CN111799460B - Method for preparing boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste - Google Patents
Method for preparing boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste Download PDFInfo
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Abstract
The invention relates to a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste. The method comprises the steps of removing impurities from cut silicon waste, carrying out metal-assisted etching treatment to obtain a nano metal/porous silicon composite material, mixing the nano metal/porous silicon composite material with a boron source, carrying out high-temperature treatment to enable boron to form substitutional doping on silicon, and compounding the silicon-doped displacement type doping with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode. According to the invention, the volume expansion of silicon can be relieved by adding the porous structure of silicon and the carbon material, the circulation stability is increased, the metal particles are physically compounded with the silicon on the surface of the silicon substrate and boron is chemically doped on the silicon on the atomic scale to realize the synergistic effect, and finally the intrinsic conductivity and the electrochemical activity of the silicon-based composite material are improved, so that the boron-doped nano metal/silicon-carbon composite negative electrode material with high charge-discharge specific capacity and long cycle life is prepared.
Description
Technical Field
The invention relates to a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste, belonging to the technical field of new energy materials and electrochemistry.
Background
At present, most commercial lithium ion batteries still use graphite materials as negative electrode materials, and the graphite materials have good cycling stability but relatively low specific capacity. The silicon-based negative electrode material has high safety of 4200mAhg -1 The upper limit of the amount of silicon that can be developed is very high, but silicon produces very severe volume effects during lithiation: (>300%) causing the silicon material to shatter during charge and discharge cycles, generating an unstable solid electrolyte interface film, resulting in rapid decay of electrode capacity. At present, most of the problems of the silicon cathode are solved by silicon-carbon compounding, but the problems of low intrinsic conductivity of the silicon cathode, low first coulombic efficiency of a battery, high irreversible capacity and the like cannot be solved by the silicon-carbon compounding.
With the development of solar energy technology, more and more solar energy devices are put into use, and in the production of the solar energy devices, a diamond wire multi-wire cutting process is mostly adopted for cutting silicon. However, during the cutting process, about 40% of high-purity silicon material enters into the cutting slurry in the form of saw dust, so that a large amount of silicon material is lost. The part of cutting waste is recycled, so that not only can the secondary utilization of resources be realized, but also certain economic benefit can be brought.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cut silicon waste, namely, the cut silicon waste is subjected to metal auxiliary etching treatment after impurity removal to obtain a nano metal/porous silicon composite material, the nano metal/porous silicon composite material is subjected to high-temperature treatment after being mixed with a boron source, so that boron forms substitutional doping on silicon, and then the boron-doped nano metal/porous silicon-carbon composite cathode is compounded with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode; according to the invention, the volume expansion of silicon can be relieved by adding the porous structure of silicon and the carbon material, the circulation stability is increased, the metal particles are physically compounded with the silicon on the surface of the silicon substrate and boron is combined with the silicon to realize the chemical doping synergistic effect on the silicon on the atomic scale, and finally the improvement of the intrinsic conductivity and the improvement of the electrochemical activity of the silicon-based composite material are realized, so that the boron-doped nano metal/silicon-carbon composite negative electrode material with high charge-discharge specific capacity and long cycle life is prepared.
A method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution under the stirring condition, carrying out solid-liquid separation, and washing the solid with deionized water until the washing liquid is neutral to obtain purified silicon powder;
(2) placing the purified silicon powder obtained in the step (1) in an HF-metal salt-alcohol solution system for metal-assisted etching treatment, ultrasonically rinsing by using deionized water, carrying out solid-liquid separation, carrying out vacuum drying on the solid, and grinding to obtain a nano metal/porous silicon composite material;
(3) uniformly mixing the nano metal/porous silicon composite material obtained in the step (2) with a boron source to obtain a mixture, and treating the mixture at the constant temperature of 400-1200 ℃ in a protective atmosphere for 0.5-12h to obtain a boron-doped nano metal/porous silicon composite material;
(4) soaking the boron-doped nano metal/porous silicon composite material obtained in the step (3) in an alkali solution, performing solid-liquid separation, performing vacuum drying on the solid, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material;
(5) and (4) uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode.
The mass concentration of the alkali in the alkali-alcohol solution in the step (1) is 0.1-30%, and the alkali is NaOH, KOH or Ba (OH) 2 、Ca(OH) 2 One or more alcohols selected from methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the soaking and purifying treatment time is 1-300 min.
In the step (2), the concentration of HF, the concentration of metal salt and the concentration of alcohols in the HF-metal salt-alcohol solution system are respectively 0.1-20 mol/L, 0.05-5 mol/L and 0.1-20 mol/L; the metal salt is one or more of silver salt, copper salt and nickel salt, the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the purified silicon powder is (10-100) to 1.
Further, the silver salt is AgNO 3 、Ag 2 SO 4 Or Ag 2 CO 3 Copper salt being Cu (NO) 3 ) 2 、CuSO 4 Or CuCO 3 The nickel salt is Ni (NO) 3 ) 2 、NiSO 4 Or NiCO 3 。
Preferably, the temperature of the metal auxiliary etching treatment in the step (2) is 1-100 ℃, and the time of the metal auxiliary etching treatment is 1-600 min.
The boron source in the step (3) is one or more of boric acid, boron oxide, boron nitride, trimethyl borate, tripropyl borate, boron tribromide and diborane, and the protective atmosphere is argon or nitrogen.
The alkali solution in the step (4) is KOH solution, Ba (OH) 2 Solution, NaOH solution, Ca (OH) 2 One or more of the solutions.
The concentration of the aqueous alkali in the step (4) is 0.1-10 mol/L, the soaking temperature is 1-100 ℃, and the soaking time is 1-120 min.
The mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is 1-20%, and when the nano metal/porous silicon composite material and the boron source are uniformly mixed in the step (2), the adding amount of the boron source is slightly higher than the calculated amount.
The carbon material is one or more of graphite, a carbon nano tube, graphene and pyrolytic carbon, the pyrolytic carbon is one or more of polydopamine, resorcinol-formaldehyde resin, polyvinylpyrrolidone, saccharide materials and aromatic compounds, and the mass fraction of the carbon material in the boron-doped nano metal/porous silicon carbon composite negative electrode is 1-50%.
Preferably, the saccharide is one or more of sucrose, glucose, glycogen and cellulose, and the aromatic compound is benzene hydrocarbon or mono-benzene aromatic hydrocarbon.
The invention has the beneficial effects that:
(1) the diamond wire cutting silicon waste is used as a raw material, so that the raw material source is wide and the price is low; the waste materials are dried, crushed, cleaned, subjected to impurity removal and the like, and are used as silicon-based negative electrode materials of the lithium ion battery, so that the material preparation cost is reduced;
(2) according to the invention, a metal-assisted etching method is adopted to etch silicon into porous silicon, so that the volume expansion of a silicon cathode in the charge-discharge cycle process is effectively relieved, and the cycle stability of the lithium ion battery is increased; the composite material is mixed with a boron source and then is subjected to high-temperature treatment, so that the boron forms substitutional doping on silicon, and the intrinsic conductivity and the electrochemical activity of the silicon material can be improved by the doping of the boron;
(3) the metal particles are physically compounded with silicon on the surface of a silicon substrate and boron is combined with the silicon to realize the chemical doping synergistic effect on the silicon on the atomic scale, so that the intrinsic conductivity of the silicon-based composite material is improved and the electrochemical activity is improved; the addition of the porous structure of silicon and the later-stage carbon material effectively relieves the volume expansion of the silicon negative electrode in the charging and discharging processes, so that the boron-doped nano metal/porous silicon carbon composite material has higher charging and discharging specific capacity and longer cycle life when being used as the negative electrode material of the lithium ion battery.
Drawings
FIG. 1 is a graph of the cycle performance at 1C rate of a half-cell assembled from raw silicon waste, nano-metal Ag/porous silicon carbon composite, and boron-doped nano-metal Ag/porous silicon carbon composite in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a diamond wire-cut silicon scrap of example 1;
FIG. 3 is a graph of the HF-AgNO passage of the cut silicon scrap of example 1 3 -Scanning Electron Microscopy (SEM) images of the methanol solution system after treatment;
FIG. 4 is a graph of example 2 cut silicon scrap through HF-CuNO 3 Scanning Electron Microscopy (SEM) images of the methanol solution system after treatment.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (NaOH-ethanol solution) for 180min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of NaOH in the alkali-alcohol solution (NaOH-methanol solution) is 10 percent,
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-AgNO) 3 -methanol solution system) and at a temperature of 60 ℃ carrying out metal Ag auxiliary etching treatment for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Ag/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-AgNO) 3 -methanol solution system) and purified silicon powder with the liquid-solid ratio mL to g of 35:1, HF-AgNO 3 HF concentration in the methanol solution system of 3.5mol/L, AgNO 3 The concentration is 0.1mol/L, and the methanol concentration is 3.5 mol/L;
(3) mixing the nano metal Ag/porous silicon composite material obtained in the step (2) with a boron source (B) 2 O 3 ) Uniformly mixing to obtain a mixture, and treating the mixture at 900 ℃ in a nitrogen atmosphere for 6 hours at constant temperature to obtain the boron-doped nano metal Ag/porous silicon composite material;
(4) immersing the boron-doped nano metal Ag/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 1mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal Ag/porous silicon composite material is about 5 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) and a carbon material (graphite) to obtain a boron-doped nano metal Ag/porous silicon-carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano Ag/porous silicon-carbon composite negative electrode is 30%;
the cycle performance curve of the half-cell assembled by the boron-doped nano metal Ag/porous silicon carbon composite cathode in the embodiment is shown in figure 1, compared with a pure silicon cathode and a nano metal Ag/porous silicon carbon composite cathode, the boron-doped nano metal Ag/porous silicon carbon composite cathode has better cycle stability, the first discharge specific capacity is 3300mAh/g under the multiplying power of 1C, and the capacity of more than 1600mAh/g is reserved after 50 times of cycle, which indicates that the electrochemical activity of the composite material is improved by the doping of boron, and the electrochemical performance of the composite material is improved; in the embodiment, a Scanning Electron Microscope (SEM) image of the cut silicon waste is shown in fig. 2, and it can be seen that the cut silicon waste has a large size and a non-uniform particle size distribution, and has a strip-shaped structure; in the embodiment, a Scanning Electron Microscope (SEM) image of porous silicon formed by the cutting silicon waste through Ag-assisted etching is shown in fig. 3, and it can be seen that the particle size of the material is significantly reduced, the strip-shaped structure is no longer present, and the porous structure can be seen on the silicon particles.
Example 2: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (NaOH-methanol solution) for 150min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of NaOH in the alkali-alcohol solution (NaOH-methanol solution) is 15 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-CuNO) 3 -methanol solution system) and at a temperature of 60 ℃ carrying out metal Cu auxiliary etching treatment for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 60 ℃ for vacuum drying, and grinding to obtain the nano metal Cu/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-CuNO) 3 A methanol solution system) and the purified silicon powder have a liquid-solid ratio of mL to g of 10:1, and HF-CuNO 3 HF concentration in the methanol solution system 10mol/L, CuNO 3 The concentration is 5mol/L, and the methanol concentration is 10 mol/L;
(3) mixing the nano metal Cu/porous silicon composite material obtained in the step (2) with a boron source (B) 2 O 3 ) Uniformly mixing to obtain a mixture, and treating the mixture at 900 ℃ in a nitrogen atmosphere for 6 hours at a constant temperature to obtain the boron-doped nano metal Cu/porous silicon composite material;
(4) immersing the boron-doped nano metal Cu/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 5mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 20 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal Cu/porous silicon composite material obtained in the step (4) and a carbon material (graphite) to obtain a boron-doped nano metal Cu/porous silicon-carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Cu/porous silicon-carbon composite negative electrode is 25%;
in the embodiment, a scanning electron microscope image of the material after the silicon waste material is subjected to the Cu-assisted etching is shown in FIG. 4, and it can be seen that the particle size of the material after the Cu-assisted etching is obviously reduced and the particle size distribution is relatively uniform; after the boron-doped nano metal Cu/porous silicon-carbon composite negative electrode of the embodiment is assembled into a half cell, the cycle performance of the half cell is tested, and the initial discharge specific capacity is 2322mAh/g and is 0.5CThe capacity of 1230mAh/g still remains after the circulation for 100 times under the multiplying power, and the reduction of the capacity is attributed to CuNO when metal-assisted etching is carried out 3 Too high a concentration results in a large amount of copper remaining in the composite, resulting in a capacity fade; but compared with a pure silicon cathode, the composite material has better cycle stability under the condition of high-rate charge and discharge current.
Example 3: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (NaOH-methanol solution) for 200min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of NaOH in the alkali-alcohol solution (NaOH-methanol solution) is 20 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-NiNO) 3 -methanol solution system) and at a temperature of 70 ℃ carrying out metal Ni auxiliary etching treatment for 100min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Ni/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-NiNO) 3 -methanol solution system) and the liquid-solid ratio mL/g of the purified silicon powder is 100:1, and HF-NiNO 3 HF concentration in the methanol solution system of 20mol/L, NiNO 3 The concentration is 2.5mol/L, and the methanol concentration is 20 mol/L;
(3) mixing the nano metal Ni/porous silicon composite material obtained in the step (2) with a boron source (B) 2 O 3 ) Uniformly mixing to obtain a mixture, and treating the mixture at 900 ℃ in a nitrogen atmosphere for 6 hours at constant temperature to obtain the boron-doped nano metal Ni/porous silicon composite material;
(4) immersing the boron-doped nano metal Ni/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 90 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 10mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 10 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal Ni/porous silicon composite material obtained in the step (4) and a carbon material (carbon nano tube) to obtain a boron-doped nano metal/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Ni/porous silicon-carbon composite negative electrode is 50%.
In the embodiment, the boron-doped nano metal Ni/porous silicon-carbon composite cathode is assembled into a half-cell and then tested for the cycle performance, the initial discharge specific capacity is 1840mAh/g, and the capacity of 1500mAh/g is still remained after the half-cell is cycled for 100 times under the multiplying power of 0.5C; the reason that the initial discharge specific capacity of the material is lower is that the mass fraction of the graphite added into the material is 50 percent, and the addition of a large amount of carbon materials reduces the integral specific capacity of the composite material; however, the addition of a large amount of graphite improves the cycle stability of the composite.
Example 4: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (KOH-ethanol solution) for 120min at room temperature under the condition of stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of KOH in the alkali-alcohol solution (KOH-ethanol solution) is 30 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-AgNO) 3 -Cu(NO 3 ) 2 -ethanol solution system) and at a temperature of 80 ℃ carrying out metal Ag and Cu cooperative auxiliary etching treatment for 120min, ultrasonically rinsing by using deionized water until the washing liquid is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Ag/Cu/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-AgNO) 3 -Cu(NO 3 ) 2 -ethanol solution system) and the liquid-solid ratio mL/g of the purified silicon powder is 40:1, and HF-AgNO 3 -Cu(NO 3 ) 2 HF concentration in the ethanol solution system of 0.5mol/L, AgNO 3 The concentration is 0.05mol/L, Cu (NO) 3 ) 2 The concentration is 0.05mol/L, and the ethanol concentration is 3.5 mol/L;
(3) mixing the nano metal Ag/Cu/porous silicon composite material obtained in the step (2) with a boron source (H) 3 BO 3 ) Adding the mixture into ethanol, uniformly mixing the mixture in a liquid phase to obtain a mixture, and treating the mixture at 1100 ℃ in a nitrogen atmosphere at a constant temperature for 8 hours to obtain the boron-doped nano metal Ag/Cu/porous silicon composite material;
(4) immersing the boron-doped nano metal Ag/Cu/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 90 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 5mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 5 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) and a carbon material (carbon nano tube) to obtain a boron-doped nano metal Ag and Cu/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Ag and Cu/porous silicon-carbon composite negative electrode is 20%.
In the embodiment, the cycle performance of the half-cell assembled by the boron-doped nano metal Ag and Cu/porous silicon-carbon composite cathode is tested, the initial discharge specific capacity is 3200mAh/g, and the capacity of 1799mAh/g is still remained after the half-cell is cycled for 100 times under the multiplying power of 0.5C; ag. Compared with single metal etching, the Cu common etching has the advantages that the grain size distribution of etched silicon is more uniform, and more holes are etched on the silicon, so that the specific surface area of the composite material is larger, and the charge-discharge specific capacity of the composite material is improved.
Example 5: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (KOH-ethanol solution) for 300min at room temperature under the condition of stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of KOH in the alkali-alcohol solution (KOH-ethanol solution) is 10 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-AgNO) 3 -Ni(NO 3 ) 2 -ethanol solution system) and at a temperature of 80 ℃ carrying out cooperative auxiliary etching treatment on the metal Ag and Ni for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying and grinding to obtain the nano metal Ag/Ni/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-AgNO) 3 -Ni(NO 3 ) 2 -ethanol solution system) and purified silicon powder, wherein the liquid-solid ratio mL/g of the purified silicon powder is 35:1, and HF-AgNO is 3 -Ni(NO 3 ) 2 HF concentration in the ethanol solution system of 0.1mol/L, AgNO 3 The concentration is 0.1mol/L, Ni (NO) 3 ) 2 The concentration is 0.1mol/L, and the ethanol concentration is 0.1 mol/L;
(3) mixing the nano metal Ag/Ni/porous silicon composite material obtained in the step (2) with a boron source (B) 2 O 3 And H 3 BO 3 ) Grinding and uniformly mixing to obtain a mixture, and treating the mixture at 1100 ℃ for 6 hours in a nitrogen atmosphere at constant temperature to obtain the boron-doped nano metal Ag/Ni/porous silicon composite material; wherein B is 2 O 3 And H 3 BO 3 The mass ratio of (A) to (B) is 1: 1;
(4) immersing the boron-doped nano metal Ag/Ni/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 0.1mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 1 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) and a carbon material (carbon nano tube) to obtain a boron-doped nano metal Ag and Ni/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Ag and Ni/porous silicon-carbon composite negative electrode is 30%.
In the embodiment, the boron-doped nano metal Ag and Ni/porous silicon-carbon composite cathode is assembled into a half-cell and then tested for cycle performance, the initial specific discharge capacity is 2500mAh/g, and the capacity of 900mAh/g is still remained after 100 cycles under the multiplying power of 0.5C; the reduction in the electrochemical performance of the material is due to the HF-AgNO 3 -Ni(NO 3 ) 2 The concentration of HF in an ethanol solution system is too low, so that silicon is not well etched into a porous structure, and meanwhile, the boron doping mass fraction is only 1%, so that the improvement effect on the electrochemical performance of the composite material is limited.
Example 6: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (KOH-methanol solution) for 180min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of KOH in the alkali-alcohol solution (KOH-methanol solution) is 15 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-CuNO) 3 -Ni(NO 3 ) 2 -propanol solution system) and at a temperature of 80 ℃ carrying out metal Cu and Ni synergistic auxiliary etching treatment for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Cu/Ni/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-CuNO) 3 -Ni(NO 3 ) 2 -propanol solution system) and purified silicon powder with the liquid-solid ratio mL/g of 40:1, and HF-CuNO 3 -Ni(NO 3 ) 2 HF concentration in the propanol solution system was 0.5mol/L, CuNO 3 The concentration is 0.05mol/L, Ni (NO) 3 ) 2 The concentration is 0.05mol/L, and the concentration of propanol is 0.5 mol/L;
(3) nano metal Cu in the step (2)Ni/porous silicon composite and boron source (B) 2 O 3 And H 3 BO 3 ) Grinding and uniformly mixing to obtain a mixture, and treating the mixture at the temperature of 1100 ℃ for 8 hours in a nitrogen atmosphere at constant temperature to obtain the boron-doped nano metal Cu/Ni/porous silicon composite material; wherein B is 2 O 3 And H 3 BO 3 The mass ratio of (A) to (B) is 1: 1.5;
(4) immersing the boron-doped nano metal Cu/Ni/porous silicon composite material in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 1mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 20 percent;
(5) uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) with glucose, and then placing the mixture in a tubular furnace to perform carbon coating on the composite material at the temperature of 600 ℃ in a nitrogen atmosphere by using glucose pyrolytic carbon as a carbon source to obtain a boron-doped nano metal Cu and Ni/porous silicon carbon composite cathode; wherein the mass fraction of the pyrolytic carbon in the boron-doped nano metal Cu and Ni/porous silicon-carbon composite negative electrode is 40%.
After the boron-doped nano metal Cu and Ni/porous silicon-carbon composite cathode is assembled into a half-cell, the cycle performance of the half-cell is tested, the initial discharge specific capacity is 2100mAh/g, and the capacity of 1600mAh/g is still reserved after the half-cell is cycled for 100 times under the multiplying power of 0.5C; the composite material has good electrochemical performance, and the initial discharge specific capacity is lower because the composite material contains 40% of carbon by mass fraction, but the addition of the carbon improves the cycle stability of the whole material.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (9)
1. A method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste is characterized by comprising the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution under the stirring condition, carrying out solid-liquid separation, and washing the solid with deionized water until the washing liquid is neutral to obtain purified silicon powder;
(2) placing the purified silicon powder obtained in the step (1) in an HF-metal salt-alcohol solution system for metal-assisted etching treatment, ultrasonically rinsing by using deionized water, carrying out solid-liquid separation, drying the solid in vacuum, and grinding to obtain a nano metal/porous silicon composite material;
(3) uniformly mixing the nano metal/porous silicon composite material obtained in the step (2) with a boron source to obtain a mixture, and treating the mixture at the constant temperature of 400-1200 ℃ in a protective atmosphere for 0.5-12h to obtain a boron-doped nano metal/porous silicon composite material;
(4) soaking the boron-doped nano metal/porous silicon composite material obtained in the step (3) in an alkali solution, performing solid-liquid separation, performing vacuum drying on the solid, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material;
(5) uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) with a carbon material to obtain a boron-doped nano metal/porous silicon-carbon composite cathode;
in the step (2), the concentration of HF, the concentration of metal salt and the concentration of alcohols in the HF-metal salt-alcohol solution system are respectively 0.1-20 mol/L, 0.05-5 mol/L and 0.1-20 mol/L; the metal salt is a plurality of silver salts, copper salts and nickel salts, the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the liquid-solid ratio mL: g of the HF-metal salt-alcohol solution system to the purified silicon powder is (10-100) to 1.
2. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the mass concentration of alkali in the alkali-alcohol solution is 1-30%, and the alkali is NaOH, KOH or Ba (OH) 2 、Ca(OH) 2 One or more alcohols selected from methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the soaking and purifying treatment time is 1-300 min.
3. The method for preparing the boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste material according to claim 1, characterized in that: the silver salt in the step (2) is AgNO 3 、Ag 2 SO 4 Or Ag 2 CO 3 Copper salt being Cu (NO) 3 ) 2 、CuSO 4 Or CuCO 3 The nickel salt is Ni (NO) 3 ) 2 、NiSO 4 Or NiCO 3 。
4. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the temperature of the metal auxiliary etching treatment is 1-100 ℃, and the time of the metal auxiliary etching treatment is 1-600 min.
5. The method for preparing a boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste according to claim 1 or 2, characterized in that: and (3) the boron source is one or more of boric acid, boron oxide, boron nitride, trimethyl borate, tripropyl borate, boron tribromide and diborane, and the protective atmosphere is argon or nitrogen.
6. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: the alkali solution in the step (4) is KOH solution, Ba (OH) 2 Solution, NaOH solution, Ca (OH) 2 One or more of the solutions.
7. The method for preparing a boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste materials according to claim 1 or 6, characterized in that: the concentration of the alkali solution in the step (4) is 0.1-10 mol/L, the soaking temperature is 1-100 ℃, and the soaking time is 1-120 min.
8. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is 1-20%.
9. The method for preparing the boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste material according to claim 1, characterized in that: the carbon material is one or more of graphite, carbon nano tubes, graphene and pyrolytic carbon, the pyrolytic carbon is one or more of polydopamine, resorcinol-formaldehyde resin, polyvinylpyrrolidone, carbohydrate materials and aromatic compounds, and the mass fraction of the carbon material in the boron-doped nano metal/porous silicon carbon composite negative electrode is 1-50%.
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