CN103606683B - Germanium nano material of a kind of Coiling-type and preparation method thereof - Google Patents

Germanium nano material of a kind of Coiling-type and preparation method thereof Download PDF

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CN103606683B
CN103606683B CN201310611096.0A CN201310611096A CN103606683B CN 103606683 B CN103606683 B CN 103606683B CN 201310611096 A CN201310611096 A CN 201310611096A CN 103606683 B CN103606683 B CN 103606683B
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germanium
electrode
electrolytic cell
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aluminium
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CN103606683A (en
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赵九蓬
郝健
刘昕
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Harbin Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Germanium nano material that the invention provides a kind of Coiling-type and preparation method thereof, this material can be used as the negative pole of lithium ion battery.The present invention adopts the method for ionic liquid electrodeposition prepare metal level and germanium layer and prepared the germanium nano material of above-mentioned Coiling-type in conjunction with crystallization inducing metal theory.The negative pole that the germanium nano material of Coiling-type provided by the invention is used as lithium ion battery effectively can slow down the volumetric expansion of germanium sill, prepares high power capacity, large multiplying power, long-life lithium-ion-power cell.

Description

Germanium nano material of a kind of Coiling-type and preparation method thereof
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, be difficult to the demand meeting the development such as space flight, military project, electric motor car, therefore find the study hotspot that the lithium cell negative pole material with high theoretical capacity becomes lithium ion battery, (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 due to the less stable of silicium cathode material.When forming intermetallic compound with silicon in Lithium-ion embeding silicon, its volumetric expansion can to 400%.After the de-lithium reaction of generation, silicon grain cannot reduce, and comes off gradually from collector, loses conductivity, and material structure is destroyed, and no longer has embedding lithium ability, makes the energy-storage property of battery not reach application standard far away.And germanium sill is relative 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 make lithium ion conduction velocity wherein be 400 times in silicon because germanium has lower can be with (EgGe=0.67ev, EgSi=1.12ev).And the conduction velocity of electric charge is 10 in silicon materials 4doubly, thus make germanium sill have higher specific capacity, it is made to have good application prospect in power vehicle direction, 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 in order to the puzzlement that the efflorescence reducing lithium cell negative pole material causes, need prepare can slow down volumetric expansion high-capacity cathode material.
The advantage maximum compared with other material of nano material is that the very little grain boundary of particle size is many, during removal lithium embedded, lithium ion also combines with it quickly through grain boundary and forms amorphous compound, recrystallization can not be there is and there is not phase transformation, therefore effectively can slow down the volumetric expansion of material.Germanium nano particle, nano wire, nanotube etc. are 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 first to plate one deck amorphous Germanium film on a silicon substrate, then evaporation last layer metallic aluminium, anneal in nitrogen atmosphere, anneal when 500 DEG C and can obtain dendritic germanium nano material under the induction of metallic aluminium in 60 minutes.But the method for hot evaporation needs there is higher requirement to vacuum degree and raw-material purity.Instrument and equipment also costly, is unsuitable for large-scale production.Although the method for electro-deposition is comparatively simple, and the pattern of the product obtained is controlled with composition.But the electrolyte due to the conventional deposition of germanium is high-temperature fusion salt, much poisonous, harmful material can be brought in reaction but also waste energy.And as reduction germanium raw material GeX 4(X=Cl, Br, I) can promptly be hydrolyzed under air and moisture or moist environment, therefore in electrodeposition process, just with the aqueous solution as electrolyte, thus can not constrain the development of electrochemical production germanium material.The various features such as ionic liquid has good conductivity, difficulty is volatilized, do not burn, electrochemical stability potential window is larger than other electrolyte aqueous solution.The deposition of Ge element and metallic element can be realized.The people such as Endres, adopt Pt ring electrode as a comparison, and Ag silk, as accurate reference electrode, uses the SiCl containing 0.1mol/L respectively in Au substrate (111) 4, 0.1mol/L GeCl 4and Si, Ge mol ratio is the SiCl of the 0.1mol/L of 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, not very obvious alleviating the effect in volumetric expansion.Therefore, seek a kind of method can preparing 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 germanium nano material that may be used for the Coiling-type of lithium ion battery negative, this nano material making lithium ion battery negative can increase the connectivity between active material and collector, effectively can reduce the volumetric expansion of negative material.
Another object of the present invention there is provided a kind of method preparing above-mentioned germanium nano material.
For achieving the above object, the present invention adopts following technical scheme:
The method of the germanium nano material of above-mentioned preparation Coiling-type, comprises the steps:
Ionic liquid EmimTf 2be placed in glove box for subsequent use after N vaccum dewatering; Preparation is containing 0.1M GeCl 4, 2.5MAlCl 3emimTf 2n solution is placed in glove box for subsequent use as electrolyte; Adopt three-electrode system codeposition germanium aluminium, connect electrolytic cell and guarantee that the Contact of electrode and electrolytic cell is not well short-circuited and breaking phenomena, the electrolytic cell connected is sent in glove box, connect electrolytic cell and electrochemical workstation, in electrolytic cell, add electrolyte, it is easy that its amount floods comparison electrode platinum loop with electrolyte; 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 is positioned at-1.0V, belong to the deposition peak of metallic aluminium and the underpotential deposition peak of germanium, second peak appears at-1.9V, belongs to the reduction peak that germanous changes elemental Germanium into, for realizing the common deposition of germanium aluminium, we elect sedimentation potential as-1.9V; Utilize potentiostatic electrodeposition method, setting sedimentation potential and sedimentation time 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, the brownish black film that one deck has metallic luster can be adhered on the working electrode (s, this film is the germanium aluminium film be deposited, wash the il electrolyte that this film removing film adsorbs with anhydrous isopropyl alcohol slowly, after washes clean, this film is placed in glove box and dries; After film dries completely, place it in and be filled with in the sample box of argon gas, take out from glove box, transfer to fast in tube furnace, close tube furnace, in its cavity, be filled with high pure nitrogen, to protect germanium aluminium film not oxidized, tube furnace is raised to 500 DEG C with the heating rate of 2 DEG C/min, 500 DEG C of insulations 60 minutes, utilizes metallic aluminium to the nanotopography of inducing germanium to form Coiling-type; Under the atmosphere of nitrogen, allow stove naturally cool to room temperature after annealing terminates, take out product, transfer to fast in glove box.
Wherein, three described electrodes are work electrode, reference electrode and comparison electrode, and above-mentioned electrode is nickel foil, high-purity filamentary silver and high-purity platinum loop respectively.
Wherein, described electrolytic cell is polytetrafluoro material, circle, electro-deposition area are 1cm 2.
Wherein, described electrolytic cell, O type circle and platinum loop soak after 4 hours before use and take out in volume ratio is the concentrated sulfuric acid of 1:1 and the mixed solution of hydrogen peroxide, be the distilled water of 1:1 and mixed solution of hydrogen peroxide, distilled water, ultra-pure water boiling washing 15 minutes successively by volume ratio, be placed in baking oven and dry.
The method that coupled ion liquid electric deposition process provided by the invention and crystallization inducing metal principle prepare the germanium nano-electrode material of Coiling-type has following advantage: can by composition and the grain size regulating the technological parameter such as composition, current density, sedimentation potential, sedimentation time of electrolyte to control sedimentation products in ionic liquid electrodeposition part.Compared with existing technique, germanium and aluminium can directly be deposited in substrate by electro-deposition 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, reduces in order to a step electro-deposition substantially increases operating efficiency from the evaporation twice (evaporation germanium, an AM aluminum metallization) of existing technique.And the particle diameter that electro-deposition goes out is smaller; in the process of electro-deposition, germanium metal aluminium is jointly deposited on matrix; utilize metallic aluminium to induce germanium crystal by annealing, the germanium nano particle be deposited out can form nanobelt gradually and further to reunite the final germanium nano material forming Coiling-type along with the increase nanobelt of annealing time.Its structure comparison of the germanium material of this pattern loosens and has the performance of monodimension nanometer material, lithium ion and electronics is not only made to have shorter transmission length diametrically, the transmission channel of more effective lithium ion and electronics can be provided simultaneously in the axial direction, be conducive to the high rate performance improving lithium ion battery.And the stress that can to produce in more effective release removal lithium embedded process due to its short texture, effective solution deviates from the volumetric expansion problem with germanium negative material in telescopiny at lithium ion, make it in cyclic process, have better structural stability, ensure that it can continue to play the advantages such as the comparatively bigger serface of nanostructure in cyclic process, 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 a current collector, by deposition materials after annealing and collector, there is good connectivity, the negative material that this legal system is standby compared with the existing method preparing lithium ion battery negative material does not need adhesive to be connected with collector, and its distribution of material be deposited is relatively more even, can improve the cycle performance of lithium ion battery.Therefore the Coiling-type germanium nano material utilizing patent of the present invention to prepare making lithium-ion negative pole 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 the cycle performance of lithium ion battery, high rate performance and security performance.
Accompanying drawing explanation
Fig. 1 is the particular flow sheet of preparation Coiling-type germanium nano material.
Fig. 2 is the SEM figure of the germanium aluminium film that ionic liquid electrodeposition goes out.
Fig. 3 is the EDS analysis chart of the germanium aluminium film that ionic liquid electrodeposition goes out.
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.Under the prerequisite not deviating from 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 Coiling-type germanium nano material
As shown in Figure 1, experimental section is mainly divided into ionic liquid electrodeposition to test and annealing experiment two large divisions to the idiographic flow of preparation Coiling-type germanium nano material.
One, ionic liquid electrodeposition germanium aluminium film
(1) experiment reagent pre-treatment
By ionic liquid EmimTf 2n is placed in glove box, and 100 DEG C of distillations 24 hours, the moisture in removing ionic liquid, made its water content be less than 2ppm, be placed in glove box for subsequent use.
(2) electrolyte is prepared
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 for subsequent use.
(3) electrolytic cell is connected
Three-electrode system is utilized 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 its floor space of container of the circle be made up of polytetrafluoro is 1cm 2, be furnished with O type for preventing electrolytic cell leakage in the part that electrolytic cell is connected with substrate (work electrode) and enclose sealing function.Take out after using front electrolytic cell, O type circle and platinum loop to soak 4 hours in the mixed solution of the volume ratio concentrated sulfuric acid that is 1:1 and hydrogen peroxide, be the distilled water of 1:1 and mixed solution of hydrogen peroxide, distilled water, ultra-pure water boiling washing 15 minutes successively by volume ratio, be placed in baking oven dry for standby.Connect electrolytic cell and guarantee that the Contact of each electrode and electrode cell does not well exist the phenomenon of short circuit and open circuit, the electrolytic cell connected is put into glove box, each electrode on electrolytic cell is connected with electrochemical workstation, the distance (being advisable at a distance of 0.2cm) of adjustment comparison electrode and work electrode, reference electrode to be positioned at directly over work electrode with work electrode at a distance of 0.1cm, in electrolytic cell, add electrolyte, it is easy that its amount floods comparison electrode platinum loop with electrolyte.
(1) cyclic voltammetry
The cyclic voltammetry curve of test system determines 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 is positioned at-1.0V, and this peak should belong to the deposition peak of metallic aluminium and the underpotential deposition peak of germanium, and second peak appears at this peak of-1.9V and belong to the reduction peak that germanous is deposited as elemental Germanium.For realizing the common deposition of germanium aluminium, we elect sedimentation potential as-1.9V.
(2) potentiostatic electrodeposition
The common consedimental current potential being obtained germanium aluminium by cyclic voltammetry is-1.9V.When depositing, sedimentation potential is set in-1.9V by us, and sedimentation time is set to 30 minutes.As can be seen from the I-T curve of electro-deposition, electric current first reduces to increase with the increase of sedimentation time again and reduces, 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, the nucleation increasing especially aluminium along with Nucleation object makes conductivity in substrate strengthen the increase of resistance drop-out current, after nucleation terminates, crystal can slowly be grown up along with the conductivity decline resistance of the continuous growth substrate of the germanium nano particle deposited increases electric current decline.After deposition terminates, 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 the working electrode (s, this film is the germanium aluminium film be deposited, wash the il electrolyte that this film removing film adsorbs with anhydrous isopropyl alcohol slowly, after washes clean, this film is placed in glove box and dries.
Two, annealing experiment
After film dries completely; place it in and be filled with in the sample box of argon gas; take out from glove box; transfer to fast in tube furnace, close tube furnace, in its cavity, be filled with high pure nitrogen; to protect germanium aluminium film not oxidized; tube furnace is raised to 500 DEG C with the heating rate of 2 DEG C/min, 500 DEG C of insulations 60 minutes, utilizes metallic aluminium to form strawy nanotopography to induce germanium.All in tube furnace, high-purity nitrogen is passed into and throughput is 10mL/min in the overall process of annealing.Under the atmosphere of nitrogen, allow stove naturally cool to room temperature after annealing terminates, take out product, transfer to fast in glove box, go bad because of oxidation to prevent product.
The morphology characterization of embodiment 2 germanium nano material
The microscopic appearance that we can see product is intuitively characterized by SEM, Fig. 2 is the SEM figure of the germanium aluminium film that ionic liquid electrodeposition goes out, from figure, we can find out that the film that direct electro-deposition goes out is that little crystal grain is assembled, analyze (Fig. 3) from EDS and can find out this film mainly containing Ge element and aluminium element, wherein a small amount of Cl, 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 also likely owing to being produced by the oxidation of fraction at the process in which materials characterized.And by after annealing, the pattern of its material there occurs obvious change due to the effect of metal inducement, Fig. 4 is the SEM figure of the germanium aluminium film after annealing, from figure, we can find out that germanium defines the microscopic appearance of Coiling-type through the induction of metallic aluminium, analyze in the material after drawing (Fig. 5) annealing main containing Ge element by EDS, wherein Ni is basis material, and Au is for the conductive paint that increases material is at sample surfaces in test SEM process.O, C adsorb in the Preparation and characterization process of material, and O element is also likely owing to being produced by the oxidation of fraction at the process in which materials characterized, and S is the component of ionic liquid.By characterizing and analyze the germanium nano material that can draw and utilize ionic liquid electrodeposition and metal inducement principle successfully can prepare Coiling-type above, and the method is simply efficient.

Claims (7)

1. prepare a method for the germanium nano material of Coiling-type, it is characterized in that, comprise the following steps: ionic liquid EmimTf 2be placed in glove box for subsequent use after N vaccum dewatering; Preparation is containing 0.1M GeCl 4, 2.5MAlCl 3emimTf 2n solution is placed in glove box for subsequent use as electrolyte; Adopt three-electrode system codeposition germanium aluminium, connect electrolytic cell and guarantee that the Contact of electrode and electrolytic cell is not well short-circuited and breaking phenomena, the part be connected with work electrode at electrolytic cell is furnished with O type circle, the electrolytic cell connected is sent in glove box, connect electrolytic cell and electrochemical workstation, in electrolytic cell, add electrolyte, make electrolyte flood comparison electrode platinum loop; Parameters carries out cyclic voltammetry to three-electrode system, to determine the sedimentation potential of germanium aluminium codeposition, the cathodic reduction curved portion of system comprises two peaks, first peak is positioned at-1.0V, belong to the deposition peak of metallic aluminium and the underpotential deposition peak of germanium, second peak appears at-1.9V, belongs to the reduction peak that germanous changes elemental Germanium into, for realizing the common deposition of germanium aluminium, elect sedimentation potential as-1.9V; Utilize potentiostatic electrodeposition method, setting sedimentation potential and sedimentation time 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, the brownish black film that one deck has metallic luster can be adhered on the working electrode (s, this film is the germanium aluminium film be deposited, wash the il electrolyte that this film removing film adsorbs with anhydrous isopropyl alcohol slowly, after washes clean, this film is placed in glove box and dries; After film dries completely, place it in and be filled with in the sample box of argon gas, take out from glove box, transfer to fast in tube furnace, close tube furnace, in its cavity, be filled with high pure nitrogen, to protect germanium aluminium film not oxidized, tube furnace is raised to 500 DEG C with the heating rate of 2 DEG C/min, 500 DEG C of insulations 60 minutes, utilizes metallic aluminium to the nanotopography of inducing germanium to form Coiling-type; Under the atmosphere of nitrogen, allow stove naturally cool to room temperature after annealing terminates, take out product, transfer to fast in glove box.
2. method according to claim 1, is characterized in that, three described electrodes are work electrode, reference electrode and comparison electrode, and work electrode, reference electrode and comparison electrode are nickel foil, high-purity filamentary silver and high-purity platinum loop respectively.
3. 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. method according to claim 1, it is characterized in that, described electrolytic cell, O type circle and platinum loop soak after 4 hours before use and take out in volume ratio is the concentrated sulfuric acid of 1:1 and the mixed solution of hydrogen peroxide, be the distilled water of 1:1 and mixed solution of hydrogen peroxide, distilled water, ultra-pure water boiling washing 15 minutes successively by volume ratio, be placed in baking oven and dry.
5. the germanium nano material of a kind of Coiling-type prepared by method according to claim 1.
6. germanium 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 germanium nano material according to claim 5.
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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
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
CN105177648B (en) * 2015-07-28 2017-07-18 吉林师范大学 A kind of utilization pulse laser assisting ion liquid electro-deposition prepares the device of semi-conducting material
JP7030115B2 (en) * 2017-05-19 2022-03-04 昭和電工株式会社 How to electrochemically produce Germanic
CN108336346B (en) * 2018-02-07 2020-06-19 吉林师范大学 Application of germanium-gallium nanowires as electrode material of lithium ion battery
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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