CN114373917A - Sodium-ion battery positive electrode composite material and preparation method and application thereof - Google Patents
Sodium-ion battery positive electrode composite material and preparation method and application thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 70
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 claims abstract description 58
- 239000002135 nanosheet Substances 0.000 claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 claims abstract description 37
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 23
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 61
- 239000011734 sodium Substances 0.000 claims description 33
- 238000005530 etching Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 9
- 238000004146 energy storage Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 30
- 239000006185 dispersion Substances 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 description 30
- 229910001220 stainless steel Inorganic materials 0.000 description 30
- 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 description 21
- 229910052708 sodium Inorganic materials 0.000 description 21
- 239000002002 slurry Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229910014507 Na0.67Ni0.33Mn0.67O2 Inorganic materials 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910019398 NaPF6 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to high-performance Na2/3Ni1/3Mn2/3O2The positive electrode composite material of the MXene sodium-ion battery and the preparation method and the application thereof comprise the following steps: uniformly dispersing MXene nanosheets in absolute ethyl alcohol, and then adding Na2/3Ni1/3Mn2/3O2And adding the positive electrode material of the sodium-ion battery into the dispersed MXene ethanol solution, performing ultrasonic treatment, and performing vacuum drying to obtain the sodium-ion battery. The invention utilizes the two-dimensional MXene nanosheet which has high conductivity, low ion diffusion barrier potential and easy dispersion as a conductive network to be uniformly dispersed in Na2/ 3Ni1/3Mn2/3O2Around the positive electrode material particles of the sodium-ion battery, the conductivity of the positive electrode material of the sodium-ion battery can be effectively improved and reducedThe corrosion of the electrolyte to the anode material finally increases Na2/3Ni1/3Mn2/3O2The electrochemical performance of the positive electrode material of the sodium-ion battery. The application prospect of the anode material in the manufacture of sodium ion batteries, electric automobiles, electronic products and smart power grids is increased.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery anode composite material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
At present, lithium ion batteries are widely applied to the fields of electric automobiles, mobile phones, notebook computers, smart power grids and the like. But the shortage and the uneven distribution of global lithium resources result in limiting the development of lithium ion batteries in the future to some extent. Sodium ion batteries are considered to be promising energy storage devices due to the wide distribution of sodium resources around the world. Na (Na)2/3Ni1/ 3Mn2/3O2The electrolyte is considered as a promising positive electrode material of the sodium-ion battery, but the electrolyte has the defects of poor conductivity, unstable structure and the like, and the electrolyte continuously erodes the positive electrode material in the charging and discharging processes, so that the multiplying power and the cycle performance of the positive electrode material are poor.
Disclosure of Invention
Aiming at the problems, the invention provides high-performance Na2/3Ni1/3Mn2/3O2A/MXene positive electrode composite material and a preparation method and application thereof. The preparation method synthesizes the sodium-ion battery anode composite material with long service life, high stability and high rate performance, and the composite material is applied to the sodium-ion battery, which has important promotion effect on the development of novel energy storage devices and the development of new energy industries and has great significance.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a positive electrode composite material for a sodium ion battery, comprising: na (Na)2/3Ni1/3Mn2/3O2Sodium ion anode material and Na uniformly distributed2/3Ni1/3Mn2/3O2MXene network around the sodium ion positive electrode material; the MXene network is composed of MXene nanosheets.
One of the characteristics of the method of the invention is as follows: high conductivity, low ion diffusion barrier and easy useDispersed two-dimensional MXene nanosheet as additive for increasing Na content2/3Ni1/3Mn2/3O2The performance of the positive electrode material of the sodium-ion battery. On the one hand, the addition of MXene can increase Na2/3Ni1/3Mn2/3O2Is used for the electrical conductivity of (1). On the other hand, in Na2/3Ni1/3Mn2/3O2The two-dimensional MXene nanosheets around the particles can reduce direct contact between the electrolyte and the surface of the anode material, relieve corrosion of the electrolyte to the anode material and increase the structural stability of the anode material. Finally improve Na2/3Ni1/3Mn2/3O2Performance of the sodium ion positive electrode material.
In a second aspect of the present invention, a method for preparing a positive electrode composite material for a sodium ion battery is provided, which comprises:
(1) preparing MXene nano-sheets, and uniformly dispersing the prepared MXene nano-sheets in absolute ethyl alcohol;
(2) mixing Na2/3Ni1/3Mn2/3O2And adding the positive electrode material of the sodium-ion battery into the dispersed MXene ethanol solution, performing ultrasonic treatment, and performing vacuum drying to obtain the sodium-ion battery.
The two-dimensional MXene nanosheet with high conductivity, low ion diffusion barrier and easy dispersion can be used as a conductive network to be uniformly dispersed in Na2/3Ni1/3Mn2/3O2The positive electrode material particles of the sodium-ion battery are surrounded.
In a third aspect of the present invention, an application of any one of the above-mentioned positive electrode composite materials for an ion battery in a sodium ion battery is provided, specifically, an application in manufacturing of electronic products, smart grids, electric vehicles, and mobile energy storage devices.
Because the invention effectively improves Na2/3Ni1/3Mn2/3O2The performance of the positive electrode material of the sodium-ion battery is expected to be widely applied to an energy storage device, so that the development of new energy industry and social progress are promoted.
The invention has the beneficial effects that:
(1) the invention adopts a solution dispersion method to prepare the sodium-ion battery anode composite material, and can effectively improve the uniformity of the composite material.
(2) The invention utilizes the two-dimensional MXene nanosheets which are high in conductivity, low in ion diffusion barrier potential and easy to disperse as the additive to further form a conductive network, so that the conductivity of the positive electrode material of the sodium-ion battery can be effectively improved, and the corrosion of electrolyte to the positive electrode material can be reduced. Finally, the performance of the cathode material is improved.
(3) The method provided by the invention has universality and expandability and can meet the requirement of large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows preparation of Na in examples 1 to 9 of the present invention2/3Ni1/3Mn2/3O2Schematic flow diagram of the/MXene sodium-ion battery positive electrode composite material.
FIG. 2 is an X-ray diffraction pattern of the samples in comparative example and example 1 of the present invention.
FIG. 3 shows Na in comparative example of the present invention0.67Ni0.33Mn0.67O2Scanning electron microscope images of the positive electrode material of the sodium-ion battery.
FIG. 4 shows Na in example 1 of the present invention2/3Ni1/3Mn2/3O2/Ti3C2TxScanning electron microscope images of the sodium ion battery anode composite material.
Fig. 5 is a graph showing the cycle curves of the positive electrodes in comparative example and example 1 at a current density of 100 mA/g.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described above, Na2/3Ni1/3Mn2/3O2The defects of poor conductivity, unstable structure and the like exist, and in addition, the multiplying power and the cycle performance of the lithium ion battery are poor due to continuous corrosion of electrolyte in the charging and discharging processes.
Therefore, the invention provides a method for increasing Na2/3Ni1/3Mn2/3O2The performance modification strategy is to use a two-dimensional MXene nanosheet which is high in conductivity, low in ion diffusion barrier and easy to disperse as an additive. On the one hand, the addition of MXene can increase Na2/ 3Ni1/3Mn2/3O2Is used for the electrical conductivity of (1). On the other hand, in Na2/3Ni1/3Mn2/3O2The two-dimensional MXene nanosheets around the particles can reduce direct contact between the electrolyte and the surface of the anode material, relieve corrosion of the electrolyte to the anode material and increase the structural stability of the anode material. Finally improve Na2/3Ni1/2Mn2/3O2Performance of the sodium ion positive electrode material.
This technical solution will now be further explained.
A positive electrode composite for a sodium ion battery, comprising: na (Na)2/3Ni1/3Mn2/3O2A sodium ion positive electrode material;
is uniformly distributed in Na2/3Ni1/3Mn2/3O2An MXene network around the positive electrode material;
the MXene network is composed of MXene nanosheets.
In some typical embodiments, the MXene nanosheets have a mass fraction of 1% to 50% in the sodium-ion battery positive electrode composite; preferably, 1% to 20%.
The preparation method of the sodium-ion battery positive electrode composite material comprises the following steps:
(1) preparing MXene nanosheets, and uniformly dispersing the prepared MXene nanosheets in absolute ethyl alcohol to obtain MXene ethyl alcohol solution;
(2) mixing Na2/3Ni1/3Mn2/3O2And (3) adding the sodium-ion battery positive electrode material into the MXene ethanol solution obtained in the step (1), performing ultrasonic treatment, and performing vacuum drying to obtain the sodium-ion battery positive electrode material.
In some typical embodiments, the MXene nanoplatelets are added in an amount of 10-500 mg; preferably, 20 mg.
In some typical embodiments, the amount of absolute ethanol is 5-30 mL; preferably, 10 mL.
In some exemplary embodiments, Na2/3Ni1/3Mn2/3O2The adding amount of the positive electrode material of the sodium-ion battery is 0.1-1 g; preferably, 0.5 g.
In some exemplary embodiments, the MXene nanoplatelets include, but are not limited to: ti3C2Tx、V2CTx、Ti2NTxAnd the like.
In some typical embodiments, the sonication is for 5-20 min; preferably, 10 min.
In some exemplary embodiments, the synthesis method of the MXene nanoplatelets includes, but is not limited to: any one of an acid etching method, a molten salt etching method, an electrochemical etching method, an alkali etching method, and the like.
In some exemplary embodiments, the vacuum drying temperature is 50-120 ℃.
The sodium ion battery anode material is applied to sodium ion batteries, in particular to the application in the manufacture of electronic products, smart power grids, electric automobiles and mobile energy storage equipment.
In some exemplary embodiments, the electrolyte of the battery is an ether, an ester, a nitrile, or the like.
In some exemplary embodiments, the inert atmosphere is argon, nitrogen, a hydrogen argon mixture, helium, a vacuum atmosphere, or the like, having an oxygen content of less than 0.1ppm and a moisture content of less than 0.1 ppm.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps (figure 1):
(1) etching Ti by acid etching3AlC2MAX phase to Ti3C2TxMXene dispersion, then freeze drying to obtain Ti3C2TxNanosheets.
(2) 20mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. Electric powerThe hydrolysate is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 2
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching V by acid etching method2AlC MAX phase yielding V2CTxMXene dispersion, followed by lyophilization to obtain V2CTxNanosheets.
(2) 20mg of V2CTxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed V2CTxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium-ion battery into the well-dispersed V2CTxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then vacuum drying at 60 ℃ to obtain V2CTxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/V2CTx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/V2CTxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 3
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching Ti by acid etching2AlN MAX phase to obtain Ti2NTxMXene dispersion, then freeze drying to obtain Ti2NTxNanosheets.
(2) 20mg of Ti2NTxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti2NTxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti2NTxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti2NTxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/2Mn2/3O2/Ti2NTx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti2NTxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 4
High-performance Na2/3Ni1/2Mn2/3O2Composite positive electrode of/MXene sodium ion batteryThe preparation of the material comprises the following steps:
(1) etching Ti by acid etching3AlC2MAX phase to Ti3C2TxMXene dispersion, then freeze drying to obtain Ti3C2TxNanosheets.
(2) 50mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 5
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching by acid etchingEtching of Ti3AlC2MAX phase to Ti3C2TxMXene dispersion, then freeze drying to obtain Ti3C2TxNanosheets.
(2) Mixing 100mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 6
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching Ti by molten salt method3AlC2MAX phase to Ti3C2TxThe MXene dispersion liquid is prepared by mixing MXene dispersion liquid,then freeze-drying to obtain Ti3C2TxNanosheets.
(2) 20mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 7
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching Ti by alkali etching3AlC2MAX phase to Ti3C2TxMXene dispersion, then freeze drying to obtain Ti3C2TxNanosheets.
(2) 20mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/2Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/2Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/2Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 8
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching Ti by acid etching3AlC2MAX phase to Ti3C2TxMXene dispersion, then freeze drying to obtain Ti3C2TxNanosheets.
(2) 20mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcoholThen ultrasonic treatment is carried out for 10min to obtain evenly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6-PC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Example 9
High-performance Na2/3Ni1/3Mn2/3O2The preparation method of the/MXene sodium-ion battery positive electrode composite material comprises the following steps:
(1) etching Ti by acid etching3AlC2MAX phase to Ti3C2TxMXene dispersion, then freeze drying to obtain Ti3C2TxNanosheets.
(2) 20mg of Ti3C2TxAdding the nanosheets into 10mL of absolute ethyl alcohol, and then carrying out ultrasonic treatment for 10min to obtain uniformly dispersed Ti3C2TxEthanol solution.
(3) 0.5g of Na2/3Ni1/3Mn2/3O2Adding the positive electrode material powder of the sodium ion battery into the well dispersed Ti3C2TxAnd (4) performing ultrasonic treatment for 10min in an ethanol solution. Then dried in vacuum at 60 ℃ to obtain Ti3C2TxModified Na0.67Ni0.33Mn0.67O2I.e. Na2/3Ni1/3Mn2/3O2/Ti3C2Tx。
(4) Mixing Na2/3Ni1/3Mn2/3O2/Ti3C2TxPVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(5) And (4) matching the positive plate in the step (4) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaClO4-PC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Comparative example
The implementation of the comparative example mainly comprises the following steps:
(1) mixing Na2/3Ni1/3Mn2/3O2PVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then are dispersed into an NMP solution to form uniform slurry. The slurry was then coated on aluminum foil and dried under vacuum at 60 ℃ to obtain a positive electrode sheet.
(2) And (3) matching the positive plate in the step (1) with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the positive material. The electrolyte is 1M NaPF6EC/DEC (1: 1 by volume) + 5% FEC. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a positive electrode, a sodium sheet, electrolyte and a diaphragm (glass fiber).
Performance testing
(1) Using the button cell assembled in example 1 as an example, Na was used as a counter electrode using a charge-discharge device (Xinwei CT-4008)2/ 3Ni1/3Mn2/3O2/Ti3C2TxThe cycle performance of the positive electrode assembled battery was evaluated. Also, as a comparison, Na was also tested2/3Ni1/3Mn2/3O2The above-described properties of the positive electrode-assembled battery (comparative example) were obtained, and the results are shown in fig. 5. At a current density of 100mA/g, Na2/3Ni1/3Mn2/3O2/Ti3C2TxThe cycle performance of the anode is superior to that of Na2/3Ni1/3Mn2/3O2And (3) the anode. After 100 weeks of circulation, Na2/3Ni1/3Mn2/3O2/Ti3C2TxThe capacity retention rate of the alloy is 62.9 percent and is obviously superior to Na2/3Ni1/3Mn2/3O2Of (1), (59.6%). The above results show that MXene modified Na2/3Ni1/3Mn2/3O2And then, the performance is obviously improved.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. 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. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A positive electrode composite material for a sodium-ion battery, comprising:
Na2/3Ni1/3Mn2/3O2a sodium ion positive electrode material;
is uniformly distributed in Na2/3Ni1/3Mn2/3O2An MXene network around the positive electrode material;
the MXene network is composed of MXene nanosheets.
2. The positive electrode composite material for sodium-ion batteries according to claim 1, wherein the MXene nanosheets are Ti3C2Tx、V2CTx、Ti2NTxAny one of them.
3. The positive electrode composite material for the sodium-ion battery as claimed in claim 1, wherein the MXene network accounts for 1-50% of the positive electrode composite material for the sodium-ion battery; preferably, 1% to 20%.
4. A method for preparing the positive electrode composite material of the sodium-ion battery as claimed in any one of the preceding claims,
(1) preparing MXene nanosheets, and uniformly dispersing the prepared MXene nanosheets in absolute ethyl alcohol to obtain MXene ethyl alcohol solution;
(2) mixing Na2/3Ni1/3Mn2/3O2And (3) adding the sodium-ion battery positive electrode material into the MXene ethanol solution obtained in the step (1), performing ultrasonic treatment, and performing vacuum drying to obtain the sodium-ion battery positive electrode material.
5. The preparation method according to claim 4, wherein the MXene nanosheets are added in an amount of 10-500 mg; preferably, 20 mg.
6. The preparation method according to claim 4, wherein the amount of the absolute ethyl alcohol is 5 to 30 mL; preferably, 10 mL.
7. According to claimThe process according to 4, wherein Na is2/3Ni1/3Mn2/3O2The adding amount of the positive electrode material of the sodium-ion battery is 0.1-1 g; preferably, 0.5 g.
8. The preparation method of claim 4, wherein the MXene nanosheet is prepared by any one of an acid etching method, a molten salt etching method, an electrochemical etching method and an alkali etching method.
9. The method of claim 4, wherein the vacuum drying temperature is 50-120 ℃; the ultrasonic treatment is carried out for 5-20min, preferably 10 min.
10. Use of the positive electrode material for sodium ion batteries according to any one of claims 1 to 3 in sodium ion batteries, preferably in the manufacture of electronic products, smart grids, electric vehicles, mobile energy storage devices.
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