CN108172406B - FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material - Google Patents
FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention relates to a method for preparing FeS2‑xSexThe material is a sodium ion capacitor of the negative electrode material, the sodium ion capacitor comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, the negative plate is obtained by mixing an active material, a conductive agent and a binder, then adding a solvent to mix into slurry, and then coating the slurry on a current collector; the active material in the negative plate of the capacitor is FeS2‑xSexMaterial, x is 0.1-1. FeS adopted by the negative electrode material of the sodium ion capacitor2‑xSexMaterial, in contrast to FeS2The peak position of the XRD diffraction pattern is slightly shifted to the left, which shows that the interlayer spacing is increased, and sodium ions are more favorably embedded and removed; at the same time, Na+Faster diffusion, enhanced electronic conductivity, greatly improved high-current charge and discharge capacity, i.e. power performance, of the sodium ion capacitor, and the power density is 172W kg‑1When the energy density is up to 67Wh kg‑1Even at 2543W kg‑1At higher power density, the energy density was still maintained at-27 Wh kg‑1。
Description
The technical field is as follows:
the invention relates to a method for preparing FeS2-xSexA sodium ion capacitor taking a cathode material as a material belongs to the technical field of capacitors.
Background art:
electrochemical energy storage devices, particularly lithium ion batteries, are widely applied to portable electronic devices, electric vehicles, power stations and the like, are one of electrochemical energy storage devices which are most mature in technical development and most widely applied at present, however, the abundance of lithium in the earth crust is very low. With the increasing demand of new energy industry for lithium ion batteries, greater demand is put on the amount of lithium resources, and the rarity of the lithium resources greatly limits the rapid development of the lithium ion batteries in large-scale energy storage devices, and the lithium ion batteries have low power density and are also limited to be applied in high-power occasions. Therefore, the search for new high-performance energy storage devices that can replace lithium resources and develop next generation is an urgent problem.
The sodium metal and the lithium metal are in the I main group of the periodic table and have similar behaviors in the electrochemical reaction process, so that the lithium in the conventional lithium ion energy storage battery can be replaced by the sodium, the abundance of the sodium metal in the earth crust is far higher than that of the lithium metal, abundant sodium resources are contained in wide oceans, and the cost is low. Therefore, it is important to develop a high energy density and high power density energy storage device based on sodium ions.
Transition metal sulfides/selenides (TMSs) have entered the eye of people because of their properties of higher specific capacity, enhanced electrical conductivity, moderate M-S bond energy, diverse crystal structures, etc. One representative transition metal sulfide/selenide is FeS2Microspheres that exhibit excellent cycling stability (90% capacity retained after 2 ten thousand cycles) and rate capability (170mAh g) at a voltage window of 0.8-3.0V-1At 20Ag-1)[Energy Environ.Sci.2015,8,1309.]. Similarly superior cycling performance and higher rate performance are also observed in other sulfides/selenides, such as FeSe2Microspheres [ adv. mater.2015,27,3305.](ii) a N-doped carbon/CoS nanotubes [ angelw chem. int. ed.2016,55,15831.](ii) a Sea urchin shaped CoSe2Nanostructure [ adv.funct.mater.2016,26,6728.](ii) a CuS nanosheet/Reduced Graphene Oxide (RGO) [ ACS appl.mater.interface 2017,9,2309.]；SnS0.5Se0.5Powder [ NanoEnergy 2017,41,377.]； MoSe2N, P codoped rGO [ adv.Funct.Mater.2017,27,1700522.]；VS2Nanosheet [ adv.mater.2017, 29,1702061]And so on. However, these sulfides/selenides undergo multiple redox reactions during cycling, resulting in severe voltage plateau overlap or ramps in the constant current charge-discharge curve, which would greatly impact the practical application of transition metal sulfides/selenides, as they are neither single nor quasi-single voltage plateau electrodes. Worse still, many redox reactions occur between 1.0 and 2.0V, which is a voltage range that is clearly too high as a negative electrode material and too low as a positive electrode material.
Sodium ion capacitorThe working principle of the device is that one electrode works by absorbing and desorbing anions on the surface, and the other electrode works by Na+And (5) de-embedding. There is no significant plateau during cycling of the sodium ion capacitor.
Through retrieval, the application of the transition metal sulfur/selenide to the sodium ion capacitor is not reported at present.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides a FeS2-xSexSodium ion capacitor taking cathode material as material, and FeS adopted by cathode material of sodium ion capacitor2-xSexMaterial, in contrast to FeS2Increased interlayer spacing, Na+The diffusion rate is accelerated, and the electronic conductivity is enhanced; the electrochemical performance of the modified material is excellent; with FeS2-xSexThe power density of the sodium ion capacitor obtained by taking the material as the negative electrode material is 172W kg-1When the energy density is up to 67Wh kg-1Even at 2543Wkg-1At higher power density, the energy density was still maintained at 27Wh kg-1。
The technical scheme of the invention is as follows:
FeS is used as a catalyst2-xSexThe material is a sodium ion capacitor of the negative pole material, the sodium ion capacitor includes positive plate, negative plate, diaphragm, electrolyte and outer casing, the negative plate is obtained by mixing active material, conductive agent, binder, then adding solvent, grinding into slurry and coating on the current collector; the active material in the negative plate of the capacitor is FeS2-xSexMaterial, FeS2- xSexThe material is granular, the granularity is 1-3 mu m, the interior of the granule is solid, x is 0.1-1, and the molar sum proportion of Fe, Se and S is as follows: 1:2-4.
Preferably, in the negative electrode sheet, the conductive agent is acetylene black, the binder is polyvinylidene fluoride (PVDF), the solvent is methyl pyrrolidone (NMP), and the active material: conductive agent: the mass ratio of the binder is (60-80): (10-30): (5-15); the current collector is mostly a copper foil, a porous titanium mesh or a porous stainless steel mesh.
According toPreferably, the negative plate is prepared by mixing the active material, the conductive agent and the binder, adding the solvent, grinding into slurry, coating on the current collector, vacuum drying at 50-70 ℃, rolling after drying, and cutting into the plate, wherein the mass of the active material per unit area is 1.0-1.5mg cm-2。
According to the invention, the positive plate is preferably prepared by the following method: uniformly mixing active carbon, acetylene black and sodium carboxymethylcellulose, dripping water, and grinding into paste, wherein the mass ratio of the active carbon to the acetylene black to the sodium carboxymethylcellulose is 8: 1: 1; the prepared paste slurry is evenly coated on an aluminum foil, vacuum drying is carried out at 50-70 ℃ after coating, rolling and cutting are carried out after drying, and the positive plate is prepared.
According to the invention, the active carbon in the positive plate and the FeS in the negative plate are preferred2-xSexThe mass ratio of the materials is controlled to be (3-6): 1.
According to the invention, the electrolyte is preferably NaClO4Dissolved in tetraethylene glycol dimethyl ether, NaClO4The concentration of (A) is 0.5-2 mol/L; the membrane material was Whatman GF/F glass microfiber.
Preferred according to the invention is the active material FeS2-xSexIs prepared by the following method:
dissolving an iron source and urea in a mixed solvent of dimethylformamide and ethylene glycol, and then adding a sulfur source and a selenium source to obtain a mixed solution; reacting the mixed solution at the high temperature of 170-210 ℃ for 16-22 h, centrifuging the product, sequentially washing with ethanol and water, and then drying in vacuum to obtain FeS2-xSexSolid solution microspheres.
According to the invention, the iron source is FeSO4·7H2O or Fe (NO)3)2。
Preferably, according to the invention, the sulphur source is sublimed sulphur.
According to the invention, the selenium source is preferably pure selenium powder.
According to the invention, the mole ratio of the added iron source to the urea is: 1:4-6.
According to the invention, the volume ratio of the dimethyl formamide to the ethylene glycol in the mixed solvent is (10-15): (15-20).
According to the invention, the mass volume ratio of the added iron source to the mixed solvent is preferably as follows: (0.5-2): (30-40); unit: mmol/mL.
According to the invention, the adding amount of the iron source and the total molar amount of the sulfur source and the selenium source are as follows: 1:5-7.
Preferably, according to the invention, the molar ratio of the sulphur source to the selenium source is (1-3): (1-9).
According to the invention, the vacuum drying temperature is preferably 50-70 ℃ and the drying time is preferably 8-16 h.
The amount of the solvent added into the slurry of the negative plate and the amount of the water added into the slurry of the positive plate are carried out according to the conventional means in the field based on the capability of stirring into the slurry.
The principle of the invention is as follows:
the active material FeS adopted by the negative electrode material of the sodium-ion capacitor2-xSexWith FeSO4·7H2O, urea, sublimed sulfur and selenium powder are taken as raw materials, Dimethylformamide (DMF) and Ethylene Glycol (EG) are taken as solvents, the FeS with different contents can be successfully obtained by changing the S/Se content through the solvothermal reaction2-xSexAnd (3) sampling. The synergistic effect of the S/Se solid solution increases the interlayer spacing and the electronic conductivity of the material, is beneficial to the diffusion of sodium ions in the material, greatly improves the dynamic performance of the material as a cathode material of a sodium ion capacitor, and has high reversible capacity of electrochemical sodium storage and excellent cycle performance.
The sodium ion capacitor of the invention has the following remarkable characteristics:
1. FeS adopted by the negative electrode material of the sodium ion capacitor2-xSexMaterial, in contrast to FeS2The peak position of the XRD diffraction pattern is slightly shifted to the left, which shows that the interlayer spacing is increased, and sodium ions are more favorably embedded and removed; at the same time, Na+The diffusion is faster, the electronic conductivity is enhanced, and the electrochemical performance of the modified material is excellent; sodium ions can be rapidly embedded in/removed from the material, so that the large electricity of the sodium ion capacitor is greatly improvedThe current charging and discharging capability, i.e. the power performance, the stored energy is well maintained even at high currents.
2. FeS adopted by the negative electrode material of the sodium ion capacitor2-xSexMaterial in 2Ag-1The current density of the capacitor is 6000 cycles, and the capacity is still maintained at 220mAh g-1About, the attenuation rate per turn is as low as 0.0044%. At 40Ag-1The capacity of the capacitor is still maintained at 211mAh g at a high current density-1Left and right.
3. The power density of the sodium ion capacitor is 172W kg-1When the energy density is up to 67Wh kg-1Even at 2543W kg-1At higher power density, the energy density was still maintained at 27Wh kg-1。
4. The sodium ion capacitor of the invention has a current density of 1Ag-1(the current density is based on FeS2-xSexAnd total mass of activated carbon), the specific energy is still maintained at 34Wh kg after 1000 cycles of circulation-1。
5. The sodium ion hybrid capacitor system FeS of the invention2-xSexThe application of the sulfur/selenide to the sodium-ion capacitor is firstly proposed, the dilemma that the number of voltage platforms is large and the potential is embarrassed when common transition metal sulfide/selenide is used for a sodium-ion battery is avoided, and the novel application of the sulfide/selenide in the aspect of electrochemical energy storage is proposed.
Description of the drawings:
FIG. 1 shows FeS used as the cathode material of the sodium-ion capacitor of the present invention2-xSexXRD diffraction pattern of the material.
FIG. 2 shows FeS used as the cathode material of the sodium-ion capacitor of the present invention2-xSexScanning electron micrographs of the material; a is a scanning electron microscope with a magnification of 5 μm, and b is a scanning electron microscope with a magnification of 1 μm.
FIG. 3 shows FeS used as the cathode material of the sodium-ion capacitor of the present invention2-xSexThe elements of the material map the photograph.
FIG. 4 shows FeS used as the cathode material of the sodium-ion capacitor of the present invention2-xSexImpedance diagram and state density diagram of the material in a sodium ion half cell, wherein a is FeS2-xSexMaterials and FeS2Impedance comparison of samples, b is FeS2-xSexMaterials and FeS2Density of states plot for the sample.
FIG. 5 shows FeS used as the cathode material of the sodium-ion capacitor of the present invention2-xSexElectrochemical performance diagram of the material in a sodium ion half cell, wherein a is FeS2-xSexThe material is 2Ag-1Cycle performance under current density, b is FeS2-xSexAnd (3) a rate performance graph of the material under different current densities.
FIG. 6 is a graph of the electrochemical performance of the sodium-ion capacitor of the present invention, in which a is a graph showing the charge and discharge curves of the capacitor of example 1 at different current densities, b is a graph showing the energy comparison of the capacitor (Ragon plots), and c is a graph showing the energy comparison of the capacitor at 1A g-1(the current density calculation is based on FeS2-xSexAnd total mass of activated carbon).
The specific implementation mode is as follows:
the invention is explained in more detail below with reference to the figures and examples.
The raw materials in the examples are all commercial products.
Example 1
FeS is used as a catalyst2-xSexThe material is a sodium ion capacitor of a negative electrode material, and the sodium ion capacitor comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell.
The mass ratio of the active material in the positive plate to the active material in the negative plate is controlled to be 4:1, and the electrolyte is NaClO4Dissolved in tetraethylene glycol dimethyl ether, NaClO4The concentration of (A) is 1 mol/L; the membrane material was Whatman GF/F glass microfiber.
The negative plate is prepared by mixing an active material, a conductive agent and a binder, adding a solvent, grinding into slurry and coating the slurry on a copper foil; the active material in the negative plate of the capacitor is FeS2-xSexThe material comprises acetylene black as conductive agent, polyvinylidene fluoride (PVDF) as binder, and methyl as solventPyrrolidone (NMP), active material: conductive agent: the mass ratio of the binder is as follows: 70:20:10, and the preparation method of the negative plate comprises the following steps: FeS2-xSexUniformly dispersing materials, acetylene black and polyvinylidene fluoride in a proper amount of methyl pyrrolidone (NMP), grinding for 30min by hand to prepare paste slurry, then uniformly coating the slurry on a copper foil, and then drying in vacuum at 60 ℃; rolling the dried copper foil, cutting into round pieces with active substance mass per unit area of 1.0-1.5mg cm-2；
The positive plate is prepared by the following method: uniformly mixing active carbon, acetylene black and sodium carboxymethylcellulose, dripping water, and grinding into pasty slurry, wherein the mass ratio of the active carbon to the acetylene black to the sodium carboxymethylcellulose is 8: 1: 1; the prepared paste slurry is evenly coated on an aluminum foil, vacuum drying is carried out at 60 ℃ after coating, rolling and cutting are carried out after drying, and the positive plate is prepared.
Active material FeS in negative plate2-xSexThe material is granular, the granularity is 3 mu m, the interior of the granules is solid, and x is 0.4.
FeS2-xSexThe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; the total molar weight of sublimed sulfur and selenium powder is 6.5mmol, and the molar ratio of sublimed sulfur to selenium powder is 1: 4;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 18h at 190 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain FeS2- xSex(x ═ 0.4) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Performance testing
One, to FeS2-xSexThe XRD test shows that the diffraction pattern is shown in figure 1, and the Se doping is shown in figure 1The phase of the sample is not changed, and all diffraction peaks can correspond to XRD standard card JCPDS No.42-1340, FeS2-xSexSample vs FeS2The XRD diffraction peak of (A) is slightly shifted to a low angle, which shows that the introduction of Se leads the lattice spacing of Se to be larger, and sodium ions are more favorably intercalated and deintercalated. For the prepared FeS2-xSexThe sample material is analyzed by scanning electron microscope, the scanning electron microscope photo is shown in figure 2, and FeS can be seen from figure 22-xSexThe sample is a microsphere consisting of small particles. For the prepared FeS2-xSexThe elemental mapping photograph of the sample material is shown in fig. 3, and it can be seen from fig. 3 that the Fe, S, and Se elements are uniformly distributed, thereby proving the formation of the solid solution again.
Electrochemical performance test
And (3) testing the performance of the sodium ion half cell:
to verify FeS2-xSexElectrical properties of the material, in FeS2-xSexThe material is a negative electrode material, the sodium sheet is a reference electrode and a counter electrode, a sodium ion half cell is assembled, the electrochemical performance is represented, and the negative electrode is prepared: FeS2-xSexUniformly dispersing materials, acetylene black and polyvinylidene fluoride in a proper amount of methyl pyrrolidone (NMP), grinding for 30min by hand to prepare paste slurry, then uniformly coating the slurry on a copper foil, and then drying in vacuum at 60 ℃; rolling the dried copper foil to obtain negative electrode, sodium sheet as reference electrode and counter electrode, Whatman GF/F glass microfiber as diaphragm, and 1.0M NaCF3SO3Dissolution in diethylene glycol dimethyl ether (DGM) as an electrolyte was carried out in an argon-filled glove box (Mikrouna, Super 1220/750/900). The charging and discharging test of the battery is carried out on a blue electricity (Land CT-2001A) test system, and the working range of the battery is 0.8-3.0V. FIG. 4a shows FeS obtained in example 12-xSexSample and unmodified FeS2Impedance of the materials is shown in comparison, 4b is FeS obtained in example 12- xSexSample and unmodified FeS2Density of states plot of material. As can be seen in FIG. 4, FeS2-xSexSample vs FeS2Conducting electricityThe sexual activity is obviously enhanced. FIG. 5a is a graph of FeS prepared in example 12-xSexSample at 2Ag-1Plot of cycling behavior at Current Density, plot b FeS from example 12-xSexAnd (3) a rate performance graph of the material under different current densities. As can be seen in FIG. 5, FeS2-xSexThe sample has excellent cycle performance and rate performance.
And (3) testing the performance of the sodium ion capacitor:
electrochemical performance was performed at different current densities on the capacitors assembled in the examples, and the results of the test are shown in fig. 6, where the negative electrode was electrochemically activated several times before the capacitor was assembled. FeS2-xSexThe specific capacity calculation of/AC is based on FeS2-xSexAnd the total mass of AC. FIG. 6a is a graph showing the charge and discharge curves of the capacitor of example 1 at different current densities, b is a graph showing the energy comparison (Ragon plots) of the capacitor of example 1, and c is a graph showing the energy comparison (Ragon plots) of the capacitor of example 1 at 1Ag-1(the current density calculation is based on FeS2-xSexAnd total mass of activated carbon). As can be seen from FIG. 6, the power density is 172W kg-1When the energy density is up to 67Wh kg-1Even at 2543W kg-1At higher power density, the energy density was still maintained at 27Wh kg-1. In addition, in 1Ag-1Under the condition of high current density, the specific energy is still maintained at 34Wh kg after 1000 cycles-1。
Example 2
FeS is used as a catalyst2-xSexThe sodium ion capacitor with the material as the negative electrode material is the same as that shown in the embodiment 1, except that:
FeS2-xSexthe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; the total molar weight of sublimed sulfur and selenium powder is 6.5mmol, and the molar ratio of sublimed sulfur to selenium powder is 1: 9;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 22 hours at 170 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 50 deg.C for 16h to obtain FeS2- xSex(x ═ 0.2) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Example 3
FeS is used as a catalyst2-xSexThe sodium ion capacitor with the material as the negative electrode material is the same as that shown in the embodiment 1, except that:
FeS2-xSexthe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; the total molar weight of sublimed sulfur and selenium powder is 6.5mmol, and the molar ratio of sublimed sulfur to selenium powder is 1: 9;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 20 hours at 180 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 52 deg.C for 14h to obtain FeS2- xSex(x ═ 0.2) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Example 4
FeS is used as a catalyst2-xSexThe sodium ion capacitor with the material as the negative electrode material is the same as that shown in the embodiment 1, except that:
FeS2-xSexthe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; the total molar weight of sublimed sulfur and selenium powder is 6.5mmol, sublimed sulfur and selenium powderThe molar ratio of the selenium powder is 1: 4;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 16 hours at 200 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain FeS2- xSex(x ═ 0.4) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Example 5
FeS is used as a catalyst2-xSexThe sodium ion capacitor with the material as the negative electrode material is the same as that shown in the embodiment 1, except that:
FeS2-xSexthe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; the total molar weight of sublimed sulfur and selenium powder is 6.5mmol, and the molar ratio of sublimed sulfur to selenium powder is 3: 7;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 17 hours at 200 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain FeS2- xSex(x ═ 0.4) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Example 6
FeS is used as a catalyst2-xSexThe sodium ion capacitor with the material as the negative electrode material is the same as that shown in the embodiment 1, except that:
FeS2-xSexthe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; sublimed sulphurThe total molar weight of the sulfur powder and the selenium powder is 6.5mmol, and the molar ratio of sublimed sulfur to the selenium powder is 2: 3;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 16 hours at 210 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain FeS2- xSex(x ═ 0.8) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Example 7
FeS is used as a catalyst2-xSexThe sodium ion capacitor with the material as the negative electrode material is the same as that shown in the embodiment 1, except that:
FeS2-xSexthe preparation method of the material comprises the following steps:
(1) 1mmol of FeSO4·7H2Dissolving O and 5mmol of urea in a mixed solvent of dimethylformamide and ethylene glycol, wherein 15mL of dimethylformamide and 20mL of ethylene glycol are contained in the mixed solvent, and then adding sublimed sulfur and selenium powder to obtain a mixed solution; the total molar weight of sublimed sulfur and selenium powder is 6.5mmol, and the molar ratio of sublimed sulfur to selenium powder is 1: 1;
(2) transferring the mixed solution to a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and reacting for 16 hours at 210 ℃;
(3) centrifuging the product, washing with ethanol and water for several times, and drying in a vacuum drying oven at 70 deg.C for 10h to obtain FeS2- xSex(x ═ 1) microspheres. The FeS thus obtained2-xSexThe inside of the material particle is solid particle.
Claims (6)
1. FeS is used as a catalyst2-xSexThe material is a sodium ion capacitor of the negative pole material, the sodium ion capacitor includes positive plate, negative plate, diaphragm, electrolyte and outer casing, the negative plate is obtained by mixing active material, conductive agent, binder, then adding solvent, grinding into slurry and coating on the current collector; the active material in the negative plate of the capacitor is FeS2-xSexMaterial, FeS2-xSexThe material is granular with the granularity of 1-3 mu mThe inside of the grain is in a solid state, x =0.1-1, Fe: the molar ratio (Se + S) is: 1: 2;
active material FeS2-xSexIs prepared by the following method:
dissolving an iron source and urea in a mixed solvent of dimethylformamide and ethylene glycol, and then adding a sulfur source and a selenium source to obtain a mixed solution; reacting the mixed solution at the high temperature of 170-210 ℃ for 16-22 h, centrifuging the product, sequentially washing with ethanol and water, and then drying in vacuum to obtain FeS2-xSexSolid solution microspheres;
the iron source is FeSO4∙7H2O or Fe (NO)3)2The sulfur source is sublimed sulfur, and the selenium source is pure selenium powder;
the molar ratio of the added iron source to the urea is as follows: 1:4-6, wherein the volume ratio of the dimethylformamide to the glycol in the mixed solvent is (10-15): (15-20);
the molar volume ratio of the added iron source to the mixed solvent is as follows: (0.5-2): (30-40), unit: mmol/mL; the proportion of the adding amount of the iron source to the total molar amount of the sulfur source and the selenium source is as follows: 1:5-7.
2. The FeS of claim 12-xSexThe material is sodium ion capacitor of negative pole material, characterized by, the conductive agent is acetylene black in the negative pole piece, the binder is polyvinylidene fluoride (PVDF), the solvent is methyl pyrrolidone (NMP), active material: conductive agent: the mass ratio of the binder is (60-80): (10-30): (5-15); the current collector is mostly a copper foil, a porous titanium mesh or a porous stainless steel mesh.
3. The FeS of claim 12-xSexThe sodium ion capacitor with the material as the negative electrode material is characterized in that the active material, the conductive agent and the binder in the negative electrode plate are mixed and then added with the solvent, ground into slurry and coated on a current collector, the slurry is coated and then dried in vacuum at 50-70 ℃, the dried product is rolled and cut into the electrode plate, the mass of the active material on the unit area is 1.0-1.5 mgcm-2。
4. The FeS of claim 12-xSexThe sodium ion capacitor taking the material as the negative electrode material is characterized in that the positive electrode plate is prepared by the following method: uniformly mixing active carbon, acetylene black and sodium carboxymethylcellulose, dripping water, and grinding into pasty slurry, wherein the mass ratio of the active carbon to the acetylene black to the sodium carboxymethylcellulose is 8: 1: 1; the prepared paste slurry is evenly coated on an aluminum foil, vacuum drying is carried out at 50-70 ℃ after coating, rolling and cutting are carried out after drying, and the positive plate is prepared.
5. FeS according to claim 2 or 42-xSexThe sodium ion capacitor taking the negative electrode material is characterized in that active carbon in the positive electrode plate and FeS in the negative electrode plate2-xSexThe mass ratio of the materials is controlled to be (3-6) 1; the electrolyte is NaClO4Dissolved in tetraethylene glycol dimethyl ether, NaClO4The concentration of (A) is 0.5-2 mol/L; the membrane material was Whatman GF/F glass microfiber.
6. The FeS of claim 12-xSexThe sodium ion capacitor taking the material as the cathode material is characterized in that the molar ratio of the sulfur source to the selenium source is (1-3): (1-9), the vacuum drying temperature is 50-70 ℃, and the drying time is 8-16 h.
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| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
| CN107452951A (en) * | 2017-08-11 | 2017-12-08 | 西南大学 | XS2@YSe2The preparation method of the anode material of lithium-ion battery of core shell structure |
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| CN107452951A (en) * | 2017-08-11 | 2017-12-08 | 西南大学 | XS2@YSe2The preparation method of the anode material of lithium-ion battery of core shell structure |
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