CN113387343B - Method for preparing silicon-carbon cathode of lithium ion battery by using retired photovoltaic module - Google Patents
Method for preparing silicon-carbon cathode of lithium ion battery by using retired photovoltaic module Download PDFInfo
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- CN113387343B CN113387343B CN202110661558.4A CN202110661558A CN113387343B CN 113387343 B CN113387343 B CN 113387343B CN 202110661558 A CN202110661558 A CN 202110661558A CN 113387343 B CN113387343 B CN 113387343B
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- 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
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
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- 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
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- 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
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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- 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
Abstract
The invention discloses a method for preparing a silicon-carbon cathode of a lithium ion battery by using a retired photovoltaic module, which comprises the following steps: crushing the silicon wafer mixed with the silver electrode and the aluminum back plate into fragments; carrying out high-energy ball milling on the fragments by a ball mill; performing ball milling on the fragments subjected to the high-energy ball milling again through a ball mill; stirring and dissolving the product after ball milling again and an organic carbon source in an organic solvent; drying the dissolved product; and putting the dried product into a furnace for high-temperature carbonization to obtain the silicon-carbon cathode material. The photovoltaic module is made of the retired raw materials, so that the high-efficiency recovery and value-added utilization of retired devices are realized; the used process is high-energy ball milling, the process is stable, and the equipment operation is simple; the carbon coating is realized by utilizing the organic carbon source, the problems of volume expansion and poor conductivity of silicon as the cathode are solved, and the electrochemical performance of the silicon-carbon cathode is improved.
Description
Technical Field
The invention relates to the field of solar cells and lithium ion batteries, in particular to a method for preparing a silicon-carbon cathode of a lithium ion battery by using a retired photovoltaic module.
Background
Solar photovoltaic power generation has the advantages of safety, reliability, cleanness, high efficiency, sustainability and the like, is expected to solve the problems of energy shortage, environmental pollution and the like, is an important support for realizing the aim of carbon neutralization, and is rapidly developed in recent years. The photovoltaic market is continuously expanded, so that the number of retired waste crystalline silicon photovoltaic modules is increased rapidly. According to the prediction of the International Renewable energy agency (IRENA), the scrappage of photovoltaic modules reaches an amazing 7800 ten thousand tons by 2050 in the world, wherein the scrappage of Chinese modules exceeds 2000 ten thousand tons. If the traditional waste treatment methods such as incineration, landfill and the like are adopted, not only can great resource waste be caused, but also the serious environmental pollution problem can be caused. Therefore, the retired photovoltaic module is recycled, so that the ecological environment pressure can be effectively relieved, and the resource recycling is realized.
Scientists made much effort to do this, and the korean DSM (ACS sustamable Chemistry & Engineering 2016,4(8), 4079-. The methods realize the high-efficiency recovery of various valuable components, but more chemical reagents such as strong acid and strong base are needed in the process, the flow is long, and the silicon particles crushed in the early stage are lost in hydrofluoric acid, so that the element recovery rate is seriously reduced.
Lithium ion batteries are increasingly used in various industries as new batteries. With the development of scientific technology, the demand of high-specific energy batteries is increasing. The negative electrode has attracted much attention as one of the determining factors for determining the capacity performance of a lithium ion battery. The graphite cathode has the advantages of safety, stability, abundant reserves and the like as a mature cathode, but the application of the graphite cathode is limited by the low theoretical capacity of the graphite cathode. The silicon-based negative electrode serving as a lithium ion battery has the advantages of high specific capacity (4200mAh/g), no toxicity, environmental protection, low voltage platform, abundant storage capacity and the like, and becomes the most potential negative electrode material.
Much attention is paid to the method, Chen et al (J Appl electrochem.2009,39: 1157-. Cui et al (Nano Lett.2011,11, 2949--1The capacity per 100 cycles drops by less than 8% in a total of 700 cycles. However, these methods use starting materials of high purity and particle size less than100nm silicon particles are expensive and require the use of precision equipment, and are not suitable for industrial production.
Chinese patent (CN 110474032A) discloses a silicon-carbon cathode material based on photovoltaic waste silicon and a preparation method thereof, the silicon-carbon cathode material prepared by the method has high first efficiency and good cycle stability, and the preparation method has the advantages of cost advantage and simple operation and is suitable for industrial production. However, the method only considers the waste silicon generated in the process of preparing the crystalline silicon and does not process the retired silicon plate.
Chinese patent (CN202011137325.6) discloses a method for comprehensively recycling waste photovoltaic modules and preparing silicon-carbon cathode materials, the method comprises the steps of disassembling a photovoltaic module frame and a junction box, heating to soften a polymer TPT (thermoplastic vulcanizate) backboard assembly, cutting and separating along an EVA (ethylene vinyl acetate) film between glass and a silicon wafer to obtain the glass and a battery piece, placing the glass in a cleaning solution to remove the surface EVA film to realize recovery of the glass, placing the battery piece in liquid nitrogen to be soaked for extremely cold embrittlement treatment, crushing to obtain battery powder, carrying out high-temperature plasma activation and impurity removal treatment on the battery powder to obtain a nano Si/M/C composite material, placing the nano Si/M/C composite material in an HF (hydrogen fluoride) metal salt alcohol solution to carry out pore-forming and metal particle nano-particle composite to obtain a porous silicon/nano-metal composite material, and carrying out carbonization composite treatment on the porous silicon/nano-metal/carbon composite negative electrode material and a carbon material. According to the invention, the waste component glass and the silicon wafer are simultaneously recycled by combining mechanical dismantling and chemical synthesis, but an impurity removal process is required during silicon wafer treatment, chemical substances such as HF, metal salts and alcohols are used, the preparation process is long, and the treatment cost is increased.
In view of the above problems, a method with stable process and simple equipment operation is urgently needed to realize the recycling and value-added utilization of the silicon plate in the photovoltaic module.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a silicon-carbon cathode of a lithium ion battery by using a retired photovoltaic module, which mainly solves the problems of recycling and value-added utilization of the retired photovoltaic module.
In order to achieve the purpose, the invention provides a method for preparing a silicon-carbon cathode of a lithium ion battery by using a retired photovoltaic module, which comprises the following steps:
crushing the silicon wafer mixed with the silver electrode and the aluminum back plate into fragments; carrying out high-energy ball milling on the fragments by a ball mill; performing ball milling on the fragments subjected to the high-energy ball milling again through a ball mill; stirring and dissolving the product after ball milling again and an organic carbon source in an organic solvent; drying the dissolved product; and putting the dried product into a furnace for high-temperature carbonization to obtain the silicon-carbon cathode material.
Preferably, during high-energy ball milling, the size of ball milling beads is 1mm-20mm, the ball milling time is 1h-20h, the ball-material ratio is 5: 1-50: 1, the rotating speed is 300-.
Preferably, when the ball milling is carried out again, the size of the ball milling beads is 0.5mm-5mm, the ball milling time is 1h-20h, the ball-to-material ratio is 5: 1-50: 1, the rotating speed is 300-1600rpm, the ball milling atmosphere is an inert atmosphere, and the ball milling medium comprises one or more of deionized water, ethanol, methanol, isopropanol, n-hexane, isohexane and cyclohexane.
Preferably, the organic carbon source comprises one or more of glucose, sucrose, starch, citric acid monohydrate and dopamine hydrochloride; the organic solvent comprises one or more of N-methylpyrrolidone, ethanol, methanol, isopropanol, N-hexane, isohexane and cyclohexane.
Preferably, the stirring speed is 100-.
Preferably, the drying is carried out in vacuum or air atmosphere, the drying temperature is 40-200 ℃, and the drying time is 6-24 h.
Preferably, the carbonization is carried out at the temperature rise rate of 1-15 ℃/min to 500-1000 ℃, and the heat preservation time is 1-10 h.
The technical concept of the invention is as follows:
the existing recovery method of the retired photovoltaic module is to separate and recover silicon and various valuable metals to obtain silicon ingots and metals with higher purity. The process flow is long, and more and complex chemical reagents are used, so that more pollution is caused. And the purity of the product cannot meet the requirements of people in the recovery process, so the economic benefit is low.
Most of the silicon-carbon cathodes are prepared by using silane and generating silicon through complex chemical reaction, and the required equipment is precise, the cost is high, and the silicon-carbon cathodes are not suitable for large-scale production.
The invention uses the retired photovoltaic module as a raw material, thereby not only avoiding the process of separating silicon from valuable metals, but also solving the problem of poor conductivity of the silicon to a certain extent.
Compared with the prior art, the invention has at least the following advantages:
(1) the retired photovoltaic module used by the invention does not need other impurity removal processes, and valuable metals of silver and aluminum remained in the silicon plate improve the conductivity of silicon, so that the retired photovoltaic module can be directly used for preparing a silicon-carbon cathode.
(2) The silicon-carbon cathode raw material is a retired photovoltaic module, a new way is found for the treatment of the retired photovoltaic module, and the silicon-carbon cathode raw material belongs to resource recycling and value-added recycling and has excellent environmental protection value.
(3) The method has the advantages of stable process, simple equipment operation, suitability for large-scale production and good economic value.
Drawings
Fig. 1 is a silicon plate in a decommissioned photovoltaic module (left panel), and silicon powder obtained after high-energy and re-ball milling (right panel).
In fig. 2, a, B and C are high-magnification SEM images, D, E and F are low-magnification SEM images, a and D are SEM images after one ball milling, B and E are SEM images after two ball milling, and C and F are SEM images after high-temperature sintering.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited thereto.
Example 1
Step (1): crushing a silicon plate in a retired solar photovoltaic module into fragments smaller than 1 cm;
step (2): selecting a ball material ratio of 15: 1; and (3) performing primary ball milling on the fragments in the step (1) by using ball milling beads with the diameter of 10mm, wherein the ball milling atmosphere is argon, the ball milling medium is isopropanol, the rotating speed is 1200rpm, and the ball milling is performed for 12 hours.
And (3): selecting the raw materials obtained in the step (2) according to a ball-to-material ratio of 15: 1; and performing secondary ball milling by using ball milling beads with the diameter of 2mm, wherein the ball milling atmosphere is argon, the ball milling medium is isopropanol, the rotating speed is 1000rpm, and the ball milling is performed for 4 hours.
And (4): dissolving the raw material obtained in the step (3) and dopamine hydrochloride in isopropanol, and stirring at 600rpm for 6h at 50 ℃.
And (5): drying the raw material obtained in the step (4) at 75 ℃ for 20 h.
And (6): and (4) heating the raw material obtained in the step (5) to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 1h to obtain the silicon-carbon negative electrode material.
Claims (7)
1. A method for preparing a silicon-carbon cathode of a lithium ion battery by using a retired photovoltaic module is characterized by comprising the following steps:
crushing the silicon wafer mixed with the silver electrode and the aluminum back plate into fragments; carrying out high-energy ball milling on the fragments by a ball mill; performing ball milling on the fragments subjected to the high-energy ball milling again through a ball mill; stirring and dissolving the product after ball milling again and an organic carbon source in an organic solvent; drying the dissolved product; and putting the dried product into a furnace for high-temperature carbonization to obtain the silicon-carbon cathode material.
2. The method for preparing the silicon-carbon cathode of the lithium ion battery by using the retired photovoltaic module as claimed in claim 1, wherein during high-energy ball milling, the size of ball milling beads is 1mm-20mm, the ball milling time is 1h-20h, the ball-to-material ratio is 5: 1-50: 1, the rotation speed is 300-.
3. The method for preparing the silicon-carbon cathode of the lithium ion battery by using the retired photovoltaic module as claimed in claim 1, wherein the ball milling beads are 0.5mm-5mm in size during ball milling again, the ball milling time is 1h-20h, the ball-to-material ratio is 5:1 to 50:1, the rotation speed is 300-.
4. The method for preparing the silicon-carbon cathode of the lithium ion battery by using the retired photovoltaic module as claimed in claim 1, wherein the organic carbon source comprises one or more of glucose, sucrose, starch, citric acid monohydrate and dopamine hydrochloride; the organic solvent comprises one or more of N-methylpyrrolidone, ethanol, methanol, isopropanol, N-hexane, isohexane and cyclohexane.
5. The method for preparing the silicon-carbon cathode of the lithium ion battery by using the retired photovoltaic module as claimed in claim 1, wherein the stirring speed is 100-1500rpm, and the stirring temperature is 20-80 ℃.
6. The method for preparing the silicon-carbon cathode of the lithium ion battery by using the retired photovoltaic module as claimed in claim 1, wherein the drying is carried out in vacuum or air atmosphere, the drying temperature is 40-200 ℃, and the drying time is 6-24 h.
7. The method for preparing the silicon-carbon cathode of the lithium ion battery by using the retired photovoltaic module as claimed in claim 1, wherein the carbonization is performed at a temperature rise rate of 1-15 ℃/min to 500-1000 ℃ for 1-10 h.
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| CN103474666B (en) * | 2013-07-23 | 2016-03-02 | 江苏华东锂电技术研究院有限公司 | The preparation method of lithium ion battery anode active material |
| CN104538607B (en) * | 2014-12-19 | 2017-06-20 | 天津巴莫科技股份有限公司 | The preparation method of lithium-ion battery silicon-carbon anode material |
| CN105576209B (en) * | 2016-02-04 | 2017-11-24 | 中南大学 | A kind of high-capacity lithium ion cell silicon based anode material and preparation method thereof, lithium ion battery |
| CN110098443B (en) * | 2019-05-17 | 2021-08-27 | 浙江卡波恩新材料有限公司 | Method for coating waste lithium battery negative electrode material with carbon |
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