CN104975336A - Preparation method of porous silicon used in lithium ion battery anode material - Google Patents
Preparation method of porous silicon used in lithium ion battery anode material Download PDFInfo
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Abstract
The invention provides a preparation method of porous silicon used in a lithium ion battery anode material, wherein the preparation method includes the steps of 1) providing a silicon alloy; 2) providing an electrolyte; 3) performing electrolysis to the silicon alloy as an anode in the electrolyte to obtain the porous silicon anode material. The preparation method is low in preparation cost and is easily controllable in process. The electrolyte is recyclable. The whole process is free of generation of waste liquid and is less in environment pollution.
Description
Technical field
The present invention relates to a kind of preparation method of the porous silicon for lithium cell cathode material, particularly a kind of electrolytic process that adopts is to prepare the method for porous silicon.
Background technology
The embedding lithium capacity (4200mAh/g) of theory of elemental silicon is 11 times of graphite negative electrodes materials theory capacity (372mAh/g), its embedding lithium/de-lithium current potential is desirable, with electrolytic solution reactive behavior low and in the earth's crust rich reserves, thus become the focus of lithium ion battery negative material research.But silicon is unsatisfactory as its reversibility of ion cathode material lithium, this causes greatly due to silicon volume change in embedding lithium/de-lithium process.On the other hand, the intrinsic conductivity of silicon is low is also hinder its important factor obtaining good cycle life.
Porous silicon has large number of orifices hole, effectively can alleviate the pressure that volumetric expansion brings, and effectively improves the cycle life of battery, is expected to become desirable lithium ion silicon based anode material.In prior art, porous silicon generally adopts the methods such as chemical corrosion method, hydrothermal etching, electrochemical erosion method to prepare.
Jiang Zhiyu etc. (Chinese patent application 201310122811.4) disclose a kind of lithium ion battery porous silicon negative material and preparation method thereof, the method is with silicon alloy powder (such as sial, ferrosilicon or Si-Mg alloy) for raw material, reacts generate porous silicon particulate with mineral acid (than example hydrochloric acid or sulfuric acid); Again after HF acid solution cleaning removing Surface Oxygen SiClx, washing, dries the porous silica material with spongy structure obtaining being connect by nano-silicon particulate.This porous silicon can be used as lithium ion battery negative material, shows high specific discharge capacity and charge and discharge cycles stability.Carry out etch silicon alloy with mineral acid in this preparation process, need to control reaction by the condition such as concentration, temperature of reaction of mineral acid, also need the silicon oxide of extra HF acid clean surface, need after reaction by a large amount of clean water to pH=7.Reaction process control ratio is more numerous and diverse, and generates a large amount of waste water, adds preparation cost.
By contrast, prepare porous silicon have obvious advantage by electrochemical method: the speed that can control the silicon generated by controlling the parameters such as electric current easily, speed of response is very fast; Required voltage is lower, and electrolysis also can Reusability, and safe and simple cost is low.Electrochemical erosion method is divided into by the structure of electrolyzer: single groove electrochemical erosion method, double-cell electrochemical etching.Single groove electrochemical erosion method adopts silicon chip to do anode, and graphite or platinized platinum (Pt) are negative electrode, and anodic oxidation forms porous silicon in the electrolytic solution; The anode of double-cell electrochemical etching is all graphite or platinized platinum (Pt) electrode with negative electrode, silicon chip is fixed on the centre of electrolyzer, independent half groove that electrolyzer is divided into two solution not connected, silicon wafer polishing is facing to negative electrode, non-polished surface is facing to anode, switch on power, electric current flows to another half groove from one and half grooves through silicon chip, and the polished surface anode dissolution facing to negative electrode forms porous silicon.
Usually, mostly adopt silicon chip to be raw material when electrochemical etching method prepares porous silicon, containing a large amount of HF acid in electrolytic solution, silicon chip is corroded thus obtained porous silicon.Its principle is: in HF acid solution, and the silicon on surface forms Si-H key or Si-H
2key, in anode oxidation process, the positive potential of applying is that Si matrix provides a large amount of hole, the F in electrolytic solution
-under the help in silicon substrate hole, bombard Si-H key, Si-H bond rupture F displaces a H, discharges an electronics simultaneously.After losing a H, another H on silicon is unstable, and then replaced by F and discharge an electronics, two H be displaced form a H
2.Silicon after losing H is dissolved by HF, produces SiF
4, then react with HF and generate H
2siF
6.Total reaction is: Si+2H
++ 6HF=SiF
6 2-+ H
2↑+4H
+.Porous silicon specific surface area prepared by the method is very large, is usually applied to photoelectric field.
Summary of the invention
The invention provides a kind of preparation method of the porous silicon for lithium cell cathode material.The method take silicon alloy as raw material, is obtained the porous silicon of nanostructure by electrolytic process.
The invention provides a kind of preparation method of the porous silicon for lithium cell cathode material, comprise the steps: 1) a kind of silicon alloy is provided; 2) a kind of electrolytic solution is provided; 3) described aluminosilicate alloy material is carried out electrolysis as anode in described electrolytic solution, generate porous silicon negative material.
According to the preparation method of the porous silicon for lithium cell cathode material of the present invention, wherein, silicon alloy is selected from least one in copper-silicon alloy, silumin, Si-Mg alloy, silicon zinc alloy, ferro-silicon, silicon nickel alloy and silicomanganese.Namely the metal in silicon alloy can be selected from least one in copper, aluminium, magnesium, zinc, iron, nickel and manganese.
According to the preparation method of the porous silicon for lithium cell cathode material of the present invention, in silicon alloy, the volume content of silicon is 4% ~ 80%, and in preferred silicon alloy, the volume content of silicon is 10% ~ 60%, and more preferably in silicon alloy, the volume content of silicon is 20% ~ 40%.
The aqueous solution that electrolytic solution of the present invention is salt metallic in silicon alloy or organic solution.Difference according to metal active contained in silicon alloy is selected to adopt aqueous electrolysis liquid or organic solution electrolytic solution.
According to one embodiment of the present invention, when institute's containing metal is copper, zinc, iron, nickel or manganese, when namely silicon alloy is copper-silicon alloy, silicon zinc alloy, ferro-silicon, silicon nickel alloy or silicomanganese, can select the aqueous solution of metallic salt as electrolytic solution.Further, electrolytic solution be metallic salt and acid mixed aqueous solution, acid be preferably the acid corresponding to metallic salt.Above-mentioned metallic salt preferably sulfuric acid salt, corresponding acid is sulfuric acid.When such as silicon alloy is copper-silicon alloy, electrolytic solution can adopt the mixed aqueous solution of copper sulfate and sulfuric acid.When silicon alloy is silicon zinc alloy, electrolytic solution can adopt the mixed aqueous solution of zinc sulfate and sulfuric acid.When silicon alloy is ferro-silicon, electrolytic solution can adopt the mixed aqueous solution of ferrous sulfate and sulfuric acid.When silicon alloy is silicomanganese, electrolytic solution can adopt the mixed aqueous solution of manganous sulfate and sulfuric acid.When silicon alloy is silicon nickel alloy, electrolytic solution can adopt the mixed aqueous solution of single nickel salt and sulfuric acid.
According to one embodiment of the present invention, if institute's containing metal is aluminium or magnesium in silicon alloy, can the organic solution of salt of aluminium or magnesium as electrolytic solution.Above-mentioned salt can be selected from least one in the halogenide of aluminium or magnesium, alkyl metal cpd and alkoxide compound.Such as, metallic salt can be selected from least one in aluminum chloride, aluminum bromide, triethyl aluminum or aluminum ethylate.
Solvent in above-mentioned organic solution can select the solvent that specific inductivity is higher usually, and metal-salt ratio is easier to dissolve, and electrolytic solution can be made to have higher conductance.Under normal circumstances, preferred dissolution Performance Ratio better, fusing point and vapour pressure is lower, boiling point is higher, electric conductivity is relatively good and toxicity is low again solution.
According to one embodiment of the present invention, the solvent in above-mentioned organic solution can be selected from least one in carbonic ether, ethers, aromatic hydrocarbon and sulfocompound etc.In above-mentioned organic solvent, carbonic ether can be selected from least one in diethyl carbonate, methylcarbonate, methyl ethyl carbonate and NSC 11801; Ethers can be selected from least one in ether and tetrahydrofuran (THF); Aromatic hydrocarbon can be selected from least one in benzene, toluene, ethylbenzene and diethylbenzene; Sulfocompound can be selected from dimethyl sulfoxide (DMSO) (DMSO).In addition, solvent in above-mentioned organic solution can also be selected from ionic liquid, above-mentioned ionic liquid can be selected from least one in quaternary ammonium salt ionic liquid and/or glyoxaline ion liquid, and preferred ion liquid is selected from least one in chlorination-3 monomethylaniline (TMPAC), 1-butyl-3-methylimidazolium chloride (BMIC) etc.
In addition, when electrolytic solution is organic solution, in electrolytic solution, additive can also be contained further.Because the specific conductivity of organic solvent is usually lower than water many, often need to add additive to improve the electric conductivity of electrolytic solution.According to the embodiment of the present invention, additive can be selected from least one in lithium salts, sylvite and sodium salt; Further, additive can be selected from least one in lithium chloride, lithiumbromide, Repone K, Potassium Bromide, sodium-chlor, Sodium Bromide, lithium hydride and lithium aluminum hydride etc.
According to one embodiment of the present invention, when such as silicon alloy is silumin, electrolytic solution can adopt the organic solution of aluminum halide, aluminum alkyls and/or aluminum alkoxide.Such as metal-salt can adopt aluminum chloride, aluminum bromide or triethyl aluminum etc.; Solvent can use the mixed solvent etc. of the mixed solvent of diethyl ether, tetrahydrofuran (THF), toluene, tetrahydrofuran (THF) and benzene, tetrahydrofuran (THF) and the mixed solvent of toluene, the mixed solvent of second Benzene and Toluene or diethyl Benzene and Toluene; Additive can be lithium aluminum hydride.
According to one embodiment of the present invention, when such as silicon alloy is ferro-silicon, electrolytic solution, except can adopting aqueous electrolysis liquid, also can adopt the ionic liquid solution containing molysite, the solution that such as iron(ic) chloride and 1-butyl-3-methylimidazolium chloride (BMIC) are formed.
According to the preparation method of the porous silicon for lithium cell cathode material of the present invention, in order to obtain purity more much higher hole silicon, should contain metal ion and/or the free acid radical ion of proper concn in electrolytic solution, the temperature of electrolytic solution is unsuitable too high, and reduces the contact of electrolytic solution and air as far as possible.
According to the embodiment of the present invention, in electrolytic solution, the concentration of the salt of metal is 20 ~ 200 g/L.
According to one embodiment of the present invention, when institute's containing metal is copper, zinc, iron, nickel or manganese, electrolytic solution can adopt the vitriol of these metals and the mixing solutions of sulfuric acid, and now in electrolytic solution, the concentration of sulfuric acid is moderate.Sulfuric acid concentration is higher, and electrolyte conductivity can be also better.But when other condition is identical, the too high viscosity that can increase electrolytic solution of sulfuric acid concentration, makes the mass transfer process in electrolytic solution more difficult; Also can reduce the solubleness of vitriol in electrolytic solution simultaneously, the vitriol in electrolytic solution just may be caused when the temperature decreases to separate out.
According to the embodiment of the present invention, the temperature of electrolytic solution should control within the specific limits.The electrolysis temperature different according to the different choice of electrolyte system.If when electrolytic solution is the aqueous solution, the temperature of electrolytic solution should control between 25 ~ 90 DEG C, and the temperature of preferred electrolytic solution should control between 40 ~ 70 DEG C.If when electrolytic solution is Organic Electricity solution, the temperature of electrolytic solution should control between 20 ~ 80 DEG C, and the temperature of preferred electrolytic solution should control between 30 ~ 50 DEG C.Electrolyte temperature is the important factor affecting electrolytic process.The temperature suitably improving electrolytic solution is conducive to the viscosity reducing electrolytic solution, is also conducive to the travelling speed improving metal simultaneously, reduces the impact of concentration polarization.For aqueous electrolysis liquid system, temperature is too high, and electrolytic solution can be more serious to the corrosion of equipment, and the evaporation of acid simultaneously also causes adverse influence to environment.
According to the embodiment of the present invention, electrolysis voltage is determined according to the kind of silicon alloy.Metal contained in such as silicon alloy is copper, zinc, iron, nickel, manganese, aluminium or magnesium, voltage required when those of ordinary skill in the art can determine electrolysis according to prior art.
According to the embodiment of the present invention, the time of electrolysis is decided according to conditions such as the amount of the silicon alloy of required electrolysis and current densities.
According to the preparation method of the porous silicon for lithium cell cathode material of the present invention, for copper-silicon alloy, carry out electrolytic reaction using copper-silicon alloy as anode, reaction formula is as follows:
Anodic reaction: Cu=Cu
2++ 2e
-
Cathodic reaction: Cu
2++ 2e=Cu
In preparation process, the copper in anode copper-silicon alloy is oxidized, and the copper ion dissolution of generation is in electrolytic solution, and the cupric ion in electrolytic solution is reduced generation copper at negative electrode.The silicon materials of porous are generated after copper in anode copper-silicon alloy is etched electrochemically.
According to the kind of metal in silicon alloy and the difference of content, adopt porous silicon prepared by method of the present invention, may containing other a small amount of inert metal particle.Usually, when such porous silica material is used for electrode materials, these inert metals can't cause unnecessary side reaction, and these metals can also improve the conductivity of porous silica material as conductive agent.
Present invention also offers a kind of lithium cell, the porous silicon that its negative material adopts preparation method as above to prepare.
The preparation method of the porous silicon for lithium cell cathode material of the present invention, preparation cost is lower, and preparation process easily controls, and electrolytic solution can recycle, and whole preparation process does not produce waste liquid, and environmental pollution is little.
Accompanying drawing explanation
Fig. 1: with the electrolytic cell device schematic diagram of copper-silicon alloy electrolytic preparation porous silicon;
Fig. 2: the SEM figure of the copper-silicon alloy in embodiment 1 before electrolysis;
Fig. 3: the SEM figure of the copper-silicon alloy in embodiment 1 after electrolysis.
Embodiment
Following specific embodiment is to invention has been detailed description, but the present invention is not restricted to following examples.
Use glass electrolyzer in embodiments of the invention, prepare porous silicon for silicon electrolyzation copper alloy, electrolytic cell device schematic diagram as shown in Figure 1.
Embodiment 1:
Load 1 copper-silicon alloy in a cell as anode, and a slice copper sheet is as negative electrode, in copper-silicon alloy, the content of silicon is 15 wt%.Electrolytic solution adopts the mixing solutions of copper sulfate (AR, Aladdin) and sulfuric acid (AR 70 wt%, Aladdin), and wherein the concentration of copper sulfate is 50 g/L, and the concentration of sulfuric acid is 180 g/L.Use the electrolytic solution of 0.4 this composition of L, control electrolyte temperature between 50 ~ 60 DEG C.Electrolysis voltage is 0.35 V, energising electrolysis 6 hours, obtained Porous Silicon Electrode material.
Claims (10)
1., for a preparation method for the porous silicon of lithium cell cathode material, comprise the steps: 1) a kind of silicon alloy is provided; 2) a kind of electrolytic solution is provided; 3) described aluminosilicate alloy material is carried out electrolysis as anode in described electrolytic solution, generate porous silicon negative material.
2. the preparation method of porous silicon according to claim 1, is characterized in that, silicon alloy is selected from least one in copper-silicon alloy, silumin, Si-Mg alloy, silicon zinc alloy, ferro-silicon, silicon nickel alloy and silicomanganese.
3. the preparation method of porous silicon according to claim 2, is characterized in that, in described silicon alloy, institute's containing metal is copper, zinc, iron, nickel or manganese, and described electrolytic solution is the aqueous solution of metallic salt.
4. the preparation method of porous silicon according to claim 3, is characterized in that, described electrolytic solution is metallic salt and sour mixed aqueous solution, the acid of described acid corresponding to metallic salt.
5. the preparation method of porous silicon according to claim 2, is characterized in that, in described silicon alloy, institute's containing metal is aluminium or magnesium, and described electrolytic solution is the organic solution of the salt of aluminium or magnesium.
6. the preparation method of porous silicon according to claim 5, is characterized in that, described salt is selected from least one in the halogenide of aluminium or magnesium, alkyl metal cpd and alkoxide compound.
7. the preparation method of porous silicon according to claim 5, is characterized in that, the solvent in described organic solution is selected from least one in carbonic ether, ethers, aromatic hydrocarbon and sulfocompound.
8. the preparation method of porous silicon according to claim 7, it is characterized in that, described solvent is selected from least one in diethyl carbonate, methylcarbonate, methyl ethyl carbonate, NSC 11801, ether, tetrahydrofuran (THF), benzene, toluene, ethylbenzene, diethylbenzene and dimethyl sulfoxide (DMSO).
9. the preparation method of porous silicon according to claim 5, is characterized in that, the solvent in described organic solution is selected from ionic liquid.
10. the preparation method of porous silicon according to claim 5, is characterized in that, described organic solution also comprises additive, and described additive is selected from least one in lithium salts, sylvite and sodium salt.
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Cited By (8)
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| CN105948058A (en) * | 2016-05-02 | 2016-09-21 | 北京工业大学 | Method for preparing micro-nano structure bulk silicon material through laser surface remelting and chemically de-alloying and compounding process |
| WO2017190587A1 (en) * | 2016-05-02 | 2017-11-09 | 北京工业大学 | Method for preparing lithium ion battery silicon anode through combination of diffusion welding and dealloying with laser surface remelting technique |
| CN107623121A (en) * | 2017-10-18 | 2018-01-23 | 山东大学 | A kind of metallic cover porous silicon composite electrode material and preparation method thereof |
| CN108011091A (en) * | 2017-12-05 | 2018-05-08 | 桂林电器科学研究院有限公司 | Indium bismuth alloy coats the method and ferrosilicon powder of magnesium ferrosilicon particle preparation ferrosilicon powder |
| CN108054355A (en) * | 2017-12-05 | 2018-05-18 | 桂林电器科学研究院有限公司 | Foam-like silica flour and preparation method thereof, lithium ion battery |
| CN110240906A (en) * | 2018-03-07 | 2019-09-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Group III-V semiconductor etching liquid and its preparation method and application |
| CN110828794A (en) * | 2019-10-28 | 2020-02-21 | 珠海格力绿色再生资源有限公司 | Preparation method of multiple modified silicon-manganese alloy composite negative electrode material |
| CN112768663A (en) * | 2021-01-26 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Nano porous silicon/carbon negative electrode material, preparation method thereof and lithium ion battery |
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| WO2017190587A1 (en) * | 2016-05-02 | 2017-11-09 | 北京工业大学 | Method for preparing lithium ion battery silicon anode through combination of diffusion welding and dealloying with laser surface remelting technique |
| CN105948058A (en) * | 2016-05-02 | 2016-09-21 | 北京工业大学 | Method for preparing micro-nano structure bulk silicon material through laser surface remelting and chemically de-alloying and compounding process |
| CN105948058B (en) * | 2016-05-02 | 2021-03-16 | 北京工业大学 | Method for preparing micro-nano structure block silicon material by compounding laser surface remelting and chemical dealloying |
| CN107623121B (en) * | 2017-10-18 | 2019-12-27 | 山东大学 | Metal-coated porous silicon composite electrode material and preparation method thereof |
| CN107623121A (en) * | 2017-10-18 | 2018-01-23 | 山东大学 | A kind of metallic cover porous silicon composite electrode material and preparation method thereof |
| CN108011091A (en) * | 2017-12-05 | 2018-05-08 | 桂林电器科学研究院有限公司 | Indium bismuth alloy coats the method and ferrosilicon powder of magnesium ferrosilicon particle preparation ferrosilicon powder |
| CN108054355B (en) * | 2017-12-05 | 2020-01-17 | 桂林电器科学研究院有限公司 | Foamed silicon powder, preparation method thereof and lithium ion battery |
| CN108011091B (en) * | 2017-12-05 | 2020-08-14 | 桂林电器科学研究院有限公司 | Method for preparing ferrosilicon powder by coating magnesium-silicon-iron particles with indium-bismuth alloy and ferrosilicon powder |
| CN108054355A (en) * | 2017-12-05 | 2018-05-18 | 桂林电器科学研究院有限公司 | Foam-like silica flour and preparation method thereof, lithium ion battery |
| CN110240906A (en) * | 2018-03-07 | 2019-09-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Group III-V semiconductor etching liquid and its preparation method and application |
| CN110828794A (en) * | 2019-10-28 | 2020-02-21 | 珠海格力绿色再生资源有限公司 | Preparation method of multiple modified silicon-manganese alloy composite negative electrode material |
| CN110828794B (en) * | 2019-10-28 | 2021-01-15 | 珠海格力绿色再生资源有限公司 | Preparation method of multiple modified silicon-manganese alloy composite negative electrode material |
| CN112768663A (en) * | 2021-01-26 | 2021-05-07 | 惠州锂威新能源科技有限公司 | Nano porous silicon/carbon negative electrode material, preparation method thereof and lithium ion battery |
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