CN112456497B - Si nanowire manufacturing method and Si nanowire lithium ion battery electrode manufacturing method - Google Patents

Si nanowire manufacturing method and Si nanowire lithium ion battery electrode manufacturing method Download PDF

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CN112456497B
CN112456497B CN202011323201.7A CN202011323201A CN112456497B CN 112456497 B CN112456497 B CN 112456497B CN 202011323201 A CN202011323201 A CN 202011323201A CN 112456497 B CN112456497 B CN 112456497B
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nanowire
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CN112456497A (en
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黄婷
曹利
肖荣诗
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Beijing University of Technology
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    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a method for manufacturing Si nanowires and a method for manufacturing Si nanowire lithium ion battery electrodes. The method firstly adopts a laser surface remelting-chemical dealloying composite manufacturing process, simply, efficiently and large-area preparation of the Si nanowire, and then the electrode is manufactured by a coating method. The Si nanowire structures of the Si nanowire lithium ion battery electrode manufactured by the method are distributed at intervals and connected with each other, so that the volume expansion of Si is relieved, and the stability of the electrode structure is improved. The method has the advantages of high efficiency, few influencing factors, high flexibility, simple process and low cost, and is favorable for promoting the industrial application of the Si nanowires.

Description

Si nanowire manufacturing method and Si nanowire lithium ion battery electrode manufacturing method
Technical Field
The invention belongs to the field of manufacturing of lithium ion battery electrodes, and particularly relates to a Si nanowire manufacturing method, a Si nanowire lithium ion battery electrode manufactured by using the method, and a lithium ion battery comprising the electrode.
Background
The lithium ion battery is an energy storage and conversion carrier which can be repeatedly used, has high specific capacity, long service life and is environment-friendly. The electrode is used as the core of the battery and needs to meet the advantages of high energy density, good cycle performance and the like. Si-based electrodes are currently considered to be a good material with high theoretical specific capacity (about 4200 mAhg) -1 ) Rich resources, low price and the like. However, silicon will generate more than 300% volume expansion during charging and discharging, which is very easy to cause electrode failure and seriously affects the cycle performance of lithium ion batteries. In addition, during the circulation process of the Si electrode, a large amount of SEI (solid electrolyte membrane) films are formed on the surface of the Si electrode, so that the internal resistance of the battery is increased, and the capacity is reduced.
Based on a great deal of research, the volume expansion effect of silicon can be effectively relieved by reducing the structural size of Si, such as Si nanowires, porous Si, Si nanoparticles and the like. For example, by Bang and the like, Si nanowires are used as electrode active materials, the battery has excellent cycling stability, the capacity after 50 cycles is 1450mAh/g, and no obvious capacity loss exists. [ non-patent document: B.M.Bang, H.Kim, J.P.Lee, J.Cho, S.park, Energy environ.Sci.4(2011) 3395-.
In the research of the existing Si electrode, the nanostructure is mostly prepared by a physical or chemical process. Taking Si nanowires as an example, Cui et al use a gas-liquid-solid growth method to prepare Si nanowires, firstly modifying a stainless steel substrate with a gold catalyst, specifically, immersing stainless steel in a 0.1% w/v polylysine aqueous solution and a gold particle colloidal solution, or depositing a 75nm gold film on the surface of the substrate by using an electron beam evaporation method, and then carrying out heat treatment at 530 ℃ for 30 min; and heating the modified substrate to 530 ℃, and simultaneously introducing Si alkane, wherein the gas flow is 80sccm, the hearth pressure is 30Torr, and finally the Si nanowire structure is obtained, and the single experiment yield is about 500 mug. [ non-patent document: chang, h.l.peng, g.liu, k.mcllwrath, x.f.zhang, r.a.huggins, y.cui, nat.nanotechnol.3(2008)31-35]As described above, the conventional Si nanowire manufacturing process has high complexity, many influencing factors, and low yield. In order to improve the manufacturing efficiency and reduce the production cost, a lot of researches are currently carried out to prepare Si nanowires by using a noble metal assisted chemical etching process, such as Chen and the like, wherein cast Si is used as a raw material, and H is used 2 SO 4 /30％H 2 O 2 The solution is cleaned on the surface for 15min at 80 ℃ and then treated with HF/AgNO 3 (5.25/0.02mol/L) Ag particles were dip plated in the solution and then placed in 10mol/L HF and 0.5mol/L H 2 O 2 And corroding in the solution to finally obtain the Si nanowire structure. [ non-patent document: Y.Chen, L.F.Liu, J.Xiong, T.Z.Yang, Y.Qin, C.L.Yan, adv.Funct.Mater.25(2015)6701-]However, the chemical preparation process has strict requirements on experimental conditions and environment, and the preparation yield is low, so that the actual production requirements are difficult to meet.
Therefore, there is a need in the art for a method for preparing Si nanowire structures with simple process, high flexibility, few influencing factors, low cost, high efficiency, and large area.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon nanowire, which has the advantages of few influencing factors, high flexibility, low cost and high efficiency, and can be used for preparing an electrode active substance rapidly in a large area.
According to a first aspect of the present invention, there is provided a method of manufacturing Si nanowires, comprising the steps of:
101, performing surface remelting treatment on the Al-Si alloy by using laser;
102, separating a remelted layer on the surface of the Al-Si alloy, and removing Al from the remelted layer by using a corrosive liquid;
and 103, grinding the remelted layer subjected to the Al removal treatment to obtain the Si nanowire.
Preferably, the method further comprises:
step 100, before the surface remelting treatment, pretreating the Al-Si alloy;
the pretreatment mode comprises at least one of grinding, acid washing or alkali washing;
the solution used for pickling is any one of hydrochloric acid, sulfuric acid and nitric acid;
the solution used in the alkaline cleaning is any one of sodium hydroxide solution and potassium hydroxide solution, the concentration of the solution is 1-20mol/L, and the pretreatment time is 0.1-2 hours.
Preferably, the content of Si element in the Al-Si alloy is 4 wt.% to 30 wt.%.
Preferably, the laser power of the surface remelting treatment in the step 1 is 3000-6000W, the diameter of a laser spot is 0.3-3mm, the scanning speed is 5-50mm/s, the scanning interval is 1-3mm or no lap joint, and the inclination angle is 5-20 degrees.
Preferably, the manner of separating the remelted layer in step 102 is wire cutting.
Preferably, the corrosion solution is any one of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide and potassium hydroxide solution, the concentration of the solution is 1-20mol/L, and the corrosion time is 0.5-12 hours.
According to a second aspect of the present invention, there is provided a method of manufacturing an electrode for a Si nanowire lithium ion battery, comprising the steps of:
step 201, performing surface remelting treatment on the Al-Si alloy by using laser;
step 202, separating a remelted layer on the surface of the Al-Si alloy, and removing Al from the remelted layer by using corrosive liquid;
step 203, grinding the remelted layer subjected to the Al removal treatment to obtain Si nanowires;
and 204, mixing the Si nanowires with a conductive agent and a binder, and coating the surface of the copper foil to obtain the Si nanowire electrode.
Preferably, the conductive agent in the step 204 is super p, and the binder is prepared by CMC and PAA in a mass ratio of 0.2-5; after the Si nanowires are mixed with the conductive agent and the adhesive, the proportion of the Si nanowires is 60-95 wt.%.
Preferably, the Si nanowires of the Si nanowire lithium ion battery electrode have the size of 50-200nm, are mutually connected and are distributed at intervals of 2-300 nm.
According to a third aspect of the invention, there is provided a lithium ion battery comprising one or more electrodes, at least one of which is manufactured using a method of manufacturing a Si nanowire lithium ion battery electrode according to any one of the second aspects of the invention.
Through the technical scheme, the invention can obtain the following technical effects.
1) The laser surface remelting-chemical dealloying composite process is used for preparing the Si nanowire, the process efficiency is high, the flexibility is high, the constraint factor is few, the cost is low, the Si nanowire can be prepared in a large area, and the industrial application of the Si nanowire is promoted.
2) The Si nanowires are arranged at intervals and connected with each other, so that the volume expansion of Si is relieved, and the structural stability of the electrode is improved.
3) The binder used in the preparation process can prevent a large amount of SEI films from being generated and improve the cycling stability of the electrode.
Drawings
FIG. 1 is a schematic diagram of the laser surface remelting-chemical dealloying composite process of the present invention for preparing Si nanowires.
FIG. 2 is a schematic diagram of the structure of Si nanowire electrode of lithium ion battery.
Fig. 3 is an SEM image of the Si nanowire material in example 1.
Fig. 4 is the electrochemical performance test results of the Si nanowire electrode in example 1.
Detailed Description
The present invention is described in further detail below with reference to specific examples, but is not limited to the following examples.
FIG. 1 is a schematic diagram of the laser surface remelting-chemical dealloying composite process of the present invention for preparing Si nanowires.
According to a first aspect of the present invention, there is provided a method of preparing Si nanowires, comprising the steps of:
and 101, carrying out surface remelting treatment on the Al-Si alloy 1 by using laser 2.
And 102, separating a remelted layer 3 on the surface of the Al-Si alloy, and removing an Al element 5 from the remelted layer by using a corrosive liquid 4.
And 103, grinding the remelted layer from which the Al element 5 is removed to obtain the Si nanowire 6.
In a preferred embodiment, before step 101, a step of pre-treating the Al — Si alloy 1 is further included. The pretreatment mode comprises at least one of grinding, acid washing or alkali washing, wherein a solution used for acid washing is any one of hydrochloric acid, sulfuric acid and nitric acid, a solution used for alkali washing is any one of sodium hydroxide and potassium hydroxide, the concentration of the solution is 1-20mol/L, and the pretreatment time is 0.1-2 hours.
In a preferred embodiment, the content of elemental silicon in the Al-Si alloy 1 is 4 wt.% to 30 wt.%.
In a preferred embodiment, the parameters of the laser 2 are such that the laser power is 3000-6000W, the laser spot is 0.3-3mm, the scanning speed is 5-50mm/s, the scanning interval is 1-3mm or no overlap, and the tilt angle is 5-20 °.
In a preferred embodiment, the manner of separating the remelted layer 3 in step 102 is wire cutting.
In a preferred embodiment, the etching solution 4 is any one of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide and potassium hydroxide solution, the solution concentration is 1-20mol/L, and the etching time is 0.5-12 hours.
The Si nanowire 6 is prepared by a laser surface remelting-chemical dealloying composite process, and has the advantages of high efficiency, high flexibility, few constraint factors, low cost, large-area preparation and the like.
As shown in fig. 2, according to a second aspect of the present invention, the present invention provides a method for manufacturing an electrode of a Si nanowire lithium ion battery, comprising the steps of:
step 201, performing surface remelting treatment on the Al-Si alloy 1 by using laser 2.
And 202, separating a remelted layer on the surface of the Al-Si alloy 1, and removing an Al element 5 from the remelted layer by using a corrosive liquid 4.
And 203, grinding the remelted layer from which the Al element 5 is removed to obtain the Si nanowire 6.
And 204, mixing the Si nanowires 6 with a conductive agent 7 and a binder 8, and coating the surface of the copper foil 9 to obtain the Si nanowire electrode.
The steps involved in the method for preparing Si nanowires are the same as in any of the above first aspects, and the technical features of the method that are the same as in the first aspect are not repeated here.
In a preferred embodiment, in step 204, the conductive agent mixed is Super P, the binder is prepared by mixing CMC (Carboxymethyl Cellulose) and PAA (Polyacrylic Acid) in a mass ratio of 0.2-5, and the active material Si nanowires is 60-95 wt.%.
In a preferred embodiment, the Si nanowire size of the Si nanowire lithium ion battery electrode prepared by the method is 50-200nm, the Si nanowires are connected with each other, and the spacing between adjacent Si nanowires is 2-300nm, so that the volume expansion is relieved, and the structural stability is maintained.
According to a third aspect of the invention, there is provided a lithium ion battery comprising one or more electrodes, at least one of which is manufactured using the method of manufacturing a Si nanowire lithium ion battery electrode of any of the second aspects.
According to a fourth aspect of the present invention, there is provided a method of manufacturing a lithium ion battery, comprising the steps of:
301, carrying out surface remelting treatment on the Al-Si alloy by using laser;
302, separating a remelted layer on the surface of the Al-Si alloy, and removing Al from the remelted layer by using a corrosive liquid;
step 303, grinding the remelted layer subjected to the Al removal treatment to obtain Si nanowires;
304, mixing the Si nanowires with a conductive agent and a binder, and coating the surface of the copper foil to obtain Si nanowire lithium ion battery electrodes;
and 305, assembling the Si nanowire lithium ion battery electrode serving as a negative electrode to obtain the lithium ion battery.
The method involves using the Si nanowire lithium ion battery electrode described in any of the above second aspects, and the same technical features as those of the second aspect will not be repeated here.
Example 1
1. Raw materials:
(1) Al-Si alloy, Al: si 80:20 wt.%.
(2) Pretreatment solution: 19mol/L NaOH.
(3) Corrosive liquid: 5mol/L HCl.
2. Manufacturing method
(1) And cleaning the Al-Si alloy 1 by 19mol/L sodium hydroxide solution for 0.3 hour, and remelting the surface by using a YLS-6000 fiber laser to obtain a surface remelting layer 3. In this embodiment, the parameters of the laser 2 are as follows: the laser power is 5500W, the scanning speed is 20mm/s, the laser spot diameter is 3mm, no overlap joint exists, and the inclination angle is 10 degrees.
(2) Separating the Al-Si alloy surface remelting layer 3 by adopting wire cutting, then immersing the remelting layer 3 into 5mol/L HCl corrosive liquid 4 for dealloying to remove Al element 5, and after dealloying for 0.5 hour, grinding to obtain the Si nanowire 6 shown in figure 3.
(3) And mixing the Si nanowire, a binder (the mass ratio of CMC to PAA is 1: 1) and a conductive agent super P, and coating the mixture on the surface of a copper foil 9 to prepare the Si nanowire electrode.
(4) And assembling the lithium ion battery by using the Si nanowire lithium ion battery electrode as a negative electrode.
3. Electrochemical performance test
As shown in fig. 4, the reversible specific capacity of the first loop of the silicon nanowire electrode is as high as 2472 mAh/g; the coulombic efficiency of the first circle is 89%, the coulombic efficiency is increased to 99% in the subsequent cycle, and the cycle reversibility of the battery is good; in addition, the battery has good cycling stability, the specific capacity is remained 1839mAh/g after 100 circles of charging and discharging, and the retention rate is 77%. From the above, it is understood that the battery has good electrochemical performance.
On one hand, the silicon nanowire is prepared by using a laser surface remelting-chemical dealloying composite process, and the process has the advantages of high efficiency, high flexibility, few constraint factors, low cost, large-area preparation and the like.
On the other hand, the Si nanowires are arranged at intervals and connected with each other, so that the volume expansion is favorably relieved, and the structural stability is kept. By using the novel binder and the conductive agent, a large amount of SEI is prevented from being generated, and the electrode cycle performance is improved.
Those skilled in the art will understand that the implementation forms of the various technical features are specifically described in the above embodiments, but the present invention is not limited thereto. The technical result of the present invention can be obtained by any equivalent or modified embodiments.

Claims (8)

1. A method of manufacturing Si nanowires, comprising the steps of:
101, performing surface remelting treatment on the Al-Si alloy by using laser;
102, separating a remelted layer on the surface of the Al-Si alloy, and removing Al from the remelted layer by using a corrosive liquid;
103, grinding the remelted layer subjected to the Al removal treatment to obtain Si nanowires;
characterized in that the content of Si element in the Al-Si alloy is 4-30 wt.%;
the laser power of the surface remelting treatment in the step 101 is 3000-6000W, the diameter of a laser spot is 0.3-3mm, the scanning speed is 5-50mm/s, the scanning interval is 1-3mm or no lap joint, and the inclination angle is 5-20 degrees.
2. The method of manufacturing Si nanowires as claimed in claim 1, further comprising:
step 100, before the surface remelting treatment, pretreating the Al-Si alloy;
the pretreatment mode comprises at least one of grinding, acid washing or alkali washing;
the solution used for pickling is any one of hydrochloric acid, sulfuric acid and nitric acid;
the solution used in the alkaline cleaning is any one of sodium hydroxide solution and potassium hydroxide solution, the concentration of the solution is 1-20mol/L, and the pretreatment time is 0.1-2 hours.
3. The method of claim 1, wherein the re-melted layer is separated in step 102 by wire cutting.
4. The method of claim 1, wherein the etching solution is any one of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, and potassium hydroxide solution, the solution concentration is 1 to 20mol/L, and the etching time is 0.5 to 12 hours.
5. A manufacturing method of an Si nanowire lithium ion battery electrode is characterized by comprising the following steps:
step 201, performing surface remelting treatment on the Al-Si alloy by using laser;
step 202, separating a remelted layer on the surface of the Al-Si alloy, and removing Al from the remelted layer by using corrosive liquid;
step 203, grinding the remelted layer subjected to the Al removal treatment to obtain Si nanowires;
step 204, mixing the Si nanowires with a conductive agent and a binder, and coating the surface of the copper foil to obtain a Si nanowire electrode;
characterized in that the content of Si element in the Al-Si alloy is 4-30 wt.%;
the laser power of the surface remelting treatment is 3000-6000W, the diameter of a laser spot is 0.3-3mm, the scanning speed is 5-50mm/s, the scanning interval is 1-3mm or no lap joint, and the inclination angle is 5-20 degrees.
6. The method of claim 5, wherein the conductive agent in step 204 is super p, and the binder is prepared from CMC and PAA at a mass ratio of 0.2-5; the ratio of the Si nanowires is 60-95 wt.% after mixing the Si nanowires with the conductive agent and the binder.
7. The method for manufacturing the Si nanowire lithium ion battery electrode according to claim 6, wherein the Si nanowires of the Si nanowire lithium ion battery electrode have a size of 50-200nm, are connected with each other, are distributed at intervals of 2-300 nm.
8. A lithium ion battery comprising one or more electrodes, characterized in that at least one of said electrodes is manufactured using a method of manufacturing Si nanowire lithium ion battery electrodes according to any of claims 5-7.
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