CN112436149A - Si NWs-rGO manufacturing method and Si NWs-rGO lithium ion battery electrode manufacturing method - Google Patents

Si NWs-rGO manufacturing method and Si NWs-rGO lithium ion battery electrode manufacturing method Download PDF

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CN112436149A
CN112436149A CN202011325113.0A CN202011325113A CN112436149A CN 112436149 A CN112436149 A CN 112436149A CN 202011325113 A CN202011325113 A CN 202011325113A CN 112436149 A CN112436149 A CN 112436149A
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黄婷
曹利
肖荣诗
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Beijing University of Technology
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Abstract

The invention provides a Si NWs-rGO manufacturing method and a Si NWs-rGO lithium ion battery electrode manufacturing method. According to the invention, the reduced graphene oxide (rGO) coated Si nanowire (Si NWs) structure is prepared through composite laser surface remelting, dealloying and heat treatment processes, so that the conductivity and the cycling stability of the electrode are optimized. The nanowires in the Si NWs-rGO structure are connected in a tree shape and have intervals, and a space is reserved for volume expansion; the rGO coating can improve the conductivity and structural stability of the electrode and improve the electrochemical performance of the battery. The electrode manufacturing process is as follows: firstly remelting the surface of the Al-Si alloy by laser, dealloying a remelting layer to obtain Si nanowires, coating rGO by a composite heat treatment process, and finally obtaining the lithium ion battery cathode by a coating method. The method has the advantages of high flexibility, simple process and low cost, and can realize high-efficiency and high-yield preparation of the lithium ion battery electrode material with good performance.

Description

Si NWs-rGO manufacturing method and Si NWs-rGO lithium ion battery electrode manufacturing method
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method of Si NWs-rGO, a manufacturing method of an Si NWs-rGO lithium ion battery electrode, an Si NWs-rGO lithium ion battery electrode manufactured by the method, and a lithium ion battery comprising the electrode.
Background
The Si nanowires (Si NWs) are materials with good application prospects, and are widely applied to the fields of sensing, energy and the like due to the characteristics of large specific surface area, one-dimensional linear structure, semiconductor characteristics, good photoelectric performance and the like. The lithium ion battery is one of the fields in which Si NWs is widely applied, and a large number of researches find that Si nanowires are used as a battery cathode material and have the characteristics of large specific capacity, high cycling stability and the like. For example, Cui and the like show in research that the Si nanowire is used as a negative active material, the battery has good cycle stability, the capacity is remained at 1000mAh/g after constant current charging and discharging for 100 circles, and the retention rate is more than 90%. [ non-patent document 1: H.Wu, Y.Cui, Nano Today,7(2012), 414-.
However, since Si NWs has semiconductor characteristics, its conductivity is poor, resulting in a decrease in specific capacity and first coulombic efficiency (ICE) of an electrode. Therefore, many researchers have conducted extensive research on the process of optimizing the conductivity of Si NWs. Ren et al proposed a Si NWs-rGO structure by first oxidizing graphene, preparing an rGO-Ag substrate by solvothermal reduction, and then preparing Si NWs on the surface thereof by Chemical Vapor Deposition (CVD); research results show that in the reduced graphene oxide (rGO) coated Si NWs structure, the reduced graphene oxide has good ductility and conductivity, so that the volume expansion effect of the Si NWs can be relieved, and meanwhile, a complete conductive network is formed, so that the battery has the characteristics of high specific capacity, stable cycle performance and the like; the battery ICE is 78%, the capacity is remained 2230mAh/g after 100 cycles, and the retention rate is 91.8%. [ non-patent document 3: J.G.ren, C.D.Wang, Q.H.Wu, X.Liu, Y.Yang, L.F.He, W.J.Zhang, Nanoscale 6(2014)3353-3360] it is thus known that the electrochemical performance of the cell can be improved by improving the conductivity of Si NWs. In addition, the rGO has good ductility and conductivity, can simultaneously improve the conductivity and structural stability of the Si NWs electrode, and is an ideal material for improving the structure and performance of the electrode. However, the current researches on the structure of Si NWs-rGO are relatively few, the conductivity of Si NWs is usually improved by amorphous carbon coating or noble metal modification, and the ductility and conductivity of the coating layer are both lower than those of rGO, and the process is complex and high in cost, which is not beneficial to practical application.
Therefore, the structure of the Si NWs-rGO needs to be further researched in the field, and a manufacturing process with simple process, low cost and high efficiency is provided for preparing Si NWs-rGO and Si NWs-rGO electrodes of lithium ion batteries.
Disclosure of Invention
The invention aims to provide a method for preparing a high-performance Si NWs-rGO lithium ion battery electrode, which has the advantages of simple process, low cost, high efficiency and the like.
According to a first aspect of the present invention there is provided a method of manufacturing Si NWs-rGO 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;
and 104, preparing Si NWs-rGO by using a heat treatment process.
Preferably, before the step 101, 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 for 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 energy of the laser line of the surface remelting treatment in the step 101 is 60-1200J/mm, the diameter of a laser spot is 0.3-3mm, 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, the etching solution 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.
Preferably, the heat treatment process in step 104 comprises mixing PVP, Si NWs and GO, wherein the Si to PVP mass ratio is 1-5; the mass ratio of Si to GO is 0.2-5, the heat treatment temperature is 700-.
The Si content in the Si NWs-rGO is 20-80 wt.%.
According to a second aspect of the invention, there is provided a method of manufacturing an electrode for a Si NWs-rGO 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, preparing Si NWs-rGO through a heat treatment process.
And step 205, mixing the Si NWs-rGO with a conductive agent and a binder, and coating the mixture on the surface of a copper foil to prepare the Si NWs-rGO electrode.
Preferably, in the step 205, the conductive agent is Super P, and the binder is prepared by CMC and PAA in a mass ratio of 0.2-5; after the Si NWs-rGO is mixed with a conductive agent and a binder, the ratio of the Si NWs-rGO is 60-95 wt.%.
Preferably, the size of Si NWs-rGO in the Si NWs-rGO lithium ion battery electrode is 50-200nm, the Si NWs-rGO are connected with each other, and the interval between adjacent Si NWs-rGO is 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 NWs-rGO 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 Si NWs-rGO is prepared by using a laser surface remelting-dealloying-heat treatment composite process, and the process has the advantages of high flexibility, high efficiency, low cost and the like.
2) The nanowires are connected with each other, and a space exists between adjacent nanowires, so that the volume expansion is favorably relieved.
3) The rGO with good ductility and conductivity is used for coating the Si NWs, so that the high conductivity and structural stability of the electrode can be ensured, and the electrode has good electrochemical performance.
Drawings
FIG. 1 is a schematic diagram of the process of the present invention for preparing Si NWs-rGO by using a laser surface remelting-dealloying-heat treatment composite process.
FIG. 2 is a schematic diagram of the structure of a Si NWs-rGO electrode of the lithium ion battery of the present invention.
FIG. 3 is a microstructure diagram of the Si NWs-rGO of example 1.
FIG. 4 is the results of electrochemical performance experiments for electrodes of Si NWs-rGO lithium battery of 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 process of the present invention for preparing Si NWs-rGO by using a laser surface remelting-dealloying-heat treatment composite process.
According to a first aspect of the present invention there is provided a process for the manufacture of Si NWs-rGO comprising the steps of:
101, carrying out surface remelting treatment on the Al-Si alloy 1 by using laser 2 to obtain a dendritic eutectic structure 3;
102, separating a remelted layer 4 on the surface of the Al-Si alloy, and removing Al from the remelted layer by using corrosive liquid;
103, grinding the remelted layer subjected to the Al removal treatment to obtain Si nanowires 5;
and 104, preparing Si NWs-rGO 6 by using a heat treatment process.
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 Si element in the Al-Si alloy 1 is 4 wt.% to 30 wt.%.
In a preferred embodiment, the parameters of the laser 2 include a laser line energy of 60-1200J/mm, a laser spot of 0.3-3mm, a scan interval of 1-3mm or no overlap, and a tilt angle of 5-20 °.
In a preferred embodiment, the manner of separating the remelted layer 4 is wire cutting, the etching solution 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.
103, preparing Si NWs-rGO 6 through a heat treatment process, wherein the Si nanowire 5 is coated by rGO 7.
In a preferred embodiment, the heat treatment process comprises mixing polyvinylpyrrolidone (PVP), Si nanowires 5(Si NWs) and graphene oxide 7(GO), wherein the Si to PVP mass ratio is 1-5; the mass ratio of Si to GO is 0.2-5, the heat treatment temperature is 700-.
The Si NWs-rGO is prepared by a laser surface remelting-dealloying-heat treatment composite process, and the process is simple, low in cost and high in preparation efficiency.
As shown in fig. 2, according to a second aspect of the present invention, the present invention provides a method for manufacturing Si NWs-rGO lithium ion battery electrode, comprising the following steps:
step 201, performing surface remelting treatment on the Al-Si alloy 1 by using laser 2 to obtain a dendritic eutectic structure 3;
202, separating a remelted layer 4 on the surface of the Al-Si alloy 1, and removing Al elements from the remelted layer by using corrosive liquid;
step 203, grinding the remelted layer from which the Al element is removed to obtain Si nanowires 5;
and 204, preparing Si NWs-rGO 6 through a heat treatment process.
And step 205, mixing the Si NWs-rGO 6 with a conductive agent 8 and a binder 9, and coating the mixture on the surface of a copper foil 10 to prepare the Si NWs-rGO lithium ion battery electrode.
The steps involved in the method for preparing Si NWs-rGO are the same as in any of the above first aspects, and the same technical features as in the first aspect will not be repeated here.
In a preferred embodiment, in step 205, 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 ratio of the active material Si NWs-rGO is 60-95 wt.%.
In a preferred embodiment, the Si NWs-rGO of the Si NWs-rGO lithium ion battery electrode prepared by the method has the size of 50-200nm, the Si NWs-rGO are connected with each other, and the interval between adjacent Si NWs-rGO is 2-300nm, so that the volume expansion is favorably relieved, and the structural stability is kept.
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 NWs-rGO lithium ion battery electrode of any one of the second aspects.
In a preferred embodiment, the Si NWs-rGO content of the Si NWs-rGO lithium ion battery electrode is 20 to 80 wt.%. The coated rGO layer can improve both the conductivity and structural stability of the electrode.
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 elements from the remelted layer by using corrosive liquid;
step 303, grinding the remelted layer subjected to the Al removal treatment to obtain Si nanowires;
304, preparing Si NWs-rGO by using a heat treatment process;
305, mixing the Si NWs-rGO with a conductive agent and a binder, and coating the mixture on the surface of a copper foil to prepare an Si NWs-rGO lithium ion battery electrode;
and 306, drying the Si NWs-rGO lithium ion battery electrode, and assembling the electrode serving as a negative electrode to obtain the lithium ion battery.
The method involves using a Si NWs-rGO lithium ion battery electrode as described in any one of the above second aspects, and the same technical features as in 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.
(4) Polyvinylpyrrolidone PVP.
(5) Graphene oxide GO.
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 the dendritic eutectic structure 3. In this embodiment, the parameters of the laser 2 are as follows: the energy of the laser beam is 60-1200J/mm, the diameter of the laser spot is 3mm, the scanning interval is no lap joint, and the inclination angle is 10 degrees.
(2) The re-melted layer 4 and the base material were separated by wire cutting, and etched in 5mol/L HCl solution for 0.5 hour to obtain silicon nanowires 5(Si NWs).
(3) Mixing Si NWs, PVP and GO, and keeping the temperature at 800 ℃ for 3 hours to obtain Si NWs-rGO 7 shown in figure 3.
(4) Mixing Si NWs-rGO 7, a binder (the mass ratio of CMC to PAA is 1: 1), and a conductive agent super P, and coating the surface of a copper foil 10 to prepare the Si NWs-rGO lithium ion battery electrode.
(5) And drying the Si NWs-rGO lithium ion battery electrode and assembling the lithium ion battery as a negative electrode.
3. Electrochemical performance test
As shown in FIG. 4, the electrode impedance Z of the Si NWs-rGO lithium ion battery is 30.8 omega, the reversible specific capacity of the first circle of the battery is up to 3729mAh/g, and the coulombic efficiency ICE of the first circle is 74%. Therefore, the rGO is coated on the Si NWs, so that the conductivity of the electrode is increased, and the specific capacity of the battery is remarkably improved.
On one hand, the reduced graphene oxide (rGO) coated silicon nanowire (Si NWs) structure is prepared by using a laser surface remelting-dealloying-heat treatment composite process, and the method has the advantages of simple process, low cost, high preparation efficiency, large-area preparation and the like.
On the other hand, in the invention, the Si NWs-rGO is mutually connected, and pores exist between adjacent nanowires, namely, the nanowires in the Si NWs-rGO structure are connected in a tree shape and have intervals, so that space is reserved for volume expansion, and the volume expansion is favorably relieved. The coated rGO layer can simultaneously improve the conductivity and stability of the electrode and improve the electrochemical performance.
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 (10)

1. A method of making Si NWs-rGO 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;
and 104, manufacturing the SiNWs-rGO by using a heat treatment process.
2. The method of 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 for 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 Al-Si alloy contains Si in an amount of 4 wt.% to 30 wt.%.
4. The method for preparing Si NWs-rGO according to claim 1, wherein the laser beam energy of the surface remelting treatment in step 101 is 60-1200J/mm, the laser spot diameter is 0.3-3mm, the scanning interval is 1-3mm or no overlap, and the tilt angle is 5-20 °.
5. The method for manufacturing the Si NWs-rGO according to claim 1, wherein the manner of separating the remelted layer in the step 102 is wire cutting, the corrosive solution 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 corrosion time is 0.5-12 hours.
6. The method of claim 1, wherein the heat treatment process of step 104 comprises mixing PVP, Si nanowires and GO, wherein the Si to PVP mass ratio is 1-5; the mass ratio of Si to GO is 0.2-5, the heat treatment temperature is 700-.
7. A manufacturing method of an Si NWs-rGO lithium ion battery electrode comprises 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;
204, preparing Si NWs-rGO through a heat treatment process;
and step 205, mixing the Si NWs-rGO with a conductive agent and a binder, and coating the mixture on the surface of a copper foil to prepare the Si NWs-rGO electrode.
8. The method of claim 7, wherein in step 205, the conductive agent is super p, and the binder is prepared from CMC and PAA at a mass ratio of 0.2-5; after the Si NWs-rGO is mixed with a conductive agent and a binder, the ratio of the Si NWs-rGO is 60-95 wt.%.
9. The method of claim 7, wherein the Si NWs-rGO lithium ion battery electrode has Si NWs-rGO size of 50-200nm, the Si NWs-rGO are connected to each other, and the spacing between adjacent Si NWs-rGO is 2-300 nm;
the Si content in the Si NWs-rGO is 20-80 wt.%.
10. A lithium ion battery comprising one or more electrodes, wherein at least one of said electrodes is manufactured using a method of manufacturing a Si NWs-rGO lithium ion battery electrode according to any one of claims 7 to 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112599758A (en) * 2021-03-03 2021-04-02 拓米(成都)应用技术研究院有限公司 Nano silicon aggregate composite negative electrode material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269515A (en) * 2014-09-19 2015-01-07 清华大学深圳研究生院 Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery
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
CN106887569A (en) * 2017-02-22 2017-06-23 上海杉杉科技有限公司 A kind of new structure graphene coated nano silicon particles and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269515A (en) * 2014-09-19 2015-01-07 清华大学深圳研究生院 Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery
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
CN106887569A (en) * 2017-02-22 2017-06-23 上海杉杉科技有限公司 A kind of new structure graphene coated nano silicon particles and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112599758A (en) * 2021-03-03 2021-04-02 拓米(成都)应用技术研究院有限公司 Nano silicon aggregate composite negative electrode material and preparation method thereof
CN112599758B (en) * 2021-03-03 2021-07-06 拓米(成都)应用技术研究院有限公司 Nano silicon aggregate composite negative electrode material and preparation method thereof
WO2022183677A1 (en) * 2021-03-03 2022-09-09 拓米(成都)应用技术研究院有限公司 Nano-silicon aggregate composite negative electrode material and preparation method therefor

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