CN102263243A - Preparation methods for arrayed nickel silicon nanowire and nickel silicon-silicon core-shell nanowire - Google Patents

Preparation methods for arrayed nickel silicon nanowire and nickel silicon-silicon core-shell nanowire Download PDF

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CN102263243A
CN102263243A CN201110167445A CN201110167445A CN102263243A CN 102263243 A CN102263243 A CN 102263243A CN 201110167445 A CN201110167445 A CN 201110167445A CN 201110167445 A CN201110167445 A CN 201110167445A CN 102263243 A CN102263243 A CN 102263243A
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nisiloy
silicon
array
nickel
metal substrate
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CN102263243B (en
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杜宁
樊星
吴平
杨德仁
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Zhejiang University ZJU
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses preparation methods for an arrayed nickel silicon nanowire and a nickel silicon-silicon core-shell nanowire. The preparation method for the nickel silicon-silicon core-shell nanowire comprises the following steps of: washing a metal substrate for a lithium ion battery anode basal body by using a hydrochloric acid and ethanol, and drying the washed metal substrate for later use; growing the arrayed nickel silicon nanowire on the surface of the washed metal substrate by using a hot wire chemical vapor deposition device; and further depositing a layer of thickness-controllable silicon on the surface of the obtained arrayed nickel silicon nanowire by using a radio frequency sputtering method to obtain the arrayed nickel silicon-silicon core-shell nanowire. The metal substrate and the arrayed nickel silicon nanowire grown on the metal substrate form a lithium ion battery anode. The preparation methods provided by the invention are simple and controllable; and the prepared nanowire materials can be used for the lithium ion battery anode and high performance can be obtained.

Description

The preparation method of array nisiloy nano wire and nisiloy-silicon core-shell nano line
Technical field
The invention belongs to material science, be specifically related to be used for the preparation method of the array nisiloy nano wire and the nisiloy-silicon core-shell nano line of lithium ion battery negative.
Background technology
Owing to have than higher theoretical capacity, silicon is considered to the substitute of desirable lithium ion battery negative graphite-like material with carbon element, thereby satisfies the demand of high energy density lithium ion battery.Yet the change in volume owing to huge in charge and discharge process can cause the efflorescence of silicon electrode material, and its capacity can sharply descend; In addition, the silicon electrode material is unstable properties under big charging and discharging currents, and these have all limited its commercial applications as lithium ion battery negative material.
Increasing at present work is devoted to improve the performance of silicon as lithium ion battery negative material, and wherein the electrode structure of array has special advantages.The first, with electrically contacting of matrix, improved the conductivity of electrode material greatly, the second, the huge volumetric expansion in cyclic process of silicon electrode material can be effectively alleviated in the gap between the array structure, thereby improves its cycle performance significantly.Up to the present, the nickel of the carbon nano-tube-silicon heterostructure of the silicon nanowires of the nano-tube of array, array, array and array-silicon nucleocapsid structure all is used in the negative pole of lithium ion battery and has obtained the raising on the performance.Yet these methods also face some problems, for example can not realize that the growth of highdensity array structure on the big matrix, course of reaction are loaded down with trivial details, comparatively the conductivity of harshness and electrode is relatively poor etc. for reaction condition.Therefore, thus also need electrode structure is carried out the lithium electrical property that careful design further improves the silicium cathode material.
Summary of the invention
The invention provides a kind of preparation method who is used for the array nisiloy nano wire and the nisiloy-silicon core-shell nano line of lithium ion battery negative, on large stretch of metal substrate, realize the high-density growth of array nisiloy nano wire by easy method, wherein nisiloy is mutually controlled, realize the preparation of high-quality array nisiloy-silicon core-shell nano line subsequently by easy method, wherein the ratio of nisiloy and silicon is controlled.
A kind of preparation method of array nisiloy nano wire may further comprise the steps:
(1) metal substrate that will be used for the lithium ion battery negative matrix is cleaned respectively with hydrochloric acid and ethanol, and subsequent drying is standby; Described drying is that vacuumize or nitrogen dry up; Described hydrochloric acid and ethanol adopt general commercially available watery hydrochloric acid and alcohol product get final product, mass fraction is lower than 37% hydrochloric acid is called watery hydrochloric acid usually;
(2) the metal substrate superficial growth array nisiloy nano wire that was cleaning through step (1) by the hot-wire chemical gas-phase deposition device, it is 10～1000sccm that silane flow rate is set, hydrogen flowing quantity is 10～1000sccm, cavity air pressure is 10～1000Pa, temperature is 200～1000 ℃, reaction time is 1～300min, obtains array nisiloy nano wire.
Described metal substrate and the array nano-material that is grown on the metal substrate constitute lithium ion battery negative.
Described metal substrate is the foam copper of nickel foam, nickel foil, plating nickel on surface, the Copper Foil of plating nickel on surface or the titanium foil of plating nickel on surface.
In the said method,, can obtain different crystalline phase (Ni by technological parameter control 3Si 2, NiSi, Ni 2Si, NiSi 2Or Ni 31Si 12) the nisiloy nano wire, therefore, described array nisiloy nano wire is Ni 3Si 2Nano wire, NiSi nano wire, Ni 2Si nano wire, NiSi 2Nano wire or Ni 31Si 12Nano wire.
The preparation method of a kind of nisiloy-silicon core-shell nano line may further comprise the steps:
(1) metal substrate that will be used for the lithium ion battery negative matrix is cleaned respectively with hydrochloric acid and ethanol, and subsequent drying is standby; Described drying is that vacuumize or nitrogen dry up; Described hydrochloric acid and ethanol adopt general commercially available watery hydrochloric acid and alcohol product get final product, mass fraction is lower than 37% hydrochloric acid is called watery hydrochloric acid usually;
(2) the metal substrate superficial growth array nisiloy nano wire that was cleaning through step (1) by the hot-wire chemical gas-phase deposition device, it is 10～1000sccm that silane flow rate is set, hydrogen flowing quantity is 10～1000sccm, cavity air pressure is 10～1000Pa, temperature is 200～1000 ℃, reaction time is 1～300min, obtains array nisiloy nano wire;
(3) silicon of surface deposition one deck controllable thickness of the array nisiloy nano wire that obtains in step (2) of the method by radio frequency sputtering, it is 20～500 ℃ that the silicon substrate temperature is set, argon flow amount is 10～1000sccm, cavity air pressure is 1～100Pa, sputtering power is 10～1000W, sputtering time is 1～300min, obtains array nisiloy-silicon core-shell nano line.
Described metal substrate and the array nano-material that is grown on the metal substrate constitute lithium ion battery negative.
Described metal substrate is the foam copper of nickel foam, nickel foil, plating nickel on surface, the Copper Foil of plating nickel on surface or the titanium foil of plating nickel on surface.
In the said method,, can obtain different crystalline phase (Ni by technological parameter control 3Si 2, NiSi, Ni 2Si, NiSi 2Or Ni 31Si 12) the nisiloy nano wire, therefore, described array nisiloy nano wire is Ni 3Si 2Nano wire, NiSi nano wire, Ni 2Si nano wire, NiSi 2Nano wire or Ni 31Si 12Nano wire.
With respect to prior art, the present invention has following beneficial technical effects:
(1) the present invention has realized the high-density growth of array nisiloy nano wire on large stretch of metal substrate by easy method;
(2) the inventive method can be controlled obtains not homophase (Ni 3Si 2, NiSi, Ni 2Si, NiSi 2Or Ni 31Si 12) array nisiloy nano wire;
(3) the inventive method obtains array nisiloy-silicon core-shell nano line by easy method, and wherein the ratio of nisiloy and silicon is controlled;
(4) because unique electrode construction designs, nisiloy nano wire that obtains among the present invention and nisiloy-silicon core-shell nano line all can be used for lithium ion battery negative and expectation obtains excellent performance.
Description of drawings
The stereoscan photograph of the array nisiloy nano wire that Fig. 1 makes for embodiment 1.
The transmission electron microscope photo of the array nisiloy nano wire that Fig. 2 makes for embodiment 1.
The X ray diffracting spectrum of the array nisiloy nano wire that Fig. 3 makes for embodiment 1.
The transmission electron microscope photo of the array nisiloy that Fig. 4 makes for embodiment 1-silicon core-shell nano line.
The lithium ion battery cycle performance curve chart of the array nisiloy nano wire that Fig. 5 makes for embodiment 1.
The lithium ion battery cycle performance curve chart of the array nisiloy that Fig. 6 makes for embodiment 1-silicon core-shell nano line.
Embodiment
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1:
(1) nickel foam is cleaned respectively with watery hydrochloric acid and alcohol, dry up standby with vacuumize or nitrogen subsequently; The mass percentage concentration of watery hydrochloric acid is 10%, and the concentration expressed in percentage by volume of alcohol is 98%;
(2) nickel foam that will clean is placed in the hot-wire chemical gas-phase deposition device, and it is 80sccm that silane flow rate is set, and hydrogen flowing quantity is 80sccm, cavity air pressure is 600Pa, temperature is 500 ℃, and the reaction time is 15min, obtains array nisiloy nano wire in the nickel foam superficial growth of cleaning;
(3) silicon of surface deposition one deck controllable thickness of the array nisiloy nano wire that obtains in step (2) of the method by radio frequency sputtering, it is 20 ℃ that the silicon substrate temperature is set, argon flow amount is 30sccm, cavity air pressure is 3Pa, sputtering power is 80W, sputtering time is 60min, obtains array nisiloy-silicon core-shell nano line.
Fig. 1, Fig. 2 and Fig. 3 are respectively stereoscan photograph, transmission electron microscope photo and the X ray diffracting spectrums by the synthetic array nisiloy nano wire of present embodiment.As seen, what obtain is the nano thread structure of array from Fig. 1～3, and wherein nanowire surface is smooth, and diameter is 30～50 nanometers, and main nisiloy crystalline phase is Ni 3Si 2Phase.
Fig. 4 is the transmission electron microscope photo of the synthetic array nisiloy-silicon core-shell nano line of present embodiment.As can be seen from Figure 4, the thickness of the silicon layer of nisiloy nanowire surface is 10～20 nanometers.
Fig. 5 constitutes lithium ion battery negative gained cycle performance of battery curve for nickel foam and the array nisiloy nano wire that is grown on the metal substrate.As can be seen from Figure 5, the capacity first of array nisiloy nano wire has reached about 800mAh/g, and curve is steady, after 8 circulations, capacity stably maintains 450mAh/g, and efficient maintains more than 95%, has shown the cycle performance of battery more more excellent than commercialization material with carbon element.
Fig. 6 constitutes lithium ion battery negative gained cycle performance of battery curve for above-mentioned nickel foam and the array nisiloy-silicon core-shell nano line that is grown on the metal substrate, and current density is 4.2A/g.As can be seen from Figure 6, the specific capacity first of array nisiloy-silicon core-shell nano line has reached about 3400mAh/g, and curve is steady, after 5 circulations, capacity stably maintains 1850mAh/g, and efficient maintains more than 95%, has shown very excellent cycle performance.
Embodiment 2:
(1) nickel foil is cleaned respectively with watery hydrochloric acid and alcohol, dry up standby with vacuumize or nitrogen subsequently; The mass percentage concentration of watery hydrochloric acid is 5%, and the concentration expressed in percentage by volume of alcohol is 90%;
(2) nickel foam that will clean is placed in the hot-wire chemical gas-phase deposition device, and it is 10sccm that silane flow rate is set, and hydrogen flowing quantity is 10sccm, cavity air pressure is 10Pa, temperature is 200 ℃, and the reaction time is 1min, obtains array nisiloy nano wire in the nickel foam superficial growth of cleaning;
(3) method by radio frequency sputtering is at the silicon of surface deposition one deck controllable thickness of array nisiloy nano wire, and it is 50 ℃ that the silicon substrate temperature is set, and argon flow amount is 10sccm, cavity air pressure is 1Pa, sputtering power is 10W, and sputtering time is 1min, obtains array nisiloy-silicon core-shell nano line.
Test result and example 1 are similar.
Embodiment 3:
(1) foam copper with plating nickel on surface cleans respectively with watery hydrochloric acid and alcohol, dries up standby with vacuumize or nitrogen subsequently; The mass percentage concentration of watery hydrochloric acid is 20%, and the concentration expressed in percentage by volume of alcohol is 80%;
(2) nickel foam that will clean is placed in the hot-wire chemical gas-phase deposition device, it is 100sccm that silane flow rate is set, hydrogen flowing quantity is 1000sccm, cavity air pressure is 1000Pa, temperature is 400 ℃, reaction time is 30min, obtains array nisiloy nano wire in the nickel foam superficial growth of cleaning;
(3) method by radio frequency sputtering is at the silicon of surface deposition one deck controllable thickness of array nisiloy nano wire, it is 100 ℃ that the silicon substrate temperature is set, argon flow amount is 100sccm, cavity air pressure is 10Pa, sputtering power is 50W, sputtering time is 30min, obtains array nisiloy-silicon core-shell nano line.
Test result and example 1 are similar.
Embodiment 4:
(1) Copper Foil with plating nickel on surface cleans respectively with watery hydrochloric acid and alcohol, dries up standby with vacuumize or nitrogen subsequently; The mass percentage concentration of watery hydrochloric acid is 30%, and the concentration expressed in percentage by volume of alcohol is 70%;
(2) nickel foam that will clean is placed in the hot-wire chemical gas-phase deposition device, it is 1000sccm that silane flow rate is set, hydrogen flowing quantity is 100sccm, cavity air pressure is 1000Pa, temperature is 800 ℃, reaction time is 150min, obtains array nisiloy nano wire in the nickel foam superficial growth of cleaning;
(3) method by radio frequency sputtering is at the silicon of surface deposition one deck controllable thickness of array nisiloy nano wire, it is 200 ℃ that the silicon substrate temperature is set, argon flow amount is 500sccm, cavity air pressure is 50Pa, sputtering power is 500W, sputtering time is 150min, obtains array nisiloy-silicon core-shell nano line.
Test result and example 1 are similar.
Embodiment 5:
(1) titanium foil with plating nickel on surface cleans respectively with watery hydrochloric acid and alcohol, dries up standby with vacuumize or nitrogen subsequently; The mass percentage concentration of watery hydrochloric acid is 37%, and the concentration expressed in percentage by volume of alcohol is 60%;
(2) nickel foam that will clean is placed in the hot-wire chemical gas-phase deposition device, it is 1000sccm that silane flow rate is set, hydrogen flowing quantity is 1000sccm, cavity air pressure is 1000Pa, temperature is 1000 ℃, reaction time is 300min, obtains array nisiloy nano wire in the nickel foam superficial growth of cleaning;
(3) method by radio frequency sputtering is at the silicon of surface deposition one deck controllable thickness of array nisiloy nano wire, it is 500 ℃ that the silicon substrate temperature is set, argon flow amount is 1000sccm, cavity air pressure is 100Pa, sputtering power is 1000W, sputtering time is 100min, obtains array nisiloy-silicon core-shell nano line.
Test result and example 1 are similar.

Claims (4)

1. the preparation method of an array nisiloy nano wire is characterized in that, may further comprise the steps:
(1) metal substrate that will be used for the lithium ion battery negative matrix is cleaned respectively with hydrochloric acid and ethanol, and subsequent drying is standby;
(2) the metal substrate superficial growth array nisiloy nano wire that was cleaning through step (1) by the hot-wire chemical gas-phase deposition device, it is 10～1000sccm that silane flow rate is set, hydrogen flowing quantity is 10～1000sccm, cavity air pressure is 10～1000Pa, temperature is 200～1000 ℃, reaction time is 1～300min, obtains array nisiloy nano wire.
2. the preparation method of array nisiloy nano wire as claimed in claim 1 is characterized in that, described metal substrate is the foam copper of nickel foam, nickel foil, plating nickel on surface, the Copper Foil of plating nickel on surface or the titanium foil of plating nickel on surface.
3. the preparation method of nisiloy-silicon core-shell nano line is characterized in that, may further comprise the steps:
(1) metal substrate that will be used for the lithium ion battery negative matrix is cleaned respectively with hydrochloric acid and ethanol, and subsequent drying is standby;
(2) the metal substrate superficial growth array nisiloy nano wire that was cleaning through step (1) by the hot-wire chemical gas-phase deposition device, it is 10～1000sccm that silane flow rate is set, hydrogen flowing quantity is 10～1000sccm, cavity air pressure is 10～1000Pa, temperature is 200～1000 ℃, reaction time is 1～300min, obtains array nisiloy nano wire;
(3) silicon of surface deposition one deck controllable thickness of the array nisiloy nano wire that obtains in step (2) of the method by radio frequency sputtering, it is 20～500 ℃ that the silicon substrate temperature is set, argon flow amount is 10～1000sccm, cavity air pressure is 1～100Pa, sputtering power is 10～1000W, sputtering time is 1～300min, obtains array nisiloy-silicon core-shell nano line.
4. the preparation method of array nisiloy nano wire as claimed in claim 3 is characterized in that, described metal substrate is the foam copper of nickel foam, nickel foil, plating nickel on surface, the Copper Foil of plating nickel on surface or the titanium foil of plating nickel on surface.
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CN105702942A (en) * 2016-01-22 2016-06-22 奇瑞汽车股份有限公司 Silicon-based negative electrode material and preparation method and application thereof
CN103474632B (en) * 2012-06-07 2016-08-03 中国科学院物理研究所 A kind of negative material for lithium battery and its preparation method and application
CN107482193A (en) * 2017-08-02 2017-12-15 合肥国轩高科动力能源有限公司 The silicon nanowires composite and preparation method that a kind of nano nickel particles and tantnickel nano-substance is modified jointly
WO2018040542A1 (en) * 2016-08-30 2018-03-08 华为技术有限公司 Silicon-based composite negative electrode sheet and preparation method therefor, and lithium ion secondary battery
CN110010864A (en) * 2019-03-21 2019-07-12 中国科学院半导体研究所 Silicon-graphene battery negative electrode material and preparation method thereof, lithium battery
CN110993906A (en) * 2019-11-21 2020-04-10 浙江大学 Silicon-based lithium ion battery cathode material and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474632B (en) * 2012-06-07 2016-08-03 中国科学院物理研究所 A kind of negative material for lithium battery and its preparation method and application
CN105702942A (en) * 2016-01-22 2016-06-22 奇瑞汽车股份有限公司 Silicon-based negative electrode material and preparation method and application thereof
WO2018040542A1 (en) * 2016-08-30 2018-03-08 华为技术有限公司 Silicon-based composite negative electrode sheet and preparation method therefor, and lithium ion secondary battery
CN107799723A (en) * 2016-08-30 2018-03-13 华为技术有限公司 A kind of silicon substrate composite negative plate and preparation method thereof and lithium rechargeable battery
CN107482193A (en) * 2017-08-02 2017-12-15 合肥国轩高科动力能源有限公司 The silicon nanowires composite and preparation method that a kind of nano nickel particles and tantnickel nano-substance is modified jointly
CN110010864A (en) * 2019-03-21 2019-07-12 中国科学院半导体研究所 Silicon-graphene battery negative electrode material and preparation method thereof, lithium battery
CN110993906A (en) * 2019-11-21 2020-04-10 浙江大学 Silicon-based lithium ion battery cathode material and preparation method thereof

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