CN111785944B - Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste - Google Patents
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Abstract
The invention relates to a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation and cutting of silicon waste, belonging to the technical fields of new energy materials and electrochemistry. According to the invention, the silicon waste material obtained by cutting the diamond wire and the carbon source powder are uniformly mixed and subjected to plasma activation treatment, the silicon and the carbon are gasified, condensed and recrystallized to obtain the nano silicon/carbon composite material, the plasma activation treatment can remove impurities in the silicon waste material and realize the nanocrystallization of the silicon and the carbon, and the nano metal particles of the silicon/carbon composite material are compounded to prepare the porous silicon/carbon/nano metal composite material. The porous silicon/carbon/nano metal composite anode material prepared by the invention can shorten the transmission distance of lithium ions and electrons, improve the overall conductivity and structural integrity of the electrode material, and effectively solve the problems of huge volume change and low rate capability in the lithium removal and intercalation process.
Description
Technical Field
The invention relates to a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation and cutting of silicon waste, belonging to the technical fields of new energy materials and electrochemistry.
Background
In the lithium ion battery structure, the important components of the cathode material directly determine the quality and application of the lithium ion battery. Hitherto, the negative electrode materials of lithium ion batteries mainly include carbon materials, lithium alloys (lithium silicon alloys, lithium tin alloys, etc.), transition metal oxides (TiO 2 、SnO 2 Etc.), nitrides. Since the graphite material has good cycle stability, excellent conductivity and a layered structure thereof has a good lithium intercalation space, the volume change in the lithium deintercalation process is in an acceptable range, and the graphite negative electrode material is widely used in the lithium battery industry. However, with the rapid development of electronic technology and the rapid popularization of electric vehicles, the market demand for lithium ion batteries with high specific capacity is increasing. However, the theoretical discharge specific capacity of the commercialized graphite anode material is only 372mAh/g, and the actual capacity of the graphite anode material put into production is very close to the theoretical discharge specific capacity, so that the requirement of the power type lithium ion battery on high-energy storage equipment in the electric automobile field and the electronic industry field is difficult to meet. Therefore, development of a lithium ion battery anode material with high specific discharge capacity has been urgently needed to solve the problem.
The Si negative electrode material has higher theoretical specific capacity which can reach 4200mAh/g, has the advantages of low voltage platform, low reactivity with electrolyte, abundant reserves in crust, low price and the like, and is a lithium battery negative electrode material with very good prospect, but the Si negative electrode also has the fatal defects of huge volume change and low intrinsic conductivity in the charge and discharge process. Volume expansion is a problem that any lithium ion electrode material faces during delithiation and intercalation, however this problem is particularly serious for Si cathodes. Under the state of completely inserting lithium, the volume expansion of the Si negative electrode can reach 300%, so that the Si negative electrode can be cracked or even broken, the structure of a negative electrode plate can be damaged, the irreversible loss of the battery capacity is caused, and meanwhile, potential safety hazards are generated. In addition, the intrinsic semiconductor nature of silicon is also a non-negligible problem. Because Si intrinsic conductivity is very low, the multiplying power performance of the battery is severely limited, and the practical application value of the battery is directly influenced.
In recent years, most of production enterprises at home and abroad process silicon wafers by adopting a diamond wire cutting process in the silicon wafer production process. In the process of linear cutting of the solar silicon wafer, due to collision and friction between the linear cutting tool and the silicon wafer, besides the generated broken silicon particles, part of broken abrasion exists on the tool, lubricating liquid and cooling liquid in the cutting process are mixed into a cutting system to form cut silicon waste, about 40% of high-purity silicon is wasted, and only 2019 is taken as an example, the cutting of 132GW silicon wafer is realized, and the cutting waste of up to 30 ten thousand tons is generated. However, the recovery method for effectively recovering the high-purity silicon powder in the waste is difficult to realize according to the current flotation, cyclone separation and other recovery methods, and the silicon is seriously polluted in the cutting process and cannot be directly used in the photovoltaic and electronic industries.
Disclosure of Invention
Aiming at the problems of high cost, huge volume change and low intrinsic conductivity in the silicon material circulation process of the lithium battery negative electrode in the prior art and difficult recovery of diamond wire cutting silicon waste in the photovoltaic industry, the invention provides a method for preparing a porous silicon/carbon/nano metal composite negative electrode material by plasma activation of cutting silicon waste. The invention prepares the cut silicon waste into the high-performance negative electrode material of the lithium ion battery, namely the porous silicon/carbon/nano metal composite negative electrode, by adopting a method of combining plasma activation composite-nano metal particle composite, can shorten the transmission distance of lithium ions and electrons, improves the overall conductivity and structural integrity of the electrode material, and effectively solves the problems of huge volume change and low multiplying power performance in the lithium removal and intercalation process.
The method for preparing the porous silicon/carbon/nano metal composite anode material by cutting silicon waste material through plasma activation comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the diamond wire cutting silicon waste to obtain waste silicon powder;
(2) Uniformly mixing the waste silicon powder obtained in the step (1) with a carbon source, and carrying out vacuum drying to obtain silicon-carbon mixed powder;
(3) Introducing argon into a plasma furnace to remove air in the furnace body, taking the argon as a shielding gas and a carrier gas, introducing the silicon-carbon mixed powder in the step (2) into the plasma furnace to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material);
(4) And (3) placing the Nano silicon/carbon composite material in the step (3) in an HF-metal salt-alcohol solution system for metal particle Nano particle compounding, washing by deionized water, and carrying out solid-liquid separation to obtain the Nano metal particle composite silicon/carbon composite material, wherein the Nano metal particle composite silicon/carbon composite material is subjected to vacuum drying treatment and grinding to obtain the porous silicon/carbon/Nano metal composite material (PSi/C/Nano-M composite material).
And (3) the mass fraction of the waste silicon powder in the silicon-carbon mixed powder in the step (2) is 3-100%. The mixing method of the waste silicon powder and the carbon source is manual mixing, mechanical stirring, ball milling mixing or high-energy ball milling mixing;
the carbon source in the step (2) is one or more of glucose, fructose, sucrose, xylose, sorbose, citric acid, starch, polyethylene, polypropylene, cellulose, graphite, graphene, carbon nanotubes, aromatic hydrocarbon, aromatic lipid, petroleum asphalt or coal tar asphalt.
The power of the plasma activation treatment in the step (3) is 10-150 KW, the argon pressure is 0.10-0.70 Mpa, and the feeding rate of the silicon-carbon mixed powder is 1-50 g/min.
Gasifying, condensing and recrystallizing the silicon-carbon mixed powder to enable carbon to be compounded on the surface of silicon to obtain a nano silicon/carbon composite material, wherein the nano silicon/carbon composite material has a graphene-coated nano silicon structure and/or a carbon nano tube-compounded nano silicon structure, and the particle size of the nano silicon/carbon composite material is controllable and is 10-150 nm;
the concentration of HF in the HF-metal salt-alcohol solution system in the step (4) is 0.1-15 mol/L, the concentration of metal salt is 0.005-10 mol/L, and the concentration of alcohol is 0.1-20 mol/L;
further, the metal salt is one or more of silver salt, copper salt, cobalt salt, nickel salt, aluminum salt and titanium salt, and the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
Preferably, the silver salt is AgNO 3 、Ag 2 SO 4 Or Ag 2 CO 3 Copper salt is Cu (NO) 3 ) 2 、CuSO 4 Or CuCO 3 The nickel salt is Ni (NO) 3 ) 2 、NiSO 4 Or NiCO 3 Cobalt salt is Co (NO) 3 ) 2 The aluminum salt is Al (NO) 3 ) 3 。
The ratio of liquid to solid of the HF-metal salt-alcohol solution system to the nano silicon/carbon composite material is (1-10): 1.
The composite temperature of the metal particle nano-particles is 20-80 ℃ and the time is 0.5-6 h.
The beneficial effects of the invention are as follows:
(1) The porous silicon/carbon/nano metal composite material has the advantages that the nano size and the porous structure can effectively remove huge volume change in the lithium intercalation process, meanwhile, the transmission distance of lithium ions and electrons is shortened, after metal particles are compounded with the porous silicon, the problem of low conductivity of the silicon material can be effectively solved, the overall conductivity of the electrode material is improved, the carbon is introduced, the stability of the overall structure of the material can be improved, and the overall conductivity of the material can be enhanced again;
(2) According to the invention, the waste silicon powder is prepared into nano-scale through a plasma activation process to solve the problems of poor intrinsic conductivity of silicon and huge volume expansion in the lithium intercalation/deintercalation process, and carbon and metal ions effectively improve the problem of low intrinsic conductivity of silicon, so that the nano-scale of the porous silicon/carbon/nano-metal composite material can ensure the structural integrity of the electrode material in charge-discharge cycle, thereby improving the cycle stability of the electrode, and the nano-scale effect can effectively accelerate the phase transition of active substances, reduce the absolute volume effect of the active substances in the lithium intercalation/deintercalation process and the diffusion distance of lithium ions in the material;
(3) The invention prepares the porous silicon/carbon/nano metal composite anode by taking the photovoltaic wire-cut silicon waste as the raw material, has simple process, is suitable for industrial production, greatly saves the raw material cost, improves the resource utilization rate, and realizes changing waste into valuables.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the original diamond wire cut silicon scrap of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the pSi/C/Nano-Ag composite material in example 1;
fig. 3 is a graph showing the cycle performance at a rate of 0.5C after the initial silicon scrap and porous silicon/carbon/nano-silver composite material were assembled into a half cell in example 1.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 50%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current 110A of the plasma furnace, the voltage 140V, the argon pressure of 0.2MPa and the feeding rate of the silicon-carbon mixed powder of 1g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form to realize the purification of silicon due to the extremely low condensing temperature relative to the silicon-carbon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-AgNO 3 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 80 ℃ for 4 hours, wherein HF-AgNO 3 HF concentration in ethanol solution system of 0.5mol/L, agNO 3 The concentration is 0.1mol/L, and the concentration of ethanol is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano silver composite material (PSi/C/Nano-Ag composite material);
as can be seen from fig. 1, the original Scanning Electron Microscope (SEM) image of the silicon scrap cut by the diamond wire is uneven in particle size and huge in difference, if the silicon scrap cut by the diamond wire is directly applied to the negative electrode of the lithium ion battery, huge volume change of the negative electrode can be generated in the lithium intercalation and deintercalation process in the discharging process, so that the capacity is quickly attenuated, and the negative electrode is damaged, so that the lithium ion battery of the negative electrode is quickly deactivated in the circulating process;
the Scanning Electron Microscope (SEM) diagram of the pSi/C/Nano-Ag composite material is shown in figure 2, and as can be seen from figure 2, nano silver particles are uniformly distributed on the surface of porous silicon particles, the porous silicon/carbon/Nano metal composite anode material has a porous structure formed by stacking porous nanospheres, and a large number of porous structures exist in the spheres and among the spheres; the diffusion speed of lithium ions in the anode material is greatly increased, and meanwhile, a large amount of space is reserved for the volume expansion caused by lithium intercalation and deintercalation in the charging and discharging process by the porous structure in the sphere, so that the volume expansion is greatly relieved;
the cycle performance curve of the original silicon waste and the porous silicon/carbon/nano silver composite material at the multiplying power of 0.5C after being assembled into a half cell is shown in FIG. 3, the initial capacity of the original silicon waste anode is 2970mAh/g, but after 20 cycles, the capacity of the original silicon waste anode is less than 500mAh/g, the capacity decay is extremely fast, and meanwhile, the initial coulombic efficiency is only 58%; the initial capacity of the porous silicon/carbon/nano silver composite anode is 2788mAh/g, which is only slightly lower than that of the original silicon waste anode, and after 50 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite anode material is basically stable at 1250mAh/g, and the transmission of lithium ions can be greatly improved due to nano silver ions in the porous silicon/carbon/nano silver composite anode.
Example 2: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 18 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 60%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current of the plasma furnace is 120A, the voltage is 130V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 1.5g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form due to extremely low condensing temperature relative to silicon-carbon to realize the purification of silicon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-Cu (NO) 3 ) 2 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 40 ℃ for 6h, wherein HF-Cu (NO 3 ) 2 HF concentration in ethanol solution system of 0.5mol/L, cu (NO) 3 ) 2 The concentration is 0.2mol/L, and the ethanol concentration is 0.5mol/L; ultrasonic rinsing with deionized water until the washing liquid is neutral, and solid-liquid separation to obtain nanometer metal particle composite silicon/carbon compositeVacuum drying and grinding the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Cu composite material); the composite material is prepared into a silicon negative electrode half cell, and after 50 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stabilized at 1200mAh/g.
Example 3: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 3 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 60%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current of the plasma furnace is 120A, the voltage is 130V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form due to extremely low condensing temperature relative to silicon-carbon to realize the purification of silicon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-Ni (NO) 3 ) 2 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 80 ℃ for 2h, wherein HF-Ni (NO 3 ) 2 HF concentration in ethanol solution system of 0.5mol/L, ni (NO) 3 ) 2 The concentration is 0.2mol/L, and the ethanol concentration is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Ni composite material); the composite material is made intoThe porous silicon/carbon/nano silver composite anode material is prepared into a silicon anode half cell, and the capacity of the porous silicon/carbon/nano silver composite anode material is basically stable at 1100mAh/g after 60 charge and discharge cycles.
Example 4: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 5 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 16 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 80%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current of the plasma furnace is 120A, the voltage is 130V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form due to extremely low condensing temperature relative to silicon-carbon to realize the purification of silicon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-Co (NO) 3 ) 2 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 60 ℃ for 3h, wherein HF-Co (NO 3 ) 2 HF concentration in ethanol solution system of 0.5mol/L, co (NO) 3 ) 2 The concentration is 0.2mol/L, and the ethanol concentration is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Co composite material); the composite material is prepared into a silicon negative electrode half cell, and after 50 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stabilized at 1180mAh/g.
Example 5: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 6 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 12 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 90%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current 110A of the plasma furnace, the voltage 140V, the argon pressure of 0.15MPa and the feeding rate of the silicon-carbon mixed powder of 2.0g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form to realize the purification of silicon due to the extremely low condensing temperature relative to the silicon-carbon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-Al (NO) 3 ) 3 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 60 ℃ for 3h, wherein HF-Al (NO 3 ) 3 HF concentration in ethanol solution system of 0.5mol/L, al (NO) 3 ) 3 The concentration is 0.15mol/L, and the concentration of ethanol is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Al composite material); the composite material is prepared into a silicon negative electrode half cell, and after 40 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stabilized at 1150mAh/g.
Example 6: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 90%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current 110A of the plasma furnace, the voltage 140V, the argon pressure of 0.15MPa and the feeding rate of the silicon-carbon mixed powder of 2.0g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form to realize the purification of silicon due to the extremely low condensing temperature relative to the silicon-carbon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-AgNO 3 -Cu(NO 3 ) 2 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 80 ℃ for 4 hours, wherein HF-AgNO 3 -Cu(NO 3 ) 2 HF concentration in ethanol solution system of 0.5mol/L, agNO 3 At a concentration of 0.10mol/L, cu (NO 3 ) 2 The concentration is 0.05mol/L, and the concentration of ethanol is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Ag@Cu composite material); the composite material is prepared into a silicon negative electrode half cell, and after 50 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stable at 1100mAh/g.
Example 7: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 80%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current 110A of the plasma furnace, the voltage 140V, the argon pressure of 0.15MPa and the feeding rate of the silicon-carbon mixed powder of 2.0g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form to realize the purification of silicon due to the extremely low condensing temperature relative to the silicon-carbon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-AgNO 3 -Co(NO 3 ) 2 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 80 ℃ for 4 hours, wherein HF-AgNO 3 -Co(NO 3 ) 2 HF concentration in ethanol solution system of 0.5mol/L, agNO 3 At a concentration of 0.10mol/L, co (NO 3 ) 2 The concentration is 0.10mol/L, and the concentration of ethanol is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Ag@Co composite material); the composite material is prepared into a silicon negative electrode half cell, and after 40 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stabilized at 1150mAh/g.
Example 8: a method for preparing a porous silicon/carbon/nano metal composite anode material by plasma activation of cut silicon waste material comprises the following specific steps:
(1) Crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) Ball-milling and mixing the waste silicon powder obtained in the step (1) and a carbon source in a high-energy ball mill, sieving with a 300-mesh sieve, and vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 70%;
(3) Introducing pure argon into a plasma furnace to remove air in the furnace body, taking argon as shielding gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein, the current 110A of the plasma furnace, the voltage 140V, the argon pressure of 0.15MPa and the feeding rate of the silicon-carbon mixed powder of 2.0g/min, and the organic impurities in the waste silicon powder can be directly carried out by argon in a gas form to realize the purification of silicon due to the extremely low condensing temperature relative to the silicon-carbon;
(4) Placing the nano silicon/carbon composite material in the step (3) in HF-Co (NO) 3 ) 2 -Cu(NO 3 ) 2 -Ni(NO 3 ) 2 Compounding metal particles nanoparticles in an ethanol solution system at a temperature of 80 ℃ for 4h, wherein HF-Co (NO 3 ) 2 -Cu(NO 3 ) 2 -Ni(NO 3 ) 2 HF concentration in ethanol solution system of 0.5mol/L, co (NO) 3 ) 2 The concentration was 0.06mol/L, cu (NO 3 ) 2 At a concentration of 0.10mol/L, ni (NO 3 ) 2 The concentration is 0.04mol/L, and the ethanol concentration is 0.5mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, performing vacuum drying treatment on the Nano metal particle composite silicon/carbon composite material, and grinding to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Co@Cu@Ni composite material); the composite material is prepared into a silicon negative electrode half cell, and after 60 charge and discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stabilized at 1200mAh/g.
While the present invention has been described in detail with reference to the specific embodiments, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. The method for preparing the porous silicon/carbon/nano metal composite anode material by plasma activating and cutting silicon waste is characterized by comprising the following specific steps:
(1) Crushing, grinding and vacuum drying the diamond wire cutting silicon waste to obtain waste silicon powder;
(2) Uniformly mixing the waste silicon powder obtained in the step (1) with a carbon source, and carrying out vacuum drying to obtain silicon-carbon mixed powder;
(3) Introducing argon into a plasma furnace to remove air in the furnace body, taking the argon as a shielding gas and a carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace to perform plasma activation treatment, and gasifying, condensing and recrystallizing the silicon-carbon mixed powder to obtain the nano silicon/carbon composite material;
(4) Placing the nano silicon/carbon composite material in the step (3) in an HF-metal salt-alcohol solution system for metal particle nano particle compounding, washing by deionized water, and carrying out solid-liquid separation to obtain the nano metal particle composite silicon/carbon composite material, wherein the nano metal particle composite silicon/carbon composite material is subjected to vacuum drying treatment and grinding to obtain the porous silicon/carbon/nano metal composite material;
the carbon source in the step (2) is one or more of glucose, fructose, sucrose, xylose, sorbose, citric acid, starch, polyethylene, polypropylene, cellulose, graphite, graphene, carbon nanotubes, aromatic hydrocarbon, aromatic lipid, petroleum asphalt or coal tar asphalt;
the power of the plasma activation treatment in the step (3) is 10-150 KW, the argon pressure is 0.10-0.70 MPa, and the feeding rate of the silicon-carbon mixed powder is 1-50 g/min;
the mass fraction of the waste silicon powder in the silicon-carbon mixed powder in the step (2) is 3-90%.
2. The method for preparing the porous silicon/carbon/nano metal composite anode material by using the plasma activated cut silicon waste material according to claim 1, wherein the method comprises the following steps of: in the step (4), the concentration of HF in the HF-metal salt-alcohol solution system is 0.1-15 mol/L, the concentration of metal salt is 0.005-10 mol/L, and the concentration of alcohol is 0.1-20 mol/L.
3. The method for preparing the porous silicon/carbon/nano metal composite anode material by using the plasma activated cut silicon waste material according to claim 1, wherein the method comprises the following steps of: the metal salt is one or more of silver salt, copper salt, cobalt salt, nickel salt, aluminum salt and titanium salt, and the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
4. The method for preparing the porous silicon/carbon/nano metal composite anode material by using the plasma activated cut silicon waste material according to claim 3, wherein the method comprises the following steps of: silver salt is AgNO 3 、Ag 2 SO 4 Or Ag 2 CO 3 Copper salt is Cu (NO) 3 ) 2 、CuSO 4 Or CuCO 3 The nickel salt is Ni (NO) 3 ) 2 、NiSO 4 Or NiCO 3 Cobalt salt is Co (NO) 3 ) 2 The aluminum salt is Al (NO) 3 ) 3 。
5. The method for preparing the porous silicon/carbon/nano metal composite anode material by using the plasma activated cut silicon waste material according to claim 1 or 2, wherein the method comprises the following steps of: liquid-solid ratio of HF-metal salt-alcohol solution system to nano silicon/carbon composite mL: g is (1-10): 1.
6. the method for preparing the porous silicon/carbon/nano metal composite anode material by using the plasma activated cut silicon waste material according to claim 1 or 2, wherein the method comprises the following steps of: the composite temperature of the metal particle nano-particles is 20-80 ℃ and the time is 0.5-6 h.
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