CN113732013A - Microwave catalytic treatment method for waste photovoltaic module and silicon-carbon composite material obtained by microwave catalytic treatment method - Google Patents
Microwave catalytic treatment method for waste photovoltaic module and silicon-carbon composite material obtained by microwave catalytic treatment method Download PDFInfo
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- CN113732013A CN113732013A CN202110994947.9A CN202110994947A CN113732013A CN 113732013 A CN113732013 A CN 113732013A CN 202110994947 A CN202110994947 A CN 202110994947A CN 113732013 A CN113732013 A CN 113732013A
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02W30/20—Waste processing or separation
-
- 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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Abstract
The invention provides a catalytic assisted microwave pyrolysis treatment method for a waste photovoltaic module and a silicon-carbon composite material obtained by the catalytic assisted microwave pyrolysis treatment method. The processing method comprises the following steps: (1) carrying out glass dismantling treatment on the abandoned photovoltaic module to obtain glassGlass and a battery piece attached with organic matters; (2) embrittlement and crushing are carried out on the battery piece attached with the organic matter to obtain silicon/organic matter mixed powder; (3) mixing the silicon/organic matter mixed powder with a catalyst, performing microwave pyrolysis, and separating the catalyst in the product to obtain a silicon-carbon composite material and hydrogen; the catalyst is a metal and/or a metal oxide. The method utilizes the microwave pyrolysis assisted by catalysis to decompose the plastic in the waste photovoltaic module into C and H in one step2C may form a silicon-carbon composite anode material with the silicon material, and H2The solar photovoltaic module can be further used as clean energy, and the problems that the silicon material in the photovoltaic module is difficult to efficiently recover with added value and the organic matter glue film on the surface or the plastic backboard is difficult to degrade are solved.
Description
Technical Field
The invention belongs to the technical field of waste photovoltaic module treatment, and relates to a microwave catalytic treatment method of a waste photovoltaic module and a silicon-carbon composite material obtained by the microwave catalytic treatment method, namely a treatment method and application of a silicon-based cell in the waste photovoltaic module.
Background
In recent years, photovoltaic technology is rapidly developed, the global photovoltaic loading capacity exceeds 750GW in 2020, the number is still increasing rapidly, the service life of a photovoltaic module is only 25 years, and the huge loading capacity is achieved, so that the disposal of waste modules is a problem. The silicon-based photovoltaic module mainly comprises toughened glass, an encapsulating adhesive film (ethylene-vinyl acetate copolymer), a silicon-based battery piece (containing Ag, Al, Cu, Pb and other metals), a back plate (TPT, TPE, KPK, KPE, PPE and other metals), a metal electrode, a metal aluminum frame and a junction box. If the photovoltaic module is simply buried, a large amount of valuable metals can be wasted, and the existence of heavy metals and difficultly degraded adhesive films in the module can cause great harm to the ecological environment. Therefore, the development of green and environment-friendly low-energy-consumption recovery technology is of great significance.
At present, the retired photovoltaic module is mainly recovered by a physical splitting method, a chemical dissolving method, a heat treatment method and the like, and a certain effect is achieved in the field of photovoltaic module recovery. Meanwhile, the silicon-based battery piece is easy to crack in the recovery process and enter a complex system consisting of glass, plastic and metal impurities, so that the silicon-based battery piece is difficult to separate and purify, and the recovery value of silicon is reduced. In view of the above problems, it is urgent to provide a feasible recycling scheme to achieve efficient recycling and value-added utilization of components in the module.
CN110961432A discloses a photovoltaic module recovery method and equipment. According to the method, the frame and the junction box of the photovoltaic assembly are disassembled, and the back substrate is peeled off, so that the pretreated photovoltaic assembly without the frame, the junction box and the back substrate is obtained. And then, carrying out high-temperature pyrolysis on the pretreated photovoltaic module to obtain a pyrolyzed photovoltaic module, and sequentially carrying out heat preservation and cooling treatment on the pyrolyzed photovoltaic module to obtain a photovoltaic cell, a welding strip and a front substrate which are separated from each other, so that the photovoltaic module is separated and recovered. The traditional pyrolysis mode is adopted for treatment, and the waste gas treatment capacity is large.
CN110328216A discloses a photovoltaic module recycling method. According to the method, a backboard of the frameless photovoltaic module is peeled off to obtain the backboard and the peeled photovoltaic module, the peeled photovoltaic module is pyrolyzed, a film layer in the peeled photovoltaic module is completely pyrolyzed to obtain a cell piece and a substrate, the frameless photovoltaic module is completely separated to obtain the complete backboard, the cell piece and the substrate which are mutually separated, and the photovoltaic module is recycled. The method in the patent has the problems of complex process, large waste gas treatment capacity and the like, and the back plate structure after high-temperature pyrolysis is damaged to some extent, so that the utilization value of the back plate is reduced. In the current literature, an organic glue film or a plastic back plate on the surface of a battery piece needs to be separated by a traditional pyrolysis mode or soaking treatment, and the back plate structure after high-temperature treatment is damaged, so that the utilization value of the back plate is reduced, and the photovoltaic component cannot be comprehensively recycled.
Therefore, how to solve the problems of efficient value-added recovery of silicon-based battery pieces in the waste photovoltaic modules and difficult degradation of surface organic matter glue films or plastic back plates is urgently needed to be researched.
Disclosure of Invention
The invention aims to provide a microwave catalytic treatment method of a waste photovoltaic module and a silicon-carbon composite material obtained by the microwave catalytic treatment method. The invention decomposes high molecular polymer plastics in the waste photovoltaic module into C and H in one step by using a catalyst-assisted microwave pyrolysis technology2Wherein C can form a silicon-carbon composite cathode material with a silicon raw material of a cell slice, and H2The solar photovoltaic module can be further used as clean energy, comprehensive utilization of the waste photovoltaic module is realized, waste is changed into valuable, and the problems that a silicon-based cell in the photovoltaic module is efficient, value-added and recycled and a surface organic matter adhesive film or a plastic back plate is difficult to degrade are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for treating a waste photovoltaic module, the method comprising the steps of:
(1) carrying out glass dismantling treatment on the waste photovoltaic module to obtain glass and a cell attached with organic matters;
(2) carrying out embrittlement and crushing treatment on the battery piece attached with the organic matter in the step (1) to obtain silicon/organic matter mixed powder;
(3) mixing the silicon/organic matter mixed powder obtained in the step (2) with a catalyst, and performing microwave pyrolysis to obtain a silicon-carbon composite material and hydrogen;
wherein, the catalyst in the step (3) is metal and/or metal oxide.
In the invention, the organic matter in the cell attached with the organic matter is various high molecular material polymers (such as various adhesive films and back sheets on the surface of a silicon wafer) on the surface of the cell in a conventional photovoltaic module, including but not limited to TPT, TPE, KPK, KPE, PPE or EVA, etc.
According to the invention, various attached organic matters on the surface of the silicon wafer in the photovoltaic module do not need to be removed; the method comprises the steps of carrying out microwave pyrolysis on silicon/organic matter mixed powder, taking metal or metal oxide as a catalyst, and decomposing organic matters (high molecular polymers) in the waste photovoltaic module into C and H in one step2Wherein C can form silicon with the silicon raw materialCarbon composite anode material, and H2The catalyst can be further used as clean energy, comprehensive utilization of the waste photovoltaic module is realized, waste is changed into valuable, the problems of high efficiency and value-added recovery of silicon-based cells in the photovoltaic module and difficulty in degradation of organic matter adhesive films or plastic back plates on the surface are solved, the catalyst can be recycled for multiple times after being separated, and high efficiency recovery and value-added utilization of components of the module are realized.
According to the invention, microwave pyrolysis and a catalyst have synergistic effect, organic matters on the surface of the cell can be efficiently degraded into carbon and hydrogen on the premise of ensuring the minimization of side reaction, other pyrolysis means is adopted, the side reaction is greatly increased, the value of a product and the recovery efficiency of plastics are greatly reduced due to the generation of a large amount of by-products, and a large amount of harmful gases are generated. If no catalyst is added in the microwave pyrolysis process, the high-efficiency decomposition and activation of the plastic are difficult to realize, the absorption capacity of the plastic to the microwave is very weak, and meanwhile, the catalytic cracking (carbon-hydrogen bond is preferentially broken) and induced growth of the catalyst are avoided, so that the nano carbon material (carbon nano tube, graphene and the like) and hydrogen are difficult to form.
Preferably, the silicon-carbon composite material obtained in the step (3) is subjected to metal-assisted chemical etching to obtain a porous silicon-carbon composite material or a porous silicon-carbon composite material loaded with nano metal.
In the invention, the introduced nano metal particles can be left to obtain the porous silicon-carbon composite material loaded with nano metal after completing catalytic etching pore-forming, and the porous silicon-carbon composite material can also be obtained after removing the nano metal particles.
According to the invention, by further etching the silicon-carbon composite material, on one hand, the obtained porous structure can effectively relieve the volume expansion of silicon, and on the other hand, the nano metal particles loaded in the silicon-carbon composite material can improve the conductivity of the silicon-carbon material and improve the electrochemical performance of the material, so that the high-performance lithium ion battery porous silicon-carbon composite negative electrode material is obtained, and meanwhile, harmful metal components such as Al, Fe, Pb and the like doped in the preparation of a battery piece can be removed through metal-assisted chemical etching.
Preferably, the solution for metal-assisted chemical etching comprises a hydrogen fluoride solution, a metal salt solution and alcohol.
In the invention, the hydrogen fluoride plays a role in assisting the nano metal particles to etch the pore forming on the surface and inside of the silicon material, and simultaneously can effectively remove harmful metals (such as Al, Fe, Pb and the like) doped in the preparation of the solar silicon battery, and the pore forming treatment of the silicon material and the compounding treatment of the nano metal particles are realized by etching the metal salt solution.
Preferably, the molar concentration of the hydrogen fluoride solution is 0.1-10 mol/L, such as 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10 mol/L.
Preferably, the metal salt solution has a molar concentration of 0.01 to 10mol/L, such as 0.01mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10 mol/L.
Preferably, the molar concentration of the alcohol in the solution for metal-assisted chemical etching is 1-10 mol/L, such as 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10 mol/L.
Preferably, the liquid-solid ratio of the metal-assisted chemical etching solution to the silicon-carbon composite material in the step (3) is mL: g (20-200): 1, for example, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, or 200: 1.
Preferably, the metal salt in the metal salt solution comprises AgNO3、Cu(NO3)2、Ni(NO3)2、CuCl2、CuSO4Or NiSO4Any one or a combination of at least two of them.
Preferably, the alcohol in the solution for metal-assisted chemical etching includes any one of ethanol, propanol, butanol, ethylene glycol or propylene glycol or a combination of at least two thereof.
Preferably, the waste photovoltaic module in the step (1) is subjected to aluminum frame removal and junction box treatment.
Preferably, the glass in the step (1) is cleaned and recycled.
Preferably, the cleaning solution comprises an organic cleaning solution and/or an inorganic cleaning solution.
Preferably, the inorganic cleaning solution has a molar concentration of 0.5 to 4mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, or 4 mol/L.
Preferably, the organic cleaning solution comprises any one of toluene, ethanol or acetone or a combination of at least two of the toluene, the ethanol and the acetone.
Preferably, the inorganic cleaning solution includes any one or a combination of at least two of hydrochloric acid, nitric acid, acetic acid, potassium hydroxide, or sodium hydroxide.
Preferably, in the silicon/organic matter mixed powder in the step (2), the mass ratio of silicon to organic matter is 1 (1 to 9), for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, or 1: 9.
Preferably, the equipment for the pulverization treatment in the step (2) comprises any one of a crusher, a vibration mill, a high-energy ball mill or a planetary ball mill.
Preferably, in the pulverizing treatment process in the step (2), when a high-energy ball mill is adopted, the rotating speed is 200-800 r/min, such as 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min, the ball milling time is 1-24 h, such as 1h, 5h, 10h, 15h, 20h or 24h, and the ball-to-material ratio is (10-100): 1, such as 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100: 1.
In the present invention, the material of the grinding ball in the ball mill includes, but is not limited to, forged steel, cast iron, manganese steel, ceramics or metal oxide, etc., and the diameter of the grinding ball may be selected from 1 to 10mm, for example, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, etc.
Preferably, the silicon/organic matter mixed powder of step (2) has a median particle diameter of 100 μm or less, for example 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, 20 μm or 10 μm, etc.
Preferably, the metal comprises Fe and/or Ni.
In the invention, Fe and/or Ni are/is selected as the catalyst, which is more favorable for inducing the catalytic pyrolysis carbon to regrow into the nano carbon material.
Preferably, the metal oxide comprises FeAlOx、Fe2O3、Fe3O4、Al2O3Or Co3O4Any one or a combination of at least two of them.
In the invention, the metal oxide is selected as the catalyst, so that the effect of catalyzing the hydrocarbon bond fracture is achieved, and the hydrogen production capacity is improved.
Preferably, in the step (3), the size of the catalyst is 50-1000 nm, such as 50nm, 60nm, 70nm, 80nm, 90nm or 100 nm.
In the step (2), the molar ratio of the silicon/organic matter mixed powder to the catalyst is preferably (1 to 10: 1), for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10: 1.
In the invention, the molar ratio of the silicon/organic matter mixed powder to the catalyst is too large, which is not beneficial to the catalytic reaction, and too small, which can lead to the great reduction of the plastic recovery efficiency.
Preferably, in the microwave pyrolysis in the step (3), the power of the microwave is 1000-5000W, such as 1000W, 1500W, 2000W, 2500W, 3000W, 3500W, 4000W, 4500W or 5000W.
In the invention, the microwave pyrolysis power is too low to reach the condition of catalytic pyrolysis reaction, and the power is too high, which leads to the waste of a large amount of microwave radiation energy.
Preferably, the microwave pyrolysis time in the step (3) is 5-120 min, such as 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 80min, 100min, or 120 min.
Preferably, the microwave pyrolysis process of step (3) is carried out under a protective atmosphere.
Preferably, sorting the products after microwave pyrolysis in the step (3) by using physicochemical property difference.
In the invention, the product after microwave pyrolysis also comprises the catalyst, and the catalyst needs to be removed and recovered through sorting.
Preferably, the method of sorting comprises any one or a combination of at least two of magnetic separation, flotation, electrical separation, gravity separation or chemical separation.
Preferably, the form of carbon in the silicon-carbon composite material in step (3) includes any one or a combination of at least two of amorphous carbon, graphitic carbon, carbon nanotubes, graphene or fullerene.
As a preferred technical solution, the processing method comprises the steps of:
(1) after the waste photovoltaic module is subjected to aluminum frame and wire box dismantling treatment, glass dismantling treatment is carried out to obtain glass and a battery piece attached with organic matters;
(2) carrying out soaking embrittlement treatment on the battery piece attached with the organic matter in the step (1), and crushing to obtain mixed powder of silicon and the organic matter with the mass ratio of 1 (1-9);
(3) mixing the silicon/organic matter mixed powder obtained in the step (2) with a catalyst according to the molar ratio of (1-10) to (1), performing microwave pyrolysis for 5-60 min under a protective atmosphere at the power of 1000-5000W, and sorting products by using physicochemical property difference to obtain a silicon-carbon composite material and hydrogen;
(4) carrying out metal-assisted chemical etching on the silicon-carbon composite material obtained in the step (3) to obtain a porous silicon-carbon composite material or a porous silicon-carbon composite material loaded with nano metal;
wherein, the catalyst in the step (3) is metal and/or metal oxide; the metal comprises Fe and/or Ni; the metal oxide comprises FeAlOx、Fe2O3、Fe3O4、Al2O3Or Co3O4Any one or a combination of at least two of them.
In a second aspect, the invention provides a use of a waste photovoltaic module, wherein the use comprises that the waste photovoltaic module is treated by the treatment method of the waste photovoltaic module according to the first aspect to obtain glass, a silicon-carbon composite material and hydrogen.
Preferably, the silicon-carbon composite material is a porous silicon-carbon composite negative electrode material or a porous silicon-carbon negative electrode material loaded with nano metal.
Compared with the prior art, the invention has the following beneficial effects:
the invention decomposes high molecular polymers in the waste photovoltaic module into C and H in one step by using catalyst-assisted microwave pyrolysis2Wherein C can form a silicon-carbon composite anode material with a silicon raw material, and H2The silicon-carbon composite material can be further used as clean energy, realizes comprehensive utilization of waste photovoltaic modules, changes waste into valuable, solves the problems of high efficiency and value-added recovery of silicon-based battery pieces in the photovoltaic modules and difficulty in degradation of organic matter adhesive films or plastic back plates on the surfaces of the silicon-based battery pieces and the problems of high efficiency and value-added recovery of the components of the modules, can be recycled for multiple times, and realizes high efficiency recovery and value-added utilization of the components of the modules-1The first effect can reach more than 75.5 percent, the capacity retention rate after 200 cycles can reach more than 71.7 percent, and the specific discharge capacity of the battery prepared by the silicon-carbon cathode loaded with metal can reach 2341mAh g after further metal-assisted chemical etching-1The first effect can reach more than 91.6 percent, the capacity retention rate after 200 cycles can reach more than 92.5 percent, and meanwhile, the technical scheme provided by the invention can also obtain a certain amount of hydrogen with higher purity.
Drawings
Fig. 1 is an SEM image of the silicon carbon composite material in example 1.
Fig. 2 is a graph showing cycle performance of the battery of example 1, in which different materials are used as negative electrodes, wherein the negative electrodes are respectively a silicon/organic matter mixed powder, a silicon-carbon composite material and a porous silicon-carbon negative electrode material loaded with nano Ag.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) after the aluminum frame and the junction box of the waste photovoltaic module are removed, the surface glass is separated from a cell piece matrix (a glue film/a cell piece/a back plate) by adopting hot knife cutting, and cleaning and drying are carried out;
(2) putting the glass in the step (1) into a cleaning solution (the volume ratio of nitric acid to hydrochloric acid is 3:1) for cleaning and impurity removal, and realizing recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (1) in liquid nitrogen for 12 hours, and crushing the battery piece into powder with the particle size of less than 100 microns by using a crusher to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with FeAlOxMixing the materials according to a molar ratio of 1:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 25min under the protection of nitrogen at a power of 3000W to obtain the FeAlO-doped materialxSilicon carbon anode material and H2And collecting H with a gas collecting device2；
(5) Will be doped with FeAlOxThe silicon-carbon cathode material utilizes the density difference to sort FeAlO by adopting a gravity separation methodxObtaining a silicon-carbon cathode material;
(6) placing the silicon-carbon negative electrode material in HF-AgNO3Ethanol solution (with HF concentration of 0.1mol/L, AgNO)3The concentration is 0.1mol/L, the ethanol concentration is 1mol/L, and the liquid-solid ratio is 50:1), metal-assisted chemical etching (MACE) treatment is carried out at room temperature, deionized water is used for ultrasonic cleaning, and then the porous silicon-carbon negative electrode material loaded with nano Ag is obtained after suction filtration and drying.
Fig. 1 shows an SEM image of a silicon carbon anode material in example 1; fig. 2 is a graph showing cycle performance of the battery of example 1 in which different materials were used as negative electrodes, i.e., a silicon/organic matter mixed powder, a silicon carbon negative electrode material, and a porous silicon carbon negative electrode material loaded with Ag. As can be seen from fig. 1, the organic matter has been pyrolyzed into carbon and coated on the surface of the silicon particles to form a core-shell structure. As can be seen from FIG. 2, the capacity of the silicon/organic matter mixed powder negative electrode material is attenuated very fast, and the cycle performance is poor; the Ag-loaded porous silicon carbon negative electrode material has excellent cycle performance, and has high specific capacity of 2165mAh/g after 200 cycles of cycle.
Example 2
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) removing the aluminum frame and the junction box from the waste photovoltaic module to obtain a glass-covered battery module substrate (comprising a glue film, a battery piece and a back plate);
(2) soaking the assembly in the step (1) in toluene for 24h, performing ultrasonic treatment for 10min to enable glass to fall off to obtain a glass and glue film/battery piece/back plate composite, and putting the glass in a cleaning solution (the volume ratio of toluene to hydrochloric acid is 2:1) to clean and remove impurities to realize recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (2) in liquid nitrogen for 12 hours, and crushing the battery piece into powder with the particle size of less than 100 microns by using a crusher to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with FeAlOxMixing the materials according to a molar ratio of 2:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 10min under the protection of nitrogen and with the power of 5000W to obtain the FeAlO doped with the nitrogenxSilicon carbon anode material and H2And collecting H with a gas collecting device2；
(5) Will be doped with FeAlOxThe silicon-carbon cathode material utilizes the density difference to sort FeAlO by adopting a gravity separation methodxObtaining a silicon-carbon cathode material;
(6) placing the silicon-carbon negative electrode material in HF-AgNO3Ethanol solution (with HF concentration of 0.1mol/L, AgNO)3The concentration is 0.01mol/L, the ethanol concentration is 2mol/L, the liquid-solid ratio is 80:1), metal-assisted chemical etching (MACE) treatment is carried out at room temperature, deionized water is used for ultrasonic cleaning, and then the porous silicon-carbon negative electrode material loaded with the nano Ag is obtained after suction filtration and drying.
Example 3
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) after the aluminum frame and the junction box of the waste photovoltaic module are removed, mechanically cutting the waste photovoltaic module into small blocks, and cleaning and drying the small blocks;
(2) placing the small block assembly in the step (1) in n-hexane for soaking for 36h, performing ultrasonic treatment for 10min to enable glass to fall off to obtain glass and a battery piece attached with organic matters, and placing the glass in a cleaning solution (toluene) to clean and remove impurities to realize recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (2) in liquid nitrogen for 12 hours, and crushing the battery piece into powder with the particle size of less than 100 microns by using a crusher to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with Fe3O4Mixing the materials according to a molar ratio of 1:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 55min under the protection of nitrogen at 3000W to obtain Fe-doped material3O4Silicon carbon anode material and H2And collecting H with a gas collecting device2；
(5) Will be doped with Fe3O4The silicon-carbon cathode material utilizes the magnetic difference to separate Fe by magnetic separation3O4Obtaining a silicon-carbon cathode material;
(6) placing the silicon-carbon negative electrode material in HF-AgNO3Ethanol solution (with HF concentration of 0.5mol/L, AgNO)3The concentration is 0.05mol/L, the ethanol concentration is 1mol/L, the liquid-solid ratio is 100:1), metal-assisted chemical etching (MACE) treatment is carried out at room temperature, deionized water is used for ultrasonic cleaning, and then the porous silicon-carbon negative electrode material loaded with the nano Ag is obtained after suction filtration and drying.
Example 4
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) after the aluminum frame and the junction box of the waste photovoltaic module are removed, mechanically cutting the waste photovoltaic module into small blocks, and cleaning and drying the small blocks;
(2) placing the small block assembly in the step (1) in n-hexane for soaking for 24h, performing ultrasonic treatment for 20min to enable glass to fall off to obtain glass and a battery piece attached with organic matters, and placing the glass in a cleaning solution (the volume ratio of toluene to nitric acid is 1:1) to clean and remove impurities to realize recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (2) in liquid nitrogen for 12 hours, and crushing the battery piece into powder with the particle size of less than 100 microns by using a crusher to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with Fe3O4Mixing the materials according to a molar ratio of 3:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 55min under the protection of nitrogen at 3000W to obtain Fe-doped material3O4Silicon carbon anode material and H2And collecting H with a gas collecting device2；
(5) Will be doped with Fe3O4The silicon-carbon cathode material utilizes the magnetic difference to separate Fe by adopting a magnetic separation method3O4Obtaining a silicon-carbon cathode material;
(6) placing the silicon-carbon negative electrode material in HF-Cu (NO)3)2Ethanol solution (with HF concentration of 0.1mol/L, Cu (NO)3)2Carrying out metal-assisted chemical etching (MACE) treatment at room temperature in a concentration of 0.01mol/L, an ethanol concentration of 1mol/L and a liquid-solid ratio of 150:1), carrying out ultrasonic cleaning by using deionized water, and carrying out suction filtration and drying to obtain the porous silicon-carbon negative electrode material loaded with the nano Cu particles.
Example 5
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) after the aluminum frame and the junction box of the waste photovoltaic module are removed, mechanically cutting the waste photovoltaic module into small blocks, and cleaning and drying the small blocks;
(2) placing the small block assemblies in the step (1) in toluene for soaking for 48h, performing ultrasonic treatment for 30min to enable the glass to fall off to obtain glass and a battery piece attached with organic matters, and placing the glass in a cleaning solution (the volume ratio of the toluene to the trichloroethylene is 1:1) to clean and remove impurities to realize recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (2) in liquid nitrogen for 24 hours, and then crushing the battery piece into powder with the particle size of less than 100 microns by using a ball mill to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with Fe according to a molar ratio of 4:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 25min at 3000W under the protection of nitrogen, and obtaining a silicon-carbon negative electrode material doped with Fe and H2And collecting H with a gas collecting device2；
(5) Separating Fe from the Fe-doped silicon-carbon negative electrode material by using magnetic difference and adopting a magnetic separation method to obtain the silicon-carbon negative electrode material;
(6) placing the silicon-carbon negative electrode material in HF-Cu (NO)3)2Ethanol solution (with HF concentration of 0.1mol/L, Cu (NO)3)2Carrying out metal-assisted chemical etching (MACE) treatment at room temperature in a concentration of 0.5mol/L, an ethanol concentration of 1mol/L and a liquid-solid ratio of 180:1), carrying out ultrasonic cleaning by using deionized water, and carrying out suction filtration and drying to obtain the porous silicon-carbon cathode material loaded with the nano Cu.
Example 6
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) after the aluminum frame and the junction box of the waste photovoltaic module are removed, mechanically cutting the waste photovoltaic module into small blocks, and cleaning and drying the small blocks;
(2) placing the small block assembly in the step (1) in n-hexane for soaking for 48h, performing ultrasonic treatment for 30min to enable glass to fall off to obtain glass and a battery piece attached with organic matters, and placing the glass in a cleaning solution (trichloroethylene) to clean and remove impurities to realize recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (2) in liquid nitrogen for 24 hours, and then crushing the battery piece into powder with the particle size of less than 100 microns by using a ball mill to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with Al2O3Mixing the materials according to a molar ratio of 3:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 25min under the protection of nitrogen at a power of 3000W to obtain Al-doped material2O3Silicon carbon anode material and H2And collecting H with a gas collecting device2；
(5) Will be doped with Al2O3The silicon-carbon cathode material utilizes the density difference to separate Al by adopting a gravity separation method2O3Obtaining a silicon-carbon cathode material;
(6) placing the silicon-carbon negative electrode material in HF-Cu (NO)3)2Ethanol solution (with HF concentration of 0.3mol/L, Cu (NO)3)2Carrying out metal-assisted chemical etching (MACE) treatment at room temperature in a concentration of 0.05mol/L, an ethanol concentration of 3mol/L and a liquid-solid ratio of 200:1), carrying out ultrasonic cleaning by using deionized water, and carrying out suction filtration and drying to obtain the porous silicon-carbon cathode material loaded with the nano Cu.
Example 7
The embodiment provides a method for treating a waste photovoltaic module, which comprises the following steps:
(1) after the aluminum frame and the junction box of the waste photovoltaic module are removed, the surface glass is separated from a cell piece matrix (a glue film/a cell piece/a back plate) by adopting hot knife cutting, and cleaning and drying are carried out;
(2) putting the glass in the step (1) into a cleaning solution (the volume ratio of nitric acid to hydrochloric acid is 3:1) for cleaning and impurity removal, and realizing recovery of the glass;
(3) soaking and embrittling the battery piece attached with the organic matter in the step (1) in liquid nitrogen for 24 hours, and crushing the battery piece into powder with the particle size of less than 100 microns by using a crusher to obtain silicon/organic matter mixed powder;
(4) mixing the silicon/organic matter mixed powder in the step (3) with FeAlOxMixing the materials according to a molar ratio of 3:1, placing the mixture in a mixer to be uniformly mixed, placing the mixed material in a microwave tube furnace to be pyrolyzed for 40min under the protection of nitrogen and with the power of 2000W to obtain the FeAlO-doped materialxSilicon carbon anode material and H2And collecting H with a gas collecting device2；
(5) Will be doped with FeAlOxThe silicon-carbon cathode material utilizes the density difference to sort FeAlO by adopting a gravity separation methodxObtaining a silicon-carbon cathode material;
(6) placing the silicon-carbon negative electrode material in HF-AgNO3Ethanol solution (with HF concentration of 0.1mol/L, AgNO)3The concentration is 0.01mol/L, the ethanol concentration is 1mol/L, the liquid-solid ratio is 100:1), metal-assisted chemical etching (MACE) treatment is carried out at room temperature, deionized water is used for ultrasonic cleaning, and then the porous silicon-carbon negative electrode material loaded with nano Ag is obtained after suction filtration and drying.
(7) Immersing the porous silicon-carbon negative electrode material loaded with the nano Ag into a nitric acid solution (20% HNO)3) Soaking for 15min to remove Ag nano particles and obtain the porous silicon-carbon negative electrode material.
Comparative example 1
The present comparative example is different from example 1 in that in the step (4) of the present comparative example, pyrolysis was performed at a temperature of 800 ℃ in a tube furnace.
The rest of the preparation methods and parameters were in accordance with the examples.
Comparative example 2
The present comparative example is different from example 1 in that FeAlO was not added in step (4) of the present comparative examplexA catalyst.
The rest of the preparation methods and parameters were in accordance with the examples.
The silicon-carbon negative electrode materials provided in examples 1 to 7 and comparative examples 1 to 2, the porous silicon-carbon negative electrode material loaded with metal particles, and the porous silicon-carbon negative electrode material in example 7 were assembled into a lithium ion button type half cell, and electrochemical performance tests were performed on the half cell:
test conditions were 1A g-1The results are shown in Table 1, and Table 1 also shows the results for H in examples 1 to 7 and comparative examples 1 to 22The yield of (2).
TABLE 1
From the data results in examples 1-7, it can be seen that the silicon carbon anode material further treated by MACE shows more excellent electrochemical performance due to the design of the porous structure.
From the data results of example 1 and comparative examples 1 and 2, it can be seen that the single carbon nanomaterial and hydrogen gas can not be obtained by pyrolysis methods other than microwave pyrolysis, and during the microwave pyrolysis, the high-efficiency pyrolysis of the high-molecular polymer adhesive film can not be realized without adding a catalyst.
In summary, the invention utilizes the microwave and the catalyst to decompose the high molecular polymer in the waste photovoltaic module into C and H in one step2Wherein C can form a silicon-carbon composite anode material with a silicon raw material, and H2The catalyst can be further used as clean energy, comprehensive utilization of the waste photovoltaic module is realized, waste is changed into valuable, the problems that silicon is difficult to purify and plastics are difficult to degrade are solved, the catalyst can be recycled for multiple times, and efficient recovery and value-added utilization of components of the module are realized.
According to the invention, through further etching the silicon-carbon negative electrode material, the obtained porous structure can effectively relieve the volume expansion of silicon, and the metal particles loaded in the porous structure can improve the conductivity of the silicon-carbon material and improve the electrochemical performance of the material, so that the high-performance lithium ion battery silicon-carbon composite negative electrode material is obtained, and meanwhile, through metal-assisted chemical etching, harmful metals such as Al, Fe, Pb and the like doped in the silicon material can be removed-1The first effect can reach more than 75.5 percent, the capacity retention rate after 200 cycles can reach more than 71.7 percent, and the specific discharge capacity of the battery prepared by the silicon-carbon cathode loaded with metal can reach 2341mAh g after further metal-assisted chemical etching-1The first effect can reach more than 91.6 percent, and the capacity retention rate after 200 cycles can reach more than 92.5 percent, and meanwhile, the technical method provided by the inventionA certain amount of hydrogen with higher purity can be obtained.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for processing a waste photovoltaic module is characterized by comprising the following steps:
(1) carrying out glass dismantling treatment on the waste photovoltaic module to obtain glass and a cell attached with organic matters;
(2) carrying out embrittlement and crushing treatment on the battery piece attached with the organic matter in the step (1) to obtain silicon/organic matter mixed powder;
(3) mixing the silicon/organic matter mixed powder obtained in the step (2) with a catalyst, and performing microwave pyrolysis to obtain a silicon-carbon composite material and hydrogen;
wherein, the catalyst in the step (3) is metal and/or metal oxide.
2. The method for treating the waste photovoltaic module as claimed in claim 1, wherein the silicon-carbon composite material obtained in the step (3) is subjected to metal-assisted chemical etching to obtain a porous silicon-carbon composite material or a porous silicon-carbon composite material loaded with nano-metal;
preferably, the solution for metal-assisted chemical etching comprises a hydrogen fluoride solution, a metal salt solution and alcohol;
preferably, the molar concentration of the hydrogen fluoride solution is 0.1-10 mol/L;
preferably, the molar concentration of the metal salt solution is 0.01-10 mol/L;
preferably, the molar concentration of alcohol in the solution for metal-assisted chemical etching is 1-10 mol/L;
preferably, the liquid-solid ratio of the solution for metal-assisted chemical etching to the silicon-carbon composite material in the step (3) is mL, g is (20-200): 1;
preferably, the metal salt in the metal salt solution comprises AgNO3、Cu(NO3)2、Ni(NO3)2、CuCl2、CuSO4Or NiSO4Any one or a combination of at least two of;
preferably, the alcohol in the solution for metal-assisted chemical etching includes any one of ethanol, propanol, butanol, ethylene glycol or propylene glycol or a combination of at least two thereof.
3. The method for processing the waste photovoltaic module as claimed in claim 1 or 2, wherein the waste photovoltaic module in the step (1) is subjected to aluminum frame dismantling and junction box treatment;
preferably, the glass in the step (1) is cleaned and recycled;
preferably, the cleaning solution comprises an organic cleaning solution and/or an inorganic cleaning solution;
preferably, the molar concentration of the inorganic cleaning liquid is 0.5-4 mol/L;
preferably, the organic cleaning solution comprises any one or a combination of at least two of toluene, ethanol or acetone;
preferably, the inorganic cleaning solution includes any one or a combination of at least two of hydrochloric acid, nitric acid, acetic acid, potassium hydroxide, or sodium hydroxide.
4. The method for treating the waste photovoltaic module as claimed in any one of claims 1 to 3, wherein in the mixed powder of silicon/organic matter in the step (2), the mass ratio of silicon to organic matter is 1 (1-9);
preferably, the equipment for the pulverization treatment in the step (2) comprises any one of a crusher, a vibration mill, a high-energy ball mill or a planetary ball mill;
preferably, in the crushing treatment process in the step (2), when a high-energy ball mill is adopted, the rotating speed is 200-800 r/min, the ball milling time is 1-24 h, and the ball-to-material ratio is (10-100): 1;
preferably, the median particle diameter of the silicon/organic matter mixed powder in the step (2) is less than or equal to 100 μm.
5. The method for treating waste photovoltaic modules according to any one of claims 1 to 4, wherein the metal comprises Fe and/or Ni;
preferably, the metal oxide comprises FeAlOx、Fe2O3、Fe3O4、Al2O3Or Co3O4Any one or a combination of at least two of;
preferably, in the step (3), the size of the catalyst is 50-1000 nm;
preferably, in the step (3), the molar ratio of the silicon/organic matter mixed powder to the catalyst is (1-10): 1.
6. The method for treating the waste photovoltaic module as claimed in any one of claims 1 to 5, wherein in the microwave pyrolysis in the step (3), the power of the microwave is 1000-5000W;
preferably, the microwave pyrolysis time in the step (3) is 5-120 min;
preferably, the microwave pyrolysis process of step (3) is carried out under a protective atmosphere.
7. The method for treating the waste photovoltaic module as claimed in any one of claims 1 to 6, wherein the product after the microwave pyrolysis in the step (3) is sorted by using physicochemical property difference;
preferably, the method of sorting comprises any one or a combination of at least two of magnetic separation, flotation, electrical separation, gravity separation or chemical separation.
8. The method for treating waste photovoltaic modules according to any one of claims 1 to 7, wherein the form of carbon in the silicon-carbon composite material in step (3) comprises any one or a combination of at least two of amorphous carbon, graphitic carbon, carbon nanotubes, graphene or fullerene.
9. The method for treating waste photovoltaic modules according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) removing an aluminum frame and a junction box from the waste photovoltaic module, and then removing glass to obtain glass and a battery piece attached with organic matters;
(2) carrying out embrittlement treatment on the battery piece attached with the organic matter in the step (1), and crushing to obtain mixed powder of silicon and the organic matter with the mass ratio of 1 (1-9);
(3) mixing the silicon/organic matter mixed powder obtained in the step (2) with a catalyst according to the molar ratio of (1-10) to (1), performing microwave pyrolysis for 5-120 min at the power of 1000-5000W in a protective atmosphere, and sorting products by using physicochemical property difference to obtain a silicon-carbon composite material and hydrogen;
(4) carrying out metal-assisted chemical etching on the silicon-carbon composite material obtained in the step (3) to obtain a porous silicon-carbon composite material or a porous silicon-carbon composite material loaded with nano metal;
wherein, the catalyst in the step (3) is metal and/or metal oxide; the metal comprises Fe and/or Ni; the metal oxide comprises FeAlOx、Fe2O3、Fe3O4、Al2O3Or Co3O4Any one or a combination of at least two of them.
10. Use of a waste photovoltaic module, wherein the use comprises subjecting the waste photovoltaic module to a treatment method of a waste photovoltaic module according to any one of claims 1 to 9 to obtain glass, a silicon-carbon composite material and hydrogen;
preferably, the silicon-carbon composite material is a porous silicon-carbon composite material or a porous silicon-carbon composite material loaded with nano metal.
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