CN115133017A - Carbon-supported niobium pentoxide microsphere and preparation method and application thereof - Google Patents
Carbon-supported niobium pentoxide microsphere and preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 54
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 239000010955 niobium Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical group Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000013507 mapping Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- -1 niobium ions Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention belongs to the technical field of electrochemical energy materials, and discloses a carbon-supported niobium pentoxide microsphere as well as a preparation method and application thereof. The preparation method comprises the steps of uniformly mixing a niobium source, a surfactant, an organic ligand and ethanol to prepare a precursor solution; heating the precursor solution to carry out hydrothermal reaction to obtain a precursor; and sintering the precursor at high temperature to obtain the carbon-supported niobium pentoxide microspheres. The carbon-supported niobium pentoxide microspheres prepared by the method have the particle size of 1-2 microns, are formed by densely stacking niobium pentoxide nanoparticles and a carbon network, have excellent electrochemical performance, and can be widely applied to the field of electrochemical energy storage; when the material is used as a negative active material of a lithium ion battery, the material has higher specific capacity, good cycling stability and excellent rate capability, and is a potential application material of a quick-charging lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy materials, and particularly relates to a carbon-supported niobium pentoxide microsphere as well as a preparation method and application thereof.
Background
By virtue of its high energy density, lithium ion batteries have seen recent yearsHas already been commercialized. With the development of intelligent electronic products and electric vehicles, the development of lithium ion batteries with high power density has become one of the major challenges. However, the graphite-based negative electrode material, which is commercialized, has slow lithium ion diffusion kinetics, is difficult to achieve rapid discharge/charge, and thus cannot meet the requirement of high power density. In addition, when the operating voltage is low, safety problems such as short-circuiting are liable to occur, which is particularly serious at high magnification. Although other insertion type materials such as Li 4 Ti 5 O 12 (LTO) has excellent rate capability and safe working potential (1.55V vs Li) + /Li), but the low theoretical capacity limits its energy density. Therefore, development of an anode material having a high rate, high safety, and high energy density is urgently required.
Recently, orthorhombic niobium pentoxide (T-Nb) 2 O 5 ) Due to small volume change, high capacity, high rate behavior and safe operating potential (1.1-2V), it has been extensively studied in lithium ion batteries. In T-Nb 2 O 5 The structure of (2) has many octahedral voids between its (001) planes, providing a rapid ion transport tunnel, thereby having high ion conductivity. However, T-Nb 2 O 5 Is an electronic insulator and has low electrical conductivity, greatly limiting the high power density of lithium ion batteries. To solve this problem, various strategies must be developed to improve it so as to improve its electrochemical performance. Wherein various carbon materials are mixed with Nb 2 O 5 Bonding is an effective method for improving electron conductivity. Furthermore, nanostructured Nb can be engineered 2 O 5 E.g., nanoparticles, nanoplatelets, nanowires, etc., to allow for a smaller ionic and electronic diffusion distance during charging/discharging. However, Nb with low tap density 2 O 5 Nanostructures are difficult to apply in commercial electrodes with high loading. Meanwhile, the high specific surface area increases the reaction interface between the electrode and the electrolyte, which causes side reactions and poor long cycle performance. With nanostructured Nb 2 O 5 In contrast, micron-sized Nb with higher tap density 2 O 5 It is more likely to meet the requirements of a practical battery. Meanwhile, in order to achieve high area capacity and excellent cycle performance under high load conditions, micron-sized Nb is required 2 O 5 Higher ionic and electronic conductivity over longer diffusion distances. Thus, further exploration and preparation of carbon-supported Nb 2 O 5 Microstructure for lifting Nb 2 O 5 The electrochemical performance of the electrolyte is of great significance in accelerating the popularization and application of the electrolyte in batteries.
Disclosure of Invention
The invention aims to solve the technical problem of the existing material in the aspect of electrochemical performance, and provides a carbon-supported niobium pentoxide microsphere, a preparation method and application thereof.
In order to solve the technical problem provided by the invention, the invention provides a preparation method of carbon-supported niobium pentoxide microspheres, which comprises the following steps:
1) dissolving a niobium source and a surfactant in ethanol to form a mixed solution A;
2) dissolving an organic ligand in ethanol to form a mixed solution B;
3) uniformly mixing the mixed solution A and the mixed solution B to prepare a precursor solution;
4) heating the precursor solution to carry out hydrothermal reaction, carrying out solid-liquid separation after the reaction, and washing and drying the obtained solid to obtain a precursor;
5) and sintering the precursor at high temperature to obtain the carbon-supported niobium pentoxide microspheres.
In the above scheme, the niobium source is niobium pentachloride.
In the above scheme, the surfactant is polyvinylpyrrolidone.
In the above scheme, the organic ligand is dimethyl imidazole.
In the above scheme, the mass ratio of the niobium source to the surfactant is (1-2): 1.
in the above scheme, the molar ratio of the organic ligand to the niobium source is (10-15): 1.
in the scheme, the step 1) is carried out under the protection of inert atmosphere, so that the niobium source can be prevented from being oxidized.
In the above scheme, in step 1), the volume ratio of the amount of the niobium source substance to ethanol is 1 mmol: (15-23) mL.
In the above scheme, in step 2), the volume ratio of the substance amount of the organic ligand to ethanol is 1 mmol: (1-1.6) mL.
In the scheme, in the step 4), the hydrothermal temperature is 160-220 ℃, and the hydrothermal time is 6-24 h.
In the scheme, in the step 4), the washing process is to wash with ethanol for 3 to 6 times.
In the scheme, in the step 4), the drying temperature is 60-70 ℃, and the drying time is 12-24 h.
In the scheme, in the step 5), the sintering process is to heat up to 750-850 ℃ at a heating rate of 2-5 ℃/min under the protection of inert atmosphere, preserve heat for 3-6h, and then cool to room temperature.
The invention also provides a carbon-supported niobium pentoxide micro-sphere which is prepared according to the preparation method, has a particle diameter of 1-2 mu m and is formed by densely stacking niobium pentoxide nanoparticles and a carbon network with internal connection.
The invention also provides an application of the carbon-supported niobium pentoxide microspheres in a lithium ion battery, which comprises the following steps: the carbon-supported niobium pentoxide microspheres are used as negative electrode active substances, added into a solvent together with a conductive agent and a bonding agent, uniformly mixed, coated on a copper foil, and dried to prepare a lithium ion battery negative electrode sheet; the lithium ion battery negative plate is used for assembling the lithium ion battery.
In the above scheme, the conductive agent is acetylene black.
In the above scheme, the adhesive is polyvinylidene fluoride.
In the above scheme, the solvent is N-methylpyrrolidone.
In the above scheme, the mass ratio of the negative electrode active material, the conductive agent and the binder is 7:2: 1.
In the above scheme, the mass-to-volume ratio of the adhesive to the solvent is 10 mg: 1 mL.
In the scheme, the drying temperature is 60-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1) in the preparation process, due to the fact that bond angles of pentavalent niobium ions and dimethyl imidazole are not matched, mismatch reaction occurs in the hydrothermal process, polyvinylpyrrolidone serving as a surfactant reduces the rate of the mismatch reaction, a uniform microsphere precursor is formed in the reaction process, then in-situ pyrolysis is performed on the precursor, the shape of the precursor is well maintained, the shape of the carbon-supported niobium pentoxide microsphere finally obtained is uniform and compact, the particle size of the carbon-supported niobium pentoxide microsphere is 1-2 microns, internal components are uniformly distributed, disorder agglomeration is avoided, and the electrochemical performance of the microsphere can be effectively promoted.
2) The micro-sphere prepared by the invention is formed by compactly stacking niobium pentoxide nanoparticles and a carbon network with internal connection, has higher tap density compared with a nano-grade material, can realize high volume capacity and high quality load, and simultaneously, carbon can provide an electron transmission path to further improve the overall electron conductance of the material. The material can be widely applied to the field of electrochemical energy storage, has higher specific capacity, good cycling stability and excellent rate capability when being used as a negative electrode active material of a lithium ion battery, can also show high capacity and excellent cycling stability under the condition of high load, and is a potential application material of a quick-charging lithium ion battery.
3) The invention combines a simple hydrothermal method with later-stage heat treatment, has simple preparation process and mild conditions, can realize controllable synthesis of products, meets the requirement of green chemistry, and is beneficial to marketization popularization.
Drawings
FIG. 1 is a) XRD, b) SEM, c) TEM and d-h) EDS mapping of the precursor prepared in example 1;
FIG. 2 is a) an XRD, b) an SEM, c) a TEM, and d-h) an EDS mapping of carbon-supported niobium pentoxide microspheres prepared in example 1;
FIG. 3 is a cross-section of a carbon-supported niobium pentoxide microsphere prepared in example 1, a) STEM, b) TEM, c) ADF, d-f) EDS mapping;
FIG. 4 is a graph of a) Raman, b) TG, and c) BET of carbon-supported niobium pentoxide microspheres prepared in example 1;
FIG. 5 shows the results obtained in application example 1 for a) in a range of 0.1 A.g -1 Cycle plot at current density, b) rate performance plot at different current densities, c) 2A · g -1 Long cycle plot at current density;
fig. 6 is a graph of a) cycle comparison at different loading amounts and b) a plot of surface capacity versus surface loading amount for the lithium ion half cell prepared in application example 1.
Detailed Description
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of carbon-supported niobium pentoxide microspheres comprises the following steps:
1) weighing 0.27g of niobium pentachloride and 0.25g of polyvinylpyrrolidone, and dissolving in 18mL of ethanol under an argon atmosphere to form a colorless and transparent mixed solution A;
2) weighing 0.9g of dimethyl imidazole, and dissolving in 17mL of ethanol to form a colorless and transparent mixed solution B;
3) uniformly mixing the mixed solution A and the mixed solution B to prepare a colorless and transparent precursor solution;
4) placing the precursor solution in a reaction kettle, heating to 200 ℃ for hydrothermal reaction, carrying out solid-liquid separation after 12h of reaction, washing the obtained solid with ethanol for 3 times, and placing in a 70 ℃ drying oven for drying for 12h to obtain a precursor;
5) and (3) placing the precursor in a high-temperature tube furnace, heating to 750 ℃ at the heating rate of 2 ℃/min under the protection of argon atmosphere, preserving the temperature for 3h, and then cooling to room temperature to obtain the carbon-supported niobium pentoxide microspheres.
FIG. 1 shows a) an XRD pattern, b) an SEM pattern, c) a TEM pattern, and d-h) an EDS mapping pattern of the precursor prepared in this example; the XRD pattern shows that the precursor has no obvious diffraction peak and is amorphous; EDS mapping chart shows that elements are distributed as Nb, O, N and C; SEM and TEM images show that the precursor is uniform solid microspheres, the spherical size is 1-2 μm, and the morphology and the size are uniform.
FIG. 2 is a) XRD, b) SEM, c) TEM and d-h) EDS mapping of carbon-supported niobium pentoxide microspheres prepared in this example; the XRD pattern shows that the phase of the carbon-supported niobium pentoxide micro-spheres is Nb 2 O 5 Diffraction peak and orthorhombic Nb 2 O 5 The standard cards are corresponding to each other and have no other miscellaneous phase; EDS mapping chart shows that elements are distributed into Nb, O, N and C; SEM and TEM images show that the carbon-supported niobium pentoxide microspheres are uniform solid microspheres, the spherical size is 1-2 μm, the morphology and the size are uniform and are consistent with those of the precursor.
The carbon-supported niobium pentoxide microspheres prepared in this example were cut and polished to cross-sections using a focused ion beam, and fig. 3 is a) a STEM diagram, b) a TEM diagram, c) an ADF diagram, d-f) an EDS mapping diagram of the cross-sections of the carbon-supported niobium pentoxide microspheres prepared in this example; STEM, TEM and ADF graphs show that the cross-section is made of multiple Nb 2 O 5 Nb composed of nanoparticles with carbon embedded in single crystal 2 O 5 Inside the nanoparticle; the EDS mapping graph shows that Nb and C are unevenly distributed in the whole cross section, Nb is distributed in a region with bright contrast, C is distributed in the whole cross section region, and a region with black contrast is filled with carbon.
FIG. 4 shows a) a Raman, b) a TG and c) a BET plot of carbon-supported niobium pentoxide microspheres prepared in this example; the BET diagram shows that the specific surface area of the microspheres reaches 6.67m 2 g -1 The carbon-supported niobium pentoxide microspheres are proved to have higher tap density; TG picture shows that the carbon content of the micro-spheres is about 5 percent, the conductivity is improved, and simultaneously the higher specific capacity is ensured(ii) a The Raman image shows that carbon has higher graphitization degree, and the electronic conductivity of the whole material is improved.
Application example 1
An application method of carbon-supported niobium pentoxide microspheres in a lithium ion battery is as follows:
weighing 70mg of carbon-supported niobium pentoxide microspheres prepared in example 1 as a negative electrode active substance, 20mg of acetylene black as a conductive agent and 10mg of polyvinylidene fluoride as a bonding agent, adding the carbon-supported niobium pentoxide microspheres into 1mL of N-methylpyrrolidone, uniformly mixing, coating the mixture on a copper foil, and drying at 70 ℃ to obtain a lithium ion battery negative electrode sheet; cutting the negative plate of the lithium-ion battery into pieces with the area of 0.78cm 2 The total weight of the wafer (1.5 mg) and the area mass load of 1.92mg cm -2 And the lithium ion semi-cell is assembled with the lithium metal electrode plate.
FIG. 5 shows the lithium ion half-cell prepared in this application example with a) at 0.1 A.g -1 A cycle plot at current density, b) a rate performance plot at different current densities, c) at 2A · g -1 Long cycle plot at current density; a shows that the lithium ion half cell is at 0.1 A.g -1 The current density is up to 196mAh g after 100 cycles -1 The discharge capacity of (4); b shows that the lithium-ion half-cell has excellent rate performance, and the current density can be from 0.1 A.g -1 Gradually increase to 6A g -1 At 6 A.g -1 Under high current density, the specific capacity can reach 124 mAh.g -1 And the current density is returned to 0.1A · g -1 When the specific capacity is higher than the standard, the specific capacity can reach 215 mAh.g -1 (ii) a c shows that at 2A g -1 The specific capacity can reach 106mAh g after 2000 times of circulation under the current density -1 And the excellent cycle stability is embodied.
FIG. 6 is a graph of a) cycle comparison under different loading capacity and b) a relationship between surface capacity and surface loading capacity of the lithium ion half cell prepared by the application example; graph a shows that the concentration of the active ingredients is 1.5, 3.8, 7.6 and 12.8 mg-cm -2 Under the loading condition, the specific capacity can respectively reach 202.7, 188.8, 186.5 and 171.5 mAh.g -1 Exhibit high capacity; b shows that the concentration is 12.8 mg/cm -2 Has a concentration of 2.05 mAh.cm under high load conditions -2 The surface capacity of (a) demonstrates that the carbon-supported niobium pentoxide microspheres have excellent electrochemical properties.
Example 2
A preparation method of carbon-supported niobium pentoxide microspheres comprises the following steps:
1) weighing 0.54g of niobium pentachloride and 0.4g of polyvinylpyrrolidone, and dissolving in 45mL of ethanol under the argon atmosphere to form a colorless and transparent mixed solution A;
2) weighing 1.74g of dimethylimidazole, and dissolving in 25mL of ethanol to form a colorless and transparent mixed solution B;
3) uniformly mixing the mixed solution A and the mixed solution B to prepare a colorless and transparent precursor solution;
4) placing the precursor solution in a reaction kettle, heating to 200 ℃ for hydrothermal reaction, carrying out solid-liquid separation after 12h of reaction, washing the obtained solid with ethanol for 4 times, and placing in a 70 ℃ drying oven for drying for 16h to obtain a precursor;
5) and (3) placing the precursor in a high-temperature tube furnace, heating to 800 ℃ at the heating rate of 3 ℃/min under the protection of argon atmosphere, preserving the temperature for 4h, and then cooling to room temperature to obtain the carbon-supported niobium pentoxide microspheres.
Example 3
A preparation method of carbon-supported niobium pentoxide microspheres comprises the following steps:
1) weighing 0.27g of niobium pentachloride and 0.18g of polyvinylpyrrolidone, and dissolving in 20mL of ethanol under an argon atmosphere to form a colorless and transparent mixed solution A;
2) weighing 1.2g of dimethylimidazole, and dissolving in 15mL of ethanol to form a colorless and transparent mixed solution B;
3) uniformly mixing the mixed solution A and the mixed solution B to prepare a colorless and transparent precursor solution;
4) placing the precursor solution in a reaction kettle, heating to 200 ℃ for hydrothermal reaction, carrying out solid-liquid separation after 24h of reaction, washing the obtained solid with ethanol for 5 times, and placing in a 70 ℃ drying oven for drying for 18h to obtain a precursor;
5) and (3) placing the precursor in a high-temperature tube furnace, heating to 800 ℃ at the heating rate of 4 ℃/min under the protection of argon atmosphere, preserving the temperature for 5h, and then cooling to room temperature to obtain the carbon-supported niobium pentoxide microspheres.
Example 4
A preparation method of carbon-supported niobium pentoxide microspheres comprises the following steps:
1) weighing 0.27g of niobium pentachloride and 0.15g of polyvinylpyrrolidone, and dissolving in 20mL of ethanol under the argon atmosphere to form a colorless and transparent mixed solution A;
2) weighing 1g of dimethyl imidazole, and dissolving in 15mL of ethanol to form a colorless and transparent mixed solution B;
3) uniformly mixing the mixed solution A and the mixed solution B to prepare a colorless and transparent precursor solution;
4) placing the precursor solution in a reaction kettle, heating to 180 ℃ for hydrothermal reaction, carrying out solid-liquid separation after 24h of reaction, washing the obtained solid with ethanol for 6 times, and placing in a 70 ℃ drying oven for drying for 24h to obtain a precursor;
5) and (3) placing the precursor in a high-temperature tube furnace, heating to 850 ℃ at the heating rate of 5 ℃/min under the protection of argon atmosphere, preserving the temperature for 6h, and then cooling to room temperature to obtain the carbon-supported niobium pentoxide microspheres.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessarily exhaustive of all embodiments, and are therefore intended to be within the scope of the invention.
Claims (10)
1. A preparation method of carbon-supported niobium pentoxide microspheres is characterized by comprising the following steps:
1) dissolving a niobium source and a surfactant in ethanol to form a mixed solution A;
2) dissolving an organic ligand in ethanol to form a mixed solution B;
3) uniformly mixing the mixed solution A and the mixed solution B to prepare a precursor solution;
4) heating the precursor solution to carry out hydrothermal reaction, carrying out solid-liquid separation after the reaction, and washing and drying the obtained solid to obtain a precursor;
5) and sintering the precursor at high temperature to obtain the carbon-supported niobium pentoxide microspheres.
2. The method of preparing carbon-supported niobium pentoxide microspheres of claim 1, wherein the niobium source is niobium pentachloride, the surfactant is polyvinylpyrrolidone, and the mass ratio of niobium source to surfactant is (1-2): 1.
3. the method of making carbon-supported niobium pentoxide microspheres of claim 1, wherein the organic ligand is dimethylimidazole and the molar ratio of organic ligand to niobium source is (10-15): 1.
4. the method for preparing carbon-supported niobium pentoxide microspheres as claimed in claim 1, wherein in step 1), the ratio of the amount of the substance of niobium source to the volume of ethanol is 1 mmol: (15-23) mL.
5. The method for preparing carbon-supported niobium pentoxide microspheres of claim 1, wherein in step 2), the volume ratio of the amount of the substance of the organic ligand to ethanol is 1 mmol: (1-1.6) mL.
6. The method for preparing carbon-supported niobium pentoxide microspheres as claimed in claim 1, wherein in the step 4), the hydrothermal temperature is 160-220 ℃ and the hydrothermal time is 6-24 h; the drying temperature is 60-70 ℃, and the drying time is 12-24 h.
7. The method for preparing carbon-supported niobium pentoxide microspheres as claimed in claim 1, wherein in the step 4), the washing is performed 3 to 6 times with ethanol.
8. The method as claimed in claim 1, wherein the sintering process in step 5) comprises raising the temperature to 750-850 ℃ at a temperature raising rate of 2-5 ℃/min under the protection of inert atmosphere, keeping the temperature for 3-6h, and then cooling to room temperature.
9. Carbon-supported niobium pentoxide micro-spheres prepared by the method of any one of claims 1 to 8, wherein the carbon-supported niobium pentoxide micro-spheres have a particle size of 1 to 2 μm and are stacked from niobium pentoxide nanoparticles and a carbon network with internal linkages.
10. Use of the carbon-supported niobium pentoxide microspheres of claim 9 in a lithium ion battery.
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