WO2017113755A1 - Method for recycling crystalline silicon solar cell assemblies - Google Patents

Method for recycling crystalline silicon solar cell assemblies Download PDF

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WO2017113755A1
WO2017113755A1 PCT/CN2016/090287 CN2016090287W WO2017113755A1 WO 2017113755 A1 WO2017113755 A1 WO 2017113755A1 CN 2016090287 W CN2016090287 W CN 2016090287W WO 2017113755 A1 WO2017113755 A1 WO 2017113755A1
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solar cell
crystalline silicon
cell chip
recycling
cutting device
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PCT/CN2016/090287
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French (fr)
Chinese (zh)
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苏冠贤
刘建
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东莞珂洛赫慕电子材料科技有限公司
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Publication of WO2017113755A1 publication Critical patent/WO2017113755A1/en

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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
    • 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
    • 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

A method for recycling crystalline silicon solar cell assemblies, comprising the following process steps: a. disassembling an aluminum frame and a junction box from a solar panel by means of a mechanical disassembling approach; b. removing, by a cutting device, rubber seals around the edges of the solar panel with the aluminum frame and the junction box disassembled; c. separating, by the cutting device, ultra-clear glass, an EVA film, a cell sheet, a back sheet film, and a back sheet from the solar panel with the rubber seals around the edges removed; d. dissolving the cell sheet obtained by separation and the cross-linked EVA in a solvent to obtain a solar cell chip; and e. processing the solar cell chip by a chemical method to obtain a silicon material and silver powder. By means of the design of the process steps, resources of crystalline silicon solar cell assemblies can be effectively recycled, thereby achieving desirable energy saving and environmental protection effects as well as high social and economic benefits.

Description

一种晶体硅太阳电池组件资源化的方法Method for recycling crystalline silicon solar cell components 技术领域Technical field
本发明涉及物料回收循环利用技术领域，尤其涉及一种晶体硅太阳电池组件资源化的方法。The invention relates to the technical field of material recycling and recycling, and in particular to a method for recycling a crystalline silicon solar cell module.
背景技术Background technique
太阳能被视为一种废物产生量最小的能源，在组件的使用过程中不会产生对环境有害的废物；然而，太阳能电池报废后产生的固体废弃物也不能够忽视。其中，太阳电池组件资源的寿命周期一般为20-25年，当转化效率降低到一定程度时，电池失效，需要报废更新；另外，在电池、电池组件生产、光伏电站维护过程中也会产生大量报废组件。预计从2020年之后，全球及我国的太阳能电池的固体废弃物会出现大幅度增长，累计废弃量也会逐渐增加，届时太阳能电池的处理处置和回收利用将会成为一个重要的环保课题。Solar energy is regarded as an energy source with the least amount of waste generated. It does not produce environmentally harmful waste during the use of the components; however, the solid waste generated after the solar cells are scrapped cannot be ignored. Among them, the life cycle of solar cell component resources is generally 20-25 years. When the conversion efficiency is reduced to a certain extent, the battery fails and needs to be scrapped and updated; in addition, a large amount is generated in the battery, battery component production, and photovoltaic power plant maintenance process. Retirement components. It is expected that after 2020, the solid waste of solar cells in the world and China will increase significantly, and the accumulated waste will gradually increase. At that time, the disposal, disposal and recycling of solar cells will become an important environmental issue.
另一方面，晶体硅电池生产过程中会产生大量电池废品，对其进行回收利用可以降低成本，特别是在生产中实现物料可循环利用以及排废再利用具有极大的经济价值和环保生态效益。On the other hand, a large amount of battery waste will be produced in the production process of crystalline silicon cells, and recycling thereof can reduce the cost, especially in the production of materials that can be recycled and waste recycling and reuse have great economic value and environmental protection ecological benefits. .
截止2015年，光伏累计装机量接近190GW，晶体硅太阳能电池组件及芯片中主要含有的材料为硅、银、铝、铜、钢化玻璃、EVA膜等，潜在待回收的硅料约589000吨、白银5700000kg、铝材2270000吨、超白玻璃9450000吨、铜84400吨，对其实现环保处理并循环利用具有十分积极的意义，光伏发电将不仅作为清洁能源被使用，更将转变为可持续发展利用的清洁能源。As of 2015, the cumulative installed capacity of photovoltaics is close to 190GW. The main materials contained in crystalline silicon solar modules and chips are silicon, silver, aluminum, copper, tempered glass, EVA film, etc. The potential silicon material to be recycled is about 589,000 tons and silver. 5700000kg, 2.27 million tons of aluminum, 9450000 tons of ultra-clear glass, and 84,400 tons of copper have very positive significance for environmentally friendly treatment and recycling. Photovoltaic power generation will be used not only as clean energy but also for sustainable development. clean energy.
然而，现有技术中并没有能够有效地对晶体硅太阳电池组件资源化的方法。However, there is no method in the prior art that can effectively resource a crystalline silicon solar cell module.
发明内容Summary of the invention
本发明的目的在于针对现有技术的不足而提供一种晶体硅太阳电池组件资源化的方法，该晶体硅太阳电池组件资源化的方法能够有效地对晶体硅太阳电池组件资源进行再资源化处理，节能环保效果好，社会经济效益好。The object of the present invention is to provide a method for recycling a crystalline silicon solar cell module according to the deficiencies of the prior art, and the method for recycling the crystalline silicon solar cell module can effectively re-resource the crystalline silicon solar cell component resources. The energy saving and environmental protection effect is good and the social and economic benefits are good.
为达到上述目的，本发明通过以下技术方案来实现。In order to achieve the above object, the present invention is achieved by the following technical solutions.
一种晶体硅太阳电池组件资源化的方法，包括有以下工艺步骤，具体为：A method for recycling a crystalline silicon solar cell module, comprising the following process steps, specifically:
a、通过机械拆解方式将太阳能电池板的铝边框、接线盒进行拆卸；a. Disassemble the aluminum frame and junction box of the solar panel by mechanical disassembly;
b、利用切割设备将拆卸铝边框、接线盒后的太阳能电池板的四周边缘橡胶封条进行去除；b. Using a cutting device to remove the rubber seal on the peripheral edge of the solar panel after removing the aluminum frame and the junction box;
c、利用切割设备将去除四周边缘橡胶封条后的太阳能电池板的超白玻璃、EVA膜、电池 片、背板膜、背板进行分离；c. Using the cutting device to remove the ultra-white glass, EVA film and battery of the solar panel after the rubber seal around the periphery Separating the sheet, the back sheet, and the back sheet;
d、将分离后的电池片与交联的EVA在溶剂中溶解，以分离出太阳电池芯片；d. Dissolving the separated cell sheet and the crosslinked EVA in a solvent to separate the solar cell chip;
e、将太阳电池芯片通过化学法进行处理，以获得硅料、银粉。e. The solar cell chip is processed by a chemical method to obtain a silicon material and a silver powder.
其中，所述步骤a中的机械拆解方式为人工借助机械工具的拆解方式或者自动化设备自动完成的拆解方式。Wherein, the mechanical dismantling mode in the step a is a dismantling method manually by means of a mechanical tool or a dismantling method automatically completed by an automatic device.
其中，所述步骤b、所述步骤c中的切割设备为常规切割器具或者精密自动化数控设备。Wherein, the cutting device in the step b and the step c is a conventional cutting device or a precision automatic numerical control device.
其中，所述步骤b中的切割设备为精密切边机。Wherein, the cutting device in the step b is a precision trimming machine.
其中，所述步骤c中的切割设备为超精密线切割机或者超精密激光切割机。Wherein, the cutting device in the step c is an ultra-precision wire cutting machine or an ultra-precision laser cutting machine.
其中，所述步骤e中的化学法处理方式包括有以下工艺步骤，具体为：Wherein, the chemical treatment method in the step e includes the following process steps, specifically:
1、将太阳电池芯片浸泡于碱溶液中，以除去太阳电池芯片铝背场的铝层；1. Soaking the solar cell chip in an alkali solution to remove the aluminum layer of the aluminum back field of the solar cell chip;
2、待太阳电池芯片完成碱反应后，将去铝太阳电池芯片进行清洗；2. After the solar cell chip completes the alkali reaction, the aluminum solar cell chip is removed for cleaning;
3、将清洗后的去铝太阳电池芯片置于硝酸溶液中进行浸泡，以浸出太阳电池芯片表面的Ag，并得到去银太阳电池芯片以及含银酸液；3. The cleaned aluminum solar cell chip is placed in a nitric acid solution for immersion to leaching Ag on the surface of the solar cell chip, and a silver-free solar cell chip and a silver-containing acid solution are obtained;
4、将含银酸液通过还原剂进行还原，得到银粉以供电子浆料生产制备；将去银太阳电池芯片置于强酸溶液中，以得到去氮化硅的硅片。4. The silver-containing acid solution is reduced by a reducing agent to obtain silver powder for production of an electronic slurry; the silver-free solar cell chip is placed in a strong acid solution to obtain a silicon nitride-removed silicon wafer.
本发明的有益效果为：本发明所述的一种晶体硅太阳电池组件资源化的方法，其包括有以下工艺步骤，具体为：a、通过机械拆解方式将太阳能电池板的铝边框、接线盒进行拆卸；b、利用切割设备将拆卸铝边框、接线盒后的太阳能电池板的四周边缘橡胶封条进行去除；c、利用切割设备将去除四周边缘橡胶封条后的太阳能电池板的超白玻璃、EVA膜、电池片、背板膜、背板进行分离；d、将分离后的电池片与交联的EVA在溶剂中溶解，以分离出太阳电池芯片；e、将太阳电池芯片通过化学法进行处理，以获得硅料、银粉。通过上述工艺步骤设计，本发明能够有效地对晶体硅太阳电池组件资源进行再资源化处理，节能环保效果好，社会经济效益好。The invention has the beneficial effects of the method for recycling a crystalline silicon solar cell module according to the present invention, which comprises the following process steps, specifically: a. aluminum frame and wiring of the solar panel by mechanical disassembly The box is disassembled; b. the aluminum frame and the rubber seal of the peripheral edge of the solar panel after the junction box are removed by using a cutting device; c. the ultra-white glass of the solar panel after the rubber seal of the peripheral edge is removed by using a cutting device, Separating the EVA film, the battery sheet, the back sheet film, and the back sheet; d, dissolving the separated battery sheet and the crosslinked EVA in a solvent to separate the solar cell chip; e, performing the chemical method on the solar cell chip Processing to obtain silicon material, silver powder. Through the above process step design, the invention can effectively re-resource the resources of the crystalline silicon solar cell module, has good energy saving and environmental protection effect, and has good social and economic benefits.
具体实施方式detailed description
下面结合具体的实施方式来对本发明进行说明。The invention will now be described in connection with specific embodiments.
一种晶体硅太阳电池组件资源化的方法，包括有以下工艺步骤，具体为：A method for recycling a crystalline silicon solar cell module, comprising the following process steps, specifically:
a、通过机械拆解方式将太阳能电池板的铝边框、接线盒进行拆卸；a. Disassemble the aluminum frame and junction box of the solar panel by mechanical disassembly;
b、利用切割设备将拆卸铝边框、接线盒后的太阳能电池板的四周边缘橡胶封条进行去除；b. Using a cutting device to remove the rubber seal on the peripheral edge of the solar panel after removing the aluminum frame and the junction box;
c、利用切割设备将去除四周边缘橡胶封条后的太阳能电池板的超白玻璃、EVA膜、电池 片、背板膜、背板进行分离；c. Using the cutting device to remove the ultra-white glass, EVA film and battery of the solar panel after the rubber seal around the periphery Separating the sheet, the back sheet, and the back sheet;
d、将分离后的电池片与交联的EVA在溶剂中溶解，以分离出太阳电池芯片；d. Dissolving the separated cell sheet and the crosslinked EVA in a solvent to separate the solar cell chip;
e、将太阳电池芯片通过化学法进行处理，以获得硅料、银粉。e. The solar cell chip is processed by a chemical method to obtain a silicon material and a silver powder.
需进一步解释，步骤a中的机械拆解方式为人工借助机械工具的拆解方式或者自动化设备自动完成的拆解方式；步骤b、步骤c中的切割设备为常规切割器具或者精密自动化数控设备，优选的，步骤b中的切割设备为精密切边机，步骤c中的切割设备为超精密线切割机或者超精密激光切割机。It should be further explained that the mechanical dismantling method in step a is a manual dismantling method by means of a mechanical tool or a dismantling method automatically completed by an automatic device; the cutting device in step b and step c is a conventional cutting device or a precision automatic numerical control device. Preferably, the cutting device in step b is a precision trimming machine, and the cutting device in step c is an ultra-precision wire cutting machine or an ultra-precision laser cutting machine.
需进一步指出，步骤e中的化学法处理方式包括有以下工艺步骤，具体为：It should be further pointed out that the chemical treatment in step e includes the following process steps, specifically:
1、将太阳电池芯片浸泡于碱溶液中，以除去太阳电池芯片铝背场的铝层；1. Soaking the solar cell chip in an alkali solution to remove the aluminum layer of the aluminum back field of the solar cell chip;
2、待太阳电池芯片完成碱反应后，将去铝太阳电池芯片进行清洗；2. After the solar cell chip completes the alkali reaction, the aluminum solar cell chip is removed for cleaning;
3、将清洗后的去铝太阳电池芯片置于硝酸溶液中进行浸泡，以浸出太阳电池芯片表面的Ag，并得到去银太阳电池芯片以及含银酸液；3. The cleaned aluminum solar cell chip is placed in a nitric acid solution for immersion to leaching Ag on the surface of the solar cell chip, and a silver-free solar cell chip and a silver-containing acid solution are obtained;
4、将含银酸液通过还原剂进行还原，得到银粉以供电子浆料生产制备；将去银太阳电池芯片置于强酸溶液中，以得到去氮化硅的硅片。4. The silver-containing acid solution is reduced by a reducing agent to obtain silver powder for production of an electronic slurry; the silver-free solar cell chip is placed in a strong acid solution to obtain a silicon nitride-removed silicon wafer.
下面结合具体的实施例来对本发明进行说明，具体为：将1000W组件通过机械拆解可得到铝10kg、铜0.5kg、塑料16kg、超白玻璃50kg，再将晶体硅太阳电池芯片用化学法处理；化学法处理过程如下：将太阳电池芯片浸泡于400L浓度为5％强碱溶液中直至铝背场完全去除；然后将无铝太阳电池芯片投入50L浓度为1.5％的硝酸溶液，使银溶解完全；而后把无银太阳电池芯片投入到20L含氢氟酸0.5％的溶液中，除去氮化硅，以得到纯净硅料30kg，硅料回收率约为90％；最后将含铝液体中的铝转化为氧化铝，得到约3kg氧化铝，铝回收率约为93％，含银溶液提取银粉0.028g银粉，银粉回收率约为95％。The present invention will be described below in conjunction with specific embodiments. Specifically, the 1000W component can be mechanically disassembled to obtain 10 kg of aluminum, 0.5 kg of copper, 16 kg of plastic, and 50 kg of ultra-clear glass, and then the crystalline silicon solar cell chip is chemically treated. The chemical treatment process is as follows: the solar cell chip is immersed in a 400 L concentration of 5% strong alkali solution until the aluminum back field is completely removed; then the aluminum-free solar cell chip is put into 50 L of a 1.5% nitric acid solution to completely dissolve the silver. Then, the silver-free solar cell chip is put into a 20L solution containing 0.5% hydrofluoric acid to remove silicon nitride to obtain 30 kg of pure silicon material, and the silicon material recovery rate is about 90%; finally, the aluminum in the aluminum-containing liquid is used. Conversion to alumina yields about 3 kg of alumina, the aluminum recovery is about 93%, the silver-containing solution extracts 0.028 g of silver powder, and the silver powder recovery is about 95%.
以上内容仅为本发明的较佳实施例，对于本领域的普通技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，本说明书内容不应理解为对本发明的限制。 The above content is only a preferred embodiment of the present invention, and those skilled in the art will have a change in the specific embodiment and application scope according to the idea of the present invention. The content of the present specification should not be construed as the present invention. limits.

Claims (6)

  1. 一种晶体硅太阳电池组件资源化的方法，其特征在于，包括有以下工艺步骤，具体为：A method for recycling a crystalline silicon solar cell module, comprising the following process steps, specifically:
    a、通过机械拆解方式将太阳能电池板的铝边框、接线盒进行拆卸；a. Disassemble the aluminum frame and junction box of the solar panel by mechanical disassembly;
    b、利用切割设备将拆卸铝边框、接线盒后的太阳能电池板的四周边缘橡胶封条进行去除；b. Using a cutting device to remove the rubber seal on the peripheral edge of the solar panel after removing the aluminum frame and the junction box;
    c、利用切割设备将去除四周边缘橡胶封条后的太阳能电池板的超白玻璃、EVA膜、电池片、背板膜、背板进行分离；c. separating the ultra-white glass, the EVA film, the battery sheet, the back sheet film and the back sheet of the solar panel after removing the rubber seal on the peripheral edge by using a cutting device;
    d、将分离后的电池片与交联的EVA在溶剂中溶解，以分离出太阳电池芯片；d. Dissolving the separated cell sheet and the crosslinked EVA in a solvent to separate the solar cell chip;
    e、将太阳电池芯片通过化学法进行处理，以获得硅料、银粉。e. The solar cell chip is processed by a chemical method to obtain a silicon material and a silver powder.
  2. 根据权利要求1所述的一种晶体硅太阳电池组件资源化的方法，其特征在于：所述步骤a中的机械拆解方式为人工借助机械工具的拆解方式或者自动化设备自动完成的拆解方式。The method for recycling a crystalline silicon solar cell module according to claim 1, wherein the mechanical disassembly method in the step a is a manual dismantling by means of a mechanical tool or an automatic dismantling by an automatic device. the way.
  3. 根据权利要求1所述的一种晶体硅太阳电池组件资源化的方法，其特征在于：所述步骤b、所述步骤c中的切割设备为常规切割器具或者精密自动化数控设备。The method for recycling a crystalline silicon solar cell module according to claim 1, wherein the cutting device in the step b and the step c is a conventional cutting device or a precision automatic numerical control device.
  4. 根据权利要求3所述的一种晶体硅太阳电池组件资源化的方法，其特征在于：所述步骤b中的切割设备为精密切边机。The method for recycling a crystalline silicon solar cell module according to claim 3, wherein the cutting device in the step b is a precision trimming machine.
  5. 根据权利要求3所述的一种晶体硅太阳电池组件资源化的方法，其特征在于：所述步骤c中的切割设备为超精密线切割机或者超精密激光切割机。The method for recycling a crystalline silicon solar cell module according to claim 3, wherein the cutting device in the step c is an ultra-precision wire cutting machine or an ultra-precision laser cutting machine.
  6. 根据权利要求1至5任意一项所述的一种晶体硅太阳电池组件资源化的方法，其特征在于，所述步骤e中的化学法处理方式包括有以下工艺步骤，具体为：The method for recycling a crystalline silicon solar cell module according to any one of claims 1 to 5, wherein the chemical processing method in the step e comprises the following process steps, specifically:
    1、将太阳电池芯片浸泡于碱溶液中，以除去太阳电池芯片铝背场的铝层；1. Soaking the solar cell chip in an alkali solution to remove the aluminum layer of the aluminum back field of the solar cell chip;
    2、待太阳电池芯片完成碱反应后，将去铝太阳电池芯片进行清洗；2. After the solar cell chip completes the alkali reaction, the aluminum solar cell chip is removed for cleaning;
    3、将清洗后的去铝太阳电池芯片置于硝酸溶液中进行浸泡，以浸出太阳电池芯片表面的Ag，并得到去银太阳电池芯片以及含银酸液；3. The cleaned aluminum solar cell chip is placed in a nitric acid solution for immersion to leaching Ag on the surface of the solar cell chip, and a silver-free solar cell chip and a silver-containing acid solution are obtained;
    4、将含银酸液通过还原剂进行还原，得到银粉以供电子浆料生产制备；将去银太阳电池芯片置于强酸溶液中，以得到去氮化硅的硅片。 4. The silver-containing acid solution is reduced by a reducing agent to obtain silver powder for production of an electronic slurry; the silver-free solar cell chip is placed in a strong acid solution to obtain a silicon nitride-removed silicon wafer.
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