CN111769272A - Bi @ C hollow nanosphere composite material and preparation method and application thereof - Google Patents
Bi @ C hollow nanosphere composite material and preparation method and application thereof Download PDFInfo
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- CN111769272A CN111769272A CN202010734209.6A CN202010734209A CN111769272A CN 111769272 A CN111769272 A CN 111769272A CN 202010734209 A CN202010734209 A CN 202010734209A CN 111769272 A CN111769272 A CN 111769272A
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000002077 nanosphere Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910017953 NH4Bi3F10 Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 20
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- FIMTUWGINXDGCK-UHFFFAOYSA-H dibismuth;oxalate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FIMTUWGINXDGCK-UHFFFAOYSA-H 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 230000002441 reversible effect Effects 0.000 description 7
- 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 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- -1 bismuth metals Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/027—Negative electrodes
-
- 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 a Bi @ C hollow nanosphere composite material and a preparation method and application thereof. The method comprises the following steps: NH evenly mixed in glycol after centrifugal dissolution treatment4F and BiCl3Immediately reacted with each other, and NH is prepared in advance in large amounts by a conventional liquid reaction process4Bi3F10Nano meterBall of NH4Bi3F10Adding the mixture into an environmental solvent, adding a carbon source after ultrasonic dispersion, stirring for reaction, centrifuging and drying to obtain NH4Bi3F10And (2) combining the @ PDA with a precursor, carrying out thermal reduction treatment on the precursor in an inert atmosphere, and naturally cooling to obtain the Bi @ C composite material for the lithium ion/sodium ion battery. The preparation method has the advantages of simple process, wide raw material source and low cost, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a lithium/sodium ion battery cathode material technology, in particular to a Bi @ C hollow nanosphere composite material and a preparation method and application thereof.
Background
Lithium ion batteries have enjoyed great commercial success and widespread use due to their advantages of high energy density, long cycle life and no pollution. At present, the negative electrode materials of commercial lithium ion batteries mainly comprise graphite, lithium titanate, hard carbon and the like, and although the materials have very good cycle performance, the lower theoretical specific capacity of the materials cannot meet the requirements of people on the lithium ion batteries with high energy density. Therefore, it is important to find new high capacity anode materials. On the other hand, with the large-scale application of lithium ion batteries, the shortage of lithium resources and the high cost of lithium ion batteries limit the application of lithium ion batteries to some extent. Sodium and lithium are in the same main group, and sodium resources are abundant, so that the sodium-ion battery is considered as a next-generation secondary energy storage battery with relatively high potential.
In recent years, research on sodium ion batteries has attracted much attention and has been intensively studied. The negative electrode material is one of the key technologies of the sodium ion battery, and plays an important role in the performance of the sodium ion battery. However, since the radius of sodium ions is larger than that of lithium ions, the insertion and extraction of sodium ions in a graphite negative electrode is more difficult than that of lithium ions, and the graphite negative electrode has lower sodium storage capacity and cycle stability, so that the commercial graphite negative electrode material is difficult to meet the practical application of a sodium ion battery, and the development of a high-performance sodium ion battery negative electrode material becomes the key of the development of the sodium ion battery.
Metallic bismuth (Bi) in view of its high volumeSpecific volumetric capacity (3800 mAh cm-3) And highly reversible redox behavior, have received much attention. However, a Bi negative electrode in a large-volume or nano-scale form inevitably suffers from severe structural pulverization and aggregation during repeated charge/discharge processes, resulting in poor cycling stability and rate capability of the electrode, and, at the same time, active sites are cracked, more surfaces are easily attacked by an electrolyte, resulting in continuous formation and decomposition of an SEI film, and finally forming a thick film to prevent Li in the active material+/Na+Diffusion, reducing the capacity of the battery, and worse still, this short cycle problem is difficult to alleviate by conventional mechanical protection/enhancement strategies, e.g., by biomass carbonized carbon (C) coatings, because their melting point is as low as-271.3 ℃, which means that bulky bismuth metals cannot be directly engineered by thermal methods, let alone reduced size bismuth nanoparticles, and therefore the development of bismuth-based composite anode materials with high specific capacity, high cycling stability and excellent rate capability is a very important issue, important for accelerating the commercial application of high energy density lithium ion batteries, and important for developing bismuth-based anode materials with high specific capacity, good cycling stability and long cycle life.
Disclosure of Invention
The invention aims to provide a Bi @ C hollow nanosphere composite material and a preparation method and application thereof aiming at the defects of the prior art. The method has the advantages of short liquid reaction flow, simple process, cheap and easily-obtained raw materials, high yield, uniform product structure and appearance and easy control, and meets the requirement of large-scale industrial application.
The technical scheme for realizing the purpose of the invention is as follows:
a preparation method of a Bi @ C hollow nanosphere composite material comprises the following steps:
1) weighing bismuth source and NH4F are respectively dissolved in the same volume of ethylene glycol, wherein, bismuthSource and ammonium fluoride as NH4Bi3F10The molar ratio of Bi to F elements in the chemical formula of the material is 3: 10 weighing, and marking as A and B solutions;
2) simultaneously transferring the A and B homogeneous solutions obtained in the step 1) into the same beaker, uniformly mixing by magnetic stirring, aging at 25 ℃ for 8-15 hours, filtering, washing and drying to obtain white powder, namely NH4Bi3F10A precursor;
3) weighing a carbon source and adding the carbon source into NH obtained in the step 2)4Bi3F10In the solution, the amount of the carbon source is 5-20% of the mass of the metal bismuth, a magnetic stirrer is used for continuously stirring for 4-8 hours, and black powder is obtained after filtering, washing and drying;
4) placing the intermediate black powder obtained in the step 3) in a ceramic ark, sealing the tube furnace, introducing inert protective gas, and reacting at 400 DEGoC-600oAnd C, heating for 0.5-1 hour, and naturally cooling to room temperature to obtain the carbon-coated bismuth Bi @ C hollow nanosphere composite material, wherein the diameter of the Bi @ C hollow nanosphere composite material is 50-100 nm, and the size distribution of the Bi @ C hollow nanosphere composite material is uniform.
The bismuth source in the step 1) is one or a mixture of bismuth nitrate, bismuth sulfate and bismuth oxalate.
The bismuth source in the step 1) is one or more of bismuth nitrate, bismuth sulfate and bismuth oxalate.
The carbon source in the step 3) is one or more of dopamine, resorcinol polyacrylonitrile, glucose and citric acid.
The inert atmosphere in the step 4) is one of pure nitrogen or pure argon.
The carbon-coated bismuth Bi @ C hollow nanosphere composite material prepared by the preparation method.
The carbon-coated bismuth Bi @ C hollow nanosphere composite material prepared by the preparation method is applied to a lithium ion/sodium ion battery.
The technical proposal adopts NH4Bi3F10As a precursor, bismuth nano-metal is put into a protective carbonaceous sheath layer by carbothermic reductionIn the matrix, on one hand, the unique open Bi @ C nanostructure can ensure effective electrode and electrolyte contact, and can provide an expanded active reaction site and a shorter ion diffusion path; on the other hand, the external C sheath is mechanically firm to reduce the structural collapse of Bi, the metal C-shaped negative electrode is integrally conductive, the high-rate charge/discharge requirement in practical application is well supported, and excellent rate performance is provided.
Compared with the prior art, the technical scheme has the following beneficial technical effects:
1. the prepared Bi @ C hollow nanosphere composite material is a lithium/sodium ion battery cathode material, and has the advantages of high purity, strong crystallinity and uniform appearance, and the size of the prepared Bi @ C hollow nanosphere composite material reaches dozens to hundreds of nanometers;
2. the Bi @ C hollow nanosphere composite material obtained by the technical scheme is made into a lithium/sodium ion battery electrode, and has high specific capacity and long cycle life;
3. the one-step method used in the technical scheme has the advantages of short liquid reaction flow, simple process, cheap and easily-obtained raw materials, high yield, uniform product structure and appearance, easy control and accordance with the requirements of large-scale industrial application.
The method has the advantages of short liquid reaction flow, simple process, cheap and easily-obtained raw materials, high yield, uniform product structure and appearance and easy control, and meets the requirement of large-scale industrial application.
Drawings
Fig. 1 is a SEM pictorial illustration of the Bi @ C hollow nanosphere composite obtained in the example;
fig. 2 is a schematic XRD diagram of the Bi @ C hollow nanosphere composite obtained in the example;
FIG. 3 is a schematic diagram of the first charge-discharge curve of the Bi @ C hollow nanosphere composite material obtained in the example;
FIG. 4 is a schematic diagram of a cycle performance curve of the Bi @ C hollow nanosphere composite material obtained in the example as a lithium ion battery;
FIG. 5 is a graph showing the cycle performance of the Bi @ C hollow nanosphere composite obtained in the example as a sodium ion battery;
FIG. 6 is a schematic diagram of a rate performance curve of the Bi @ C hollow nanosphere composite material obtained in the example as a lithium ion battery;
FIG. 7 is a graph showing the rate performance curve of the Bi @ C hollow nanosphere composite material obtained in the example as a sodium ion battery.
Detailed Description
The invention will be further elucidated with reference to the drawings and examples, without however being limited thereto.
Example (b):
example 1:
a preparation method of a Bi @ C hollow nanosphere composite material comprises the following steps:
1) 0.2g of bismuth nitrate and 0.6g of NH were weighed4F is respectively dissolved in 25ml of ethylene glycol and marked as A and B solutions;
2) simultaneously transferring the A and B homogeneous solutions obtained in the step 1) into the same 150ml beaker, uniformly mixing by magnetic stirring, aging at 25 ℃ for 12 h, filtering, washing and drying to obtain white powder, namely NH4Bi3F10A precursor;
3) weighing 0.4g of NH obtained in step 2)4Bi3F10Adding the precursor into 10mM Tris buffer solution to uniformly disperse the precursor;
4) weighing 0.1g of dopamine, adding the dopamine into the solution obtained in the step 3), continuously stirring for 6 hours by using a magnetic stirrer, and filtering, washing and drying to obtain black powder;
5) placing the intermediate obtained in the step 4) in a ceramic square boat, sealing the tube furnace, introducing argon, and sealing at 400 DEGoAnd C, heating for 0.5 hour, and naturally cooling to room temperature to obtain the Bi @ C hollow nanosphere composite material.
SEM analysis was performed on the composite material obtained in example 1, the SEM spectrum of the Bi/C composite material obtained in this example is shown in fig. 1, it can be seen from fig. 1 that each Bi @ C nano unit of the Bi/C composite material is a mesoporous, open nanosphere structure, the XRD spectrum of fig. 2 verifies the successful preparation of the Bi @ C composite material, the preparation of the hollow spherical Bi @ C composite material lithium/sodium ion battery negative electrode and the electrochemical performance analysis: according to the following steps: 1.5: 1.5 mixing the Bi @ C composite material prepared in the example 1, conductive carbon black super P, a binder CMC and deionized water in a mass ratio, stirring, coating the slurry on a current collector copper foil, drying at 60 ℃ to prepare a negative plate, taking a metal lithium/sodium plate as a positive electrode, taking polypropylene as a diaphragm and taking LiPF6The electrolyte is used, the CR2025/CR2032 type button experiment battery is obtained by assembling in a glove box filled with argon, when the battery is used as a negative electrode material of a lithium/sodium ion battery, the initial discharge specific capacity of the obtained Bi @ C hollow nanosphere composite material is 1028.9/848.4 mAh/g, the charge specific capacity is 766.4/525.1 mAh/g, the initial charge-discharge curve of the battery is shown in figure 3, and the initial charge-discharge curve is 25oUnder C, after the current is circulated for 100 circles at a current density of 1000 mA/g, the reversible specific capacity is 440.2/250.1 mAh/g, as shown in figures 4 and 5, the reversible capacity of 101.9/74.1 mAh/g can be still stored under a large current density of 5A/g, as shown in figures 6 and 7, the capacity retention rate is high, the stability is good, and the excellent electrochemical performance is shown.
Example 2:
a preparation method of a Bi @ C hollow nanosphere composite material comprises the following steps:
1) 0.2g of bismuth nitrate and 0.6g of NH were weighed4F is respectively dissolved in 25ml of ethylene glycol and marked as A and B solutions;
2) simultaneously transferring the A and B homogeneous solutions obtained in the step 1) into the same 150ml beaker, uniformly mixing by magnetic stirring, aging at 25 ℃ for 12 h, filtering, washing and drying to obtain white powder, namely NH4Bi3F10A precursor;
3) 0.1g of NH obtained in step 2) was taken4Bi3F10Dissolving the precursor in 140ml ethanol, performing ultrasonic stirring at 60 ℃ for 30min, adding 0.159g of resorcinol, stirring for 24h, washing with deionized water for 3 times, and vacuum-drying the washed product at 60 ℃ for 8 hours;
4) placing the black solid product obtained in the step 3) in a ceramic square boat, sealing the tube furnace, introducing argon, and performing reaction at 600 DEG CoAnd C, heating for 1 hour, and naturally cooling to room temperature to obtain the spherical Bi @ C composite material.
SEM analysis was performed on the composite material obtained in example 1, the SEM spectrum of the Bi/C composite material obtained in this example is shown in fig. 1, it can be seen from fig. 1 that each Bi @ C nano unit of the Bi/C composite material is a mesoporous, open nanosphere structure, the XRD spectrum of fig. 2 verifies the successful preparation of the Bi @ C composite material, the preparation of the hollow spherical Bi @ C composite material lithium/sodium ion battery negative electrode and the electrochemical performance analysis: according to the following steps: 1.5: 1.5 mixing the Bi @ C composite material prepared in the example 1, conductive carbon black super P, a binder CMC and deionized water in a mass ratio, stirring, coating the slurry on a current collector copper foil, drying at 60 ℃ to prepare a negative plate, taking a metal lithium/sodium plate as a positive electrode, taking polypropylene as a diaphragm and taking LiPF6The electrolyte is used, the CR2025/CR2032 type button experiment battery is obtained by assembling in a glove box filled with argon, when the battery is used as a negative electrode material of a lithium/sodium ion battery, the initial discharge specific capacity of the obtained Bi @ C hollow nanosphere composite material is 1028.9/848.4 mAh/g, the charge specific capacity is 766.4/525.1 mAh/g, the initial charge-discharge curve of the battery is shown in figure 3, and the initial charge-discharge curve is 25oC, after circulating for 100 circles at a current density of 1000 mA/g, the reversible specific capacity is 440.2/250.1 mAh/g, as shown in figures 4 and 5, the reversible capacity of 101.9/74.1 mAh/g can be still stored at a large current density of 5A/g, as shown in figures 6 and 7, the capacity is maintainedHigh holding rate and good stability, and shows excellent electrochemical performance.
Example 3:
a preparation method of a Bi @ C hollow nanosphere composite material comprises the following steps:
1) 0.1g of bismuth oxalate and 0.3g of NH were weighed out4F is respectively dissolved in 25ml of ethylene glycol and marked as A and B solutions;
2) simultaneously transferring the A and B homogeneous solutions obtained in the step 1) into the same 150ml beaker, uniformly mixing by magnetic stirring, aging at 25 ℃ for 12 h, filtering, washing and drying to obtain white powder, namely NH4Bi3F10A precursor;
3) weighing 0.1g of NH obtained in step 2)4Bi3F10Adding the precursor into a Tris buffer solution (10 mM) to uniformly disperse the precursor;
4) weighing 0.03g of dopamine, adding the dopamine into the solution obtained in the step (3), continuously stirring for 6 hours by using a magnetic stirrer, filtering, washing and drying to obtain black powder;
5) placing the intermediate obtained in the step 4) in a ceramic square boat, sealing the tube furnace, introducing argon, and performing reaction at 600 DEG CoAnd C, heating for 1 hour, and naturally cooling to room temperature to obtain the spherical Bi @ C composite material.
SEM analysis is carried out on the composite material obtained in the example 3, the SEM spectrogram of the Bi/C composite material prepared in the example is shown in figure 1, each Bi @ C nano unit of the Bi/C composite material is a mesoporous and open nanosphere structure as can be seen from figure 1, and the XRD spectrogram of figure 2 verifies the successful preparation of the Bi @ C composite material. Preparing a hollow spherical Bi @ C composite material lithium/sodium ion battery cathode and analyzing electrochemical properties: according to the following steps: 1.5: 1.5 mixing the Bi @ C composite material prepared in the example 1, conductive carbon black super P, a binder CMC and deionized water in a mass ratio, stirring, coating the slurry on a current collector copper foil, drying at 60 ℃ to prepare a negative plate, taking a metal lithium/sodium plate as a positive electrode, taking polypropylene as a diaphragm and taking LiPF6Assembling the electrolyte in a glove box filled with argon to obtain a CR2025/CR2032 type button experiment battery. When the Bi @ C hollow nanosphere composite material is used as a lithium/sodium ion battery cathode material, the initial discharge specific capacity of the obtained Bi @ C hollow nanosphere composite material is 1028.9/848.4 mAh/g, the charge specific capacity is 766.4/525.1 mAh/g, the initial charge-discharge curve of the battery is shown in figure 3, and the initial charge-discharge curve is 25oUnder C, after circulating for 100 circles at a current density of 1000 mA/g, the reversible specific capacity is 440.2/250.1 mAh/g, as shown in figures 4 and 5, the reversible capacity of 101.9/74.1 mAh/g can be still stored at a large current density of 5A/g, as shown in figures 6 and 7, the capacity retention rate is high, the stability is good, and the excellent electrochemical performance is shown.
Claims (7)
1. A preparation method of a Bi @ C hollow nanosphere composite material is characterized by comprising the following steps:
1) weighing bismuth source and NH4F are respectively dissolved in the same volume of ethylene glycol, wherein the bismuth source and the ammonium fluoride are in accordance with NH4Bi3F10The molar ratio of Bi to F elements in the chemical formula of the material is 3: 10 weighing, and marking as A and B solutions;
2) simultaneously transferring the A and B homogeneous solutions obtained in the step 1) into the same beaker, uniformly mixing by magnetic stirring, aging at 25 ℃ for 8-15 hours, filtering, washing and drying to obtain white powder, namely NH4Bi3F10A precursor;
3) weighing a carbon source and adding the carbon source into NH obtained in the step 2)4Bi3F10In the solution, the amount of the carbon source is 5-20% of the mass of the metal bismuth, a magnetic stirrer is used for continuously stirring for 4-8 hours, and black powder is obtained after filtering, washing and drying;
4) placing the intermediate black powder obtained in the step 3) in a ceramic ark, sealing the tube furnace, introducing inert protective gas, and reacting at 400 DEGoC-600oAnd C, heating for 0.5-1 hour, and naturally cooling to room temperature to obtain the carbon-coated bismuth Bi @ C hollow nanosphere composite material, wherein the diameter of the carbon-coated bismuth Bi @ C hollow nanosphere composite material is 50-100 nm, and the size distribution is uniform.
2. The preparation method of the Bi @ C hollow nanosphere composite material of claim 1, wherein the bismuth source in step 1) is one or more of bismuth nitrate, bismuth sulfate and bismuth oxalate.
3. The method for preparing the Bi @ C hollow nanosphere composite of claim 1, wherein the bismuth source in step 1) is one or more of bismuth nitrate, bismuth sulfate and bismuth oxalate.
4. The method for preparing the Bi @ C hollow nanosphere composite material of claim 1, wherein the carbon source in step 3) is one or more of dopamine, resorcinol polyacrylonitrile, glucose and citric acid.
5. The method for preparing the Bi @ C hollow nanosphere composite of claim 1, wherein the inert atmosphere in step 4) is one of pure nitrogen or pure argon.
6. The Bi @ C hollow nanosphere composite prepared by the preparation method of any one of claims 1 to 5.
7. Use of the Bi @ C hollow nanosphere composite prepared by the preparation method of any one of claims 1-5 in a lithium ion/sodium ion battery.
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