CN111009661A - Flexible self-supporting Na3(VO)2(PO4)2F material and preparation method and application thereof - Google Patents
Flexible self-supporting Na3(VO)2(PO4)2F material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 239000004744 fabric Substances 0.000 claims abstract description 38
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 7
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- 239000000203 mixture Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000007774 positive electrode material Substances 0.000 abstract description 2
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- 229910052708 sodium Inorganic materials 0.000 description 5
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910017677 NH4H2 Inorganic materials 0.000 description 3
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- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
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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
- H01M4/58—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
- H01M4/582—Halogenides
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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Abstract
The invention discloses a flexible self-supporting Na3(VO)2(PO4)2F material, a preparation method and application thereof, belonging to the technical field of electrode materials. The preparation method comprises the following steps: (1) according to the formula Na3(VO)2(PO4)2Weighing NH according to the stoichiometric ratio of F4H2PO4、VOC2O4·5H2O、Na2CO3Dissolving NaF in the graphene solution, and adjusting the pH value to be less than or equal to 7 after stirring; (2) putting the carbon cloth after acid treatment into the solution obtained in the step (1), heating to 180-200 ℃ for reaction, and cleaning to obtain the flexible self-supporting Na3(VO)2(PO4)2And F, materials. N prepared by the method of the inventiona3(VO)2(PO4)2The F material directly grows on the carbon cloth, has the characteristics of controllable material appearance and self-support, and can be used as a positive electrode material of a battery.
Description
Technical Field
The invention belongs to electricityThe technical field of pole materials, in particular to flexible self-supporting Na3(VO)2(PO4)2F material, and a preparation method and application thereof.
Background
With the development of technology, people are continuously pursuing portable electronic devices with portability, entertainment and health, and the corresponding energy storage devices are promoted to develop towards high specific energy, light weight, softness, cleanness, safety and the like. The traditional lithium/sodium ion battery has the defects of being thick and heavy, not easy to bend, low in specific energy and the like, and is not suitable for serving as a power source of a future flexible electronic device. Therefore, it is urgent to develop a novel electrode material and an energy storage device having high specific energy, light weight and flexibility.
The sodium vanadyl fluorophosphate material has the advantages of rich resources, high theoretical capacity, high discharge potential and the like, and is a potential positive electrode material of a lithium/sodium battery. At present, the preparation methods of the flexible anode materials mainly comprise the following four types: 1. growth through template (Hui Xia, Yunhai Wan, Wilfried Assenmacher, et al, factor synthesis of chain-like LiCoO)2nanowire arrays as three-dimensional cathode for microbatteries[J]NPG Asia Materials (2014)6, e 126.); 2. direct growth of simple compounds (e.g. VO)2、V2O5)(Dongliang Chao,Xinhui Xia,Jilei Liu,et al.A V2O5/Conductive-Polymer Core/Shell Nanobelt Array on Three-Dimensional Graphite Foam:A High-Rate,Ultrastable,and Freestanding Cathode for Lithium-Ion Batteries[J]Adv.mater.2014.); 3. pouring the sol on carbon cloth, re-sintering, re-pouring and re-sintering, repeating the above steps (DongleiGuo, Jinwen Qin, Zhigangyin, et al. Achieveing high mass loading of Na3V2(PO4)3@ carbon on carbon cloth by confining the same, and then-two network ceramic fibers for the same, and then-both the cycle-life and the overall high carbon-ions]Nano Energy,2018(45), 136-); 4. first growing simple compounds, such as VO, on carbon cloth2Then grow VO2On a carbon cloth of a multi-element compound, such as Na3(VO)2(PO4)2F(Dongliang Chao,Chun-Han(Matt)Lai,Pei Liang.Sodium Vanadium Fluorophosphates(NVOPF) Array cathodeDesigned for High-Rate Full glue Storage device. adv. energy Mater.2018, 1800058.); 5. growing on an expensive substrate; such as graphene, carbon nanoplatelets and carbon nanotubes (Weihua Zhu, Ruizhi Li, Pan xu. Vanadium trioxide @ carbon nanoshell array-based ultrahigh molecular hydrophilic surfactants with 2V voltage and high volume carbon energy density [ J].Journal of Materials Chemistry A,2017.DebinKong,Xianglong Li,Yunbo Zhang.Encapsulating V2O5into carbon nanotubes enablesthe synthesis of flexible high-performance lithium ion batteries[J].Energy&Environmental Science,2016.)。
Preparation of Na3(VO)2(PO4)2The method of F material can not directly grow Na on the carbon cloth at one time3(VO)2(PO4)2F, long process and high cost.
Disclosure of Invention
The invention aims to provide flexible self-supporting Na3(VO)2(PO4)2F material, and a preparation method and application thereof.
The invention firstly provides a flexible self-supporting Na3(VO)2(PO4)2The preparation method of the F material comprises the following steps:
(1) according to the formula Na3(VO)2(PO4)2Weighing NH according to the stoichiometric ratio of F4H2PO4、VOC2O4·5H2O、Na2CO3Dissolving NaF in the graphene solution, uniformly stirring, and adjusting the pH value to be less than or equal to 7;
(2) putting the carbon cloth after acid treatment into the solution obtained in the step (1), heating to 180-200 ℃ for reaction, and cleaning to obtain the flexible self-supporting Na3(VO)2(PO4)2And F, materials.
Wherein the flexible self-supporting Na3(VO)2(PO4)2The preparation method of the F material comprises the step (1), wherein the concentration of graphene in the graphene solution is 1-2mg/mL。
Wherein the flexible self-supporting Na3(VO)2(PO4)2The preparation method of the F material comprises the step (1), wherein the pH value is 5-7.
Wherein the flexible self-supporting Na3(VO)2(PO4)2And (3) the preparation method of the F material, wherein in the step (2), the acid treatment is to put the carbon cloth into strong acid, then to heat up to 70-100 ℃, and to keep the temperature for 1-24 hours.
Wherein the flexible self-supporting Na3(VO)2(PO4)2The preparation method of the F material comprises the step (2), wherein the acid is concentrated nitric acid, aqua regia or a mixture of the concentrated nitric acid and the aqua regia in a volume ratio of 1:1 concentrated sulfuric acid and concentrated hydrochloric acid.
Wherein the flexible self-supporting Na3(VO)2(PO4)2The preparation method of the F material comprises the step (2), wherein the acid treatment is to put the carbon cloth into concentrated nitric acid or aqua regia, heat the carbon cloth to 70 ℃, and keep the temperature for 12-24 hours; or putting the carbon cloth into a reactor with the volume ratio of 1:1, boiling the mixed acid consisting of concentrated sulfuric acid and hydrochloric acid, and then preserving the heat for 1-4 hours.
Wherein the flexible self-supporting Na3(VO)2(PO4)2In the preparation method of the F material, in the step (2), the reaction time is 12-24 hours.
The invention also provides the flexible self-supporting Na3(VO)2(PO4)2Flexible self-supporting Na prepared by preparation method of F material3(VO)2(PO4)2And F, materials.
The invention also provides the flexible self-supporting Na3(VO)2(PO4)2Use of the F material in the preparation of an electrode material.
Further, the electrode material is a lithium ion battery anode material or a sodium ion battery anode material.
The invention has the beneficial effects that:
the flexible self-supporting Na prepared by the invention3(VO)2(PO4)2The F material directly grows on the carbon cloth, the process flow is simple, and the shape of the material is controllable; meanwhile, when the material is used as an electrode material, a conductive agent and a bonding agent are not required to be added, and the material has the characteristics of self-support and flexibility and does not need a current collector.
Drawings
FIG. 1 shows Na prepared in example 13(VO)2(PO4)2XRD analysis pattern and Rictvcld refinement of F type refractory corrosion resistant material;
FIG. 2 shows Na in example 13(VO)2(PO4)2SEM picture of F;
FIG. 3 shows Na in example 13(VO)2(PO4)2SEM images of F grown on carbon cloth;
FIG. 4 shows Na in example 23(VO)2(PO4)2SEM picture of F;
FIG. 5 shows Na in example 23(VO)2(PO4)2SEM images of F grown on carbon cloth;
FIG. 6 shows Na in example 23(VO)2(PO4)2F is taken as an electrochemical performance characterization chart of the sodium battery electrode; wherein, (a) is a charge-discharge curve with different multiplying power; (b) is a rate performance curve; (c) long cycle performance curves; (d) is a Raegong curve;
FIG. 7 shows Na in example 23(VO)2(PO4)2F is taken as an electrochemical performance characterization diagram of the lithium battery electrode; wherein, (a) is a constant current charge-discharge curve; (b) is a cyclic voltammetry curve; (c) is a rate performance curve; (d) charge-discharge curves of different multiplying powers; 1st, 2nd and 3rd in 7(a) represent the number of charge and discharge; 1st, 2nd, 3rd in 7(b) represent the number of cycles;
FIG. 8 shows Na in example 33(VO)2(PO4)2SEM images of F grown on carbon cloth.
Detailed Description
Flexible self-supporting Na3(VO)2(PO4)2Method for preparing F material, bagThe method comprises the following steps:
(1) according to the formula Na3(VO)2(PO4)2Weighing NH according to the stoichiometric ratio of F4H2PO4、VOC2O4·5H2O、Na2CO3Dissolving NaF in the graphene solution, uniformly stirring, and adjusting the pH value to be less than or equal to 7;
(2) putting the carbon cloth after acid treatment into the solution obtained in the step (1), heating to 180-200 ℃ for reaction, and cleaning to obtain the flexible self-supporting Na3(VO)2(PO4)2And F, materials.
In the method of the present invention, if the temperature of the hydrothermal reaction is less than 180 ℃, Na cannot be synthesized3(VO)2(PO4)2F; if the temperature is higher than 200 ℃, the particles grow abnormally, and the loss of the reaction kettle caused by high temperature is large.
In the method, the graphene is used as a conductive agent and a dispersing agent, but the added graphene can be added with Na3(VO)2(PO4)2F, in mass, the active material Na is reduced3(VO)2(PO4)2Gram volume of F. Therefore, the inventors of the present invention set the concentration of graphene in the graphene solution to 1-2 mg/mL.
In the method, the pH of the solution influences the morphology of the material, if the pH exceeds 5-7, the morphology of the material is not good, and the particles grow abnormally, which seriously influences the electrochemical performance of the material, because the larger the particles are, the longer the diffusion path is, and the less the discharge capacity is.
The carbon cloth is hydrophobic, if the untreated carbon cloth is directly placed in the solution obtained in the step (1) for hydrothermal reaction, the material of the invention cannot be obtained, the surface of the carbon cloth is treated into a hydrophilic surface by adopting strong acid, so that Na is facilitated3(VO)2(PO4)2And F growing.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The raw materials and instruments used in the embodiments of the present invention are commercially available.
Example 1
(1) Taking 0.02mol of NH4H2PO4、0.02mol VOC2O4·5H2O and 0.01mol of Na2CO3And 0.01mol of NaF are respectively dissolved in 28ml of graphene solution (1mg/ml), the mixture is magnetically stirred for 10 minutes, the pH value is adjusted to 5, the mixture is continuously stirred for 20 minutes, and the mixture is transferred into a hydrothermal kettle.
(2) Washing commercial carbon cloth with distilled water and alcohol in sequence, putting the washed commercial carbon cloth into a hydrothermal kettle filled with 1/3 volume content concentrated nitric acid, heating to 70 ℃, and preserving heat for 24 hours.
(3) Placing the carbon cloth with the diameter of 18mm after the concentrated nitric acid treatment in the step (2) into the hydrothermal kettle in the step (1), then moving the hydrothermal kettle into a constant temperature furnace, heating to 180 ℃, preserving heat for 24 hours, taking out the carbon cloth, and cleaning for 2-3 times by using distilled water to obtain the flexible Na3(VO)2(PO4)2F. The material is characterized in FIGS. 1-3, and Na can be seen from FIG. 13(VO)2(PO4)2The F material being single Na3(VO)2(PO4)2And F phase.
Example 2
(1) Taking 0.02mol of NH4H2PO4、0.02mol VOC2O4·5H2O and 0.01mol of Na2CO3And 0.01mol of NaF are respectively dissolved in 28ml of graphene solution (1mg/ml), the mixture is magnetically stirred for 10 minutes, the pH value is adjusted to 7, the mixture is continuously stirred for 20 minutes, and the mixture is transferred into a hydrothermal kettle.
(2) Washing commercial carbon cloth with distilled water and alcohol in sequence, putting the washed cloth into a hydrothermal kettle filled with 1/3 volume content of aqua regia, heating to 70 ℃, and preserving heat for 12 hours.
(3) Putting the carbon cloth with the diameter of 18mm after the aqua regia treatment in the step (2) into the hydrothermal kettle in the step (1), then moving the hydrothermal kettle into a constant temperature furnace, heating to 180 ℃, preserving heat for 24 hours, taking out the carbon cloth, and cleaning with distilled water for 2-3 times to obtain the flexible Na3(VO)2(PO4)2F. The morphology of the material is shown in FIGS. 4-5, and the material is used as the electrodeThe chemical property profiles are shown in FIGS. 6-7.
Example 3
(1) Taking 0.02mol of NH4H2PO4、0.02mol VOC2O4·5H2O and 0.01mol of Na2CO3And 0.01mol of NaF are respectively dissolved in 28ml of graphene solution (1mg/ml), the mixture is magnetically stirred for 10 minutes, the pH value is adjusted to 5, the mixture is continuously stirred for 20 minutes, and the mixture is transferred into a hydrothermal kettle.
(2) After washing commercial carbon cloth with distilled water and alcohol in sequence, putting the carbon cloth into mixed acid of concentrated sulfuric acid and concentrated hydrochloric acid with the volume ratio of 1:1 for boiling, and preserving heat for 3 hours.
(3) Putting the carbon cloth with the diameter of 18mm treated by the concentrated sulfuric acid and the hydrochloric acid in the ratio of 1:1 in the step (2) into the hydrothermal kettle in the step (1), then moving the hydrothermal kettle into a constant temperature furnace, heating to 180 ℃, preserving heat for 24 hours, taking out the carbon cloth, and cleaning the carbon cloth with distilled water for 2-3 times to obtain the flexible Na3(VO)2(PO4)2F. The topography of the material is shown in FIG. 8.
Claims (10)
1. Flexible self-supporting Na3(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps:
(1) according to the formula Na3(VO)2(PO4)2Weighing NH according to the stoichiometric ratio of F4H2PO4、VOC2O4·5H2O、Na2CO3Dissolving NaF in the graphene solution, and adjusting the pH value to be less than or equal to 7 after stirring;
(2) putting the carbon cloth after acid treatment into the solution obtained in the step (1), heating to 180-200 ℃ for reaction, and cleaning to obtain the flexible self-supporting Na3(VO)2(PO4)2And F, materials.
2. Flexible self-supporting Na according to claim 13(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps: in the step (1), the concentration of graphene in the graphene solution is 1-2 mg/mL.
3. Flexible self-supporting Na according to claim 13(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps: in the step (1), the pH value is 5-7.
4. Flexible self-supporting Na according to claim 13(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps: in the step (2), the acid treatment is to put the carbon cloth into strong acid, then to heat up to 70-100 ℃, and to keep the temperature for 1-24 hours.
5. Flexible self-supporting Na according to claim 43(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps: in the step (2), the acid is concentrated nitric acid, aqua regia or a mixture of the following materials in a volume ratio of 1:1 concentrated sulfuric acid and concentrated hydrochloric acid.
6. Flexible self-supporting Na according to claim 53(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps: in the step (2), the acid treatment is to put the carbon cloth into concentrated nitric acid or aqua regia, heat the carbon cloth to 70 ℃, and preserve heat for 12-24 hours; or putting the carbon cloth into a reactor with the volume ratio of 1:1, boiling the mixed acid consisting of concentrated sulfuric acid and hydrochloric acid, and then preserving the heat for 1-4 hours.
7. Flexible self-supporting Na according to claim 13(VO)2(PO4)2The preparation method of the F material is characterized by comprising the following steps: in the step (2), the reaction time is 12-24 hours.
8. Flexible self-supporting Na according to any one of claims 1 to 73(VO)2(PO4)2Flexible self-supporting Na prepared by preparation method of F material3(VO)2(PO4)2And F, materials.
9. Flexible self-supporting Na according to claim 83(VO)2(PO4)2Use of the F material in the preparation of an electrode material.
10. Use according to claim 9, characterized in that: the electrode material is a lithium ion battery anode material or a sodium ion battery anode material.
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