CN112694079B - Heteropolyacid etching capsule-shaped hollow porous carbon shell, preparation method and application thereof in lithium-sulfur battery - Google Patents
Heteropolyacid etching capsule-shaped hollow porous carbon shell, preparation method and application thereof in lithium-sulfur battery Download PDFInfo
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Abstract
The invention provides a heteropoly acid etched capsule-shaped hollow porous carbon shell, which comprises Fe3O4、P2W18And C; the invention also provides a preparation method and application of the hollow porous carbon shell. Aiming at the defect of poor conductivity of sulfur and reaction products thereof, the invention utilizes metal organic framework material as a template body to obtain metal oxygen cluster P through a carbonization process2W18A hybrid capsule-shaped hollow porous carbon shell composite material. The prepared capsule-shaped hollow porous carbon shell composite material has the advantages that the nano-scale polyoxometallate material modified on the surface of the material framework of the composite material has high-valence transition metal elements, so that the uniform deposition of sulfur and lithium sulfide can be directionally guided, the agglomeration of the sulfur and the lithium sulfide is inhibited, and the polyoxometallate contains a large number of polar O-W-O units inside, so that polysulfide can be effectively adsorbed, and the capacity and the cycle performance of a lithium-sulfur battery are improved.
Description
Technical Field
The invention relates to a capsule-shaped hollow porous carbon shell for a lithium-sulfur battery cathode material and a preparation method thereof, in particular to a preparation method for a sulfur/ferroferric oxide/polyoxometallate/carbon composite material, and belongs to the field of lithium batteries.
Background
With rapid economic development and rapid increase in energy consumption, the ever-increasing energy demand of portable electronic devices and large-scale energy storage systems has driven the search for high energy density and high power density batteries. The lithium-sulfur battery with active sulfur as positive material and metal lithium as negative electrode can provide 1675 mAh g-1High theoretical specific capacity and 2600 Wh kg-1The theoretical specific energy of the lithium-sulfur battery is far higher than the energy density of the lithium-ion battery, and meanwhile, the active material sulfur has the advantages of abundant reserves (extremely low cost), environmental friendliness and the like, so that the lithium-sulfur battery becomes the most potential next-generation secondary battery.
However, practical application of lithium sulfur batteries is still hindered by some troublesome problems. First of all due to sulphur and its discharge products (Li)2S) are both electronic and ionic insulators, resulting in slow redox kinetics and low sulfur utilization, thereby limiting the rate capability of the cell. Secondly, polysulfide (LiPSs) of a discharge intermediate product dissolved in ether-based electrolyte between two electrodes can penetrate through a diaphragm under the diffusion action to reach a negative electrode to react with lithium, so that a shuttle phenomenon is generated in the lithium-sulfur battery during continuous charge and discharge, deposition can be generated on the surface of the positive electrode, active substances are finally lost, and the capacity of the lithium-sulfur battery is rapidly attenuated, and the cycle performance is poor. In addition, sulfur is also susceptible to severe volume expansion during lithiation (approximately 80%), which may also lead to collapse of the positive electrode during cycling.
Disclosure of Invention
The present invention is directed to the existing lithiumThe problems of low sulfur carrying capacity, obvious shuttle effect, poor circulation stability and the like of the positive electrode material of the sulfur battery are solved, and the heteropoly acid etching capsule-shaped hollow porous carbon shell is skillfully constructed, and the material is porous carbon, ferroferric oxide and tungsten phosphate (K)6P2W18O62·14H2O, abbreviated as P2W18) The three phases of the composition. P as surface layer of capsule shell of positive electrode material2W18The double-function auxiliary agent not only can play a role in etching and modification, but also can stabilize the hollow porous carbon shell skeleton, shows good chemical interaction and active catalytic capability, and provides strong chemical bonding and effective catalytic activity for polysulfide. In addition, the porous and firm capsule thin carbon shell can provide a larger volume change space for the active material due to larger gaps, not only physically limits the active material, but also ensures higher sulfur content of the lithium-sulfur battery, improves the conductivity, and thus realizes the following purposes:
the capsule-shaped hollow porous carbon shell with the multifunctional sulfur carrier, which is prepared by the invention, is used as a positive electrode material, can be applied to a lithium-sulfur battery, and shows high specific capacity, excellent rate capability and long-term cycling stability.
The invention adopts the following technical scheme:
a heteropoly acid etched capsule-like hollow porous carbon shell comprising Fe3O4、P2W18、C。
The following is a further improvement of the above technical solution:
the capsule-shaped hollow porous carbon shell has the length of 1.8-2.2 mu m and the diameter of 480-520 nm.
The capsule-shaped hollow porous carbon shell has the pore diameter of 5-8 nm and the specific surface area of 200-220 m2 g-1。
A preparation method of a heteropoly acid etched capsule-shaped hollow porous carbon shell comprises MIL-88A (Fe)/P2W18Preparing the composite material and calcining.
The MIL-88A (Fe)/P2W18Preparing composite material by adding MIL-88A (Fe) into dispersant and then adding P2W18Heating at 115-125 deg.C for 18-22 h, centrifuging to obtain MIL-88A (Fe)/P2W18A composite material.
The mass volume ratio of the MIL-88A (Fe) to the dispersing agent is 1g: 90-110 ml;
the dispersant is preferably water;
the MIL-88A (Fe) and P2W18The mass ratio of (A) to (B) is 1: 0.25-0.35.
The calcination temperature is 380-420 ℃.
The application of the heteropoly acid etched capsule-shaped hollow porous carbon shell in the lithium-sulfur battery comprises the preparation of S/Fe3O4/P2W18Preparing a/C composite material and a lithium-sulfur battery.
The S/Fe3O4/P2W18The mass content of S in the/C composite material is 68-72%.
The preparation of S/Fe3O4/P2W18a/C composite material of Fe3O4/P2W18Mixing the/C material with pure-phase nano sulfur powder, performing ball milling treatment, and performing heat treatment at the temperature of 150-160 ℃ for 10-15 h to obtain S/Fe3O4/P2W18a/C composite material.
P according to the invention2W18Is a abbreviation of tungsten phosphate, chemical formula K6P2W18O62·14H2O。
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the defect of poor conductivity of sulfur and reaction products thereof, the invention utilizes metal organic framework materials as templates to obtain metal oxygen clusters P through a carbonization process2W18A hybrid capsule-shaped hollow porous carbon shell composite material.
(2) The prepared capsule-shaped hollow porous carbon shell composite material has the advantages that the nano-scale polyoxometallate material modified on the surface of the material framework of the composite material has high-valence transition metal elements, so that uniform deposition of sulfur and lithium sulfide can be directionally guided, and agglomeration of the sulfur and the lithium sulfide is inhibited. And the polyoxometallate contains a large amount of polar O-W-O units inside, can effectively adsorb polysulfide, and can inhibit the dissolution (high thiophilic property) of the intermediate product lithium polysulfide through adsorption and catalysis, thereby improving the capacity and the cycle performance of the lithium-sulfur battery.
(3) The capsule-shaped hollow porous carbon shell structure of the composite material prepared by the invention can well encapsulate sulfur and reaction products, is suitable for volume expansion in the discharge process, and limits the shuttle effect of polysulfide, so that the sulfur and the reaction products thereof can still be uniformly distributed in the material in the charge and discharge processes, the reversible conversion of sulfur to lithium sulfide in the charge process is facilitated, but the structural damage caused by the increase of cycle times is avoided, and the cycle stability of the battery is improved.
(4) Fe according to the invention3O4/P2W18the/C composite material is prepared to obtain S/Fe with S content of 68-72wt%3O4/P2W18the/C composite material is assembled into the lithium-sulfur battery with the surface loading of 1.0 mg cm-2 Under the condition, the first discharge capacity can reach 1275-plus 1278 mAh g under the current density of 0.1C-1(ii) a Under the 0.2C discharge state, the first discharge capacity can reach 1164 mAh g-1(ii) a Under the 0.5C discharge state, the first discharge capacity can reach 1083 mAh g-1(ii) a In 1C discharge state, the first discharge capacity can reach 1025 mAh g-1(ii) a The discharge capacity can reach 912 mAh g for the first time when the discharge is carried out under the high-rate 2C state-1；
The material can stabilize the long-term cycle stability of 2000 times of charge and discharge under 1C, the decay rate of each cycle is only 0.021-0.022 percent on average, and the material is the anode material with the best service life at present. Based on the material, the lithium-sulfur battery prepared from the material has higher capacity density and excellent cycle performance.
Drawings
FIG. 1 Fe3O4/P2W18TEM and EDX characterization patterns of the/C composite.
FIG. 2 MIL-88A(Fe), P2W18, MIL-88A(Fe)/P2W18And Fe3O4/P2W18Infrared spectrogram of the/C composite material.
FIG. 3 MIL-88A (Fe), MIL-88A (Fe)/P2W18And Fe3O4/P2W18XRD spectrum of the/C composite material.
FIG. 4 is Fe3O4/P2W18the/C sample adsorption and desorption isotherms and the corresponding pore size distribution diagram.
FIG. 5 is based on S @ Fe3O4/P2W18The lithium-sulfur battery prepared from the/C composite material has a constant current charging and discharging curve under different current densities of 0.1C to 3C.
FIG. 6 is based on S @ Fe3O4/P2W18The lithium-sulfur battery prepared from the/C composite material has long-term charge-discharge cycle performance at the current density of 1C.
Detailed Description
Example 1 preparation method of heteropolyacid etching capsule-shaped hollow porous carbon shell
The method comprises the following steps:
1. preparation of Fe3O4/P2W18Composite material/C
(1) Preparation of organic framework material MIL-88A (Fe):
dissolving 1.3 g of fumaric acid in 100 mL of mixed solution of N, N-dimethylformamide and absolute ethyl alcohol in a volume ratio of 1:1, performing ultrasonic treatment and stirring for 30 min, adding 3 g of ferric nitrate, and continuing stirring at room temperature for 24 h. And after the reaction is finished, collecting a product through centrifugal separation, repeatedly washing the product for three times by using deionized water, and drying and washing the product in vacuum to obtain the metal organic framework material MIL-88A (Fe).
The chemical formula of MIL-88A (Fe) is C12H6O13Fe3。
（2）MIL-88A(Fe)/P2W18Preparing a composite material:
1g of metal organic framework material MIL-88A (Fe) is put into a polymer filled with 100 mL of aqueous solutionTetrafluoroethylene into the autoclave, 0.3 g P was added2W18Heating at 120 deg.C for 20 h, and centrifuging to obtain MIL-88A (Fe)/P2W18A composite material.
（3）Fe3O4/P2W18Preparation of the/C composite material:
mixing MIL-88A (Fe)/P2W18The composite material is placed in a tube furnace and calcined at the high temperature of 400 ℃ under the argon atmosphere to obtain Fe3O4/P2W18a/C composite material.
(4) Structural and topographical characterization
Etching capsule-shaped hollow porous carbon shell Fe of prepared heteropoly acid by using transmission electron microscope3O4/P2W18the/C composite was tested and FIG. 1 shows that the material exhibits a regular capsule-like hollow porous carbon shell structure, about 2 μm in length and about 500 nm in diameter. Meanwhile, the EDX result analysis shows that the capsule-shaped hollow porous carbon shell contains Fe, W, O, P and C elements.
MIL-88A (Fe), P were tested2W18、MIL-88A(Fe)/P2W18And capsule-like hollow porous carbon shell Fe3O4/P2W18Infrared spectrum of the/C composite material, as shown in FIG. 2, except for sample P2W18(solid gray line), MIL-88A (Fe) and MIL-88A (Fe)/P2W18 All have typical infrared characteristic peaks of MIL-88A (Fe), the abscissa is the spectral wavelength, and the position is 638 cm-1 、669 cm-1 、993 cm-1。
And is being controlled by P2W18Etching modified MIL-88A (Fe)/P2W18The main infrared characteristic peak main peak (grey dotted line) of the composite material has no obvious change compared with the MIL-88A (Fe) (light grey dotted line), and the structure of the MIL-88A (Fe) template is not damaged after etching. Furthermore from MIL-88A (Fe)/P2W18Also, a characteristic peak (800 cm) of the W-O group was clearly observed in the infrared spectrum of (A)-1、907 cm-1And 975 cm-1) Prove P2W18Is successfully repairedDecorated on the surface of MIL-88A (Fe) shell. In addition, the material is calcined at the high temperature of 400 ℃ to obtain Fe3O4/P2W18The IR spectrum of the/C composite (solid black line) shows that the MIL-88A (Fe) skeleton has collapsed and P2W18The skeleton structure is preserved (800 cm)-1，907 cm-1，1080 cm-1）。
For demonstration of phase purity and crystal structure, MIL-88A (Fe)/P2W18，Fe3O4/P2W18the/C was also analyzed by X-ray differentiation (XRD). As shown in FIG. 3, the XRD pattern of the MIL-88A (Fe) prepared is consistent with the data reported in the literature, indicating that a relatively pure MIL-88A (Fe) template was synthesized. And MIL-88A (Fe)/P2W18XRD spectrum of (1) in which P is in2W18The characteristic peak of (A) is obviously shown, further showing that P2W18Successfully modified on MIL-88A (Fe). Mixing MIL-88A (Fe)/P2W18After the composite material is calcined at the high temperature of 400 ℃, the strongest diffraction peak and Fe in the spectrum peaks of the obtained composite material3O4The most obvious peaks of the diffraction patterns are 18.27 degrees, 30.09 degrees, 35.42 degrees, 43.05 degrees, 53.39 degrees, 56.94 degrees and 62.52 degrees, which respectively correspond to Fe3O4(110), (220), (311), (400), (422), (511) and (440) of (PDF No. 00-019-. In addition, the structure also contains P2W18 (9.11 °, 24.61 °, 25.32 °, 27.16 °, 30.41 °), C (26.30 °), indicating Fe3O4/P2W18The phase purity of the components/C is very high. This result is also consistent with the characterization of EDX.
FIG. 4 is Fe3O4/P2W18the/C sample adsorption and desorption isotherms and the corresponding pore size distribution maps. And (3) testing and analyzing: the sample shows an IV-type isotherm and an H4-type hysteresis loop, and shows that the sample is a mesoporous material and has a specific surface area of 214 m2g-1Corresponding to an average pore diameter of 7.1 nm.
And lithium-sulfur battery preparation and electrical property test:
（1) Preparation of S/Fe3O4/P2W18Composite material/C
Mixing Fe3O4/P2W18Putting the material/C and the pure-phase nano sulfur powder into a ball milling tank according to the mass ratio of 3:7, mixing for 5 hours by using a planetary ball mill, putting the mixture obtained after ball milling into a vacuum glass tube, and carrying out heat treatment for 12 hours at the temperature of 155 ℃ in a tube furnace under the protection of nitrogen to obtain S/Fe3O4/P2W18a/C composite material;
the nano sulfur powder is purchased from Anan Ji-resistant chemical, sublimed sulfur and has the particle size of 500 nm.
(2) Lithium sulfur battery preparation
Mixing the above composite material (S/Fe)3O4/P2W18and/C) mixing the conductive carbon black and the binder according to the mass ratio of 7:2:1, adding N-methyl pyrrolidone (NMP) (the mass ratio of NMP to the mixed slurry is about 5 wt%), uniformly grinding and mixing for 30 min to obtain coating slurry, wherein the binder and the conductive carbon black are common materials of a lithium-sulfur battery system. And (3) uniformly coating the slurry on the surface of the aluminum foil by using a scraper, and drying in vacuum at 60 ℃ to obtain the lithium-sulfur battery anode. The positive electrode was cut into sheets having a diameter of 10 mm to prepare positive electrode sheets. Using metal lithium as a counter electrode, and manufacturing a CR2032 type button cell in a glove box filled with argon: wherein the diaphragm adopts Celgard 2400 diaphragm; dissolving l M lithium bistrifluoromethanesulfonylimide (LiTFSI) in a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1: 1; the additive is anhydrous lithium nitrate with the mass fraction of 1 wt%.
The additive is added into the electrolyte, and the mass ratio of the anhydrous lithium nitrate to the electrolyte is 1: 100.
(3) Lithium sulfur battery electrical performance testing
The charge and discharge performance of the sample is tested by adopting a Land CT2001A battery test system at 25 ℃, and the charge and discharge voltage is in a range of 1.7-2.8V. The cyclic voltammetry test adopts the electrochemical workstation of Shanghai Chenghua CHI660E to test, and the scanning rate is 0.1 mV s-1And the voltage range is 1.7-2.8V.
With S/Fe3O4/P2W18And preparing the lithium-sulfur battery positive plate by the/C composite material, finally assembling the lithium-sulfur battery, and carrying out charge-discharge experiments on the prepared lithium-sulfur battery under different multiplying powers. As shown in FIG. 5, when the sulfur loading was 70%, the surface loading was 1.0 mg cm-2At 0.1C (1C = 1675 mAh g)-1) Under the condition, the first discharge capacity can reach 1278 mAh g-1(ii) a Under the 0.2C discharge state, the first discharge capacity can reach 1164 mAh g-1(ii) a Under the 0.5C discharge state, the first discharge capacity can reach 1083 mAh g-1(ii) a In 1C discharge state, the first discharge capacity can reach 1025 mAh g-1(ii) a The discharge capacity can reach 912 mAh g for the first time when the discharge is carried out under the high-rate 2C state-1。
FIG. 6 shows the formation of a capsule-like hollow porous carbon shell Fe3O4/P2W18S/Fe prepared by loading pure-phase nano sulfur powder on/C composite material3O4/P2W18Discharge capacity curve and efficiency curve of the/C composite material at a current density of 1C. The initial specific capacity is 1025 mAh g-1And the specific discharge capacity after 2000 charge-discharge cycles was 57% (581 mAh g) of the first specific discharge capacity-1) An average cyclic decay rate of only 0.022% and an average coulombic efficiency of 99% were maintained.
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The above embodiments describe the main features and advantages of the present invention, the patent is not limited to the above embodiments, and those skilled in the art can make various changes without inventive work from the above conception and the protection scope of the patent.
Claims (7)
1. The application of the heteropoly acid etched capsule-shaped hollow porous carbon shell in the lithium-sulfur battery is characterized in that: said application, packageIncluding the preparation of S/Fe3O4/P2W18Preparing a/C composite material and a lithium-sulfur battery;
the hollow porous carbon shell comprises Fe3O4、P2W18、C；
The preparation method of the hollow porous carbon shell comprises MIL-88A (Fe)/P2W18Preparing and calcining a composite material;
the MIL-88A (Fe)/P2W18Preparing composite material by adding MIL-88A (Fe) into dispersant and then adding P2W18115-125 ℃ for 18-22 h, and obtaining MIL-88A (Fe)/P by centrifugation2W18A composite material;
the P is2W18Is a abbreviation of tungsten phosphate, chemical formula K6P2W18O62·14H2O。
2. The use of a heteropolyacid-etched capsule-like hollow porous carbon shell in a lithium-sulfur battery according to claim 1, wherein: the capsule-shaped hollow porous carbon shell has the length of 1.8-2.2 mu m and the diameter of 480-520 nm.
3. The use of a heteropoly acid etched capsule-shaped hollow porous carbon shell in a lithium sulfur battery as claimed in claim 1, wherein: the capsule-shaped hollow porous carbon shell has the pore diameter of 5-8 nm and the specific surface area of 200-220 m2 g-1。
4. The use of a heteropolyacid-etched capsule-like hollow porous carbon shell in a lithium-sulfur battery according to claim 1, wherein: the MIL-88A (Fe) and P2W18The mass ratio of (A) to (B) is 1: 0.25-0.35.
5. The use of a heteropolyacid-etched capsule-like hollow porous carbon shell in a lithium-sulfur battery according to claim 1, wherein: the calcination temperature is 380-420 ℃.
6. The use of a heteropolyacid-etched capsule-like hollow porous carbon shell in a lithium-sulfur battery according to claim 1, wherein: the S/Fe3O4/P2W18The mass content of S in the/C composite material is 68-72%.
7. The use of a heteropolyacid-etched capsule-like hollow porous carbon shell in a lithium-sulfur battery according to claim 1, wherein: the preparation of S/Fe3O4/P2W18a/C composite material of Fe3O4/P2W18Mixing the/C material with pure-phase nano sulfur powder, performing ball milling treatment, and performing heat treatment at the temperature of 150-160 ℃ for 10-15 h to obtain S/Fe3O4/P2W18a/C composite material.
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