CN115148984B - O3-P2 composite phase sodium ion positive electrode material and preparation method and application thereof - Google Patents
O3-P2 composite phase sodium ion positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an O3-P2 composite phase sodium ion positive electrode material, a preparation method and application thereof, and relates to the technical field of sodium ion batteries. The O3-P2 composite phase sodium ion positive electrode material comprises an O3 type oxide layer and a P2 type oxide layer, wherein the structural formula of the O3-P2 composite phase sodium ion positive electrode material is Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1, M comprises at least one of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F; the P2 type oxide layer is generated on the surface of the O3 type oxide layer in situ to form a core-shell structure. The material has excellent charge-discharge specific capacity, excellent cycle performance, low surface residual alkali content and excellent comprehensive performance, and can be widely applied to the preparation of sodium ion batteries, energy storage devices or electric vehicles.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to an O3-P2 composite phase sodium ion positive electrode material and a preparation method and application thereof.
Background
With the rapid development of social economy, energy and environment become the focus of increasing attention of people. The lithium ion battery is used as an environment-friendly energy storage device, and has the advantages of high energy density, long cycle life, small pollution and the like, so that the lithium ion battery is widely applied to the fields of electronic consumption, energy storage and electric automobiles. However, with the increasing demand of lithium batteries, the development of lithium batteries is severely restricted by the shortage of lithium resources and the rising price. The sodium and the lithium have similar physical and chemical properties, the earth crust abundance of the sodium element is sixth, the resource distribution is uniform, the price is low, and the sodium and the lithium are expected to be widely applied to the fields of energy storage, low-speed electric vehicles and the like.
The anode material is one of the key factors influencing the performance of the sodium ion battery, and the layered oxide anode is paid more and more attention due to higher oxidation-reduction potential, high specific capacity, low price and the like. According to Na + The coordination configuration of (2) and the stacking number of oxygen layers, the layered oxide is divided into P2, P3, O2 and O3 phases, wherein the two structures of P2 and O3 are most common. For P2 type oxide, the diffusion channel of prism space is wider, sodium ion energy is stable, diffusion is easy, and the oxide has higher Na + Electrical conductivity and better structural stability; but its relatively low sodium content results in a material with a low gram capacity that is difficult to use in high energy density full cell systems. In contrast, the O3 type oxide has a higher content of sodium and a higher gram capacity, but the O3 type oxide has Na + The diffusion channel is tortuous, the structure is relatively unstable, and in addition, O3 type oxide has the problems of poor air stability and the like. Therefore, how to treat in Na + Improving the ionic conductivity and stabilizing the lattice structure of the O3 type material in the de-intercalation process become hot spots for research. At present, researchers usually adopt modification means such as doping or coating to improve Na + The structure stability of the material is improved by the deintercalation dynamics, but the improvement effect of the mode is limited, and the material performance is difficult to be essentially improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide an O3-P2 composite phase sodium ion positive electrode material, and a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, the invention provides an O3-P2 composite phase sodium ion positive electrode material, which comprises an O3 type oxide layer and a P2 type oxide layer, wherein the structural formula of the O3-P2 composite phase sodium ion positive electrode material is Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1, M comprises at least one of Ti, V, cr, mn, fe, co, ni, cu, li, B, ta and La; the P2 type oxide layer is generated on the surface of the O3 type oxide layer in situ to form a core-shell structure.
In a second aspect, the present invention provides a method for preparing an O3 — P2 composite phase sodium ion positive electrode material, comprising: uniformly mixing a sodium source and an M source, sintering, and carrying out ultrafast cooling at a speed of more than or equal to 20 ℃/min after sintering to obtain a sintering material Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1 and is used as an O3 type oxide layer, wherein the M source comprises at least one of compounds of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F;
annealing the sintering material at 200-800 ℃ for post-treatment of 2h-20h to form a P2 type oxide layer on the surface of the O3 type oxide layer in situ to obtain the O3-P2 composite phase sodium ion cathode material with the core-shell structure.
In a third aspect, the present invention provides a sodium ion battery, which includes the O3 — P2 composite phase sodium ion positive electrode material according to the foregoing embodiment or the O3 — P2 composite phase sodium ion positive electrode material obtained by the preparation method of the O3 — P2 composite phase sodium ion positive electrode material according to the foregoing embodiment.
In a fourth aspect, the present invention provides the use of a sodium ion battery according to the previous embodiments in the manufacture of an energy storage device or an electric vehicle.
The invention has the following beneficial effects:
the O3-P2 composite phase sodium ion positive electrode material has a core-shell structure of an O3-P2 composite phase, has excellent charge-discharge specific capacity and excellent cycle performance, has low content of residual alkali on the surface of a shell layer, and is favorable for improving the performance of the material. The preparation method provided by the application can inhibit the dynamic formation process of residual alkali through an ultra-fast cooling process, can obviously reduce the surface residual alkali content of the material, and can improve the performance of the material. Annealing post-treatment is carried out after the ultra-fast cooling process, so that the structural defects possibly caused in the ultra-fast cooling process can be improved, the internal stress existing between primary particles is relieved, the brittleness of secondary particles is reduced, and the mechanical property of the material is improved, which is important for keeping the particle integrity of the material in the charging and discharging process. Meanwhile, the annealing post-treatment can also decompose and volatilize residual alkali on the surface of the material, and can further induce the in-situ generation of a high-stability P2 phase on the surface of the material, which is favorable for improving the comprehensive performance of the material. The O3-P2 composite phase sodium ion positive electrode material provided by the present application can be widely applied to the preparation of sodium ion batteries, and for this reason, the present application provides a sodium ion battery, which includes the O3-P2 composite phase sodium ion positive electrode material according to the foregoing embodiment. In addition, the sodium ion battery can be widely applied to the preparation of energy storage devices or electric vehicles.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a simplified schematic representation of a sintering process provided in an embodiment of the present application;
FIG. 2 is a first-turn charge-discharge curve diagram of materials under different sodium sources according to a first experimental example of the present application;
FIG. 3 is a first-turn charge-discharge curve diagram of a material under different cooling processes provided in experimental example two of the present application;
FIG. 4 is a schematic diagram of material rate capability under different cooling processes provided in experimental example two of the present application;
FIG. 5 is a first-cycle charge-discharge curve diagram of a material under different post-treatment processes provided in experimental example III of the present application;
FIG. 6 is a schematic diagram of cycle performance of materials under different post-treatment processes provided in Experimental example III of the present application;
FIG. 7 is an XRD pattern of the material under different post-treatment processes provided in Experimental example III of the present application;
FIG. 8 is a schematic diagram of the distribution of Na elements in EDS line scan of a material under different post-treatment processes provided in Experimental example III of the present application;
fig. 9 is a first-turn charge-discharge curve diagram of a material under different processes provided in experimental example four of the present application;
fig. 10 is a schematic diagram of cycle performance of materials under different processes provided in experimental example four of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The invention provides an O3-P2 composite phase sodium ion positive electrode material which comprises an O3 type oxide layer and a P2 type oxide layer, wherein the structural formula of the O3-P2 composite phase sodium ion positive electrode material is Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1, M comprises at least one of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F; the P2 type oxide layer is generated on the surface of the O3 type oxide layer in situ to form a core-shell structure; wherein, the surface of the O3-P2 composite phase sodium ion anode material has residual alkali Na 2 CO 3 The content of (A) is less than 0.6%, and the content of surface residual alkali NaOH is less than 0.5%.
In the application, the P2 phase is formed on the surface of the O3 type oxide layer in situ to serve as the P2 type oxide layer, the bonding strength of the P2 type oxide layer and the O3 type oxide layer is high, the surface residual alkali content is low, the performance of the material is favorably improved, the excellent charge-discharge specific capacity is realized, and meanwhile, the cycle performance is excellent.
Further, the average grain diameter of the O3-P2 composite phase sodium ion positive electrode material is 8-12 μm, wherein the O3 type oxide layer accounts for 50-95% of the grain size, and the P2 type oxide layer accounts for 5-50% of the grain size; the Na content of the O3 type oxide layer is 90-100%, the Na content of the P2 type oxide layer is 50-90%, and the Na content gradually decreases in a direction away from the O3 type oxide layer. It can be seen that the O3 type oxide layer of the core layer accounts for a larger proportion than the P2 type oxide layer of the shell layer, and the Na element content of the core layer is significantly higher than that of the shell layer.
Correspondingly, the invention also provides a preparation method of the O3-P2 composite phase sodium ion cathode material, which comprises the following steps:
and S1, sintering.
And (3) uniformly mixing the sodium source and the M source, and sintering.
The sodium source comprises a first sodium source and a second sodium source, wherein the first sodium source is Na 2 CO 3 The second sodium source is NaHCO 3 And NaOH; the molar ratio of the first sodium source to the second sodium source is 1 to 9:1 to 9; and when a sodium source is added, the sodium excess is designed to be 1% -10%.
The M source comprises at least one of compounds of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F; the M source may be a combination of a coprecipitation precursor and a dopant, or the M source may be a solid phase sintering raw material. Two different M source selections correspond to two different raw material synthesis processes.
Wherein the coprecipitation precursor comprises MCO 3 、M(OH) 2 Or MC 2 O 4 M is one or more of Ti, V, cr, mn, fe, co, ni and Cu; the preparation method of the coprecipitation precursor is a conventional method, and is not further described in the application. The present application provides several typical but non-limiting co-precipitation precursors, which may be, for example, ni 0.28 Mn 0.59 Fe 0.13 (OH) 2 、Ni 1/3 Mn 1/3 Fe 1/ 3 CO 3 、Cu 0.22 Fe 0.30 Mn 0.48 (OH) 2 Or Ni 0.46 Mn 0.44 Mg 0.1 C 2 O 4 The molar ratio of the coprecipitation precursor to the sodium source is 1:0.8 to 1, the present application provides several typical but non-limiting values, for example, a range value between 1.
The dopant comprises one or more of compounds containing Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B, F. Several exemplary, but non-limiting, dopants are provided herein, such as may be TiO 2 、MnO 2 、FeO 2 、Co 2 O 3 NiO, cuO or B 2 O 3 The molar ratio of the coprecipitation precursor to the dopant is 1:0.001 to 0.2, the present application provides several typical but non-limiting values, which may be, for example, any one or a range between 1.
The solid phase sintering raw material comprises one or more of compounds containing Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F. The present application provides several typical but non-limiting solid phase sintering materials, which may be, for example, tiO 2 、Fe 2 O 3 、Li 2 CO 3 Or MnO 2 The molar ratio of the solid-phase sintering raw material to the sodium source is 1:0.8 to 1, the present application provides several typical but non-limiting values, for example, any one or a range between 1.
The sintering processes of the two raw materials are the same, specifically, the sintering comprises two-section type heat preservation sintering, the sintering atmosphere is air or oxygen, the temperature of the first section is 450-650 ℃, the heat preservation time is 2-10 h, and the heating rate is 1-5 ℃/min; the second-stage heat preservation temperature is 800-1200 ℃, the heat preservation time is 10-25 h, and the temperature rise rate is 1-5 ℃/min.
Due to Na 2 CO 3 Has a high melting point (about 851 ℃), and therefore has a single Na component 2 CO 3 When used as a sodium source, the sodium source is sintered at a relatively low primary sintering temperatureIn degree below, na 2 CO 3 The material is difficult to be completely decomposed into the bulk phase structure of the material, so that structural defects of the material are caused, and unreacted inert sodium sources are accumulated on the surface of the material to cause Na + The de-intercalation of the material is hindered, and the performance of the material is influenced. At the same time, due to the single NaOH and/or NaHCO 3 Has a low melting point, so that NaOH and/or NaHCO 3 When the material is used as a sodium source for sintering, the sodium source is easy to volatilize excessively, and finally, the material performance is poor.
In this application, na is used 2 CO 3 And NaOH/NaHCO 3 The composite sodium source is sintered, so that the defect of a single sodium source is overcome, and the comprehensive performance of the material is improved.
And S2, ultra-fast cooling.
After sintering, carrying out ultra-fast cooling at the speed of more than or equal to 20 ℃/min to obtain sintering material Na x MO 2 ，0.8≤X≤1。
During cooling after the sintering soak, cooling-induced surface restructuring (typically above 300 ℃) can occur, resulting in surface alkali residues (NaOH/Na) 2 CO 3 ) Thereby affecting the gram capacity and rate capability of the material. Through an ultra-fast cooling process, the kinetic formation process of residual alkali is inhibited, the surface residual alkali content of the material can be obviously reduced, and the performance of the material is improved.
And S3, annealing and post-treatment.
Heating the sintering material to 200-800 ℃ at a heating rate of 1-5 ℃/min, annealing for 2h-20h to form a P2 phase on the surface of the O3 type oxide in situ, forming an O3-P2 composite phase sodium ion anode material with a core-shell structure, and then cooling along with a furnace.
According to the method, the structure defect possibly caused by the ultra-fast cooling process can be improved through annealing post-treatment, the internal stress existing between primary particles is relieved, the brittleness of secondary particles is reduced, the mechanical property of the material is improved, and the method is very important for keeping the particle integrity of the material in the charging and discharging process. In addition, the annealing post-treatment can decompose and volatilize residual alkali on the surface of the material, and can further induce the surface of the material to generate a high-stability P2 phase in situ, which is beneficial to improving the comprehensive performance of the material.
The O3-P2 composite phase sodium ion positive electrode material provided by the application can be widely applied to the preparation of sodium ion batteries, and in contrast, the application provides a sodium ion battery which comprises the O3-P2 composite phase sodium ion positive electrode material according to the embodiment. In addition, the sodium ion battery can be widely applied to the preparation of energy storage devices or electric vehicles.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides an O3-P2 composite phase sodium ion positive electrode material, and the preparation method comprises the following steps:
and S1, sintering.
With the molecular formula Ni 0.28 Mn 0.59 Fe 0.13 (OH) 2 The doping agent is TiO 2 Respectively using Na 2 CO 3 + NaOH (in a complex sodium source, na) 2 CO 3 The mole percentage of the Na content in the composite sodium source is 40 percent), and the molar ratio of the excessive sodium is 5 percent.
Specifically, 100g of coprecipitation precursor and TiO are weighed 2 14.13g、Na 2 CO 3 22.58g and 25.57g of NaOH are uniformly mixed, and two-stage heat preservation sintering is carried out, wherein the first-stage heat preservation temperature is 500 ℃, the heat preservation time is 3 hours, and the heating rate is 2 ℃/min; the second-stage heat preservation temperature is 800 ℃, the heat preservation time is 15h, the temperature rise rate is 3 ℃/min, and the sintering atmosphere is air.
And S2, ultra-fast cooling.
After sintering, carrying out ultra-fast cooling at the speed of 25 ℃/min to obtain a sintering material Na 0.86 Ni 0.22 Mn 0.45 Fe 0.1 Ti 0.15 O 2 。
And S3, annealing and post-treatment.
And heating the sintering material to 500 ℃ at the heating rate of 2 ℃/min, carrying out annealing post-treatment for 6h, wherein the annealing atmosphere is oxygen, and cooling along with the furnace to obtain the O3-P2 composite phase sodium ion cathode material.
Example 2
The embodiment provides an O3-P2 composite phase sodium ion positive electrode material, and the preparation method comprises the following steps:
and S1, sintering.
Adopting a solid phase sintering process to synthesize materials, wherein the synthesis raw materials are NiO and MnO respectively 2 、Fe 2 O 3 And Na 2 CO 3 Sodium source (Na) in combination with NaOH 2 CO 3 The mole percentage of the Na content in the composite sodium source is 60 percent), and the molar ratio of the excessive Na is 5 percent.
Specifically, the method comprises the following steps: 50g of NiO and 47.48g of MnO were weighed respectively 2 、53.44g Fe 2 O 3 ，67.03g Na 2 CO 3 33.73g of NaOH are evenly mixed and then sintered, the first-stage heat preservation temperature is 450 ℃, the heat preservation time is 5 hours, and the heating rate is 3 ℃/min; the second-stage heat preservation temperature is 930 ℃, the heat preservation time is 10h, the temperature rise rate is 5 ℃/min, and the sintering atmosphere is air.
And S2, ultra-fast cooling.
After sintering, carrying out ultra-fast cooling at the speed of 25 ℃/min to obtain a sintering material NaNi 1/3 Mn 1/3 Fe 1/3 O 2 。
And S3, annealing and post-treatment.
And heating the sintering material to 500 ℃ at the heating rate of 2 ℃/min, carrying out annealing post-treatment for 6h, wherein the annealing atmosphere is oxygen, and cooling along with the furnace to obtain the O3-P2 composite phase sodium ion cathode material.
Example 3
The embodiment provides an O3-P2 composite phase sodium ion positive electrode material, and the preparation method comprises the following steps:
s1, sintering.
Adopts a molecular formula of Ni 1/3 Mn 1/3 Fe 1/3 CO 3 The doping agent is CuO, and respectively adopts Na 2 CO 3 + NaHCO 3 Sintering (in a complex sodium source, na) 2 CO 3 The mole percentage of the Na content in the composite sodium source is 40 percent), and the molar ratio of the excessive sodium is 10 percent.
Specifically, 100g and 0.26g of Cu of coprecipitation precursor are weighedO、Na 2 CO 3 24.51g and NaHCO 3 58.28g of the mixture is uniformly mixed, and two-section type heat preservation sintering is carried out, wherein the temperature of the first section is 650 ℃, the heat preservation time is 2 hours, and the heating rate is 5 ℃/min; the second-stage heat preservation temperature is 1200 ℃, the heat preservation time is 10h, the temperature rise rate is 5 ℃/min, and the sintering atmosphere is air.
And S2, ultra-fast cooling.
After sintering, ultra-fast cooling is carried out at the speed of 30 ℃/min to obtain a sintering material NaNi 1/3 Mn 1/3 Fe 1/ 3 Cu 0.01 O 2 。
And S3, annealing and post-treatment.
And heating the sintering material to 800 ℃ at the heating rate of 5 ℃/min, carrying out annealing post-treatment for 4h, wherein the annealing atmosphere is air, and cooling along with the furnace to obtain the O3-P2 composite phase sodium ion cathode material.
The first experimental example: effect of different sodium sources on Material Properties
With the molecular formula Ni 0.28 Mn 0.59 Fe 0.13 (OH) 2 The dopant is TiO 2 Respectively using Na 2 CO 3 、NaOH、NaHCO 3 And Na 2 CO 3 +NaOH，Na 2 CO 3 +NaHCO 3 Sintering (in a complex sodium source, na) 2 CO 3 The mole percentage of the Na content in the composite sodium source is 40 percent), and the molar ratio of the excessive sodium is 5 percent.
Specifically, the method comprises the following steps:
Na 2 CO 3 as a sodium source: 100g of precursor, 14.13g of TiO were weighed 2 ，56.45g Na 2 CO 3 Sintering after uniformly mixing;
NaOH is used as a sodium source: 100g of precursor, 14.13g of TiO were weighed 2 42.61g of NaOH are uniformly mixed and sintered;
NaHCO 3 as a sodium source: 100g of precursor, 14.13g of TiO were weighed 2 ，89.49g NaHCO 3 Sintering after uniformly mixing;
Na 2 CO 3 + NaOH as sodium source: 100g of precursor, 14.13g of TiO were weighed 2 ，22.58g Na 2 CO 3 25.57g NaOH, and sintering;
Na 2 CO 3 +NaHCO 3 as a sodium source: 100g of precursor, 14.13g of TiO were weighed 2 ，22.58g Na 2 CO 3 、53.69g NaHCO 3 Sintering after uniformly mixing;
and (3) sintering: the first-stage heat preservation temperature is 500 ℃, the heat preservation time is 3h, and the heating rate is 2 ℃/min; the second-stage heat preservation temperature is 800 ℃, the heat preservation time is 15h, the temperature rise rate is 3 ℃/min, the sintering atmosphere is air, and the finished product Na is obtained after furnace cooling 0.86 Ni 0.22 Mn 0.45 Fe 0.1 Ti 0.15 O 2 。
FIG. 2 shows the first-turn charge-discharge curves at 0.1C for samples of different sodium sources, with charge-discharge cut-off voltages of 4.3V and 2.0V, respectively. As can be seen from FIG. 2, the first charge specific capacity and the discharge specific capacity of the composite sodium source are both significantly greater than those of the single sodium source.
Experimental example II: effect of ultrafast cooling Process on Material Properties
Adopts a molecular formula of Ni 0.28 Mn 0.59 Fe 0.13 (OH) 2 The dopant is TiO 2 By using Na 2 CO 3 Sintering with a complex sodium source of NaOH (Na) 2 CO 3 The mole percentage of the Na content in the composite sodium source is 40 percent), and the molar ratio of the excessive sodium is 3 percent.
Specifically, the method comprises the following steps: 100g of precursor, 14.13g of TiO are taken 2 ，22.15g Na 2 CO 3 25.08g of NaOH is evenly mixed and sintered; the first-stage heat preservation temperature is 600 ℃, the heat preservation time is 3h, and the heating rate is 5 ℃/min; the second-stage heat preservation temperature is 900 ℃, the heat preservation time is 10 hours, the temperature rising rate is 2 ℃/min, the sintering atmosphere is air, and then furnace cooling or ultra-fast cooling is respectively carried out, wherein the ultra-fast cooling rate is 25 ℃/min.
As can be seen from FIG. 3, the ultra-fast cooling mode can enable the first charge specific capacity and the discharge specific capacity of the material to be obviously superior to those of the furnace cooling mode. As can be seen from FIG. 4, the specific capacity of the ultra-fast cooling mode circulating under different multiplying factors (0.1C-5C) is remarkably superior to that of the furnace cooling mode.
In addition, the content of residual alkali on the surface of the material under different cooling processes is detected by the method: potentiometric titration.
See table 1 for test results:
TABLE 1 influence of ultra-fast Cooling Process on the residual alkali content on the surface of the Material
| Type of process | Na 2 CO 3 Content/% | NaOH content/%) |
| Furnace cooling | 1.526 | 1.231 |
| Ultra-fast cooling | 0.793 | 0.572 |
As can be seen from Table 1, the content of residual alkali on the surface of the material can be effectively reduced by adopting the ultra-fast cooling mode provided by the application.
Experimental example three: effect of post-treatment Process on Material Properties
Adopting a solid phase sintering process to synthesize materials, wherein the synthesis raw materials are NiO and MnO respectively 2 、Fe 2 O 3 And Na 2 CO 3 Sodium source (Na) in combination with NaOH 2 CO 3 The mole percentage of the Na content in the composite sodium source is 60 percent), and the molar ratio of the excessive Na is 5 percent.
Specifically, the method comprises the following steps: 50g of NiO and 47.48g of MnO were weighed respectively 2 、53.44g Fe 2 O 3 ，67.03g Na 2 CO 3 33.73g of NaOH is evenly mixed and sintered, the first-stage heat preservation temperature is 450 ℃, the heat preservation time is 5 hours, and the heating rate is 3 ℃/min; the second-stage heat preservation temperature is 930 ℃, the heat preservation time is 10 hours, the temperature rising rate is 5 ℃/min, the sintering atmosphere is air, and the material NaNi is obtained by furnace cooling 1/3 Mn 1/3 Fe 1/3 O 2 。
And annealing the sintered material, wherein the annealing temperature is 500 ℃, the annealing time is 6h, the annealing atmosphere is oxygen, and the sintered material is cooled along with the furnace to obtain a finished product material.
Referring to fig. 1, the product performance can be seen from fig. 5, and the specific capacity of the material subjected to the post-treatment process provided by the application is significantly better than that of the product which is not subjected to post-treatment after the first charge and discharge. And, as can be seen from fig. 6, the cycle performance of the material subjected to the post-treatment process provided by the present application is better.
Further, the method for detecting the residual alkali content on the surface of the material under different post-treatment processes comprises the following steps: potentiometric titration. And meanwhile, the residual alkali content on the surface of the material after the material is placed under the relative humidity of 80 percent is detected.
See tables 2 and 3 for the results of the tests:
TABLE 2 Effect of post-treatment Process on residual alkali content on Material surface
| Type of process | Na 2 CO 3 Content/%) | NaOH content/%) |
| Without post-treatment | 1.358 | 1.311 |
| Post-treatment | 0.527 | 0.412 |
TABLE 3.80% residual alkali content on the surface of the material after standing at 3D relative humidity
| Type of process | Na 2 CO 3 Content/%) | NaOH content/%) |
| Without post-treatment | 6.753 | 3.267 |
| Post-treatment | 1.137 | 1.458 |
As can be seen from tables 2 and 3, the post-treatment process provided by the application can significantly reduce the residual alkali content on the surface of the material, and meanwhile, the material subjected to the post-treatment process has better air stability, and the residual alkali increment after being placed for three days is far less than that of the material which is not subjected to post-treatment.
In addition, in this experimental example, XRD examination and EDS line scan were performed on the above-described post-treated and non-post-treated materials, and it can be seen from fig. 7 that the non-post-treated material contains only O3 phase, while the post-treated material generates P2 phase in situ on the surface of O3 phase, and it can be seen from fig. 8 that Na element in the non-post-treated material is uniformly distributed from the core portion to the surface of the secondary particles, while the Na element content of the post-treated material in the core portion is significantly higher than that of the surface layer, and particularly, the Na content is gradually decreased in the direction away from the core layer.
Experimental example four: effect of the Integrated Process on Material Properties
With the molecular formula Ni 0.28 Mn 0.59 Fe 0.13 (OH) 2 The dopant is TiO 2 By using Na 2 CO 3 + NaOH (in a complex sodium source, na) 2 CO 3 The mole percentage of the Na content in the composite sodium source is 40 percent), and the molar ratio of the excessive sodium is 5 percent. And was carried out with reference to the overall process of example 1 while setting comparative examples 1 to 5.
Specifically, the method comprises the following steps:
comparative example 1: this comparative example is essentially the same as example 1, except that: in this comparative example, step S2 was omitted, and furnace cooling was performed directly after the end of sintering, followed by post-treatment as in example 1.
Comparative example 2: this comparative example is essentially the same as example 1, except that: step S3 is omitted in this comparative example.
Comparative example 3: this comparative example is essentially the same as example 1, except that: the cooling rate of the ultrafast cooling in this comparative example was 10 deg.C/min.
Comparative example 4: this comparative example is essentially the same as example 1, except that: the temperature of the post-annealing treatment in this comparative example was 100 ℃ and the post-annealing treatment was carried out for 24 hours.
Comparative example 5: this comparative example is essentially the same as example 1, except that: the temperature of the post-annealing treatment in this comparative example was 1000 ℃ and the post-annealing treatment was carried out for 2 hours.
The materials obtained in the above example 1 and comparative examples 1 to 5 were subjected to the first cycle charge and discharge test, the cycle performance test and the surface residual alkali content test, and the test results are shown in table 4, fig. 9 and fig. 10.
TABLE 4. Surface residual alkali content of materials synthesized by different processes
| Experiment number | Na 2 CO 3 Content/% | NaOH content/%) |
| Example 1 | 0 .325 | 0 .336 |
| Comparative example 1 | 0 .858 | 0 .913 |
| Comparative example 2 | 0.937 | 0 .879 |
| Comparative example 3 | 0 .726 | 0 .897 |
| Comparative example 4 | 0 .958 | 1 .012 |
| Comparative example 5 | 0 .376 | 0 .358 |
As can be seen from Table 4, the ultra-rapid cooling and post-treatment process contributes to the reduction of the residual alkali content on the surface of the material. As can be seen from fig. 9 and 10, the ultra-fast cooling and post-treatment process improves the gram capacity of the material and improves the cycle performance of the material.
In summary, the O3-P2 composite phase sodium ion positive electrode material provided by the application has a core-shell structure of an O3-P2 composite phase, has excellent charge-discharge specific capacity and excellent cycle performance, has low content of residual alkali on the surface of a shell layer, and is beneficial to improving the performance of the material. The preparation method of the application is carried out by adding Na 2 CO 3 And NaOH/NaHCO 3 The composite sodium source is sintered, the defect of a single sodium source is overcome, the comprehensive performance of the material is improved, and meanwhile, the ultra-fast cooling process is adopted to inhibit the dynamic formation process of residual alkali, so that the surface residual alkali content of the material can be obviously reduced, and the performance of the material is improved. Annealing post-treatment is carried out after the ultra-fast cooling process, so that the structural defects possibly caused in the ultra-fast cooling process can be improved, the internal stress existing between primary particles is relieved, the brittleness of secondary particles is reduced, and the mechanical property of the material is improved, which is important for keeping the particle integrity of the material in the charging and discharging process. Meanwhile, the annealing post-treatment can also decompose and volatilize residual alkali on the surface of the material, and can further induce the in-situ generation of a high-stability P2 phase on the surface of the material, which is favorable for improving the comprehensive performance of the material. The O3-P2 composite phase sodium ion positive electrode material provided by the application can be widely applied to the preparation of sodium ion batteries, and in contrast, the application provides a sodium ion battery which comprises the O3-P2 composite phase sodium ion positive electrode material according to the embodiment. In addition, the sodium ion battery can be widely applied to the preparation of energy storage devices or electric vehicles.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. O3-PThe 2 composite phase sodium ion positive electrode material is characterized by comprising an O3 type oxide layer and a P2 type oxide layer, wherein the structural formula of the O3-P2 composite phase sodium ion positive electrode material is Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1, M comprises at least one of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F; the P2 type oxide layer is generated on the surface of the O3 type oxide layer in situ to form a core-shell structure;
the preparation method of the O3-P2 composite phase sodium ion positive electrode material comprises the following steps: uniformly mixing a sodium source and an M source, sintering, and carrying out ultra-fast cooling at a speed of more than or equal to 20 ℃/min after sintering to obtain a sintering material Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1 and is used as an O3 type oxide layer, wherein the M source comprises at least one of compounds of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F;
annealing the sintering material at 200-800 ℃ for post-treatment of 2h-20h to form a P2 type oxide layer on the surface of the O3 type oxide layer in situ to obtain the O3-P2 composite phase sodium ion cathode material with the core-shell structure.
2. The O3-P2 composite phase sodium ion cathode material according to claim 1, wherein the surface of the O3-P2 composite phase sodium ion cathode material contains residual alkali Na 2 CO 3 The content of (A) is less than 0.6%, and the content of surface residual alkali NaOH is less than 0.5%.
3. The O3-P2 composite phase sodium ion cathode material according to claim 1, wherein the average particle size of the O3-P2 composite phase sodium ion cathode material is 8-12 μm, wherein the O3 type oxide layer accounts for 50-95% of the grain size, and the P2 type oxide layer accounts for 5-50% of the grain size; the Na content of the O3 type oxide layer is 90-100%, the Na content of the P2 type oxide layer is 50-90%, and the Na content gradually decreases along the direction far away from the O3 type oxide layer.
4. O3-P2 compositeThe preparation method of the phase sodium ion cathode material is characterized by comprising the following steps: uniformly mixing a sodium source and an M source, sintering, and carrying out ultrafast cooling at a speed of more than or equal to 20 ℃/min after sintering to obtain a sintering material Na x MO 2 X is more than or equal to 0.8 and less than or equal to 1 and is used as an O3 type oxide layer, wherein the M source comprises at least one of compounds of Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F;
annealing the sintering material at 200-800 ℃ for post-treatment of 2h-20h to form a P2 type oxide layer on the surface of the O3 type oxide layer in situ to obtain the O3-P2 composite phase sodium ion cathode material with the core-shell structure.
5. The method for preparing an O3-P2 composite phase sodium ion cathode material according to claim 4, wherein the sodium source comprises a first sodium source and a second sodium source, and the first sodium source is Na 2 CO 3 The second sodium source is NaHCO 3 And NaOH; the molar ratio of the first sodium source to the second sodium source is 1 to 9:1 to 9.
6. The method for preparing the O3-P2 composite phase sodium ion cathode material according to any one of claims 4 to 5, wherein the M source is a composition of a coprecipitation precursor and a dopant;
the coprecipitation precursor comprises MCO 3 、M(OH) 2 Or MC 2 O 4 M is one or more of Ti, V, cr, mn, fe, co, ni and Cu; the dopant comprises one or more of compounds containing Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F; the molar ratio of the coprecipitation precursor to the sodium source is 1:0.8 to 1; the molar ratio of the coprecipitation precursor to the dopant is 1:0.001 to 0.2.
7. The method for preparing an O3-P2 composite phase sodium ion cathode material according to any one of claims 4 to 5, wherein the M source is a solid phase sintering raw material;
the solid phase sintering raw material comprises one or more of compounds containing Ti, V, cr, mn, fe, co, ni, cu, li, ta, la, nb, zr, mg, al, sn, ru, sr, W, mo, B and F; the molar ratio of the solid-phase sintering raw material to the sodium source is 1:0.8 to 1.
8. The preparation method of the O3-P2 composite phase sodium ion cathode material according to any one of claims 4 to 5, characterized in that the sintering comprises two-stage heat preservation sintering, wherein the temperature of the first stage heat preservation is 450 ℃ to 650 ℃, the time of the first stage heat preservation is 2h to 10h, and the temperature rise rate is 1 ℃/min to 5 ℃/min; the second-stage heat preservation temperature is 800-1200 ℃, the heat preservation time is 10-25 h, and the temperature rise rate is 1-5 ℃/min.
9. A sodium ion battery, characterized in that it comprises the O3-P2 composite phase sodium ion positive electrode material according to any one of claims 1 to 3 or the O3-P2 composite phase sodium ion positive electrode material prepared by the method for preparing the O3-P2 composite phase sodium ion positive electrode material according to any one of claims 4 to 8.
10. Use of the sodium-ion battery of claim 9 in the manufacture of an energy storage device or an electric vehicle.
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| CN115557546B (en) * | 2022-12-06 | 2023-03-21 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN115911343B (en) * | 2023-02-27 | 2023-06-02 | 南开大学 | Sodium ion battery composite positive electrode material with high sodium content and high voltage |
| CN116443946A (en) * | 2023-03-15 | 2023-07-18 | 深圳市比克动力电池有限公司 | Positive electrode material, preparation method thereof and battery |
| CN116495799A (en) * | 2023-04-27 | 2023-07-28 | 南通瑞翔新材料有限公司 | O3 type sodium ion positive electrode material, preparation method thereof and sodium ion battery |
| CN116190561B (en) * | 2023-04-28 | 2023-09-15 | 宁德时代新能源科技股份有限公司 | Battery monomer of sodium ion battery, sodium ion battery and power utilization device |
| CN116598462A (en) * | 2023-06-09 | 2023-08-15 | 巴斯夫杉杉电池材料有限公司 | Layered positive electrode material of sodium ion battery and preparation method thereof |
| CN116581286B (en) * | 2023-07-11 | 2023-10-20 | 天津国安盟固利新材料科技股份有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN117457887A (en) * | 2023-12-18 | 2024-01-26 | 江苏正力新能电池技术有限公司 | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
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