CN109360942B - Method for preparing lithium ion battery cathode based on recycled solar battery - Google Patents
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Abstract
The invention discloses a method for preparing a lithium ion battery cathode based on a recycled solar battery, which comprises the following steps: (1) mechanically removing a waste solar cell aluminum frame and a junction box to obtain a silicon solar cell module, removing EVA bonding layers and back plate organic matters of the module through high-temperature heating, and stripping surface layer toughened glass to obtain a silicon wafer; (2) soaking the silicon wafer in sulfuric acid to remove the aluminum back electrode and tin and lead on the surface of the silicon wafer; (3) cleaning the silicon wafer obtained in the step (2) with clear water, mechanically crushing the silicon wafer, and grinding the crushed silicon wafer to obtain silicon powder with the granularity of less than 2 mm; (4) and (3) placing the silicon powder in a high-energy ball mill for ball milling to obtain the nano-scale lithium ion battery silicon cathode. The invention avoids the defects that a large amount of acid and alkali liquor is consumed for recycling the traditional solar cell and high energy consumption is caused during subsequent processing and utilization, silicon nitride, silver and copper on the surface of the solar cell are not required to be treated, and the components are directly utilized by a high-energy ball milling and calcining method to obtain the silicon cathode material of the lithium ion battery.
Description
Technical Field
The invention relates to the field of solar cell recycling and lithium ion batteries, in particular to a method for preparing a lithium ion battery cathode based on a recycled solar cell.
Background
The loading capacity of the photovoltaic power station in China has been rapidly developed since 2005, and by 2015, the accumulated loading capacity of the photovoltaic power generation in China is 4318 ten thousand kilowatts, so that the photovoltaic power station becomes the country with the largest loading capacity of the photovoltaic power generation in the world. Meanwhile, the accumulated waste amount of the silicon solar cell reaches 60-70 GW (ground wire) by 2034 years as the service life approaches, wherein the waste amount of the silicon reaches 1.6 multiplied by 104t. The waste solar cells contain a large amount of silicon and a small amount of valuable metals such as silver and aluminum, and have recycling value.
The traditional solar cell recovery process mainly adopts strong acid (nitric acid, aqua regia, hydrofluoric acid) and the like, uses the acid for multiple times to remove silicon nitride on the surface of a silicon wafer and dissolve valuable metals such as silver, tin and the like to obtain a high-purity silicon wafer, and then melts the recovered silicon wafer to prepare the silicon wafer for the solar cell. Journal article "research on environmental recycling of crystalline silicon solar cell" reports the work of removing aluminum on an aluminum back surface by using waste alkali liquor, removing silver by using nitric acid liquor, reducing silver, and removing silicon nitride by using hydrofluoric acid. The patent application number 201310572107.9, entitled "solar cell cleaning and recycling process", sequentially adopts alcohol, pure water, sulfuric acid, aqua regia + hydrofluoric acid, hydrochloric acid, sodium hydroxide and aluminum powder to carry out cleaning, dissolving and reducing processes and the like, so as to obtain silicon and silver recycled products. The process has serious acid consumption and high requirement on equipment, the use of hydrofluoric acid has certain influence on the environment, and the silicon wafer for preparing the solar cell by the recycled silicon wafer has higher energy consumption in the melting process, so that the recycling cost is higher.
Silicon is taken as a lithium ion battery negative electrode material, has the theoretical specific capacity of up to 4200mAh/g, and has the content of the silicon in the earth crust second to oxygen, so that the silicon is an ideal electrode material. The waste solar cell is recycled to prepare the silicon cathode of the lithium ion battery, so that the resource recycling is facilitated, and the resource and energy consumption is reduced.
Disclosure of Invention
The invention aims to solve the defects of the existing solar cell that the recycling resources (acid, alkali and reducing agent) and the energy consumption are large, and provides a method for preparing a silicon-based composite cathode of a lithium ion battery by recycling crystalline silicon with low consumption.
In order to achieve the purpose, the method for preparing the lithium ion battery cathode based on the recycled solar battery comprises the following steps:
(1) mechanically removing the recycled waste solar cell aluminum frame and junction box to obtain a silicon solar cell assembly, removing EVA bonding layers and back plate organic matters of the assembly through high-temperature heating, and mechanically stripping surface layer toughened glass to obtain a silicon wafer;
(2) soaking the obtained silicon wafer in sulfuric acid to remove the aluminum back electrode and tin and lead on the surface of the silicon wafer;
(3) cleaning the silicon wafer which is obtained in the step (2) and retains silver, copper and silicon nitride with clear water, mechanically crushing the silicon wafer, and grinding the silicon wafer to obtain silicon powder with the granularity of less than 2 mm;
(4) and placing the obtained silicon powder in a high-energy ball mill for ball milling to obtain the nano-scale lithium ion battery silicon cathode.
Preferably, the step (3) is followed by a step (5): and placing the obtained silicon powder and the carbon-based material and/or the metal-based material in a high-energy ball mill for ball milling to obtain the nano-scale silicon-based composite cathode of the lithium ion battery.
Preferably, the EVA adhesive layer and the back field organic matter are removed in the step (1) by evaporation in nitrogen or argon, and the evaporation temperature is 300-600 ℃.
Preferably, the concentration of the sulfuric acid in the step (2) is 0.5-4mol/L, and the soaking time is 0.5-10 h.
Preferably, the rotation speed of the high-energy ball mill is 100-.
Preferably, the batch ball milling is carried out for 1-2h per grinding material, and the machine is stopped for 10 min.
Preferably, the carbon-based material is a carbon simple substance and/or a carbon-containing organic substance, the carbon simple substance comprises at least one of graphite, carbon powder, graphene, a carbon nanotube, hard carbon and soft carbon, the carbon-containing organic substance comprises at least one of a high molecular polymer and a short chain organic substance, the mass ratio of the silicon powder to the ball grinding material of the carbon-based material in the step (5) is 100:1-100, and the silicon-based composite negative electrode of the nanoscale lithium ion battery obtained in the step (5) is a silicon-carbon composite negative electrode.
Preferably, the step (5) further comprises sintering the material ball-milled with the carbon-containing organic substance in argon at 350-.
Preferably, the metal-based material comprises at least one of a simple metal, a metal sulfide and a metal oxide, the simple metal comprises at least one of Ni, Fe, Co, Al, Mn, Ag, Ca, Mg, Cu, Ge, Sn and Sb, and the metal sulfide comprises MoS2、FeS、CuS、Sb2S3At least one of, the metal oxide comprises TiO2、SnO、SnO2、Co3O4、Sb2O4At least one of the silicon powder and the metal-based material in the step (5) has a ball grinding material mass ratio of 100:1-100, and the nano-scale lithium ion battery silicon-based composite cathode obtained in the step (5) is a silicon-metal or silicon-metal oxide or silicon-metal sulfide composite cathode.
Preferably, the silicon powder, the carbon-based material and the metal-based material are placed in a high-energy ball mill for ball milling, wherein the mass ratio of the metal-based material to the carbon-based material is 100:1-1:100, the mass ratio of the silicon to the carbon-based material and the mass ratio of the silicon to the metal-based material are both 100:1-100, and the silicon-based composite cathode of the nanoscale lithium ion battery obtained in the step (5) is a silicon-carbon-metal or silicon-carbon-metal sulfide or silicon-carbon-metal oxide composite cathode.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the defects that a large amount of acid and alkali liquor is consumed for recycling the traditional solar cell and high energy consumption is caused during subsequent processing and utilization are overcome, the silicon and silicon-based cathode materials of the lithium ion battery are directly obtained only by a high-energy ball milling and calcining method, the method and equipment are simple, the raw materials are wide in application source, and the method is suitable for industrial popularization.
(2) The method does not need to remove the silicon nitride layer, and can directly use silver and copper as the silicon-silver-copper composite cathode. The silicon nitride is a substance with high hardness and strong chemical stability, and the silicon nitride formed on the surface of the silicon particles is beneficial to relieving the volume effect of the silicon cathode in the charge and discharge processes of the lithium ion battery, and inhibits the formation of an SEI film on the surface of the silicon to reduce the loss of active substances.
(3) The negative electrode material obtained by the recovery and utilization method is granular, the particle size is 200-900nm, the particle size is small, the particles are uniform, and the cycle and rate performance is good.
Drawings
FIG. 1 is a scanning electron micrograph of a silicon-carbon composite anode prepared in example 1;
fig. 2 is a rate performance graph of the silicon-carbon composite anode prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1:
and mechanically removing the aluminum frame and the junction box from the recovered waste solar cell panel, the defective products in the battery factory and the like, evaporating in nitrogen to remove EVA bonding layers and back surface field organic matters, wherein the evaporation temperature is 450 ℃, and peeling the surface layer toughened glass to obtain the silicon wafer.
Soaking the silicon wafer in sulfuric acid with the concentration of 1mol/L for 6 hours, removing tin and lead on the aluminum back electrode and the surface of the silicon wafer, cleaning the silicon wafer with clear water, mechanically crushing the silicon wafer, and preparing silicon powder by grinding, wherein the granularity of the silicon powder is 1.2-1.8 mm.
And placing the obtained silicon powder and graphite in a ball mill for ball milling to obtain the silicon-carbon composite cathode. During ball milling, the mass ratio of silicon to graphite is 2:1, the rotating speed of the high-energy ball mill is 300r/min, the ball milling time is 30 hours, the ball-material ratio is 25:1, and argon is introduced during ball milling to carry out ball milling so as to avoid oxidation reaction caused by heat generation during ball milling.
The electrochemical performance test of the silicon-carbon composite cathode adopts a lithium sheet as a counter electrode and a reference electrode, and the electrolyte is 1M LiPF6+ EC/DEC/DMC (1:1:1, v/v/v), assembled into a CR2032 button cell using Celgard 2032 separator, with charge and discharge properties determined by the LAND test system.
From the scanning electron microscope image in fig. 1, it can be found that the silicon-carbon composite negative electrode prepared by the high-energy ball milling is a nanoparticle, which is beneficial to relieving the volume effect of silicon in the charging and discharging process. As can be found from figure 2, the first discharge specific capacity reaches 1225.6mAh/g under the multiplying power of 0.01V-1V and 0.5C in the charging and discharging process, the first charge specific capacity reaches 761.5mAh/g, the first-turn coulombic efficiency reaches 62.13%, the discharge specific capacity after 5-turn circulation under the multiplying power of 5C is 334.4mAh/g, the charge specific capacity is 335mAh/g, the coulombic efficiency reaches 100.17%, the charge specific capacity returns to 928.5mAh/g after the multiplying power of 0.5C, and the capacity retention rate is higher.
The performances show that the silicon-based nano anode material obtained by the recovery and utilization method has small particle size, uniform particles, better rate capability and higher capacity retention rate.
Example 2:
and mechanically removing the aluminum frame and the junction box from the recovered waste solar cell panel, the defective products in the battery factory and the like, evaporating in nitrogen to remove EVA bonding layers and back surface field organic matters, wherein the evaporation temperature is 350 ℃, and peeling the surface layer toughened glass to obtain the silicon wafer.
Soaking the silicon wafer in sulfuric acid with the concentration of 2mol/L for 2 hours, removing tin and lead on the surface of the aluminum back electrode and the silicon wafer, cleaning the silicon wafer with clear water, mechanically crushing the silicon wafer, and preparing silicon powder by grinding, wherein the granularity of the silicon powder is 0.8-1.2 mm.
And placing the obtained silicon powder and the carbon-containing organic matter into a ball mill for intermittent ball milling, wherein the mass ratio of silicon to the carbon-containing organic matter is 1:1, the rotating speed of the high-energy ball mill is 500r/min, the ball milling time is 20 hours, the ball-material ratio is 1:1, the intermittent ball milling process is 1 hour per grinding material, and the ball mill is stopped for 10 minutes to avoid oxidation reaction caused by heat generation during ball milling.
And sintering the ball-milled material in argon at 500 ℃ for 4h to obtain the silicon-carbon composite cathode.
The electrochemical performance test of the silicon-carbon composite cathode adopts a lithium sheet as a counter electrode and a reference electrode, and the electrolyte is 1M LiPF6+ EC/DEC/DMC (1:1:1, v/v/v), assembled into a CR2032 button cell using Celgard 2032 separator, with charge and discharge properties determined by the LAND test system. The first discharge specific capacity reaches 1355.7mAh/g under the multiplying power of 0.01V-1V and 0.5C in the charging and discharging process, the first charge specific capacity reaches 987.4mAh/g, the first-cycle coulombic efficiency reaches 72.8%, the discharge specific capacity is 782mAh/g after 5-cycle circulation under the multiplying power of 10C, the charge specific capacity is 760.3mAh/g, the capacity retention rate reaches 77%, the charge specific capacity returns to 936.5mAh/g after the multiplying power of 0.5C, and the capacity retention rate is high.
Example 3:
and mechanically removing the aluminum frame and the junction box from the recovered waste solar cell panel, the defective products in the battery factory and the like, evaporating in nitrogen to remove EVA bonding layers and back surface field organic matters, wherein the evaporation temperature is 500 ℃, and peeling the surface layer toughened glass to obtain the silicon wafer.
Soaking the silicon wafer in 3mol/L sulfuric acid for 1h, removing tin and lead on the aluminum back electrode and the surface of the silicon wafer, cleaning the silicon wafer with clear water, mechanically crushing the silicon wafer, and preparing silicon powder with the particle size of 1mm by grinding.
And placing the obtained silicon powder and iron powder in a ball mill for ball milling to obtain the silicon-metal composite cathode. During ball milling, the mass ratio of silicon to metal is 10:3, the rotating speed of the high-energy ball mill is 800r/min, the ball milling time is 10 hours, the ball-material ratio is 10:1, and argon is introduced during ball milling to perform ball milling so as to avoid oxidation reaction caused by heat generation during ball milling.
The electrochemical performance test of the silicon-metal composite cathode adopts a lithium sheet as a counter electrode and a reference electrode, and the electrolyte is 1M LiPF6+ EC/DEC/DMC (1:1:1, v/v/v), assembled into a CR2032 button cell using Celgard 2032 separator, with charge and discharge properties determined by the LAND test system. In the charging and discharging process, the first discharging specific capacity is 1587.6mAh/g under the multiplying power of 0.01V-1V and 0.5C, the first charging specific capacity is 1273.4mAh/g, the first-turn coulombic efficiency is 80.2%, 300 turns can be stably circulated under the multiplying power of 1C, and the capacity is kept at 1150 mAh/g.
Example 4:
and mechanically removing the aluminum frame and the junction box from the recovered waste solar cell panel, the defective products in the battery factory and the like, evaporating in nitrogen to remove EVA bonding layers and back surface field organic matters, wherein the evaporation temperature is 550 ℃, and peeling the surface layer toughened glass to obtain the silicon wafer.
Soaking the silicon wafer in sulfuric acid with the concentration of 4mol/L for 0.5h, removing tin and lead on the surfaces of the aluminum back electrode and the silicon wafer, cleaning the silicon wafer with clear water, mechanically crushing the silicon wafer, and preparing silicon powder with the granularity of 1.5mm by grinding ores.
And placing the obtained silicon powder, graphene and nickel powder in a ball mill for ball milling to obtain the silicon-carbon-metal composite cathode. During ball milling, the mass ratio of nickel powder to graphene is 1:1, the mass ratio of silicon powder to graphene is 2:1, the mass ratio of silicon powder to nickel powder is 2:1, the rotating speed of a high-energy ball mill is 650r/min, the ball milling time is 25 hours, the ball material ratio is 2:1, argon is introduced during ball milling for ball milling, and oxidation reaction caused by heat generation during ball milling is avoided.
The electrochemical performance test of the silicon-carbon-metal composite negative electrode adopts a lithium sheet as a counter electrode and a reference electrode, and the electrolyte is 1M LiPF6+ EC/DEC/DMC (1:1:1, v/v/v), assembled into a CR2032 button cell using Celgard 2032 separator, with charge and discharge properties determined by the LAND test system. In the charging and discharging processes, the current is 1A/g, the first discharging specific capacity is 2599.3mAh/g under the voltage of 0.01-1V, the first charging specific capacity is 1989mAh/g, and the first-turn coulombic efficiency is 76.5%. After 500 cycles, the charging specific capacity is 1621mAh/g, the charging capacity retention rate is 81.5%, and the battery has good cycle and rate capability.
Example 5:
and (3) evaporating the recycled silicon solar cell modules such as fragments, leftover materials and the like in nitrogen to remove EVA bonding layers and back surface field organic matters, wherein the evaporation temperature is 450 ℃, and peeling the surface layer toughened glass to obtain the silicon wafer.
Soaking the silicon wafer in sulfuric acid with the concentration of 2.5mol/L for 5h, removing tin and lead on the surfaces of the aluminum back electrode and the silicon wafer, cleaning the silicon wafer with clear water, mechanically crushing the silicon wafer, and preparing silicon powder with the granularity of 0.6mm by grinding ores.
And placing the obtained silicon powder and graphite in a ball mill for ball milling to obtain the silicon-carbon composite cathode. During ball milling, the mass ratio of silicon to graphite is 5:4, the rotating speed of the high-energy ball mill is 500r/min, the ball milling time is 20 hours, the ball-material ratio is 35:1, and argon is introduced during ball milling to prevent oxidation reaction caused by heat generation during ball milling.
The electrochemical performance test of the silicon-carbon composite cathode adopts a lithium sheet as a counter electrode and a reference electrode, and the electrolyte is 1M LiPF6+ EC/DEC/DMC (1:1:1, v/v/v), assembled into a CR2032 button cell using Celgard 2032 separator, with charge and discharge properties determined by the LAND test system.
The first discharge specific capacity reaches 1228.6mAh/g under the multiplying power of 0.01V-1V and 0.5C in the charging and discharging process, the first charge specific capacity reaches 763.8mAh/g, the first-circle coulombic efficiency reaches 62.16%, the discharge specific capacity after 5-circle circulation under the multiplying power of 5C is 336mAh/g, the charge specific capacity is 338mAh/g, the coulombic efficiency reaches 100.05%, the charge specific capacity returns to 931.8mAh/g after the multiplying power of 0.5C, and the capacity retention rate is high.
The performances show that the silicon-based nano anode material obtained by the recovery and utilization method has small particle size, uniform particles, better rate capability and higher capacity retention rate.
Example 6:
and (3) evaporating the recycled silicon solar cell modules such as fragments, leftover materials and the like in nitrogen to remove EVA bonding layers and back surface field organic matters, wherein the evaporation temperature is 450 ℃, and peeling the surface layer toughened glass to obtain the silicon wafer.
Soaking the silicon wafer in 3mol/L sulfuric acid for 1h, removing tin and lead on the aluminum back electrode and the surface of the silicon wafer, cleaning the silicon wafer with clear water, mechanically crushing the silicon wafer, and preparing silicon powder with the particle size of 1mm by grinding.
And placing the obtained silicon powder and tin powder into a ball mill for intermittent ball milling, wherein the mass ratio of silicon to tin powder is 5:4, the rotating speed of the high-energy ball mill is 800r/min, the ball milling time is 10 hours, the ball-material ratio is 1:3, the intermittent ball milling process is 1.5 hours per grinding material, and the ball mill is stopped for 10 minutes to avoid oxidation reaction caused by heat generation during ball milling.
The electrochemical performance test of the silicon-tin composite cathode adopts a lithium sheet as a counter electrode and a reference electrode, and the electrolyte is 1M LiPF6+ EC/DEC/DMC (1:1:1, v/v/v), assembled into a CR2032 button cell using Celgard 2032 separator, with charge and discharge properties determined by the LAND test system. When the current is 1A/g, the voltage is 0.01-3V, the first discharge specific capacity is 1542.7mAh/g, the charge specific capacity is 1213mAh/g, the charge specific capacity can still reach 856.6mAh/g after 800 cycles, and the cycle performance is excellent.
Claims (8)
1. A method for preparing a lithium ion battery cathode based on a recycled solar battery is characterized by comprising the following steps:
(1) mechanically removing the recycled waste solar cell aluminum frame and junction box to obtain a silicon solar cell assembly, removing EVA bonding layers and back plate organic matters of the assembly through high-temperature heating, and mechanically stripping surface layer toughened glass to obtain a silicon wafer;
(2) soaking the obtained silicon wafer in sulfuric acid to remove the aluminum back electrode and tin and lead on the surface of the silicon wafer;
(3) cleaning the silicon wafer which is obtained in the step (2) and retains silver, copper and silicon nitride with clear water, mechanically crushing the silicon wafer, and grinding the silicon wafer to obtain silicon powder with the granularity of less than 2 mm;
(4) placing the obtained silicon powder in a high-energy ball mill for ball milling to obtain a nanoscale lithium ion battery silicon cathode; alternatively, step (5): and (3) placing the obtained silicon powder and a carbon-based material and/or a metal-based material in a high-energy ball mill for ball milling to obtain the nano-scale silicon-based lithium ion battery composite cathode, wherein the carbon-based material is a carbon elementary substance and/or a carbon-containing organic substance, the carbon elementary substance comprises at least one of graphite, graphene, a carbon nano tube, hard carbon and soft carbon, the carbon-containing organic substance comprises a high polymer, the mass ratio of the silicon powder to the ball grinding material of the carbon-based material in the step (5) is 100:1-100, and the nano-scale silicon-based lithium ion battery composite cathode obtained in the step (5) is a silicon-carbon composite cathode.
2. The method for preparing the lithium ion battery cathode based on the recycled solar battery as claimed in claim 1, wherein the EVA bonding layer and the organic matter of the back plate are removed by evaporation in nitrogen or argon in the step (1), and the evaporation temperature is 300-600 ℃.
3. The method for preparing the lithium ion battery cathode based on the recycled solar battery according to claim 1, wherein the concentration of the sulfuric acid in the step (2) is 0.5-4mol/L, and the soaking time is 0.5-10 h.
4. The method for preparing the lithium ion battery cathode based on the recycled solar battery as claimed in claim 1, wherein the rotation speed of the high-energy ball mill is 100-1000r/min, the ball milling time is 5-50h, the ball-to-material ratio is 50:1-1:5, and argon/nitrogen is introduced for ball milling or intermittent ball milling during ball milling.
5. The method for preparing the lithium ion battery cathode based on the recycled solar battery is characterized in that the batch ball milling is carried out for 1-2h per grinding material and the shutdown is carried out for 10 min.
6. The method for preparing the lithium ion battery cathode based on the recycled solar battery as claimed in claim 1, wherein the step (5) further comprises sintering the material ball-milled with the carbon-containing organic material in argon at a sintering temperature of 350-.
7. The preparation of lithium ions based on recycled solar cells of claim 1The method for the battery cathode is characterized in that the metal-based material comprises at least one of simple metal, metal sulfide and metal oxide, the simple metal comprises at least one of Ni, Fe, Co, Al, Mn, Ag, Ca, Mg, Cu, Ge, Sn and Sb, and the metal sulfide comprises MoS2、FeS、CuS、Sb2S3At least one of, the metal oxide comprises TiO2、SnO、SnO2、Co3O4、Sb2O4At least one of the silicon powder and the metal-based material in the step (5) has a ball grinding material mass ratio of 100:1-100, and the nano-scale lithium ion battery silicon-based composite cathode obtained in the step (5) is a silicon-metal or silicon-metal oxide or silicon-metal sulfide composite cathode.
8. The method for preparing the negative electrode of the lithium ion battery based on the recycled solar battery as claimed in claim 1, wherein the silicon powder, the carbon-based material and the metal-based material are placed in a high-energy ball mill for ball milling, the mass ratio of the metal-based material to the carbon-based material is 100:1-1:100, the mass ratio of the silicon to the carbon-based material and the mass ratio of the silicon to the metal-based material are 100:1-100, and the silicon-based composite negative electrode of the nanoscale lithium ion battery obtained in the step (5) is a silicon-carbon-metal or silicon-carbon-metal sulfide or silicon-carbon-metal oxide composite negative electrode.
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| CN105336922A (en) * | 2014-08-08 | 2016-02-17 | 苏州格瑞动力电源科技有限公司 | Preparation method and application for lithium ion battery negative electrode material based on photovoltaic silicon waste material |
| CN108649197A (en) * | 2018-02-07 | 2018-10-12 | 光宇材料股份有限公司 | Nitrogen-doped carbon-silicon composite material and manufacturing method thereof |
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