CN114743807A - Inside and outside raw MoO2Preparation method of/three-dimensional carbon composite material - Google Patents
Inside and outside raw MoO2Preparation method of/three-dimensional carbon composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 15
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 68
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 18
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 18
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 18
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 16
- 239000003990 capacitor Substances 0.000 abstract description 14
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- H01G11/32—Carbon-based
-
- 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
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the field of electrode materials of supercapacitors, and particularly relates to an internal and external MoO2A preparation method of a three-dimensional carbon composite material. The method takes sodium chloride, citric acid and molybdate as raw materials, adopts a freeze-drying template method and combines a calcination process to obtain the endogenous MoO3A three-dimensional carbon composite; dilute hydrochloric acid and concentrated nitric acid are sequentially added for respective treatment to obtain endogenous MoO3A surface functionalized three-dimensional carbon composite; then adding ammonium molybdate and glycol solution for hydrothermal treatment to obtain internal and external MoO2The/three-dimensional carbon composite material realizes the uniform dispersion of MoO inside and outside the three-dimensional carbon material2Improving the conductivity of the electrode material and increasing the specific capacitanceThe stability of the electrode is enhanced, the electrode can serve as the cathode of the super capacitor, the energy density of the super capacitor is effectively improved, and the super capacitor has a very wide application prospect.
Description
Technical Field
The invention belongs to the field of electrode materials of a super capacitor, and particularly relates to a designed electrode cathode material and a preparation method thereof.
Background
With the rapid development of new energy industries, the demand for novel energy storage devices has also increased in a blowout manner. The Super Capacitor (SC) is a novel energy storage device which can safely provide high power and fast charge and discharge, has a long cycle life, and is widely applied to the field with higher requirement on power density. According to the formula of energy density (E ═ 1/2(CV)2) The energy density in the field of supercapacitors is generally increased by increasing the potential window as well as the capacity. On the basis of developing excellent electrode materials, an asymmetric super capacitor is constructed, different potential windows of two electrodes are utilized, the working voltage of the whole device is maximized, and the method is an effective way for improving the energy density of the super capacitor. In the vigorous development over 60 years since 1957, scientists have developed various cathode materials, but the development of anode materials is still very slow. The negative electrode material still has many problems such as low specific capacitance, large internal resistance and the like. The most obvious of these is the following charge matching equation:
from the formula, it can be found that in order to achieve charge matching, the traditional activated carbon cathode corresponding to the anode needs to load several times or even tens of times of active mass, but the effective area is limited, and the performance improvement of the supercapacitor is necessarily limited by the extra-heavy activated carbon cathode. Therefore, the development of a high-performance cathode material matched with a cathode material plays a crucial role in the development of the field of ASC and super capacitors, and molybdenum (Mo) is used as a transition element, and compounds such as oxides of the molybdenum (Mo) are all outstanding in the aspect of electrochemistry. However,the molybdenum dioxide can have serious volume change in the ion de-intercalation process, so that the circulation stability is poor, and the molybdenum dioxide electrode material is difficult to exert the advantages in the field of super capacitors. In further research, the molybdenum dioxide and the carbon material are uniformly compounded in a nanometer scale, so that the cycling stability of the electrode can be effectively optimized. In addition, the carbon material is a typical anode material, and the application of the carbon material to the compounding with molybdenum dioxide is also one of the best schemes for preparing the anode. For example, the patent CN107045950A discloses a method for preparing foamed nickel/graphene/MoO2Method for preparing three-layer composite electrode material from 1.0M Na2SO4The charge-discharge test is carried out in solution at 50mV s-1The sweep rate showed a higher capacitance value (317F g)-1) After 1000 times of circulation, the capacity retention rate is as high as 94.8%. The three-dimensional carbon can overcome the self-stacking problem of the traditional carbon material due to the unique frame structure, and the three-dimensional frame can effectively disperse the molybdenum dioxide nano particles, reserve space for possible volume expansion and realize high specific capacitance and cycle stability. In sodium and potassium ion batteries, Bao et al successfully prepared nano-molybdenum dioxide on three-dimensional porous carbon in 0.1Ag by a simple hydrothermal method-1Under the condition of (1), circulating for 200 times, MoO2The capacity of the/3 DPC composite decays only 20.7% (from 463mAh g)-1To 367mAh g-1). We have proposed in previous work functionalized carbon nanoplatelets as substrates composited with molybdenum dioxide. The functionalized carbon nanosheet improves the electronic conductivity, forms rich functional groups on the surface, provides more nucleation centers for molybdenum dioxide, and has a capacity retention rate of 92% after being circulated in a sodium sulfate electrolyte for 2000 times. The prepared molybdenum dioxide-based composite material has high circulation stability, and mainly shows EDLC behavior in a neutral solution. The three-dimensional carbon (3DC) serving as the composite substrate of the molybdenum dioxide can provide a foundation for enhancing the electrochemical performance of the electrode, and becomes a potential choice for the performance enhancement second phase of the molybdenum dioxide-based negative electrode material.
The functionalized three-dimensional carbon is adopted as the carrier of the molybdenum dioxide, and has the following advantages: (1) the three-dimensional carbon of endogenetic molybdenum oxide has more pores in structure, and the molybdenum trioxide and the molybdenum dioxide are subjected to phase transformation in the three-dimensional carbon through hydrothermal reaction, so that the molybdenum dioxide endogenetic in the three-dimensional carbon is realized; (2) the three-dimensional carbon can overcome self-stacking, relieve the agglomeration of molybdenum dioxide, and provide a large amount of effective attachment sites for exogenous molybdenum dioxide through functional treatment; (3) the three-dimensional carbon acts as a self-supporting substrate and, in addition to functioning as a conductive backbone, may contribute a portion of the capacitance of the electric double layer capacitance to the electrode material.
Disclosure of Invention
The invention provides a corresponding solution for various problems of molybdenum dioxide, which is characterized in that the molybdenum dioxide is taken as a main body and dispersed inside and outside a functional three-dimensional carbon matrix to form a binary composite electrode material. The binary electrode material takes framework three-dimensional carbon as a substrate and a conductive framework. The patent firstly proposes that molybdenum trioxide is internally generated in a carbon matrix in advance to obtain internally generated MoO in the preparation process of three-dimensional carbon by utilizing the characteristic of mutual conversion between molybdenum oxides3The three-dimensional carbon composite material is subjected to functional treatment to obtain endogenous MoO3The functionalized three-dimensional carbon composite material is subjected to hydrothermal treatment by adding ammonium molybdate and glycol solution to obtain internal and external MoO2A three-dimensional carbon composite. Endogenous MoO thereof3Not only introduces a large number of holes for the three-dimensional carbon matrix, but also can carry out phase transformation inside through hydrothermal to form endogenous MoO2A three-dimensional carbon composite; the functionalized three-dimensional carbon matrix can provide an attached active site for molybdenum dioxide and a conductive framework for internally and externally generated molybdenum dioxide. The abundant pores are beneficial to the ready good contact between the electrolyte and the electrode, and promote the movement of anions and cations so as to improve the activity of the electrode material, improve the electrochemical reaction rate of the electrode material from the aspect of dynamics, and provide guarantee for realizing and improving the stability. The electrode material obtained by the method has excellent rate performance, high specific capacitance and long cycle life.
Inside and outside raw MoO2The preparation method of the/three-dimensional carbon composite material is characterized by comprising the following steps:
(1) dissolving sodium chloride, citric acid and ammonium molybdate into deionized water, stirring and mixing, uniformly mixing, freezing in a refrigerator, drying in a freeze dryer, and grinding the obtained block after complete drying to obtain precursor powder;
(2) putting the precursor powder in the step (1) into a tube furnace, controlling the temperature to be 600 ℃, and calcining for 2 h; cooling, taking out the powder, cleaning, sequentially adding dilute hydrochloric acid and concentrated nitric acid, and respectively treating to obtain endogenous MoO3A surface functionalized three-dimensional carbon composite;
(3) carrying out endogenetic MoO obtained in the step (2)3Dissolving the surface functionalized three-dimensional carbon composite material, ammonium molybdate and ethylene glycol into deionized water, uniformly stirring, pouring the solution into a reaction kettle, and sealing;
(4) putting the reaction kettle obtained in the step (3) into a constant temperature box, heating to 180 ℃, keeping for 36 hours, naturally cooling to room temperature after the reaction is finished, and filtering the reaction liquid to obtain a generated primary finished product;
(5) collecting the primary finished product obtained in the step (4), then alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum oven under a vacuum environment to obtain the internal and external MoO2A three-dimensional carbon composite.
In the step (1), the mass ratio of the sodium chloride, the citric acid, the ammonium molybdate and the deionized water is 20.3-23.1: 0.8-1: 0.015-0.045: 70; the freezing temperature in the refrigerator is-50 ℃, and the freezing time is 10 hours; the drying temperature in the freeze dryer is-80 ℃, and the drying time is 72 h.
In the step (2), the concentration of the dilute hydrochloric acid is 15 wt%, and the treatment time is 1 h; the concentration of the concentrated nitric acid is 68 wt%, the treatment time is 3-10 h, and cleaning and drying are carried out after each acid treatment process.
In the step (3), endogenous MoO3The mass ratio of the surface functionalized three-dimensional carbon composite material to the ammonium molybdate to the ethylene glycol to the deionized water is 0.02-0.06: 0.5-1: 3.3-6.6: 60.
In the step (5), the drying temperature is 65 ℃, and the drying time is 12 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an internal and external MoO2The preparation method of the/three-dimensional carbon composite material selects the functionalized three-dimensional carbon as a substrate, and can provide abundant sites for the attachment of molybdenum dioxide through functionalization on the basis of overcoming self-stacking. By utilizing the characteristic of mutual conversion of molybdenum oxides, in the conventional process of preparing the three-dimensional carbon, molybdenum trioxide can be simply and conveniently endogenous in a matrix of the three-dimensional carbon in advance by additionally adding ammonium molybdate, so that the molybdenum trioxide can be converted into molybdenum dioxide through aftertreatment. And combining the experience of early-stage functional treatment to realize that the internal and external molybdenum dioxide is highly loaded on the three-dimensional carbon. In the application of the electrode material as a cathode electrode material, the three-dimensional carbon can construct a channel for ion transmission, and the electrode material is more effectively contacted with an electrolyte, so that the ion transmission is promoted, and the charge storage capacity of the super capacitor is improved.
The invention adopts the internally and externally generated MoO2Compared with the traditional cathode material, the cathode material prepared by the preparation method of the/three-dimensional carbon composite material has higher specific capacitance while obtaining more excellent cycle life. When the super capacitor is assembled, neutral and non-toxic water-based electrolyte (sodium sulfate solution) is used, so that high specific capacitance, high energy density and high cycle stability can be obtained.
Internal and external MoO prepared by the invention2The/three-dimensional carbon composite material is used as a negative electrode material and has a voltage window of-0.2 to-1V and a specific capacitance of 411.4F g-1And the capacity retention rate after 5000 cycles is 94.1%, and the capacitor has more excellent performance in device application compared with a super capacitor applying a traditional cathode.
Drawings
FIG. 1 shows an internally and externally generated MoO prepared by the present invention2Schematic flow diagram of a/three-dimensional carbon composite material.
FIG. 2 shows an internally and externally generated MoO prepared in example 12SEM image of/three-dimensional carbon composite material.
FIG. 3 shows an internally and externally generated MoO prepared in example 12A/three-dimensional carbon composite material performance test chart.
FIG. 4 shows an internally and externally generated MoO prepared in example 22ThirdAnd (5) a performance test chart of the vitamin-carbon composite material.
FIG. 5 shows an internally and externally generated MoO prepared in example 32SEM image of/three-dimensional carbon composite material.
FIG. 6 shows an internally and externally generated MoO prepared in example 32A performance test chart of the three-dimensional carbon composite material.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention is further illustrated by the following specific examples.
Example 1:
(1) dissolving 20.7g of sodium chloride, 1g of citric acid and 0.15g of ammonium molybdate into 70g of deionized water, stirring and mixing, uniformly mixing, freezing in a refrigerator at the temperature of-50 ℃ for 10h, then drying in a freeze dryer at the temperature of-80 ℃ for 72h, and grinding the obtained block to obtain precursor powder after complete drying;
(2) and (2) putting the precursor powder in the step (1) into a tube furnace, controlling the temperature to 600 ℃, and calcining for 2 h. After cooling, taking out the powder, cleaning, adding 20mL of dilute hydrochloric acid (15 wt%) for treatment for 1h, cleaning and drying, adding 20mL of concentrated nitric acid (68 wt%) for treatment for 10h, cleaning and drying to obtain endogenous MoO3A surface functionalized three-dimensional carbon composite;
(3) 40mg of endogenous MoO obtained in the step (2)3Dissolving the surface functionalized three-dimensional carbon composite material, 1g of ammonium molybdate and 6.6g of ethylene glycol into 60g of deionized water, uniformly stirring, pouring the solution into a reaction kettle, and sealing;
(4) putting the reaction kettle obtained in the step (3) into a constant temperature box, heating to 180 ℃, keeping for 36 hours, naturally cooling to room temperature after the reaction is finished, and filtering the reaction liquid to obtain a generated primary finished product;
(5) collecting the primary finished product obtained in the step (4), then alternately cleaning with deionized water and absolute ethyl alcohol, then placing into a vacuum oven, controlling the temperature to 65 ℃, and drying for 12h in a vacuum environment to obtain the internal and external MoO2A three-dimensional carbon composite. Fig. 2 is an SEM image of the composite material in this embodiment, and it can be found that molybdenum dioxide is uniformly compounded on the three-dimensional carbon surface. The maximum specific capacitance reaches 411.4F g calculated by the electrochemical test result of FIG. 3-1After 5000 cycles, the residual specific capacity is up to 94.1%.
Example 2:
(1) dissolving 20.7g of sodium chloride, 1g of citric acid and 0.15g of ammonium molybdate into 70g of deionized water, stirring and mixing, uniformly mixing, freezing in a refrigerator at the temperature of-50 ℃ for 10h, then drying in a freeze dryer at the temperature of-80 ℃ for 72h, and grinding the obtained block to obtain precursor powder after complete drying;
(2) and (2) putting the precursor powder in the step (1) into a tube furnace, controlling the temperature to 600 ℃, and calcining for 2 h. After cooling, taking out the powder for cleaning, adding 20mL of dilute hydrochloric acid (15 wt%) for treatment for 1h, adding 20mL of concentrated nitric acid (68 wt%) for treatment for 10h after cleaning and drying, and obtaining endogenous MoO after cleaning and drying3A surface functionalized three-dimensional carbon composite;
(3) 20mg of endogenous MoO obtained in the step (2)3Dissolving the surface functionalized three-dimensional carbon composite material, 1g of ammonium molybdate and 6.6g of ethylene glycol into 60g of deionized water, uniformly stirring, pouring the solution into a reaction kettle, and sealing;
(4) putting the reaction kettle obtained in the step (3) into a constant temperature box, heating to 180 ℃, keeping for 36 hours, naturally cooling to room temperature after the reaction is finished, and filtering the reaction liquid to obtain a generated primary finished product;
(5) collecting the primary finished product obtained in the step (4), then alternately cleaning with deionized water and absolute ethyl alcohol, then placing into a vacuum oven, controlling the temperature to 65 ℃, and drying for 12h in a vacuum environment to obtain the internal and external MoO2A three-dimensional carbon composite. Calculated by the electrochemical performance of FIG. 4, the specific capacitance is 125.6F g-1。
Example 3:
(1) 20.7g of sodium chloride, 1g of citric acid and 0.45g of ammonium molybdate were dissolved in 70g of deionized water, and the other steps were the same as in example 1;
(2) and (2) putting the precursor powder in the step (1) into a tube furnace, controlling the temperature to 600 ℃, and calcining for 2 h. After cooling, taking out the powder, cleaning, adding 20mL of dilute hydrochloric acid (15 wt%) for treatment for 1h, cleaning and drying, adding 20mL of concentrated nitric acid (68 wt%) for treatment for 10h, cleaning and drying to obtain endogenous MoO3A surface functionalized three-dimensional carbon composite;
(3) 40mg of endogenous MoO obtained in the step (2)3Dissolving the surface functionalized three-dimensional carbon composite material, 1g of ammonium molybdate and 6.6g of ethylene glycol into 60g of deionized water, uniformly stirring, pouring the solution into a reaction kettle, and sealing;
(4) putting the reaction kettle obtained in the step (3) into a constant temperature box, heating to 180 ℃, keeping for 36 hours, naturally cooling to room temperature after the reaction is finished, and filtering the reaction liquid to obtain a generated primary finished product;
(5) collecting the primary finished product obtained in the step (4), then alternately cleaning with deionized water and absolute ethyl alcohol, then placing into a vacuum oven, controlling the temperature to 65 ℃, and drying for 12h in a vacuum environment to obtain the internal and external MoO2A three-dimensional carbon composite. FIG. 5 is an SEM image of the composite material of example 3, calculated from the electrochemical performance of FIG. 6, and having a specific capacitance of 132.5F g-1。
Examples 1 to 3 are intended to compare the effects of the quality of three-dimensional carbon and the amount of ammonium molybdate added to the three-dimensional carbon precursor on the electrochemical performance of the composite material and the electrochemical performance of the device, and it can be seen that the composite material synthesized in example 1 has excellent properties.
The prepared molybdenum dioxide high-dispersion negative electrode material loaded on the functionalized three-dimensional carbon matrix is 1M Na2SO4Charging and discharging tests are carried out in solution at 1Ag-1Exhibits a high specific capacitance 411.4F g at a current density of-1And the constant-current charging and discharging curve keeps better symmetry, and the specific capacity of the constant-current charging and discharging curve is still up to 94.1 percent after 5000 cycles. Molybdenum dioxide and functional carbonThe specific capacitance of the meter scale is only 190.9F g-192% after 2000 cycles.
According to the invention, molybdate is used as a molybdenum source, phase transformation between molybdenum oxides is fully utilized, and the preparation process of the three-dimensional carbon is optimized, so that the preparation of the electrode material is realized with simple process and low cost, the method is suitable for future large-scale negative electrode mass production, the prepared negative electrode material with molybdenum dioxide loaded on the functionalized three-dimensional carbon matrix in a highly dispersed manner has excellent performance, and the energy density can be effectively improved when the prepared negative electrode material is applied to a super capacitor.
Claims (5)
1. Internal and external MoO2The preparation method of the/three-dimensional carbon composite material is characterized by comprising the following specific steps:
(1) dissolving sodium chloride, citric acid and ammonium molybdate into deionized water, stirring and mixing, uniformly mixing, freezing in a refrigerator, drying in a freeze dryer, and grinding the obtained block after complete drying to obtain precursor powder;
(2) putting the precursor powder obtained in the step (1) into a tube furnace for calcining, cooling, taking out the powder for cleaning, and then sequentially putting into dilute hydrochloric acid and concentrated nitric acid for respectively treating to obtain endogenous MoO3A surface functionalized three-dimensional carbon composite;
(3) carrying out endogenetic MoO obtained in the step (2)3Dissolving the surface functionalized three-dimensional carbon composite material, ammonium molybdate and ethylene glycol into deionized water, uniformly stirring, pouring the solution into a reaction kettle, and sealing;
(4) putting the reaction kettle obtained in the step (3) into a constant temperature box, heating to 180 ℃, keeping for 36 hours, naturally cooling to room temperature after the reaction is finished, and filtering the reaction liquid to obtain a generated primary finished product;
(5) collecting the primary finished product obtained in the step (4), cleaning and drying to obtain internal and external MoO2A three-dimensional carbon composite.
2. The endogenous and exogenous MoO of claim 12The preparation method of the/three-dimensional carbon composite material is characterized in that in the step (1), chlorination is carried outThe mass ratio of the sodium to the citric acid to the ammonium molybdate to the deionized water is 20.3-23.1: 0.8-1: 0.015-0.045: 70; the freezing temperature in the refrigerator is-50 ℃, and the freezing time is 10 hours; the drying temperature in the freeze dryer is-80 ℃, and the drying time is 72 h.
3. The endogenous and exogenous MoO of claim 12The preparation method of the/three-dimensional carbon composite material is characterized in that in the step (2), the calcination temperature is 600 ℃, and the calcination temperature is 2 hours; the concentration of the dilute hydrochloric acid is 15 wt%, and the treatment time is 1 h; the concentration of the concentrated nitric acid is 68 wt%, the treatment time is 3-10 h, and cleaning and drying are carried out after each acid treatment process.
4. The endogenous and exogenous MoO of claim 12The preparation method of the/three-dimensional carbon composite material is characterized in that in the step (3), the mass ratio of the endogenous MoO 3/the surface functionalized three-dimensional carbon composite material, ammonium molybdate, ethylene glycol and deionized water is 0.02-0.06: 0.5-1: 3.3-6.6: 60.
5. The endogenous and exogenous MoO of claim 12The preparation method of the/three-dimensional carbon composite material is characterized in that in the step (5), deionized water and absolute ethyl alcohol are alternately cleaned, and then the material is placed into a vacuum oven to be dried in a vacuum environment, wherein the drying temperature is 65 ℃, and the drying time is 12 hours.
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