CN115498183A - Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof - Google Patents

Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof Download PDF

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CN115498183A
CN115498183A CN202211164741.4A CN202211164741A CN115498183A CN 115498183 A CN115498183 A CN 115498183A CN 202211164741 A CN202211164741 A CN 202211164741A CN 115498183 A CN115498183 A CN 115498183A
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manganese
vanadium
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高洪才
王英帅
王猛
丁香玉
信宇航
庞彦飞
刘弘枫
陈保锐
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Beijing Institute of Technology BIT
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Abstract

The invention relates to a modified vanadium manganese sodium phosphate cathode material, and preparation and application thereof, and belongs to the technical field of sodium ion battery cathode materials. The positive electrode material is vanadium manganese sodium phosphate with a layer of amorphous carbon coated on the surface and Ga doped inside, ga doping and carbon coating are adopted for simultaneous modification, so that the ginger-Taylor effect and the dissolution reaction of a manganese element can be inhibited, the conductivity is improved, the positive electrode material serving as a sodium ion battery can show good conductivity, circulation stability and rate capability, and the positive electrode material has good application prospect in the field of sodium ion batteries; in addition, the anode material is prepared by adopting a sol-gel method, the synthesis process is simple, large-scale industrial production is easy, and the application of the sodium vanadium manganese phosphate in the field of sodium ion batteries is promoted.

Description

Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof
Technical Field
The invention relates to a modified vanadium manganese sodium phosphate cathode material, and preparation and application thereof, and belongs to the technical field of sodium ion battery cathode materials.
Background
In order to reduce pollution during the use of fossil fuels, the development of sustainable renewable energy sources, as well as novel power cells and efficient energy storage systems is of great importance. Of these, lithium ion batteries are undoubtedly the most interesting, but their increasing cost limits the further development of lithium ion batteries. And the sodium ion battery is expected to compete with the lithium ion battery due to abundant reserves and cost advantages.
The sodium vanadium manganese phosphate with a sodium super-ion conductor (NASICON) type structure has the advantages of high reversible capacity, high energy density, high working voltage, low cost, low toxicity and the like, and is a promising sodium-ion battery cathode material. However, this material has poor electronic conductivity, resulting in poor rate and cycling performance; and the manganese element has a ginger-Taylor effect and a dissolution reaction, so that the long-term circulation stability of the manganese element is limited. Therefore, the key for promoting the commercialization of the vanadium manganese sodium phosphate is to improve the composition structure and the electronic conductivity of the vanadium manganese sodium phosphate and improve the multiplying power and the cycle performance of the vanadium manganese sodium phosphate.
Disclosure of Invention
Aiming at the problems of the existing vanadium manganese sodium phosphate material, the invention provides a modified vanadium manganese sodium phosphate anode material, and preparation and application thereof, on one hand, the electrochemical inert Ga element is utilized to dope the vanadium manganese sodium phosphate, the ginger-Taylor effect and the dissolution reaction of the manganese element are inhibited, the structural stability of the material is improved, on the other hand, carbon is utilized to coat the vanadium manganese sodium phosphate, the conductivity of the material is improved, and the Ga-doped and carbon-coated vanadium manganese sodium phosphate is used as the anode material to be applied to a sodium ion battery, so that the excellent cycle stability and rate capability are shown; the Ga-doped and carbon-coated vanadium manganese sodium phosphate is prepared by a sol-gel method, the synthesis process is simple, large-scale industrial production is easy, and the application of the vanadium manganese sodium phosphate in the field of sodium ion batteries is promoted.
The purpose of the invention is realized by the following technical scheme.
A modified vanadium manganese sodium phosphate anode material is a vanadium manganese sodium phosphate material with a layer of amorphous carbon coated on the surface and Ga doped inside, and the chemical formula is abbreviated as Na 4 MnV 1-x Ga x (PO 4 ) 3 -C, wherein 0 < x < 0.5.
Preferably, na 4 MnV 1-x Ga x (PO 4 ) 3 in-C, x is more than 0.05 and less than 0.2.
Preferably, na 4 MnV 1-x Ga x (PO 4 ) 3 In the-C, the mass fraction of the amorphous carbon coating layer is 7-13%.
The preparation method of the modified vanadium manganese sodium phosphate cathode material specifically comprises the following steps:
(1) Adding water-soluble sodium source, manganese source, vanadium source, phosphate, gallium source and carbon source into water, and completely dissolving to form a mixed solution;
(2) Stirring the mixed solution at 50-90 ℃ to form a gel, and then drying to obtain a precursor;
(3) Under the protection atmosphere of nitrogen or inert gas, presintering the precursor for 1-5 h at the temperature of 150-450 ℃, and then sintering for 6-15 h at the temperature of 600-900 ℃ to obtain the modified sodium vanadium manganese phosphate cathode material.
Preferably, the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate, sodium acetate, sodium oxalate and sodium fluoride; the manganese source is at least one of manganese acetate, manganese oxalate, manganese carbonate and manganese acetylacetonate; the vanadium source is at least one of vanadium pentoxide, vanadium trioxide and ammonium metavanadate; the gallium source is at least one of gallium acetylacetonate, gallium nitrate, gallium chloride, gallium iodide and gallium selenide; the phosphate is at least one of ammonium dihydrogen phosphate, phosphoric acid and sodium dihydrogen phosphate; the carbon source is at least one of citric acid, glucose, sucrose, oxalic acid, ascorbic acid and polyvinylpyrrolidone.
Preferably, the molar ratio of the element V in the vanadium source to the element C in the carbon source is 1.
An application of a modified vanadium manganese sodium phosphate cathode material in a sodium ion battery.
Has the advantages that:
(1) In the invention, inert elements Ga and Na are adopted 4 MnV(PO 4 ) 3 V in 3+ Bit doping, in one aspect Ga 3+ Can increase Na 4 MnV(PO 4 ) 3 Middle V 3+ And Mn 2+ Degree of disorder of arrangement, thereby suppressing Mn 2+ The Taylor effect of ginger, na enhancement 4 MnV(PO 4 ) 3 Cycling stability of the material, on the other hand due to Ga 3+ And V 3+ Has the same valence of electricity, belongs to the same valence doping, and Ga 3+ (
Figure BDA0003860850950000021
) And V 3+ (
Figure BDA0003860850950000022
) Approximate radii of ions, ga 3+ Can be introduced without destroying Na 4 MnV(PO 4 ) 3 The structure improves the ionic and electronic conductivity of the material and strengthens the sodium storage performance of the material.
(2) The invention is described in Na 4 MnV(PO 4 ) 3 The surface of the material is coated with a layer of amorphous carbon, which can effectively improve the electronic conductivity of the material, thereby being beneficial to improving Na 4 MnV(PO 4 ) 3 Multiplying power and cycle performance of (c).
(3) Ga doping amount to Na in the invention 4 MnV 1-x Ga x (PO 4 ) 3 The electrochemical performance of-C has larger influence, and in the range of 0.05 < x < 0.5, na has larger effect along with the increase of the doping amount of Ga element 4 MnV 1-x Ga x (PO 4 ) 3 The cycle and rate performance of-C increases and then begins to decline after reaching the peak. In particular in the preferred range of 0.05 < x < 0.2, na 4 MnV 1-x Ga x (PO 4 ) 3 -C possesses excellent electrochemical properties. .
(4) The invention adopts a sol-gel method to obtain the nano composite granular Ga-doped and amorphous carbon-coated vanadium manganese sodium phosphate, has simple synthesis process, is easy for large-scale industrial production, and promotes the application of the vanadium manganese sodium phosphate in the field of sodium ion batteries.
(5) The invention adopts Ga doped and carbon coated simultaneously modified Na 4 MnV(PO 4 ) 3 The material is used as a positive electrode material of a sodium ion battery, has good conductivity, cycling stability and rate capability, and has good application prospect in the field of sodium ion batteries.
Drawings
FIG. 1 shows Na prepared in example 1 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C, na prepared in example 2 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 -C, na prepared in example 3 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 -C and Na prepared in comparative example 1 4 MnV(PO 4 ) 3 X-ray diffraction (XRD) contrast pattern of (a).
FIG. 2 shows Na prepared in example 1 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -Scanning Electron Microscope (SEM) image of C.
FIG. 3 is Na prepared by example 1 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C, na prepared in example 2 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 -C, na prepared in example 3 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 -C and Na prepared in comparative example 1 4 MnV(PO 4 ) 3 The batteries respectively assembled as positive electrode materials are in the voltage range of 2.5-3.8V and 1C (1C =110mA g) -1 ) And comparing the charge and discharge performance of the first circle under the current density.
FIG. 4 shows Na prepared by example 1 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C prepared in example 2Na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 -C, na prepared in example 3 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 -C and Na prepared in comparative example 1 4 MnV(PO 4 ) 3 The batteries respectively assembled as positive electrode materials are in the voltage range of 2.5-3.8V and 1C (1C =110mA g) -1 ) Comparative plot of cycling performance at current density.
Detailed Description
The present invention is further illustrated by the following figures and detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
In the following examples, the specific steps of cell assembly were as follows: weighing the positive electrode prepared in the embodiment or the comparative example, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8; sodium perchlorate (NaClO) 1M in electrolyte is used as negative electrode 4 ) A 10wt% fluoroethylene carbonate (FEC) was added while dissolving in an ethylene carbonate/diethyl carbonate (EC/DEC) system at a volume ratio of 1.
Example 1
(1) Dissolving 1.158g of citric acid, 0.445g of anhydrous sodium carbonate, 0.495g of manganese acetate, 0.212g of ammonium metavanadate, 0.669g of ammonium dihydrogen phosphate and 0.073g of gallium acetylacetonate in 20mL of deionized water solution, and uniformly stirring and mixing to form a mixed solution;
(2) Stirring the mixed solution at 80 ℃ until the solution is evaporated to dryness to form gel, and then placing the gel in a blast oven to dry for 12 hours at 120 ℃ to obtain a precursor;
(3) Fully grinding the precursor into powder, then placing the powder in a tubular furnace in an argon atmosphere, raising the temperature to 400 ℃ at a temperature rise rate of 5 ℃/min for presintering, preserving the heat for 4h, and then cooling the powder along with the furnace to obtain presintering solid;
(4) Fully grinding the presintered solid into powder, placing the powder in a tubular furnace in an argon atmosphere, heating to 720 ℃ at a heating rate of 5 ℃/min, sintering, keeping the temperature for 9 hours, and cooling along with the furnace to obtain the modified vanadium manganese sodium phosphate cathode material, wherein the chemical formula is abbreviated as Na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C。
For the prepared Na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 Phase analysis of-C, it can be seen from XRD spectrum of FIG. 1 that Na is not destroyed after gallium doping modification 4 MnV(PO 4 ) 3 The crystal structure of (1).
For the prepared Na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C for morphological characterization, SEM photograph of FIG. 2 shows, na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C is in the shape of a nanocomposite particle, the surface of which is coated with amorphous carbon.
Using the prepared Na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 -C as a positive electrode material, in a voltage range of 2.5-3.8V and 1C (1C= 110mA g) -1 ) And carrying out cycle performance test under current density. The test results in FIG. 3 show that, na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 The specific charge capacity of the first loop of the-C can reach 82.0mAh/g, the specific discharge capacity can reach 79.7mAh/g, and the-C modified Na-Ca alloy is compared with unmodified Na 4 MnV(PO 4 ) 3 The charge-discharge capacity and the coulombic efficiency of the first circle are both obviously improved. The test results in FIG. 4 show that Na 4 MnV 0.9 Ga 0.1 (PO 4 ) 3 After 100 cycles of-C circulation, the discharge specific capacity of 77mAh/g is still maintained, the capacity retention rate is up to 96.6 percent, compared with the unmodified Na 4 MnV(PO 4 ) 3 The circulation stability is obviously improved.
Example 2
(1) Dissolving 1.158g of citric acid, 0.445g of anhydrous sodium carbonate, 0.495g of manganese acetate, 0.219g of ammonium metavanadate, 0.669g of ammonium dihydrogen phosphate and 0.051g of gallium acetylacetonate in 20mL of deionized water solution, and uniformly stirring and mixing to form a mixed solution;
(2) Stirring the mixed solution at 80 ℃ until the solution is evaporated to dryness to form gel, and then placing the gel in a blast oven to dry for 12 hours at 120 ℃ to obtain a precursor;
(3) Fully grinding the precursor into powder, then placing the powder in a tubular furnace in an argon atmosphere, raising the temperature to 400 ℃ at a temperature rise rate of 5 ℃/min for presintering, preserving the heat for 4h, and then cooling the powder along with the furnace to obtain presintering solid;
(4) Fully grinding the presintered solid into powder, placing the powder in a tubular furnace in an argon atmosphere, heating to 720 ℃ at a heating rate of 5 ℃/min for sintering, keeping the temperature for 9 hours, and cooling along with the furnace to obtain the modified sodium vanadium manganese phosphate cathode material, wherein the chemical formula is abbreviated as Na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 -C。
For the prepared Na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 Phase analysis of-C, it can be seen from XRD spectrum of FIG. 1 that Na is not destroyed after gallium doping modification 4 MnV(PO 4 ) 3 The crystal structure of (1).
For the prepared Na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 The morphology of the-C is characterized, and Na is known according to the characterization result 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 -C is in the shape of a nanocomposite particle, the surface of which is coated with amorphous carbon.
Using the prepared Na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 -C as a positive electrode material, in a voltage range of 2.5-3.8V and 1C (1C= 110mA g) -1 ) And carrying out cycle performance test under current density. The test results in FIG. 3 show that Na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 The specific charge capacity of the first loop of the-C can reach 80.6mAh/g, the specific discharge capacity can reach 78.3mAh/g, compared with the unmodified Na 4 MnV(PO 4 ) 3 The charge-discharge capacity and the coulombic efficiency of the first circle are obviously obtainedAnd (4) improving. The test results of FIG. 4 show that, na 4 MnV 0.93 Ga 0.07 (PO 4 ) 3 After being cycled for 100 cycles by-C, the lithium-ion battery can still maintain the discharge specific capacity of 67.9mAh/g, and the capacity retention rate is as high as 86.7 percent compared with that of unmodified Na 4 MnV(PO 4 ) 3 The circulation stability is obviously improved.
Example 3
(1) Dissolving 1.158g of citric acid, 0.445g of anhydrous sodium carbonate, 0.495g of manganese acetate, 0.205g of ammonium metavanadate, 0.669g of ammonium dihydrogen phosphate and 0.095g of gallium acetylacetonate in 20mL of deionized water solution, and uniformly stirring and mixing to form a mixed solution;
(2) Stirring the mixed solution at 80 ℃ until the solution is evaporated to dryness to form gel, and then placing the gel in a blast oven to dry for 12 hours at 120 ℃ to obtain a precursor;
(3) Fully grinding the precursor into powder, then placing the powder in a tubular furnace in an argon atmosphere, heating to 400 ℃ at the heating rate of 5 ℃/min for pre-sintering, keeping the temperature for 4h, and then cooling along with the furnace to obtain pre-sintered solid;
(4) Fully grinding the presintered solid into powder, placing the powder in a tubular furnace in an argon atmosphere, heating to 720 ℃ at a heating rate of 5 ℃/min, sintering, keeping the temperature for 9 hours, and cooling along with the furnace to obtain the modified vanadium manganese sodium phosphate cathode material, wherein the chemical formula is abbreviated as Na 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 -C。
For the prepared Na 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 Phase analysis is carried out on-C, and as can be seen from an XRD spectrogram in figure 1, na is not damaged after gallium doping modification 4 MnV(PO 4 ) 3 The crystal structure of (1).
For the prepared Na 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 The morphology of the-C is characterized, and Na is known according to the characterization result 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 -C is in the shape of a nanocomposite particle, the surface of which is coated with amorphous carbon.
Using the prepared Na 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 -C is used as a positive electrode material to assemble a battery, the voltage is in a range of 2.5-3.8V, and 1C (1C =110mA g) -1 ) And carrying out cycle performance test at current density. The test results in FIG. 3 show that Na 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 The specific charge capacity of the first ring of-C can reach 80.7mAh/g, the specific discharge capacity can reach 75.5mAh/g, compared with the unmodified Na 4 MnV(PO 4 ) 3 The charge-discharge capacity and the coulomb efficiency of the first ring are both obviously improved. The test results of FIG. 4 show that, na 4 MnV 0.87 Ga 0.13 (PO 4 ) 3 After 100 cycles of-C circulation, the discharge specific capacity of 55.7mAh/g is still maintained, the capacity retention rate is as high as 73.8 percent, compared with the unmodified Na 4 MnV(PO 4 ) 3 The circulation stability is obviously improved.
Comparative example 1
(1) Dissolving 0.445g of anhydrous sodium carbonate, 0.495g of manganese acetate, 0.236g of ammonium metavanadate and 0.669g of ammonium dihydrogen phosphate in 20mL of deionized water solution, and uniformly stirring and mixing to form a mixed solution;
(2) Stirring the mixed solution at 80 ℃ until the solution is evaporated to dryness to form gel, and then placing the gel in a blast oven to dry for 12 hours at 120 ℃ to obtain a precursor;
(3) Fully grinding the precursor into powder, then placing the powder in a tubular furnace in an argon atmosphere, raising the temperature to 400 ℃ at a temperature rise rate of 5 ℃/min for presintering, preserving the heat for 4h, and then cooling the powder along with the furnace to obtain presintering solid;
(4) Fully grinding the presintered solid into powder, placing the powder in a tubular furnace in an argon atmosphere, heating to 720 ℃ at a heating rate of 5 ℃/min, sintering, keeping the temperature for 9 hours, and cooling along with the furnace to obtain the vanadium manganese sodium phosphate cathode material, wherein the chemical formula is abbreviated as Na 4 MnV(PO 4 ) 3 。
For the prepared Na 4 MnV(PO 4 ) 3 Phase analysis was performed and from the XRD pattern of FIG. 1, it can be seen that Na was produced by sol-gel 4 MnV(PO 4 ) 3 The XRD pattern of (A) is the same as that of standard PDF card, indicating that the synthesized Na 4 MnV(PO 4 ) 3 Is free ofPure phase of impurities. Moreover, the diffraction peak of the XRD spectrogram is sharp, which indicates that the obtained sample has good crystallinity.
For the prepared Na 4 MnV(PO 4 ) 3 Performing morphology characterization, and obtaining Na according to the characterization result 4 MnV(PO 4 ) 3 In the shape of nanocomposite particles.
Using the prepared Na 4 MnV(PO 4 ) 3 The positive electrode material is assembled into a battery with the voltage ranging from 2.5 to 3.8V and the voltage of 1C (1C= 110mA g) -1 ) And carrying out cycle performance test at current density. The test results in FIG. 3 show that Na 4 MnV(PO 4 ) 3 The specific charge capacity of the first circle can reach 74.6mAh/g, and the specific discharge capacity can reach 65.4mAh/g. The test results of FIG. 4 show that, na 4 MnV(PO 4 ) 3 The discharge specific capacity is attenuated to 44.7mAh/g after 100 cycles of circulation, and the capacity retention rate is 68.3 percent.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A modified vanadium manganese sodium phosphate cathode material is characterized in that: is a vanadium manganese sodium phosphate material with a layer of amorphous carbon coated on the surface and Ga doped inside, and the chemical formula is abbreviated as Na 4 MnV 1-x Ga x (PO 4 ) 3 -C, wherein 0 < x < 0.5.
2. The modified vanadium manganese sodium phosphate cathode material as claimed in claim 1, wherein: na (Na) 4 MnV 1-x Ga x (PO 4 ) 3 in-C, x is more than 0.05 and less than 0.2.
3. The modified vanadium manganese sodium phosphate cathode material according to claim 1 or 2, characterized in that: na (Na) 4 MnV 1-x Ga x (PO 4 ) 3 in-CThe mass fraction of the amorphous carbon coating layer is 7-13%.
4. A method for preparing the modified vanadium manganese sodium phosphate cathode material as claimed in any one of claims 1 to 3, wherein: the method specifically comprises the following steps:
(1) Adding water-soluble sodium source, manganese source, vanadium source, phosphate, gallium source and carbon source into water, and completely dissolving to form a mixed solution;
(2) Stirring the mixed solution at 50-90 ℃ to form a gel, and then drying to obtain a precursor;
(3) Under the protection atmosphere of nitrogen or inert gas, presintering the precursor for 1-5 h at 150-450 ℃, and then sintering for 6-15 h at 600-900 ℃ to obtain the modified vanadium manganese sodium phosphate cathode material.
5. The preparation method of the modified sodium vanadium manganese phosphate cathode material as claimed in claim 4, wherein the preparation method comprises the following steps: the sodium source is at least one of sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate, sodium acetate, sodium oxalate and sodium fluoride; the manganese source is at least one of manganese acetate, manganese oxalate, manganese carbonate and manganese acetylacetonate; the vanadium source is at least one of vanadium pentoxide, vanadium trioxide and ammonium metavanadate; the phosphate is at least one of ammonium dihydrogen phosphate, phosphoric acid and sodium dihydrogen phosphate; the gallium source is at least one of gallium acetylacetonate, gallium nitrate, gallium chloride, gallium iodide and gallium selenide; the carbon source is at least one of citric acid, glucose, sucrose, oxalic acid, ascorbic acid and polyvinylpyrrolidone.
6. The preparation method of the modified vanadium manganese sodium phosphate cathode material as claimed in claim 4, wherein the preparation method comprises the following steps: the molar ratio of the V element in the vanadium source to the C element in the carbon source is 1.
7. Use of the modified sodium vanadium manganese phosphate positive electrode material according to any one of claims 1 to 3 in a sodium ion battery.
CN202211164741.4A 2022-09-23 2022-09-23 Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof Pending CN115498183A (en)

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CN116741975A (en) * 2023-08-15 2023-09-12 北京理工大学 Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116741975A (en) * 2023-08-15 2023-09-12 北京理工大学 Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery
CN116741975B (en) * 2023-08-15 2023-12-01 北京理工大学 Double-carbon-layer heterogeneous composite positive electrode material, preparation method thereof and sodium ion battery

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