CN111005027A - Porous sponge carbon, one-step molten salt electrolysis preparation method thereof, electrode material and electrode - Google Patents

Porous sponge carbon, one-step molten salt electrolysis preparation method thereof, electrode material and electrode Download PDF

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CN111005027A
CN111005027A CN201911300616.XA CN201911300616A CN111005027A CN 111005027 A CN111005027 A CN 111005027A CN 201911300616 A CN201911300616 A CN 201911300616A CN 111005027 A CN111005027 A CN 111005027A
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porous sponge
molten salt
carbon
sponge carbon
preparation
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CN111005027B (en
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李芳芳
喻奥
彭平
胡雅静
马国铭
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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 supercapacitors, and relates to porous sponge carbon, a one-step molten salt electrolysis preparation method thereof, an electrode material and an electrode. The one-step molten salt electrolysis preparation method of the porous sponge carbon comprises the following steps: in an air atmosphere, with nickelThe filament is taken as an anode, the galvanized iron wire is taken as a cathode, electrolysis is carried out in a Li-Na-K carbonate electrolyte in a molten state, and the current density is 0.2A/cm2～0.9A/cm2The time is 4 h-0.89 h, and the total electric quantity is 3 Ah-5 Ah, so as to obtain the porous sponge carbon. The invention solves the problems of complex preparation procedures and high cost in the preparation process of the active carbon and electrode active materials of the super capacitor, and the obtained porous spongy carbon material has higher capacitance capacity and good cycle stability, thereby greatly promoting the commercial application of the porous spongy carbon material and relieving the greenhouse effect to a certain extent.

Description

Porous sponge carbon, one-step molten salt electrolysis preparation method thereof, electrode material and electrode
Technical Field
The invention belongs to the field of supercapacitors, and relates to porous sponge carbon, a one-step molten salt electrolysis preparation method thereof, an electrode material and an electrode, in particular to a supercapacitor electrode active material and a one-step molten salt electrolysis preparation method thereof, and particularly relates to a supercapacitor electrode active material prepared by one-step electrolysis in molten salt.
Background
Carbon dioxide (CO) in the atmosphere2) Concentrations are threatening global climate and human survival. CO per 2ppm increase in the atmosphere2Equivalent to a net increase of 156 million tons of CO2. The combustion of fossil fuels remains CO in power, transportation and industrial processes2The main cause of accumulation. Therefore, the development of clean renewable energy technology is urgently needed. High power density, long cycle life supercapacitors are promising energy conversion and storage devices. The electrode material of the capacitor is an important factor affecting its high capacitive performance. Carbon materials are widely used as electrode materials in the preparation of supercapacitors. The preparation of the material follows the principles of energy conservation, low cost and mass production, which is the basis of practical application. To date, most methods for synthesizing supercapacitor activated carbon materials require templates, high temperature carbonization, use of KOH, NaOH, or H3PO4Activating agents and the like. In addition, most processes need to be carried out in an inert gas environment to inhibit oxidation of carbon to improve the yield of the product. This is achieved byThe synthesis methods have certain limitations in the aspects of large-scale, low cost and sustainable preparation. Therefore, the development of a resource-saving and environment-friendly method has great significance for large-scale production of the supercapacitor active material.
In recent years, experts and scholars at home and abroad carry out very intensive research on the active material of the super capacitor, particularly on the active carbon material. The carbon material has excellent conductivity and good electrochemical stability, so that the cycle stability of the material can be effectively improved in the charging and discharging process, and the carbon material is considered to be a good supercapacitor material.
In the journal of Advanced Energy Materials, 2 nd volume 2, page 419-124, magnesium oxide (MgO) is used as a template, coal tar is used as a carbon source, the magnesium oxide and the coal tar are mixed to prepare slurry, the slurry is subjected to heat preservation and aging at 60 ℃ for 48h, then the slurry is carbonized at 900 ℃ under the protection of nitrogen, and finally the magnesium oxide is etched by hydrofluoric acid to prepare the porous carbon material. The specific capacity of the obtained material at a sweep rate of 2mV/s was 289F/g. The carbon material prepared by the method has complex process, uses highly toxic hydrofluoric acid, has overhigh preparation cost and is not environment-friendly.
Journal of Advanced Energy Materials on volume 6, page 1500871 2015, reports activation of C with KOH70Micron rods are used for preparing the active material of the super capacitor. In the experiment, the liquid-liquid interface method is firstly used for preparing C70Micron rods, followed by drying C70The micron rods are uniformly mixed with KOH with certain mass and then carbonized at the temperature of 600 ℃ to prepare the porous supercapacitor active carbon material. The specific capacity of the material at the current density of 0.1A/g is 362F/g, which is much lower than 667F/g (0.2A/g) in the invention. Note that in this experiment C70The cost is high, the yield is low after KOH activation, and the requirement of practical commercial production cannot be met.
Journal of Advanced sustamable Systems in 2017, volume 1, 1700047, reports on nickel as cathode, SnO2(SnO2The anode needs high-pressure compaction before use and is obtained by sintering at high temperature) as the anode in Li2CO3–Na2CO3–K2CO3–Li2SO4In the electrolyte, CO2And SO2The sulfur-doped carbon material is prepared under the atmosphere, and the capacitance of the carbon material under a two-electrode system can reach 257.6F/g (0.2A/g). However, the method has strict requirements on the preparation conditions and environment of the materials and also has strict requirements on the atmosphere.
In the above-mentioned several super capacitor active materials, there are problems of high raw material cost and complex preparation process. In the first two cases, the material must be obtained through multiple treatments, and the complicated preparation method can restrict the commercial application of the material in terms of time cost. In the third example, Li is melted2CO3–Na2CO3–K2CO3The electrolysis in the composite carbonate obtains the super capacitor electrode active material with higher capacity, but SnO used in the electrolysis process2The obtaining cost is high; in addition, CO is required to be introduced into the reaction2And SO2Gases as starting materials for the reaction, which also need to provide high costs for the large-scale preparation of active materials, and SO2The gas is toxic and has strict requirements on the sealing performance of the electrolysis equipment.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides porous sponge carbon, a one-step molten salt electrolysis preparation method thereof, an electrode material and an electrode, and aims to electrolyze CO by adopting a constant current method in an air atmosphere2The solid carbon material is reduced to be a solid carbon material and deposited on a cathode, so that one-step electrolytic preparation of the porous sponge carbon is realized, the preparation process and equipment of the porous sponge carbon and the corresponding electrode active material are simplified, and the electrode active material preparation method which is simple, convenient, capable of being produced in large scale and low in cost is obtained, so that the technical problems of high requirements and high cost of the process and equipment in the prior art are solved.
In order to achieve the above object, according to one aspect of the present invention, there is provided a one-step molten salt electrolysis preparation method of porous sponge carbon, characterized in that nickel wires are used as an anode, zinc-plated iron wires are used as a cathode, and the anode and the cathode are placed in a molten Li-Na-K carbonate electrolyte in an air atmosphereLine electrolysis with current density of 0.2A/cm2～0.9A/cm2The time is 4 h-0.89 h, and the total electric quantity is 3 Ah-5 Ah, so as to obtain the porous sponge carbon.
Furthermore, the surface areas of the electrodes of the nickel wire and the galvanized iron wire are both 4cm2～6cm2。
Further, the nickel wire has a diameter of 2mm, a length of 8cm and a surface area of 5cm2(ii) a The galvanized iron wire has a diameter of 1mm, a length of 16cm and a surface area of 5cm2。
Further, Li-Na-K carbonate is first mixed in a mass ratio of (30. + -.2): (10. + -.2): 10. + -.2), and the mixed salt is heated to 570 to 590 ℃ to melt it into a molten state after removing water from the mixed salt in a total mass of 40 to 60 g.
Further, the salt materials of Li-Na-K carbonate are Li respectively2CO3、Na2CO3And K2CO3。
Further, the distance between the cathode and the anode is 1 cm-3 cm, and the input current is 0.2A/cm2、0.3A/cm2、0.5A/cm2Or 0.9A/cm2The corresponding electrolysis time is 4h, 2.67h, 1.6h or 0.89h respectively.
In order to achieve the above object, the present invention also provides a porous sponge carbon obtained according to the one-step molten salt electrolysis production method as described in any one of the above.
In order to achieve the aim, the invention also provides a one-step molten salt electrolysis preparation method of the supercapacitor electrode active material, which comprises the steps of soaking the porous sponge carbon with 6-9 mol/L hydrochloric acid for 6-12 h, washing with deionized water to remove insoluble carbonate, and drying to obtain the supercapacitor electrode active material.
In order to achieve the above object, the present invention also provides a supercapacitor electrode active material obtained according to the one-step molten salt electrolysis preparation method as described above.
In order to achieve the above objects, the present invention also provides an electrode or a supercapacitor made of the porous sponge carbon or the supercapacitor electrode active material as described above.
In general, compared with the prior art, the above technical solution contemplated by the present invention can obtain the following beneficial effects:
(1) as the whole experimental process is carried out in the air, the air contains infinite CO2As the raw materials for the reaction, new electrolyte and other gases do not need to be added in the reaction process, the reaction condition is mild, and the requirements on equipment and raw materials are greatly reduced, so that the active carbon material can be prepared in a large scale through simple experimental equipment. Also, electrolysis in air introduces a large amount of oxygen element into the carbon material, which provides good wettability to the carbon material. The good wettability of the carbon material greatly reduces the internal resistance of the supercapacitor electrode after the electrode is subsequently manufactured, and is beneficial to the migration and diffusion of ions in the electrolyte of the supercapacitor in the material.
(2) On the other hand, the cheap iron and nickel are used as electrode materials for reaction, so that the preparation cost of the materials is also greatly reduced, and CO in air or soot can be directly used in the air atmosphere2Reducing the carbon dioxide into the active material which can be used for the electrode of the super capacitor, has low requirement on equipment and CO2The conversion can realize carbon emission reduction to a certain extent, and effectively relieve increasingly serious greenhouse effect.
(3) The electrode active material and the super capacitor prepared by the invention have the characteristics of high capacity and high cycle stability, and have practical application value for industrialization.
Drawings
FIG. 1 shows that the current density in the present invention is 0.9A/cm2SEM images of porous sponge carbon were prepared at current density, with a scale bar of 20 μm.
FIG. 2 shows that the current density in the present invention is 0.9A/cm2SEM images of porous sponge carbon were prepared at current density with a scale bar of 2 μm.
FIG. 3 shows that the current density in the present invention is 0.9A/cm2TEM and HRTEM images of porous sponge carbon were prepared at current density, scale bar 500 nm.
FIG. 4 shows that the current density in the present invention is 0.9A/cm2TEM and HRTEM images of porous sponge carbon prepared under current density, scale barIs 20 nm; in the figure (b), the fourier transform diagram of the figure (a) is shown, and the figure (c) is the electron diffraction diagram of the figure (a).
FIG. 5 shows the current density of 0.9A/cm2And preparing an XPS full spectrum of the porous sponge carbon under the current density.
FIG. 6 shows that the current density was 0.9A/cm2Contact angle test patterns of the porous sponge carbon are prepared under current density.
FIG. 7 shows that the current density was 0.9A/cm2EIS plots of porous sponge carbon were prepared at current density.
FIG. 8 is a graph showing that the current density was 0.9A/cm2Cyclic Voltammetry (CV) plots of porous sponge carbon under a three-electrode system were prepared at current density.
FIG. 9 shows that the current density was 0.9A/cm2A constant current charge and discharge (GCD) diagram of the porous sponge carbon under a three-electrode system is prepared under current density, and the current density is 0.2, 0.5, 1 and 2A/g.
FIG. 10 shows the current density of 0.9A/cm2Preparing a constant current charge-discharge (GCD) diagram of the porous sponge carbon under a three-electrode system under the current density of 5, 10, 15 and 20A/g
FIG. 11 shows that the current density was 0.9A/cm2Preparation of porous sponge carbon under current density under three-electrode system at 10Ag-1A charge-discharge capacity retention (capacitance retention) diagram at current density.
FIG. 12 shows that the current density was 0.9A/cm2Preparing a Cyclic Voltammetry (CV) diagram of a symmetrical device assembled by porous sponge carbon under current density.
FIG. 13 shows that the current density was 0.9A/cm2The porous sponge carbon is prepared under current density to assemble a constant current charging and discharging (GCD) diagram of the symmetrical device under a three-electrode system, and the current density is 0.1, 0.2, 0.5 and 1A/g.
FIG. 14 shows the current density of 0.9A/cm2The porous sponge carbon is prepared under current density to assemble a constant current charging and discharging (GCD) diagram of the symmetrical device under a three-electrode system, and the current density is 2, 5, 10 and 20A/g.
FIG. 15 shows that the current density was 0.9A/cm2Charge-discharge capacity guarantee of symmetrical devices assembled by preparing porous sponge carbon under current density at 5A/g current densityA distance coverage map.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a one-step molten salt electrolysis preparation method of porous sponge carbon, which takes nickel wires as an anode and galvanized iron wires as a cathode. Electrolyzing in molten Li-Na-K carbonic acid electrolyte with current density of 0.2A/cm2～0.9A/cm2The time is 4-0.89 h, and the total electric quantity is 3-5 Ah, thus obtaining the porous sponge carbon.
Preferably, the surface areas of the nickel wire and the galvanized iron wire are both 4cm2～6cm2. Both electrode materials used herein are inexpensive and readily available.
Preferably, Li-Na-K carbonate is firstly mixed according to the mass ratio of (30 +/-2) to (10 +/-2), mixed salt with the total mass of 40g to 60g is dried to remove moisture, and then heated to 570 ℃ to 590 ℃ for melting. The composite Li-Na-K carbonate used here has a low melting point, and can be electrolyzed without heating the molten salt to a temperature above the melting point (723 ℃) of lithium carbonate, which greatly reduces the requirements on equipment and saves energy.
Preferably, the Li-Na-K carbonates are each Li2CO3、Na2CO3And K2CO3. Li as used herein2CO3、Na2CO3And K2CO3Is cheap and easily available industrial raw materials, and has low cost.
Preferably, the cathode and the anode are assembled in the air, the distance between the cathode and the anode is 1 cm-3 cm, and then the assembly is inserted into the molten electrolyte for electrolysis, and the input current is 0.2A/cm2、0.3A/cm2、0.5A/cm2Or 0.9A/cm2The corresponding electrolysis time is 4h, 2.7h, 1.6h or 0.89h respectively.
The method for preparing the electrode active material of the supercapacitor by using the porous sponge carbon comprises the following steps: soaking the porous sponge carbon obtained by electrolysis in 6-9 mol/L hydrochloric acid for 6-12 h, then washing with a large amount of deionized water to remove insoluble carbonate, and then drying in vacuum to obtain the electrode active material of the supercapacitor.
[ example 1 ]
The embodiment provides a one-step molten salt electrolysis preparation method of porous sponge carbon and a supercapacitor electrode active material, and further detects the preparation effect, specifically:
32g of Li2CO3、10g Na2CO3And 8g K2CO3After being uniformly mixed, the mixture is placed in a muffle furnace at 150 ℃ for heat preservation for 12 hours, and then the mixed salt is heated to 580 ℃ for melting.
The diameter is 2mm, the length is 8cm, the surface area is 5cm2The nickel wire is used as an anode; the diameter is 1mm, the length is 16cm, and the surface area is 5cm2The galvanized iron wire is bent into a spring shape to be used as a cathode. Assembling the cathode and anode at a distance of 2cm, and inserting into molten Li-Na-K carbonate electrolyte at an electrolytic current density of 0.9A/cm2The time is 0.89 h. After the electrolysis was completed, the product on the cathode was soaked with 6mol/L hydrochloric acid for 12 hours, filtered, and rinsed with a large amount of deionized water, and dried in a vacuum drying oven for 12 hours, and fig. 1 and 2 are SEM images of the prepared porous sponge carbon.
The porous sponge carbon is characterized by a transmission electron microscope, and as can be seen from fig. 3 and 4, the porous sponge carbon has a plurality of discontinuous fine stripes, which indicates the low crystallinity of the porous sponge carbon; both the selected area electron diffraction pattern (c) and the fourier transform (b) corresponding to (a) of fig. 4 show amorphous rings, further demonstrating the low crystallinity of the porous sponge carbon. Proved by verification, the porous sponge carbon is 0.9A/cm2Under high current density, the yield can reach 96.9%.
As can be seen from fig. 5, the porous sponge carbon prepared by the present invention contains only two elements, i.e., carbon and oxygen, wherein the atomic content of the oxygen element is 12.45%. The porous sponge carbon can improve the wettability of the material due to the existence of the oxygen element, and the contact angle test of the porous sponge carbon finds that water drops are completely infiltrated within 3s, which shows that the material has good wettability (figure 6).
Preparing the prepared porous sponge carbon, conductive carbon black and PTFE into electrode slurry according to the mass ratio of 8:1:1, and pressing the electrode slurry at 1 x 1cm2And drying the foamed nickel in vacuum to obtain the electrode for testing. In 6mol/L KOH solution, a working electrode containing porous sponge carbon, a reference electrode containing Hg/HgO and a counter electrode containing Pt sheets are used, and a CHI660E electrochemical workstation is used for performing cyclic voltammetry and impedance test.
From the EIS chart of the material in fig. 7, it can be seen that the internal resistance of the porous sponge carbon is only 0.39 ohm, and the lower internal resistance is beneficial to reducing the internal resistance loss in the actual use process.
As can be seen from FIG. 8, the CV test voltage ranges from-1V to 0V, the scanning speeds are respectively 5 mV/s, 10 mV/s, 20 mV/s, 50 mV/s, 100 mV/s and 200mV/s, and the CV curves still keep a good quasi-rectangular shape from low to high scanning speeds, which indicates that the material has good rate capability.
The constant current charge and discharge (GCD) curve and the cycle stability curve are tested on a Blubbo 2018BT tester under the current of 0.2, 0.5, 1, 2, 5, 10, 15 and 20A/g respectively, the corresponding tested capacities are 667, 373.7, 317.9, 287.4, 267.5, 257, 255 and 244F/g respectively, as shown in FIG. 9 and FIG. 10, it can be known that the capacity of the active material prepared by the porous sponge carbon under the current density of 0.2A/g can reach 667F/g under the three-electrode system; as can be seen from FIG. 11, after 10000 cycles of charge and discharge tests at a current density of 10A/g, the capacity retention rate is as high as 94%.
FIG. 12 is a cyclic voltammetry Curve (CV) measured using CHI660E electrochemical workstation in 6M KOH solution after porous sponge carbon was assembled into a symmetric supercapacitor device, with test voltages ranging from-1 to 0V and scan speeds of 5, 10, 20, 50, 100, 200, and 300mV/s, respectively. The CV curve of the symmetric capacitor device appears quasi-rectangular, indicating that the device has good double layer capacitance performance. Testing a constant current charge and discharge (GCD) curve and a cycle stability curve on a CHI660E electrochemical workstation, as shown in FIG. 13 and FIG. 14, testing under currents of 0.1, 0.2, 0.5, 1, 2, 5, 10, 15 and 20A/g respectively, wherein the corresponding tested capacities are 65.5, 58.5, 53.5, 49.6, 47.2, 45.2, 44.4 and 42.5F/g respectively, and when the current density is increased to 20A/g, the capacity retention rate of the device can reach 64.9%; as shown in FIG. 15, after 11000 cycles of charge and discharge test at a current density of 10A/g, the capacity retention rate can reach as high as 81.6%.
Tests have shown that two devices in series can light an LED bulb with a voltage of 1.8V when assembled into a symmetrical supercapacitor device using the active material.
[ example 2 ]
The present embodiment is different from embodiment 1 in that:
in the one-step molten salt electrolysis preparation process, the electrolysis current density is 0.2A/cm2And the electrolysis time is 4 hours.
[ example 3 ]
The present embodiment is different from embodiment 1 in that:
in the one-step molten salt electrolysis preparation process, the electrolysis current density is 0.3A/cm2And the electrolysis time is 2.67 h.
[ example 4 ]
The present embodiment is different from embodiment 1 in that:
in the one-step molten salt electrolysis preparation process, the electrolysis current density is 0.5A/cm2And the electrolysis time is 1.6 h.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A one-step molten salt electrolysis preparation method of porous sponge carbon is characterized in that nickel wires are used as an anode, galvanized iron wires are used as a cathode in the air atmosphere, and the preparation method is carried out in a molten Li-Na-K carbonate electrolyteElectrolyzing at a current density of 0.2A/cm2～0.9A/cm2The time is 4 h-0.89 h, and the total electric quantity is 3 Ah-5 Ah, so as to obtain the porous sponge carbon.
2. The one-step molten salt electrolysis preparation method of porous sponge carbon according to claim 1, wherein the surface areas of the electrodes of the nickel wire and the galvanized iron wire are both 4cm2～6cm2。
3. The one-step molten salt electrolysis preparation method of porous sponge carbon according to claim 2, wherein the nickel wire has a diameter of 2mm, a length of 8cm and a surface area of 5cm2(ii) a The galvanized iron wire has a diameter of 1mm, a length of 16cm and a surface area of 5cm2。
4. A one-step molten salt electrolysis preparation method of porous sponge carbon according to any one of claims 1 to 3, characterized in that Li-Na-K carbonate is first mixed according to the mass ratio of (30 ± 2) to (10 ± 2), and the mixed salt with the total mass of 40g to 60g is heated to 570 ℃ to 590 ℃ to be melted.
5. The one-step molten salt electrolysis preparation method of porous sponge carbon according to any one of claims 1 to 3, characterized in that the salt materials of Li-Na-K carbonate are Li respectively2CO3、Na2CO3And K2CO3。
6. The one-step molten salt electrolysis preparation method of porous sponge carbon according to any one of claims 1 to 3, wherein the distance between the cathode and the anode is 1 cm-3 cm, and the input current is 0.2A/cm2、0.3A/cm2、0.5A/cm2Or 0.9A/cm2The corresponding electrolysis time is 4h, 2.7h, 1.6h or 0.89h respectively.
7. The porous sponge carbon obtained by the one-step molten salt electrolysis preparation method according to any one of claims 1 to 6.
8. A one-step molten salt electrolysis preparation method of a supercapacitor electrode active material is characterized in that the porous sponge carbon of claim 7 is soaked for 6 to 12 hours by using 6 to 9mol/L hydrochloric acid, then is washed by deionized water to remove insoluble carbonate, and then is dried to obtain the supercapacitor electrode active material.
9. The supercapacitor electrode active material obtained by the one-step molten salt electrolysis preparation method according to claim 8.
10. An electrode or supercapacitor made from the porous sponge carbon of claim 7 or the supercapacitor electrode active material of claim 9.
CN201911300616.XA 2019-12-17 2019-12-17 Porous sponge carbon, one-step molten salt electrolysis preparation method thereof, electrode material and electrode Active CN111005027B (en)

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