CN115275140A - Preparation method of high-safety sodium storage material based on boron-doped sodium vanadium phosphate - Google Patents

Preparation method of high-safety sodium storage material based on boron-doped sodium vanadium phosphate Download PDF

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CN115275140A
CN115275140A CN202210874579.9A CN202210874579A CN115275140A CN 115275140 A CN115275140 A CN 115275140A CN 202210874579 A CN202210874579 A CN 202210874579A CN 115275140 A CN115275140 A CN 115275140A
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sodium
boron
solution
doped
vanadium phosphate
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陈俊松
严东
李欣研
吴睿
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University of Electronic Science and Technology of China
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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
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a preparation method of a high-safety sodium storage material based on boron-doped sodium vanadium phosphate, belonging to the technical field of sodium ion battery anode materials. The main point is that the method can comprehensively improve two problems of poor electronic conductivity and severe volume expansion of the vanadium sodium phosphate. The main scheme comprises adding polyvinylpyrrolidone into deionized water, and stirring to obtain solution A; adding ammonium metavanadate and oxalic acid into deionized water, and uniformly stirring to obtain a solution B; adding 50-200mg of boric acid into the solution A, adding sodium dihydrogen phosphate into the solution B, and uniformly stirring; mixing the solution A and the solution B, and uniformly stirring to obtain a solution C; transferring the solution C into an injector, starting electrostatic spinning, pretreating spinning, annealing the pretreated sample in a tube furnace at 350 ℃ for 4h, cooling to room temperature, then annealing at 800 ℃ for 6h in an argon/hydrogen mixed gas atmosphere to obtain the nano-fibrous boron-doped sodium vanadium phosphate. The product of the invention is used as a battery anode material.

Description

Preparation method of high-safety sodium storage material based on boron-doped sodium vanadium phosphate
Technical Field
The invention belongs to the technical field of preparation of sodium-ion battery cathode materials, and particularly relates to a preparation method of a high-safety sodium storage material based on boron-doped sodium vanadium phosphate.
Background
The sodium ion battery has the characteristics of large sodium storage capacity, low cost, similar charge and discharge mechanism to that of a lithium ion battery and the like, so that the sodium ion battery becomes a new research hotspot. However, the radius of the sodium ions is larger than that of the lithium ions, so that the dynamic reaction is slow in the charging and discharging processes of the sodium ion battery. This problem can be effectively alleviated by using a suitable cathode material. The vanadium sodium phosphate provides a transport channel for sodium ions due to the unique sodium ion superconducting structure, has high ionic conductivity, and becomes a promising positive electrode material of the sodium ion battery. However, in the repeated sodium ion desorption process, the sodium vanadium phosphate can have severe volume expansion, which can cause structural collapse and affect the electrochemical performance. Researchers find that doping can effectively improve the electrochemical performance of the vanadium sodium phosphate cathode material. The doped atoms can replace the position of carbon to form a doped carbon layer to cover the vanadium sodium phosphate, and can also directly replace the position of phosphorus.
Most of the current reports on vanadium sodium phosphate focus on doping, carbon coating, particle size control and the like. Chinese patent (CN 202111272724.8) discloses a preparation method of doped sodium vanadium phosphate, wherein nitrogen-doped _ peony-shaped molybdenum oxide is prepared by adding a regulating agent, and sodium storage sites of the synthesized sodium vanadium phosphate are increased, and simultaneously, a sodium ion diffusion path is shortened, and the desorption rate of sodium ions during charging and discharging is improved. Chinese patent (CN 202111300358.2) discloses a vanadium sodium phosphate carbon composite material and a preparation method and application thereof. The composite material is regular spherical particles, and the particles are connected with each other to form a loose porous structure, so that the structure is favorable for shortening the diffusion path of sodium ions in the vanadium sodium phosphate material, and in addition, the carbon material can also solve the problem of insufficient intrinsic conductivity of the vanadium sodium phosphate. The modified sodium vanadium phosphate synthesized by the patent publication only improves the electrochemical performance from a single angle, and cannot comprehensively improve two problems of poor electronic conductivity and severe volume expansion of the sodium vanadium phosphate.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide a preparation technology of a high-safety sodium storage electrode material based on boron-doped carbon-coated sodium vanadium phosphate nano-fibers, which can comprehensively improve two problems of poor electronic conductivity and serious volume expansion of sodium vanadium phosphate.
In order to realize the purpose, the technical scheme of the invention is as follows:
a preparation method of a high-safety sodium storage material based on boron-doped sodium vanadium phosphate comprises the following steps:
step 1: adding polyvinylpyrrolidone into deionized water, and uniformly stirring to obtain a solution A; adding ammonium metavanadate and oxalic acid into deionized water, and uniformly stirring to obtain a solution B, wherein the concentration of polyvinylpyrrolidone is 217g/L, the concentration of ammonium metavanadate is 2.5mol/L, and the concentration of oxalic acid is 5 mol/L;
step 2: adding boric acid into the solution A, adding sodium dihydrogen phosphate into the solution B, and uniformly stirring, wherein the concentration of boric acid is 22.5-90g/L, and the concentration of sodium dihydrogen phosphate is 3.75 mol/L;
and step 3: mixing the solution A and the solution B, and uniformly stirring to obtain a solution C;
and 4, step 4: transferring the solution C into an injector, and starting spinning, wherein the spinning voltage is 30kV, the pushing speed is 0.025mm/min, and the distance between a needle head and a receiver is 15 cm;
and 5: spinning is pretreated, wherein the pretreatment condition is annealing at 220 ℃ in air for 2h.
Step 6: and annealing the pretreated sample in a tubular furnace, annealing at 350 ℃ for 4h, cooling to room temperature, and annealing at 800 ℃ for 6h to obtain the nano-fibrous boron-doped sodium vanadium phosphate with argon/hydrogen mixed gas as atmosphere.
Further, the polyvinylpyrrolidone in step 1 has an average molecular weight of 130 ten thousand. By using the polyvinylpyrrolidone with larger molecular weight, the fiber with more uniform appearance can be obtained through electrostatic spinning.
Further, the sodium dihydrogen phosphate in the step 2 is phosphoric acid dihydrateSodium dihydrogen (NaH)2PO4·2H2O)。
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, a boron source is added into a spinning solution, and high-safety is obtained after spinning, pretreatment, annealing and other treatments
The boron-doped vanadium sodium phosphate electrode material in the shape of nano fiber. The carbon fibers prevent the vanadium sodium phosphate particles from growing excessively, thereby reducing the ion diffusion path. At the same time, the introduction of boron can form BC between the carbon layer and the boron2O and BCO2Two functional groups, of which BC2O is mainly used for promoting sodium ion diffusion by reducing a sodium ion diffusion potential barrier, so that the multiplying power performance of the material is improved; and BCO2The method has higher sodium ion adsorption energy, means that the sodium ion adsorption process is more stable, and can increase the structural stability of the material in the circulating process, thereby improving the long circulating performance of the material.
2. The material prepared by the invention passes through temperature sensing test, the temperature of the material shows regular change in the repeated charging and discharging process, and the change value is small, which shows that the material has high safety characteristic.
3. The preparation method is simple and convenient, is easy to operate and is suitable for large-scale industrial production.
4. The boron-doped carbon-coated vanadium sodium phosphate prepared by the technology has excellent electrochemical performance, and depends on BC generated by successfully introducing boron2O and BCO2Two functional groups. Wherein BC2O is mainly used for promoting the diffusion of sodium ions by reducing the diffusion potential barrier of the sodium ions, so that the multiplying power performance of the material is improved; and BCO2Have higher sodium ion adsorption energy, mean that sodium ion adsorption process is more stable, can increase the structural stability of material in cyclic process to promote the long cycle stability of material. By adjusting the addition of the boric acid, the optimal doping amount of boron can be obtained, and the boron-doped sodium vanadium phosphate with the best electrochemical performance can be prepared. When the addition amount of boric acid is 100 mg, BC2O and BCO2The amount of (B) was 53.76%,38.71% of the total boron-containing functional groups, andwhen the doping amount of boron reaches the optimum value, and BC2O and BCO2The amount of the boron-doped sodium vanadium phosphate reaches an optimal value, and the obtained boron-doped sodium vanadium phosphate has optimal electrochemical performance.
Drawings
FIG. 1 is a scanning electron micrograph of boron-doped sodium vanadium phosphate at various stages of example 1 of the present invention.
The method comprises the following steps of (A) preparing a precursor fiber shape before annealing, and (B) preparing a boron-doped sodium vanadium phosphate material of a final sample after annealing.
FIG. 2 is an X-ray diffraction spectrum of boron-doped sodium vanadium phosphate according to example 1 of the present invention;
FIG. 3 is an X-ray photoelectron spectrum of C1s relating to boron-doped sodium vanadium phosphate in example 1 of the present invention;
FIG. 4 is a theoretical calculation chart relating to boron-doped sodium vanadium phosphate in example 1 of the present invention, (A) an optimized model, (B) an energy state density chart, (C) a differential electron chart, (D) a sodium ion migration path chart, (E) a sodium ion diffusion barrier chart, and (F) an adsorption energy chart;
FIG. 5 is a graph showing the X-ray photoelectron spectrum (A) of B1s of boron-doped sodium vanadium phosphate according to example 1 of the present invention and the contents of three B-containing functional groups (B);
FIG. 6 is a graph of the sodium rate performance of boron doped sodium vanadium phosphate according to example 1 of the present invention;
FIG. 7 is a graph of the sodium electrical long cycle performance of boron doped sodium vanadium phosphate according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments and accompanying drawings.
Example 1
A preparation method of a high-safety sodium storage material based on boron-doped sodium vanadium phosphate comprises the following steps:
step 1: adding 0.325 g of polyvinylpyrrolidone into 1.5 mL of deionized water, and stirring until the solution is uniform to obtain a solution A; adding 2.5 mmol of ammonium metavanadate and 5 mmol of oxalic acid into 1 mL of deionized water, and stirring for 30 min to obtain a solution B;
step 2: adding 100 mg of boric acid into the solution A, adding 3.75 mmol of sodium dihydrogen phosphate into the solution B, and uniformly stirring;
and step 3: mixing the solution A and the solution B, and stirring for 10 min to obtain a solution C;
and 4, step 4: transferring the solution C into an injector, and starting spinning, wherein the spinning voltage is 30kV, the pushing speed is 0.025mm/min, and the distance between a needle head and a receiver is 15 cm;
and 5: and (3) pretreating the spinning, wherein the pretreatment condition is to anneal for 2 hours at 220 ℃ in a muffle furnace, and the heating rate is 2 ℃/min.
Step 6: and annealing the pretreated sample in a tubular furnace, annealing at 350 ℃ for 4h, cooling to room temperature, annealing at 800 ℃ for 6h, wherein the heating rate is 2 ℃/min, and the atmosphere is argon/hydrogen mixed gas, so that the nanofiber-shaped boron-doped vanadium sodium phosphate is obtained.
Example 2
The procedure of example 1 was followed except that the amount of boric acid added in step 2 was changed to 50 mg, and the remaining steps were not changed. The obtained sample is sodium vanadium phosphate with less doping amount, and compared with the material obtained in the example 1, the appearance is not greatly different, but the electrochemical performance is poorer than that of the example 1.
Example 3
The procedure of example 1 was followed except that the amount of boric acid added in step 2 was changed to 200mg, and the remaining steps were not changed. The obtained sample is sodium vanadium phosphate with more doping amount, and compared with the material obtained in the example 1, the appearance is not greatly different, but the electrochemical performance is poorer than that of the example 1.
The carbon-coated vanadium sodium phosphate doped with nano fibrous boron prepared by the technology can simultaneously improve the conductivity and relieve the volume expansion. The carbon nano-fiber formed by spinning has a domain-limiting effect on vanadium sodium phosphate particles, and the particle size of the vanadium sodium phosphate is effectively reduced, so that the ion diffusion path is shortened. While successful doping of boron in the carbon layer results in the formation of BC3, BC2O and BCO2_Three functional groups. By XPS fitting, BC2O and BCO2The content of the two functional groups is greatly changed along with the change of the amount of the B sourceTo convert into, BC3Is substantially constant, so that BC2O and BCO2Has key effect on improving the electrochemical performance of the material. Discovery of BC by theoretical calculation2O and BCO2The two functional groups have different functions in the aspect of improving the electrochemical performance of the sodium-ion battery. Wherein BC2O is mainly used for promoting sodium ion diffusion by reducing a sodium ion diffusion potential barrier, so that the multiplying power performance of the material is improved; and BCO2The method has higher sodium ion adsorption energy, means that the sodium ion adsorption process is more stable, and can increase the structural stability of the material in the circulating process, thereby improving the long circulating performance of the material. It was found through experiments that BC had been added when boric acid was added in an amount of 100 mg2O and BCO2Reaches an optimum value, at which point BC2O and BCO2The proportion of the content of (A) in all the boron-containing functional groups is respectively as follows: 53.76% and 38.71%, the material showed the best electrochemical performance. Meanwhile, through in-situ temperature sensing tests, the material is verified to have stable and regular temperature change in the charging and discharging processes, and the change value is within an acceptable range, so that the material is further proved to have high safety characteristics.
Fig. 1 is a scanning electron microscope image related to each stage of example 1 of the present invention, the morphology of the nanofiber obtained by spinning according to the present invention is substantially unchanged before and after high temperature annealing, and the nanofiber is represented as a uniform nanofiber both before (fig. 1A) and after (fig. 1B) the high temperature annealing. The effect of the high temperature annealing at 800 ℃ is recrystallization, and the sodium vanadium phosphate can be formed only after the high temperature annealing. The pretreatment at 220 ℃ is to increase the toughness of the material and maintain the shape. Annealing at 350 ℃ is a decomposition process of the raw material. 800 ℃ is the process of recrystallization to form sodium vanadium phosphate crystals after the decomposition of the raw materials. The morphology difference before and after annealing is not large. Materials synthesized by the electrostatic spinning method generally need to ensure that the shape of the nano fibers is kept unchanged before and after annealing.
Fig. 2 is a result of X-ray diffraction measurement of boron-doped carbon-coated sodium vanadium phosphate prepared in example 1 of the present invention, from which it can be seen that no hetero-phase is generated.
FIG. 3 is an X-ray photoelectron spectrum of a high-safety nanofiber-like boron-doped carbon-coated sodium vanadium phosphate electrode material C1s according to example 1 of the present invention. The C-B bond in the figure indicates that B was successfully doped in the carbon layer.
Fig. 5 is an X-ray photoelectron spectrum of B1s in the boron-doped carbon-coated sodium vanadium phosphate prepared in example 1. As shown in fig. 5A, the boron atom is bonded to an oxygen atom and a carbon atom, respectively. As shown in fig. 5B, the amounts of the two functional groups BCO2 and BC2O of the boron-doped carbon-coated sodium vanadium phosphate prepared by example 1 of the present invention accounted for 38.71% and 53.76%, respectively, of all the B-containing functional groups. FIG. 4 is a DFT calculation of boron doped carbon coated sodium vanadium phosphate prepared in example 1, the geometric optimization model of two functional groups, BC2O and BCO2, is shown in FIG. 4 (A); as shown in fig. 4 (B) and (C), the conductivity of the material increases after doping B, with significant charge accumulation near the functional groups; fig. 4 (D) and (E) are a diffusion path diagram and a diffusion barrier diagram of sodium ions, which show that sodium ions have a lower diffusion barrier and sodium ions diffuse more easily under the BC2O model; fig. 4 (F) is an adsorption energy diagram, which shows that BCO2 has high ion adsorption energy and can improve the structural stability of the material.
Fig. 6 is a sodium ion battery rate performance of a high safety nanofiber-like boron-doped carbon-coated sodium vanadium phosphate electrode material of example 1 of the present invention, which exhibits high reversible capacity: the specific capacity at the current density of 1, 2, 5, 10, 20 and 30C is up to 113.7, 111.7, 108.9, 105.6, 100.0 and 94.2 mAh g-1And when the current density returns to 1C, the specific capacity and the initial capacity are comparable.
FIG. 7 shows the sodium electrical long cycle performance of sodium vanadium phosphate prepared in example 1, with a specific capacity of 101.3 mAh g at a rate of 10C-1After 1500 cycles, the capacity can still reach 91.4 mAh g-1The average capacity loss per revolution is only 0.08% indicating good cycle performance.
Where mentioned above are merely embodiments of the invention, any feature disclosed in this specification may, unless stated otherwise, be replaced by alternative features serving equivalent or similar purposes; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.

Claims (8)

1. A preparation method of a high-safety sodium storage material based on boron-doped sodium vanadium phosphate is characterized by comprising the following steps:
step 1: adding polyvinylpyrrolidone into deionized water, and uniformly stirring to obtain a solution A; adding ammonium metavanadate and oxalic acid into deionized water, and uniformly stirring to obtain a solution B;
step 2: adding 50-200mg of boric acid into the solution A, adding sodium dihydrogen phosphate into the solution B, and uniformly stirring;
and 3, step 3: mixing the solution A and the solution B, and uniformly stirring to obtain a solution C;
and 4, step 4: transferring the solution C into an injector, starting electrostatic spinning,
and 5: annealing pretreatment is carried out on the spinning;
step 6: and annealing the pretreated sample in a tubular furnace in an argon/hydrogen mixed gas atmosphere to obtain the nano fibrous boron-doped sodium vanadium phosphate.
2. The method for preparing the high-safety sodium storage material based on the boron-doped sodium vanadium phosphate is characterized in that the concentration of polyvinylpyrrolidone is 217g/L, the concentration of ammonium metavanadate is 2.5mol/L, and the concentration of oxalic acid is 5mol/L.
3. The method for preparing the high-safety sodium storage material based on the boron-doped sodium vanadium phosphate is characterized in that the electrostatic spinning voltage is 30kV, the pushing speed is 0.025mm/min, and the distance between a needle and a receiver is 15cm.
4. The method for preparing the high-safety sodium storage material based on the boron-doped sodium vanadium phosphate is characterized in that the concentration of boric acid is 22.5-90g/L, and the concentration of sodium dihydrogen phosphate is 3.75mol/L.
5. The method for preparing the high-safety sodium storage material based on the boron-doped sodium vanadium phosphate as claimed in claim 1, wherein the polyvinylpyrrolidone in the step 1 has an average molecular weight of 130 ten thousand.
6. The method for preparing the high-safety sodium storage material based on the boron-doped sodium vanadium phosphate, according to claim 1, wherein the sodium dihydrogen phosphate is sodium dihydrogen phosphate dihydrate.
7. The preparation method of the high-safety sodium storage material based on boron-doped sodium vanadium phosphate according to claim 1, wherein the step 5 specifically comprises: spinning is pretreated, wherein the pretreatment condition is annealing for 2h at 220 ℃ in air.
8. The preparation method of the high-safety sodium storage material based on boron-doped sodium vanadium phosphate according to claim 1, wherein the step 6 specifically comprises: and annealing the pretreated sample in a tubular furnace at 350 ℃ for 4h, cooling to room temperature, and annealing at 800 ℃ for 6h in an argon/hydrogen mixed gas atmosphere to obtain the nano fibrous boron-doped sodium vanadium phosphate.
CN202210874579.9A 2022-07-21 2022-07-21 Preparation method of high-safety sodium storage material based on boron-doped sodium vanadium phosphate Pending CN115275140A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332136A (en) * 2022-11-16 2023-06-27 电子科技大学 Preparation method of sulfur-doped iron selenide-based high-volume specific capacity sodium storage material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116332136A (en) * 2022-11-16 2023-06-27 电子科技大学 Preparation method of sulfur-doped iron selenide-based high-volume specific capacity sodium storage material

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