热力发电

成分	Si	Al	Ag	Pb	Cu	Fe
质量分数/%	90.22	8.70	0.56	0.08	0.01	0.01

成分	Si	Al	Ag	Pb	Cu	Fe
质量分数/%	90.22	8.70	0.56	0.08	0.01	0.01

从退役晶硅光伏电池片提取银和铝技术研究

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李子菡 , 刘展 , 王洪亮 , 刘向辉 , 江清潘 , 周凤翔 , 刘明辉 , 张弘锦 , 赵晶 , 杨春振 , 何发泉

热力发电 | 退役风光设备资源化利用专题 2026,55(1): 85-91

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热力发电 |退役风光设备资源化利用专题 2026 , 55 (1) : 85 -91

从退役晶硅光伏电池片提取银和铝技术研究

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李子菡, 刘展, 王洪亮, 刘向辉, 江清潘, 周凤翔, 刘明辉, 张弘锦, 赵晶, 杨春振, 何发泉

作者信息

国能龙源环保有限公司，北京 100039

通讯作者:

何发泉（1970），男，博士，正高级工程师，主要从事节能环保、固废资源化利用等工作，faquan.he@chenergy.com.cn。

作者简介:

李子菡（1999），女，硕士，主要从事新能源固废资源化利用工作，1098082725@qq.com。

Study on recovering silver and aluminium from retired crystalline silicon solar cells

Zihan LI, Zhan LIU, Hongliang WANG, Xianghui LIU, Qingpan JIANG, Fengxiang ZHOU, Minghui LIU, Hongjin ZHANG, Jing ZHAO, Chunzhen YANG, Faquan HE

Affiliations

CHN Energy Longyuan Environmental Protection Co., Ltd., Beijing 100039, China

出版时间: 2026-01-25 doi: 10.19666/j.rlfd.202508071

文章导航

摘要

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退役晶硅光伏电池资源化回收对于材料的循环和新能源绿色健康发展具有重要意义。目前，主流退役光伏组件回收企业多聚焦于铝边框回收技术，而晶硅电池片中高价值银和铝资源尚未实现有效回收。为此，提出了液碱浸铝-硝酸浸银-液相还原制备银粉湿法回收工艺。通过优化实验参数，在氢氧化钠浓度1.0 mol/L、温度20 ℃、液固比10：1（mL/g）、反应时间40 min条件下，退役晶硅光伏电池铝的浸出率达到98.88%，同时硅浸出损失率仅为0.46%；在硝酸浓度4.0 mol/L、温度70 ℃、液固比5：1（mL/g）、反应时间60 min条件下，银的浸出率达到98.00%。以抗坏血酸作为还原剂，在抗坏血酸与银离子摩尔比1.25：1.00、温度30 ℃、搅拌速度250 r/min的条件下成功制备了纯度99.9%以上的银粉。该工艺具有回收率高、产品纯度高等特点，为退役光伏组件中晶硅电池片的资源化利用提供了有效途径。

关键词

晶硅光伏组件 / 晶硅电池片 / 浸出 / 银 / 铝 / 回收

Abstract

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The resource-recycling of retired crystalline-silicon photovoltaic cells is of great significance for the recycling of materials and the green and healthy development of renewable energy. Currently, most recyclers of decommissioned photovoltaic modules mainly focus on the recycling of aluminium frames, while aluminium resources in crystalline-silicon solar cells have not been effectively recycled, leaving valuable silver within the cells. Therefore, a wet-recycling process for preparing silver powder was proposed, which involves leaching aluminum with liquid alkali, leaching silver with nitric acid, and liquid-phase reduction. By optimizing the experimental parameters, under the conditions of a sodium-hydroxide concentration of 1.0 mol/L, a temperature of 20 ℃, a liquid-to-solid ratio of 10:1 (mL/g), and a reaction time of 40 min, the leaching rate of aluminum from the retired crystalline-silicon photovoltaic cells reached 98.88%, and the leaching-loss rate of silicon was only 0.46%. Under the conditions of a nitric-acid concentration of 4.0 mol/L, a temperature of 70 ℃, a liquid-to-solid ratio of 5:1 (mL/g), and a reaction time of 60 min, the leaching rate of silver reached 98.00%. Using ascorbic acid as a reducing agent, silver powder with a purity of over 99.9% was successfully prepared under the conditions of a molar ratio of ascorbic acid to silver ions of 1.25:1.00, a temperature of 30 ℃, and a stirring speed of 250 r/min. This process achieves high recovery rates and product purity, offering a practical pathway for crystalline silicon solar cell wafers recycling.

Key words

silicon PV module / silicon solar cell / leaching / silver / aluminum / recovery

引用本文

李子菡, 刘展, 王洪亮, 刘向辉, 江清潘, 周凤翔, 刘明辉, 张弘锦, 赵晶, 杨春振, 何发泉. 从退役晶硅光伏电池片提取银和铝技术研究. 热力发电, 2026 , 55 (1) : 85 -91 . DOI: 10.19666/j.rlfd.202508071

Zihan LI, Zhan LIU, Hongliang WANG, Xianghui LIU, Qingpan JIANG, Fengxiang ZHOU, Minghui LIU, Hongjin ZHANG, Jing ZHAO, Chunzhen YANG, Faquan HE. Study on recovering silver and aluminium from retired crystalline silicon solar cells[J]. Thermal Power Generation, 2026 , 55 (1) : 85 -91 . DOI: 10.19666/j.rlfd.202508071

正文

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过去15年我国光伏新能源产业实现了跨越式发展，目前，我国光伏发电装机容量已突破9.45亿千瓦。光伏组件设计寿命为20~25年，同时因自然灾害、政策驱动等原因，每年大约有1%的光伏组件由于损坏或迭代而退役^[1-4]。从2030年左右开始，光伏组件将进入密集报废期，2035年后每年将超过100万吨退役量，2040年将有超过200万吨退役量^[5]。

退役晶硅光伏组件拆解后得到玻璃、焊带、电池片等组分，其主要的回收价值来自铝边框、焊带中的铜、电池片中的银^[6-9]，如果不对电池片和焊带中的金属进行妥善处置，银、铜等重金属元素会通过理化作用逐渐渗漏至土壤中，进而对土壤、地下水等环境和植被、动物等生态要素造成危害和污染，直至通过生物富集作用从而危害人类自身的生命健康^[10]。晶硅光伏电池片采用单晶硅或多晶硅电池片作为光吸收器，表面覆有银栅线，光伏组件的银质量分数为0.02%~0.05%，均值为0.035%^[11-12]。银因在新能源与高科技产业的不可替代性、供给刚性缺口及国家政策管控，已被明确列为战略资源和高风险等级供应金属^[13]，白银正从传统贵金属转向“光伏血液”与“AI芯片关键材料”，我国白银进口依存度超40%。

目前，关于从退役晶硅光伏电池片中提取银及铝的方法包括物理法^[14-17]和湿法^[18-21]。常见的物理法包括低温捕集技术、超声波清洗技术等。湿法即用浸出剂将银和铝溶解，再沉淀或还原为产品。董莉等^[18]提出了一种利用盐酸、硝酸溶液、硝酸-氢氟酸混酸依次溶解浸出光伏电池中的铝、银及氮化硅减反射膜的工艺。李佳艳等^[14]采用氢氧化钠溶液去除铝背电场，超声清洗剥离银电极，氢氟酸溶液去除氮化硅膜，实现了电池片中铝和银的完全去除。上述研究并未对浸出的铝和银做进一步反应和回收，存在氢氟酸使用过程中的环境污染问题。国外研究聚焦于采用更绿色温和的溶剂对非晶硅电池片上的金属进行有选择性的靶向提取和回收^[22-25]。莱斯特大学的Zante等人^[24]利用氯化胆碱配制低共熔溶剂成功提取银，该工艺成本低廉，经济性较高，实现了95%的银回收率和98%的产品纯度。该项研究采用氯化铝溶液或者氯化铁溶液来去除电池片上的铝层，实现了铝的完全去除。国外对电池片的回收技术虽然环保性较高，但也存在反应时间长、能耗大等问题^[25]。

本文为实现退役晶硅光伏电池片中银和铝的系统性回收和资源化利用，采用液碱和硝酸分步浸出电池片背板上的铝和表面银栅线中的银，用盐酸沉铝法制得氢氧化铝，再以抗坏血酸为还原剂制备银粉，并确定了最佳工艺参数。

1　实验方法

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1.1　实验原料

实验原料为退役晶硅光伏组件经过拆解和层压件分离后所得电池片，其主要化学成分见表1。电池片中主要元素为Si，占90.22%；主要有价金属为Al和Ag，分别占8.70%和0.56%。这3种元素在电池片中主要以单质形式存在。将电池片放入超声波中清洗10 min以去除电池片表面的灰尘（超声温度为25 ℃，超声功率为80 W），将清洗后的电池片放入真空干燥箱中恒温60 ℃烘干至恒重。实验用到的主要化学试剂包括氢氧化钠（分析纯）、盐酸（分析纯）、硝酸（分析纯）、氯化钠（分析纯）、氨水（优级纯）、抗坏血酸（分析纯）、聚乙烯吡咯烷酮（K16-18）。

1.2　实验方法与原理

首先，采用液碱浸泡电池片，去除其表面的铝电极，再向铝浸出液中加入盐酸得到氢氧化铝沉淀，该过程发生的主要反应见式（1）、式（2）。

2 A l + 2 N a O H + 2 H 2 O = 2 N a A l O 2 + 3 H 2 ↑

(1)

NaAlO 2 + HCl + H 2 O = Al (OH) 3 ↓ + NaCl

(2)

然后，采用稀硝酸浸泡电池片，去除其表面的银栅线，该过程发生的主要反应式见（3）。

3 A g + 4 H N O 3 = 3 A g N O 3 + N O ↑ + 2 H 2 O

(3)

最后，向银浸出液中加入氯源（氯化钠）将银选择性沉淀出来，将氯化银用氨水溶解，以抗坏血酸为还原剂，通过液相还原法从银氨溶液中制备银粉。该过程主要化学反应见式（4）—式（6）。

AgNO 3 + NaCl = AgCl ↓ + NaNO 3

(4)

AgCl + 2 NH 3 ⋅ H 2 O → [Ag (NH 3) 2] + + Cl − + 2 H 2 O

(5)

2 [Ag (NH 3) 2] OH + C 6 H 8 O 6 → 2 Ag ↓ + C 6 H 6 O 6 + 4 NH 3 + 2 H 2 O

(6)

1.3　分析方法

采用Thermo Scientific电感耦合等离子体发射光谱仪（ICP-OES），使用硝酸在220 ℃下加热40 min消解银粉，测定溶液中金属离子浓度及制得银粉纯度，并计算金属浸出（或沉淀）率，计算公式为：

η i = m 1 × w i 1 m 0 × w i 0 × 100 %

(7)

式中：η_i为金属i（i代表铝、银等）的浸出（或沉淀）率，%；m₁为生成物的质量，g；w_i1为生成物中金属i的质量分数，%；m₀为反应物的质量，g；w_i0为反应物中金属i的质量分数，%。

采用X射线衍射仪Bruker D8 Advance分析产物的物相组成，采用日本JEOL扫描电镜（SEM）对电池片进行表面形貌分析和Oxford X-aCT能谱系统（EDS）对电池片进行表面元素分布表征。

2　结果与讨论

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2.1　液碱浸出实验

2.1.1　氢氧化钠浓度对铝浸出率的影响

在电池片用量10 g，反应温度20 ℃，液固比10：1（10 mL：1 g，下同），浸出时间40 min的条件下，考察氢氧化钠浓度对铝浸出率的影响，实验结果如图1所示。由图1可知，铝浸出率随着氢氧化钠浓度增大而明显上升，在氢氧化钠浓度为1.0 mol/L时，达到了98.88%，而后出现拐点。

电池片的含铝量恒定，采用低浓度氢氧化钠浸泡时，提高氢氧化钠浓度能明显提升反应速率和铝的浸出率；当氢氧化钠浓度达到一定值后，单位体积溶液中参与铝反应的氢氧化钠活化分子数恒定，因此再提高氢氧化钠溶液浓度对铝的反应影响不大，反而会提高硅和氢氧化钠的反应；在氢氧化钠浓度为1.0 mol/L时，铝浸出率出现拐点，这是由于样品差异，铝涂层较薄的地方率先露出硅，此时溶液中同时存在铝和硅与碱的反应，影响了氢氧化钠与铝的反应。综合考虑，选择1.0 mol/L的氢氧化钠浓度较为合适。

反应过程中有黑色悬浮物漂浮在溶液上层，对该黑色悬浮物粉末进行XRD分析，结果如图2所示。由图2可见，特征峰主要由硅和铝单质的衍射峰组成。XRD分析表明，黑色粉末是脱落的Al-Si共熔区的Al-Si合金。铝与氢氧化钠反应放热并伴随大量H₂气泡生成，这些气泡使电池片上烧结的铝背场与硅片分开并形成黑色粉末。

2.1.2　反应温度、氢氧化钠浓度对硅损失率的影响

电池片铝背场和碱反应（式（1））为放热反应。在液碱浸铝过程中，硅随着铝的浸出逐渐暴露在碱液中，发生副反应：

Si + 2 NaOH + H 2 O = Na 2 SiO 3 + 2 H 2 ↑

(8)

在电池片用量10 g，液固比10：1，浸出时间40 min，氢氧化钠浓度分别为1.0、2.0、3.0、4.0、5.0 mol/L时，考察反应温度对铝浸出过程中硅损失率的影响，实验结果如图3所示。由图3可知，提高反应温度和氢氧化钠浓度会提高硅的损失率，控制低温20 ℃反应能够有效抑制副反应硅的浸出，硅损失率仅为0.46%。因此，碱浸温度应控制在20 ℃左右，工业产线需要添加冷却水循环装置。

2.1.3　浸出时间对铝浸出率的影响

在电池片用量10 g，氢氧化钠浓度1.0 mol/L，液固比10：1，反应温度20 ℃的条件下，考察浸出时间对铝浸出率的影响，实验结果如图4所示。由图4可知，铝浸出率随反应进行而上升，反应进行到约40 min时，铝浸出率趋近平稳，最终在第60 min达到98.63%。综合考虑生产效率，最佳的浸出时间为40 min。

对浸出前、后电池片表面铝背场进行SEM-EDS分析，结果如图5所示。由图5可知，经过1.0 mol/L氢氧化钠溶液在20 ℃下浸泡40 min后，电池片表面铝质量分数由70.95%减小为0.50%，可以认为电池片上的铝元素已全部浸出。

2.2　硝酸浸出实验

2.2.1　硝酸浓度对银浸出率的影响

银和稀硝酸常温下反应缓慢，需加热促进反应。在电池片用量10 g，液固比5：1，浸出温度70 ℃，反应时间60 min的条件下，考察硝酸浓度对于银浸出率的影响，结果如图6所示。由图6可知，银浸出率随着硝酸浓度增加而增加。硝酸浓度从2.0 mol/L到3.0 mol/L，银浸出率明显增大，硝酸浓度为4.0 mol/L时银的浸出率最高，为98.00%，之后随着硝酸浓度的增长，银浸出率下降，原因可能是硝酸浓度过量，阻碍了硝酸和金属反应，导致银浸出率下降。

对浸出前、后电池片表面银栅线位置处进行SEM-EDS分析，结果如图7所示。由图7可知，经过4.0 mol/L的硝酸浸泡后，电池片表面银的质量分数由21.73%减小为0.32%，可以认为银栅线上的银全部浸出。

2.2.2　浸出时间对银浸出率的影响

在电池片用量10 g，硝酸浓度3.0 mol/L，液固比5：1，浸出温度为70 ℃的条件下，考察浸出时间对银浸出率的影响，实验结果如图8所示。由图8可知，随着时间推移，浸出液中银离子浓度不断升高，在60 min时达到95.28%，之后银浸出率基本保持不变。考虑到浸出效率，浸出时间选择60 min。

2.3　液相还原制备银粉实验

通过向银浸出液中加入氯源实现银的选择性沉淀。取5 g氯化银固体，将其溶于140 mL氨水，通过液相还原反应制备银粉。在反应温度30 ℃，搅拌速度250 r/min的条件下，考察还原剂浓度对银沉淀率以及银粉纯度的影响，结果如图9所示。如图9可知，当还原剂抗坏血酸与银离子摩尔比为1.25：1.00时，银沉淀率和银粉纯度水平综合最优，银沉淀率为94.81%，银粉纯度达到99.91%。

在液相还原制备银粉的过程中，向反应器中加入适量分散剂聚乙烯吡咯烷酮（PVP），对制得银粉的形貌进行SEM分析，结果如图10所示。由图10可知，该工艺条件下制得的银粉颗粒呈球状，表面光滑。

3　结论

收起

本文以退役晶硅光伏电池片为原料，采用液碱浸出铝，稀硝酸浸出银，以及抗坏血酸作为还原剂制备银粉的提取工艺。该工艺具有回收效率高、产品纯度高的特点，为退役光伏组件中晶硅电池片的资源化利用提供了有效途径。分别考察了试剂浓度、反应温度、时间等参数对提取结果的影响，得到以下主要结论。

1）碱浸出铝实验中在氢氧化钠浓度1.0 mol/L，温度20 ℃，液固比10：1，反应时间40 min条件下，铝的浸出率达到98.88%。通过控制反应温度20 ℃，在保证铝浸出效率的同时能有效抑制硅的损失，硅损失率仅为0.46%。

2）稀硝酸浸出银实验中通过将反应温度升至70 ℃提高浸出效率，采用4.0 mol/L硝酸，在液固比5：1，反应时间仅为60 min条件下，银的浸出率达到98.00%。

3）以抗坏血酸作为还原剂，在抗坏血酸与银离子摩尔比1.25：1.00，温度30 ℃，搅拌速度250 r/min的条件下，银的沉淀率达到94.81%，制备出球状银粉，表面光滑，纯度达到99.91%。

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2026年第55卷第1期

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doi: 10.19666/j.rlfd.202508071

接收时间：2025-08-31
首发时间：2026-06-10
出版时间：2026-01-25

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收稿日期：2025-08-31
修回日期：2025-10-13
录用日期：2025-10-15

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国能龙源环保有限公司，北京 100039

通讯作者:

何发泉（1970），男，博士，正高级工程师，主要从事节能环保、固废资源化利用等工作，faquan.he@chenergy.com.cn。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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