CN113851626A - Element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material and preparation method thereof - Google Patents
Element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material and preparation method thereof Download PDFInfo
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- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 35
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- 239000011734 sodium Substances 0.000 claims description 40
- 239000011268 mixed slurry Substances 0.000 claims description 24
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- 238000001035 drying Methods 0.000 claims description 20
- 239000000499 gel Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 12
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 12
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 12
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 12
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 12
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 11
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical group O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
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- 230000008014 freezing Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- 229910019892 NaxLiy Inorganic materials 0.000 claims description 4
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- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- ODUIXUGXPFKQLG-QWRGUYRKSA-N [2-(4-chloro-2-fluoroanilino)-5-methyl-1,3-thiazol-4-yl]-[(2s,3s)-2,3-dimethylpiperidin-1-yl]methanone Chemical class C[C@H]1[C@@H](C)CCCN1C(=O)C1=C(C)SC(NC=2C(=CC(Cl)=CC=2)F)=N1 ODUIXUGXPFKQLG-QWRGUYRKSA-N 0.000 description 3
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- 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 2
- 150000001450 anions Chemical class 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
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Images
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- 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
-
- 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
Abstract
The invention discloses an element-doped synergistic graphene-coated layered manganese-based sodium-ion battery positive electrode material and a preparation method thereof, wherein the positive electrode material has a chemical formula as follows: na (Na)xLiy[Ni,Mn]1‑yO2@ graphene, of which 1/2<x is less than or equal to 1; y is more than or equal to 0 and less than or equal to 3/10; the stoichiometric ratios of Ni and Mn are added to be 1-y; the coating amount of the graphene accounts for 1-8 wt% of the mass of the layered positive electrode material. The element-doped graphene-coated sodium-ion battery positive electrode material prepared by the invention has a smooth charge-discharge curve in a voltage range of 2.0-4.5V, has no obvious voltage platform, and shows higher reversible capacity, excellent rate performance and good cycle stability. The sol-gel method and the freeze drying process adopted by the invention have simple preparation process, nontoxic and safe required raw materials and high yield, and are beneficial to industrial production.
Description
Technical Field
The invention relates to the field of secondary batteries, in particular to an element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material and a preparation method thereof.
Background
In recent years, with the large-scale application of lithium ion batteries, the lithium price is increasing due to the large-scale exploitation of lithium resources, and people are concerned about the large-scale low-cost energy storage industry. The sodium resource reserves are very abundant and widely distributed, and the physical and chemical properties of sodium and lithium are similar, so that the technology of adopting sodium ions to replace lithium ions for energy storage is completely feasible, and in addition to the gradual development of some high-performance electrode materials, the sodium ion battery is expected to gradually replace a lithium ion battery to realize cheap large-scale energy storage. With the improvement of electrode material performance, commercialization of sodium ion batteries is accelerated, and it is expected that in the near future, the complementary pattern of lithium/sodium ion batteries will provide an important guarantee of long-term stability for the energy storage field.
As an important functional component of a sodium ion battery, a positive electrode material is a key factor influencing factors such as energy density, reversible capacity, service life and working voltage of the battery, so that development of a positive electrode material with excellent performance is important for promoting overall commercialization of the sodium ion battery. Among various anode materials, the layered manganese-based anode material has the advantages of high energy density, simple preparation process, low price, good industrialization compatibility and the like, and provides an effective solution for the industrialization of the sodium-ion battery. However, the layered manganese-based positive electrode material has the following drawbacks: (1) mn3+Taylor effect of ginger and Mn3+Dissolving, destroying crystal structure, and reducing Na+The disorder degree of the vacancy further influences the conductivity of the material, so that the process of the deintercalation of sodium ions becomes difficult; (2) irreversible phase change occurs during charging and discharging under high voltage, the structural stability of the material is damaged, and the electrochemical performance is influenced; (3) the layered oxide has strong hygroscopicity, and the storage and transportation difficulty of the material is increased.
Doping other elements (Ni, Ti, Cu, Al, Li, Mg, etc.) and surface coating, etc. are common methods for improving the electrochemical performance of the cathode material. However, the existing modification mode is difficult to simultaneously improve specific capacity, structural stability, rate capability, conductivity and the like.
Disclosure of Invention
The first purpose of the invention is to provide an element-doped and graphene-coated layered manganese-based positive electrode material, which has the advantages of high charge-discharge specific capacity, stable structure, good cycle performance and the like.
The second purpose of the invention is to provide a preparation method of the element-doped graphene-coated layered manganese-based positive electrode material.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides an element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material, which has a chemical formula as follows: na (Na)xLiy[Ni,Mn]1-yO2@ graphene including NaxLiy[Ni,Mn]1-yO2Granules and coating with NaxLiy[Ni,Mn]1-yO2Graphene on the surface of the particles, wherein 1/2<x is less than or equal to 1; y is more than or equal to 0 and less than or equal to 3/10; the stoichiometric ratio of the elements Ni and Mn is added to be 1-y.
Further, the graphene is physically-processed graphene, and the coating amount of the graphene accounts for 1-8 wt% of the mass of the positive electrode material.
The invention provides a preparation method of an element-doped synergistic graphene-coated layered manganese-based sodium-ion battery positive electrode material, which comprises a sol-gel method and a freeze-drying process, and specifically comprises the following steps:
(1) weighing anhydrous sodium acetate, lithium acetate dihydrate, nickel acetate tetrahydrate and manganese acetate tetrahydrate according to a stoichiometric ratio, dissolving in deionized water, adding a chelating agent, and stirring to obtain a mixed solution;
(2) preparing the mixed solution obtained in the step (1) into wet gel;
(3) drying the wet gel obtained in the step (2) to obtain dry gel, and grinding the dry gel into powder;
(4) pre-sintering the powder obtained in the step (3) in an air atmosphere at 300-600 ℃ for 3-10 hours, then continuously heating to 350-1000 ℃, and calcining for 8-24 hours to obtain an element-doped layered manganese-based sodium ion battery anode material;
(5) mixing the element-doped layered manganese-based sodium-ion battery positive electrode material obtained in the step (4) and physical graphene, adding the mixture into absolute ethyl alcohol, and stirring and performing ultrasonic treatment to obtain mixed slurry;
(6) freezing the mixed slurry obtained in the step (5) by liquid nitrogen to obtain solid mixed slurry;
(7) and (4) freeze-drying the solid mixed slurry obtained in the step (6) for 6-24 hours, and finally drying at 60-150 ℃ for 2-10 hours to obtain the element-doped synergistic graphene-coated layered manganese-based sodium-ion battery positive electrode material.
Further, the anhydrous sodium acetate, the lithium acetate dihydrate, the nickel acetate tetrahydrate and the manganese acetate tetrahydrate in the step (1) are weighed according to the stoichiometric ratio of Na: Li: [ Ni, Mn ] ═ x: y: 1-y;
the chelating agent is citric acid monohydrate, and the molar weight of the chelating agent is 1.5 times of that of the metal cations.
Further, stirring the mixed solution in the step (2) for 4-10 hours at 40-120 ℃ to obtain wet gel.
Further, the drying temperature in the step (3) is 60-150 ℃, and the drying time is 10-24 hours.
Further, the stirring time in the step (5) is 0.5-3 hours, and the ultrasonic treatment time is 0.5-2 hours; the invention also provides application of the element-doped synergistic graphene-coated layered manganese-based sodium-ion battery positive electrode material as a sodium-ion battery positive electrode material.
According to the invention, the Li element is doped and the graphene is coated to modify the layered manganese-based sodium-ion battery anode material, so that the anion redox reaction in a high voltage range can be excited, the specific capacity of the material is improved, and the structural stability, the rate capability and the cycling stability of the material can be improved. The element-doped graphene-coated sodium-ion battery positive electrode material prepared by the invention has a smooth charge-discharge curve in a voltage range of 2.0-4.5V under a large current of 2C, has no obvious voltage platform, shows higher reversible capacity, excellent rate capability and good cycle stability, and under the conditions, the reversible capacity reaches 100mAh/g, and the capacity retention rate is 58% after 200 cycles.
The invention discloses the following technical effects:
(1) the invention discloses a synergistic modification mechanism of element doping and graphene coating. On one hand, Li doping excites the redox reaction of anions in a high voltage range, thereby improving the reversible capacity, structural stability and electrochemical performance of the material. On the other hand, the graphene has excellent conductivity and a larger specific surface, and can provide a diffusion channel for sodium ions and battery transmission in the charge and discharge process of the material, so that the cycle stability, rate capability and conductivity of the material are improved.
(2) The layered manganese-based sodium-ion battery anode material prepared by adopting the sol-gel method and the freeze drying process has the advantages of simple preparation process, non-toxic and safe required raw materials, high yield and contribution to industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 shows Na as a product prepared in example 23/4Li1/20Ni3/10Mn13/20O2XRD pattern of (a).
FIG. 2 shows Na as a product prepared in example 39/10Li1/10Ni3/10Mn3/5O2The first three circles of charge-discharge capacity of 1.5-4.5V under 0.1C.
FIG. 3 shows Na as a product prepared in example 519/20Li3/20Ni1/4Mn3/5O2The former three-turn charge-discharge capacity diagram of 2.0-4.5V at 0.1C of @1 wt% graphene composite material.
FIG. 4 shows Na as a product prepared in example 519/20Li3/20Ni1/4Mn3/5O2@1 wt% graphene composite and Na3/ 4Li1/20Ni3/10Mn13/20O2A rate performance graph of 2.0-4.5V.
FIG. 5 shows Na as a product prepared in example 719/20Li3/20Ni1/4Mn3/5O2@5 wt% graphene composite and example 4 preparation of product Na19/20Li3/20Ni1/4Mn3/5O2A cycle performance diagram of 2.0-4.5V at 2C.
FIG. 6 shows Na as a product prepared in example 719/20Li3/20Ni1/4Mn3/5O2TEM image of @5 wt% graphene composite.
FIG. 7 shows Na as a product prepared in example 719/20Li3/20Ni1/4Mn3/5O2The former three-turn charge-discharge capacity diagram of 2.0-4.5V at 0.1C of @5 wt% graphene composite material.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
In this example Na3/5Ni3/10Mn7/10O2The preparation method comprises the following steps:
first, 1.477g of anhydrous sodium acetate, 2.240g of nickel acetate tetrahydrate and 5.147g of manganese acetate tetrahydrate are weighed according to the stoichiometric ratio and dissolved in 30mL of deionized water, 15mL of an aqueous solution in which 10.087g of citric acid monohydrate is dissolved is added, and after sufficient stirring, a wet gel is obtained in a water bath at 60 ℃ for 5 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 100 ℃ for 8 hours to obtain a dry gel, and the obtained dry gel was pulverized. Finally, the powder material is put into a tube furnace to be pre-sintered for 6 hours at 400 ℃ in the air atmosphere, and then the temperature is increased to 800 ℃ to be sintered for 10 hours to obtain Na3/5Ni3/10Mn7/10O2。
Example 2
In this example Na3/4Li1/20Ni3/10Mn13/20O2The preparation method comprises the following steps:
firstly, 1.935g of anhydrous sodium acetate, 0.160g of lithium acetate dihydrate, 2.240g of nickel acetate tetrahydrate and 4.780g of manganese acetate tetrahydrate are weighed according to the stoichiometric ratio and dissolved in 30mL of deionized water, 20mL of aqueous solution in which 16.550g of citric acid monohydrate is dissolved is added, and after full stirring, the wet gel is obtained by water bath at 70 ℃ for 8 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 24 hours to obtain a dry gel, and the obtained dry gel was pulverized. Finally, the powder material is put into a tube furnace to be pre-sintered for 6 hours at 500 ℃ in the air atmosphere, and then the temperature is increased to 900 ℃ to be sintered for 12 hours to obtain Na3/4Li1/20Ni3/ 10Mn13/20O2. This implementationNa prepared in example3/4Li1/20Ni3/10Mn13/20O2Material XRD is shown in figure 1.
Example 3
In this example Na9/10Li1/10Ni3/10Mn3/5O2The preparation method comprises the following steps:
firstly, 2.260g of anhydrous sodium acetate, 0.312g of lithium acetate dihydrate, 2.240g of nickel acetate tetrahydrate and 4.412g of manganese acetate tetrahydrate are weighed according to the stoichiometric ratio and dissolved in 35mL of deionized water, 20mL of an aqueous solution in which 17.967g of citric acid monohydrate is dissolved is added, and after full stirring, water bath is carried out at 70 ℃ for 8 hours to obtain wet gel. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 24 hours to obtain a dry gel, and the obtained dry gel was pulverized. Finally, the powder material is put into a tube furnace to be pre-sintered for 6 hours at 500 ℃ in the air atmosphere, and then the temperature is increased to 900 ℃ to be sintered for 12 hours to obtain Na9/10Li1/10Ni3/10Mn3/ 5O2. Na prepared in this example9/10Li1/10Ni3/10Mn3/5O2The charge-discharge capacity of the material at 0.1 ℃ for the first three circles of 1.5-4.5V is shown in figure 2. As can be seen from FIG. 2, the charge-discharge curve of the material is relatively smooth, the first discharge specific capacity is 136.4mAh/g, and the coulombic efficiency of the third circle is 93.3%.
Example 4
In this example Na19/20Li3/20Ni1/4Mn3/5O2The preparation method comprises the following steps:
firstly, 2.386g of anhydrous sodium acetate, 0.468g of lithium acetate dihydrate, 1.866g of nickel acetate tetrahydrate and 4.412g of manganese acetate tetrahydrate are weighed according to stoichiometric ratio and dissolved in 35mL of deionized water, 20mL of aqueous solution in which 18.440g of citric acid monohydrate is dissolved is added, and after full stirring, the wet gel is obtained by water bath at 70 ℃ for 8 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 18 hours to obtain a dry gel, and the obtained dry gel was pulverized. Finally, the powder material is put into a tube furnace to be pre-sintered for 6 hours at 500 ℃ in the air atmosphere, and then the temperature is increased to 900 ℃ to be sintered for 12 hoursThen Na is obtained19/20Li3/20Ni1/4Mn3/ 5O2. Na prepared in this example19/20Li3/20Ni1/4Mn3/5O2The cycle performance chart of the material at 2.0-4.5V under 2C is shown in figure 5. As can be seen from fig. 5, the capacity of the material decays faster in the first 20 cycles, the capacity retention rate after 200 cycles is 45.4%, while the reversible capacity of the graphene-coated material is 100mAh/g under the same condition, and the capacity retention rate after 200 cycles is improved to 58%.
Example 5
In this example Na19/20Li3/20Ni1/4Mn3/5O2The preparation method of the @1 wt% graphene composite material comprises the following steps:
firstly, 2.386g of anhydrous sodium acetate, 0.468g of lithium acetate dihydrate, 1.866g of nickel acetate tetrahydrate and 4.412g of manganese acetate tetrahydrate are weighed according to stoichiometric ratio and dissolved in 35mL of deionized water, 20mL of aqueous solution in which 18.440g of citric acid monohydrate is dissolved is added, and after full stirring, the wet gel is obtained by water bath at 70 ℃ for 8 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 18 hours to obtain a dry gel, and the obtained dry gel was pulverized. Putting the powder material into a tube furnace, presintering for 6 hours at 500 ℃ in air atmosphere, then heating to 900 ℃ and sintering for 12 hours to obtain Na19/20Li3/20Ni1/4Mn3/5O2. Weighing 4.95gNa19/20Li3/20Ni1/4Mn3/5O2Mixing with 0.05g of physical graphene powder, adding into a proper amount of absolute ethyl alcohol, magnetically stirring for 2 hours and ultrasonically treating for 1 hour to obtain mixed slurry, and putting into liquid nitrogen for freezing for 1 hour to obtain solid mixed slurry. Putting the solid mixed slurry into a vacuum freeze dryer for freeze drying for 16 hours, and finally putting the solid mixed slurry into a vacuum drying oven for drying for 5 hours at the temperature of 80 ℃ to obtain Na19/20Li3/20Ni1/4Mn3/5O2@1 wt% graphene composite. Na prepared in this example19/20Li3/ 20Ni1/4Mn3/5O2@1 wt% graphene composite material at 0.1C for 2.0-4.5V for three front circlesThe charge and discharge capacity is shown in FIG. 3, and the rate capability of 2.0-4.5V is shown in FIG. 4. As can be seen from figure 3, the charge-discharge curve of the material is smooth, no obvious voltage platform exists, the first discharge specific capacity is 109.1mAh/g, and the cycle is stable. As can be seen from FIG. 4, the reversible specific capacities at 0.1C, 0.5C, 1C and 2C are 96.5mAh/g, 87.1mAh/g, 79.7mAh/g and 72.8mAh/g, respectively, and the reversible specific capacity under 2C condition is obviously higher than that of uncoated Na3/4Li1/20Ni3/10Mn13/20O2A material.
Example 6
In this example Na19/20Li3/20Ni1/4Mn3/5O2The preparation method of the @2 wt% graphene composite material comprises the following steps:
firstly, 2.386g of anhydrous sodium acetate, 0.468g of lithium acetate dihydrate, 1.866g of nickel acetate tetrahydrate and 4.412g of manganese acetate tetrahydrate are weighed according to stoichiometric ratio and dissolved in about 35mL of deionized water, 20mL of aqueous solution in which 18.440g of citric acid monohydrate is dissolved is added, and after full stirring, the wet gel is obtained by water bath at 70 ℃ for 8 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 18 hours to obtain a dry gel, and the obtained dry gel was pulverized. Putting the powder material into a tube furnace, presintering for 6 hours at 400 ℃ in air atmosphere, then heating to 800 ℃ and sintering for 10 hours to obtain Na19/20Li3/20Ni1/4Mn3/ 5O2. Weighing 1.62gNa19/20Li3/20Ni1/4Mn3/5O2Mixing with 0.05g of physical graphene powder, adding into a proper amount of absolute ethyl alcohol, magnetically stirring for 2 hours and ultrasonically treating for 1 hour to obtain mixed slurry, and putting into liquid nitrogen for freezing for 1 hour to obtain solid mixed slurry. Putting the solid mixed slurry into a vacuum freeze dryer for freeze drying for 7 hours, and finally putting the solid mixed slurry into a vacuum drying oven for drying for 5 hours at the temperature of 80 ℃ to obtain Na19/20Li3/20Ni1/4Mn3/5O2@2 wt% graphene composite.
Example 7
In this example Na19/20Li3/20Ni1/4Mn3/5O2@5 wt% stoneThe preparation method of the graphene composite material comprises the following steps:
firstly, 2.386g of anhydrous sodium acetate, 0.468g of lithium acetate dihydrate, 1.866g of nickel acetate tetrahydrate and 4.412g of manganese acetate tetrahydrate are weighed according to stoichiometric ratio and dissolved in about 35mL of deionized water, 20mL of aqueous solution in which 18.440g of citric acid monohydrate is dissolved is added, and after full stirring, the wet gel is obtained by water bath at 70 ℃ for 8 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 18 hours to obtain a dry gel, and the obtained dry gel was pulverized. Putting the powder material into a tube furnace, presintering for 6 hours at 500 ℃ in air atmosphere, then heating to 900 ℃ and sintering for 12 hours to obtain Na19/20Li3/20Ni1/4Mn3/ 5O2. Weighing 0.95gNa19/20Li3/20Ni1/4Mn3/5O2Mixing with 0.05g of physical graphene powder, adding into a proper amount of absolute ethyl alcohol, magnetically stirring for 2 hours and ultrasonically treating for 1 hour to obtain mixed slurry, and freezing in liquid nitrogen for 1 hour to obtain the mixed slurry. Putting the mixed slurry into a vacuum freeze dryer for freeze drying for 16 hours, and finally putting the mixed slurry into a vacuum drying oven for drying for 5 hours at the temperature of 80 ℃ to obtain Na19/20Li3/20Ni1/4Mn3/5O2@5 wt% graphene composite. Na prepared in this example19/20Li3/ 20Ni1/4Mn3/5O2The 2.0-4.5V cycle performance of the @5 wt% graphene composite material at 2C is shown in FIG. 5, and the TEM is shown in FIG. 6. The charge-discharge capacity of the first three cycles at 0.1C of 2.0-4.5V is shown in FIG. 7. As can be seen from FIG. 7, the charge-discharge curve of the material is smooth, no obvious voltage platform exists, the first discharge specific capacity is about 104.1mAh/g, and the coulombic efficiency of the third circle is 94.3%.
Example 8
In this example Na19/20Li3/20Ni1/4Mn3/5O2The preparation method of the @8 wt% graphene composite material comprises the following steps:
firstly, 2.386g of anhydrous sodium acetate, 0.468g of lithium acetate dihydrate, 1.866g of nickel acetate tetrahydrate and 4.412g of manganese acetate tetrahydrate are weighed according to stoichiometric ratio and dissolved in 35mAbout L deionized water, 20mL of an aqueous solution containing 18.440g of citric acid monohydrate was added, and after stirring sufficiently, a wet gel was obtained in a water bath at 60 ℃ for 5 hours. Subsequently, the wet gel was dried in an air-blast drying oven at 120 ℃ for 18 hours to obtain a dry gel, and the obtained dry gel was pulverized. Putting the powder material into a tube furnace, presintering for 6 hours at 400 ℃ in air atmosphere, then heating to 800 ℃ and sintering for 10 hours to obtain Na19/20Li3/20Ni1/4Mn3/ 5O2. Weighing 0.575gNa19/20Li3/20Ni1/4Mn3/5O2Mixing with 0.05g of physical graphene powder, adding into a proper amount of absolute ethyl alcohol, magnetically stirring for 2 hours and ultrasonically treating for 1 hour to obtain mixed slurry, and freezing in liquid nitrogen for 1 hour to obtain the mixed slurry. Putting the mixed slurry into a vacuum freeze dryer for freeze drying for 7 hours, and finally putting the mixed slurry into a vacuum drying oven for drying for 3 hours at the temperature of 100 ℃ to obtain Na19/20Li3/20Ni1/4Mn3/5O2@8 wt% graphene composite.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (8)
1. The element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material is characterized by having a chemical formula as follows: na (Na)xLiy[Ni,Mn]1-yO2@ graphene including NaxLiy[Ni,Mn]1-yO2Granules and coating with NaxLiy[Ni,Mn]1-yO2Graphene on the surface of the particles, wherein 1/2<x is less than or equal to 1; y is more than or equal to 0 and less than or equal to 3/10; the stoichiometric ratio of the elements Ni and Mn is added to be 1-y.
2. The element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material as claimed in claim 1, wherein the graphene is physically graphene, and the coating amount of the graphene accounts for 1-8 wt% of the mass of the positive electrode material.
3. The preparation method of the element-doped synergetic graphene-coated layered manganese-based sodium-ion battery positive electrode material as claimed in any one of claims 1 to 2, wherein the preparation process comprises a sol-gel method and a freeze-drying process, and specifically comprises the following steps:
(1) weighing anhydrous sodium acetate, lithium acetate dihydrate, nickel acetate tetrahydrate and manganese acetate tetrahydrate according to a stoichiometric ratio, dissolving in deionized water, adding a chelating agent, and stirring to obtain a mixed solution;
(2) preparing the mixed solution obtained in the step (1) into wet gel;
(3) drying the wet gel obtained in the step (2) to obtain dry gel, and grinding the dry gel into powder;
(4) pre-sintering the powder obtained in the step (3) in an air atmosphere at 300-600 ℃ for 3-10 hours, then continuously heating to 350-1000 ℃, and calcining for 8-24 hours to obtain an element-doped layered manganese-based sodium ion battery anode material;
(5) mixing the element-doped layered manganese-based sodium-ion battery positive electrode material obtained in the step (4) and physical graphene, adding the mixture into absolute ethyl alcohol, and stirring and performing ultrasonic treatment to obtain mixed slurry;
(6) freezing the mixed slurry obtained in the step (5) by liquid nitrogen to obtain solid mixed slurry;
(7) and (4) freeze-drying the solid mixed slurry obtained in the step (6) for 6-24 hours, and finally drying at 60-150 ℃ for 2-10 hours to obtain the element-doped synergistic graphene-coated layered manganese-based sodium-ion battery positive electrode material.
4. The method according to claim 3, wherein the anhydrous sodium acetate, lithium acetate dihydrate, nickel acetate tetrahydrate, and manganese acetate tetrahydrate of step (1) are weighed in a stoichiometric ratio of Na: Li: [ Ni, Mn ] ═ x: y: 1-y; the chelating agent is citric acid monohydrate, and the molar weight of the chelating agent is 1.5 times of that of the metal cations.
5. The preparation method according to claim 3, wherein the mixed solution of the step (2) is stirred at 40 to 120 ℃ for 4 to 10 hours to obtain a wet gel.
6. The method according to claim 3, wherein the drying temperature in step (3) is 60 to 150 ℃ and the drying time is 10 to 24 hours.
7. The preparation method according to claim 3, wherein the stirring time in the step (5) is 0.5 to 3 hours, and the ultrasonic treatment time is 0.5 to 2 hours.
8. The application of the element-doped and graphene-coated layered manganese-based sodium-ion battery positive electrode material disclosed by any one of claims 1-2 as a sodium-ion battery positive electrode material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114373917A (en) * | 2022-01-18 | 2022-04-19 | 山东大学 | Sodium-ion battery positive electrode composite material and preparation method and application thereof |
| CN115367804A (en) * | 2022-09-23 | 2022-11-22 | 东莞理工学院 | Preparation method of manganese-based sodium-ion battery positive electrode material with stable air |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617251A (en) * | 2014-12-09 | 2015-05-13 | 贺灿辉 | Preparation method for graphene/spinel LiMn2O4 nanometer composite material |
| CN108140826A (en) * | 2015-05-26 | 2018-06-08 | 尤米科尔公司 | To cathode material of the sodium manganese oxide doping divalent metal as sodium-ion battery |
| CN108878826A (en) * | 2018-06-26 | 2018-11-23 | 上海汉行科技有限公司 | A kind of sodium manganate/graphene combination electrode material and its preparation method and application |
| CN111162250A (en) * | 2018-11-07 | 2020-05-15 | 中国科学院物理研究所 | Pure cation valence-change high-sodium-content P2 phase layered oxide material, preparation method and application |
| CN111180704A (en) * | 2020-01-07 | 2020-05-19 | 湖南工程学院 | Sodium-ion battery positive electrode material and preparation method and application thereof |
-
2021
- 2021-09-23 CN CN202111113796.8A patent/CN113851626A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617251A (en) * | 2014-12-09 | 2015-05-13 | 贺灿辉 | Preparation method for graphene/spinel LiMn2O4 nanometer composite material |
| CN108140826A (en) * | 2015-05-26 | 2018-06-08 | 尤米科尔公司 | To cathode material of the sodium manganese oxide doping divalent metal as sodium-ion battery |
| CN108878826A (en) * | 2018-06-26 | 2018-11-23 | 上海汉行科技有限公司 | A kind of sodium manganate/graphene combination electrode material and its preparation method and application |
| CN111162250A (en) * | 2018-11-07 | 2020-05-15 | 中国科学院物理研究所 | Pure cation valence-change high-sodium-content P2 phase layered oxide material, preparation method and application |
| CN111180704A (en) * | 2020-01-07 | 2020-05-19 | 湖南工程学院 | Sodium-ion battery positive electrode material and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114373917A (en) * | 2022-01-18 | 2022-04-19 | 山东大学 | Sodium-ion battery positive electrode composite material and preparation method and application thereof |
| CN115367804A (en) * | 2022-09-23 | 2022-11-22 | 东莞理工学院 | Preparation method of manganese-based sodium-ion battery positive electrode material with stable air |
| CN115367804B (en) * | 2022-09-23 | 2024-04-16 | 东莞理工学院 | Preparation method of air-stable manganese-based sodium ion battery positive electrode material |
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