CN115148978A - Layered oxide positive electrode material, preparation method thereof and sodium ion battery - Google Patents
Layered oxide positive electrode material, preparation method thereof and sodium ion battery Download PDFInfo
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Abstract
The invention provides a layered oxide anode material, a preparation method thereof and a sodium ion battery x Mn a M 1‑a O 2 Said shell comprising Na x Ni b Mn c Fe d O 2 Wherein x is more than 0.7 and less than or equal to 0.9,0.8 and less than or equal to a and less than 1,0.2 and less than or equal to b and less than 0.5,0.2 and less than or equal to c and less than 0.6,0.2 and less than or equal to d and less than or equal to 0.5, and M comprises any one or combination of at least two of Ni, ti, fe and Cu. According to the invention, through the synergistic effect of the core and the shell, mn is prevented from dissolving, the side reaction of the material and the electrolyte in the reaction process is reduced, and the layered oxygen is improvedThe discharge capacity and the cycle performance of the compound cathode material.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a layered oxide positive electrode material, a preparation method thereof and a sodium ion battery.
Background
Lithium Ion Batteries (LIBs) have been used with initial success in large-scale electrochemical energy storage systems, and solid-state LIBs using metallic lithium as the anode have also been well developed. However, the dramatic increase in demand and cost and the limited reserves of the important metallic elements lithium and cobalt in LIBs have raised concerns for future development. Sodium Ion Batteries (SIBs) equipped with advanced cobalt-free cathodes have shown great potential in addressing "lithium panic" and "cobalt panic" and have made significant progress in recent years.
As one of the most core materials of the sodium ion battery, a sodium electrode material is a major concern of researchers. The positive electrode material of the sodium-ion battery researched at present is mainly a crystalline material and comprises a transition metal oxide, a polyanion compound and a prussian blue compound. The transition metal layered oxide anode material has the advantages of wide raw material source, good processing performance, high specific capacity and the like, and has great application potential in the fields of low cost and large-scale energy storage. CN112563484A provides a sodium ion battery anode material and a preparation method thereof, wherein sodium salt, nickel salt and M salt solution are mixed, and are sintered after reaction under the conditions of high temperature and high pressure to obtain Na with a layered structure x Ni y M 1-y O 2 The positive electrode material improves the capacity and the cycle performance of the material. CN108899538A provides a ternary sodium-ion battery anode material and a preparation method thereof, wherein the ternary sodium-ion battery anode material contains divalent nickel salt, divalent cobalt salt and di-nickel saltAnd mixing the salt solution of the manganese salt with the alkali solution, carrying out coprecipitation reaction, then presintering, adding the sodium source and the titanium source after sintering, and calcining again to obtain the ternary sodium-ion battery anode material with good cycle stability and discharge voltage platform. CN109607624B adds soluble carbonate, manganese salt and cobalt salt into water to stir and react, and after generating precipitate, sodium hydroxide is added to sinter to obtain the sodium ion battery anode material with a layered-tunnel composite structure.
The transition metal layered oxide of the sodium ion battery in the prior art comprises single metal oxide, double metal oxide and multi-metal oxide, and for the sodium manganate of single metal oxide, although the capacity is higher, the material has higher internal resistance and serious polarization in the circulation process, and Mn 3+ Octahedral compounds usually show a strong Jahn-Teller effect, which results in a fast capacity attenuation and an unsatisfactory cycle performance of the material; the multi-metal nickel-iron-manganese layered oxide cathode material has good air stability and excellent cycling stability under normal pressure, but the gram capacity of the multi-metal nickel-iron-manganese layered oxide cathode material is low, so that the application of the multi-metal nickel-iron-manganese layered oxide cathode material in the field of high-energy density batteries is hindered.
In conclusion, the preparation of the positive electrode material of the sodium-ion battery with higher specific capacity and good cycling stability has important significance for the research and development of the sodium-ion battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a layered oxide positive electrode material, a preparation method thereof and a sodium ion battery x Mn a M 1-a O 2 The outer shell comprises Na x Ni b Mn c Fe d O 2 The core and the shell have synergistic effect, so that Mn can be prevented from being dissolved, the side reaction of the material and the electrolyte in the reaction process is reduced, and the discharge capacity and the cycle performance of the layered oxide anode material are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a layered oxide cathode material, which includes an inner core and an outer shell coated on the surface of the inner core, wherein the inner core includes Na x Mn a M 1-a O 2 Said housing comprising Na x Ni b Mn c Fe d O 2 Wherein x is more than 0.7 and less than or equal to 0.9,0.8 and less than or equal to a and less than 1,0.2 and less than or equal to b and less than 0.5,0.2 and less than or equal to c and less than 0.6,0.2 and less than or equal to d and less than or equal to 0.5, and M comprises any one or combination of at least two of Ni, ti, fe and Cu.
In the present invention, 0.7 < x.ltoreq.0.9, for example, 0.71, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88 or 0.9, etc., 0.8 < a < 1, for example, 0.8, 0.82, 0.84, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96, 0.98 or 0.99, etc., 0.2 < b < 0.5, for example, it may be 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.49, etc., 0.2. Ltoreq. C < 0.6, for example, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55 or 0.59, etc., and 0.2. Ltoreq. D.ltoreq.0.5, for example, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, etc.
The layered oxide anode material prepared by the invention has a core-shell structure, and the core contains Na with high manganese content x Mn a M 1-a O 2 The outer shell comprises Na x Ni b Mn c Fe d O 2 The core material can provide higher specific capacity for the anode, and the shell can effectively block Na x Mn a M 1-a O 2 The material is contacted with the electrolyte, so that the dissolution of Mn is avoided, and the occurrence of side reaction of the material and the electrolyte in the reaction process is reduced; meanwhile, the core-shell materials are mutually synergistic, so that the comprehensive electrochemical performance of the material, particularly the discharge capacity and the cycle performance, can be improved.
The cathode material provided by the invention has less Ni content, does not contain Co rare noble metals, has the advantages of low price, simple preparation method and the like, and has better application prospect in the fields of energy storage and the like.
Preferably, the D50 particle size of the layered oxide positive electrode material is 3 to 15 μm, and may be, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm.
Preferably, the thickness of the outer shell is 5 to 10% of the D50 particle diameter of the layered oxide positive electrode material, and may be, for example, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, or the like.
In the present invention, the thickness of the outer shell means the average thickness of the outer shell in the layered oxide positive electrode material; for example, when the layered oxide layer is a sphere, if the D50 particle size thereof is 10 μm and the D50 particle size of the core is 8 μm, the total length of the outer shell in the thickness direction thereof in the cross section is 2 μm, that is, the thickness of the outer shell is 1 μm.
According to the invention, the structural stability of the sodium-electricity positive electrode material can be improved by optimizing the size of the layered oxide positive electrode material and adjusting the thickness of the shell, and the cycle stability and the thermal stability of the material are further improved.
In a second aspect, the present invention provides a method for producing the layered oxide positive electrode material according to the first aspect, the method comprising:
(1) Mixing a first salt solution, a precipitator and a complexing agent to carry out a first coprecipitation reaction to obtain a core precursor, adding a second salt solution to carry out a second coprecipitation reaction, and generating a shell precursor on the surface of the core precursor to obtain a hydroxide precursor;
the core precursor comprises Mn a M 1-a (OH) 2 The housing precursor includes Ni b Mn c Fe d (OH) 2 ；
(2) And mixing and sintering the hydroxide precursor and a sodium source to obtain the layered oxide cathode material.
According to the invention, a two-step feeding and two-step coprecipitation mode is adopted to generate the hydroxide precursor with the core-shell structure, and the layered oxide anode material is obtained by adding the sodium source and sintering.
In the present invention, when performing the second coprecipitation, the second salt solution may be directly added, and the coprecipitation reaction may be performed under the effect of the original precipitant and the complexing agent, or a certain amount of precipitant and the complexing agent may be added again to perform the coprecipitation reaction.
Preferably, the D50 particle diameter of the core precursor is 80 to 90% of the D50 particle diameter of the hydroxide precursor, and may be, for example, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%.
In the invention, when the coprecipitation is carried out, the core precursor is fed again to carry out the second coprecipitation reaction when the core precursor grows to 80-90% of the target size grain diameter, so that the components and the thickness of the shell can be effectively regulated and controlled.
Preferably, the first salt solution comprises Mn and M in a molar ratio of a (1-a).
Preferably, the second salt solution comprises Ni, mn and Fe in a molar ratio b: c: d.
Preferably, the kind of the salt in the first salt solution and the second salt solution is independently any one of chloride, oxalate, sulfate and nitrate or a combination of at least two of them, and for example, it may be a combination of chloride and nitrate, a combination of oxalate and sulfate, a combination of sulfate and nitrate, a combination of chloride, oxalate and sulfate, or a combination of chloride, oxalate, sulfate and nitrate, etc.
In the present invention, "independently" means that the selection of the two is not interfered, for example, the types of the salts in the first salt solution and the second salt solution are independently any one or a combination of at least two of chloride, oxalate, sulfate and nitrate, which means that when the type of the salt in the first salt solution is chloride, the type of the salt in the second salt solution may be chloride, oxalate, a combination of sulfate and nitrate, etc., and the selection of the types of the salts in the first salt solution and the second salt solution is not interfered with each other.
Preferably, the concentration of the first salt solution and the second salt solution is independently 80 to 120g/L, and may be, for example, 80g/L, 85g/L, 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g/L, or 120g/L, etc.
Preferably, the precipitating agent comprises an aqueous sodium hydroxide solution.
Preferably, the mass fraction of the solute in the precipitant is 20 to 40%, for example, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, or the like, based on 100% by mass of the precipitant.
Preferably, the complexing agent includes any one or combination of at least two of ammonia, oxalic acid, lactic acid, sodium oxalate and EDTA solution, and may be, for example, a combination of oxalic acid and lactic acid, a combination of sodium oxalate and EDTA solution, a combination of ammonia and sodium oxalate, or a combination of oxalic acid, lactic acid, sodium oxalate and EDTA solution, etc.
Preferably, the concentration of the complexing agent is 8 to 10mol/L, for example, 8mol/L, 8.2mol/L, 8.4mol/L, 8.6mol/L, 8.8mol/L, 9mol/L, 9.2mol/L, 9.4mol/L, 9.6mol/L, 9.8mol/L, or 10mol/L based on the volume of the complexing agent.
In a preferred embodiment of the preparation method of the present invention, the temperature of the first coprecipitation and the temperature of the second coprecipitation are independently 40 to 70 ℃, and may be, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃.
Preferably, the pH of the first co-precipitate and the second co-precipitate is independently 9.5 to 11.5, and may be, for example, 9.5, 9.8, 10, 10.2, 10.5, 10.8, 11, 11.2, or 11.5, etc.
In the invention, the coprecipitation reaction is carried out at a proper temperature and pH value, and the sphericity and crystallinity of the precursor can be improved.
Preferably, based on the volume of the first coprecipitated solution and the second coprecipitated solution, the concentration of the complexing agent is independently 0.1 to 0.5mol/L, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, and the like, and the coprecipitated solution contains the complexing agent with a suitable concentration, which is beneficial to controlling the growth rate of the precursor and improving the sphericity of the precursor.
Preferably, the rotation speed of the first co-precipitation and the second co-precipitation is independently 320 to 380rpm/min, for example 320rpm/min, 330rpm/min, 340rpm/min, 350rpm/min, 360rpm/min, 370rpm/min or 380rpm/min, etc.
Preferably, the method further comprises the steps of aging, filtering, washing and drying after the second coprecipitation and before sintering.
Preferably, the drying temperature is 100-120 ℃, for example, can be 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ or 120 ℃.
Illustratively, the drying manner includes any one of rotary kiln drying, microwave drying, tray dryer drying and box oven drying or a mixed drying of at least two.
Preferably, the molar ratio of Na in the sodium source to the sum of Ni, mn, fe, and M in the hydroxide precursor is 0.7 to 0.9, and may be, for example, 0.7, 0.75, 0.8, 0.85, or 0.9.
Preferably, the sodium source includes any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium oxalate, sodium chloride and sodium nitrate, and may be, for example, a combination of sodium hydroxide and sodium carbonate, a combination of sodium oxalate and sodium chloride, a combination of sodium chloride and sodium nitrate, or a combination of sodium hydroxide, sodium carbonate, sodium oxalate, sodium chloride and sodium nitrate, or the like.
As a preferable embodiment of the preparation method of the present invention, the sintering includes first sintering and second sintering.
Preferably, the temperature of the first sintering is 450 to 550 ℃, for example, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃ or the like can be used.
Preferably, the time of the first sintering is 4 to 6 hours, and for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, etc. may be used.
Preferably, the temperature increase rate of the first sintering is 3 to 5 ℃/min, and may be, for example, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min or the like.
Preferably, the temperature of the second sintering is 600 to 800 ℃, for example, 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃ or the like.
Preferably, the time of the second sintering is 10 to 16h, for example, 10h, 11h, 12h, 13h, 14h, 15h or 16h, etc.
Preferably, the temperature increase rate of the second sintering is 3 to 5 ℃/min, and may be, for example, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min or the like.
According to the invention, by carrying out two-step sintering at a proper temperature and time, the diffusion of sodium ions in the high-temperature sintering process is facilitated, and the residual sodium on the surface of the material is reduced.
As a preferable technical scheme of the preparation method of the invention, the preparation method comprises the following steps:
(1) Mixing a first salt solution, a precipitator and a complexing agent to carry out a first coprecipitation reaction, wherein the first salt solution comprises Mn and M with a molar ratio of (a) - (1-a) to obtain a core precursor, then adding a second salt solution to carry out a second coprecipitation reaction, wherein the second salt solution comprises Ni, mn and Fe with a molar ratio of b: c: d, and generating a shell precursor on the surface of the core precursor to obtain a hydroxide precursor;
the temperature of the first coprecipitation and the temperature of the second coprecipitation are 40-70 ℃ independently, the pH value of the first coprecipitation and the pH value of the second coprecipitation are 9.5-11.5 independently, the volume of the solution of the first coprecipitation and the volume of the solution of the second coprecipitation are taken as reference, the concentration of the complexing agent is 0.1-0.5 mol/L independently, and the core precursor comprises Mn a M 1-a (OH) 2 The housing precursor includes Ni b Mn c Fe d (OH) 2 The D50 particle size of the core precursor is 80-90% of the D50 particle size of the hydroxide precursor;
(2) And mixing the hydroxide precursor with a sodium source, sintering at 450-550 ℃ for 4-6 h, and sintering again at 600-800 ℃ for 10-16 h to obtain the layered oxide anode material.
In a third aspect, the present invention provides a sodium ion battery, wherein the positive electrode of the sodium ion battery comprises the layered oxide positive electrode material according to the first aspect.
The sodium ion battery prepared by the layered oxide cathode material has high specific capacity and good cycling stability, and shows excellent comprehensive electrochemical performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) The layered oxide anode material prepared by the invention has a core-shell structure, and the core contains Na with high manganese content x Mn a M 1-a O 2 The outer shell comprises Na x Ni b Mn c Fe d O 2 The core material can provide higher specific capacity for the anode, and the shell can effectively block Na x Mn a M 1-a O 2 The material is contacted with the electrolyte, so that the dissolution of Mn is avoided, and the occurrence of side reaction of the material and the electrolyte in the reaction process is reduced; meanwhile, the core-shell materials are mutually synergistic, so that the comprehensive electrochemical performance of the material, particularly the discharge capacity and the cycle performance, can be improved.
(2) The cathode material provided by the invention has less Ni content, does not contain Co rare noble metals, has the advantages of low price, simple preparation method and the like, and has better application prospect in the fields of energy storage and the like.
Drawings
FIG. 1 is a sectional SEM photograph of a hydroxide precursor prepared in example 1 of the present invention.
FIG. 2 is a sectional view of a Ni element in the hydroxide precursor prepared in example 1 of the present invention.
Fig. 3 is an SEM image of the layered oxide positive electrode material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
This example provides a layered oxide cathode material comprising an inner core of Na 0.8 Mn 0.85 Cu 0.15 O 2 And a shell Na coated on the surface of the inner core 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The thickness of the outer shell was 1 μm, and the D50 particle size of the layered oxide positive electrode material was 12 μm.
The embodiment also provides a preparation method of the layered oxide cathode material, which comprises the following steps:
(1) Sequentially weighing manganese sulfate and copper sulfate to enable the molar ratio of manganese to copper to be 0.85; weighing manganese sulfate, ferrous sulfate and nickel sulfate in sequence, enabling the molar ratio of nickel to iron to manganese to be 0.33;
(2) Simultaneously adding a first salt solution, a precipitator and a complexing agent into a reaction kettle in parallel for a first coprecipitation reaction, controlling the reaction temperature to be 60 ℃, the pH to be 10.5, the concentration of ammonia water to be 0.34mol/L, the rotating speed of the reaction kettle to be 350rmp, stopping introducing the first salt solution when the particle size reaches 10 mu m, adding a second salt solution for reaction, aging and standing for 12h when the particle size reaches 12 mu m, filtering, washing for 2 times by deionized water, and drying for 10h at 100 ℃ to obtain a core precursor Mn 0.85 Cu 0.15 (OH) 2 The precursor of the shell is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The hydroxide precursor of core-shell structure of (1);
(3) Uniformly mixing the hydroxide precursor obtained in the step (2) with sodium carbonate according to the molar ratio of Na to transition metal (Ni, fe, mn and Cu) of 0.8 0.8 Mn 0.85 Cu 0.15 O 2 The outer shell is Na 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The layered oxide positive electrode material with a core-shell structure.
Example 2
This example provides a layered oxide cathode material comprising an inner core of Na 0.8 Mn 0.8 Ni 0.2 O 2 And a shell Na coated on the surface of the inner core 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The thickness of the outer shell was 0.8. Mu.m, and the D50 particle diameter of the layered oxide positive electrode material was 8 μm.
The embodiment also provides a preparation method of the layered oxide cathode material, which comprises the following steps:
(1) Sequentially weighing manganese sulfate and nickel sulfate to enable the molar ratio of manganese to nickel to be 0.8; weighing manganese sulfate, ferrous sulfate and nickel sulfate in sequence, enabling the molar ratio of nickel to iron to manganese to be 0.33;
(2) Simultaneously adding a first salt solution, a precipitator and a complexing agent into a reaction kettle in parallel for a first coprecipitation reaction, controlling the reaction temperature to be 70 ℃, the pH to be 10, the concentration of ammonia water to be 0.3mol/L, the rotating speed of the reaction kettle to be 380rmp, stopping introducing the first salt solution when the particle size reaches 6.4 mu m, adding a second salt solution for reaction, aging and standing for 12h when the particle size reaches 8 mu m, filtering, washing for 2 times by deionized water, and drying for 10h at 110 ℃ to obtain a core precursor Mn 0.8 Ni 0.2 (OH) 2 The precursor of the shell is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The sectional SEM image and the sectional Ni element distribution diagram of the hydroxide precursor with the core-shell structure are respectively shown in FIG. 1 and FIG. 2;
(3) Uniformly mixing the hydroxide precursor obtained in the step (2) with sodium carbonate according to the molar ratio of Na to transition metal (Ni, fe, mn and Cu) of 0.85 0.8 Mn 0.85 Cu 0.15 O 2 The outer shell is Na 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The SEM image of the layered oxide positive electrode material having a core-shell structure of (1) is shown in fig. 3.
Example 3
This example provides a layered oxide cathode material comprising an inner core of Na 0.8 Mn 0.85 Cu 0.15 O 2 And a shell Na coated on the surface of the inner core 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The thickness of the outer shell was 1.5 μm, and the D50 particle diameter of the layered oxide positive electrode material was 15 μm.
The embodiment also provides a preparation method of the layered oxide cathode material, which comprises the following steps:
(1) Sequentially weighing manganese sulfate and copper sulfate to enable the molar ratio of manganese to copper to be 0.85; weighing manganese sulfate, ferrous sulfate and nickel sulfate in sequence, enabling the molar ratio of nickel to iron to manganese to be 0.33;
(2) Simultaneously adding the first salt solution, a precipitator and a complexing agent into a reaction kettle in parallel for carrying out a first coprecipitation reaction, controlling the reaction temperature to be 55 ℃, the pH to be 11, the concentration of ammonia water to be 0.4mol/L, the rotating speed of the reaction kettle to be 380rmp, stopping introducing the first salt solution when the particle size reaches 12 mu m, adding a second salt solution for carrying out a reaction, aging and standing for 12h when the particle size reaches 15 mu m, filtering, washing for 2 times with deionized water, and drying for 10h at 100 ℃ to obtain a core precursor Mn which is a core precursor 0.85 Cu 0.15 (OH) 2 The precursor of the shell is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The hydroxide precursor of core-shell structure of (1);
(3) Uniformly mixing the hydroxide precursor obtained in the step (2) with sodium carbonate according to the molar ratio of Na to transition metal (Ni, fe, mn and Cu) of 0.8 0.8 Mn 0.85 Cu 0.15 O 2 The outer shell is Na 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 The core-shell structure of the layered oxide positive electrode material.
Example 4
The same procedure as in example 1 was repeated, except that in the step (2), the first salt solution was stopped from being introduced when the particle size reached 9 μm, and the second salt solution was added to react so that the thickness of the outer shell was 15% of the D50 particle size of the layered oxide positive electrode material.
Example 5
The same procedure as in example 1 was repeated, except that in the step (2), the introduction of the first salt solution was stopped when the particle size reached 11 μm, and the second salt solution was added to react so that the thickness of the outer shell was 3% of the D50 particle size of the layered oxide positive electrode material.
Example 6
The same procedure as in example 1 was followed, except that the pH of the first coprecipitation and the second coprecipitation were changed to 8.5.
Example 7
The same procedure as in example 1 was followed, except that the pH of the first coprecipitation and the second coprecipitation were changed to 12.
Example 8
The procedure was repeated in the same manner as in example 1 except that the concentration of aqueous ammonia (complexing agent) in the coprecipitation reaction in step (2) was changed to 0.09 mol/L.
Example 9
The procedure was repeated as in example 1 except that the concentration of aqueous ammonia (complexing agent) in the coprecipitation reaction in step (2) was changed to 0.6 mol/L.
Example 10
The same procedure as in example 1 was repeated, except that the temperature of the first sintering in step (3) was changed to 500 ℃ instead of 400 ℃.
Example 11
The same procedure as in example 1 was repeated, except that the temperature of the first sintering in step (3) was changed to 500 ℃ instead of 600 ℃.
Example 12
The same procedure as in example 1 was repeated, except that the temperature of the second sintering in step (3) was changed to 700 ℃.
Example 13
The same procedure as in example 1 was repeated, except that the temperature of the second sintering in step (3) was changed to 700 ℃ instead of 850 ℃.
Comparative example 1
The same procedure as in example 1 was repeated, except that only the first salt solution was fed in the step (2), and the second salt solution was not fed in;
this comparative example prepared Na having a D50 particle size of 12 μm 0.8 Mn 0.85 Cu 0.15 O 2 And (3) a positive electrode material.
Comparative example 2
The same procedure as in example 1 was repeated, except that only the second salt solution was introduced in the step (2) and the first salt solution was not introduced;
this comparative example prepared Na having a D50 particle size of 12 μm 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 And (3) a positive electrode material.
Comparative example 3
The procedure of example 1 was repeated except that the first salt solution and the second salt solution were not introduced, and only the manganese sulfate solution having a concentration of 98g/L was introduced;
this comparative example prepared Na having a D50 particle size of 12 μm 0.8 MnO 2 And (3) a positive electrode material.
1. Preparation of sodium ion battery
Uniformly mixing the positive electrode material prepared in the above examples and comparative examples with conductive carbon black and polyvinylidene fluoride in a mass ratio of 90; rolling the dried pole piece to a proper thickness, punching the pole piece into a pole piece with the diameter of 10mm, and drying the pole piece and the diaphragm in a vacuum environment for 12 hours; and finally, assembling the 2025 type button cell by taking a sodium sheet as a counter electrode in a glove box.
2. Electrochemical Performance test
The method comprises the steps of carrying out charge and discharge tests by adopting a blue current CT2001A type electrochemical tester, wherein the voltage range is 2.5-4.0V, the test current density is 0.2C, the number of cycles is 50, recording the initial specific capacity of the battery and the specific capacity after 50 cycles, dividing the initial specific capacity by the specific capacity after 50 cycles to obtain the capacity retention ratio after 50 cycles, and the experimental results are shown in Table 1.
TABLE 1
| Serial number | Initial specific capacity (mAh g) -1 ) | Capacity retention after 50 cycles (%) |
| Example 1 | 160.3 | 84.1 |
| Example 2 | 159.3 | 84.5 |
| Example 3 | 161.2 | 85.1 |
| Example 4 | 158.1 | 82.2 |
| Example 5 | 159.5 | 82.1 |
| Example 6 | 158.1 | 80.2 |
| Example 7 | 157.2 | 81.3 |
| Example 8 | 157.3 | 80.4 |
| Example 9 | 156.6 | 82.2 |
| Example 10 | 158.2 | 80.1 |
| Example 11 | 159.9 | 80.9 |
| Example 12 | 157.2 | 75.8 |
| Example 13 | 157.3 | 78.9 |
| Comparative example 1 | 155.2 | 71.1 |
| Comparative example 2 | 150.3 | 83.2 |
| Comparative example 3 | 158.2 | 50.1 |
As can be seen from the above examples 1 to 13, the layered oxide positive electrode material of the present invention has a core-shell structure, and the core includes Na having a high manganese content x Mn a M 1-a O 2 The outer shell comprises Na x Ni b Mn c Fe d O 2 The core and the shell have synergistic effect, so that Mn can be prevented from being dissolved, the side reaction of the material and the electrolyte in the reaction process is reduced, and the discharge capacity and the cycle performance of the layered oxide anode material are improved.
As can be seen from comparison between the embodiment 1 and the embodiments 4 to 5, the invention fully exerts the synergistic effect between the core and the shell by controlling the particle sizes of the core and the shell, and improves the initial specific capacity and the cycle performance of the material. In example 4, the outer shell is thicker, which causes lower material capacity and lower cycle performance; example 5, which has a thinner outer shell, results in a lower cycling performance of the material, and thus example 1 has a higher capacity and better cycling performance.
It can be seen from the comparison between example 1 and examples 6-9 that the structural stability of the material can be further optimized by controlling the reaction conditions of the two coprecipitation reactions and the concentration of the complexing agent, in examples 6-7, too high or too low of the pH results in unsatisfactory cycle performance of the material, in examples 8-9, too high or too low of the complexing agent results in unsatisfactory cycle performance of the material, and therefore, example 1 has higher capacity and better cycle performance than examples 6-9.
As can be seen from the comparison of example 1 with examples 10-13, the residual sodium in the material can be reduced by two-step sintering and further optimizing the temperature of the second sintering of the first sintering in the invention; the cycle performance of example 1 was better than that of examples 10-13.
As is clear from comparison of example 1 with comparative examples 1 to 3, na alone was used in the present invention 0.8 Mn 0.85 Cu 0.15 O 2 Positive electrode Material, na 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 Positive electrode material or Na 0.8 MnO 2 The positive electrode material cannot realize the effect of improving the specific capacity and the cycle performance of the material by the synergistic interaction of the core and the shell in the application; comparative example 1 using Na 0.8 Mn 0.85 Cu 0.15 O 2 The manganese of the anode material is easily dissolved in the electrolyte, and the specific capacity and the cycling stability of the material are influenced, so that the initial specific capacity and the capacity retention rate after 50 circles of comparison are obviously inferior to those of the anode material in the embodiment 1; comparative example 2 in which Na was used 0.8 Ni 0.33 Fe 0.33 Mn 0.33 O 2 A positive electrode material having an initial specific capacity of less than 10mAh g -1 The effect is obviously inferior to that of the application; na in comparative example 3 0.8 MnO 2 Although the initial specific capacity of the cathode material is not much different from that of the cathode material in embodiment 1, the capacity retention rate is only 50.1% after 50 circles, and the cycle performance is extremely poor; in summary, the overall electrochemical performance of comparative examples 1-3 is significantly inferior to that of the present application.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The layered oxide cathode material is characterized by comprising an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises Na x Mn a M 1-a O 2 Said housing comprising Na x Ni b Mn c Fe d O 2 Wherein x is more than 0.7 and less than or equal to 0.9,0.8 and less than or equal to a and less than 1,0.2 and less than or equal to b and less than 0.5,0.2 and less than or equal to c and less than 0.6,0.2 and less than or equal to d and less than or equal to 0.5, and M comprises any one or combination of at least two of Ni, ti, fe and Cu.
2. The layered oxide positive electrode material according to claim 1, wherein the D50 particle diameter of the layered oxide positive electrode material is 3 to 15 μm;
preferably, the thickness of the outer shell is 5 to 10% of the D50 particle diameter of the layered oxide positive electrode material.
3. A production method of the layered oxide positive electrode material according to claim 1 or 2, characterized by comprising:
(1) Mixing a first salt solution, a precipitator and a complexing agent to carry out a first coprecipitation reaction to obtain a core precursor, adding a second salt solution to carry out a second coprecipitation reaction, and generating a shell precursor on the surface of the core precursor to obtain a hydroxide precursor;
the core precursor comprises Mn a M 1-a (OH) 2 The housing precursor includes Ni b Mn c Fe d (OH) 2 ；
(2) And mixing and sintering the hydroxide precursor and a sodium source to obtain the layered oxide cathode material.
4. The production method according to claim 3, wherein the D50 particle diameter of the core precursor is 80 to 90% of the D50 particle diameter of the hydroxide precursor.
5. The method of claim 3 or 4, wherein the first salt solution comprises Mn and M in a molar ratio of a (1-a);
preferably, the second salt solution comprises Ni, mn and Fe in a molar ratio of b: c: d;
preferably, the salt species in the first salt solution and the second salt solution are independently any one or a combination of at least two of chloride, oxalate, sulfate and nitrate;
preferably, the concentrations of the first salt solution and the second salt solution are independently 80-120 g/L;
preferably, the precipitating agent comprises an aqueous sodium hydroxide solution;
preferably, the mass fraction of the solute in the precipitating agent is 20-40% based on 100% of the mass of the precipitating agent;
preferably, the complexing agent comprises any one of ammonia, oxalic acid, lactic acid, sodium oxalate and EDTA solution or the combination of at least two of the ammonia water, the oxalic acid, the lactic acid, the sodium oxalate and the EDTA solution;
preferably, the concentration of the complexing agent is 8-10 mol/L based on the volume of the complexing agent.
6. The method of any one of claims 3-5, wherein the temperatures of the first co-precipitation and the second co-precipitation are independently 40 to 70 ℃;
preferably, the pH of the first and second co-precipitates is independently from 9.5 to 11.5;
preferably, the concentration of the complexing agent is independently 0.1 to 0.5mol/L based on the volume of the first co-precipitated solution and the second co-precipitated solution;
preferably, the rotation speed of the first coprecipitation and the second coprecipitation is 320-380 rpm/min independently;
preferably, the method further comprises the steps of aging, filtering, washing and drying after the second coprecipitation and before sintering;
preferably, the drying temperature is 100 to 120 ℃.
7. The production method according to any one of claims 3 to 6, characterized in that the molar ratio of Na in the sodium source to the sum of Ni, mn, fe and M in the hydroxide precursor is 0.7 to 0.9;
preferably, the sodium source comprises any one of sodium hydroxide, sodium carbonate, sodium oxalate, sodium chloride and sodium nitrate or a combination of at least two thereof.
8. The production method according to any one of claims 3 to 7, wherein the sintering includes a first sintering and a second sintering;
preferably, the temperature of the first sintering is 450-550 ℃;
preferably, the time of the first sintering is 4-6 h;
preferably, the heating rate of the first sintering is 3-5 ℃/min;
preferably, the temperature of the second sintering is 600-800 ℃;
preferably, the time of the second sintering is 10-16 h;
preferably, the temperature rise rate of the second sintering is 3 to 5 ℃/min.
9. The production method according to any one of claims 3 to 8, characterized by comprising:
(1) Mixing a first salt solution, a precipitator and a complexing agent to carry out a first coprecipitation reaction, wherein the first salt solution comprises Mn and M with a molar ratio of (a) - (1-a) to obtain a core precursor, adding a second salt solution to carry out a second coprecipitation reaction, and the second salt solution comprises Ni, mn and Fe with a molar ratio of b: c: d to generate a shell precursor on the surface of the core precursor to obtain a hydroxide precursor;
the temperature of the first coprecipitation and the temperature of the second coprecipitation are 40-70 ℃ independently, the pH value of the first coprecipitation and the pH value of the second coprecipitation are 9.5-11.5 independently, the volume of the solution of the first coprecipitation and the volume of the solution of the second coprecipitation are taken as reference, the concentration of the complexing agent is 0.1-0.5 mol/L independently, and the core precursor comprises Mn a M 1-a (OH) 2 The housing precursor includes Ni b Mn c Fe d (OH) 2 The D50 particle size of the core precursor is 80-90% of the D50 particle size of the hydroxide precursor;
(2) And mixing the hydroxide precursor with a sodium source, sintering at 450-550 ℃ for 4-6 h, and sintering again at 600-800 ℃ for 10-16 h to obtain the layered oxide anode material.
10. A sodium-ion battery characterized in that the layered oxide positive electrode material according to claim 1 or 2 is included in a positive electrode of the sodium-ion battery.
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| CN202210950001.7A CN115148978A (en) | 2022-08-09 | 2022-08-09 | Layered oxide positive electrode material, preparation method thereof and sodium ion battery |
| PCT/CN2022/140550 WO2024031913A1 (en) | 2022-08-09 | 2022-12-21 | Layered oxide positive electrode material and preparation method therefor, and sodium-ion battery |
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| CN115954463A (en) * | 2023-03-09 | 2023-04-11 | 江苏正力新能电池技术有限公司 | Sodium ion battery layered oxide composite material and preparation method thereof, positive plate and sodium ion battery |
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| CN116826162A (en) * | 2023-08-28 | 2023-09-29 | 河南新太行电源股份有限公司 | Solid sodium ion battery and preparation method thereof |
| CN117023662A (en) * | 2023-10-09 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | Concentration gradient multi-shell structure sodium ion battery anode material |
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| US20150333325A1 (en) * | 2012-11-19 | 2015-11-19 | Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) | Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same |
| CN110277540B (en) * | 2018-03-14 | 2020-08-04 | 中国科学院物理研究所 | Core-shell structure sodium ion battery positive electrode material and preparation method and application thereof |
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| WO2022126253A1 (en) * | 2020-12-14 | 2022-06-23 | HYDRO-QUéBEC | Electrode materials comprising a lamellar metal oxide coated with a tunnel-type metal oxide, electrodes comprising same and use thereof in electrochemistry |
| CN115148978A (en) * | 2022-08-09 | 2022-10-04 | 格林美股份有限公司 | Layered oxide positive electrode material, preparation method thereof and sodium ion battery |
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