CN114300665B - Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same - Google Patents
Niobium-based metal oxide mesoporous carbon sphere composite material and sodium ion battery anode material containing same Download PDFInfo
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- CN114300665B CN114300665B CN202111649183.6A CN202111649183A CN114300665B CN 114300665 B CN114300665 B CN 114300665B CN 202111649183 A CN202111649183 A CN 202111649183A CN 114300665 B CN114300665 B CN 114300665B
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- 239000010955 niobium Substances 0.000 title claims abstract description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 39
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 37
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 230000007547 defect Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 230000002950 deficient Effects 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 8
- 238000004435 EPR spectroscopy Methods 0.000 description 6
- 238000009830 intercalation Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 6
- 229910052799 carbon 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 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 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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 provides a niobium-based metal oxide mesoporous carbon sphere composite material and a sodium ion battery anode material containing the same. The invention designs a niobium base based on defect engineeringThe metal oxide mesoporous carbon sphere is used as a negative electrode material of a sodium ion battery, and provides a method for controllably introducing defects so as to prepare the niobium-based metal oxide mesoporous carbon sphere composite material with oxygen defects. The invention prepares Nb which is rich in oxygen defects by adopting an ultrasonic dipping and high-temperature sintering method 2 O 5‑x A mesoporous carbon composite material. The composite material can be used as the negative electrode material of the sodium ion battery to achieve the high temperature of 20A g ‑1 Has important value in developing a feasible sodium ion battery and materials in the related energy storage and conversion fields.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to an oxygen-defect niobium-based metal oxide mesoporous carbon sphere composite material and a sodium ion battery anode material containing the same.
Background
With the rise of medium-to-large energy storage devices, in recent years, next-generation energy storage devices such as lithium sulfur batteries, lithium air batteries, sodium ion batteries have been attracting attention. However, lithium ion batteries are costly and have limited distribution of lithium resources on earth, and the energy storage mechanism of such lithium batteries is based on metallic lithium as anode and a cathode component (sulfur or O 2 ) The chemical reaction between them is very slow and unstable, and there are problems of rapid capacity fade and low energy density.
Sodium metal is abundant in resources on the earth and low in cost, and is considered as an ideal substitute for lithium ion batteries, so that a great deal of work is used for exploring anode materials suitable for sodium ion batteries. According to the reaction mechanism of the charge-discharge process, the anode materials are classified into three types, namely a conversion type, an alloy type and an intercalation type. The first two types of materials exhibit high theoretical specific capacities but can cause during the sodium removal/intercalation reactionThe volume is greatly changed, so that the structure is collapsed, and the sodium storage performance is poor. Intercalation materials can exhibit excellent cycling stability at low current densities, but the reversible capacity at high current densities is currently inadequate for human needs. Recently, due to the "intercalation pseudocapacitance" behavior, orthorhombic niobium pentoxide (T-Nb 2 O 5 ) Has been demonstrated to be an electrochemical energy storage material with high rate capability that helps to promote the fast charge capability of the battery. In addition, nb 2 O 5 Has a (001) crystal face ofIs favorable for rapid diffusion of sodium ions between layers, thereby realizing high rate performance. To further improve Nb 2 O 5 Is of the conductivity of Nb 2 O 5 The introduction of a defect structure and the combination of the defect structure and carbon to prepare the niobium oxide porous carbon composite material with the defect structure have important research significance for improving the electrochemical performance of the battery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a niobium-based metal oxide mesoporous carbon sphere composite material containing specific oxygen defect content, which can be used as a negative electrode material of a sodium ion battery to realize high-efficiency sodium storage capacity and excellent structural stability. The composite material Nb 2 O 5-x When applied to a negative electrode of a sodium ion battery, the @ MEC shows higher specific discharge capacity, long-cycle stability and excellent rate capability.
It is another technical object of the present invention to provide a method for preparing the above composite material.
Another technical object of the present invention is to provide a negative electrode material for sodium ion battery comprising the above composite material.
It is still another technical object of the present invention to provide a sodium ion battery comprising the above-mentioned negative electrode material for sodium ion battery.
Accordingly, in one aspect, the present invention provides a method of preparing a niobium-based metal oxide mesoporous carbon sphere composite having an oxygen defect, the method comprising the steps of:
s1, preparing an ethanol solution of niobium pentachloride, and uniformly mixing by ultrasonic waves to obtain a solution A;
s2, adding the solution A obtained in the step S1 into mesoporous carbon spheres, and carrying out ultrasonic impregnation to obtain a precursor B;
s3, placing the precursor B obtained in the step S2 in a vacuum oven for drying;
s4, placing the dried sample in the step S3 into a tube furnace filled with hydrogen-argon mixed gas, sintering at 450-750 ℃, naturally cooling to room temperature, and collecting the product to obtain the niobium-based metal oxide mesoporous carbon sphere composite material with oxygen defects, which can be expressed as Nb 2 O 5-x And @ MEC, wherein x ranges from 0.1 to 0.5, and the volume ratio of hydrogen in the hydrogen-argon mixed gas is 5% -20%.
In a specific embodiment, in step S1, the concentration of niobium pentachloride in solution A is 100 to 150mM.
In a specific embodiment, in step S1, the ultrasonic time is 0.5 to 2.5 hours.
In a specific embodiment, in the step S2, the mass ratio of the mesoporous carbon sphere to the niobium pentachloride is 0.2-4.5: 1, preferably 1.15:1, the ultrasonic time is 2 to 6 hours, preferably, the specific surface area of the mesoporous carbon sphere is 1000 to 1500m 2 And/g, wherein the pore diameter is between 3nm and 8 nm.
In a specific embodiment, in step S3, vacuum drying is performed at 60 to 100 ℃ at, for example, 70 ℃,80 ℃,90 ℃.
In a specific embodiment, in the sintering in step S4, the temperature rising rate is 1 to 5 ℃ for min -1 The sintering temperature is 600-750 ℃ and the sintering time is 2-6 h,
in a specific embodiment, in step S4, the volume ratio of hydrogen to argon in the hydrogen-argon mixture is 10:90 to 20:80, preferably, the volume ratio of hydrogen to argon is 15:85.
On the other hand, the invention provides the niobium-based metal oxide mesoporous carbon sphere composite material with the oxygen defect, which is prepared by the method, wherein the shape of the composite material is spherical, the size of the composite material is in the range of 20-300nm, and the particle size of the niobium-based metal oxide nano particles with the oxygen defect in the composite material is 2-10nm.
In yet another aspect, the present invention provides a sodium ion negative electrode material comprising the niobium-based metal oxide mesoporous carbon sphere composite material having oxygen defects as described above.
In specific embodiments, the sodium ion negative electrode material further comprises a conductive agent and a binder.
In specific embodiments, the conductive agent includes, but is not limited to, super P, carbon fiber (VGCF), carbon Nanotube (CNT), graphene, and the like.
In particular embodiments, the binder includes, but is not limited to, polyvinylidene fluoride (PVDF), sodium carboxymethyl Cellulose (CMA), styrene Butadiene Rubber (SBR), and the like.
In specific embodiments, the sodium ion negative electrode material comprises 60 to 80 parts by weight of the composite material, 10 to 20 parts by weight of the conductive agent, and 10 to 20 parts by weight of the binder.
In yet another aspect, the present invention provides a sodium ion battery comprising a negative electrode made of the sodium ion negative electrode material described above.
The beneficial effects are that:
in the invention, a precursor niobium ethoxide (Nb (OEt)) is synthesized by an impregnation method 5 ) A @ mesoporous carbon sphere; nb (OEt) 5 The precursor of the mesoporous carbon sphere is placed in an inert gas environment for high-temperature treatment, and Nb (OEt) is adopted in the process 5 The precursor of the mesoporous carbon sphere can generate a fine composite structure under high temperature and reducing atmosphere, so that the superfine Nb is prepared 2 O 5-x The nano particles are limited in the mesoporous to obtain Nb 2 O 5-x A mesoporous carbon sphere composite material.
The composite material of the invention is applied to the negative electrode material of the sodium ion battery, and shows that the content of the composite material is up to 20Ag -1 And an ultralong cycle life exceeding 5000 times. Therefore, the invention has important value in developing materials for practical sodium ion batteries and related energy storage and conversion fields.
The invention relates to a niobium-based metal oxide mesoporous carbon sphere composite material with oxygen defectsThe mesoporous carbon sphere has the excellent properties, and the mechanism is that the mesoporous carbon sphere can serve as a buffer layer to avoid structural collapse caused in the process of sodium ion intercalation and deintercalation, so that the structural integrity of an electrode material is ensured, and the mesoporous carbon sphere provides a fully-encapsulated large-range conductive network for niobium-based metal oxide, thereby realizing rapid electron transmission and Na + Fast motion. Meanwhile, the finite field effect of the porous carbon sphere avoids the agglomeration of active substances so as to adapt to the volume change of sodium ions during intercalation and deintercalation. In addition, the carbon sphere skeleton has rich active interfaces and channels for rapid ion/electron transmission, so that the redox reaction kinetics of the material in the sodium storage process is enhanced. On the other hand, the controllable oxygen defect introduction can regulate and control Nb 2 O 5 The chemical environment and the electronic structure of the battery, thereby promoting charge transfer and structural integrity, exerting synergistic effect, and remarkably improving the reaction kinetics, the cycle stability and the rate capability of the battery.
Drawings
FIG. 1 is an XRD pattern of a niobium-based metal oxide mesoporous carbon sphere composite with oxygen defects prepared in example 1 in comparison with a PDF standard card.
FIG. 2 is a morphology diagram of the niobium-based metal oxide mesoporous carbon sphere composite with oxygen defects prepared in example 1. Wherein A shows Nb 2 O 5-x TEM picture of @ MEC; b shows Nb 2 O 5-x TEM pictures of @ MEC.
Fig. 3 is an electron spin resonance (EPR) contrast chart of the niobium-based metal oxide mesoporous carbon sphere composite material with oxygen defect prepared in example 1 and the niobium-based metal oxide mesoporous carbon sphere composite material without oxygen defect prepared in comparative example 1.
FIG. 4 is a comparison of Nb 3dXPS for the oxygen-deficient niobium-based metal oxide mesoporous carbon sphere composite prepared in example 1 and the oxygen-deficient niobium-based metal oxide mesoporous carbon sphere composite prepared in comparative example 1.
FIG. 5 is a graph comparing the O1sXPS of the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in example 1 and the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in comparative example 1.
FIG. 6 is a graph showing the diffuse reflection of the Kubelka-Munk ultraviolet of the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in example 1 and the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in comparative example 1.
FIG. 7 is a schematic view showing Nb L of the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in example 1 and the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in comparative example 1 3 -edge XANES contrast map.
FIG. 8 shows an oxygen-deficient niobium-based metal oxide mesoporous carbon sphere composite Nb L prepared in example 1 3 -edge XANES and its linear combination fit (Linear Combination Fitting) map.
Fig. 9 is a graph showing charge-discharge rate performance of the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in example 1 and the oxygen-defective niobium-based metal oxide mesoporous carbon sphere prepared in comparative example 1 as a negative electrode material for a sodium ion battery.
Fig. 10 is a long cycle performance graph of the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in example 1 and the oxygen-defective niobium-based metal oxide mesoporous carbon sphere composite material prepared in comparative example 1 as a negative electrode material for a sodium ion battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail with reference to specific examples and comparative examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The equipment used in this example, comparative example and experimental example was conventional experimental equipment, and the materials and reagents used were all commercially available, except for the specific description.
Mesoporous carbon spheres (MEC) using Ketjen black porous carbon material KJ from Ara Ding Mai600 xrd powder diffractometer tests were performed using bruck D8 (Cu ka,) The morphology of the compound is tested by adopting a transmission electron microscope (HRTEM, tecnai G2F 20S-TWIN), the state of a substance element can be obtained from an X-ray photoelectron spectrometer (XPS, PHI 5300), EPR signal response is provided by a paramagnetic resonance spectrometer (Bruker EMXPLUS), and the constant-current charge and discharge test adopts a blue-electric battery test system (LAND CT 2001A) voltage test range from 0.01V to 3V.
Example 1
(1) Preparation of 100mM NbCl 5 And (5) ethanol solution, and carrying out ultrasonic treatment for 2 hours to uniformly mix to obtain solution A.
(2) According to m (mesoporous carbon sphere): m (NbCl) 5 ) The solution a in the step (1) is dripped into the mesoporous carbon sphere in a ratio of (i.e. mass ratio of the two) of 1.15, and the mesoporous carbon sphere is immersed by ultrasonic treatment for 2 hours.
(3) Vacuum drying the solution A obtained in the step (2) at 80 ℃ to obtain Nb (OEt) 5 Mesoporous carbon sphere (Nb (OEt)) 5 @MEC) precursor (here Nb (OEt) 5 Is an abbreviation for niobium ethoxide).
(4) Placing the dried sample in the step (3) in a tube furnace, and adopting high temperature of 600 ℃ with a heating rate of 5 ℃/min and a treatment time of 2 hours; the inert gas is hydrogen-argon mixed gas, wherein the volume ratio of hydrogen in the mixed gas is 15%, and Nb can be obtained after natural cooling 2 O 5-x @MEC。
Example 2
The procedure of example 1 was repeated except that m (mesoporous carbon spheres) in step (2) was replaced with m (NbCl) 5 ) Instead of 4.43.
Example 3
The procedure of example 1 was repeated except that m (mesoporous carbon spheres) in step (2) was replaced with m (NbCl) 5 ) Instead of 0.49.
Comparative example 1
The procedure of example 1 was repeated except that the mixture gas in step (4) was replaced with argon to obtain an oxygen defect-free composite material Nb 2 O 5 @MEC。
Negative electrode material of sodium ion battery and preparation of sodium ion battery
Uniformly mixing the composite materials obtained in the examples 1-3 and the comparative example 1 with a conductive agent Super P and a binder PVDF in an NMP solvent to prepare slurry, coating the slurry on carbon-containing aluminum foil, and drying the slurry at 60-80 ℃ for 12 hours to obtain the sodium ion battery anode material. The composite material comprises, by mass, 80% of a composite material, 10% of a conductive agent and 10% of a binder in the anode material.
The negative electrode plate is manufactured into a sodium ion battery for subsequent electrochemical performance test. Wherein, the assembled battery is carried out in a glove box (the water oxygen value is less than 0.01 ppm) filled with argon, a 2032 button cell shell is selected as a diaphragm, GF/D glass fiber is used as a counter electrode, and the electrolyte is ethylene carbonate with the volume ratio: dimethyl carbonate = 3:7 (EC: DMC) to the mixed solvent was added 1M sodium hexafluorophosphate and 5% fluorovinylene carbonate (FEC).
Experimental example:
the composite materials prepared in the above examples and comparative examples were subjected to various performance tests, and the performance of the prepared sodium ion battery was tested, and the results were analyzed as follows.
Nb obtained in example 1 2 O 5-x The results of the X-ray diffraction test at MEC, shown in fig. 1, were consistent with standard card PDF #27-1003, demonstrating that the nanoparticles embedded in MEC are orthorhombic Nb 2 O 5 。
Observation of Nb under Transmission Electron microscope 2 O 5-x The microstructure of @ MEC is shown in FIG. 2, where the oxygen defect Nb 2 O 5 The nanoparticles are uniformly dispersed within the pores.
As shown in FIG. 3, EPR test results indicate Nb 2 O 5-x The @ MEC had a pronounced EPR signal around a g-factor of 2.004, indicating Nb 2 O 5 Oxygen vacancies exist in the reactor. However, in Nb 2 O 5 No EPR signal was observed in @ MEC, demonstrating Nb 2 O 5 Oxygen vacancies are absent.
As shown in FIG. 4, nb 2 O 5 Nb 3d XPS spectra of (c) showed that the spectra were at 210.34eV and 207.59eVTwo peaks corresponding to Nb 3d 3/2 And Nb 3d 5/2 A peak. However, nb 2 O 5-x And Nb (Nb) 2 O 5-x These two peaks in @ MEC move towards the low Binding Energy (BE) region, corresponding to the change in electronic structure caused by the formation of defects.
As shown in FIG. 5, in the O1s XPS spectrum, the spectrum can be obtained in Nb 2 O 5 Two peaks associated with Nb-O bonds and hydroxylated surfaces (O1, O2), nb, respectively, were observed in @ MEC 2 O 5-x The @ MEC shows an O3 peak at 531.7eV, corresponding to the formation of oxygen defects.
As shown in FIG. 6, nb 2 O 5-x @ MEC and Nb 2 O 5 The Kubelka-Munk plot of @ MEC shows band gap values of 3.08 and 3.91eV, respectively. Nb of defective structure 2 O 5-x The @ MEC has a narrower band gap, demonstrating the effectiveness of defect engineering, thereby facilitating electron transport.
As shown in FIG. 7, in the X-ray near-edge absorption spectrum (XANES) of Nb L-edge, nb 2 O 5-x The @ MEC shows higher peak intensity and lower E 0 This indicates an increase in the density of Nb 4d unoccupied states near the fermi level caused by oxygen vacancies.
As shown in FIG. 8, for Nb L 3 -linear combination fitting (Linear Combination Fitting, LCF) of edge's X-ray near-edge absorption spectrum (XANES), controlling the ratio of hydrogen in the hydrogen-argon mixture, can produce niobium-based porous carbon composites with specific oxygen defect content. The XANES test was performed on a sample obtained by sintering in a 10% hydrogen-argon mixture for 1 hour, and Nb was used as the sample 2 O 5 NbO (NbO) 2 L of (2) 3 After LCF fitting based on the edge XANES spectrum, the chemical composition of the prepared defective niobium oxide composite material can be determined to be Nb 2 O 4.82 。
As shown in fig. 9, nb 2 O 5-x At 0.2, 0.4, 1, 2, 4, 6, 10, 20Ag -1 Exhibits extremely high discharge capacities at current densities of 450, 325, 250, 215, 192, 179, 156, 130mAh g, respectively -1 Far higher than Nb 2 O 5 @MEC。
Long cycle performance test, nb as shown in fig. 10 2 O 5-x Still 105mAh g can be obtained after 5000 cycles of @ MEC -1 And a stable coulombic efficiency approaching 100%, indicating excellent electrochemical stability in ultra-long run. Conversely, nb 2 O 5 The @ MEC electrode exhibited rapid capacity fade during cycling, indicating poor stability. Thus, with Nb 2 O 5 Comparative @ MEC, nb 2 O 5-x The @ MEC shows good synergy of sodium ion storage, electron conduction and volume change alleviation, and meets the requirement of prolonging the cycle life in practical application.
In addition, the same test as in example 1 was performed on the materials of example 2 and example 3, and the results were similar to those of example 1.
Claims (14)
1. A method of preparing a niobium-based metal oxide mesoporous carbon sphere composite material having an oxygen defect, the method comprising the steps of:
s1, preparing an ethanol solution of niobium pentachloride, and uniformly mixing by ultrasonic waves to obtain a solution A;
s2, adding the solution A obtained in the step S1 into mesoporous carbon spheres, and carrying out ultrasonic impregnation to obtain a precursor B;
s3, placing the precursor B obtained in the step S2 in a vacuum oven for drying;
s4, placing the dried sample in the step S3 into a tube furnace filled with hydrogen-argon mixed gas, sintering at 450-750 ℃, cooling to room temperature, and collecting the product to obtain the niobium-based metal oxide mesoporous carbon sphere composite material with oxygen defects, which is expressed as Nb 2 O 5-x And @ MEC, wherein x ranges from 0.1 to 0.5, and the volume ratio of hydrogen in the hydrogen-argon mixed gas is 5-20%.
2. The method according to claim 1, wherein in step S1, the concentration of niobium pentachloride in solution a is 100 to 150mM and the sonication time is 0.5 to 2.5h.
3. The method according to claim 1, wherein in the step S2, the mass ratio of the mesoporous carbon spheres to the niobium pentachloride is 0.2-4.5:1, and the ultrasonic time is 2-6 h.
4. The method according to claim 1, wherein in step S2, the mass ratio of mesoporous carbon spheres to niobium pentachloride is 1.15:1.
5. The method according to claim 1, wherein in the step S2, the specific surface area of the mesoporous carbon sphere is 1000 to 1500m 2 And/g, wherein the pore diameter is between 3nm and 8 nm.
6. The method according to claim 1, wherein in step S3, vacuum drying is performed at 60 to 100 ℃.
7. The method according to claim 1, wherein in step S4, the temperature rise rate is 1 to 5℃for min -1 The sintering temperature is 600-750 ℃ and the sintering time is 2-6 h.
8. The method according to claim 1, wherein in step S4, the volume ratio of hydrogen to argon in the hydrogen-argon mixture is 10:90 to 20:80.
9. The method according to claim 1, wherein in step S4, the volume ratio of hydrogen to argon in the hydrogen-argon mixture is 15:85.
10. An oxygen-deficient niobium-based metal oxide mesoporous carbon sphere composite material prepared by the method of any one of claims 1 to 9, which has a spherical morphology and a size in the range of 20 to 300nm, and in which the oxygen-deficient niobium-based metal oxide nanoparticles have a particle diameter of 2 to 10nm.
11. A sodium ion negative electrode material comprising the niobium-based metal oxide mesoporous carbon sphere composite having oxygen defects of claim 10.
12. The sodium ion negative electrode material of claim 11, further comprising a conductive agent and a binder,
the conductive agent includes Super P, vapor Grown Carbon Fiber (VGCF), carbon Nanotube (CNT), or graphene;
the binder includes polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC-Na), or Styrene Butadiene Rubber (SBR).
13. The sodium ion negative electrode material of claim 12, wherein the sodium ion negative electrode material comprises 60-80 parts by weight of the oxygen-deficient niobium-based metal oxide mesoporous carbon sphere composite, 10-20 parts by weight of a conductive agent, and 10-20 parts by weight of a binder.
14. A sodium ion battery comprising a negative electrode made of the sodium ion negative electrode material of any one of claims 11-13.
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