CN109686942A - A kind of preparation method of silicon based anode material - Google Patents
A kind of preparation method of silicon based anode material Download PDFInfo
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- CN109686942A CN109686942A CN201811572253.0A CN201811572253A CN109686942A CN 109686942 A CN109686942 A CN 109686942A CN 201811572253 A CN201811572253 A CN 201811572253A CN 109686942 A CN109686942 A CN 109686942A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of silicon based anode material of the invention sequentially includes the following steps: the preparation and pretreatment of (1) silica-base material；(2) roughening of silica-base material, sensitization activation；(3) it prepares plating solution: after main salt solution and enveloping agent solution are mixed, sequentially adding stabilizer and surfactant；(4) product for obtaining step (2) is added in the plating solution that step (3) are prepared, and adjusts pH value, is slowly added to reducing agent and carries out chemical plating；(5) it is dried after being cleaned with deionized water, silicon substrate lithium ion battery negative material is made.The present invention is by the way of nano-silicon and porous silicon surface chemical nickel plating, to improve the electric conductivity of material, and buffers the volume expansion problem in silicon based anode material cyclic process, improves chemical property.
Description
Technical field:
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of silicon based anode material.
Background technique:
Lithium ion battery is widely used in power because having many advantages, such as that energy density is high, having extended cycle life, memory-less effect
Field of batteries, and gradually expanded to fields such as new energy energy storage.Graphite is the most common material of current negative electrode of lithium ion battery, but
Its theoretical specific capacity only has 372mAh/g, it is difficult to meet high-performance, high capacity lithium ion battery demand.The theory of silicon materials
Specific capacity 4200mAh/g, but its Volumetric expansion and lower electrical conductance, seriously limit making full use of for its capacity.
Summary of the invention:
The purpose of the present invention is overcoming above-mentioned the shortcomings of the prior art, a kind of preparation side of silicon based anode material is provided
Method, the electric conductivity of material is improved by the surface chemical plating of silicon based anode material, and the volume expansion in cyclic process is inhibited to ask
Topic, prepares a kind of high performance silicon based anode material.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of silicon based anode material, comprising the following steps:
(1) silica-base material is taken, is roughened, sensitization activation；
(2) it prepares plating solution: after main salt solution and enveloping agent solution are mixed, sequentially adding stabilizer and surface-active
Agent is uniformly mixed, and plating solution is made, and main salt solution concentration is 10-40g/L, complexing agent concentration 0.03- in the plating solution
006mol/L, stabilizer concentration are (1-3) × 10-6Mol/L, surfactant concentration are (0.5-1.5) × 10-6mol/L；
(3) silica-base material is added in plating solution after activating, and adjusting bath pH value is 9-14, is slowly added to reducing agent, carries out
Chemical plating, wherein the chemical plating temperature is 30-90 DEG C, plating time 10-120min；
(4) it is dried after cleaning silica-base material after chemical plating with deionized water, silicon substrate lithium ion battery negative material is made.
In the step (1), silica-base material is nano-silicon powder or porous silicon powder.
In the step (1), pre-processed before nano-silicon powder roughening, detailed process are as follows: by commercially available nano silicone
Powder, which is placed in 2% hydrofluoric acid, to be impregnated, to remove silicon face SiO that may be present2, clean and dry using deionized water, obtain
To nano-silicon powder.
In the step (1), the preparation process of porous silicon powder are as follows: the alusil alloy of fritter is placed in 10% hydrochloric acid
Middle etch shows that metallic aluminium has completely removed after reacting and terminating bubble-free generation, and after washing filtering, obtained silicon powder is same
It is impregnated in 2% hydrofluoric acid, after cleaning and dry using deionized water, obtains porous silicon powder.
In the step (1), the coarsening process of silica-base material are as follows: silicon powder is put into acid coarsening solution, at room temperature
Stirring, is cleaned by deionized water to neutrality.Acid coarsening solution is mainly one of sulfuric acid, nitric acid.
In the step (1), the sensitization activation of silica-base material uses Salt-Based Colloid Palladium activation method, is sensitized matching for activating solution
Side are as follows: 0.5g/L palladium chloride, 30g/L stannous chloride, 37% hydrochloric acid of 60ml/L, the mixed solution of 160g/L sodium chloride.
In the step (2), main salt is nickel salt, specially one of nickel nitrate, nickel sulfate or nickel chloride.
In the step (2), complexing agent is one of ethylenediamine, sodium citrate or disodium ethylene diamine tetraacetate, surely
Determining agent is one of thiocarbamide, urea or ammonium sulfide, and surfactant is lauryl sodium sulfate, dodecyl sodium sulfate or ten
One of dialkyl benzene sulfonic acids sodium.
In the step (3), reducing agent is hydrazine hydrate, and additive amount is the 10-150ml/L of plating solution.
In the step (4), chemical plating number is 1~3 time, to avoid plating leakage situation.
In the step (4), when the silicon based anode material of preparation is used as negative electrode of lithium ion battery, current density is
100mA/g, after 100 circulations, specific capacity is stablized in 1500-1700mAh/g, and coulombic efficiency reaches 98.5-99.5%.
In the present invention, silicon particle nanosizing and porous can be increased to the contact area of silicon, enhance battery performance.Chemistry
Plating is a kind of process for treating surface easy to operate, can be deposited on silicon materials surface, and coating is uniform, has good packet
The property covered, anticorrosive and wear-resisting property.Therefore, to plate one layer of electric conductivity on the surface of silicon based anode material by chemical plating preferable
Substance, can be improved the electric conductivity of material, and inhibit the volume expansion problem in cyclic process, repeat progress 2-3 time change
It learns plating process and avoids plating leakage phenomenon, to further improve the chemical property of negative electrode material.
Beneficial effects of the present invention:
The present invention is using nano-silicon and porous silicon surface chemical nickel plating or even secondary chemical plating, to improve leading for material
Electrically, and the volume expansion problem in silicon based anode material cyclic process is buffered, improves chemical property.
Detailed description of the invention:
Fig. 1 is the SEM figure of silicon based anode material prepared by the embodiment of the present invention 1；
Fig. 2 is the cyclic curve figure that silicon based anode material prepared by the embodiment of the present invention 1 is used as negative electrode of lithium ion battery；
Fig. 3 is the SEM figure of silicon based anode material prepared by the embodiment of the present invention 4.
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail.
Silicon powder is from commercially available in following embodiment.
Embodiment 1
(1) silicon powder is placed in 2% hydrofluoric acid and is impregnated, to remove silicon face SiO that may be present2, using deionization
Water cleaning and drying, obtain nano-silicon powder；(2) nano silica fume is put into sulfuric acid coarsening solution, is stirred at room temperature, by going
Ionized water uses Salt-Based Colloid Palladium activation method to carry out sensitization activation after cleaning to neutrality；(3) by nickel sulfate solution and 0.05mol/L
After ethylenediamine solution mixing, 2 × 10 are sequentially added-6Mol/L thiocarbamide and 1 × 10-6Mol/L lauryl sodium sulfate, wherein leading
Salinity is 20g/L；(4) product for obtaining step (2) is added in the plating solution that step (3) are prepared, adjusting pH value to 13, slowly
Hydrazine hydrate solution chemical plating 60min at 80 DEG C is added, wherein hydrazine hydrate dosage is 50ml/L；(5) after being cleaned with deionized water
Drying；(6) repeat secondary chemical plating, silicon based anode material is made, SEM figure is as shown in Figure 1.The negative electrode material is used as lithium
Ion battery cathode, for cyclic curve figure as shown in Fig. 2, in the case where current density is 100mA/g after 100 circulations, specific capacity is steady
It is scheduled on 1557mAh/g, coulombic efficiency 98.78%.
Embodiment 2
(1) silicon powder is placed in 2% hydrofluoric acid and is impregnated, to remove silicon face SiO that may be present2, using deionization
Water cleaning and drying, obtain nano-silicon powder；(2) nano silica fume is put into nitric acid coarsening solution, is stirred at room temperature, by going
Ionized water uses Salt-Based Colloid Palladium activation method to carry out sensitization activation after cleaning to neutrality；(3) by nickel nitrate solution and 0.05mol/L
After ethylenediamine solution mixing, 2 × 10 are sequentially added-6Mol/L thiocarbamide and 1 × 10-6Mol/L lauryl sodium sulfate, wherein leading
Salinity is 30g/L；(4) product for obtaining step (2) is added in the plating solution that step (3) are prepared, adjusting pH value to 12, slowly
Hydrazine hydrate solution chemical plating 100min at 70 DEG C is added, wherein hydrazine hydrate dosage is 100ml/L；(5) it is cleaned with deionized water
After dry；(6) repeat secondary and chemical plating three times, silicon based anode material is made.The negative electrode material is in current density
Under 100mA/g after 100 circulations, specific capacity is stablized in 1623mAh/g, coulombic efficiency 99.33%.
Embodiment 3
(1) alusil alloy of fritter is placed in etch in 10% hydrochloric acid, after reacting and terminating bubble-free generation, shows gold
Belong to aluminium to have completely removed, obtained silicon powder equally impregnates in 2% hydrofluoric acid after washing filtering, using deionized water cleaning and
Porous silicon powder is obtained after drying；(2) porous silicon powder is put into sulfuric acid coarsening solution, is stirred at room temperature, pass through deionized water
Sensitization activation is carried out using Salt-Based Colloid Palladium activation method after cleaning to neutrality；(3) by nickel chloride solution and 0.05mol/L ethylenediamine
After solution mixing, 2 × 10 are sequentially added-6Mol/L thiocarbamide and 1 × 10-6Mol/L lauryl sodium sulfate, wherein main salt concentration
For 40g/L；(4) product for obtaining step (2) is added in the plating solution that step (3) are prepared, and adjusts pH value to 11, is slowly added to water
Hydrazine solution chemical plating 120min at 75 DEG C is closed, wherein hydrazine hydrate dosage is 120ml/L；(5) it is dried after being cleaned with deionized water；
(6) repeat secondary chemical plating, silicon based anode material is made.The negative electrode material passes through 100 in the case where current density is 100mA/g
After circulation, specific capacity is stablized in 1607mAh/g, coulombic efficiency 99.05%.
Embodiment 4
(1) alusil alloy of fritter is placed in etch in 10% hydrochloric acid, after reacting and terminating bubble-free generation, shows gold
Belong to aluminium to have completely removed, obtained silicon powder equally impregnates in 2% hydrofluoric acid after washing filtering, using deionized water cleaning and
Porous silicon powder is obtained after drying；(2) porous silicon powder is put into sulfuric acid coarsening solution, is stirred at room temperature, pass through deionized water
Sensitization activation is carried out using Salt-Based Colloid Palladium activation method after cleaning to neutrality；(3) by nickel nitrate solution and 0.05mol/L ethylenediamine
After solution mixing, 2 × 10 are sequentially added-6Mol/L thiocarbamide and 1 × 10-6Mol/L lauryl sodium sulfate, wherein main salt concentration
For 35g/L；(4) product for obtaining step (2) is added in the plating solution that step (3) are prepared, and adjusts pH value to 13, is slowly added to water
Hydrazine solution chemical plating 110min at 80 DEG C is closed, wherein hydrazine hydrate dosage is 90ml/L；(5) it is dried after being cleaned with deionized water；
(6) repeat secondary and chemical plating three times, silicon based anode material is made, SEM figure is as shown in Figure 3.The negative electrode material is in electricity
Current density is under 100mA/g after 100 circulations, and specific capacity is stablized in 1649mAh/g, coulombic efficiency 99.39%.
Claims (9)
1. a kind of preparation method of silicon based anode material, which comprises the following steps:
(1) silica-base material is taken, is roughened, sensitization activation；
(2) it prepares plating solution: after main salt solution and enveloping agent solution are mixed, sequentially adding stabilizer and surfactant, mix
It closing uniformly, plating solution is made, main salt solution concentration is 10-40g/L, complexing agent concentration 0.03-006mol/L in the plating solution,
Stabilizer concentration is (1-3) × 10-6Mol/L, surfactant concentration are (0.5-1.5) × 10-6mol/L；
(3) silica-base material is added in plating solution after activating, and adjusting bath pH value is 9-14, is slowly added to reducing agent, carries out chemistry
Plating, wherein the chemical plating temperature is 30-90 DEG C, plating time 10-120min；
(4) it is dried after cleaning silica-base material after chemical plating with deionized water, silicon substrate lithium ion battery negative material is made.
2. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (1)
In, silica-base material is nano-silicon powder or porous silicon powder.
3. a kind of preparation method of silicon based anode material according to claim 2, which is characterized in that the step (1)
In, it is pre-processed before nano-silicon powder roughening, detailed process are as follows: nanoscale silicon powder is placed in 2% hydrofluoric acid and is impregnated, to remove
Remove silicon face SiO that may be present2, clean and dry using deionized water, obtain nano-silicon powder.
4. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (1)
In, the preparation process of porous silicon powder are as follows: the alusil alloy of fritter is placed in etch in 10% hydrochloric acid, without gas to the end of reacting
After bubble generates, show that metallic aluminium has completely removed, after washing filtering, obtained silicon powder equally impregnates in 2% hydrofluoric acid, then passes through
After crossing deionized water cleaning and drying, porous silicon powder is obtained.
5. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (1)
In, the sensitization activation of silica-base material uses Salt-Based Colloid Palladium activation method, is sensitized the formula of activating solution are as follows: 0.5g/L palladium chloride,
30g/L stannous chloride, 37% hydrochloric acid of 60ml/L, the mixed solution of 160g/L sodium chloride.
6. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (2)
In, main salt is nickel salt, specially one of nickel nitrate, nickel sulfate or nickel chloride.
7. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (2)
In, complexing agent is one of ethylenediamine, sodium citrate or disodium ethylene diamine tetraacetate, and stabilizer is thiocarbamide, urea or vulcanization
One of ammonium, surfactant are one in lauryl sodium sulfate, dodecyl sodium sulfate or neopelex
Kind.
8. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (3)
In, reducing agent is hydrazine hydrate, and additive amount is the 10-150ml/L of plating solution.
9. a kind of preparation method of silicon based anode material according to claim 1, which is characterized in that the step (4)
In, when the silicon based anode material of preparation is used as negative electrode of lithium ion battery, current density 100mA/g, after 100 circulations, than
Capacity is stablized in 1500-1700mAh/g, and coulombic efficiency reaches 98.5-99.5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110444733A (en) * | 2019-08-22 | 2019-11-12 | 中南大学 | Lithium ion battery photoreduction silver modified nano silicon cathode and preparation method thereof |
| CN112164780A (en) * | 2020-09-29 | 2021-01-01 | Oppo广东移动通信有限公司 | Silicon-based negative electrode material, preparation method thereof and related product |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112164780A (en) * | 2020-09-29 | 2021-01-01 | Oppo广东移动通信有限公司 | Silicon-based negative electrode material, preparation method thereof and related product |
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Application publication date: 20190426 |