CN110993371A - LiMnxOy@ C three-dimensional nanosheet array, preparation method and application thereof - Google Patents
LiMnxOy@ C three-dimensional nanosheet array, preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82—NANOTECHNOLOGY
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a three-LiMn alloyxOy@ C three-dimensional nanosheet array, preparation method and application thereof. The surface of the three-dimensional nano sheet array is rich in oxygen vacancy and is coated by MnO, gamma-MnO of a carbon layer2And LiMn2O4Composed of Mn (CH)3COO)2As a raw material, Na2SO4Preparing a precursor by an electrochemical deposition method, transferring the precursor into a LiOH aqueous solution to embed lithium by a hydrothermal reaction, soaking the embedded precursor in a glucose aqueous solution, and performing Ar/H (argon/hydrogen) treatment on the embedded precursor2Annealing to obtain the three-dimensional LiMn with the surface rich in oxygen vacancy defectsxOy@ C nanosheet array material. The material has a three-dimensional array structure, is beneficial to the entering of electrolyte to react with an active material, is rich in oxygen vacancies, effectively improves the electrochemical performance, and simultaneously can improve the conductivity and the mechanical stability of the electrode material by the coated carbon layer; the preparation method is simple and environment-friendly, and does not need a complex post-treatment process.
Description
Technical Field
The invention relates to LiMn with oxygen vacancy defect-rich surface grown on foamed nickelxOyA @ C three-dimensional nanosheet array material and a preparation method thereof, belonging to the field of new materials and energy chemical industry
Background
The super capacitor material has high power density, long cycle life and rapid charge and discharge process, but the further application of the super capacitor material in the field of energy storage is limited by the lower energy density, so the lithium ion capacitor combining the high cycle life of the super capacitor material and the high capacity of the lithium ion material battery is widely concerned. Spinel-type LiMn2O4Has higher theoretical capacity and wider working potential window, has wide application in the field of batteries, but has poor cycle performance caused by the dissolution of Mn in the long-term charge-discharge process, and gamma-MnO2Compared with MnO of other crystal forms2The performance decay in the electrochemical process is much slower. Thus, in combination with gamma-MnO2And LiMn2O4The material is coated with a carbon layer on the surface of the electrode and oxygen vacancies are introduced, so that the electrochemical stability of the electrode material can be effectively improved and higher specific capacity can be maintained. Reference 1(Wu H M, Tu J P, Yuan Y F, et. one-step synthesis LiMn2O4cathode by a hydrothermal method[J]Journal of power sources,2006,161(2):1260, 1263) reports the hydrothermal synthesis of LiMn2O4The method of the material, however, has poor shape controllability, and the cycle performance needs to be further improved. Document 2(Shu D, Chung K Y, Cho W I, et. electrochemical in-situ on electrochemical projected LiMn)2O4films[J]Journal of power sources,2003,114(2):253-2O4The process has high requirement on equipment and high cost of raw materials, and is not suitable for large-scale production. Document 3(Quan Z, Ohguchi S, Kawase M, et al2O4thin film by electrodeposition method and its electrochemicalperformance for lithium battery[J]Journal of Power Sources,2013,244:375-2O4A film. LiMn obtained by the method2O4The thickness is not uniform, and meanwhile, the thin film is covered with a plurality of irregular small particles, so that the cycle performance is further improved.
Disclosure of Invention
The invention aims to provide LiMn with oxygen vacancy defect enriched surfacexOyThe @ C three-dimensional nanosheet array material, the preparation method and the application thereof in the lithium ion capacitor.
The technical solution for realizing the purpose of the invention is as follows: LiMnxOyThe @ C three-dimensional nanosheet array is rich in oxygen vacancies on the surface and is coated by a carbon layer, namely MnO, gamma-MnO2And LiMn2O4The formed compound consists of Mn ions with multiple valence states.
Preferably, the three-dimensional nanosheet array is supported on foamed nickel.
Preferably, the three-dimensional nanosheet array is a three-dimensional array structure formed by interweaving and staggering nanosheets.
The preparation method of the three-dimensional nanosheet array comprises the following steps:
and 3, soaking the obtained dried sample in a glucose solution for a period of time, and then calcining at a high temperature.
Preferably, in step 1, the foam nickel is used as a working electrode, the Pt sheet is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the precursor solution is used as a deposition solution, cyclic voltammetry electrodeposition is performed firstly, then constant voltage electrodeposition is performed, washing is performed, drying is performed, and then high temperature annealing is performed to obtain the precursor.
Specifically, the potential interval of cyclic voltammetry electrodeposition is 0.5-1V, the deposition time is 30-60 s, the deposition potential of constant potential electrodeposition is 0.7-1V, the deposition time is 30-60 s, the annealing temperature is 150-250 ℃, the annealing time is 1-2 h, and the annealing atmosphere is N2。
Preferably, in step 1, Mn (CH)3COO)2With Na2SO4Is 1: 1.
Preferably, in the step 2, the hydrothermal reaction time is 18-24 hours, and the temperature of the hydrothermal reaction is 180-200 ℃.
Preferably, in step 3, the concentration of the glucose solution is 0.01-0.02mol L-1The high-temperature calcination temperature is 400-500 ℃, the calcination time is 1-2 h, and the calcination atmosphere is N2Or Ar/H2。
Compared with the prior art, the invention has the following remarkable advantages: 1. the reaction reagents used in the invention are all nontoxic reagents, the environmental pollution is small, the energy requirement required by the reaction is low, and the reaction condition is mild. 2. Prepared LiMnxOyThe @ C three-dimensional nanosheet array is uniform in shape and large in specific surface area, and the surface of the @ C three-dimensional nanosheet array is rich in oxygen vacancy defects. 3. Gamma-MnO due to high conductivity and protection of carbon layer2The prepared material has excellent cycle performance, higher specific capacity and strong practical applicability.
Drawings
Fig. 1 is an XRD spectrum of the lithium manganese oxide three-dimensional nanosheet array of examples 1 and 2 of the present invention and comparative example (curves a, b and c correspond to the XRD spectrum of the samples obtained in examples 1 and 2 and comparative example, respectively).
FIG. 2 shows LiMn in example 1 of the present inventionxOySEM and TEM images of @ C (a is an SEM image, and b is a TEM image).
FIG. 3 shows LiMn obtained in example 1 of the present inventionxOyThe cyclic voltammogram at @ C, the constant current charge-discharge diagram.
Fig. 4 is a cycle life chart of the lithium manganese oxide three-dimensional nanosheet arrays of examples 1, 2 of the present invention and comparative example.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
According to the invention, the three-dimensional structure nanosheet array is prepared by adopting an electrochemical deposition method, and the oxygen vacancy defect and the coated carbon layer are simultaneously manufactured on the surface of the material, so that the high-performance supercapacitor electrode material is obtained.
Example 1
0.7353g of Mn (CH)3COO)2And 0.42612g of Na2SO4Dissolved in 30ml of deionized water, and sufficiently dissolved by magnetic stirring for 5 minutes. Next, a piece of 1X1cm was cut2The foam nickel is used as a working electrode, a Pt sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, cyclic voltammetry electrodeposition is firstly carried out in a prepared solution, the potential interval is 0.5-0.8V, the deposition time is 30s, then constant voltage electrodeposition is carried out, the deposition potential is 0.7V, the deposition time is 30s, and after washing and drying, annealing is carried out for 2h under nitrogen at 200 ℃ to obtain a precursor. The obtained precursor was dissolved in 30ml of solution 0.03776g of LiOH. H2And in a beaker of the O aqueous solution, transferring the precursor and the solution into a polytetrafluoroethylene reaction kettle, and reacting for 24 hours at 200 ℃. And after the reaction is finished, washing and drying. The resulting sample was soaked in 0.02M aqueous glucose solution for 5H and finally transferred to a tube furnace Ar/H2Calcining for 2h at the high temperature of 450 ℃ in the atmosphere to obtain the final Ni foam @ LiMnxOy@ C three-dimensional nanosheet array material.
Ni foam@LiMnxOyThe XRD pattern of the @ C composite is shown in figure 1. FIG. 1a demonstrates the passage of Ar/H2After high temperature calcination in a reducing atmosphere, the sample contains MnO, gamma-MnO2And spinel-type LiMn2O4。Ni foam@LiMnxOySEM image of @ C composite As shown in FIG. 2a, illustrating that the carbon layer was successfully coated on LiMnxOyA nanoplatelet array surface. Ni foam @ LiMnxOyThe TEM image of the @ C composite is shown in FIG. 2b, and FIG. 2b demonstrates the formation of γ -MnO2The nano-sheet contains a plurality of micropores and has a carbon layer of 2-3nm coated on LiMnxOyAnd (4) nano-chips.
For the Ni foam @ LiMn prepared in example 1xOyThe @ C product was tested for energy storage performance. The specific test method comprises the following steps: a nickel wire was threaded through the sample and suspended as the working electrode. Electrochemical tests were performed in 3M KOH solution with Hg/HgO as a reference electrode and a platinum sheet as a counter electrode. FIG. 3a shows that the cyclic voltammogram 3a has two pairs of redox peaks, illustrating LiMnxOy@ C is a Faraday capacitive material, which undergoes a reversible redox reaction. The scanning speed is increased from 5mV/s to 100mV/s, and the CV curve is not required to deform, which indicates that the material has good rate capability. Figure 3b shows a significant discharge plateau for the constant current charge-discharge curve, further demonstrating the pseudocapacitive faraday behavior of the material. FIG. 4 shows that at 5A g-1After 10000 cycles of circulation under the current density, the specific capacitance can still keep the initial 100 percent. Showing very excellent cycling stability. The specific capacity of the material under different current densities is measured as shown in the following table 1.
TABLE 1 Ni foam @ LiMn obtained in example 1xOyTest data of @ C lithium ion capacitor material
Example 2
0.7353g of Mn (CH)3COO)2And 0.42612g of Na2SO4Dissolved in 30ml of deionized water, and sufficiently dissolved by magnetic stirring for 5 minutes. Then, the process of the present invention is carried out,a piece of 1x1cm2The foam nickel is used as a working electrode, a Pt sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, cyclic voltammetry electrodeposition is firstly carried out in a prepared solution, the potential interval is 0.6-0.9V, the deposition time is 60s, then constant voltage electrodeposition is carried out, the deposition potential is 1V, the deposition time is 40s, and the precursor is obtained by washing, drying and annealing for 1h under nitrogen at 150 ℃. The obtained precursor is put into a beaker with 30ml of water solution of 0.03776g of LiOH & H2O dissolved in the precursor, and then the precursor and the solution are transferred into a polytetrafluoroethylene reaction kettle to react for 18H at 190 ℃. And after the reaction is finished, washing and drying. The resulting sample was soaked in 0.01M aqueous glucose solution for 5h and transferred to a tube furnace N2Calcining for 1h at the high temperature of 400 ℃ in the atmosphere to obtain the final Ni foam @ LiMnxOy@ C three-dimensional nanosheet array material.
Ni foam @ LiMn obtained in example 2xOyThe XRD pattern of the @ C composite is shown in FIG. 1b, and the same cycling stability test as in example 1 was performed thereon, with the results shown in FIG. 4. After 10000 cycles of cycling, the specific capacity is only 90% of the initial specific capacity, and the stability is not as good as that of the Ni foam @ LiMn prepared in example 1xOy@ C, which indicates that the introduction of oxygen vacancy by the bag is beneficial to the improvement of the cycle performance. Ni foam @ LiMn prepared in example 2xOyThe specific capacity measured by @ C under different current densities is lower than that of Ni foam @ LiMn prepared in example 1xOySpecific capacity of @ C is shown in Table 2.
TABLE 2 Ni foam @ LiMn obtained in example 2xOyTest data of @ C lithium ion capacitor material
Comparative example
0.7353g of Mn (CH)3COO)2And 0.42612g of Na2SO4Dissolved in 30ml of deionized water and then dissolved,the mixture is magnetically stirred for 5 minutes to be fully dissolved. Next, a sheet of 1x1cm was placed2The foam nickel is used as a working electrode, a Pt sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, cyclic voltammetry electrodeposition is firstly carried out in a prepared solution, the potential interval is 0.7-1V, the deposition time is 50s, then constant voltage electrodeposition is carried out, the deposition potential is 0.8V, the deposition time is 60s, and the precursor is obtained by washing, drying and annealing for 1.5h under nitrogen at 250 ℃. The obtained precursor was dissolved in 30ml of solution 0.03776g of LiOH. H2And in a beaker of the O aqueous solution, transferring the precursor and the solution into a polytetrafluoroethylene reaction kettle, and reacting for 20 hours at 180 ℃. And after the reaction is finished, washing and drying. The resulting sample was soaked in 0M aqueous glucose solution for 5h and transferred to a tube furnace N2Calcining for 1.5h at the high temperature of 500 ℃ in the atmosphere to obtain the final Ni foam @ LiMnxOyThree-dimensional nano-sheet array material.
Comparative example Ni foam @ LiMnxOyThe XRD pattern of the composite material is shown in fig. 1c, and the same cycle stability test as in example 2 was performed, and the result is shown in fig. 4. After 8000 cycles of cycling, the specific capacity is only 50 percent of the original specific capacity, and the stability of the Ni foam @ LiMn composite material is far inferior to that of Ni foam @ LiMn prepared in example 2xOyIt is shown that carbon coating is beneficial for cycle performance improvement. Ni foam @ LiMn prepared in example 3xOyThe specific capacity measured under different current densities is greatly lower than that of the Ni foam @ LiMn prepared in example 1xOySpecific capacity of @ C is shown in Table 3. It is shown that the introduction of oxygen vacancies has a significant effect on increasing the capacity of the electrode.
TABLE 3 comparative example resulting Ni foam @ LiMnxOyTest data of @ C lithium ion capacitor material
Claims (10)
1. LiMnxOyThe @ C three-dimensional nanosheet array is characterized in that the surface of the three-dimensional nanosheet array is rich in oxygen vacancies and coated by a carbon layerMnO，γ-MnO2And LiMn2O4The formed compound.
2. A three-dimensional nanoplatelet array according to claim 1 wherein the three-dimensional nanoplatelet array is supported on foamed nickel.
3. The three-dimensional nanoplate array of claim 1, wherein the three-dimensional nanoplate array is a three-dimensional array structure formed by nanoplate interleave phases.
4. A method of making a three-dimensional nanoplatelet array according to any of claims 1-3 comprising the steps of:
step 1, Mn (CH)3COO)2And Na2SO4The aqueous solution is used as a precursor solution, and an electrochemical deposition method is adopted to prepare a precursor;
step 2, placing the precursor in a LiOH aqueous solution for hydrothermal reaction, cooling, washing and drying;
and 3, soaking the obtained dried sample in a glucose solution for a period of time, and then calcining at a high temperature.
5. The method of claim 4, wherein in step 1, the precursor is obtained by taking the foamed nickel as a working electrode, the Pt sheet as a counter electrode and the saturated calomel electrode as a reference electrode, taking the precursor solution as a deposition solution, performing cyclic voltammetry electrodeposition, then performing constant-voltage electrodeposition, washing, drying and then performing high-temperature annealing.
6. The method according to claim 5, wherein the cyclic voltammetry electrodeposition potential range is 0.5 to 1V, the deposition time is 30s to 60s, the deposition potential of potentiostatic electrodeposition is 0.7 to 1V, the deposition time is 30s to 60s, the annealing temperature is 150 to 250 ℃, the annealing time is 1 to 2h, and the annealing atmosphere is N2。
7. The method of claim 4The method is characterized in that in step 1, Mn (CH)3COO)2With Na2SO4Is 1: 1.
8. The method according to claim 4, wherein in the step 2, the hydrothermal reaction time is 18-24 h, and the temperature of the hydrothermal reaction is 180-200 ℃.
9. The method of claim 4, wherein in step 3, the concentration of the glucose solution is 0.01 to 0.02mol L-1The high-temperature calcination temperature is 400-500 ℃, the calcination time is 1-2 h, and the calcination atmosphere is N2Or Ar/H2。
10. Use of a three-dimensional nanoplatelet array of any of claims 1-3 as an electrode material in a lithium storage device.
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