CN115745004B - Method for preparing ferric molybdate by electrostatic spinning - Google Patents
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- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002086 nanomaterial Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
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- 238000001523 electrospinning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
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- 238000001228 spectrum Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910002521 CoMn Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 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
- 229910003266 NiCo Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 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 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 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
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
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- 230000037361 pathway Effects 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of electrode material preparation, and provides a method for preparing ferric molybdate by electrostatic spinning. Mixing an iron source, a molybdenum source, a high polymer, an organic solvent and hydrochloric acid to obtain a spinning precursor; the volume ratio of the organic solvent to the hydrochloric acid is 4-5 mL, 50-170 mu L; the mass concentration of the hydrochloric acid is 35-40%; carrying out electrostatic spinning by adopting the obtained spinning precursor, and then sequentially carrying out primary heat treatment and secondary heat treatment to obtain Fe 2 (MoO 4 ) 3 Material elemental analysis and morphology analysis were performed via XPS, TG, XRD, SEM and TEM. The prepared sample is applied to the anode of a Lithium Ion Battery (LIBs), fe 2 (MoO 4 ) 3 The electrode exhibits excellent cycle stability and high conductivity.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a method for preparing ferric molybdate by electrostatic spinning.
Background
Due to the pressure of energy crisis and ecological environment, the demand of wind energy, solar energy and other green energy sources is increased, and LIBs are considered to be the most promising choice due to the advantages of high energy density, small self-discharge, low cost, high safety and the like. However, the development of electrode materials has a critical impact on LIBs. At present, a commercial LIBs cathode is usually made of an embedded material represented by graphite as a main body, and the low theoretical capacity (372 mAh/g) of the embedded material is difficult to meet the endurance requirements of Electric Vehicles (EV) and partial electronic products. The theoretical capacity of the alloy type negative electrode material represented by silicon exceeds 4000mAh/g, but the lattice stress generated by the huge volume change (about 400%) causes the structural deterioration in the lithiation/delithiation process. In order to overcome the defects of low capacity and large volume expansion, the attention is focused on a Transition Metal Oxide (TMOs) as a representative of a negative electrode material. Although much work has shown that TMOs have the advantages of high capacity, low cost, environmental friendliness, etc. However, TMOs also suffer from the following problems: the volume changes during lithium ion intercalation and extraction, resulting in pulverization and agglomeration of the active material, and low conductivity in electrochemical reactions.
Recently, some important studies have shown that binary metal oxides can effectively overcome the above problems. Binary metal oxides have advantages in enhancing electron/ion conductivity, reversible capacity and electrode stability because of the synergistic effect and higher oxidation state between the different metals. Wherein Fe is 2 (MoO 4 ) 3 Is made of FeO 6 Octahedron and MoO 4 The tetrahedron structure has a three-dimensional structure, can provide favorable gap vacancies for diffusion and storage of lithium ions, and more importantly, has rich element reserves and is environment-friendly, so that the tetrahedron structure has attractive prospects in the application aspect of anode materials, but has certain limitations in the process of lithium intercalation and deintercalation of capacity, multiplying power and stability.
To solve these problems, it can be achieved by rationally designing with fine nanostructures. The unique morphology of stacked nanoplatelet structures and open gaps facilitates lithium ion diffusion, making Fe using in situ bubble template method 2 (MoO 4 ) 3 As LIBs negative electrode material, the hollow layered porous microsphere has high energy/power density, excellent cycling stability, excellent low-temperature electrochemical performance and high reversible discharge capacity. Fe (Fe) 2 (MoO 4 ) 3 And the composite material is compounded with a carbon material, so that on one hand, the conductivity of the material can be improved, and on the other hand, a stable electrochemical reaction interface can be provided. Synthesis of graphene oxide modified Fe by simple one-step water bath method 2 (MoO 4 ) 3 Nanomaterial, reinforcedThe electrochemical properties can be attributed to Fe 2 (MoO 4 ) 3 And a combination of conductive graphene oxide, which provides a pathway for electron transport and buffers volume changes during discharge/charge; hydrothermal synthesis of Fe 2 (MoO 4 ) 3 MWCNT (multi-walled carbon nanotube) nanomaterial as LIBs negative electrode, li due to high specific surface area of nanomaterial + The diffusion length is shortened resulting in faster kinetics and improved rate performance. In addition, MWCNTs provide an effective conductive network for electron transport during lithiation/delithiation while acting as strain buffers, maintaining the mechanical stability of the composite electrode.
Electrospinning is well known as an easy method of preparing nanomaterials. The electrostatic spinning and the heat treatment are combined to prepare the porous ZnO-SnO 2 -Zn 2 SnO 4 A nanofiber; preparation of one-dimensional hollow porous NiCo by changing different mass ratios of metal precursor and PVP in electrostatic spinning 2 O 4 A nanotube; volatile organic solvents can also be selected to produce CoMn with unique hollow structures 2 O 4 A nanofiber. However, at present, electrostatic spinning for preparing Fe does not appear 2 (MoO 4 ) 3 A method for preparing nanometer material.
Disclosure of Invention
The invention aims to provide a method for preparing ferric molybdate by electrostatic spinning, which overcomes the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing Fe by electrostatic spinning 2 (MoO 4 ) 3 Comprising the steps of:
(1) Mixing an iron source, a molybdenum source, a high polymer, an organic solvent and hydrochloric acid to obtain a spinning precursor; the volume ratio of the organic solvent to the hydrochloric acid is 4-5 mL, 50-170 mu L; the mass concentration of the hydrochloric acid is 35-40%;
(2) Carrying out electrostatic spinning by adopting the obtained spinning precursor, and then sequentially carrying out primary heat treatment and secondary heat treatment to obtain Fe 2 (MoO 4 ) 3 。
Preferably, the iron source is ferric nitrate, the molybdenum source is ammonium molybdate, and the mass ratio of the iron source to the molybdenum source to the polymer is 0.08-0.13:0.05-0.09:0.9.
Preferably, the organic solvent comprises N, N-dimethylformamide, and the dosage ratio of the iron source to the organic solvent is 0.08-0.13 g:4.2-5.4 mL.
Preferably, the inner diameter of the injector used for electrostatic spinning is 0.4-0.8 mm, the receiving distance is 15-19 cm, the voltage is 15-19 KV, the injection speed is 0.1-0.2 mL/h, and the environmental humidity is 45-55%.
Preferably, the temperature of the primary heat treatment is 230-270 ℃ and the time is 0.5-1.5 h; the temperature of the secondary heat treatment is 530-570 ℃ and the time is 2-4 h; the rate of heating to the primary heat treatment and the rate of heating to the secondary heat treatment are independently 3-7 ℃/min.
Preferably, the primary heat treatment and the secondary heat treatment are both performed under an air atmosphere.
The invention synthesizes the primary spinning material by adopting an electrostatic spinning method, and synthesizes Fe by heat treatment 2 (MoO 4 ) 3 The nano material is subjected to material element analysis and morphology analysis through XPS, TG, XRD, SEM and TEM. The prepared sample is applied to LIBs cathode, fe 2 (MoO 4 ) 3 The electrode exhibits excellent cycle stability and high conductivity.
The method takes HCl solution as a regulator to prepare Fe 2 (MoO 4 ) 3 Nanomaterial and applied to LIBs electrodes. When the HCl solution is 110 mu l (FMO-110), the electrode has very good electrochemical performance, the electrode is charged and discharged at a current density of 1A/g, the first-circle discharge capacity is 1130.6mAh/g, and after 400 cycles, the discharge capacity is kept at 901.7mAh/g. The samples prepared with HCl solutions of 50 (FMO-50), 110 (FMO-110), 170 (FMO-170) were found to have more stable circulation performance with losses per cycle of 0.141%, 0.051% and 0.119%, respectively. In addition, the FMO-110 electrode has very small charge transfer resistance in EIS spectra, which suggests that hydrochloric acid improves the conductivity properties of the electrode material.
Drawings
FIG. 1 is an XRD pattern for a FMO-110 sample;
FIG. 2 is an X-ray photoelectron spectroscopy of FMO-110 sample: wherein (a) a full spectrum, (b) Fe 2p, (c) O1 s, and (d) Mo3d;
FIG. 3 is a TG plot of FMO-110;
FIG. 4 is an SEM of the as-spun fiber of FMO-110 and a TEM of the sample of FMO-110; wherein (a) is a SEM image of as-spun fibers (5 μm), (b) is a SEM image of as-spun fibers (500 nm), and (c) is a TEM image of FMO-110;
FIG. 5 is a CV plot of FMO-110 samples;
FIG. 6 is a plot of charge and discharge voltage for FMO-110 sample electrodes;
FIG. 7 is a graph of FMO-110 sample half cell cycle performance and coulombic efficiency;
FIG. 8 is a graph of FMO-110 sample half cell rate performance;
FIG. 9 is a chart of FMO-110 sample half cell electrochemical impedance testing;
FIG. 10 is a graph showing the contribution of various portions of the total charge storage of FMO-110 electrode sample, (a) CV curves at scan speeds of 0.2-5 mV/s; (b) a corresponding log (i) vs. log (v) plot of the negative electrode; (c-g) are graphical estimates of pseudocapacitance contributions at scan rates of 0.2, 0.5, 1.0, 2.0 and 5.0mV/s, respectively; (h) The contribution of pseudocapacitance and diffusion control effects to the total charge storage;
FIG. 11 is an XRD pattern and half cell cycle performance plot of FMO-50 samples; (a) is XRD pattern, and (b) is half cell cycle performance pattern;
FIG. 12 is an XRD pattern and half cell cycle performance plot of FMO-170 samples; (a) is XRD pattern, and (b) is half cell cycle performance pattern.
Detailed Description
The invention provides a method for preparing Fe by electrostatic spinning 2 (MoO 4 ) 3 Comprising the steps of:
(1) Mixing an iron source, a molybdenum source, a high polymer, an organic solvent and hydrochloric acid to obtain a spinning precursor; the volume ratio of the organic solvent to the hydrochloric acid is 4-5 mL, 50-170 mu L; the mass concentration of the hydrochloric acid is 35-40%;
(2) Using the spinning precursorCarrying out primary heat treatment and secondary heat treatment in sequence after electrostatic spinning to obtain Fe 2 (MoO 4 ) 3 。
In the present invention, the iron source is ferric nitrate, and may be specifically commercially available Fe (NO 3 ) 3 ·9H 2 O; the molybdenum source is ammonium molybdate, which may be specifically commercially available (NH 4 ) 6 Mo 7 O 24 ·4H 2 O; the high polymer is polyvinylpyrrolidone, the molecular weight is preferably 1800000, and the high polymer can be PVP and K90 sold in the market; the mass ratio of the iron source to the molybdenum source to the polymer is 0.08-0.13:0.05-0.09:0.9, preferably 0.09-0.12:0.06-0.08:0.9, and more preferably 0.105-0.108 g:0.065-0.075:0.9.
In the present invention, the organic solvent contains N, N-dimethylformamide, and the ratio of the iron source to the organic solvent is 0.08 to 0.13g:4.2 to 5.4mL, preferably 0.09 to 0.12g:4.4 to 5.2mL, and more preferably 0.105 to 0.108g:4.6 to 5.0mL.
In the present invention, the volume ratio of the organic solvent to the hydrochloric acid is 4 to 5mL, 50 to 170. Mu.L, preferably 4 to 5mL, 70 to 150. Mu.L, more preferably 4 to 5mL, 100 to 120. Mu.L, and even more preferably 4 to 5mL, 110. Mu.L; the mass concentration of the hydrochloric acid is 35-40%, preferably 37-38%.
In the invention, the inner diameter of the injector used for electrostatic spinning is 0.4-0.8 mm, preferably 0.5-0.6 mm; the receiving distance is 15 to 19cm, preferably 16 to 18cm, more preferably 17cm; the voltage is 15-19 KV, preferably 16-18 KV, and more preferably 17KV; the injection rate is 0.1 to 0.2mL/h, preferably 0.13 to 0.17mL/h, and more preferably 0.15 to 0.16mL/h; the ambient humidity is 45 to 55%, preferably 48 to 52%, and more preferably 50%.
In the present invention, the temperature of the primary heat treatment is 230 to 270 ℃, preferably 240 to 260 ℃, and more preferably 250 to 255 ℃; the time is 0.5 to 1.5 hours, preferably 0.8 to 1.2 hours, and more preferably 1 to 1.1 hours; the temperature of the secondary heat treatment is 530-570 ℃, preferably 540-560 ℃, and more preferably 550-555 ℃; the time is 2 to 4 hours, preferably 2.5 to 3.5 hours, and more preferably 3 to 3.2 hours; the rate of heating to the primary heat treatment and the rate of heating to the secondary heat treatment are independently 3 to 7 ℃/min, preferably 4 to 6 ℃/min, and more preferably 5 ℃/min.
In the present invention, the primary heat treatment and the secondary heat treatment are both performed under an air atmosphere.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
S1: 0.1077g of analytically pure ferric nitrate nonahydrate and 0.0706g of ammonium molybdate tetrahydrate are weighed and dissolved in 4.8ml of DMF, 110 μl of 37% HCl solution is added and stirred at room temperature for 20min to obtain a clear liquid, and 0.9g of PVP (k 90) is added and stirred uniformly to form a spinning precursor.
S2: the spinning precursors were moved to a syringe with a stainless steel needle having an inner diameter of 0.6mm, the parameters set as follows: the receiving distance is 17cm, the voltage is 17kV, the injection speed is 0.15mL/h, the humidity is 50%, and then the electrostatic spinning is started at room temperature;
s3: the primary spinning material obtained by electrostatic spinning is heated to 250 ℃ at the heating rate of 5 ℃/min for 1h under the air atmosphere, and then is heated to 550 ℃ for 2h, thus obtaining Fe 2 (MoO 4 ) 3 Nanomaterial (denoted as FMO-110).
S4: weighing the prepared nano material, acetylene black and CMC (sodium carboxymethylcellulose) according to a certain mass ratio of 8:1:1, adding 0.3ml of deionized water, and stirring for 10 hours; uniformly adhering the stirred electrode slurry to foam nickel, and drying in an oven at 80 ℃ for 12 hours to obtain Fe 2 (MoO 4 ) 3 An electrode;
s5: the present example produced half-cells, but in practical cells, the resulting nanomaterial could be used as the negative electrode of the cell. The composite electrode is assembled in a glove box filled with argon, a foam nickel electrode adhered with an active substance is used as a LIBs positive electrode, a lithium sheet is used as a battery negative electrode, gelgard2400 is used as a diaphragm, a proper amount of electrolyte is dripped, a CR2032 button cell is assembled, and electrochemical performance test is carried out.
Example 2
The sample obtained was designated FMO-50 as in example 1, except that 50. Mu.l of HCl solution was added.
Example 3
The sample obtained was designated FMO-170 as in example 1, except that the HCl solution was added at 170. Mu.l.
As shown in FIG. 1, XRD patterns of FMO-110 samples obtained in example 1 at a hydrochloric acid level of 110. Mu.l, the results obtained for the samples and Fe can be seen from the patterns 2 (MoO 4 ) 3 The standard card (PDF # 72-0935) of (C) was well matched, indicating that the prepared sample contained Fe 2 (MoO 4 ) 3 。
As shown in FIG. 2, the XPS scan spectrum and the fitted curve of the FMO-110 sample prepared in example 1. Fig. 2 (a) shows that the XPS spectra of the samples detected characteristic signals of Fe, mo and O, confirming the expected composition of the product, and the results are consistent with XRD results. Further researching the chemical states of Fe, mo and O elements, and fitting each peak in the spectrogram respectively. FIG. 2 (b) shows an X-ray electron spectrum of Fe 2p, wherein two main peaks at 725.5 and 711.7eV indicate that Fe in the sample is trivalent, two satellite peaks appear at 728.4 and 714.6eV on the sides of the peaks, and further prove that Fe 3+ Exists. The X-ray electron energy spectrum of O1 s can be superimposed as two curves as shown in fig. 2 (c). FIG. 2 (d) XPS spectrum of Mo3d region shows 232.6eV (Mo 3d 5/2 ) And 235.8eV (Mo 3 d) 3/2 ) Due to Mo 6+ . The chemical states of Mo, fe and O well define Fe 2 (MoO 4 ) 3 Is present. As a result of the XRD pattern shown in FIG. 1, the sample obtained in example 1 was Fe 2 (MoO 4 ) 3 A nanomaterial.
As shown in FIG. 3, fe prepared in example 1 2 (MoO 4 ) 3 The as-spun material was heated in air from room temperature to 1000 ℃ at a heating rate of 10 ℃/min, resulting in a corresponding TGA profile. The weight loss below 190 ℃ is 12.6%, mainly caused by volatilization of residual DMF in spinning and water of crystallization in the material. The weight loss ratio is 18.8% at 190-250deg.C, which is attributable to the decomposition of ferric nitrate and ammonium molybdate to generate gas and the decomposition of PVPSo that. TG curves also show a major weight loss step from 250 ℃ to 480 ℃ with a weight loss of 59.2% due to complete decomposition of PVP. There was substantially no loss of mass in the temperature change after 480 ℃.
As shown in FIG. 4, the SEM of the as-spun fiber and the TEM of FMO-110 were obtained in example 1. It can be seen from fig. 4 (a) and (b) that the as-spun fiber surface is smooth. After high temperature annealing, smooth surface in the FMO-110 sample (FIG. 4 (c)) was granulated at 550℃and particle size around 220nm, the nanomaterial appeared to have a crosslinked structure.
As shown in FIG. 5, the first three Cyclic Voltammetry (CV) curves of the sample prepared in example 1, these curves are compared with Fe 2 (MoO 4 ) 3 Sample XRD testing was combined to explain Fe 2 (MoO 4 ) 3 Is used for the lithiation/delithiation of the polymer.
As shown in FIG. 6, the capacity voltage curve of the sample obtained in example 1 shows that the initial cycle coulombic efficiency of the FMO-110 electrode is 76.6%. The large irreversible capacity of the sample in the first cycle is due to the decomposition of the electrolyte and the formation of the SEI layer during the first discharge, with distinct discharge plateaus around about 0.2V, 0.6V and 1.3V, which are the result of the redox reaction, consistent with the analysis in CV. In the subsequent cycles, it can be seen that FMO-110 sample capacity retention works well.
As shown in FIG. 7, the sample prepared in example 1 has a current density of 1A/g at room temperature, and a performance chart of 400 cycles. As can be seen from the graph, the initial discharge capacity of FMO-110 is 1130.6mAh/g, and the first charge is 865.8mAh/g. In subsequent cycles, the specific capacity undergoes various levels of descent and ascent. Notably, after the decay period, the specific battery capacity begins to steadily rise back. FMO-110 is finally stabilized at 901.7mAh/g after two rounds of rising and 400 times of circulation, and is kept at a high current density (1A/g) for a long time, and the average specific capacity of each circulation is reduced by only 0.051%, which indicates that the material has excellent circulation performance.
As shown in FIG. 8, the sample electrode obtained in example 1 was subjected to a rate performance test in which the current density was increased from 1A/g to 20A/g and then decreased from 20A/g to 1A/g. FMO-110 still provides a reversible capacity of 140mAh/g at a high current density of 20A/g, and when the current density is returned to 1A/g, the discharge capacity of the battery is returned to 747.5mAh/g. Since the battery has a decay period, the full capacity of the corresponding current cannot be recovered, but can correspond to the capacity in the cyclic test, which indicates that the battery has good rate capability.
As shown in FIG. 9, the Nyquist plot of the sample prepared in example 1, wherein the scattered points represent the measured EIS raw data and the solid lines represent the fitted curve. The equivalent circuit diagram model used to fit the EIS data is shown in the lower right hand corner of fig. 9. Fitting is performed according to an inserted equivalent circuit, and the charge transfer resistance of the sample is found to be very small and is only 220.3 omega, which indicates that the FMO-110 has very good conductivity.
As shown in FIG. 10, the extent of contribution of each portion of the total charge storage of the FMO-110 electrode sample prepared in example 1 can be determined by comparing the ratio of Li/Li at different scan rates of 0.2-5.0mV/s + A series of CV diagrams were determined (fig. 10 a). The b values of the cathode and anode were 0.65 and 0.82, respectively, after fitting and analysis (fig. 10 b), indicating that the capacitance was dominant in the L-FMO anode lithium ion storage. Further calculation of capacitance contribution rate as shown in FIGS. 10c-g, the pseudocapacitance contribution rate in the FMO-110 component electrode increased from 48.82% (scan rate 0.2 mV/s) to 93.85% (scan rate 5 mV/s) with increasing scan rate.
As shown in FIG. 11, XRD patterns (FIG. 11 a) of FMO-50 samples obtained in example 2 at a hydrochloric acid level of 50. Mu.l were obtained, the results obtained for the samples in the figure being correlated with Fe 2 (MoO 4 ) 3 The standard card (PDF # 72-0935) of (C) was well matched, indicating that the prepared sample was Fe 2 (MoO 4 ) 3 . FIG. 11b is a graph of the performance of the sample at room temperature using a current density of 1A/g over 400 cycles. As can be seen from the figure, the initial capacity of FMO-50 is 1152.9mAh/g, the first charge is 919mAh/g, and the capacity after 400 cycles is stabilized at 503.5mAh/g.
As shown in FIG. 12, the XRD pattern of the FMO-170 sample obtained in example 1 at 170. Mu.l hydrochloric acid level (FIG. 12 a) is shown, the results obtained for the sample obtained in the figure are related to Fe 2 (MoO 4 ) 3 Standard card (PDF #72-0935 Good matching, and the prepared sample is Fe 2 (MoO 4 ) 3 . FIG. 12b is a graph of the performance of the sample at room temperature using a current density of 1A/g over 400 cycles. As can be seen from the figure, FMO-170 has an initial capacity of 1220.7mAh/g, a first charge of 921.1mAh/g, and a capacity of 641mAh/g after 400 cycles.
The invention combines electrostatic spinning with heat treatment, and prepares Fe by changing the content of HCl solution 2 (MoO 4 ) 3 Nanomaterial and applied to LIBs cathodes. Of these, FMO-110 possesses the most excellent long cycle and rate capability, and the specific capacity remains 901.7mAh/g even after 400 cycles at high current density (1A/g). The result of the invention will be Fe 2 (MoO 4 ) 3 The research of the cathode material provides a new idea.
Comparative example 1
Otherwise, as in example 1, the molybdenum source can not be completely dissolved when preparing the spinning precursor by reducing the amount of HCl solution to 50 μl; the HCl solution is increased to 170 mu l, and is extremely easy to be wet and liquefied in the spinning process; therefore, too much acid will greatly affect the spinning effect and Fe will not be produced 2 (MoO 4 ) 3 A nanomaterial.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (3)
1. Electrostatic spinning preparation of Fe 2 (MoO 4 ) 3 Is characterized by comprising the following steps:
(1) Mixing an iron source, a molybdenum source, a high polymer, an organic solvent and hydrochloric acid to obtain a spinning precursor; the volume ratio of the organic solvent to the hydrochloric acid is 4-5 mL, 50-170 mu L; the mass concentration of the hydrochloric acid is 35-40%;
(2) Carrying out electrostatic spinning by adopting the obtained spinning precursor, and then sequentially carrying out primary heat treatment and secondary heat treatment to obtain Fe 2 (MoO 4 ) 3 ；
The iron source is ferric nitrate, the molybdenum source is ammonium molybdate, and the mass ratio of the iron source to the molybdenum source to the polymer is 0.08-0.13:0.05-0.09:0.9;
the dosage ratio of the iron source to the organic solvent is 0.08-0.13 g:4.2-5.4 mL;
the organic solvent comprises N, N-dimethylformamide;
the temperature of the primary heat treatment is 230-270 ℃ and the time is 0.5-1.5 h; the temperature of the secondary heat treatment is 530-570 ℃ and the time is 2-4 h; the rate of heating to the primary heat treatment and the rate of heating to the secondary heat treatment are independently 3-7 ℃/min;
the receiving distance of the electrostatic spinning is 15-19 cm, the voltage is 15-19 KV, the injection speed is 0.1-0.2 mL/h, and the environmental humidity is 45-55%;
preparation of Fe 2 (MoO 4 ) 3 Nanomaterial and applied to LIBs electrodes.
2. The method according to claim 1, wherein the inside diameter of the syringe used for the electrospinning is 0.4 to 0.8mm.
3. The method of claim 1, wherein the primary heat treatment and the secondary heat treatment are both performed under an air atmosphere.
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| "Experimental and DFT study of peapod-like Fe2(MoO4)3 nanofibers for photodegradation of ciprofloxacin";Jiashun Lv等;《Materials Letters》(第第290期期);第1页第3段，附加信息页第2页第1-2段 * |
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