CN118431441A - Layered sodium ion high-entropy oxide positive electrode material and preparation method and application thereof - Google Patents
Layered sodium ion high-entropy oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 32
- 239000011812 mixed powder Substances 0.000 claims abstract description 30
- 238000000227 grinding Methods 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 230000008859 change Effects 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000003801 milling Methods 0.000 description 18
- 239000010406 cathode material Substances 0.000 description 11
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
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- 150000003624 transition metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- -1 Prussian blue compound Chemical class 0.000 description 2
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a layered sodium ion high-entropy oxide positive electrode material, a preparation method and application thereof, and relates to the technical field of new energy battery positive electrode materials. The chemical general formula of the positive electrode material provided by the invention is Na nNixMnyFezTMmO2, and the TM is at least five of Mg, cu, ti, li, K, nb, al, ca, mn, zr, sn, ce, mo, W, sb; wherein n is more than or equal to 0.8 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, and x+y+z+m=1. The method provided by the invention comprises the following steps: mixing and grinding a sodium source, a nickel source, a manganese source, an iron source and a TM source to obtain mixed powder; and carrying out sectional heat treatment on the mixed powder in an oxygen-containing atmosphere, and then cooling and grinding to obtain the high-entropy oxide anode material. The positive electrode material provided by the invention has a stable structure, and can relieve phase change and effectively improve the capacity and cycle performance of the sodium ion battery.
Description
Technical Field
The invention relates to the technical field of new energy battery anode materials, in particular to a layered sodium ion high-entropy oxide anode material, a preparation method and application thereof.
Background
In the society which is continuously developed nowadays, non-renewable fossil energy sources such as coal, petroleum, natural gas and the like are energy sources which are used daily by people, however, the large-scale exploitation and application of the fossil energy sources have caused the problems of resource shortage, environmental pollution and the like, and the requirements of strictly controlling the consumption of the fossil energy sources and developing renewable clean energy sources become sustainable development are necessarily met. In recent years, renewable clean energy sources such as solar energy, wind energy and tidal energy are rapidly developed, but cannot be directly applied to grid connection due to the restriction of factors such as territory, seasonality and climaticity.
Currently, combining the clean energy source with a large-scale energy storage system is an effective means for improving the problems, and electrochemical energy storage in various energy storage technologies has the advantages of high energy conversion efficiency, low equipment maintenance cost, high response speed, long service life and the like, and is concerned by the energy storage market. The Lithium Ion Battery (LIB) is widely applied to portable energy storage devices such as mobile phones, cameras, notebook computers and the like due to the advantages of high working voltage, high energy density, long cycle life and the like, and gradually develops to large-scale application of electric automobiles, military equipment, artificial intelligence and the like.
However, the reserve of lithium resources in the crust is more effective, the regional distribution of the lithium resources is uneven, the exploitation is difficult, and the recovery cost is higher, so that the price of the lithium resources is always continuously increased after the lithium ion battery is used in a large scale, the application of a large-scale energy storage system is difficult to meet, the metal sodium and the lithium are positioned in the same main group, the metal sodium and the lithium have similar physical and chemical properties, the adoption of sodium to replace lithium is technically feasible, the reserve of the metal sodium is abundant, the distribution is wide, the cost is low, and the development of the sodium ion battery can effectively meet the increasingly growing energy storage market demand.
The positive electrode material is used as an important component of the sodium ion battery, the performance of the positive electrode material can directly influence the capacity performance and the cycle performance of the sodium ion battery, and the positive electrode material of the sodium ion battery mainly comprises an organic compound, a polyanion compound, a Prussian blue compound and a layered oxide, wherein the layered oxide is paid attention to because of low cost, high capacity and simple synthesis method, however, the positive electrode material of the layered oxide can generate complex problems of phase change, transition metal migration and the like when in use, and the positive electrode of the layered oxide has poor stability in air and is easy to generate side reaction with electrolyte, which restricts the development of the sodium ion battery, so that a scheme is needed to be provided for improving the problems.
Disclosure of Invention
The invention aims to provide a layered sodium ion high-entropy oxide positive electrode material, a preparation method and application thereof, which can improve the stability of the positive electrode material, relieve phase change and effectively improve the capacity and cycle performance of a sodium ion battery.
In a first aspect, the invention provides a layered sodium ion high-entropy oxide positive electrode material, the chemical general formula of which is Na nNixMnyFezTMmO2, and the TM is at least five of Mg, cu, ti, li, K, nb, al, ca, mn, zr, sn, ce, mo, W, sb; wherein n is more than or equal to 0.8 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, and x+y+z+m=1.
According to the invention, through doping the element TM, the interlayer spacing is increased when the doped element enters the crystal lattice, the diffusion kinetics of sodium ions is increased, and the structural stability of the positive electrode material can be improved after the doping of the element, and the phase change of the positive electrode material in the charge and discharge process is relieved, so that the capacity and the cycle performance of the sodium ion battery are effectively improved.
Optionally, the TM is Mg, cu, ti, li, K; or, the TM is Mg, cu, al, li, zn.
In a second aspect, the invention also provides a preparation method of the layered sodium ion high-entropy oxide positive electrode material, which comprises the following steps: mixing and grinding a sodium source, a nickel source, a manganese source, an iron source and a TM source to obtain mixed powder; carrying out sectional heat treatment on the mixed powder in an oxygen-containing atmosphere, and then cooling and grinding to obtain a high-entropy oxide positive electrode material; wherein the TM source comprises at least five of a magnesium source, a copper source, a titanium source, a lithium source, a potassium source, a niobium source, an aluminum source, a calcium source, a manganese source, a zirconium source, a tin source, a cerium source, a molybdenum source, a tungsten source and an antimony source; the chemical general formula of the high-entropy oxide positive electrode material is Na nNixMnyFezTMmO2, wherein n is more than or equal to 0.8 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, m is more than or equal to 0 and less than or equal to 0, and x+y+z+m=1.
Optionally, the step of subjecting the mixed powder to the stepwise heat treatment in an oxygen-containing atmosphere comprises: and (3) preserving the temperature of the mixed powder for 3-8 hours in an oxygen-containing atmosphere at 400-600 ℃, heating to 850-1050 ℃ and calcining for 10-20 hours to obtain the sintering material.
Optionally, in the process of cooling the mixed powder after the sectional heat treatment in the oxygen-containing atmosphere, the temperature change rate of the heating process and the cooling process is 1-10 ℃/min independently.
Optionally, mixing and grinding a sodium source, a nickel source, a manganese source, an iron source and a TM source to obtain mixed powder, wherein the average particle size of the mixed powder is 5-100 mu m; and/or grinding to obtain the high-entropy oxide positive electrode material, wherein the average particle size of the high-entropy oxide positive electrode material is 2-10 mu m.
Optionally, in the process of mixing and grinding the sodium source, the nickel source, the manganese source, the iron source and the TM source to prepare mixed powder, the sodium source, the nickel source, the manganese source, the iron source and the TM source are mixed according to stoichiometric ratio, and the sodium-to-sodium ratio of the sodium source is 101-110%.
Optionally, in the process of mixing and grinding the sodium source, the nickel source, the manganese source, the iron source and the TM source to prepare mixed powder: the sodium source comprises at least one of NaOH and Na 2CO3、Na2CO3·H2 O; and/or the nickel source comprises at least one of Ni (OH) 2, niO; and/or, the manganese source comprises at least one of MnO, mnO 2、Mn3O4; And/or, the iron source comprises at least one of FeO, fe 2O3、Fe3O4; and/or, the magnesium source comprises at least one of MgO, mg (OH) 2; and/or, the copper source comprises at least one of CuO, cu 2 O; And/or, the titanium source comprises TiO 2; and/or, the lithium source comprises at least one of LiNO 3、Li2CO3、LiOH·H2 O; and/or, the potassium source comprises at least one of K 2CO3、K(NO3)2、K(OH)2·H2 O; and/or, the aluminum source comprises at least one of Al 2O3、Al(NO3)3; And/or the zinc source comprises ZnO, zn (at least one of NO 3)2; and/or the niobium source comprises Nb 2O5; and/or the calcium source comprises CaCO 3; and/or the zirconium source comprises ZrO 2; And/or, the tin source comprises at least one of SnO, sn 2O3; and/or, the cerium source comprises at least one of Ce 2O3、CeO2; and/or, the tungsten source comprises WO 3; and/or, the molybdenum source comprises at least one of MoO 3、MoO2; and/or, the antimony source comprises Sb 2O3.
In a third aspect, the invention also provides the use of any of the above-described alternative positive electrode materials in a sodium ion battery.
Drawings
FIG. 1 is a flow chart of a method for preparing a layered sodium ion high entropy oxide positive electrode material according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of the Na 0.9Ni0.2Mn0.4Fe0.4O2 positive electrode material prepared in comparative example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of Na0.9Ni0.2Mn0.35Fe0.4Mg0.01Cu0.01Ti0.01Li0.01K0.01O2 positive electrode materials prepared in example 1 of the present invention;
fig. 4 is a graph showing the rate performance at different rates after the positive electrode materials prepared in example 1 and comparative example 1 of the present invention are assembled into a battery;
fig. 5 is a cycle performance curve at a current density of 1C after the positive electrode materials prepared in example 1 and comparative example 1 of the present invention are assembled into a battery.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The embodiment of the invention provides a layered sodium ion high-entropy oxide positive electrode material, which has a chemical general formula of Na nNixMnyFezTMmO2, wherein TM is at least five elements in Mg, cu, ti, li, K, nb, al, ca, mn, zr, sn, ce, mo, W, sb. Specifically, in the Na nNixMnyFezTMmO2 positive electrode material, n is more than or equal to 0.8 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, m is more than or equal to 0 and less than 0, and x+y+z+m=1.
Therefore, the interlayer distance is increased by doping elements into the lattice after the TM element is doped, the diffusion kinetics of sodium ions can be improved, the stability of the positive electrode material can be improved, the phase change phenomenon is relieved, meanwhile, the transition metal layers are formed by Ni, mn, fe and TM elements together, and the transition metal layers and the Na layers are alternately arranged in the middle of the oxygen layers to form a layered oxide structure.
In some embodiments, the TM element in the Na nNixMnyFezTMmO2 positive electrode material may be a combination of five elements, mg, cu, ti, li, K; in other embodiments, the TM element can be a combination of the five elements Mg, cu, al, li, zn.
Specifically, the plurality of constituent elements in the TM element may be mixed in an arbitrary molar ratio. In some embodiments, the minimum mole percent of any constituent element in the TM element is 0.1%.
Referring to fig. 1, the embodiment of the invention also provides a preparation method of the layered sodium ion high-entropy oxide positive electrode material, which comprises the following steps:
s1, mixing and grinding: mixing and grinding a sodium source, a nickel source, a manganese source, an iron source and a TM source to obtain mixed powder;
s2, calcining to prepare powder: and carrying out sectional heat treatment on the mixed powder in an oxygen-containing atmosphere, and then cooling and grinding to obtain the high-entropy oxide anode material.
Specifically, the TM source in step S1 includes at least five of a magnesium source, a copper source, a titanium source, a lithium source, a potassium source, a niobium source, an aluminum source, a calcium source, a manganese source, a zirconium source, a tin source, a cerium source, a molybdenum source, a tungsten source, and an antimony source.
Specifically, after step S2 is completed to prepare the high-entropy oxide cathode material, the chemical formula of the high-entropy oxide cathode material is Na nNixMnyFezTMmO2, where n is 0.8-1, x is 0-0.2, y is 0-0.4, z is 0-0.4, m is 0-0.4, and x+y+z+m=1.
In fact, in the process of performing the mixing and grinding in step S1, na nNixMnyFezTMm is used as a stoichiometric ratio to respectively perform material weighing and mixing on the sodium source, the nickel source, the manganese source, the iron source and the TM source. Specifically, since the sodium source is burned during the execution of step S2, the sodium source may be excessively weighed to supplement the loss amount, that is, the sodium source has a sodium-to-sodium ratio of 101-110% during the mixing of the sodium source in step S1, wherein the sodium-to-sodium ratio is a ratio of a molar amount of sodium in the preset positive electrode material to a molar amount of sodium in the weighed sodium source.
In some embodiments, during the performing of step S1 of the mixed milling, the sodium source comprises at least one of NaOH, na 2CO3、Na2CO3·H2 O.
In some embodiments, during the performing of step S1 of the hybrid milling, the nickel source comprises at least one of Ni (OH) 2, niO.
In some embodiments, the manganese source includes at least one of MnO, mnO 2、Mn3O4 during the performing of step S1 of the mixed milling.
In some embodiments, during the performing of step S1 of the mixed milling, the iron source includes at least one of FeO, fe 2O3、Fe3O4.
In some embodiments, during the performing of step S1 the mixed milling, the magnesium source comprises at least one of MgO, mg (OH) 2.
In some embodiments, the copper source includes at least one of CuO, cu 2 O during the performing of step S1 hybrid milling.
In some embodiments, during the performing of step S1 of the hybrid milling, the titanium source comprises TiO 2.
In some embodiments, during the performing of step S1 of the mixed milling, the lithium source comprises at least one of LiNO 3、Li2CO3、LiOH·H2 O.
In some embodiments, in performing step S1 of the mixed milling, the potassium source comprises at least one of K 2CO3、K(NO3)2、K(OH)2·H2 O.
In some embodiments, during the performing of step S1 the mixed milling, the aluminum source includes at least one of Al 2O3、Al(NO3)3.
In some embodiments, during the performing of step S1 the mixed milling, the zinc source comprises at least one of ZnO, zn (NO 3)2).
In some embodiments, during the performing of step S1, the niobium source includes Nb 2O5.
In some embodiments, the calcium source includes CaCO 3 during the step S1 mixed grinding.
In some embodiments, during the performing of step S1 of the hybrid milling, the zirconium source comprises ZrO 2.
In some embodiments, during the performing of step S1 of the hybrid milling, the tin source includes at least one of SnO, sn 2O3.
In some embodiments, during the performing of step S1 of the hybrid milling, the cerium source comprises at least one of Ce 2O3、CeO2.
In some embodiments, the molybdenum source comprises WO 3 during the step S1 mixed milling.
In some embodiments, during the performing of step S1 hybrid milling, the tungsten source comprises at least one of MoO 3、MoO2.
In some embodiments, during the step S1 mixed milling, the antimony source includes Sb 2O3.
In some embodiments, in the process of performing the mixed grinding in step S1, the grinding duration is controlled to be 0.5-1h, so that the particle sizes of the raw material particles can be effectively unified, and meanwhile, the influence of excessive breakage of the raw material particles on the performance of the final positive electrode material is avoided.
In some embodiments, after the step S1 of mixed milling is performed, the average particle size of the obtained mixed powder is 5 to 100 μm.
In some embodiments, in performing step S2, the method includes: and (3) preserving the temperature of the mixed powder for 3-8 hours in an oxygen-containing atmosphere at 400-600 ℃, heating to 850-1050 ℃ and calcining for 10-20 hours to obtain the sintering material.
In practice, in the execution of step S2, it includes: under the oxygen-containing atmosphere, heating the mixed powder from room temperature to 400-600 ℃, preserving heat for 3-8h, presintering, heating to 850-1050 ℃ and preserving heat for 10-20h, and sintering to obtain a sintered material; and cooling the sintered material to room temperature, and grinding to obtain the high-entropy oxide anode material with the average particle size of 2-10 mu m.
Specifically, in the process of executing step S2, the temperature change rates of the performed heating process and cooling process are 1-10 ℃/min independently of each other. Specifically, in the process of performing step S2 to grind the cooled sinter, the grinding duration is controlled to be 0.5-1h. Specifically, in the process of performing step S2, the oxygen-containing atmosphere used may be air or an oxygen atmosphere.
Example 1
The embodiment 1 provides a preparation method of a layered sodium ion high-entropy oxide positive electrode material, which comprises the following steps:
S1, mixing and grinding: 4.6454g (sodium blend ratio 1:1.05) of Na 2CO3, 1.3855g of NiO, 2.3029g of MnO 2, 2.9623g of Fe 2O3, 0.0374g of MgO, 0.0738g of CuO, 0.0741g of TiO 2, 0.0343g of Li 2CO3 and 0.064g of K 2CO3 were weighed, mixed and then ground for 0.5 hours to prepare a mixed powder;
S2, calcining to prepare powder: placing the mixed powder in a crucible, transferring the crucible into a muffle furnace, heating the muffle furnace to 500 ℃ at a speed of 2 ℃/min under the air atmosphere, preserving heat for 4 hours for presintering, heating the presintered solid to 850 ℃ at a speed of 2 ℃/min, preserving heat for 10 hours, and sintering and forming to obtain a sintered material; cooling the sintered material to room temperature along with a furnace, and grinding to obtain the high-entropy oxide cathode material (Na0.9Ni0.2Mn0.35Fe0.4Mg0.01Cu0.01Ti0.01Li0.01K0.01O2).
Example 2
The present example 2 provides a method for preparing a layered sodium ion high entropy oxide cathode material, which is different from the method of example 1 in that the solid after pre-sintering is heated to 950 ℃ at a rate of 2 ℃/min in the calcination and pulverization of step S2.
Example 3
The present example 3 provides a method for preparing a layered sodium-ion high-entropy oxide cathode material, which is different from example 1 in that the pre-sintered solid is heated to 1050 ℃ at a rate of 2 ℃/min in the calcination and pulverization step S2, and is kept for 15 hours.
Example 4
The present example 4 provides a method for preparing a layered sodium-ion high-entropy oxide cathode material, which is different from the method of example 1 in that the pre-sintered solid material is heated to 1050 ℃ at a rate of 2 ℃/min in the calcination and pulverization step S2, and is kept for 20 hours.
Example 5
The present embodiment 5 provides a method for preparing a layered sodium ion high entropy oxide cathode material, which is different from embodiment 1 in that step S1 is mixed grinding: mixing and grinding 4.6431g (sodium mixing ratio 1:1.05) of Na 2CO3, 1.3848g of NiO, 2.3017g of MnO 2, 2.9608g of Fe 2O3, 0.0374g of MgO, 0.0737g of CuO, 0.0437g of Al 2O3, 0.0343g of Li 2CO3 and 0.0109g of ZnO to prepare mixed powder; the chemical general formula of the high entropy oxidation anode material prepared in the step S2 is Na0.9Ni0.2Mn0.35Fe0.4Mg0.01Cu0.01Al0.01Li0.01Zn0.01.
Example 6
The present example 6 provides a method for preparing a layered sodium ion high entropy oxide cathode material, which is different from the method of example 5 in that the solid after pre-sintering is heated to 950 ℃ at a rate of 2 ℃/min in the calcination and pulverization of step S2.
Example 7
The present example 7 provides a method for preparing a layered sodium ion high entropy oxide cathode material, which is different from example 5 in that the pre-sintered solid material is heated to 1050 ℃ at a rate of 2 ℃/min in the calcination and pulverization step S2, and is kept for 25 hours.
Example 8
The present example 8 provides a method for preparing a layered sodium-ion high-entropy oxide cathode material, which is different from example 5 in that the pre-sintered solid material is heated to 1050 ℃ at a rate of 2 ℃/min in the calcination and pulverization step S2, and is kept for 20 hours.
Comparative example 1
The comparative example 1 provides a method for preparing a sodium ion oxide positive electrode material, comprising the following steps:
S1, mixing and grinding: 4.6057g (Na ratio 1:1.05) of Na 2CO3, 1.3737g of NiO, 2.6094g of MnO 2 and 2.937g of Fe 2O3 were weighed and mixed, and then ground for 0.5 hours to prepare a mixed powder;
S2, calcining to prepare powder: placing the mixed powder in a crucible, transferring the crucible into a muffle furnace, heating the muffle furnace to 500 ℃ at a speed of 2 ℃/min under the air atmosphere, preserving heat for 4 hours for presintering, heating the presintered solid to 1050 ℃ at a speed of 2 ℃/min, preserving heat for 20 hours, and sintering and forming to obtain a sintered material; and cooling the sintered material with a furnace to room temperature, and grinding to obtain the oxide cathode material (Na 0.9Ni0.2Mn0.4Fe0.4O2).
Performance detection
The positive electrode materials prepared in example 1, example 5 and comparative example 1 were fully mixed with polyvinylidene fluoride and conductive carbon black in a mass ratio of 8:1:1, then uniformly coated on an aluminum foil, the coating thickness was controlled to be 200 μm, the materials were dried in a vacuum drying oven at 100 ℃, rolled and then cut into round positive electrode plates with diameters of 12mm, respectively, a metal sodium plate was used as the positive electrode plate, GF/D glass fiber was used as a separator, naPF 6 was used as an electrolyte, and 2025 type button cells were assembled in an argon glove box, and electrochemical performance tests were performed on button cells corresponding to example 1, example 5 and comparative example 1 at 25 ℃, the rate performance of which is shown in FIG. 4 and the cycle performance of which is shown in FIG. 5.
As can be seen from the scanning electron microscope image of comparative example 1 (Na 0.9Ni0.2Mn0.4Fe0.4O2) in FIG. 2, more residual alkali exists in the surface morphology, resulting in poor air stability. The crystallinity of the material is poor, and the material has small and not-grown particles, the layered structure is incomplete, the performance is affected, and the size of the material particles is uneven.
As can be seen from the scanning electron microscope of example 1(Na0.9Ni0.2Mn0.35Fe0.4Mg0.01Cu0.01Ti0.01Li0.01K0.01O2) in FIG. 3, the residual alkali of the material after the TM element doping is reduced to a certain extent, the particles are more round, the layered structure is complete, the size distribution of the particles is more uniform, and the performance is better.
As can be seen from fig. 4, the specific discharge capacity of the battery using comparative example 1 for preparing the positive electrode material was 133.5mAh/g, the specific discharge capacity of the battery using example 1 for preparing the positive electrode material was 140.2mAh/g, and the specific discharge capacity of the battery using example 5 for preparing the positive electrode material was 136.4mAh/g at 2.0 to 4.0V and 0.1C; the specific discharge capacities of the batteries of application example 1 were 94.3mAh/g and 70.2mAh/g, respectively, and the specific discharge capacities of the batteries of application example 5 were 85.5mAh/g and 60.9mAh/g, respectively, each higher than the 79.1mAh/g and 45.1mAh/g of the batteries of application comparative example 1, respectively, at the current densities of 2C and 5C.
As can be seen from fig. 5, after 50 cycles of charge-discharge test at a current density of 1C, the specific discharge capacity of the battery using the positive electrode material of example 1 was maintained at 101.8mAh/h, with a capacity retention of 91.8%, the specific discharge capacity of the battery using the positive electrode material of example 5 was maintained at 94.5mAh/h, with a capacity retention of 89.7%, and the specific discharge capacity of the battery using the positive electrode material of comparative example 1 was maintained at 84.4mAh/g, with a capacity retention of only 85.2%.
In conclusion, the layered sodium ion high-entropy oxide positive electrode material provided by the invention has higher discharge capacity, better cycle stability and more excellent rate capability.
While embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (9)
1. The layered sodium ion high-entropy oxide positive electrode material is characterized by having a chemical formula of Na nNixMnyFezTMmO2, wherein the TM is at least five of Mg, cu, ti, li, K, nb, al, ca, zn, zr, sn, ce, mo, W, sb; wherein n is more than or equal to 0.8 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, m is more than or equal to 0 and less than or equal to 0.4, and x+y+z+m=1.
2. The positive electrode material according to claim 1, wherein the TM is Mg, cu, ti, li, K; or, the TM is Mg, cu, al, li, zn.
3. The preparation method of the layered sodium ion high-entropy oxide positive electrode material is characterized by comprising the following steps of: mixing and grinding a sodium source, a nickel source, a manganese source, an iron source and a TM source to obtain mixed powder; carrying out sectional heat treatment on the mixed powder in an oxygen-containing atmosphere, and then cooling and grinding to obtain a high-entropy oxide positive electrode material; wherein the TM source comprises at least five of a magnesium source, a copper source, a titanium source, a lithium source, a potassium source, a niobium source, an aluminum source, a calcium source, a manganese source, a zirconium source, a tin source, a cerium source, a molybdenum source, a tungsten source and an antimony source; the chemical general formula of the high-entropy oxide positive electrode material is Na nNixMnyFezTMmO2, wherein n is more than or equal to 0.8 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, 0<m is more than or equal to 0.4, and x+y+z+m=1.
4. A method according to claim 3, wherein the step of subjecting the mixed powder to the stepwise heat treatment in an oxygen-containing atmosphere comprises: and (3) preserving the temperature of the mixed powder for 3-8 hours in an oxygen-containing atmosphere at 400-600 ℃, heating to 850-1050 ℃ and calcining for 10-20 hours to obtain the sintering material.
5. The method according to claim 4, wherein the temperature change rates of the heating process and the cooling process are 1 to 10 ℃ per minute independently of each other in the process of cooling the mixed powder after the stepwise heat treatment in the oxygen-containing atmosphere.
6. The method according to claim 3, wherein the average particle size of the mixed powder is 5 to 100 μm after the sodium source, the nickel source, the manganese source, the iron source and the TM source are mixed and ground to obtain the mixed powder; and/or grinding to obtain the high-entropy oxide positive electrode material, wherein the average particle size of the high-entropy oxide positive electrode material is 2-10 mu m.
7. The method according to claim 3, wherein the sodium source, the nickel source, the manganese source, the iron source and the TM source are mixed in stoichiometric ratio and the sodium-to-sodium ratio of the sodium source is 101-110% in the process of mixing and grinding the sodium source, the nickel source, the manganese source, the iron source and the TM source to prepare the mixed powder.
8. The method according to claim 3, wherein in the process of mixing and grinding the sodium source, the nickel source, the manganese source, the iron source and the TM source to prepare the mixed powder:
The sodium source comprises at least one of NaOH and Na 2CO3、Na2CO3·H2 O;
And/or the nickel source comprises at least one of Ni (OH) 2, niO;
And/or, the manganese source comprises at least one of MnO, mnO 2、Mn3O4;
And/or, the iron source comprises at least one of FeO, fe 2O3、Fe3O4;
And/or, the magnesium source comprises at least one of MgO, mg (OH) 2;
And/or, the copper source comprises at least one of CuO, cu 2 O;
and/or, the titanium source comprises TiO 2;
And/or, the lithium source comprises at least one of LiNO 3、Li2CO3、LiOH·H2 O;
and/or, the potassium source comprises at least one of K 2CO3、K(NO3)2、K(OH)2·H2 O;
And/or, the aluminum source comprises at least one of Al 2O3、Al(NO3)3;
And/or, the zinc source comprises at least one of ZnO, zn (NO 3)2;
And/or, the niobium source comprises Nb 2O5;
And/or, the calcium source comprises CaCO 3;
and/or, the zirconium source comprises ZrO 2;
and/or, the tin source comprises at least one of SnO, sn 2O3;
and/or, the cerium source comprises at least one of Ce 2O3、CeO2;
and/or, the tungsten source comprises WO 3;
And/or, the molybdenum source comprises at least one of MoO 3、MoO2;
and/or, the antimony source comprises Sb 2O3.
9. Use of a positive electrode material according to any one of claims 1 to 2, or a positive electrode material prepared by a preparation method according to any one of claims 3 to 8, in a sodium ion battery.
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