CN102699334B - Preparation method of nanocrystal lithium-rich single-phase Li-Si compound block material - Google Patents
Preparation method of nanocrystal lithium-rich single-phase Li-Si compound block material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nanocrystal lithium-rich single-phase Li-Si compound block material, belonging to the technical field of nanometer functional materials. The preparation method comprises the steps of: firstly weighing certain quantity of Li and Si according to target components and preparing a LixSi alloy ingot by utilizing a discharge plasma sintering technology; crushing the alloy ingot into powder and then ball-milling to obtain alloy powder in an amorphous structure; and finally sintering-molding the amorphous powder rapidly by utilizing the discharge plasma sintering technology to obtain a single-phase LixSi nanocrystal block material. The preparation method of the nanocrystal lithium-rich single-phase Li-Si compound block material, disclosed by the invention, has the advantages of pure phase, fine crystal particles, high density, simple and practicable process route and short synthetic cycle.
Description
Technical field
The preparation method of the single-phase Li-Si compound of a kind of nanocrystalline rich lithium block materials, belong to the nano-functional material technical field.
Background technology
The first choice in the rechargeable source that lithium ion battery is high with its capacitance, have extended cycle life, the cost performance advantages of higher becomes portable type electronic product.In the evolution of lithium ion battery, the exploitation of negative material occupies critical role, and its characteristic directly affects the performance of lithium ion battery, and can become the bottleneck that the restriction lithium ion battery is applied on a large scale.Therefore, development and design has the Novel cathode material for lithium ion battery of good charge and discharge performance, is the emphasis of battery industry area research and development.
In lithium ion battery, the negative material of research mainly comprises: (Wu Yuping, Zhang Hanping etc., " the green power supply materials " such as graphitized carbon material, silica-base material, tin-based material, nitride, alloy material and nano-oxide, Beijing Chemical Industry Press, 2008).The theoretical lithium storage content (reaching 4200mAh/g) that silica-base material is very high because Si has becomes the study hotspot of negative material.Yet silicon based anode material large Volume Changes in charge and discharge process can cause the negative material efflorescence to be lost efficacy, and seriously reduces the cycle performance of lithium ion battery.It is the effective way that improves lithium ion battery negative material chemical property (as capacitance, cycle performance etc.) that the anticathode material carries out nano-structured.Because silicon based anode material in lithium ion battery can form Li with lithium ion generation reciprocation in charge and discharge process
xThereby the Si compound directly affects the chemical property of lithium ion battery, therefore be starved of the Li of research nanocrystalline structure
xThe Si alloy is understood the embedding lithium of lithium ion battery nanocrystalline negative material in charge and discharge process/de-lithium effect with deep, thereby the lithium ion battery nanocrystalline negative material of important application potentiality is prepared in design.
Li-Si alloy character is very active, can chemical reaction occur with airborne moisture, oxygen, nitrogen and carbon dioxide etc., in humid air, spontaneous combustion can occur.Therefore, at present very limited about the technology of preparing of the Li-Si alloy of pure phase, and have no report about the preparation method of the Li-Si alloy of nanostructured.Based on above background, we have developed even, the pure single-phase nanocrystalline rich lithium type Li of composition for the rich lithium type Li-Si alloy that has the maximum chemical activity in the Li-Si alloy
xThe technology of preparing of Si alloy.
Summary of the invention
The object of the invention is to solve the difficulty of the pure Li-Si alloy preparation method of current high chemism, nanostructured and phase, and the preparation method of the single-phase Li-Si compound of a kind of nanocrystalline rich lithium block materials is provided.In the present invention, the target component of rich lithium type Li-Si compound refers to according to chemical formula Li
xSi(2.3≤x≤4.4) atom ratio in and the composition that designs (also available Li
mSi
nMean, as long as ratio meets).At first take Li and the Si of certain mass according to target component, utilize discharge plasma sintering technique to prepare Li
xThe Si alloy cast ingot.Alloy cast ingot is broken for to powder, then ball milling obtains the alloy powder of non crystalline structure.Finally utilize discharge plasma sintering technique by the moulding of amorphous powder Fast Sintering, obtain single-phase Li
xThe Si bulk nanometer material.
The preparation method of the single-phase Li-Si compound of a kind of nanocrystalline rich lithium provided by the invention block materials, is characterized in that, specifically comprises the following steps:
(1) raw material is used commercially available Li sheet and Si powder, according to x:1(2.3≤x≤4.4) mol ratio take Li sheet and the Si powder of respective quality, take on the basis of quality add mass percent 3%-5% the Li sheet for compensating the loss of preparation process Li, the mould that the carbide alloy of take is made is container, (preferred ambient oxygen content<0.3ppm in being full of the glove box of argon gas, water content<0.1ppm, down together) mould of first part Si powder being packed into makes it to cover the mould bottom surface, then one deck Li sheet of packing into, again according to Si/Li/Si/Li ... the mode charging feedstock that the order multilayer of/Si is alternately arranged, and the edge that makes all Li sheets does not contact the inwall of mould, and the top one deck of raw material is the Si powder, send in discharging plasma sintering equipment and add hot smelting after raw material in mould is colded pressing, technological parameter is: vacuum condition, and normal pressure, holding temperature is 200-600 ℃, and temperature retention time is 20-40min, and preparing composition is Li
xthe alloy cast ingot of Si,
(2) in being full of the glove box of argon gas by Li
xThe Si alloy cast ingot is broken into powder, according to the ball material mass ratio of 60:1, packs in ball grinder, and rotational speed of ball-mill is 400-700r/min, and Ball-milling Time is 12-20 hour, obtains the Li of non crystalline structure
xThe Si alloy powder;
(3) in being full of the glove box of argon gas by the Li of non crystalline structure
xSi alloy powder pack into sintered-carbide die pre-molding, put into subsequently discharging plasma sintering equipment and carry out sintering densification, adopt following sintering process parameter: pressure is 200-400MPa, the final state sintering temperature is 180-350 ℃, be incubated 2-5min after reaching the final state sintering temperature, prepare nanocrystalline single-phase Li
xSi compound block materials.
In step (1), the Li that to add mass percent during blanking be 3%-5% can make up the volatilization loss of a small amount of Li in preparation process, thereby ensures that in the alloy of preparation Li and Si keep the stoichiometric proportion of initial designs.The mould that the carbide alloy of take is made as container be to utilize its chemical stability to ensure that raw material does not react with container inner wall.Operation in the glove box that is full of argon gas of ambient oxygen content<0.3ppm, water content<0.1ppm is to ensure in order to prevent from introducing impurity in raw material the purity for preparing material.The mode that adopts multilayer alternately to arrange Si powder and Li sheet is placed and colds pressing, thereby is in order to make Li sheet and Si powder have maximum contact area to be conducive to diffusion reaction fast and carry out fully; Make the edge of all Li sheets not contact the inwall of mould, be in the particularity assurance fusion process of rich lithium alloy, after the Li fusing, along mould inner wall, not flowing and cause the insufficient alloy cast ingot that can not get even composition of local reaction, thereby also for the contact area that reduces Li and environment, reduce the probability of introducing impurity simultaneously.In adding the process of hot smelting, adopting not pressurized conditions is to prevent from being extruded because of pressurized the rich lithium composition that causes the alloy cast ingot off-design after the Li fusing.Under design temperature, insulation is in order to ensure that the reaction between Li and Si carries out fully, the Li that the acquisition composition is even, phase is single
xThe Si alloy cast ingot.
In step (2), according to the heterogeneity proportioning of alloy, Ball-milling Time and rotational speed of ball-mill are adjusted, thereby prepared the alloy powder of non crystalline structure under high-effect condition.
In step (3), pressure and final state sintering temperature are mutually to mate, elevated pressures adopts lower sintering temperature, vice versa, this is because adopt lower sintering temperature can reach densified under larger pressure, and if under larger pressure, adopt higher sintering temperature easily cause alloy in grain growth and can't obtain nanometer crystal microstructure.
The object of the invention is to solve the single-phase Li of rich lithium
xThe technology of preparing difficult problem of Si nanocrystalline alloy block material, and the technology of preparing that a kind of phase is pure, crystal grain is tiny, density is high, process route is simple, synthesis cycle is short provided.The present invention has following features and advantage:
(1) method of the existing Li-Si of preparation coarse-grain alloy has high melt method, electrochemical deposition method etc., due to rich lithium type Li
xThe chemical property of Si alloy is very active, and existing preparation method is difficult to guarantee the purity of the final alloy obtained, the especially extremely difficult rich lithium type alloy block material that obtains single phase.The present invention is directed to rich lithium type Li
xThe characteristic of Si alloy, all operations in the glove box that is full of argon gas of ambient oxygen content<0.3ppm, water content<0.1ppm of the preparation whole process from the coarse-grain alloy cast ingot to bulk nanometer material, guarantee the nanocrystalline Li finally obtained
xThe Si alloy has pure single phase, and free from admixture is introduced.
(2) in step (1), the discharge plasma sintering system is used as to smelting apparatus, utilize its Fast Heating, high vacuum, the advantage such as cooling fast, in conjunction with the Si powder with the Li sheet is successively alternately placed and the technical scheme of pre-molding, guarantee rich lithium type Li prepared by melting
xSi alloy cast ingot composition evenly, react completely and correctly become phase.
(3) so far both at home and abroad about the single-phase Li of nanocrystalline rich lithium
xThe technology of preparing of Si alloy block material there is no report.The present invention at first in the discharge plasma sintering system melting prepare the Li of coarse-grain
xThe Si alloy cast ingot, the ball-milling technology of recycling under argon shield prepares amorphous powder, determines the crystallization behavior feature of amorphous powder by the differential thermal analysis experimental study, with the single Li of formulations optimum
xThe preparation technology of the nanocrystalline alloy block material of Si phase, finally obtain rich lithium single-phase nano crystalline Li
xThe Si alloy block material.
Technical scheme of the present invention can realize the preparation of highly active rich lithium composition Li-Si compound-material, can guarantee again to obtain pure single phase and the grain structure of nanoscale.Above-mentioned technique effect is referring to embodiments of the invention and accompanying drawing.
The accompanying drawing explanation
The coarse-grain Li of Fig. 1 embodiment 1 preparation
7Si
3Alloy cast ingot and nanocrystalline Li
7Si
3The X ray diffracting spectrum of compound block materials;
The coarse-grain Li of Fig. 2 embodiment 2 preparations
7Si
3Alloy cast ingot and nanocrystalline Li
7Si
3The X ray diffracting spectrum of compound block materials;
The coarse-grain Li of Fig. 3 embodiment 4 preparations
22Si
5Alloy cast ingot and nanocrystalline Li
22Si
5The X ray diffracting spectrum of compound block materials.
The specific embodiment
All embodiment Raw Li sheets are purchased from Tianjin China Energy Lithium Co., Ltd., and purity is 99.9%, is of a size of Φ 18.5 * 1.05mm; The Si powder is purchased from Beijing chemical reagent factory, and purity is 99.9%, and granularity is 300 orders.
Embodiment 1
(1) with nanocrystalline single-phase Li
7Si
3The compound block materials is the final goal material.According to 2.3:1(x=2.3) atomic ratio take Li sheet and the Si powder of respective quality, extra add take the Li tablet quality 3% Li sheet for compensating the loss of preparation process Li.The mould that the carbide alloy of take is made is container, (ambient oxygen content<0.3ppm in being full of the glove box of argon gas, water content<0.1ppm, down together) mould of first a small amount of Si powder being packed into makes it to cover the mould bottom surface, then one deck Li sheet of packing into, again according to Si/Li/Si/Li ... the mode charging feedstock that the order multilayer of/Si is alternately arranged, and make the edge of all Li sheets not contact the inwall of mould, and the top one deck of raw material is the Si powder.Send in discharging plasma sintering equipment and add hot smelting after raw material in mould is colded pressing, technological parameter is: vacuum condition, not pressurize, and holding temperature is 500 ℃, and temperature retention time is 30min, and preparing composition is Li
7Si
3Alloy cast ingot.
(2) in being full of the glove box of argon gas by Li
7Si
3Alloy cast ingot is broken into powder, according to the ball material mass ratio of 60:1, packs in ball grinder, and rotational speed of ball-mill is 500r/min, and Ball-milling Time is 16 hours, obtains the Li of non crystalline structure
xThe Si alloy powder.
(3) in being full of the glove box of argon gas by the Li of non crystalline structure
7Si
3Alloy powder pack into sintered-carbide die pre-molding, put into subsequently discharging plasma sintering equipment and carry out sintering densification, adopt following sintering process parameter: pressure is 300MPa, the final state sintering temperature is 240 ℃, be incubated 3min after reaching the final state sintering temperature, prepare nanocrystalline single-phase Li
7Si
3The compound block materials.
Coarse-grain Li prepared by the present embodiment
7Si
3Alloy cast ingot and nanocrystalline Li
7Si
3The X ray diffracting spectrum of alloy block material is shown in Fig. 1.From test result, the alloy block material finally obtained is single-phase Li
7Si
3The compound block materials, its average grain size is about 15nm.
Embodiment 2
(1) with nanocrystalline single-phase Li
7Si
3The compound block materials is the final goal material.According to 2.3:1(x=2.3) atomic ratio take Li sheet and the Si powder of respective quality, extra add take the Li tablet quality 4% Li sheet for compensating the loss of preparation process Li.The mould that the carbide alloy of take is made is container, (ambient oxygen content<0.3ppm in being full of the glove box of argon gas, water content<0.1ppm, down together) mould of first a small amount of Si powder being packed into makes it to cover the mould bottom surface, then one deck Li sheet of packing into, again according to Si/Li/Si/Li ... the mode charging feedstock that the order multilayer of/Si is alternately arranged, and make the edge of all Li sheets not contact the inwall of mould, and the top one deck of raw material is the Si powder.Send in discharging plasma sintering equipment and add hot smelting after raw material in mould is colded pressing, technological parameter is: vacuum condition, not pressurize, and holding temperature is 600 ℃, and temperature retention time is 20min, and preparing composition is Li
7Si
3Alloy cast ingot.
(2) in being full of the glove box of argon gas by Li
7Si
3Alloy cast ingot is broken into powder, according to the ball material mass ratio of 60:1, packs in ball grinder, and rotational speed of ball-mill is 700r/min, and Ball-milling Time is 12 hours, obtains the Li of non crystalline structure
7Si
3Alloy powder.
(3) in being full of the glove box of argon gas by the Li of non crystalline structure
7Si
3Alloy powder pack into sintered-carbide die pre-molding, put into subsequently discharging plasma sintering equipment and carry out sintering densification, adopt following sintering process parameter: pressure is 200MPa, the final state sintering temperature is 350 ℃, be incubated 2min after reaching the final state sintering temperature, prepare nanocrystalline single-phase Li
7Si
3The compound block materials.
Nanocrystalline Li prepared by the present embodiment
7Si
3The X ray diffracting spectrum of alloy block material is shown in Fig. 2.From test result, the alloy block material finally obtained is single-phase Li
7Si
3The compound block materials, its average grain size is about 45nm.
Embodiment 3
(1) with nanocrystalline single-phase Li
13Si
4The compound block materials is the final goal material.According to 3.3:1(x=3.3) atomic ratio take Li sheet and the Si powder of respective quality, extra add take the Li tablet quality 4% Li sheet for compensating the loss of preparation process Li.The mould that the carbide alloy of take is made is container, (ambient oxygen content<0.3ppm in being full of the glove box of argon gas, water content<0.1ppm, down together) mould of first a small amount of Si powder being packed into makes it to cover the mould bottom surface, then one deck Li sheet of packing into, again according to Si/Li/Si/Li ... the mode charging feedstock that the order multilayer of/Si is alternately arranged, and make the edge of all Li sheets not contact the inwall of mould, and the top one deck of raw material is the Si powder.Send in discharging plasma sintering equipment and add hot smelting after raw material in mould is colded pressing, technological parameter is: vacuum condition, not pressurize, and holding temperature is 500 ℃, and temperature retention time is 30min, and preparing composition is Li
13Si
4Alloy cast ingot.
(2) in being full of the glove box of argon gas by Li
13Si
4Alloy cast ingot is broken into powder, according to the ball material mass ratio of 60:1, packs in ball grinder, and rotational speed of ball-mill is 500r/min, and Ball-milling Time is 16 hours, obtains the Li of non crystalline structure
13Si
4Alloy powder.
(3) in being full of the glove box of argon gas by the Li of non crystalline structure
13Si
4Alloy powder pack into sintered-carbide die pre-molding, put into subsequently discharging plasma sintering equipment and carry out sintering densification, adopt following sintering process parameter: pressure is 300MPa, the final state sintering temperature is 200 ℃, be incubated 3min after reaching the final state sintering temperature, prepare nanocrystalline single-phase Li
13Si
4The compound block materials.
Embodiment 4
(1) with nanocrystalline single-phase Li
22Si
5The compound block materials is the final goal material.According to 4.4:1(x=4.4) atomic ratio take Li sheet and the Si powder of respective quality, extra add take the Li tablet quality 5% Li sheet for compensating the loss of preparation process Li.The mould that the carbide alloy of take is made is container, (ambient oxygen content<0.3ppm in being full of the glove box of argon gas, water content<0.1ppm, down together) mould of first a small amount of Si powder being packed into makes it to cover the mould bottom surface, then one deck Li sheet of packing into, again according to Si/Li/Si/Li ... the mode charging feedstock that the order multilayer of/Si is alternately arranged, and make the edge of all Li sheets not contact the inwall of mould, and the top one deck of raw material is the Si powder.Send in discharging plasma sintering equipment and add hot smelting after raw material in mould is colded pressing, technological parameter is: vacuum condition, not pressurize, and holding temperature is 200 ℃, and temperature retention time is 40min, and preparing composition is Li
22Si
5Alloy cast ingot.
(2) in being full of the glove box of argon gas by Li
22Si
5Alloy cast ingot is broken into powder, according to the ball material mass ratio of 60:1, packs in ball grinder, and rotational speed of ball-mill is 400r/min, and Ball-milling Time is 20 hours, obtains the Li of non crystalline structure
22Si
5Alloy powder.
(3) in being full of the glove box of argon gas by the Li of non crystalline structure
22Si
5Alloy powder pack into sintered-carbide die pre-molding, put into subsequently discharging plasma sintering equipment and carry out sintering densification, adopt following sintering process parameter: pressure is 400MPa, the final state sintering temperature is 180 ℃, be incubated 5min after reaching the final state sintering temperature, prepare nanocrystalline single-phase Li
22Si
5The compound block materials.
Nanocrystalline Li prepared by the present embodiment
22Si
5The X ray diffracting spectrum of alloy block material is shown in Fig. 3.From test result, the alloy block material finally obtained is single-phase Li
22Si
5The compound block materials, its average grain size is about 10nm.
Claims (3)
1. the preparation method of the single-phase Li-Si compound of a nanocrystalline rich lithium block materials, is characterized in that, specifically comprises the following steps:
(1) raw material is used commercially available Li sheet and Si powder, take Li sheet and the Si powder of respective quality according to the mol ratio of x:1, 2.3≤x≤4.4, take on the basis of quality add mass percent 3%-5% the Li sheet for compensating the loss of preparation process Li, the mould that the carbide alloy of take is made is container, the mould of first part Si powder being packed in being full of the glove box of argon gas makes it to cover the mould bottom surface, then one deck Li sheet of packing into, again according to Si/Li/Si/Li ... the mode charging feedstock that the order multilayer of/Si is alternately arranged, and the edge that makes all Li sheets does not contact the inwall of mould, and the top one deck of raw material is the Si powder, send in discharging plasma sintering equipment and add hot smelting after raw material in mould is colded pressing, technological parameter is: vacuum condition, and normal pressure, holding temperature is 200-600 ℃, and temperature retention time is 20-40min, and preparing composition is Li
xthe alloy cast ingot of Si,
(2) in being full of the glove box of argon gas by Li
xThe Si alloy cast ingot is broken into powder, according to the ball material mass ratio of 60:1, packs in ball grinder, and rotational speed of ball-mill is 400-700r/min, and Ball-milling Time is 12-20 hour, obtains the Li of non crystalline structure
xThe Si alloy powder;
(3) in being full of the glove box of argon gas by the Li of non crystalline structure
xSi alloy powder pack into sintered-carbide die pre-molding, put into subsequently discharging plasma sintering equipment and carry out sintering densification, adopt following sintering process parameter: pressure is 200-400MPa, the final state sintering temperature is 180-350 ℃, be incubated 2-5min after reaching the final state sintering temperature, prepare nanocrystalline single-phase Li
xSi compound block materials.
2. according to the method for claim 1, it is characterized in that ambient oxygen content<0.3ppm in glove box, water content<0.1ppm.
3. according to the method for claim 1, it is characterized in that, in step (3), pressure and final state sintering temperature are mutually to mate, and elevated pressures adopts lower sintering temperature, and lower pressure adopts higher sintering temperature.
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| CN105720249B (en) * | 2016-02-22 | 2018-03-13 | 北京工业大学 | A kind of preparation method of Sn Si alloy-type nano composite powders |
| CN106799497A (en) * | 2017-02-15 | 2017-06-06 | 中卫市创科知识产权投资有限公司 | A kind of nanometer Li-Si Alloy Powder production technology |
| WO2018183909A1 (en) | 2017-03-31 | 2018-10-04 | Kratos LLC | Precharged negative electrode material for secondary battery |
| CN108306002B (en) * | 2018-01-19 | 2020-04-03 | 北京工业大学 | Li applied to negative electrode of lithium ion battery21Si5Preparation of graphene composite material |
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