CN101402115A - Synthesis in situ of intermetallic compound nano-particle - Google Patents
Synthesis in situ of intermetallic compound nano-particle Download PDFInfo
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- CN101402115A CN101402115A CNA2008102281019A CN200810228101A CN101402115A CN 101402115 A CN101402115 A CN 101402115A CN A2008102281019 A CNA2008102281019 A CN A2008102281019A CN 200810228101 A CN200810228101 A CN 200810228101A CN 101402115 A CN101402115 A CN 101402115A
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Abstract
The invention provides an in situ synthesis method for an intermetallic compound nano particle, which belongs to the technical field of synthesizing a nano particle material. The method is characterized in that tin or magnesium and alloy micron powder which are low in melting point as well as a metal and alloy micron powder which are high in melting point are taken as materials; the materials are evenly mixed and pressed into a block target material which is used as a self-consumption anode; in the mixing atmosphere of active and inert gases, by utilizing a plasma heat source, the block target material is evaporated and subjected to gas-liquid-solid phase change; and the tin based and magnesium based binary or multiple intermetallic compound nano particle is prepared on the normal position. The method has the advantages of adopting the composite block target material, and synthesizing the intermetallic compound nano particle on the normal position, and has the characteristics of simple method, low cost, less impurities, clear and neat particle shape and suitability for mass production. The tin based or magnesium based intermetallic compound nano particle prepared by the method has wide application prospect in fields such as lithium ion cathode materials, hydrogen storage materials and the like.
Description
Technical field
The invention belongs to the nano-particle material synthesis technical field, relate to a kind of in-situ synthetic method of intermetallic compound nano-particle.
Background technology
Intermetallic compound has the physics and the chemical property of many uniquenesses, its bonding force is strong, have the operating temperature higher than alloy, higher specific strength, specific stiffness and non-oxidizability ability are the critical materials of high and new technologies such as Aero-Space, national defense and military, novel energy, bioengineering, information technology.That developed now and drop into practical application mainly contain intermetallic compound high-temperature structural material, light, electricity, magnetic functional material, marmem, hydrogen storage material, functional coat material etc.Because the room temperature fragility of intermetallic compound, most intermetallic compound preparation of devices adopt powder metallurgic method to obtain.For the intermetallic compound that fusing point between constituent element differs greatly, these powder stocks are relatively more difficult with traditional smelting method for preparing.
At present, the commercial li-ion battery extensively adopts graphite and modified graphite as negative material, and its theoretical specific capacity is 372mAh/g, and volume and capacity ratio also has only 800mAh/cm
3Because Sn can form Li with Li
22Sn
5, theoretical capacity is very high, so the Sn base alloy material caused people's great attention, become present study lithium ion battery alloy negative material the most widely.Tin base alloy anode material has following advantage: metal Sn is as negative pole, the about 994mAh/g of theoretical specific capacity, because bulk density is big, volume and capacity ratio is up to 7200mAh/cm simultaneously
3To Li
+The operation current potential of/Li is 0.3-0.5V, can solve the deposition problems of lithium metal; There is not the common embedding of solvent in the charge and discharge process, very friendly to choice of Solvent.Yet the metal Sn electrode can produce very big Volume Changes in cyclic process, make the very fast fragmentation of active material, come off, thereby cause electrode to lose efficacy rapidly, therefore can not use the negative material of metallic tin merely as lithium ion battery.So, add another kind of inactive metal and form very necessity of combination electrode.Because combination electrode exists different lithium to embed two-phase or multiphase of current potential, thereby it can suppress electrode preferably and expand, thereby alleviates the expansion issues of long-term puzzlement alloy electrode.Such structure is when the embedding lithium, and one is on good terms cushions another expansion when the embedding lithium, thereby very effective to suppressing the electrode Volume Changes.Sn base alloy forms intermetallic compound A usually
xB
yWherein A is non-reacting phase, and it does not react with lithium metal.B is active phase Sn, and it can take off the embedding reaction with lithium.These intermetallic compounds can form alloy phase in embedding lithium process, also may form Li
4.4The mixing of Sn and metal A mutually.Wherein non-reacting phase A provides buffering matrix, alleviate to take off/embedding lithium process in the Volume Changes of electrode interior, play keep between the particle and electrode slice and collector between the effect of integrality.Can have much with the unit that Sn forms intermetallic compound, as Fe, Ni, Cu, Sb, Ca, Mg, Co, Mn, Zn, S etc., some alloys are studied comparatively deep in the tool, and that some alloy research get is less relatively.
Since finding that lithium can form alloys with some metals by electrochemical reduction in organic electrolyte, directly used lithium metal alloy replacement carbon to obtain a lot of researchs as negative material.But up to now, the lithium battery that with the lithium alloy is negative pole does not enter commodity market, a subject matter is, in cyclic process, the reversible generation of Li-M (M refers to form with lithium the metal of alloy) alloy is accompanied by huge Volume Changes with decomposition, cause the division (producing crack and efflorescence) of alloy, cause electrode failure at last.Address this problem, need to reduce the mechanical stress that forms because of Volume Changes, a solution is the superfine active material of preparation particle, makes it to form big cluster, and when forming alloy with lithium like this, volumetric expansion is comparatively even, and stress reduces; Other method is to use activity/nonactive composite alloy, does not wherein hold alloy compositions with the 'inertia' metal of lithium reaction as matrix and conductive compositions.The reduction of granularity has been widened people to the selection of electrode materials scope, breakthrough in the nano-scale research may promptly change people the chemical/electrochemical of inorganic material is reacted original understanding, thinks that the material that does not satisfy traditional lithium intercalation standard and vetoed is worth having thought deeply again now.The nanometer negative material mainly is a nano-meter characteristic of wishing to utilize material, reduces volumetric expansion and the influence of shrinking structure in the charge and discharge process, thereby improves cycle performance.There are some potential pluses and minuses in the lithium ion cell nano electrode.Its advantage applies exists: discharge lithium better and embed and take off stress in the embedding process, improve cycle life; Can occur in the reaction that can not occur in the block materials; Higher electrode/electrolyte contact area has improved charge/discharge rate; Short electron transport path (allow low electricity lead or high power under use); Short lithium ion transmission path (allowing under low lithium ion conduction medium or high power, to use).Its shortcoming is: the electrode/electrolyte that can not the expect reaction that high-specific surface area brings increases, and causes self-discharge phenomenon, the cycle performance and the life-span of difference; Of inferior quality granule packaging technology makes its volume energy density very low, unless develop a kind of special compression process, otherwise can limit its application; The electrode building-up process may be complicated more.Be familiar with these pluses and minuses, people have strengthened the R﹠D intensity in negative pole and anodal nano material.
Metal hydride is desirable hydrogen source, and the hydride hydrogen-storing material that has developed at present can be divided into (the AB of rare earth metal system
5Type), (AB of zirconium system
2Type), ferrotitanium system (AB type) and (A of magnesium system
2B) 4 kinds.Rare earth metal base hydrogen storage alloy (AB
5Type) drop into industrial production, be used to produce the negative pole of secondary alkaline batteries, but because AB
5Type hydrogen storage material hydrogen little (about about 1.4～1.5wt.%) is so development space is little.Because magnesium resource is abundant, cheap, magnesium has bigger advantage aspect the scale accumulating of hydrogen, and magnesium base alloy hydrogen storage capability big (7.6wt.%), long, (density 1.74g/cm in light weight of life-span
3), volume is little, pollution-free, therefore is considered to the alloy material storing hydrogen of usefulness such as most promising fuel cell, hydrogen-burning automobile, and at secondary alkaline batteries application prospect arranged greatly also, thereby attracted numerous scientists to be devoted to the development of new magnesium base alloy.From report MgNi
2Had since the hydrogen storage property, the development of magnesium-base hydrogen storage material has obtained unprecedented development.Its typical case is represented as Mg
2Ni, such alloy hydrogen storage content is up to 3.6wt.%, and theoretical capacity is 999mAh/g, and is in light weight, and desorption isotherm is smooth, and it is little to lag behind, and is the hydrogen bearing alloy of mobile device coideal.Yet the major defect of magnesium base alloy is: (1) inhales the hydrogen discharging temperature height, speed for hydrogen absorbing and releasing is slower, and kinetics performance and thermodynamic property are relatively poor; (2) character of magnesium and alloy thereof is active, easily generates oxide-film in the air on the top layer, easily is oxidized to Mg (OH) in the aqueous solution
2In the research of hydrogen bearing alloy, it is found that the particle of material is contracted to nanoscale, and its hydrogen storage property will be significantly improved.In general, it is little to the macroscopic property influence to dwindle particle scale, but very big to the kinetic property influence, and such as inhaling hydrogen discharging rate quickening, decomposition temperature reduction etc., the reversible hydrogen storage capacity also can increase to some extent because of dynamic (dynamical) improvement.Therefore, the nanocrystalization of material is a development trend of chemisorbed material.
At present, the method for preparing intermetallic compound nano-particle is generally ball-milling method or elevated temperature heat diffusion method.For the elevated temperature heat diffusion method, the one, consuming time longer, often needed tens hours even longer; The 2nd, the nanoparticle powder of producing is difficult to reach nanoscale, and at high temperature powder is reunited easily, has to carry out depolymerization and handle in subsequent treatment.For ball-milling method, for this low-melting-point metal of similar Sn, Mg, in mechanical milling process, be easy to generate the cold welding phenomenon, cause the powder agglomeration produced more serious.In recent years, adopt arc discharge method to produce the close solid solution type alloy nano particles of fusing point such as Fe-Ni, Fe-Cr, Fe-Co and obtained very big success.But segregation phenomena as Fe-Sn, Ni-Sn (fusing point of Sn is 505K, and Fe is 1808K, and Ni is 1726K) etc., takes place in alloy to fusing point differs greatly easily in the master alloy melting process; Simultaneously, because Sn or Mg are much bigger with the evaporation rate that Fe, Ni compare in a vacuum, so also higher to the requirement of raw material proportioning.Direct-current arc hydrogen plasma evaporation has characteristics such as evaporation rate height, purity height, composition are controlled, easy operating, for the preparation nano material provides desirable physicochemical environment, be a kind of large-scale industrial production that is applicable to, and the technology of the very perfect preparation nano-powder of technology.
Summary of the invention
In order to solve difficult, the easy problems such as reunion of complex process, cost height, control that present preparation intermetallic compound nano-particle exists, the invention provides a kind of in-situ synthetic method of intermetallic compound nano-particle.
Technical solution of the present invention is to utilize DC arc plasma to be thermal source, the metal or alloy micro-powder that differs greatly with fusing point is a raw material, it is pressed into the bluk recombination target and in active and inertia mixed atmosphere, evaporates, by evaporation, condensation, passivating process, compound nano-particle material between synthetic binary or multi-element metal.Preparation process specifically comprises as follows:
1. at first tin or magnesium metal and other refractory metal powder and micron raw material are evenly mixed by certain mass ratio, are pressed into the block target, and through behind the cryogenic vacuum sintering as anode, tungsten bar (or carbon-point) is as negative electrode, water cooling plant is all installed at the two poles of the earth.
2. reative cell is evacuated to 10
-3Torr feeds the argon gas (or helium) of about 350 torr hydrogen and about 350 torrs, the evaporation of discharging in DC arc plasma.Discharge current is 150～300 amperes; Voltage is 20～40 volts.
3. the block target is ignited by electric arc, forms localized regions of elevated temperature and by rapid evaporation, through gaseous state-liquid state-solid-state transformation, spreads and solidify the formation intermetallic compound nano-particle, is deposited on the reaction chamber wall of water cooling plant.Evaporation process can be passed through the adjustment of electrode spacing, voltage and electric current and be controlled.Evaporation process finishes behind the outage arc.After treating that floating powder is deposited on reaction chamber wall, extract hydrogen and argon gas to 10 out
-1～1.0 torrs are also imported micro amount of oxygen (or air), leave standstill 6～12 hours, finish passivation technology.Extract the reaction indoor gas out and also charge into air to an atmospheric pressure, finish circulation after, open reactor chamber door and take out powder sample.
Effect of the present invention and benefit be have that preparation technology is simple, cost is low, easy to control, characteristics such as original position is synthetic.Nano particle is chondritic, and particle diameter is in 20～100 nanometer range, and the outer oxide coated thin layer of nano particle is to protect particle not by further deep oxidation.Can realize a large amount of different materials kinds, comprise tinbase intermetallic compound nano-particles such as Sn-Ni, Sn-Cu, Sn-Fe, Sn-Mn, Sn-Co, Sn-Cr, and compound nano-particle synthetic between Mg-Ni, Mg-Cu, Mg-Fe, Mg-Mn, magnesium-base metals such as Mg-Co, Mg-Cr.
Description of drawings
Fig. 1 is the transmission electron micrograph of Sn-Fe intermetallic compound nano-particle.The quality proportioning of metal constituent element is Sn/Fe=40/60 in its block composite target material.
Fig. 2 is the X-ray diffraction spectrogram of Sn-Fe intermetallic compound nano-particle.The quality proportioning of metal constituent element is Sn/Fe=40/60 in its block composite target material.
Fig. 3 is the transmission electron micrograph of Mg-Cu intermetallic compound nano-particle.The mole proportioning of metal constituent element is Mg/Cu=2/1 in its block composite target material.
Fig. 4 is the X-ray diffraction spectrogram of Mg-Cu intermetallic compound nano-particle.The mole proportioning of metal constituent element is Mg/Cu=2/1 in its block composite target material.
The specific embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Synthetic Sn-Fe intermetallic compound nano-particle:
1. the preparation work of block composite target material.Earlier with the micron powder of Sn and Fe by certain quality proportioning (for example Sn/Fc=40/60), mix by V or Y type blender, again with compound at 50KN/cm
2Pressure down use particular manufacturing craft to be pressed into cylindrical target (diameter is 10mm, and height is 50mm).This compacting target also can carry out vacuum-sintering below the temperature that is lower than the Sn fusing point, to improve electric conductivity.
2. target being packed into reative cell as from the consumption anode, is negative electrode with tungsten bar or carbon-point, the water-cooled cooling electrode.
3. reative cell is evacuated to 10
-3Torr feeds the argon gas (or helium) of about 350 torr hydrogen and about 350 torrs, opens recirculated cooling water.Light electric arc, the evaporation of discharging in DC arc plasma is regulated arc distance at any time with stabilising arc.Discharge current is 150～300 amperes; Voltage is 20～40 volts.
4. after powder preparation is finished, the outage arc, treat that floating powder is deposited on reaction chamber wall after, close recirculated cooling water, extract hydrogen and argon gas to 10 out
-1～1.0 torrs.
5. charge into micro amount of oxygen (or air) to an atmospheric pressure, left standstill 6～12 hours, finish passivation technology.Open reactor chamber door and take out powder sample after the abundant passivation of powder, collect and packing.
Synthetic Mg-Cu intermetallic compound nano particle:
1. the preparation work of block composite target material.Earlier with the micron powder of Mg and Cu by certain molar ratio proportioning (for example Mg/Cu=2/1), mix by V or Y type blender, again with compound at 50KN/cm
2Pressure under be pressed into the cylindrical target material.(diameter is 10mm, and height is 50mm).
2. the reative cell of cylindrical target being packed into is negative electrode also as from the consumption anode with the tungsten bar, the water-cooled cooling electrode.
3. reative cell is evacuated to 10
-3Torr feeds the argon gas (or helium) of about 350 torr hydrogen and about 350 torrs, opens recirculated cooling water.Light electric arc, the evaporation of discharging in DC arc plasma is regulated arc distance at any time with stabilising arc.Discharge current is 150～300 amperes; Voltage is 20～40 volts.
4. after powder preparation is finished, the outage arc, treat that floating powder is deposited on reaction chamber wall after, close recirculated cooling water, extract hydrogen and argon gas to 10 out
-1～1.0 torrs.
5. charge into micro amount of oxygen (or air) to an atmospheric pressure, left standstill 6～12 hours, finish passivation technology.Open reactor chamber door and take out powder sample after the abundant passivation of powder, collect and packing.
Claims (7)
1, a kind of in-situ synthetic method of intermetallic compound nano-particle, comprise low-melting-point metal and refractory metal or alloy micro-powder as raw material, evenly mix and be pressed into the block target as anode, in active and inert gas mixed atmosphere, utilize plasma heat source evaporation block target, through gas-liquid-solid phase transition process, original position forms compound nano-particle between tinbase and magnesium base binary or multi-element metal, and its concrete feature process step is as follows:
(1) at first low-melting-point metal and refractory metal powder and micron are evenly mixed and be pressed into the block target, raw material mass mixture ratio is specifically determined according to the design feature and the block target electric conductivity of intermetallic compound nano-particle 20: 1～1: 20 scope; As preliminary treatment, block target low-temperature sintering in a vacuum is beneficial to all even raising electric conductivity of composition; As anode, tungsten bar or carbon-point are as negative electrode with the block target, and water cooling plant is all installed at the two poles of the earth;
(2) reative cell is vacuumized, charges into activity and inert mixed gas, utilize the DC arc plasma thermal source, in reative cell to the evaporation of discharging of block target;
(3) anode block target is by the high-temperature plasma rapid evaporation, through gaseous state-liquid state-solid-state transformation, promptly evaporates, diffusion and process of setting formation intermetallic compound nano-particle powder, is deposited on the reaction chamber wall of water cooling plant; After evaporation finishes, the outage arc; After treating that floating powder is deposited on reaction chamber wall, extract hydrogen and argon gas or helium mix gas out; Pour trace oxygen or air, leave standstill and finished passivation technology in 6～12 hours; Pour an atmospheric air,, open reactor chamber door, take out powder sample through charging and discharging the gas cyclic process.
2, the in-situ synthetic method of a kind of intermetallic compound nano-particle according to claim 1, it is characterized in that, described raw material is low-melting-point metal or alloy powder and micron and refractory metal or alloy powder and micron, and both evenly mix and are pressed into the block target; Low-melting-point metal is tin metal or alloy powder and micron, and the refractory metal raw material comprises iron, cobalt, nickel, copper, manganese, chromium etc. and alloy powder and micron thereof.
3, the in-situ synthetic method of a kind of intermetallic compound nano-particle according to claim 1 is characterized in that, described raw material is low-melting-point metal or alloy powder and micron and refractory metal powder and micron, and both evenly mix and are pressed into the block target; Low-melting-point metal is a magnesium metal or alloy powder and micron, and the refractory metal raw material comprises iron, cobalt, nickel, copper, manganese, chromium etc. and alloy powder and micron thereof.
4, the in-situ synthetic method of a kind of intermetallic compound nano-particle according to claim 1 is characterized in that, intermetallic compound is for containing Sn intermetallic compound or containing the magnesium intermetallic compound.
5, the in-situ synthetic method of a kind of intermetallic compound nano-particle according to claim 1 is characterized in that, described active gases is hydrogen or methane.
6, the in-situ synthetic method of a kind of intermetallic compound nano-particle according to claim 1 is characterized in that, described inert gas is argon gas, helium or nitrogen.
7, the in-situ synthetic method of a kind of intermetallic compound nano-particle according to claim 1 is characterized in that, the arc discharge electric current is 150～300 amperes, and arc-over voltage is 20～40 volts.
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Cited By (9)
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| CN102616780A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Method for preparing titanium carbide nanometer particles and composite materials thereof by direct current arc method |
| CN102686021A (en) * | 2011-03-08 | 2012-09-19 | 纳普拉有限公司 | Electronic device |
| CN104404327A (en) * | 2014-11-10 | 2015-03-11 | 大连理工大学 | Preparation method of in-situ nano particle enhanced magnesium-based composite material |
| CN104607648A (en) * | 2015-01-15 | 2015-05-13 | 太原理工大学 | Method for preparing nanometer or submicron order tin or tin alloy microspheres |
| CN105720249A (en) * | 2016-02-22 | 2016-06-29 | 北京工业大学 | Preparation method of Sn-Si alloy-type nano-composite powder |
| CN107117645A (en) * | 2017-05-21 | 2017-09-01 | 吉林大学 | By obtaining metal-doped porous SnO containing Sn intermetallic compound2The preparation method of material |
| CN108927154A (en) * | 2018-06-11 | 2018-12-04 | 大连理工大学 | A kind of preparation method of intermetallic compound nanocatalyst |
| CN112387979A (en) * | 2020-10-14 | 2021-02-23 | 宁波中乌新材料产业技术研究院有限公司 | Preparation method of silver nanoparticles |
| CN112676569A (en) * | 2020-12-09 | 2021-04-20 | 中南大学 | Preparation method of nickel-zinc intermetallic compound alloy |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686021A (en) * | 2011-03-08 | 2012-09-19 | 纳普拉有限公司 | Electronic device |
| CN102686021B (en) * | 2011-03-08 | 2014-12-31 | 纳普拉有限公司 | Electronic device |
| CN102616780A (en) * | 2012-03-31 | 2012-08-01 | 大连理工大学 | Method for preparing titanium carbide nanometer particles and composite materials thereof by direct current arc method |
| CN104404327A (en) * | 2014-11-10 | 2015-03-11 | 大连理工大学 | Preparation method of in-situ nano particle enhanced magnesium-based composite material |
| CN104607648B (en) * | 2015-01-15 | 2017-03-01 | 太原理工大学 | A kind of method preparing nanometer or submicron order stannum or tin alloy microsphere |
| CN104607648A (en) * | 2015-01-15 | 2015-05-13 | 太原理工大学 | Method for preparing nanometer or submicron order tin or tin alloy microspheres |
| CN105720249A (en) * | 2016-02-22 | 2016-06-29 | 北京工业大学 | Preparation method of Sn-Si alloy-type nano-composite powder |
| 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 |
| CN107117645A (en) * | 2017-05-21 | 2017-09-01 | 吉林大学 | By obtaining metal-doped porous SnO containing Sn intermetallic compound2The preparation method of material |
| CN107117645B (en) * | 2017-05-21 | 2018-10-16 | 吉林大学 | Metal-doped porous SnO is obtained by containing Sn intermetallic compound2The preparation method of material |
| CN108927154A (en) * | 2018-06-11 | 2018-12-04 | 大连理工大学 | A kind of preparation method of intermetallic compound nanocatalyst |
| CN112387979A (en) * | 2020-10-14 | 2021-02-23 | 宁波中乌新材料产业技术研究院有限公司 | Preparation method of silver nanoparticles |
| CN112676569A (en) * | 2020-12-09 | 2021-04-20 | 中南大学 | Preparation method of nickel-zinc intermetallic compound alloy |
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