CN110350181B - Preparation method of nano porous silicon negative electrode material of lithium ion battery - Google Patents
Preparation method of nano porous silicon negative electrode material of lithium ion battery Download PDFInfo
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Abstract
The invention relates to a preparation method of a nano porous silicon negative electrode material of a lithium ion battery, belonging to the technical field of new energy materials and electrochemistry. In a protective gas atmosphere, crushing and finely grinding a silicon material to obtain micro-nano silicon powder, then carrying out crushing pretreatment, washing off metal nano particles on the surface of the silicon powder, and drying to obtain nano silicon powder; performing one-step or two-step metal nanoparticle-assisted chemical etching on the nanoscale silicon powder, performing solid-liquid separation, and drying to obtain a nano porous silicon/metal composite material; or removing the metal nano particles on the surface of the nano porous silicon by using a detergent, carrying out solid-liquid separation, and drying to obtain the nano porous silicon; and oxidizing the nano porous silicon/metal composite material or the nano porous silicon to obtain an oxidized nano porous silicon/metal composite material or oxidized nano porous silicon, wherein the nano porous silicon/metal composite material, the nano porous silicon, the oxidized nano porous silicon/metal composite material or the oxidized nano porous silicon is the lithium ion battery nano porous silicon negative electrode material.
Description
Technical Field
The invention relates to a preparation method of a nano porous silicon negative electrode material of a lithium ion battery, belonging to the technical field of new energy materials and electrochemistry.
Background
Among many energy storage systems, lithium ion batteries have long life, light weight, safe use, environmental protection, and are regarded as the most promising energy storage devices and are receiving much attention. In recent years, with the development of electric vehicles, hybrid vehicles and large-scale energy storage devices, higher requirements are put on the cost, energy density, rate capability and cycle stability of the next generation of novel lithium ion batteries. The low theoretical specific capacity (372 mAh/g) of the traditional graphite cathode is difficult to meet the application requirement of a novel high-specific-energy battery, and the development of a high-capacity, long-service-life and safe lithium ion battery cathode material becomes a problem which needs to be solved in related researches.
Among them, silicon materials are considered to be the most potential lithium battery negative electrode materials due to the advantages of high theoretical capacity, abundant resource reserves, environmental friendliness and the like. When the silicon negative electrode material is charged, lithium ions are released from the positive electrode material and enter silicon crystals to form a silicon-lithium alloy, which causes the silicon negative electrode material to expand greatly (up to 400%); during discharging, lithium ions are released from the silicon negative electrode material to form a large gap, and the silicon negative electrode material is violently crushed and the intrinsic conductivity of the silicon negative electrode material is reduced, so that the capacity of the silicon negative electrode material is quickly attenuated, and the cycle performance of the silicon negative electrode material is poor. Overcoming a series of problems caused by large volume expansion and poor conductivity of silicon cathode materials has become a main challenge facing current research and application.
Around the bottleneck problems of large volume effect, poor conductivity and the like of silicon materials, researchers can better improve the capacity performance, the circulation stability and the like of the silicon-based negative electrode material by carrying out nano treatment, porous treatment and composite treatment on the silicon-based negative electrode material. Among them, the nano-size and porous structure are the determining factors for effectively overcoming the negative effect of the silicon volume effect. On the basis, the electronic conductivity of the silicon material can be further improved by combining the compounding, and meanwhile, the mechanical deformation resistance of the composite material can be effectively improved by the composite structure, so that the stability of an electrode structure and a conductive environment is kept, and the cycle performance of the silicon material is improved. However, the conventional methods for preparing nanoporous silicon and composite materials thereof (such as chemical vapor deposition, magnetron sputtering, plasma processing, magnesiothermic reduction, etc.) often require expensive equipment, and have relatively complex processing processes, low yield and high cost, which makes it difficult to implement the commercial scale application of silicon-based negative electrode materials. Therefore, developing a novel efficient, low-energy and environment-friendly preparation technology of the nano porous silicon composite material is an important problem to be solved in large-scale application of the current nano porous silicon negative electrode material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a nano porous silicon negative electrode material of a lithium ion battery, the method is simple to operate and strong in practicability, the leaching solution and the metal salt can be recycled, the resource utilization of silicon waste can be realized, and the cost in the prior art can be effectively reduced.
A preparation method of a nano porous silicon negative electrode material of a lithium ion battery comprises the following specific steps:
(1) in the protective gas atmosphere, crushing and finely grinding the silicon material to obtain micro-nano silicon powder, washing by using deionized water at room temperature and drying;
(2) adding the silicon powder obtained in the step (1) into a metal salt/HF/alcohol mixed solution system A, wherein the metal salt/HF/alcohol mixed solution system A contains a reducing agent which can enhance the crushing effect of the silicon powder; carrying out crushing pretreatment by adopting a one-step metal nanoparticle auxiliary etching method, removing metal nanoparticles on the surface of the silicon powder by adopting a detergent, carrying out solid-liquid separation, and drying to obtain nanoscale silicon powder;
(3) adding the nanoscale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B to deposit metal nanoparticles for 0.1-10 min, and adding H2O2Etching at 0-80 deg.C for 1-600 min to convert the nanometer silicon powder into nanometer porous silicon; carrying out solid-liquid separation and drying to obtain the nano porous silicon/metal composite material; or removing the metal nano particles on the surface of the nano porous silicon by using a detergent, carrying out solid-liquid separation, and drying to obtain the nano porous silicon; the nano porous silicon/metal composite material or the nano porous silicon is the lithium ion battery nano porous silicon cathode material.
H2O2When the addition amount of (2) is 0, the method is a one-step metal nanoparticle assisted chemical etching method; h2O2When the addition amount of (2) is more than 0, the two-step metal nanoparticle assisted chemical etching method is adopted;
and (3) placing the nano porous silicon/metal composite material or the nano porous silicon in an oxidizing substance environment for oxidation treatment to obtain an oxidized nano porous silicon/metal composite material or oxidized nano porous silicon, wherein the oxidized nano porous silicon/metal composite material or the oxidized nano porous silicon is the lithium ion battery nano porous silicon negative electrode material.
The temperature of the oxidation treatment is 0-500 ℃, and the time of the oxidation treatment is 1 min-50 h.
Further, the oxidizing substance environment is F-containing2、Cl2、O2Or O3In a gaseous atmosphere of, or containing Ag+、Cu2+、Fe3 +、Br-、I-、HNO3、H2SO4、H2O2、KMnO4、HClO、SO2、SO3Or NO2The physical environment of (a).
The protective gas in the step (1) is argon or nitrogen, the silicon material is high-purity silicon, industrial silicon, silicon waste materials for cutting in photovoltaic industry or silicon waste residues in photovoltaic industry, and the particle size of the micro-nano silicon powder is less than 30 mu m.
The liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A to the silicon powder in the step (2) is (5-100): 1, the crushing pretreatment temperature is 0-80 ℃, and the crushing pretreatment time is 1-600 min; the concentration of HF in the metal salt/HF/alcohol mixed solution system A is 0.5-10 mol/L, and the concentration of the metal salt is 0.001-1 mol-L, the concentration of the alcohols is 0.1-20 mol/L; the metal salt is CuSO4、CuCl2、Cu(NO3)2The alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
Preferably, the liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A to the silicon powder is (20-40): 1.
Further, the concentration of the reducing agent in the metal salt/HF/alcohol mixed solution system A is 0.001-5 mol/L, and the reducing agent is H3PO2、H3PO3、H2C2O4、Na2HPO3、NaHSO3、Na2SO3、Na2SO3、K2S2O5、Na2S2O5Or Na2S2O4。
The liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder in the step (3) is (5-100): 1, the concentration of HF in the metal salt/HF/alcohol mixed solution system B is 0.5-10 mol/L, the concentration of metal salt is 0.0001-10 mol/L, and the concentration of alcohol is 0.1-20 mol/L; the metal salt is KAuCl4、HAuCl4、K2PtCl6、H2PtCl6、PdCl2、AgNO3、Fe(NO3)3、Ni(NO3)2、NiSO4、CuSO4、CuCl2Or Cu (NO)3)2The alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
The metal salt/HF/alcohol mixed solution system B selects HF/AgNO3The reaction of the alcohol mixed solution system needs to be protected from light;
preferably, the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder is (20-40): 1.
Further, H in the step (3)2O2The addition amount of (b) is 0-5 mol/L.
Said step (2) or step(3) The detergent is dilute sulfuric acid, dilute nitric acid, dilute hydrochloric acid or ammonia water/H2O2The concentration of the mixture of dilute sulfuric acid, dilute nitric acid and dilute hydrochloric acid is 1-30 wt%, and the concentration of ammonia water/H2O2Ammonia and H in the mixture2O2The volume ratio of (1) - (5).
The invention has the beneficial effects that:
(1) the invention can not only carry out nano-grade and porous treatment on the micron-grade silicon material, but also effectively purify the silicon material; the obtained nano porous silicon has obvious effects on overcoming the volume expansion and structure pulverization effects of silicon materials in the charging and discharging processes of the lithium ion battery and improving the cycle performance of the battery;
(2) according to the invention, the metal nano particles in silicon are selectively retained or not retained, and the oxidation film is selectively introduced on the surfaces of the nano porous silicon particles, so that the first coulombic efficiency and the conductivity of the lithium ion battery silicon cathode material can be effectively improved, and the lithium ion battery silicon cathode material with excellent electrochemical performance is obtained;
(3) the method has simple operation and strong practicability, the leaching solution and the metal salt can be recycled, the resource utilization of the silicon waste can be realized, and the cost of the prior art can be effectively reduced.
Drawings
FIG. 1 is a morphology of the nanoporous silicon/Ag composite material of example 1 under a transmission electron microscope;
FIG. 2 is a morphology chart of the crushed pretreated nano-scale silicon powder under a transmission electron microscope in example 2;
FIG. 3 is a morphology chart of the crushed pretreated nano-sized silicon powder under a transmission electron microscope in example 3;
FIG. 4 is a morphology chart of the crushed pretreated nano-sized silicon powder under a transmission electron microscope in example 4;
FIG. 5 is a morphology chart of the crushed and pretreated nano-scale silicon powder in example 5 under a transmission electron microscope.
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 preparation method of a nano porous silicon negative electrode material of a lithium ion battery comprises the following specific steps:
(1) in the atmosphere of protective gas (nitrogen), crushing and finely grinding a high-purity silicon material to obtain micro-nano silicon powder with the particle size of less than 30 microns, washing for 3 times by using deionized water at room temperature, washing for 20min each time, and drying;
(2) adding the silicon powder obtained in the step (1) into a metal salt/HF/alcohol mixed solution system A, wherein the metal salt/HF/alcohol mixed solution system A contains a reducing agent to enhance the crushing effect, performing crushing pretreatment for 120min by adopting a one-step metal nanoparticle auxiliary etching method at the temperature of 80 ℃, cleaning for 30min by adopting a detergent to remove metal nanoparticles on the surface of the silicon powder, performing solid-liquid separation, and drying to obtain nanoscale silicon powder; wherein the metal salt in the metal salt/HF/alcohol mixed solution system A is Cu (NO)3)2Alcohol is ethanol, and reducing agent is H3PO2(ii) a HF concentration of 2mol/L, Cu (NO)3)2Concentration of 0.1mol/L, ethanol concentration of 4mol/L, H3PO2The concentration is 0.001mol/L, and the liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A to the silicon powder is 20: 1; the detergent is 20 wt% of dilute nitric acid;
(3) adding the nanoscale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B at the temperature of 0 ℃ to deposit metal nanoparticles for 0.1min in a dark place, and continuously etching for 600min to change the nanoscale silicon powder into the nanoporous silicon (namely, the one-step metal nanoparticle assisted chemical etching method); carrying out solid-liquid separation and drying to obtain a nano porous silicon/metal composite material (nano porous silicon/Ag composite material); the nano porous silicon/Ag composite material can be used as a lithium ion battery nano porous silicon negative electrode material; wherein the metal salt in the metal salt/HF/alcohol mixed solution system B is AgNO3The alcohol is ethylene glycol; HF concentration of 3mol/L, metal salt AgNO3The concentration is 0.01mol/L, the concentration of alcohol glycol is 0.1 mol/L; the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder is 20: 1;
the appearance diagram of the nano-porous silicon/Ag composite material under a transmission electron microscope is shown in FIG. 1, as can be seen from FIG. 1, the nano-silver particles are scattered in silicon to enhance conductivity, and the porous appearance on the surface is helpful for relieving the volume expansion effect;
(4) placing the nano porous silicon/Ag composite material obtained in the step (3) in an oxygen atmosphere, and carrying out oxidation heat treatment for 25 hours at the temperature of 60 ℃ to obtain an oxidized nano porous silicon/Ag composite material;
after the oxidized nano-porous silicon/Ag composite material, a conductive agent and a sodium alginate binder are mixed according to the mass ratio of 3:1:1, a battery is assembled in a glove box by taking a lithium sheet as a counter electrode, and the battery is charged and discharged under the condition of 0.5A/g, wherein the first reversible capacity of the material reaches 3850mAh/g, and the first coulombic efficiency of the electrode reaches 88%.
Example 2: a preparation method of a nano porous silicon negative electrode material of a lithium ion battery comprises the following specific steps:
(1) crushing and finely grinding the screened photovoltaic industry waste silicon slag in a protective gas (nitrogen) atmosphere to obtain micro-nano silicon powder with the particle size of less than 30 microns, washing for 3 times by using deionized water at room temperature, washing for 20min each time, and drying;
(2) adding the silicon powder obtained in the step (1) into a metal salt/HF/alcohol mixed solution system A, wherein the metal salt/HF/alcohol mixed solution system A contains a reducing agent to enhance the crushing effect, performing crushing pretreatment for 60min by adopting a one-step metal nanoparticle auxiliary etching method at the temperature of 25 ℃, cleaning for 100min by adopting a detergent to remove metal nanoparticles on the surface of the silicon powder, performing solid-liquid separation, and drying to obtain nanoscale silicon powder; wherein the metal salt in the metal salt/HF/alcohol mixed solution system A is Cu (NO)3)2Alcohol is ethanol, and reducing agent is H3PO3(ii) a HF concentration of 5mol/L, Cu (NO)3)2Concentration of 0.005mol/L, ethanol concentration of 2mol/L, H3PO3The concentration is 0.1mol/L, and the liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A to the silicon powder is 20: 1; the detergent is ammonia water/H2O2Mixture, aqueous ammonia/H2O2Ammonia and H in the mixture2O2In a volume ratio of 1:1, ammonia and H2O2Is a commercially available product;
the appearance of the nano-scale silicon powder in the embodiment is shown in fig. 2 under a transmission electron microscope, and as can be seen from fig. 2, the original micro-scale silicon material is effectively crushed into nano-scale particles;
(3) adding the nano-scale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B at the temperature of 40 ℃ to deposit metal nano-particles for 0.1min, and adding H2O2Continuously etching for 60min to change the nano-scale silicon powder into nano-porous silicon (namely a two-step metal nano-particle assisted chemical etching method); removing metal nano particles on the surface of the nano porous silicon by using a detergent, carrying out solid-liquid separation, and drying to obtain nano porous silicon; the nano porous silicon/Ag composite material can be used as a lithium ion battery nano porous silicon negative electrode material; wherein the metal salt in the metal salt/HF/alcohol mixed solution system B is Cu (NO)3)2The alcohol is propanol, butanol, mixed alcohol of ethylene glycol and propylene glycol, and the volume ratio of the propanol, the butanol, the ethylene glycol and the propylene glycol is 1:1:1: 1; HF concentration of 2mol/L, metal salt Cu (NO)3)2The concentration is 0.01mol/L and the alcohol concentration is 1 mol/L; the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder is 5: 1; h2O2The addition amount of (A) is 0.2 mol/L; the detergent is ammonia water/H2O2Mixture, aqueous ammonia/H2O2Ammonia and H in the mixture2O2In a volume ratio of 1:1, ammonia and H2O2Is a commercially available product;
after mixing nano porous silicon with a conductive agent and a sodium alginate adhesive according to a mass ratio of 3:1:1, assembling a battery in a glove box by taking a lithium sheet as a counter electrode, and charging and discharging at 0.5A/g, wherein the first reversible capacity of the material reaches 2980mAh/g, and the first coulombic efficiency of the electrode reaches 84%.
Example 3: a preparation method of a nano porous silicon negative electrode material of a lithium ion battery comprises the following specific steps:
(1) crushing and finely grinding the screened photovoltaic industry waste silicon slag in a protective gas (nitrogen) atmosphere to obtain micro-nano silicon powder with the particle size of less than 30 microns, washing for 3 times by using deionized water at room temperature, washing for 20min each time, and drying;
(2) adding the silicon powder obtained in the step (1) into metal salt/HF/alcoholsIn the mixed solution system A, a reducing agent is contained in the metal salt/HF/alcohol mixed solution system A to enhance the crushing effect, a one-step metal nanoparticle auxiliary etching method is adopted for crushing pretreatment for 90min at the temperature of 40 ℃, a detergent is adopted for cleaning for 30min to remove metal nanoparticles on the surface of silicon powder, and the nano-scale silicon powder is obtained through solid-liquid separation and drying; wherein the metal salt in the metal salt/HF/alcohol mixed solution system A is CuSO4Alcohol is ethylene glycol, and reducing agent is Na2HPO3(ii) a HF concentration is 8mol/L, CuSO4The concentration is 0.01mol/L, the concentration of ethylene glycol is 5mol/L, Na2HPO3The concentration is 1mol/L, and the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system A to the silicon powder is 15: 1; the detergent is 20 wt% dilute nitric acid;
the appearance of the nano-scale silicon powder in the embodiment is shown in fig. 3 under a transmission electron microscope, and as can be seen from fig. 3, the original micro-scale silicon material is effectively crushed into the nano-scale silicon powder, and crushing traces can be obviously seen;
(3) adding the nano-scale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B at the temperature of 25 ℃ to deposit metal nano-particles for 2min, and adding H2O2Continuously etching for 60min to change the nano-scale silicon powder into nano-porous silicon (namely a two-step metal nano-particle assisted chemical etching method); removing metal nano particles on the surface of the nano porous silicon by using a detergent, carrying out solid-liquid separation, and drying to obtain nano porous silicon; the nano porous silicon/Ag composite material can be used as a lithium ion battery nano porous silicon negative electrode material; wherein the metal salt in the metal salt/HF/alcohol mixed solution system B is Cu (NO)3)2The alcohol is propanol, butanol, mixed alcohol of ethylene glycol and propylene glycol, and the volume ratio of the propanol, the butanol, the ethylene glycol and the propylene glycol is 1:1:1: 1; HF concentration of 2mol/L, metal salt Cu (NO)3)2The concentration is 0.01mol/L and the alcohol concentration is 1 mol/L; the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder is 5: 1; h2O2The addition amount of (A) is 0.5 mol/L; the detergent is 20 wt% dilute nitric acid;
(4) placing the nano porous silicon in the step (3) in H2SO4/H2O2Carrying out oxidation heat treatment for 0.5h in the mixed solution at the temperature of 80 ℃ to obtain oxidized nano porous silicon; wherein H2SO4/H2O2H in the mixed solution2SO4And H2O2In a volume ratio of 1:1, H2SO4And H2O2Are all commercial products;
after mixing the oxidized nano-porous silicon with the conductive agent and the sodium alginate adhesive according to the mass ratio of 3:1:1, assembling the battery in a glove box by taking a lithium sheet as a counter electrode, and charging and discharging at 0.5A/g, wherein the first reversible capacity of the material reaches 3030mAh/g, and the first coulombic efficiency of the electrode can reach 85%.
Example 4: a preparation method of a nano porous silicon negative electrode material of a lithium ion battery comprises the following specific steps:
(1) crushing and finely grinding the silicon cutting waste of the photovoltaic industry in a protective gas (nitrogen) atmosphere to obtain micro-nano silicon powder with the particle size of less than 30 microns, washing for 3 times by using deionized water at room temperature, cleaning for 20min each time, and drying;
(2) adding the silicon powder obtained in the step (1) into a metal salt/HF/alcohol mixed solution system A, wherein the metal salt/HF/alcohol mixed solution system A contains a reducing agent to enhance the crushing effect, performing crushing pretreatment for 120min by adopting a one-step metal nanoparticle auxiliary etching method at the temperature of 80 ℃, cleaning for 30min by adopting a detergent to remove metal nanoparticles on the surface of the silicon powder, performing solid-liquid separation, and drying to obtain nanoscale silicon powder; wherein the metal salt in the metal salt/HF/alcohol mixed solution system A is CuCl2The alcohol is ethanol, propanol, mixed alcohol of ethylene glycol and propylene glycol, the volume ratio of the ethanol, the propanol, the ethylene glycol and the propylene glycol is 2:2:1:1, and the reducing agent is H2C2O4(ii) a HF concentration of 4mol/L, CuCl2Concentration of 0.1mol/L, alcohol concentration of 0.1mol/L, H2C2O4The concentration is 5mol/L, and the liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A to the silicon powder is 20: 1; the detergent is 30 wt% of dilute nitric acid;
the appearance of the nano-scale silicon powder in the embodiment is shown in FIG. 4 under a transmission electron microscope, and the original micron-scale silicon material is effectively crushed into nano-scale particles;
(3) adding the nano-scale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B at the temperature of 60 ℃ to deposit metal nano-particles for 1min in a dark place, and adding H2O2Continuously etching for 120min to change the nano-scale silicon powder into nano-porous silicon (namely a two-step metal nano-particle assisted chemical etching method); carrying out solid-liquid separation and drying to obtain a nano porous silicon/metal composite material (nano porous silicon/Fe composite material); the nano porous silicon/Ag composite material can be used as a lithium ion battery nano porous silicon negative electrode material; wherein the metal salt in the metal salt/HF/alcohol mixed solution system B is Fe (NO)3)3The alcohol is ethylene glycol; HF concentration of 3mol/L, metal salt Fe (NO)3)3The concentration is 1mol/L, and the concentration of alcohol glycol is 1 mol/L; the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder is 10: 1; h2O2The addition amount of (A) is 0.5 mol/L;
after the nano porous silicon/Fe composite material, a conductive agent and a sodium alginate adhesive are mixed according to the mass ratio of 3:1:1, a battery is assembled in a glove box by taking a lithium sheet as a counter electrode, and the battery is charged and discharged under 0.5A/g, wherein the first reversible capacity of the material reaches 3170mAh/g, and the first coulombic efficiency of the electrode reaches 87%.
Example 5: a preparation method of a nano porous silicon negative electrode material of a lithium ion battery comprises the following specific steps:
(1) in the atmosphere of protective gas (nitrogen), crushing and finely grinding an industrial silicon material to obtain micro-nano silicon powder with the particle size of less than 30 microns, washing for 3 times by using deionized water at room temperature, washing for 20min each time, and drying;
(2) adding the silicon powder obtained in the step (1) into a metal salt/HF/alcohol mixed solution system A, wherein the metal salt/HF/alcohol mixed solution system A contains a reducing agent to enhance the crushing effect, performing crushing pretreatment for 1min by adopting a one-step metal nanoparticle auxiliary etching method at the temperature of 20 ℃, cleaning for 20min by adopting a detergent to remove metal nanoparticles on the surface of the silicon powder, performing solid-liquid separation, and drying to obtain nanoscale silicon powder; wherein the metal salt in the metal salt/HF/alcohol mixed solution system A is Cu (NO)3)2Alcohol is ethanol, and reducing agent is H3PO3(ii) a HF concentration of 10mol/L, Cu (NO)3)2Concentration of 0.001mol/L, ethanol concentration of 0.1mol/L, H3PO3The concentration is 0.1mol/L, and the liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A to the silicon powder is 100: 1; the detergent is 30 wt% dilute nitric acid;
the appearance of the nano-scale silicon powder in the embodiment is shown in FIG. 5 under a transmission electron microscope, and the original micro-scale silicon material is effectively crushed and can obviously see crushing cracks;
(3) adding the nano-scale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B at the temperature of 80 ℃ to deposit metal nano-particles for 1min in a dark place, and adding H2O2Continuously etching for 120min to change the nano-scale silicon powder into nano-porous silicon (namely a two-step metal nano-particle assisted chemical etching method); carrying out solid-liquid separation and drying to obtain a nano porous silicon/metal composite material (nano porous silicon/Ni composite material); the nano porous silicon/Ag composite material can be used as a lithium ion battery nano porous silicon negative electrode material; wherein the metal salt in the metal salt/HF/alcohol mixed solution system B is Ni (NO)3)2The alcohol is ethanol; HF concentration of 0.1mol/L, metal salt Ni (NO)3)2The concentration is 0.005mol/L, and the ethanol concentration is 10 mol/L; the liquid-solid ratio mL/g of the metal salt/HF/alcohol mixed solution system B to the nano-scale silicon powder is 100: 1; h2O2The addition amount of (A) is 0.1 mol/L;
the battery is assembled by mixing the nano porous silicon/Ni composite material, the conductive agent and the sodium alginate adhesive according to the mass ratio of 3:1:1 in a glove box by taking a lithium sheet as a counter electrode, and the battery is charged and discharged under 0.5A/g, so that the first reversible capacity of the material reaches 3530mAh/g, and the first coulombic efficiency of the electrode reaches 86%.
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 preparation method of a lithium ion battery nano porous silicon negative electrode material is characterized by comprising the following specific steps:
(1) in the protective gas atmosphere, crushing and finely grinding the silicon material to obtain micro-nano silicon powder, washing by using deionized water at room temperature and drying;
(2) adding the silicon powder obtained in the step (1) into a metal salt/HF/alcohol mixed solution system A, wherein the metal salt/HF/alcohol mixed solution system A contains a reducing agent, performing crushing pretreatment by adopting a one-step metal nanoparticle assisted etching method, removing metal nanoparticles on the surface of the silicon powder by adopting a detergent, performing solid-liquid separation, and drying to obtain nanoscale silicon powder;
(3) adding the nanoscale silicon powder obtained in the step (2) into a metal salt/HF/alcohol mixed solution system B to deposit metal nanoparticles for 0.1-10 min, and adding H2O2Etching at 0-80 deg.C for 1-600 min to convert the nanometer silicon powder into nanometer porous silicon; carrying out solid-liquid separation and drying to obtain the nano porous silicon/metal composite material; or removing the metal nano particles on the surface of the nano porous silicon by using a detergent, carrying out solid-liquid separation, and drying to obtain the nano porous silicon; and placing the nano porous silicon/metal composite material or the nano porous silicon in an oxidizing substance environment for oxidation treatment to obtain an oxidized nano porous silicon/metal composite material or oxidized nano porous silicon, wherein the oxidized nano porous silicon/metal composite material or oxidized nano porous silicon is the lithium ion battery nano porous silicon negative electrode material.
2. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 1, characterized by comprising the following steps: the temperature of the oxidation treatment is 0-500 ℃, and the time of the oxidation treatment is 1 min-50 h.
3. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 1, characterized by comprising the following steps: the oxidizing substance environment is F-containing2、Cl2、O2Or O3In a gaseous atmosphere of, or containing Ag+、Cu2+、Fe3+、Br-、I-、HNO3、H2SO4、H2O2、KMnO4、HClO、SO2、SO3Or NO2The physical environment of (a).
4. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 1, characterized by comprising the following steps: the protective gas in the step (1) is argon or nitrogen, the silicon material is high-purity silicon, industrial silicon, silicon waste materials for cutting in photovoltaic industry or silicon waste residues in photovoltaic industry, and the particle size of the micro-nano silicon powder is less than 30 mu m.
5. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 1, characterized by comprising the following steps: the liquid-solid ratio mL of the metal salt/HF/alcohol mixed solution system A containing the reducing agent to the silicon powder in the step (2) is (5-100): 1, the crushing pretreatment temperature is 0-80 ℃, and the crushing pretreatment time is 1-600 min; in the metal salt/HF/alcohol mixed solution system A, the concentration of HF is 0.5-10 mol/L, the concentration of metal salt is 0.001-1 mol/L, and the concentration of alcohol is 0.1-20 mol/L; the metal salt is CuSO4、CuCl2、Cu(NO3)2The alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
6. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 5, characterized by comprising the following steps: the concentration of the reducing agent in the metal salt/HF/alcohol mixed solution system A is 0.001-5 mol/L, and the reducing agent is H3PO2、H3PO3、H2C2O4、Na2HPO3、NaHSO3、Na2SO3、K2S2O5、Na2S2O5Or Na2S2O4。
7. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 1, characterized by comprising the following steps: step (3) Metal salt/HF/alcohol mixed solution system B and nanometer levelThe liquid-solid ratio mL of the silicon powder is (5-100): 1, the concentration of HF in a metal salt/HF/alcohol mixed solution system B is 0.5-10 mol/L, the concentration of metal salt is 0.0001-10 mol/L, and the concentration of alcohol is 0.1-20 mol/L; the metal salt is KAuCl4、HAuCl4、K2PtCl6、H2PtCl6、PdCl2、AgNO3、Fe(NO3)3、Ni(NO3)2、NiSO4、CuSO4、CuCl2Or Cu (NO)3)2The alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
8. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 7, characterized by comprising the following steps: step (3) H2O2The addition amount of (b) is 0-5 mol/L.
9. The preparation method of the lithium ion battery nano-porous silicon negative electrode material according to claim 1, characterized by comprising the following steps: the detergent in the step (2) or the step (3) is dilute sulfuric acid, dilute nitric acid, dilute hydrochloric acid or ammonia water/H2O2The concentration of the mixture of dilute sulfuric acid, dilute nitric acid and dilute hydrochloric acid is 1-30 wt%, and the concentration of ammonia water/H2O2Ammonia and H in the mixture2O2The volume ratio of (1) - (5).
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| CN111082033B (en) * | 2019-11-28 | 2020-11-27 | 中南大学 | Lithium ion battery nano silicon negative electrode material, and preparation method and application thereof by utilizing silicon cutting scraps |
| CN111785944B (en) * | 2020-07-20 | 2023-04-28 | 昆明理工大学 | Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste |
| CN111799460B (en) * | 2020-07-20 | 2022-09-09 | 昆明理工大学 | Method for preparing boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste |
| CN111799461A (en) * | 2020-07-20 | 2020-10-20 | 昆明理工大学 | Method for preparing high-energy-density lithium ion battery cathode material based on silicon waste alloying method |
| CN112952068B (en) * | 2021-04-03 | 2022-06-21 | 昆明理工大学 | Porous silicon composite powder embedded with metal nano-particles |
| CN113594441A (en) * | 2021-07-21 | 2021-11-02 | 昆明理工大学 | Method for preparing 3D high-capacity cathode material by metal salt assisted chemical etching method |
| CN113991099A (en) * | 2021-10-27 | 2022-01-28 | 昆明理工大学 | Method for preparing nano silicon-based negative electrode material from silicon cutting waste |
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