CN102738464A - Preparation method of lithium based compound - Google Patents

Preparation method of lithium based compound Download PDF

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CN102738464A
CN102738464A CN2012102246416A CN201210224641A CN102738464A CN 102738464 A CN102738464 A CN 102738464A CN 2012102246416 A CN2012102246416 A CN 2012102246416A CN 201210224641 A CN201210224641 A CN 201210224641A CN 102738464 A CN102738464 A CN 102738464A
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lithium
based compound
preparation
ball
ball milling
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刘永锋
马瑞军
潘洪革
贺燕萍
高明霞
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a lithium based compound, comprising the following steps of: carrying out one-time ball milling and mixing on the element M and LiH, heating the obtained mixture under vacuum or at the atmosphere of inert gas for hydrogen desorption, and carrying out secondary ball milling on the obtained hydrogen desorption product to obtain the lithium based compound. The element M is metal and nonmetal which can form a compound when being compounded with lithium. The preparation method of the lithium based compound has a simple process, is easy to operate, requires low cost, and has advantages of low energy consumption and no environmental pollution. The obtained lithium based compound has high yield and high purity, and each phase is uniformly distributed. The preparation method is easy to integrate with processes of sintering, carbon coating, alloyage and the like, thus saving production cost. As an anode material for lithium ion secondary cells, the obtained lithium based compound has advantages of high coulomb efficiency and good charge-discharge cycle stability.

Description

A kind of preparation method of lithium-based compound
Technical field
The present invention relates to ion secondary battery cathode material lithium, be specifically related to a kind of preparation method of lithium-based compound.
Background technology
Along with the fast development of human society, environment and energy problem become increasingly conspicuous, and the Conversion of energy memory technology and the energy utilization mode of new and effective cleaning become the key that addresses these problems, and help realizing the sustainable development of human society.
Lithium rechargeable battery is with its high-energy-density, strong retention of charge, wide operating temperature range, long circulation life and advantage such as environment friendly preferably; Be widely used in portable mobile electronic device field; Yet; Along with the miniaturization and the lightness of electronic equipment, to lithium rechargeable battery require increasingly high, simultaneously; Have good application development prospect based on lithium rechargeable battery in fields such as electric automobiles, develop focus and difficult point that the efficient lithium rechargeable battery material of new type of safe with high power capacity and long circulation life becomes present research.
In numerous ion secondary battery cathode material lithiums; The charge/discharge capacity of lithium-based compound Yin Qigao receives extensive concern; But the irreversible capacity first of lithium-based compound negative material is bigger, and simultaneously at embedding lithium/take off the bigger change in volume of experience in the lithium process, cyclical stability is relatively poor.With silicon is example, and its theoretical capacity is up to 4200mAh/g, yet forms Li by initial silicon embedding lithium 4Si 4Process in cubical expansivity surpass 300%, huge change in volume causes serious structural failure and the forfeiture that electrically contacts in the cyclic process, capacity is decayed rapidly, thereby makes that the cyclical stability of material is relatively poor.
Reduce embedding lithium/take off the particle efflorescence that volumetric expansion caused that lithium-based compound is huge in the lithium process and keep that the lithium-based compound good electrical contact is to improve the lithium-based compound performance in the cyclic process, make it to can be used for doing the key of ion secondary battery cathode material lithium.The part in advance lithium-based compound of embedding lithium has bigger initial volume because of it, greatly reduces at the volume change of circulation embedding lithium/take off in the lithium process, can suppress the particle efflorescence of material in cyclic process effectively, improves the capacity hold facility of material.With the silicon-based anode is example, if be unit volume with original amorphous silicon, and the Li of then original amorphous silicon, part embedding lithium attitude 12Si 7Li with the complete embedding lithium of room temperature attitude 15Si 4Volume be respectively 1,2.21 and 3.65, with Li 12Si 7For playing primary state, the maximum volume expansion rate of storage lithium process is 65%, and shrinkage is 55%, thereby the maximum volume expansion rate is reduced to 65% by 265%.
Because the fusing point (180.5 ℃) of lithium is significantly less than other metals, its saturated vapor pressure is higher under higher temperature simultaneously, adopts conventional high melt or sintering process to prepare very difficulty of lithium-based compound; Generally; The lithium-based compound preparation need be carried out at higher temperature (be higher than or near the fusing point of refractory metal), and complex steps, is usually directed to the interval annealing in process of a plurality of different temperatures; The lithium-based compound purity of preparation is also lower, and homogeneity of ingredients is poor.
In sum; Adopting lithium-based compound to replace metal simple-substance is the effective way of improving performance of lithium-ion secondary battery as ion secondary battery cathode material lithium; The lithium-based compound energy consumption is big, efficient is low, product purity is also lower yet conventional high-temperature melting or sintering process prepare; Therefore, the method for preparing the ion secondary battery cathode material lithium lithium-based compound that needs a kind of high-efficiency low energy consumption of exploitation.
Summary of the invention
The invention provides a kind of preparation method of lithium-based compound simple to operate, energy consumption is low, and environmentally safe can obtain highly purified lithium-based compound, is used as the ion secondary battery cathode material lithium of function admirable.
A kind of preparation method of lithium-based compound may further comprise the steps: with element M and ball mill mixing of LiH, the mixture that obtains heats under vacuum or inert gas atmosphere puts hydrogen, gained is put the hydrogen product carry out secondary ball milling, obtains lithium-based compound; Described element M is for forming the metal of compound and nonmetal with lithium.
With element M with carry out ball milling one time after LiH mixes according to certain mol proportion; The alloy phase that used mol ratio can form according to element M and LiH is formed and is decided; After element M was confirmed, based on the chemical valence of element M, the mol ratio of element M and LiH can be confirmed; If element M has different valence states, the different valence state of the mol ratio respective element M of element M and LiH is done respective change.
As preferably, described element M is Si, Ge, Sn, Pb, Mg, Al, Zn, P or Sb.Generally, use Si, Ge, Sn, Pb, Mg, Al, Zn, P or Sb and lithium to form lithium-based compound, reaction is easy to carry out.
As long as the ball milling method that can described element M and LiH be mixed all can, preferably, a said ball mill mixing is that planetary type ball-milling mixes or the oscillatory type ball mill mixing.
As preferably, the ratio of grinding media to material that said planetary type ball-milling mixes is 30 ~ 120:1, and rotational speed of ball-mill is 200 ~ 600 rev/mins, and the ball milling time is 1 ~ 10h.Than, rotational speed of ball-mill and ball milling in the time, can guarantee the efficient of grinding at said ball milling, give full play to the impact grinding effect of ball, element M that obtains mixing and LiH mixture; In like manner, the oscillatory type ball milling condition is carried out preferably, the ratio of grinding media to material of said oscillatory type ball mill mixing is 30 ~ 120:1, and vibration frequency is 1200 cycle per minute clocks, and the ball milling time is 10 ~ 60min.
Based on different element M, the element M of gained has different heating hydrogen discharging temperatures with the LiH mixture, and preferably, the heating-up temperature scope that hydrogen is put in said heating is 200 ~ 600 ℃.
Put steadily carrying out of hydrogen process in order to guarantee to heat, the rate of heat addition that hydrogen is put in said heating is 1 ~ 15 ℃/min.
Under inert gas atmosphere, grind, inert gas does not participate in heating the hydrogen process of putting, and improves degree of purity of production, and preferably, said inert gas is argon gas or nitrogen.
The hydrogen product of putting to element M and LiH mixture carries out secondary ball milling, and the crystal habit of putting the hydrogen product of element M and LiH mixture is changed, and preferably, said secondary ball milling is with stainless steel ball or zirconia ball.
In order to guarantee the effect of ball milling, preferably, the ratio of grinding media to material of said secondary ball milling is 20 ~ 60:1, and rotational speed of ball-mill is 350 ~ 600 rev/mins, and the ball milling time is 8 ~ 96h.
A kind of method for preparing lithium-based compound of the present invention has the following advantages:
1) preparation method's process is simple, and easy operating, cost are comparatively cheap, low energy consumption and non-environmental-pollution;
2) productive rate of gained lithium-based compound is high, and purity is high, and each evenly distributes mutually;
3) preparation method is easy to operations such as sintering, carbon coating, alloying integratedly, saves production cost;
4) the gained lithium-based compound has the coulombic efficiency height as ion secondary battery cathode material lithium, the advantage of charge and discharge cycles good stability.
Description of drawings
Fig. 1 is that the hydrogen desorption capacity of the 12LiH-7Si mixture in the embodiment of the invention 1 preparation process is with temperature variation curve and differential scanning calorimetric curve;
Fig. 2 is for putting the product Li behind the hydrogen in the embodiment of the invention 1 preparation process 12Si 7And secondary ball milling afterproduct amorphous Li 12Si 7X-ray diffraction spectrum;
The amorphous Li that Fig. 3 prepares for the embodiment of the invention 1 12Si 7Stereoscan photograph;
The amorphous Li that Fig. 4 prepares for the embodiment of the invention 1 12Si 7Change comparison diagram with the specific discharge capacity of crystalline silicon with period;
Fig. 5 is that the hydrogen desorption capacity of the 7Li-3Sn mixture in the embodiment of the invention 2 preparation processes is with temperature variation curve;
Fig. 6 is for putting the product crystal Li behind the hydrogen in the embodiment of the invention 2 preparation processes 7Sn 3And the nanocrystalline Li of secondary ball milling afterproduct 7Sn 3X-ray diffraction spectrum;
The nanocrystalline Li that Fig. 7 prepares for the embodiment of the invention 2 7Sn 3Change comparison diagram with the specific discharge capacity of simple substance Sn with period.
Embodiment
Embodiment 1
In the glove box of argon gas atmosphere, 12:7 takes by weighing LiH and Si sample in molar ratio, the ball grinder of packing into, and ratio of grinding media to material is 30:1, abrading-ball is a zirconia ball.The ball grinder that fills LiH and Si mixture is placed on the planetary ball mill,, obtains the 12LiH-7Si mixture with 300 rev/mins rotating speed ball mill mixing 10 hours.
Gained 12LiH-7Si mixture heated in vacuum atmosphere put hydrogen; Heating rate is 10 degrees celsius/minute, be warming up to 600 degrees centigrade after, be incubated 6 hours; At holding stage; Whenever system is vacuumized once, be cooled to room temperature then, obtain the 12LiH-7Si mixture and put the hydrogen product at a distance from 0.5 hour.
Fig. 1 is that the hydrogen desorption capacity of 12LiH-7Si mixture is with temperature variation curve and differential scanning calorimetric curve; As can be seen from Figure 1; The initial temperature of hydrogen discharge reaction is in 390 deg.c; Speed reaches maximum near 410 degrees centigrade, and the hydrogen desorption capacity that is warming up to 520 degrees centigrade of 12LiH-7Si mixtures is 3.89wt%, and hydrogen discharge reaction is an endothermic process.
In the glove box of argon gas atmosphere, gained 12LiH-7Si mixture is put the hydrogen product, the ball grinder of packing into is placed on and carries out secondary ball milling on the planetary ball mill, and abrading-ball is a zirconia ball, and ratio of grinding media to material is 20:1,48 hours ball milling time, obtains lithium-based compound amorphous Li 12Si 7Sample.
Fig. 2 is put the XRD of hydrogen product and secondary ball milling product thereof for the 12LiH-7Si mixture, and the result shows that the 12LiH-7Si mixture puts the hydrogen product for belonging to the Li of Pnma space group 12Si 7Crystal becomes amorphous Li behind secondary ball milling 12Si 7
Fig. 3 is the product amorphous Li behind the secondary ball milling 12Si 7Stereoscan photograph, stereoscan photograph shows, amorphous Li 12Si 7Be graininess, particle size is about 500nm.
Fig. 4 is the product amorphous Li behind the secondary ball milling 12Si 7Change comparison diagram with the specific discharge capacity of crystalline silicon with period, the result shows, amorphous Li 12Si 7Specific discharge capacity be greatly improved the big and good cycling stability of specific discharge capacity than crystalline silicon.
Embodiment 2
In the glove box of argon gas atmosphere, 7:3 takes by weighing LiH and Sn sample, the ball grinder of packing in molar ratio; Ratio of grinding media to material is 120:1, and abrading-ball is a stainless steel ball, with the ball grinder that LiH and Sn mixture are housed; Be placed in the oscillatory type ball mill; With the frequency of 1200 cycle per minute clocks, vibratory milling mixed 20 minutes, obtained the 7LiH-3Sn mixture.Gained 7LiH-3Sn mixture is taken out from the argon gas atmosphere glove box; Under nitrogen atmosphere, heat and put hydrogen, nitrogen flow is 30 ml/min; The rate of heat addition is 5 degrees celsius/minute; After being heated to 450 degrees centigrade, be incubated 12 hours, be cooled to room temperature then and obtain the 7LiH-3Sn mixture and put the hydrogen product.
Fig. 5 be the hydrogen desorption capacity of the 7LiH-3Sn mixture behind the ball milling with temperature variation curve, can find out that the hydrogen process of putting of system divided for three steps carried out, putting the hydrogen initial temperature is 190 degrees centigrade, when being heated to 400 degrees centigrade, hydrogen desorption capacity is about 1.62wt%.
In the argon gas atmosphere glove box, gained 7LiH-3Sn mixture is put the hydrogen product ball grinder of packing into, be placed on then and carry out secondary ball milling on the planetary ball mill; Abrading-ball is a stainless steel ball, and ratio of grinding media to material is 60:1, and rotating speed is 600 rev/mins; Ball milling 12 hours obtains the nanocrystalline Li of lithium-based compound 7Sn 3
Fig. 6 is put the XRD of hydrogen product and secondary ball milling product thereof for the 7LiH-3Sn mixture.As can be seen from the figure, the product of putting behind the hydrogen is mainly Li 7Sn 3Crystal, behind secondary ball milling, product crystal Li 7Sn 3The obvious nanometerization of crystallite dimension, crystal grain is along Li 7Sn 3(221) the normal direction preferred orientation of crystal face.
Fig. 7 is the nanocrystalline Li of present embodiment preparation 7Sn 3Change comparison diagram with the specific discharge capacity of simple substance Sn with period, as can be seen from the figure, nanocrystalline Li 7Sn 3, good cycling stability big than simple substance Sn specific discharge capacity.
Embodiment 3 ~ 14
Prepare lithium-based compound by embodiment 1 described preparation method, the ball of secondary ball milling can be stainless steel ball or zirconia ball, and the preparation condition difference is seen table 1.
Sample composition shows the mol ratio of element M and LiH in the table, 3LiH-Ge for example, and promptly the mol ratio of LiH and Ge is 3:1.
Table 1
Figure BDA00001818909000061
Figure BDA00001818909000071
Can know that by table 1 data adopt lithium-based compound preparation method of the present invention, preparation temperature reduces than smelting process greatly; Product purity is high, and productive rate is big, and the phase uniformity coefficient is good; It is good to store the lithium performance, and the discharge capacitance after 20 charge and discharge cycles obviously improves than simple substance.

Claims (10)

1. the preparation method of a lithium-based compound; It is characterized in that, may further comprise the steps: with element M and ball mill mixing of LiH, the mixture that obtains heats under vacuum or inert gas atmosphere puts hydrogen; Gained is put the hydrogen product carry out secondary ball milling, obtain lithium-based compound; Described element M is for forming the metal of compound and nonmetal with lithium.
2. the preparation method of lithium-based compound as claimed in claim 1 is characterized in that, described element M is Si, Ge, Sn, Pb, Mg, Al, Zn, P or Sb.
3. the preparation method of lithium-based compound as claimed in claim 2 is characterized in that, a said ball mill mixing is that planetary type ball-milling mixes or the oscillatory type ball mill mixing.
4. the preparation method of lithium-based compound as claimed in claim 3 is characterized in that, the ratio of grinding media to material that said planetary type ball-milling mixes is 30 ~ 120:1, and rotational speed of ball-mill is 200 ~ 600 rev/mins, and the ball milling time is 1 ~ 10h.
5. the preparation method of lithium-based compound as claimed in claim 3 is characterized in that, the ratio of grinding media to material of said oscillatory type ball mill mixing is 30 ~ 120:1, and vibration frequency is 1200 cycle per minute clocks, and the ball milling time is 10 ~ 60min.
6. like the preparation method of claim 4 or 5 described lithium-based compounds, it is characterized in that the heating-up temperature scope that hydrogen is put in said heating is 200 ~ 600 ℃.
7. the preparation method of lithium-based compound as claimed in claim 6 is characterized in that, the rate of heat addition that hydrogen is put in said heating is 1 ~ 15 ℃/min.
8. the preparation method of lithium-based compound as claimed in claim 7 is characterized in that, said inert gas is argon gas or nitrogen.
9. the preparation method of lithium-based compound as claimed in claim 8 is characterized in that, said secondary ball milling is with stainless steel ball or zirconia ball.
10. the preparation method of lithium-based compound as claimed in claim 9 is characterized in that, the ratio of grinding media to material of said secondary ball milling is 20 ~ 60:1, and rotational speed of ball-mill is 350 ~ 600 rev/mins, and the ball milling time is 8 ~ 96h.
CN2012102246416A 2012-06-28 2012-06-28 Preparation method of lithium based compound Pending CN102738464A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103258992A (en) * 2013-04-28 2013-08-21 浙江大学 Preparation method for lithium-ion battery cathode material with high initial coulomb efficiency
CN108134059A (en) * 2017-12-20 2018-06-08 成都新柯力化工科技有限公司 A kind of negative electrode active material and preparation method for low temperature lithium battery
CN111564628A (en) * 2019-02-13 2020-08-21 通用汽车环球科技运作有限责任公司 Method of prelithiating an electroactive material and electrode comprising prelithiated electroactive material
CN114784279A (en) * 2022-04-25 2022-07-22 安徽工业大学 Preparation method of silicon-based negative electrode material of lithium ion battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1958823A (en) * 2006-11-17 2007-05-09 中国科学院上海微系统与信息技术研究所 Magnesium based alloy of storing up hydrogen with Li based hydride being added

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1958823A (en) * 2006-11-17 2007-05-09 中国科学院上海微系统与信息技术研究所 Magnesium based alloy of storing up hydrogen with Li based hydride being added

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. J. VAJO等: ""Altering Hydrogen Storage Properties by Hydride Destabilization through Alloy Formation: LiH and MgH2 Destabilized with Si"", 《THE JOURNAL OF PHYSICAL CHEMISTRY B》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103258992A (en) * 2013-04-28 2013-08-21 浙江大学 Preparation method for lithium-ion battery cathode material with high initial coulomb efficiency
CN103258992B (en) * 2013-04-28 2016-02-24 浙江大学 The preparation method of the lithium ion battery negative material that a kind of initial coulomb efficiency is high
CN108134059A (en) * 2017-12-20 2018-06-08 成都新柯力化工科技有限公司 A kind of negative electrode active material and preparation method for low temperature lithium battery
CN111564628A (en) * 2019-02-13 2020-08-21 通用汽车环球科技运作有限责任公司 Method of prelithiating an electroactive material and electrode comprising prelithiated electroactive material
CN114784279A (en) * 2022-04-25 2022-07-22 安徽工业大学 Preparation method of silicon-based negative electrode material of lithium ion battery

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Application publication date: 20121017