CN108808033B - Method for preparing electrode material of supercapacitor by using waste zinc-manganese battery - Google Patents
Method for preparing electrode material of supercapacitor by using waste zinc-manganese battery Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 25
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 22
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- 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
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a method for preparing a supercapacitor electrode material by using waste zinc-manganese batteries, wherein the supercapacitor electrode material comprises a Zn-Mn blended oxide nano electrode material and a composite nano electrode material, zn and Mn elements are respectively recovered from the waste zinc-manganese batteries to obtain Mn (NO) 3 ) 2 Solution and ZnCl 2 A solution; then using Mn (NO) 3 ) 2 Solution and ZnCl 2 The solution is used for preparing Zn-Mn blended oxide nano electrode materials and composite nano electrode materials respectively. The invention not only can solve the environmental protection problem brought by the waste battery, but also can realize the recycling of waste resources. Realizes the reutilization of waste resources from the dual angles of environmental protection and energy development.
Description
Technical Field
The invention relates to the technical field of waste battery recycling, in particular to a method for preparing a supercapacitor electrode material by using a waste zinc-manganese battery.
Background
Since the 21 st century, the continuous development of the electronic industry has made batteries become indispensable products in people's life and production, wherein 80 ten thousand tons of automobile batteries, 19 ten thousand tons of industrial batteries and 16 ten thousand tons of portable batteries are put into the market in the european union alone every year, the production of waste batteries is also increasing year by year, and the average recovery rate of the waste batteries is only 13.6%. Among the consumable portable batteries, the zinc-manganese battery (including acidic and alkaline batteries) accounts for 90.8%, and since these waste batteries are not rechargeable, they are discarded after rapidly consuming the electricity, and a large amount of solid waste, including Zn, mn and other heavy metals, is generated, which causes serious pollution to the environment where human beings live. At present, IThe country has become the biggest battery producing country and consumer country in the world, and is also the biggest waste battery producing country. The waste portable batteries are generally treated as household garbage to be landfilled and burned, and the waste batteries enter the soil to threaten the ecological environment and human health and cause a great deal of waste of resources and energy. Therefore, it is important to recycle and recycle the waste batteries in a simple manner. At present, high-efficiency recycling methods with simple processes and low cost have been developed, and the new methods not only have positive influence on the environment, but also can prepare advanced functional materials. For example, tu et al recovered Zn-Mn waste batteries to prepare high efficiency nano-adsorbent for removing toxic metals; hu et al prepared Zn-Mn ferrite; qu et al prepared high efficiency ZnMnO photocatalysts for bisphenol A degradation; preparation of LiMn by Chen et al 2 O 4 The lithium ion battery positive electrode material is used for lithium battery positive electrode materials. Besides, the Zn-Mn waste battery can be used as an electrode material for preparing a super capacitor by recovering Zn-Mn waste batteries: ali, etc 5 The super capacitor is prepared by combining the nano flower-shaped manganese dioxide obtained by leaching and electrolytic deposition technologies, the good circulation stability is shown, and the capacitance can reach 294F/g at the sweeping speed of 10 mV/s; deng et al physically mix waste battery powder with graphene oxide or reduced graphene oxide to prepare manganese dioxide/graphene nano electrode material for a super capacitor to show high specific capacitance. From the above, it can be known that Zn and Mn recovered from waste batteries can be used as raw materials of supercapacitor electrode materials.
In addition, activated carbon materials prepared from sustainable biomass materials are receiving attention from researchers due to their advantages of abundant raw materials, simple preparation, low cost, and wide working temperature range. The rice straw, the wheat straw, the corn stalk, the peanut shell and the like are used as agricultural byproducts, and the agricultural byproducts are rich in resources and have reproducibility and cleanness. Apart from a small part of the biological materials used as feed or fertilizer, most of the biological materials are thrown away as fuel or waste, the utilization rate is low, not only is the natural resources greatly wasted, but also the environment is polluted. The crop byproducts can generate novel environment-functional biochar through a series of processes such as high-temperature calcination, carbonization and the like, and the surface of the biochar has rich functional groups and pore structures. The composite material mainly comprises carboxyl, phenolic hydroxyl, carbonyl, lactone, pyrone, anhydride and the like, and can fully utilize the surface functional group and the pore-size structure of biochar to prepare an excellent supercapacitor electrode material, thereby realizing double recycling of waste batteries and crop byproducts.
Disclosure of Invention
The invention aims to provide a method for preparing a supercapacitor electrode material by using a waste zinc-manganese battery, aiming at the defects in the prior art.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a supercapacitor electrode material by using a waste zinc-manganese battery, wherein the supercapacitor electrode material comprises a Zn-Mn blended oxide nano electrode material and a composite nano electrode material, and the method specifically comprises the following steps:
step 2, using Mn (NO) 3 ) 2 Solution and ZnCl 2 Respectively preparing a Zn-Mn blended oxide nano electrode material and a composite nano electrode material by using the solution:
1) Preparing a Zn-Mn blended oxide nano electrode material:
mixing Mn (NO) 3 ) 2 Solution and ZnCl 2 Mixing the solution according to a molar ratio of 4;
2) Preparing a composite nano electrode material: mixing charcoal powder according to a mass ratio of 1:0.5-3 to ZnCl 2 Fully soaking in the solution, filtering out precipitates, calcining for 2-6 hours at 700-1000 ℃ under an inert atmosphere, fully washing with HCl with the concentration of 0.1-0.5mol/L to remove residual oxides in the biochar, washing with deionized water and drying to obtain activated biochar; then carrying out oxidation modification treatment on the activated charcoal to obtain surface oxidation modified charcoal; adding surface oxidation modified charcoal into Mn (NO) 3 ) 2 Mixing and fully soaking in the solution, adding organic solvent and ligand, ultrasonic pulverizing and emulsifying, thermally reacting at 120-200 deg.C for 12-24 hr to obtain solid powder, and adding N 2 Or calcining at 700-1000 ℃ for 2-8 h under Ar atmosphere to obtain the composite nano electrode material.
In a further design scheme of the invention, in the step 1, the specific steps of respectively recovering Zn and Mn elements from the waste zinc-manganese battery are as follows: crushing the waste zinc-manganese dry batteries by adopting a mechanical crushing method, and respectively collecting a waste positive Mn compound and a waste negative Zn compound;
ultrasonically cleaning and filtering the Mn compound until the filtrate is neutral to obtain primary powder, and calcining the primary powder in a muffle furnace at 250-500 ℃ for 2-5 hours to obtain a recovered Mn compound; using 0.5-3 mol/L HNO 3 Solution with 30wt% H 2 O 2 Co-dissolving the calcined Mn compound, and filtering the filtrate to obtain recovered Mn (NO) 3 ) 2 A solution;
putting the Zn compound into 0.5-3 mol/L HCl solution to be stirred until the Zn compound is dissolved, thus obtaining the recovered ZnCl 2 And (3) solution.
In a further design scheme of the invention, the preparation of the charcoal powder in step 2 comprises the following specific steps: crushing peanut shells, corncobs, rice husks and wheat straws by a crusher, fully washing the crushed peanut shells, the corncobs, the rice husks and the wheat straws by deionized water to remove dust on the surfaces of the crushed peanut shells, drying the crushed peanut shells in an oven, calcining the crushed peanut shells for 2 to 6 hours at the temperature of between 400 and 550 ℃ in an inert atmosphere, and fully grinding the calcined peanut shells, the corncobs, the rice husks and the wheat straws to obtain the charcoal powder.
In a further design scheme of the invention, the specific step of carrying out oxidation modification treatment on the activated biochar in the step 2Comprises the following steps: mixing activated biochar with concentrated H 2 SO 4 Mixing with active biochar and concentrated H 2 SO 4 About 0.1g:10-50 mL. Cooling at 0-5 deg.C, adding KMnO 4 And NaNO 3 The mass ratio of the two is 1 (0.1-9), the reaction is carried out for 0.5-5H at the temperature of 40-80 ℃, the reaction product is diluted by deionized water after being cooled, and H is dropwise added 2 O 2 And standing until the mixture turns golden yellow or earthy yellow, and centrifugally washing to separate out solid powder to obtain the biochar with the surface oxidized and modified.
In a further design scheme of the invention, the ligand in the step 2 is any one of terephthalic acid, trimesic acid, p-xylylenediamine, trimethylamine, 1-methylimidazole and benzimidazole.
In a further design scheme of the invention, the organic solvent in step 2 is one or a mixture of any two of methanol, ethanol, ethylene glycol, N-octanol and N, N-dimethylformamide.
The invention has the following outstanding advantages:
the invention provides a method for preparing a high-performance supercapacitor electrode material by recycling waste batteries and agricultural and forestry wastes. The method comprises the steps of firstly recovering Mn and Zn metal elements from waste batteries as precursors to synthesize a nano porous super capacitor electrode material, and then compounding the recovered Mn and Zn metal elements with biochar derived from agricultural and forestry waste to obtain a high-performance super capacitor electrode material, so that the environmental protection problem brought by the waste batteries can be solved, and the recycling rate of agricultural and forestry waste resources can be realized to a certain extent. The waste resources are recycled from the dual aspects of environmental protection and energy development. The electrode material obtained by the invention has the advantages of higher specific surface area, better energy storage effect and easy operation of the preparation process.
Drawings
FIG. 1 is a flowchart of a method for producing an electrode material for a supercapacitor using a used zinc-manganese battery according to example 2;
FIG. 2 is a cyclic voltammogram of the Zn-Mn blended oxide nanoelectrode of example 1;
FIG. 3 is a charge and discharge curve of the Zn-Mn blended oxide nanoelectrode in example 1;
FIG. 4 is a cyclic voltammogram of the composite nanoelectrode material of example 2;
FIG. 5 is a charge and discharge curve of the composite nanoelectrode material in example 2.
Detailed Description
The invention is further explained below with reference to the drawings and examples.
Example 1
The method for preparing the Zn-Mn blended oxide nano electrode material by utilizing the waste zinc-manganese battery specifically comprises the following steps:
the method comprises the steps of crushing the waste zinc-manganese dry batteries by adopting a mechanical crushing method, and respectively collecting a waste positive Mn compound and a waste negative Zn compound. And (3) carrying out ultrasonic cleaning and filtering on the Mn compound until the filtrate is neutral to obtain primary powder, and calcining the primary powder in a muffle furnace at 400 ℃ for 3 hours to obtain the recovered Mn compound. Then, 60mL of 1 mol/L HNO was used 3 With 10 mL 30wt% H 2 O 2 Dissolving the calcined Mn compound together, and filtering to obtain filtrate, namely the recovered Mn (NO) 3 ) 2 And (3) solution.
For the Zn collected, the clear solution was first washed with a large amount of deionized water, then weighed, 0.2g was taken, 0.5M HCl solution was added dropwise thereto and stirred until dissolved and filtered, and the filtrate was taken to obtain ZnCl 2 And (3) solution.
Step 2, using Mn (NO) 3 ) 2 Solution and ZnCl 2 Respectively preparing Zn-Mn blended oxide nano electrode materials by using the solution:
20mL of Mn (NO) 3 ) 2 Solution and ZnCl 2 And (2) blending the solutions, adding urea until the pH value of the solution is neutral, then adding ethanol until the total solution amount is 60mL, reacting at 120 ℃ for 24 hours, fully washing, filtering and drying precipitates by using deionized water and ethanol according to the volume ratio of 1.
Uniformly mixing the Zn-Mn blended oxide with acetylene black and Polyvinylidene Fluoride (PVDF) in a mass ratio of 7 4 The electrolyte is used as the electrolyte, ag/AgCl is used as a reference electrode, pt wires are used as a counter electrode, a cyclic voltammetry characteristic curve and constant current charge and discharge performance under different current densities are represented, detailed electrochemical performance is shown in figures 2 and 3, it can be seen that Zn-Mn blended nano oxide recovered from waste batteries shows good capacitance performance, the cyclic voltammetry curve in figure 2 shows that the nano oxide has good multiplying power as a super capacitor electrode material, and the constant current charge and discharge curve shows that the capacitance capacity can reach 135 mF/cm 2 。
Example 2
In this example, mn recovered from waste batteries is compounded with biochar derived from corncobs, and the obtained nanocomposite is used as a supercapacitor electrode, referring to fig. 1, the specific embodiment is as follows:
first, mn (NO) was obtained from the waste batteries by the method of example 1 3 ) 2 Solution and ZnCl 2 Solution, wherein Zn is weighed.
Secondly, taking agricultural and sideline products corncobs, crushing the corncobs into small particles, washing the corncobs with a large amount of deionized water to remove dust, ultrasonically washing the corncobs with 5 wt% of HCl to remove soluble impurities, washing the corncobs to be neutral, and drying the corncobs. Then placing the mixture in a tube furnace at N 2 Pre-calcining at 450 deg.c to obtain charcoal powder. Reacting ZnCl 2 Soaking the solution with 0.5 g charcoal powder, steaming to remove excessive water, and oven dryingAfter drying, placing in N 2 And (3) calcining for 4 hours in a tubular furnace, fully washing with 80 mL of 0.5mol/L HCl to remove residual oxides in the biochar, and drying after washing with deionized water to obtain the activated biochar.
Then, znCl is put into 2 0.1g of activated charcoal after treatment and 10 mL of concentrated H 2 SO 4 Mixing well, placing in ice water for cooling, then slowly adding 0.2g KMnO 4 ，0.1 g NaNO 3 Reacting at 60 deg.C for 3H, cooling, diluting with deionized water, and dripping H dropwise 2 O 2 And standing until the mixture turns golden yellow, and then centrifugally washing to obtain the biochar with the surface subjected to oxidation modification.
Further, mn (NO) recovered from waste batteries is taken 3 ) 2 Fully soaking and mixing 20mL of the solution with 0.1g of biochar subjected to surface oxidation modification, adding 20mL of ethylene glycol and 20mL of ethanol, adding ligand terephthalic acid, performing ultrasonic grinding and emulsification, placing the mixture into a reaction kettle, reacting for 24 hours at 150 ℃, washing the obtained product by using a mixed solvent of ethanol and water, placing the product into a vacuum oven, drying the product at 80 ℃ overnight, and then performing N-phase oxidation on the product 2 Or calcining the mixture in Ar at the high temperature of 800 ℃ for 4 hours to finally obtain the composite nano electrode material.
And finally, uniformly mixing the composite nano electrode material with acetylene black and Polyvinylidene Fluoride (PVDF) according to the mass ratio of 7 4 Hg/HgO is used as a reference electrode and ZnCl is used as an electrolyte 2 The treated biochar is used as a counter electrode, an asymmetric capacitor is prepared, a cyclic voltammetry characteristic curve and constant current charging and discharging performance of the capacitor under different current densities are represented, and a cyclic voltammetry curve and a charging and discharging curve thereof are shown in fig. 3. The discovery of Mn element and ZnCl recovered from waste batteries 2 When the composite nano material obtained by compounding the activated and surface oxidation modified biochar is treated as the anode and the activated biochar is treated as the cathode, the assembled water system asymmetric super capacitor shows better capacitance performance, and the energy density is about 31.3 under the current density of 1A/gWh•g -1 The power density is about 834W.g -1 。
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (6)
1. A method for preparing a supercapacitor electrode material by using a waste zinc-manganese battery is characterized in that the supercapacitor electrode material comprises a Zn-Mn blended oxide nano electrode material and a composite nano electrode material, and specifically comprises the following steps:
step 1, respectively recovering Zn and Mn from waste zinc-manganese batteries to obtain Mn (NO) 3 ) 2 Solution and ZnCl 2 A solution;
step 2, using Mn (NO) 3 ) 2 Solution and ZnCl 2 Respectively preparing a Zn-Mn blended oxide nano electrode material and a composite nano electrode material by using the solution:
1) Preparing a Zn-Mn blended oxide nano electrode material:
mixing Mn (NO) 3 ) 2 Solution and ZnCl 2 Mixing the solution according to a molar ratio of 4;
2) Preparing a composite nano electrode material: mixing charcoal powder according to a mass ratio of 1:0.5-3 to ZnCl 2 Fully soaking in the solution, filtering out precipitates, calcining for 2-6 hours at 700-1000 ℃ under an inert atmosphere, fully washing with HCl with the concentration of 0.1-0.5mol/L to remove residual oxides in the biochar, washing with deionized water and drying to obtain activated biochar; then carrying out oxidation modification treatment on the activated charcoal to obtain surface oxidation modified charcoal; general watchAdding surface oxidation modified charcoal into Mn (NO) 3 ) 2 Mixing and fully soaking in the solution, adding organic solvent and ligand, ultrasonic pulverizing and emulsifying, thermally reacting at 120-200 deg.C for 12-24 hr to obtain solid powder, and adding N 2 Or calcining at 700-1000 ℃ for 2-8 h under Ar atmosphere to obtain the composite nano electrode material.
2. The method for preparing the electrode material of the supercapacitor by using the waste zinc-manganese battery as claimed in claim 1, wherein in the step 1, the specific steps of respectively recovering Zn and Mn from the waste zinc-manganese battery are as follows: crushing the waste zinc-manganese dry batteries by adopting a mechanical crushing method, and respectively collecting a waste positive Mn compound and a waste negative Zn compound;
carrying out ultrasonic cleaning and filtering on the Mn compound until the filtrate is neutral to obtain primary powder, and calcining the primary powder in a muffle furnace at 250-500 ℃ for 2-5 hours to obtain a recovered Mn compound; using 0.5-3 mol/L HNO 3 Solution with 30wt% H 2 O 2 Co-dissolving the calcined Mn compound and filtering the filtrate to obtain recovered Mn (NO) 3 ) 2 A solution;
putting the Zn compound into 0.5-3 mol/L HCl solution, stirring until the Zn compound is dissolved, and obtaining the recovered ZnCl 2 And (3) solution.
3. The method for preparing the electrode material of the supercapacitor by using the waste zinc-manganese battery according to claim 1, wherein the preparation of the charcoal powder in the step 2 comprises the following specific steps: crushing peanut shells, corncobs, rice husks and wheat straws by a crusher, fully washing the crushed peanut shells, the corncobs, the rice husks and the wheat straws by deionized water to remove dust on the surfaces of the crushed peanut shells, drying the crushed peanut shells in an oven, calcining the crushed peanut shells for 2 to 6 hours at the temperature of between 400 and 550 ℃ in an inert atmosphere, and fully grinding the calcined peanut shells, the corncobs, the rice husks and the wheat straws to obtain the charcoal powder.
4. The method for preparing the electrode material of the supercapacitor by using the waste zinc-manganese battery according to claim 1, wherein the step 2 of carrying out oxidation modification treatment on the activated charcoal comprises the following specific steps: will be aliveBiochar and concentrated H 2 SO 4 Mixing with active biochar and concentrated H 2 SO 4 In a ratio of 0.1g:10-50 mL, fully cooling at 0-5 ℃, and then adding KMnO 4 And NaNO 3 The mass ratio of the two is 1:0.1-9, the reaction is carried out for 0.5-5H at the temperature of 40-80 ℃, the reaction solution is diluted by deionized water after being cooled, and H is dropwise added 2 O 2 And standing until the mixture turns golden yellow or earthy yellow, and centrifugally washing and separating solid powder to obtain the biochar with the surface subjected to oxidation modification.
5. The method for preparing the electrode material of the supercapacitor by using the waste zinc-manganese dioxide battery according to claim 1, wherein the ligand in the step 2 is any one of terephthalic acid, trimesic acid, p-xylylenediamine, trimethylamine, 1-methylimidazole and benzimidazole.
6. The method for preparing the electrode material of the supercapacitor by using the waste zinc-manganese dioxide battery according to claim 1, wherein the organic solvent in the step 2 is one or a mixture of any two of methanol, ethanol, ethylene glycol, N-octanol and N, N-dimethylformamide.
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