CN102769125A - Alkaline-earth metal silicide preparation method - Google Patents
Alkaline-earth metal silicide preparation method Download PDFInfo
- Publication number
- CN102769125A CN102769125A CN2012102359787A CN201210235978A CN102769125A CN 102769125 A CN102769125 A CN 102769125A CN 2012102359787 A CN2012102359787 A CN 2012102359787A CN 201210235978 A CN201210235978 A CN 201210235978A CN 102769125 A CN102769125 A CN 102769125A
- Authority
- CN
- China
- Prior art keywords
- earth metal
- alkaline earth
- metal silicide
- preparation
- alkaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an alkaline-earth metal silicide preparation method. The preparation method comprises the following steps: achieving ball-milling mixing of alkaline-earth metal hydride and silicon, heating the obtained mixture in a vacuum or inert gas atmosphere to release hydrogen, and then cooling to the room temperature to obtain the alkaline-earth metal silicide. The alkaline-earth metal silicide preparation method has the advantages of simple process, easiness in operation, lower cost, low energy consumption and no environmental pollution; hydrogen used in the method can be recycled, so that the cost is saved; the alkaline-earth metal silicide obtained by adopting the method has high productivity, high purity and good phase homogeneous degree; and when serving as the anode material of a lithium ion secondary battery, the alkaline-earth metal silicide has high coulombic efficiency and good charge-discharge circulating stability.
Description
Technical field
The present invention relates to a kind of ion secondary battery cathode material lithium, be specifically related to a kind of preparation method of alkaline earth metal silicide.
Background technology
Along with the fast development of human society, environment and energy problem become increasingly conspicuous, and for realizing the sustainable development of human society, need the Conversion of energy and the memory by using mode of development of new high-efficiency cleaning.
Lithium ion battery is widely used in portable mobile electronic device field, electric tool, energy storage device, electric motor car and field of hybrid electric vehicles owing to have advantages such as high workload current potential, high-energy-density density, high-specific-power, wide operating temperature range, long circulation life and environment friendly.Yet; Miniaturization and lightness along with electronic equipment; To lithium rechargeable battery require increasingly high; Simultaneously, have good application development prospect 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 based on lithium rechargeable battery.
In numerous negative materials; Silica-base material has bright development prospect; But elemental silicon can meet with huge volumetric expansion (surpassing 300% under the embedding lithium state fully) in embedding lithium process, and serious efflorescence appears in material in cyclic process; Electrical contact performance constantly worsens, and causes its capacity to fail rapidly.Adopt the compound of silicon to replace silicon to make lithium ion secondary battery negative pole, can effectively reduce the volumetric expansion of system, alleviate the efflorescence of silicon-based anode in charge and discharge cycles, thereby effectively improved the cyclical stability of silicon-based anode material.
In recent years, alkaline earth metal silicide has caused people's extensive concern as a kind of ion secondary battery cathode material lithium.On the one hand, Mg2Si can at room temperature realize reversible electrochemical storage lithium, and its electrochemistry capacitance can reach 1370 MAH/grams, and in storing the lithium process, has the unit cell volume expansion rate littler than elemental silicon; On the other hand, alkali earth metal content in the earth's crust is abundant, and it produces on a large scale, use and not limited by resource reserve; Relative low price; Therefore, utilize alkaline earth metal silicide to do ion secondary battery cathode material lithium, significant for the reply energy crisis.
At present, the preparation method of alkaline earth metal silicide mainly contains three kinds: smelting process, machine-alloying and powder metallurgic method, and these preparation methods are defectiveness; At first; The fusing point of alkaline-earth metal, particularly Mg and Ca and Si differ bigger, and high smelting temperature can cause the volatilization loss of Mg or Ca and the carbonization of Si; Cause the phase homogeneity of product poor, crystal grain is thick; Secondly, in the mechanical alloy method, long-time ball milling is prone to introduce impurity phases such as Fe, and the purity of products therefrom is low; Once more, powder metallurgy process is because temperature is higher in the preparation process, temperature retention time is longer, also faces sample oxidation and carbonization problem.
Therefore, need exploitation a kind of with low cost, the preparation method is simple, the alkaline earth metal silicide preparation method of productive rate height and controllable components.
Summary of the invention
The invention provides a kind of simple to operate, the preparation method of the alkaline earth metal silicide that controllability is strong, energy consumption is low, environmentally safe, productive rate is high, the alkaline earth metal silicide purity for preparing is high, can be used as ion secondary battery cathode material lithium.
A kind of preparation method of alkaline earth metal silicide may further comprise the steps: alkaline earth metal hydride and silicon are carried out ball mill mixing, the gained mixture is heated under vacuum or inert gas atmosphere put hydrogen, be cooled to room temperature, obtain alkaline earth metal silicide.
With alkaline earth metal hydride with carry out ball milling after silicon mixes with certain mol proportion; The alloy phase that used mol ratio can form according to alkaline earth metal hydride and silicon is formed and is decided; Because the difference of alkaline earth metal atom radius; Ligancy when forming crystal structure with silicon is different, and the mol ratio that can select also can be different.
Can the ball milling method that alkaline earth metal hydride and silicon mix all can be selected for use, preferably, said ball milling is planetary type ball-milling or oscillatory type ball milling.
As preferably, the ratio of grinding media to material of said planetary type ball-milling is 30～120: 1, and rotational speed of ball-mill is 200～600r/min, 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, the alkaline earth metal hydride that obtains mixing and the mixture of silicon; 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 milling is 30～120: 1, and vibration frequency is 1200 cycle per minute clocks, and the ball milling time is 10～60min.
Put steadily carrying out of hydrogen process in order to guarantee to heat, preferably, the rate of heat addition that hydrogen is put in said heating is 1～15 ℃/min.
Based on different alkaline earth metal silicides, the heating hydrogen discharging temperature is different, and in order to guarantee suitable hydrogen discharging rate, the heating-up temperature that hydrogen is put in said heating is 200～600 ℃.
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 said inert gas is argon gas or nitrogen.
Alkaline earth metal hydride all can with the silicon mixing and ball milling after, put hydrogen through heating, the preparation alkaline earth metal silicide; But different alkaline earth metal hydrides is different with the complexity of pasc reaction; Preferably, said alkaline earth metal hydride is a magnesium hydride, and the mol ratio of said magnesium hydride and silicon is 0.5～4: 1.In this ratio, the productive rate that said magnesium hydride and silicon form alkaline earth metal silicide is the highest, exceeds this proportion, has partial hydrogenation magnesium or silicon and can not form alkaline earth metal silicide, causes raw material availability to reduce; In like manner, as preferably, said alkaline earth metal hydride is a calcium hydride, and the mol ratio of said calcium hydride and silicon is 0.5～9: 1.
The preparation method of alkaline earth metal silicide of the present invention has the following advantages:
(1) preparation method's process is simple, and easy operating, cost are comparatively cheap, the low and non-environmental-pollution of energy consumption, and used hydrogen reusable edible in the method is practiced thrift cost;
(2) productive rate of gained alkaline earth metal silicide is high, and purity is high, the phase good evenness;
(3) the gained alkaline earth metal silicide is as ion secondary battery cathode material lithium, and coulombic efficiency is high, the charge and discharge cycles good stability.
Description of drawings
Fig. 1 is the 2MgH behind the embodiment of the invention 1 ball milling
2The hydrogen desorption capacity of-Si mixture is with temperature changing curve diagram;
Fig. 2 is 2MgH in the embodiment of the invention 2
2The XRD figure (X-ray diffractogram) of hydrogen afterproduct is put in the heating of-Si mixture;
Fig. 3 is 2MgH in the embodiment of the invention 3
2The stereoscan photograph of hydrogen afterproduct is put in the heating of-Si mixture;
The Mg that Fig. 4 prepares for the embodiment of the invention 4
2The curve that Si sample charging matter specific capacity (being gram volume) and discharge matter specific capacity change with period;
The CaH that Fig. 5 prepares for the embodiment of the invention 6
2-2Si mixture is put the XRD figure of hydrogen products therefrom;
The CaSi that Fig. 6 prepares for the embodiment of the invention 6
2The curve chart that sample changes with discharge capacity as 5 discharge potentials of ion secondary battery cathode material lithium circulation.
Embodiment
In the glove box of argon gas atmosphere, took by weighing MgH in 2: 1 in molar ratio
2With Si sample, the ball grinder of packing into, ratio of grinding media to material is 60: 1, and abrading-ball is a stainless steel ball, will fill MgH
2Be placed on the planetary ball mill with the ball grinder of Si mixture,, obtain 2MgH with 300 rev/mins rotating speed ball millings 8 hours
2-Si mixture.With 2MgH
2-Si mixture heats in a vacuum puts hydrogen, and the rate of heat addition is 2 degrees celsius/minute, is heated to after temperature rises to 400 degrees centigrade; Be incubated 4 hours and system is vacuumized; The cold room temperature that is cooled to of stove is taken out the gained sample from the glove box of argon gas atmosphere then, obtains Mg
2The Si sample.
Fig. 1 is the 2MgH behind the ball milling
2The hydrogen desorption capacity of-Si mixture is with temperature changing curve diagram, and as can be seen from the figure, the initial temperature of hydrogen discharge reaction is in 200 deg.c, and hydrogen is put in beginning fast near 280 degrees centigrade, is warming up to 400 degrees centigrade of insulation 2MgH
2(quality that is releasing hydrogen gas accounts for 2MgH to the hydrogen desorption capacity of-Si mixture
2The percentage of-Si mixture quality) be 4.68wt%.
In the glove box of argon gas atmosphere, took by weighing MgH in 2: 1 in molar ratio
2With Si sample, the ball grinder of packing into, ratio of grinding media to material is 90: 1, and abrading-ball is a zirconia ball, will fill MgH
2Be placed on the planetary ball mill with the ball grinder of Si mixture,, obtain 2MgH with 400 rev/mins rotating speed ball millings 4 hours
2-Si mixture.With 2MgH
2-Si mixture heats in a vacuum puts hydrogen, and the rate of heat addition is 10 degrees celsius/minute, is heated to after temperature rises to 400 degrees centigrade; Be incubated 4 hours and system is vacuumized; The cold room temperature that is cooled to of stove is taken out the gained sample from the glove box of argon gas atmosphere then, obtains Mg
2The Si sample.
Fig. 2 is 2MgH
2The XRD figure (X-ray diffractogram) of hydrogen afterproduct is put in the heating of-Si mixture, as can be seen from the figure, puts the Mg that the hydrogen product is the Fm-3m space group
2The Si crystal, product degree of crystallinity is good, does not have other impurity.
In the glove box of argon gas atmosphere, took by weighing MgH in 2: 1 in molar ratio
2With Si sample, the ball grinder of packing into, ratio of grinding media to material is 120: 1, and abrading-ball is a stainless steel ball, will fill MgH
2Be placed on the planetary ball mill with the ball grinder of Si mixture,, obtain 2MgH with 600 rev/mins rotating speed ball millings 2 hours
2-Si mixture.With 2MgH
2-Si mixture heats in a vacuum puts hydrogen, and the rate of heat addition is 10 degrees celsius/minute, is heated to after temperature rises to 400 degrees centigrade; Be incubated 4 hours and system is vacuumized; The cold room temperature that is cooled to of stove is taken out the gained sample from the glove box of argon gas atmosphere then, obtains Mg
2The Si sample.
Fig. 3 is 2MgH
2The stereoscan photograph of hydrogen afterproduct is put in the heating of-Si mixture, and stereoscan photograph shows that particle is a submicron order, is cotton-shaped after the reunion.
Embodiment 4
In the glove box of argon gas atmosphere, took by weighing MgH in 2: 1 in molar ratio
2With Si sample, the ball grinder of packing into, ratio of grinding media to material is 90: 1, and abrading-ball is a stainless steel ball, will fill MgH
2Be placed on the planetary ball mill with the ball grinder of Si mixture,, obtain 2MgH with 400 rev/mins rotating speed ball millings 4 hours
2-Si mixture.With 2MgH
2-Si mixture heats in a vacuum puts hydrogen, and the rate of heat addition is 15 degrees celsius/minute, is heated to after temperature rises to 400 degrees centigrade; Be incubated 4 hours and system is vacuumized; The cold room temperature that is cooled to of stove is taken out the gained sample from the glove box of argon gas atmosphere then, obtains Mg
2The Si sample.
Fig. 4 is the Mg for preparing
2Si sample charging matter specific capacity and the curve of discharge matter specific capacity with the period variation, as can be seen from the figure, the Mg that the inventive method prepares
2The discharge capacity first of Si can reach 1100 MAH/grams, is much higher than present commercialization carbon material, and this material has good circulation volume hold facility simultaneously.
Prepare calcium silicide by embodiment 1 described preparation method, abrading-ball can be selected stainless steel ball or zirconia ball for use, and the preparation condition difference is seen table 1.
Sample composition shows CaH in the table
2With the mol ratio of Si, for example CaH
2-2Si, i.e. CaH
2With the mol ratio of Si be 1: 2.
Table 1
The CaH that Fig. 5 prepares for embodiment 6
2-2Si mixture is put the XRD figure of hydrogen products therefrom.
The CaSi that Fig. 6 prepares for embodiment 6
2The curve chart that sample changes with discharge capacity as 5 discharge potentials of ion secondary battery cathode material lithium circulation, as can be seen from the figure, gained CaSi
2Sample is as ion secondary battery cathode material lithium; Discharge capacity is at 888mAh/g first for it, and the initial charge capacity is at 701mAh/g, and coulombic efficiency reaches more than 80%; Charging capacity remains on more than the 650mAh/g after 5 circulations, and sample demonstrates charge and discharge cycles stability preferably.
Claims (9)
1. the preparation method of an alkaline earth metal silicide; It is characterized in that, may further comprise the steps: alkaline earth metal hydride and silicon are carried out ball mill mixing, the gained mixture is heated under vacuum or inert gas atmosphere put hydrogen; Be cooled to room temperature, obtain alkaline earth metal silicide.
2. the preparation method of alkaline earth metal silicide as claimed in claim 1 is characterized in that, said ball milling is planetary type ball-milling or oscillatory type ball milling.
3. the preparation method of alkaline earth metal silicide as claimed in claim 2 is characterized in that, the ratio of grinding media to material of said planetary type ball-milling is 30～120: 1, and rotational speed of ball-mill is 200～600r/min, and the ball milling time is 1～10h.
4. the preparation method of alkaline earth metal silicide as claimed in claim 2 is characterized in that, the ratio of grinding media to material of said oscillatory type ball milling is 30～120: 1, and vibration frequency is 1200 cycle per minute clocks, and the ball milling time is 10～60min.
5. like the preparation method of claim 3 or 4 described alkaline earth metal silicides, it is characterized in that the rate of heat addition that hydrogen is put in said heating is 1～15 ℃/min.
6. the preparation method of alkaline earth metal silicide as claimed in claim 5 is characterized in that, the heating-up temperature that hydrogen is put in said heating is 200～600 ℃.
7. the preparation method of alkaline earth metal silicide as claimed in claim 6 is characterized in that, said inert gas is argon gas or nitrogen.
8. the preparation method of alkaline earth metal silicide as claimed in claim 7 is characterized in that, said alkaline earth metal hydride is a magnesium hydride, and the mol ratio of said magnesium hydride and silicon is 0.5～4: 1.
9. the preparation method of alkaline earth metal silicide as claimed in claim 7 is characterized in that, said alkaline earth metal hydride is a calcium hydride, and the mol ratio of said calcium hydride and silicon is 0.5～9: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102359787A CN102769125A (en) | 2012-07-10 | 2012-07-10 | Alkaline-earth metal silicide preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102359787A CN102769125A (en) | 2012-07-10 | 2012-07-10 | Alkaline-earth metal silicide preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102769125A true CN102769125A (en) | 2012-11-07 |
Family
ID=47096433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102359787A Pending CN102769125A (en) | 2012-07-10 | 2012-07-10 | Alkaline-earth metal silicide preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102769125A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112786949A (en) * | 2019-11-06 | 2021-05-11 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and device containing same |
| 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 |
| CN115417375A (en) * | 2022-09-30 | 2022-12-02 | 中国计量大学 | Silicon/metal hydride composite material for rapid hydrolysis hydrogen production and preparation method thereof |
-
2012
- 2012-07-10 CN CN2012102359787A patent/CN102769125A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| HUI WU ET AL: "Structure and hydrogenation properties of the ternary alloys Ca2−xMgxSi (0 ≤ x ≤ 1)", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| HUI WU ET AL: "Structure and hydrogenation properties of the ternary alloys Ca2−xMgxSi (0 ≤ x ≤ 1)", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 446447, 12 January 2007 (2007-01-12) * |
| JOHN J. VAJO: "Altering Hydrogen Storage Properties by Hydride Destabilization through Alloy Formation: LiH and MgH2 Destabilized with Si", 《THE JOURNAL OF PHYSICAL CHEMISTRY B》 * |
| 刘寅峰等: "制约Mg2Si体系可逆储氢的原因", 《安徽工业大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112786949A (en) * | 2019-11-06 | 2021-05-11 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and device containing same |
| CN112786949B (en) * | 2019-11-06 | 2022-06-07 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module, battery pack and device containing same |
| 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 |
| CN115417375A (en) * | 2022-09-30 | 2022-12-02 | 中国计量大学 | Silicon/metal hydride composite material for rapid hydrolysis hydrogen production and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101635349B (en) | Method for preparing metal-silver-doped carbon-covering lithium iron phosphate of lithium-ion battery cathode material | |
| CN100567142C (en) | The preparation method of lithium iron phosphate series composite oxides | |
| CN104993104B (en) | Preparation method of multi-element polyphase composite lithium ion battery negative material | |
| CN102361073B (en) | Preparation method of lithium ion battery silicon aluminium carbon composite cathode material | |
| CN101964415B (en) | Method for preparing lithium-ion battery anode material | |
| CN103258992B (en) | The preparation method of the lithium ion battery negative material that a kind of initial coulomb efficiency is high | |
| CN101877405A (en) | Preparation method of lithium titanate-graphene combination electrode material | |
| CN104617265B (en) | Method for preparing silica carbon composite lithium ion battery cathode material | |
| CN102226243A (en) | Magnesium-containing superlattice hydrogen storage alloy and preparation method thereof | |
| CN101830453A (en) | Secondary sintering synthesis method for lithium iron phosphate | |
| CN102386408B (en) | Preparation method for manganese lithium borate cathode material of lithium ion battery | |
| CN103545508B (en) | A kind of lithium iron borate anode material of lithium ion battery and its preparation method | |
| CN102079530A (en) | Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology | |
| CN104638230A (en) | Method for preparing selenium-carbon composite material from supercritical carbon dioxide | |
| CN102790205B (en) | A kind of preparation method of multielement silicon based compound | |
| CN104617297B (en) | Method for preparing lithium ion battery anode material LiMnBO3 by using molten salt method | |
| CN103137966A (en) | Preparation method for modified lithium iron phosphate doped positive electrode material | |
| CN102769125A (en) | Alkaline-earth metal silicide preparation method | |
| CN104868113B (en) | Preparation method of metallic oxide lithium ion battery cathode material | |
| CN102738464A (en) | Preparation method of lithium based compound | |
| CN106521382B (en) | A kind of single-phase superlattices A5B19The preparation method of type La Mg Ni base hydrogen-storing alloys | |
| CN102517481B (en) | High-capacity germanium-cobalt alloy lithium ion battery anode material and preparation method thereof | |
| CN108155361A (en) | A kind of iron lithium phosphate battery | |
| CN110660980B (en) | Silicon-based Si-B anode material and electrochemical synthesis method and application thereof | |
| CN103326021A (en) | Preparation method of lithium iron phosphate positive pole material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20121107 |