 The 300-cycle capacity retention was 77%, indicating excellent cycle performance.
TABLE 1 reversible specific Capacity and 300 cycle Retention of different cathode materials of examples 1-6

Claims (10)

1. An oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material is characterized in that:
the positive electrode material is represented by Na x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 @Mg e Al f Zn g Mn k Cu l O h The inside of the positive electrode material particles is Na x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 Layered oxide positive electrode material with external oxide Mg e Al f Zn g Mn k Cu l O h External oxide Mg e Al f Zn g Mn k Cu l O h Densely covered with internal Na x Ni a Fe b Mn c Mg m Al n Zn p O 2 A surface of a layered oxide positive electrode material, wherein 0<x is less than or equal to 1, a+b+c+m+n+p+s=1, M is at least one of K, ca, sc, ti, V, cr, co, cu, ga, ge, mg e Al f Zn g Mn k Cu l O h MgO, znO, al of a shape of MgO, znO, al 2 O 3 、MnO 2 And one or more of CuO.
2. An oxide-coated multi-element co-doped layered oxide sodium ion battery positive electrode material according to claim 1, wherein: 0.ltoreq.a.ltoreq.1, 0.ltoreq.b.ltoreq.1, 0.ltoreq.c.ltoreq.1, 0.ltoreq.m.ltoreq.1, 0.ltoreq.n.ltoreq.1, 0.ltoreq.p.ltoreq.1, 0.ltoreq.s.ltoreq.1, e.gtoreq.1, f.gtoreq.0, k.gtoreq. 0,l.gtoreq.0, h.gtoreq.0.
3. A method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 1 or 2, comprising the following steps:
the first step: according to the positive electrode material Na to be prepared x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 The corresponding metal sulfate or nitrate is weighed according to the mol ratio of the Ni, fe, mn, mg, al, zn, M element in the water, dissolved in deionized water to prepare an aqueous solution, marked as a solution A, and then a certain volume of NaOH solution is prepared;
and a second step of: gradually adding the prepared sulfate or nitrate solution, naOH solution and ammonia water solution into a continuous stirring reaction kettle containing a certain base solution at a certain dropping speed through a peristaltic pump to react, and keeping the temperature, stirring speed, pH and ammonia water concentration constant in the reaction process;
and a third step of: after the sulfate solution is completely dripped, the substance Mg is coated according to oxide e Al f Zn g Mn k Cu l O h The metal element molar ratio and the corresponding coating amount are weighed, metal sulfate or nitrate is dissolved in deionized water to prepare an aqueous solution, the aqueous solution is marked as solution B, the solution B, naOH solution and the ammonia water solution are continuously and gradually added into a continuously stirred reaction kettle at a certain dropping speed for carrying out the reaction of the second stage, and the temperature, the stirring speed, the pH value and the ammonia water concentration are kept constant in the reaction process;
fourth step: after the reaction is completed and aged for a certain time, collecting a reaction product by a filter pressing method, washing the reaction product by pure water, drying the reaction product in an oven to obtain a precursor of the positive electrode material, mixing the precursor material with sodium carbonate according to a certain mass ratio, sintering the mixture for a certain time in an air atmosphere at a certain temperature after the precursor material is uniformly mixed to obtain the multi-element co-doped sodium ion battery layered oxide positive electrode material Na coated with oxide x Ni a Fe b Mn c Mg m Al n Zn p M s O 2 @Mg e Al f Zn g Mn k Cu l O h 。
4. The method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 3, wherein the method comprises the following steps of: in the first step, preparing an aqueous solution with the total molar concentration of metal elements of 2.0-3.0M, namely a solution A, and then preparing a certain volume of 4.0-8.0M NaOH solution.
5. The method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 3, wherein the method comprises the following steps of: in the reaction process of the second step, the temperature in the reaction kettle is constant between 50 and 64 ℃, the stirring speed is constant between 600 and 1000rmp, the pH value is constant between 10.6 and 11.2, the concentration of ammonia water is constant between 0.8 and 1.2M, the sulfate dropping speed is 0.5 to 3000L/h (the dropping speed can be larger or smaller according to the volume of the reaction kettle and the volume of the base solution), the base solution is an ammonia water solution with the concentration of 0.8 to 1.2M, and the volume of the base solution is 1.0 to 2000L.
6. The method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 3, wherein the method comprises the following steps of: in the third step, preparing an aqueous solution with the total molar concentration of metal elements of 2.0-3.0M, and reacting for 10-100h.
7. The method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 3, wherein the method comprises the following steps of: and step four, washing 3 times by pure water, and drying in an oven for 48 hours to obtain the positive electrode material precursor.
8. The method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 3, wherein the method comprises the following steps of: in the fourth step, the aging time is 0-100h, and the mass ratio of sodium carbonate to precursor material is 0.57:1 to 0.62:1, the sintering temperature is 800-900 ℃ and the sintering time is 10-15h.
9. The method for preparing the oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material according to claim 3, wherein the method comprises the following steps of: the grain size distribution of the positive electrode material prepared in the fourth step is 2-10um, the D50 is 5-7um, the tap density is 1.6-1.8g/ml, the discharge specific capacity of 0.1C multiplying power is 165-175 in the voltage range of 2.0-4.2V, and the capacity retention rate is more than 80% after 300 times of circulation in the button half cell.
10. Use of an oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material prepared according to the preparation method of any one of claims 3-9 in a sodium ion secondary battery.
CN202311640162.7A 2023-12-01 2023-12-01 Oxide-coated multi-element co-doped sodium ion battery layered oxide positive electrode material, preparation method and application thereof Pending CN117577826A (en)

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