CN103606683A - Coiling-type germanium nanomaterial and preparation method thereof - Google Patents
Coiling-type germanium nanomaterial and preparation method thereof Download PDFInfo
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Abstract
The invention provides a coiling-type germanium nanomaterial and a preparation method thereof. The coiling-type germanium nanomaterial can be used as a negative electrode of a lithium ion battery. According to the preparation method, a metal layer prepared by adopting an ionic liquid electroposition method and a germanium layer are combined, and the coiling-type germanium nanomaterial is prepared by combining with a metal induced crystallization theory. The coiling-type germanium nanomaterial provided by the invention can be used as the negative electrode of the lithium ion battery, so that volume expansion of the germanium-based material can be effectively slowed down; the coiling-type germanium nanomaterial can be used for preparing the lithium ion power battery with high capacity, large multiplying power and long service life.
Description
Technical field
The present invention relates to electrochemical field, be specifically related to a kind of germanium nano material and preparation thereof.
Background technology
Because the theoretical capacity of graphite-like material with carbon element is very little, be only 373mAhg
-1, the demand that is difficult to meet the development such as space flight, military project, electric motor car, therefore finds the study hotspot that the lithium cell negative pole material with high theoretical capacity becomes lithium ion battery, and (theoretical capacity of silicium cathode is up to 4200mAhg due to its higher embedding lithium capacity for silicon and germanium
-1, the theoretical capacity of germanium negative pole is up to 1600mAhg
-1) become the best substitution material of graphite negative electrodes material.But the less stable due to silicium cathode material.While forming intermetallic compound with silicon in lithium ion embedding silicon, its volumetric expansion can arrive 400%.After there is de-lithium reaction, silicon grain cannot reduce, and comes off gradually from collector, loses conductivity, and material structure is destroyed, no longer has embedding lithium ability, makes the energy-storage property of battery not reach application standard far away.And germanium sill is with respect to silicon, its stability is relatively better, although its theoretical capacity is lower than silicon materials, but its capacity is far away higher than graphite material, and because having lower can be with (EgGe=0.67ev, EgSi=1.12ev), germanium make lithium ion conduction velocity therein for 400 times in silicon.And the conduction velocity of electric charge is 10 in silicon materials
4doubly, thereby make germanium sill there is higher specific capacity, make it in power vehicle direction, there is good application prospect, but also there is larger volumetric expansion in same germanium sill in the process of embedding lithium and de-lithium, its volumetric expansion can reach 370%, therefore the puzzlement causing in order to reduce the efflorescence of lithium cell negative pole material, need to prepare can slow down volumetric expansion high power capacity negative material.
Nano material is compared maximum advantage and is that the very little grain boundary of particle size is many with other material, during removal lithium embedded, lithium ion is fast by grain boundary and with it in conjunction with forming amorphous compound, can there is not recrystallization and not have phase transformation, therefore can effectively slow down the volumetric expansion of material.Germanium nano particle, nano wire, nanotube etc. have been prepared at present.As far back as 20 century 70s, the phenomenon of crystallization inducing metal (metal induced crystallization, MIC) is just found and studies.Utilize this principle, the people such as Minghong Wu, utilize the method for hot evaporation in silicon base, first to plate one deck amorphous Germanium film, then evaporation last layer metallic aluminium, in nitrogen atmosphere, anneal, in the time of 500 ℃, anneal and can under the induction of metallic aluminium, obtain dendritic germanium nano material in 60 minutes.But the method for hot evaporation need to have higher requirement to vacuum degree and raw-material purity.Instrument and equipment is also more expensive, is unsuitable for large-scale production.Although the method for electro-deposition is comparatively simple, and the pattern of the product obtaining is controlled with composition.But because the electrolyte of the conventional deposition of germanium is high-temperature fusion salt, in reaction, can bring much poisonous, harmful material but also waste energy.And the raw material GeX of conduct reduction germanium
4(X=Cl, Br, I) be promptly hydrolysis under air and moisture or moist environment, therefore in electrodeposition process, just can not use the aqueous solution as electrolyte, thereby has restricted the development of electrochemical production germanium material.Ionic liquid has good conductivity, difficult volatilizees, does not burn, electrochemical stability potential window is than various features such as other electrolyte aqueous solution are large.Can realize the deposition of Ge element and metallic element.The people such as Endres, adopt Pt to encircle electrode as a comparison, and Ag silk, as accurate reference electrode, is used respectively in Au substrate (111) SiCl that contains 0.1mol/L
4, 0.1mol/L GeCl
4and the SiCl of Si, the Ge mol ratio 0.1mol/L that is 1:1
4and GeCl
4the ionic liquid [Py of mixed solution
isosorbide-5-Nitrae] Tf
2n is as electrolyte, and electro-deposition has gone out Si, Ge and Si
xge
1-xalloy.But its pattern of film that directly electro-deposition has gone out is nano particle, alleviate effect aspect volumetric expansion be not very obviously.Therefore, seek a kind of method that can prepare the germanium nano material of special appearance, imperative to solve the pulverizing problem of germanium negative material in charge and discharge process.
Summary of the invention
For the problems referred to above, an object of the present invention is to provide a kind of can be for the germanium nano material of the ball of string shape of lithium ion battery negative, this nano material is made lithium ion battery negative can increase the connectivity between active material and collector, can effectively reduce the volumetric expansion of negative material.
Another object of the present invention has been to provide a kind of method of preparing above-mentioned germanium nano material.
For achieving the above object, the present invention adopts following technical scheme:
The above-mentioned method of preparing the germanium nano material of ball of string shape, comprises the steps:
Ionic liquid EmimTf
2after N vaccum dewatering, be placed in glove box standby; Preparation is containing 0.1M GeCl
4, 2.5MAlCl
3emimTf
2n solution is placed in glove box standby as electrolyte; Adopt three-electrode system codeposition germanium aluminium, connecting electrolytic cell guarantees to contact and be not well short-circuited and breaking phenomena between electrode and electrolytic cell, the electrolytic cell connecting is sent in glove box, connect electrolytic cell and electrochemical workstation, in electrolytic cell, add electrolyte, its amount be take electrolyte and is flooded comparison electrode platinum loop for easy; Parameters carries out cyclic voltammetry to this system, to determine the sedimentation potential of germanium aluminium codeposition, the cathodic reduction curved portion of system comprises two peaks, first peak position is in-1.0V, belong to the deposition peak of metallic aluminium and the underpotential deposition peak of germanium, second appear at-1.9V of peak, belongs to the reduction peak that germanous changes elemental Germanium into, for realizing the common deposition of germanium aluminium, we are sedimentation potential is elected as-1.9V; Utilize potentiostatic electrodeposition method, set sedimentation potential and sedimentation time and realize the common deposition of germanium aluminium, deposit after 30 minutes, close electrochemical workstation, sucking-off electrolyte, in glove box, electrolytic cell is dismantled, take out work electrode, on work electrode, can adhere to one deck has the brownish black film of metallic luster, this film is the germanium aluminium film being deposited, with anhydrous isopropyl alcohol, wash slowly this film and remove the il electrolyte of adsorbing on film, after washes clean, this film is placed in glove box and is dried; After film dries completely, place it in the sample box that is filled with argon gas, from glove box, take out, transfer to fast in tube furnace, sealing tube furnace is filled with high pure nitrogen in its cavity, not oxidized with protection germanium aluminium film, tube furnace is raised to 500 ℃ with the heating rate of 2 ℃/min, 500 ℃ of insulations 60 minutes, utilizes metallic aluminium to induce germanium to form the nanotopography of ball of string shape; After annealing finishes, under the atmosphere of nitrogen, allow stove naturally cool to room temperature, take out product, transfer in glove box fast.
Wherein, three described electrodes are work electrode, reference electrode and comparison electrode, and above-mentioned electrode is respectively nickel foil, high-purity filamentary silver and high-purity platinum loop.
Wherein, described electrolytic cell is that polytetrafluoro material, circle, electro-deposition area are 1cm
2.
Wherein, in the concentrated sulfuric acid that described electrolytic cell, O type circle and platinum loop are 1:1 in volume ratio before use and the mixed solution of hydrogen peroxide, soak after 4 hours and take out, the distilled water that is 1:1 by volume ratio and mixed solution of hydrogen peroxide, distilled water, ultra-pure water be boiling washing 15 minutes successively, is placed in baking oven and dries.
The method that coupled ion liquid electro-deposition method provided by the invention and crystallization inducing metal principle are prepared the germanium nano-electrode material of ball of string shape has following advantage: can be by regulating the technological parameters such as composition, current density, sedimentation potential, sedimentation time of electrolyte to control composition and the grain size of sedimentation products in ionic liquid electrodeposition part.Compare with existing technique, electro-deposition can directly be deposited on germanium and aluminium in substrate simultaneously, and deposition process does not simply need high vacuum greatly to save the time of experiment.Electro-deposition germanium aluminium processing step is easy, from twice (an evaporation germanium, an AM aluminum metallization) reduction of the evaporation of existing technique, has greatly improved operating efficiency for a step electro-deposition.And the particle diameter that electro-deposition goes out is smaller; in the process of electro-deposition, germanium metal aluminium is to be jointly deposited on matrix; by annealing, utilize metallic aluminium induction germanium crystal, the germanium nano particle being deposited out can form nanobelt and gradually along with the increase nanobelt of the annealing time final germanium nano material that forms ball of string shape of can further reuniting.Its structure of the germanium material of this pattern is relatively loose and have a performance of monodimension nanometer material, not only make lithium ion and electronics there is diametrically shorter transmission length, can provide the transmission channel of more effective lithium ion and electronics in the axial direction, be conducive to improve the high rate performance of lithium ion battery simultaneously.And the stress producing in can more effective release removal lithium embedded process due to its short texture, effectively solve lithium ion deviate from telescopiny in the volumetric expansion problem of germanium negative material, make it in cyclic process, there is better structural stability, guarantee its in cyclic process, can continue performance nanostructure compared with advantages such as bigger serfaces, be conducive to lithium ion battery and obtain good cycle performance and higher specific capacity.
In addition, electro-deposition experiment can directly be carried out on collector, by deposition materials after annealing and collector, there is good connectivity, comparing the standby negative material of this legal system with the existing method of preparing lithium ion battery negative material does not need adhesive to be connected with collector, and its distribution of material being deposited is more even, can improve the cycle performance of lithium ion battery.Therefore utilize the ball of string shape germanium nano material making lithium ion negative pole that patent of the present invention prepares can increase the connectivity between active material and collector, reduce the volumetric expansion of negative material, improve lithium ion and the transmission rate of electronics in negative material, effectively improve cycle performance, high rate performance and the security performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the particular flow sheet of preparing ball of string shape germanium nano material.
Fig. 2 is the SEM figure of the germanium aluminium film that goes out of ionic liquid electrodeposition.
Fig. 3 is the EDS analysis chart of the germanium aluminium film that goes out of ionic liquid electrodeposition.
Fig. 4 is the SEM figure of the germanium aluminium film after annealing.
Fig. 5 is the EDS analysis chart of the germanium aluminium film after annealing.
Embodiment:
Following examples are used for further illustrating the present invention, but should not be construed as limitation of the present invention.Do not deviating under the prerequisite of the present invention's spirit and essence, modification made for the present invention or replacement, all belong to category of the present invention.
The preparation of embodiment 1 ball of string shape germanium nano material
Prepare the idiographic flow of ball of string shape germanium nano material as shown in Figure 1, experimental section is mainly divided into ionic liquid electrodeposition experiment and annealing experiment two large divisions.
One, ionic liquid electrodeposition germanium aluminium film
(1) experiment reagent pre-treatment
By ionic liquid EmimTf
2n is placed in glove box, 100 ℃ of distillations 24 hours, removes the moisture in ionic liquid, makes its water content be less than 2ppm, is placed in glove box standby.
(2) preparation electrolyte
In glove box, preparation is containing 0.1mol/L GeCl
4, 2.5mol/L AlCl
3emimTf
2n solution, after stirring, is placed in glove box standby.
(3) connect electrolytic cell
Utilize three-electrode system to carry out sedimentation experiment, work electrode (WE), reference RE(or accurate reference electrode Quasi-RE), comparison electrode (CE) is respectively nickel foil, high-purity Ag wires, high-purity Pt ring, electrolytic cell is that its floor space of circular container of being made by polytetrafluoro is 1cm
2, for preventing that part that electrolytic cell leakage is connected with substrate (work electrode) at electrolytic cell is furnished with O type and encloses sealing function.In the concentrated sulfuric acid that before using, electrolytic cell, O type circle and platinum loop are 1:1 in volume ratio and the mixed solution of hydrogen peroxide, soak after 4 hours and take out, the distilled water that is 1:1 by volume ratio and mixed solution of hydrogen peroxide, distilled water, ultra-pure water be boiling washing 15 minutes successively, is placed in baking oven dry for standby.Connecting electrolytic cell guarantees contact the good phenomenon that does not have short circuit and open circuit between each electrode and electrode cell, the electrolytic cell connecting is put into glove box, each electrode on electrolytic cell is connected with electrochemical workstation, adjust the distance (being advisable at a distance of 0.2cm) of comparison electrode and work electrode, reference electrode be positioned at work electrode directly over work electrode at a distance of 0.1cm, in electrolytic cell, add electrolyte, its amount be take electrolyte and is flooded comparison electrode platinum loop for easy.
(1) cyclic voltammetry
The cyclic voltammetry curve of test system is determined germanium aluminium consedimental current potential altogether, and sweep limits is 1.0--2.7V, and sweep speed is 10mVs
-1, generally its cathodic reduction curved portion there will be two reduction peak, and first peak position is in-1.0V, and this peak should belong to the deposition peak of metallic aluminium and the underpotential deposition peak of germanium, and this peak of appear at-1.9V, second peak belongs to the reduction peak that germanous is deposited as elemental Germanium.For realizing the common deposition of germanium aluminium, we are sedimentation potential is elected as-1.9V.
(2) potentiostatic electrodeposition
The common consedimental current potential that obtains germanium aluminium by cyclic voltammetry is-1.9V.In when deposition, our sedimentation potential is set in-1.9V, sedimentation time is made as 30 minutes.From the I-T curve of electro-deposition, can find out, electric current first reduces to increase and reduce again with the increase of sedimentation time, this curve conforms to the curve shape of electrodeposit metals, its correspondence be the nano particle that electro-deposition goes out, the process of growing up after first nucleation, along with increasing the especially nucleation of aluminium, Nucleation object make conductivity in substrate strengthen the increase of resistance drop-out current, after nucleation finishes, crystal can slowly be grown up along with the conductivity decline resistance increase electric current decline of the continuous growth substrate of the germanium nano particle depositing.After deposition finishes, close electrochemical workstation, sucking-off electrolyte, in glove box, electrolytic cell is dismantled, take out work electrode, can adhere to the brownish black film that this one deck has metallic luster on work electrode, this film is the germanium aluminium film being deposited, with anhydrous isopropyl alcohol, wash slowly this film and remove the il electrolyte of adsorbing on film, after washes clean, this film is placed in glove box and is dried.
Two, annealing experiment
After film dries completely; place it in the sample box that is filled with argon gas; from glove box, take out; transfer to fast in tube furnace, sealing tube furnace is filled with high pure nitrogen in its cavity; not oxidized with protection germanium aluminium film; tube furnace is raised to 500 ℃ with the heating rate of 2 ℃/min, 500 ℃ of insulations 60 minutes, utilizes metallic aluminium to induce germanium to form strawy nanotopography.In the overall process of annealing, all in tube furnace, passing into high-purity nitrogen and throughput is 10mL/min.Annealing allows stove naturally cool to room temperature after finishing under the atmosphere of nitrogen, takes out product, transfers to fast in glove box, to prevent that product from going bad because of oxidation.
The morphology characterization of embodiment 2 germanium nano materials
By SEM, characterize the microscopic appearance that we can see product intuitively, Fig. 2 is the SEM figure of the germanium aluminium film that goes out of ionic liquid electrodeposition, from figure, we can find out that the film that direct electro-deposition goes out is that little crystal grain gathering forms, from EDS, analyze (Fig. 3) and can find out that this film mainly contains Ge element and aluminium element, a small amount of Cl wherein, S, F is the component of ionic liquid, and Ni element is basis material, O, C adsorbs in the Preparation and characterization process of material, O element is likely also because material in the process characterizing is produced by the oxidation of fraction.And by after annealing, the pattern of its material is because obvious variation has occurred in the effect of metal inducement, the SEM figure that Fig. 4 is the germanium aluminium film after annealing, from figure, we can find out that germanium has formed the microscopic appearance of ball of string shape through the induction of metallic aluminium, by EDS, analyze in the material drawing after (Fig. 5) annealing and mainly contain Ge element, wherein Ni is basis material, and Au is sprayed on sample surfaces for increasing the conductivity of material in test SEM process.O, C adsorb in the Preparation and characterization process of material, and O element is likely also because material in the process characterizing is produced by the oxidation of fraction, the component that S is ionic liquid.By above sign and analysis, can draw the germanium nano material of utilizing ionic liquid electrodeposition and metal inducement principle can successfully prepare ball of string shape, and the method is simply efficient.
Claims (7)
1. a method of preparing the germanium nano material of ball of string shape, is characterized in that, comprises the following steps: ionic liquid EmimTf
2after N vaccum dewatering, be placed in glove box standby; Preparation is containing 0.1M GeCl
4, 2.5MAlCl
3emimTf
2n solution is placed in glove box standby as electrolyte; Adopt three-electrode system codeposition germanium aluminium, connecting electrolytic cell guarantees to contact and be not well short-circuited and breaking phenomena between electrode and electrolytic cell, the electrolytic cell connecting is sent in glove box, connect electrolytic cell and electrochemical workstation, in electrolytic cell, add electrolyte, its amount be take electrolyte and is flooded comparison electrode platinum loop for easy; Parameters carries out cyclic voltammetry to this system, to determine the sedimentation potential of germanium aluminium codeposition, the cathodic reduction curved portion of system comprises two peaks, first peak position is in-1.0V, belong to the deposition peak of metallic aluminium and the underpotential deposition peak of germanium, second appear at-1.9V of peak, belongs to the reduction peak that germanous changes elemental Germanium into, for realizing the common deposition of germanium aluminium, we are sedimentation potential is elected as-1.9V; Utilize potentiostatic electrodeposition method, set sedimentation potential and sedimentation time and realize the common deposition of germanium aluminium, deposit after 30 minutes, close electrochemical workstation, sucking-off electrolyte, in glove box, electrolytic cell is dismantled, take out work electrode, on work electrode, can adhere to one deck has the brownish black film of metallic luster, this film is the germanium aluminium film being deposited, with anhydrous isopropyl alcohol, wash slowly this film and remove the il electrolyte of adsorbing on film, after washes clean, this film is placed in glove box and is dried; After film dries completely, place it in the sample box that is filled with argon gas, from glove box, take out, transfer to fast in tube furnace, sealing tube furnace is filled with high pure nitrogen in its cavity, not oxidized with protection germanium aluminium film, tube furnace is raised to 500 ℃ with the heating rate of 2 ℃/min, 500 ℃ of insulations 60 minutes, utilizes metallic aluminium to induce germanium to form the nanotopography of ball of string shape; After annealing finishes, under the atmosphere of nitrogen, allow stove naturally cool to room temperature, take out product, transfer in glove box fast.
2. preparation method according to claim 1, is characterized in that, three described electrodes are work electrode, reference electrode and comparison electrode, and above-mentioned electrode is respectively nickel foil, high-purity filamentary silver and high-purity platinum loop.
3. preparation method according to claim 1 and 2, is characterized in that, described electrolytic cell is polytetrafluoro material, circle, and electro-deposition area is 1cm
2.
4. preparation method according to claim 1, it is characterized in that, in the concentrated sulfuric acid that described electrolytic cell, O type circle and platinum loop are 1:1 in volume ratio before use and the mixed solution of hydrogen peroxide, soak after 4 hours and take out, the distilled water that is 1:1 by volume ratio and mixed solution of hydrogen peroxide, distilled water, ultra-pure water be boiling washing 15 minutes successively, is placed in baking oven and dries.
5. the germanium nano material of a kind of ball of string shape preparing by method claimed in claim 1.
6. nano material according to claim 5, is characterized in that, it can be used as the negative pole of lithium ion battery.
7. a lithium ion battery, is characterized in that, its negative pole is prepared by nano material claimed in claim 5.
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| CN103943836A (en) * | 2014-04-01 | 2014-07-23 | 太原理工大学 | Hollow germanium nanotube array electrode of lithium ion battery anode material and preparation method of array electrode |
| CN104894618A (en) * | 2015-04-28 | 2015-09-09 | 哈尔滨工业大学 | Method for preparing germanium/aluminum nano film by electrodeposition of ionic liquid |
| CN105177648A (en) * | 2015-07-28 | 2015-12-23 | 吉林师范大学 | Device for preparing semiconductor material by using pulse laser for assisting ionic liquid electrolytic deposition |
| CN108336346A (en) * | 2018-02-07 | 2018-07-27 | 吉林师范大学 | A kind of application of germanium gallium nano wire as lithium ion battery electrode material |
| CN108987674A (en) * | 2018-07-25 | 2018-12-11 | 山东大学 | A kind of flexibility MXene self-supported membrane/metallic composite and preparation method thereof, application |
| CN110612365A (en) * | 2017-05-19 | 2019-12-24 | 昭和电工株式会社 | Method for electrochemically producing germane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103943836A (en) * | 2014-04-01 | 2014-07-23 | 太原理工大学 | Hollow germanium nanotube array electrode of lithium ion battery anode material and preparation method of array electrode |
| CN103943836B (en) * | 2014-04-01 | 2016-09-21 | 太原理工大学 | Lithium ion battery negative material hollow Ge nano-tube array electrode and preparation method thereof |
| CN104894618A (en) * | 2015-04-28 | 2015-09-09 | 哈尔滨工业大学 | Method for preparing germanium/aluminum nano film by electrodeposition of ionic liquid |
| CN104894618B (en) * | 2015-04-28 | 2017-05-03 | 哈尔滨工业大学 | Method for preparing germanium/aluminum nano film by electrodeposition of ionic liquid |
| CN105177648A (en) * | 2015-07-28 | 2015-12-23 | 吉林师范大学 | Device for preparing semiconductor material by using pulse laser for assisting ionic liquid electrolytic deposition |
| CN110612365A (en) * | 2017-05-19 | 2019-12-24 | 昭和电工株式会社 | Method for electrochemically producing germane |
| CN110612365B (en) * | 2017-05-19 | 2022-04-05 | 昭和电工株式会社 | Method for electrochemically producing germane |
| CN108336346A (en) * | 2018-02-07 | 2018-07-27 | 吉林师范大学 | A kind of application of germanium gallium nano wire as lithium ion battery electrode material |
| CN108987674A (en) * | 2018-07-25 | 2018-12-11 | 山东大学 | A kind of flexibility MXene self-supported membrane/metallic composite and preparation method thereof, application |
| CN108987674B (en) * | 2018-07-25 | 2020-06-05 | 山东大学 | Flexible MXene self-supporting film/metal composite material and preparation method and application thereof |
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| CN103606683B (en) | 2015-09-16 |
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