CN108315770B - A kind of germanium gallium nano wire and its growth in situ method - Google Patents

A kind of germanium gallium nano wire and its growth in situ method Download PDF

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CN108315770B
CN108315770B CN201810124315.5A CN201810124315A CN108315770B CN 108315770 B CN108315770 B CN 108315770B CN 201810124315 A CN201810124315 A CN 201810124315A CN 108315770 B CN108315770 B CN 108315770B
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germanium
gallium
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CN108315770A (en
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孟祥东
于兆亮
王多
李海波
孙萌
尹默
袁梦
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Jilin Normal University
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Abstract

The present invention provides a kind of growth in situ methods of germanium gallium nano wire, comprising the following steps: in environment of the water oxygen content lower than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the electrolyte constant pressure electro-deposition gallium under conditions of 55~65 DEG C, -1.4~-1.6V, obtain gallium nanosphere on the surface of the working electrode；Continue constant pressure deposition growth germanium under conditions of 55~65 DEG C, -2~-2.3V, grows germanium gallium nano wire in the surface in situ of the working electrode.Germanium gallium nano wire provided by the invention can improve the cycle performance of battery and high rate performance of pure germanium anode；And growth in situ method provided by the invention is easy to operate, at low cost.

Description

A kind of germanium gallium nano wire and its growth in situ method
Technical field
The present invention relates to nano wire preparation technical field more particularly to a kind of germanium gallium nano wire and its growth in situ methods.
Background technique
Lithium ion battery has become portable device because of the advantage that it has extended cycle life, self-discharge rate is low, operating voltage is high With the energy most important in industrial energy-storage system.However, the low energy densities of about 150Wh/kg are to the following mobile device of satisfaction Demand is a challenge.Since graphite anode only has the low reversible capacity of 372mAh/g, replaced using materials such as silicon, germanium, tin and antimony The lithium alloy anode that high capacity is developed for graphite has become worldwide one big hot spot.Wherein, silicon and germanium Yin Qili 4200mAh/g and 1600mAh/g is up to respectively by capacity and becomes very promising material.But silicon and germanium are as electrode The common drawback of material is that volume expansion is very big (Si:400%, Ge:370%) during lithium insertion and deintercalation, this is being recycled It will lead to crushing and the cracking of electrode material in the process.
In order to overcome this difficulty, a large amount of research is done to design the material for capableing of buffer volumes variation Material, such as nano particle, nano wire, nanotube and 3-D nano, structure.In all nano materials, nano wire is not only effective Reduce bulk strain, and the interfacial area with higher when contacting with electrolyte, and is passed for electronics along its length It is defeated to provide effective channel.Therefore, Ge nanoline receives significant attention.Although the theoretical capacity of germanium is lower than silicon, germanium has Some very promising characteristics, for example, high conductivity (being higher by 10000 times than silicon) and excellent lithium ion diffusion coefficient (room temperature It is lower to be higher by 400 times or more than silicon), this makes germanium become very promising high-performance lithium ion anode material.
The conventional method of growing Ge nanoline is gas-liquid-solid (VLS) or solid-liquid-liquid (SLS) method.Although both sides Method can effectively synthesize Ge nanoline, but there are also intrinsic disadvantages, such as high temperature either wants low pressure It asks；In addition, both methods is usually using refining and expensive toxic semiconductor precursor.Electrochemistry liquid-liquid-(Gu EC LLS) Method is a kind of directly from the new method of aqueous solution electrodeposition Ge nanoline, uses liquid metal nano-liquid droplet as ultra micro electricity The seed of pole and crystal growth.However, there are also disadvantages, such as very intractable liberation of hydrogen for electro-deposition Ge nanoline in aqueous solution The complexing agent that reaction may result in hydrogen embrittlement, need similar cyanide.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of germanium gallium nano wires and its growth in situ method, the present invention to mention The germanium gallium nano wire of confession can improve the cycle performance of battery and high rate performance of pure germanium anode；And growth in situ side provided by the invention Method is easy to operate, at low cost.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of growth in situ methods of germanium gallium nano wire, comprising the following steps:
In environment of the water oxygen content lower than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；
Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the electrolyte 55~ 65 DEG C, constant pressure electro-deposition gallium under conditions of -1.4~-1.6V, obtain gallium nanosphere on the surface of the working electrode；Continue 55~65 DEG C, constant pressure deposition growth germanium under conditions of -2~-2.3V are received in the surface in situ growth germanium gallium of the working electrode Rice noodles.
Preferably, the ionic liquid includes bis- (trimethyl fluoride sulfonyl) inferior amine salts of 1- ethyl-3-methylimidazole, 1- fourth Bis- (trimethyl fluoride sulfonyl) inferior amine salts of base -3- methylimidazole or bis- (fluoroform sulphonyl) inferior amine salts of N- butyl-N- methyl piperidine.
Preferably, GaCl in the electrolyte3Concentration be 0.09~0.11mol/L；GeCl4Concentration be 0.09~ 0.11mol/L。
Preferably, the working electrode is ITO substrate or copper base, and the reference electrode is filamentary silver, described to be to electrode Platinized platinum.
Preferably, the method for required voltage includes when obtaining the constant pressure electro-deposition gallium and the constant pressure deposition growth germanium Following steps:
In environment of the water oxygen content lower than 2ppm, by GaCl3It is mixed with ionic liquid, obtains GaCl3Electrolyte；It will GeCl4It is mixed with ionic liquid, obtains GeCl4Electrolyte；
Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the GaCl3Electrolyte And GeCl4Electrolyte carries out cyclic voltammetry curve scanning respectively, and the recovery voltage of gallium is constant pressure electricity in gained cyclic voltammetry curve Deposit voltage when gallium, the voltage when recovery voltage of germanium is constant pressure deposition growth germanium in gained cyclic voltammetry curve.
Preferably, the time of gallium described in constant pressure electro-deposition is 30~60s；The time of germanium described in constant pressure deposition growth is 150~300s.
Preferably, the gallium nanosphere is liquid nanometer ball, and the partial size of the gallium nanosphere is 50~200nm.
The present invention provides the germanium gallium nano wire that growth in situ method described in above-mentioned technical proposal obtains, wrapped in chemical composition Include elemental Germanium and Metallic Gallium.
Preferably, the atomic ratio of elemental Germanium and Metallic Gallium is (4~9) in the germanium gallium nano wire: 1.
Preferably, the diameter of the germanium gallium nano wire is 100~200nm, and length is 2.2~2.5 μm.
The present invention provides a kind of growth in situ methods of germanium gallium nano wire, comprising the following steps: is lower than in water oxygen content In the environment of 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；Using include working electrode, to electrode and By the electrolyte, constant pressure electricity under conditions of 55~65 DEG C, -1.4~-1.6V sinks the three-electrode electro Chemical system of reference electrode Product gallium, obtains gallium nanosphere on the surface of the working electrode；Continue constant pressure electricity under conditions of 55~65 DEG C, -2~-2.3V Deposition growing germanium grows germanium gallium nano wire in the surface in situ of the working electrode.The present invention starts constant pressure at 55~65 DEG C Electro-deposition Ga, since the fusing point of Ga is 29.4 DEG C, so the gallium nanosphere that deposition obtains is liquid condition, and in surface tension Under the action of keep spherical droplets state (i.e. Ga nanosphere)；Then at 55~65 DEG C, the constant pressure electricity on the Ga nanosphere Deposition growing germanium.According to theory of electrodeposition, metal ion can preferentially discharge in the position of working electrode protrusion.It is being deposited with On the working electrode of Ga nanosphere, Ga nanosphere is raised point relative to working electrode, so germanium ion can preferentially enter Ga Within nanosphere, and working electrode is reached by Ga nanosphere, it is heavy to form germanium in the interface of Ga nanosphere and working electrode Product object.With the progress of constant pressure electro-deposition, germanium deposit is increasing, and gallium is doped in the deposit of germanium in the process, most Whole gallium nanosphere and germanium deposit form nanowire structure, obtain germanium gallium nano wire.
The present invention uses ionic liquid environment when preparing germanium gallium nano wire, can effectively improve electrodeposition efficiency, solves Certainly hydrogen embrittlement problem caused by liberation of hydrogen in aqueous solution, the nano wire for obtaining deposition is especially suitable for lithium ion battery as electrode material Material.
Germanium gallium nano wire provided by the invention can improve the cycle performance of battery and high rate performance of pure germanium anode.In embodiment The experimental results showed that being assembled in CR2025 button using germanium gallium nano wire provided by the invention as working electrode (negative electrode material) Half-cell is made in battery case, under experimental conditions, the first time electric discharge of germanium gallium nano wire and charge specific capacity are respectively 1730 And 1537mAh/g, initial coulombic efficiency are 89%；And since the second circle circulation, coulombic efficiency is able to maintain 95% or more； Discharge capacity after 50 circulations is 1414mAh/g, and after 150 circulations, Ge-Ga nano line electrode is still able to maintain The capacity of 1146mAh/g.By germanium gallium nano line electrode half-cell under different current densities test loop specific capacity, germanium gallium nanometer Discharge capacity of the line in 0.16,0.32,0.8,1.6,3.2,8 and 16A/g be 1621 respectively, 1506,1409,1331,1242, 977 and 687mAh/g；Also, when current density again returns to 0.16A/g, capacity restoration to 1422mAh/g, capacity retention ratio Reach 87%.
In addition, growth in situ method provided by the invention is easy to operate, at low cost.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is GaCl in embodiment 13The cyclic voltammetry curve (a) and GeCl of electrolyte4The cyclic voltammetry curve of electrolyte (b)；
Fig. 2 is the schematic diagram in embodiment 2 in ITO deposition on substrate germanium gallium nano wire；
Fig. 3 be embodiment 2 on ITO substrate after constant pressure electro-deposition 60s gallium nanosphere scanning electron image, times magnification 20,000 times of number；
Fig. 4 be embodiment 2 on ITO substrate after constant pressure electro-deposition 300s germanium gallium nano wire scanning electron image, put Big 20,000 times of multiple；
Fig. 5 be embodiment 2 in germanium gallium nano wire cross section scanning electron image, 20,000 times of amplification factor；
Fig. 6 is the X-ray diffraction curve of germanium gallium nano wire in embodiment 2；
Fig. 7 is the transmission electron microscope image of single germanium gallium nano wire in embodiment 2；
Fig. 8 is the content curve of different elements after argon ion etching germanium gallium nano wire different time in embodiment 2；
Fig. 9 be embodiment 3 on copper base after constant pressure electro-deposition 60s gallium nanosphere scanning electron image, times magnification 20,000 times of number；
Figure 10 be embodiment 3 on copper base after constant pressure electro-deposition 300s germanium gallium nano wire scanning electron image, put Big 20,000 times of multiple；
Figure 11 is germanium gallium nano line electrode half-cell test loop stability and coulombic efficiency figure in embodiment 3；
Figure 12 is that germanium gallium nano line electrode half-cell tests the circulation figure under different current densities in embodiment 3.
Specific embodiment
The present invention provides a kind of growth in situ methods of germanium gallium nano wire, comprising the following steps:
In environment of the water oxygen content lower than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；
Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the electrolyte 55~ 65 DEG C, constant pressure electro-deposition gallium under conditions of -1.4~-1.6V, obtain gallium nanosphere on the surface of the working electrode；Continue 55~65 DEG C, constant pressure deposition growth germanium under conditions of -2~-2.3V are received in the surface in situ growth germanium gallium of the working electrode Rice noodles.
The present invention prepares the germanium gallium nano wire in environment of the water oxygen content lower than 2ppm.The present invention is preferably in glove box It is interior to prepare the germanium gallium nano wire；The glove box can control water oxygen content lower than 2ppm.
The present invention is in environment of the water oxygen content lower than 2ppm, by GaCl3、GeCl4It mixes, is electrolysed with ionic liquid Liquid.In the present invention, GaCl in the electrolyte3Concentration be preferably 0.09~0.11mol/L, more preferably 0.1mol/L； GeCl4Concentration be 0.09~0.11mol/L, more preferably 0.1mol/L.In the present invention, the GaCl3Purity be preferably 99.999%；The GeCl4Purity be preferably 99.9999%.The present invention is for the GaCl3And GeCl4Source without spy Different restriction, using commercial goods well known to those skilled in the art.In an embodiment of the present invention, the GaCl3 (99.999%) it buys from AlfaAesar company；The GeCl4(99.9999%) it buys from Guo Jing scientific & technical corporation.
In the present invention, the ionic liquid preferably includes bis- (trimethyl fluoride sulfonyl) imines of 1- ethyl-3-methylimidazole Salt ([EMIm] Tf2N), bis- (trimethyl fluoride sulfonyl) inferior amine salt ([BMIm] Tf of 1- butyl -3- methylimidazole2) or N- butyl-N- N Bis- (fluoroform sulphonyl) the inferior amine salt ([Py of methyl piperidine1,4]Tf2N).In the present invention, the ionic liquid uses preceding preferred Water process is carried out in environment of the water oxygen content lower than 2ppm.The present invention goes to remove water described in water process and progress for described Equipment used by handling does not have special restriction, i.e. using the technical solution well known to those skilled in the art for going water process It can.In an embodiment of the present invention, described to go water process specifically in the hand full of protective gas and water oxygen content lower than 2ppm In casing, at 100 DEG C for 24 hours to ionic liquid vacuum distillation.Present invention spy no for the source of the ionic liquid Different restriction, using commercial goods well known to those skilled in the art.In an embodiment of the present invention, the ionic liquid It buys from Kate's science, industry and trade Co., Ltd, section in Io-Li-Tec company, Germany or Lanzhou.In the present invention, the ionic liquid energy Enough effective raising electrodeposition efficiencies, solve the problems, such as hydrogen embrittlement caused by liberation of hydrogen in aqueous solution, the nano wire for obtaining deposition is special Suitable for lithium ion battery as electrode material.
The present invention is for the GaCl3、GeCl4The not special restriction with the mixing of ionic liquid, using art technology The technical solution of the mixing of material known to personnel.In the present invention, the mixing preferably carries out at 20~35 DEG C；At this In the embodiment of invention, the mixing specifically carries out at room temperature, that is, does not need additionally to be heated or cooled.In the present invention, The mixing preferably carries out under agitation, and the revolving speed of the stirring is preferably 400~600rpm, more preferably 500rpm； The time of the stirring is preferably 10~14h, more preferably 12h.In embodiment in the present invention, the mixing specifically exists It is carried out in glove box full of protective gas and water oxygen content lower than 2ppm.
After obtaining electrolyte, the present invention is used including working electrode, to the three-electrode electro Chemical body of electrode and reference electrode System's constant pressure electro-deposition gallium under conditions of 55~65 DEG C, -1.4~-1.6V by the electrolyte, on the surface of the working electrode Obtain gallium nanosphere；Continue constant pressure deposition growth germanium under conditions of 55~65 DEG C, -2~-2.3V, in the working electrode Surface in situ grow germanium gallium nano wire (Ge-Ga nano wire).
The present invention does not have special restriction for holding the electrolytic cell of the electrolyte, using known to those skilled in the art Electrolytic cell, it is specific such as polytetrafluoroethylene (PTFE) electrolytic cell.In an embodiment of the present invention, the germanium for the ease of will be prepared Gallium nano wire is tested for the property applied to lithium battery, specifically utilizes the heavy of polytetrafluoroethylene (PTFE) electrolytic cell limitation germanium gallium nano wire Product area is 1.5cm2。
The present invention in the three-electrode electro Chemical system working electrode, do not have to electrode and reference electrode it is special It limits, using working electrode well known to those skilled in the art, to electrode and reference electrode；In the embodiment of the present invention In, it is specifically to electrode using ITO substrate or copper base as working electrode, using filamentary silver as reference electrode, with platinized platinum.In this hair In bright, filamentary silver is capable of providing sufficiently stable electrode voltage.In the present invention, the ITO substrate or copper base are using preceding excellent Choosing is washed, and the washing preferably includes successively to carry out acetone to wash washes with isopropanol；Number of the present invention for the washing And the amount for washing washing reagent used every time does not have special restriction, using the technology of washing well known to those skilled in the art Scheme.In an embodiment of the present invention, the copper base is after washing, it is also necessary to use mass content for 10% hydrochloric acid 1min is impregnated to remove surface oxides.
Used electrochemical workstation does not have special restriction when the present invention is for preparing the germanium gallium nano wire, uses The electrochemical workstation well known to those skilled in the art for being able to carry out cyclic voltammetry curve scanning with constant voltage test, such as 2273 electrochemical workstations or occasion China electrochemical workstation.In an embodiment of the present invention, 2273 electrochemistry works are specifically used The cyclic voltammetry curve that Power CV and Power CORR software carries out in (PrincetonApplied Research) of standing is swept It retouches and is tested with constant voltage.
In the present invention, the time of gallium described in constant pressure electro-deposition is preferably 30~60s.In the present invention, the gallium nanometer Ball is liquid nanometer ball, and the partial size of the gallium nanosphere is preferably 50~200nm.
In the present invention, the time of germanium described in constant pressure deposition growth is preferably 150~300s.
In the present invention, the method for required voltage when the constant pressure electro-deposition gallium and the constant pressure deposition growth germanium is obtained Preferably include following steps:
In environment of the water oxygen content lower than 2ppm, by GaCl3It is mixed with ionic liquid, obtains GaCl3Electrolyte；It will GeCl4It is mixed with ionic liquid, obtains GeCl4Electrolyte；
Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the GaCl3Electrolyte And GeCl4Electrolyte carries out cyclic voltammetry curve scanning respectively, and the recovery voltage of gallium is constant pressure electricity in gained cyclic voltammetry curve Deposit voltage when gallium, the voltage when recovery voltage of germanium is constant pressure deposition growth germanium in gained cyclic voltammetry curve.
In the present invention, the GaCl3Concentration of electrolyte is preferably 0.09~0.11mol/L, more preferably 0.1mol/L； The GeCl4The concentration of electrolyte is preferably 0.09~0.11mol/L, more preferably 0.1mol/L.In the present invention, described GaCl3、GeCl4It is consistent that reagent used by germanium gallium nano wire is preferably prepared with the application above-mentioned technical proposal with ionic liquid.
In the present invention, by the GaCl3When electrolyte carries out cyclic voltammetry curve scanning, scanning range is preferably -2.5 ~2V；Sweep speed is preferably 50mV/s；Equilibration time is preferably 15s.
In the present invention, by the GeCl4When electrolyte carries out cyclic voltammetry curve scanning, scanning range is preferably -2.5 ~2V；Sweep speed is preferably 50mV/s；Equilibration time is preferably 15s.
The present invention does not have special limit for the working electrode, to the three-electrode electro Chemical system of electrode and reference electrode It is fixed, using three-electrode electro Chemical system well known to those skilled in the art；In an embodiment of the present invention, it is followed described in progress Three-electrode electro Chemical system used by ring volt-ampere curve scans preferably prepares germanium gallium nano wire with the application above-mentioned technical proposal Used three-electrode electro Chemical system is consistent.
After the completion of constant pressure deposition growth germanium, the present invention, which preferably immerses gained print in isopropanol, to be cleaned to remove deionization Liquid residue obtains germanium gallium nano wire.In the present invention, the gallium Ge nanoline does not need to separate with the working electrode, Specifically, if can choose ITO substrate working electrode to be scanned Electronic Speculum characterization to the gallium Ge nanoline；Such as Fruit is then to can choose copper base working electrode using gallium Ge nanoline as lithium ion cell electrode.
The present invention starts constant pressure electro-deposition Ga at 55~65 DEG C, since the fusing point of Ga is 29.4 DEG C, so deposition obtains Gallium nanosphere be liquid condition, and under the action of surface tension keep spherical droplets state (i.e. Ga nanosphere)；Then At 55~65 DEG C, the constant pressure deposition growth germanium on the Ga nanosphere.According to theory of electrodeposition, metal ion can preferentially exist It discharges the position of working electrode protrusion.On the working electrode for being deposited with Ga nanosphere, Ga nanosphere is relative to work electricity Pole is the point of protrusion, so germanium ion can preferentially enter within Ga nanosphere, and reach working electrode by Ga nanosphere, The interface of Ga nanosphere and working electrode forms germanium deposit.With the progress of constant pressure electro-deposition, germanium deposit is increasing, Gallium is doped in the deposit of germanium in the process, and final gallium nanosphere and germanium deposit form nanowire structure, obtains germanium gallium Nano wire.
The present invention provides the germanium gallium nano wire that growth in situ method described in above-mentioned technical proposal obtains, wrapped in chemical composition Include elemental Germanium and Metallic Gallium.In the present invention, in the germanium gallium nano wire atom of elemental Germanium and Metallic Gallium preferably than for (4~ 9): 1.In the present invention, the diameter of the germanium gallium nano wire is preferably 100~200nm, and length is preferably 2.2~2.5 μm.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to In the scope of protection of the invention.
Embodiment 1
In full of the glove box of argon gas and water oxygen content lower than 2ppm, by the bis- (trifluoromethyls of 1- ethyl-3-methylimidazole Sulphonyl) inferior amine salt ([EMIm] Tf2N) ionic liquid be evaporated in vacuo at 100 DEG C for 24 hours, by gained ionic liquid respectively with GaCl3 (99.999%) and GeCl4(99.9999%) it mixes, 500rpm stirs 12h at room temperature, obtains the GaCl of 1mol/L3Electrolyte and The GeCl of 1mol/L4Electrolyte；
Successively clean ITO substrate with acetone and isopropanol, using ITO substrate as working electrode, filamentary silver as reference electrode, Platinized platinum is used as to electrode, is 1.5cm using polytetrafluoroethylene (PTFE) electrolytic cell limitation depositional area2, using 2273 electrochemical workstations (Princeton Applied Research) will warm up 60 DEG C of GaCl respectively3Electrolyte and GeCl4Electrolyte is recycled Volt-ampere curve scans, the voltage when recovery voltage of gallium is constant pressure electro-deposition gallium in gained cyclic voltammetry curve, gained circulation volt The voltage when recovery voltage for pacifying germanium in curve is constant pressure deposition growth germanium；Wherein, by the GaCl3Electrolyte is recycled When volt-ampere curve scans, scanning range is -2.5~2V；Sweep speed is 50mV/s；Equilibration time is 15s；By the GeCl4 When electrolyte carries out cyclic voltammetry curve scanning, scanning range is -2.5~2V；Sweep speed is 50mV/s；Equilibration time is 15s。
Fig. 1 is GaCl3The cyclic voltammetry curve (a) and GeCl of electrolyte4The cyclic voltammetry curve (b) of electrolyte, from Fig. 1 (a) negative potential region can observe a reduction peak, be Ga3+The peak of → Ga, the peak in positive potential region are Ga nanosphere Oxidation peak；Two reduction peaks in negative potential region are respectively Ge in Fig. 1 (b)4+→Ge2+With Ge2+The reduction peak of → Ge, positive potential The peak in region is the oxidation peak of Ge deposit.According to Fig. 1, the present invention selects constant pressure electro-deposition under conditions of -1.4~-1.6V Gallium, constant pressure deposition growth germanium under conditions of -2~-2.3V.
Embodiment 2
Fig. 2 is the process schematic in ITO deposition on substrate germanium gallium nano wire, the specific steps are as follows:
In full of the glove box of argon gas and water oxygen content lower than 2ppm, by the bis- (trifluoromethyls of 1- ethyl-3-methylimidazole Sulphonyl) inferior amine salt ([EMIm] Tf2N) ionic liquid is evaporated in vacuo for 24 hours at 100 DEG C, by gained ionic liquid and GaCl3 (99.999%) and GeCl4(99.9999%) it mixes, 500rpm stirs 12h at room temperature, obtains GaCl3Concentration and GeCl4Concentration It is the electrolyte of 1mol/L；
Successively clean ITO substrate with acetone and isopropanol, using ITO substrate as working electrode, filamentary silver as reference electrode, Platinized platinum is used as to electrode, is 1.5cm using polytetrafluoroethylene (PTFE) electrolytic cell limitation depositional area2, using 2273 electrochemical workstations (PrincetonAppliedResearch) by the electrolyte under 60 DEG C of temperature, -1.5V voltage constant pressure electro-deposition gallium 60s, Gallium nanosphere is obtained on the surface of the working electrode；Continue constant pressure deposition growth germanium under conditions of 60 DEG C, -2.2V 300s grows germanium gallium nano wire in the surface in situ of the working electrode.
Gallium nanosphere obtained in constant pressure electrodeposition process and final gained germanium gallium nano wire are characterized, as a result such as Under:
Fig. 3 is the scanning electron image of the gallium nanosphere after constant pressure electro-deposition 60s on ITO substrate, 20,000 times of amplification factor； From the figure 3, it may be seen that the size range of gallium nanosphere is 50~200nm.
Fig. 4 is the scanning electron image of the germanium gallium nano wire after constant pressure electro-deposition 300s on ITO substrate, amplification factor 20,000 Times；As shown in Figure 4, final deposit obtained is nano wire, and the diameter of the nano wire is 100~200nm, is largely received Rice noodles obviously attenuate in twisting contour and along axial direction.
Fig. 5 be germanium gallium nano wire cross section scanning electron image, 20,000 times of amplification factor；It can by the sectional view in Fig. 5 It is about 2.4 μm to calculate the length of germanium gallium nano wire.
Fig. 6 is the X-ray diffraction image of the germanium gallium nano wire prepared on ITO substrate；It will be appreciated from fig. 6 that being in 2 θ angles 27.61 °, 45.67 °, 53.95 °, 66.24 ° and 73.09 ° of peak position correspond respectively to (111) of crystal germanium, (220), (311), (400) and (331) diffraction maximum；Remaining diffraction maximum is from ITO substrate.The diffraction of gallium is not observed in germanium gallium nano wire Peak illustrates that gallium is possible to exist with noncrystalline state.
Fig. 7 is the transmission electron microscope image of single germanium gallium nano wire；It is shown by the elemental map in the upper right corner Fig. 7 Ge element is uniformly distributed in the surface of germanium gallium nano wire with Ga element.
Fig. 8 is the content curve with elements different after argon ion etching germanium gallium nano wire different time.In Fig. 8, oxygen element Appearance with carbon is since sample is put into inevitably air contact during test equipment；With etch period Increase, the content of oxygen and carbon is all declining, and illustrates that germanium gallium nano wire is surface oxidation.Also, the content of germanium is with the content of gallium All increasing, after etching 120s, the content of germanium and gallium is respectively 77% and 8.7%, it follows that the atom content of germanium and gallium Than being about 9:1.This also illustrates that gallium has been doped into inside nano wire, is not the surface for being merely present in nano wire.
Embodiment 3
Germanium gallium nano wire is prepared according to the method for embodiment 2, wherein using copper base as working electrode, the copper base exists Successively cleaned with acetone and isopropanol using preceding, then mass content be 10% salt acid soak 1min to remove superficial oxidation Object；Voltage when depositing the gallium is -1.6V, and voltage when depositing the germanium is -2.2V.
Fig. 9 is the scanning electron image of the gallium nanosphere after constant pressure electro-deposition 60s on copper base, 20,000 times of amplification factor；By Fig. 6 is it is found that compared to the Ga nanosphere on ITO substrate, and more evenly, average grain diameter is about for the particle diameter distribution of Ga nanosphere on copper base For 50nm.
Figure 10 is the scanning electron image of the germanium gallium nano wire after constant pressure electro-deposition 300s on copper base, amplification factor 20,000 Times；As shown in Figure 7, due to Ga nanosphere uniform particle sizes and smaller, so the length for the germanium gallium nano wire that deposition obtains is also more Uniformly, nanowire diameter is thinner, is more applicable in lithium ion battery.
Using the germanium gallium nano wire as working electrode, it is assembled in CR2025 button cell shell and half-cell, lithium piece is made As to electrode, polyethene microporous membrane as diaphragm, with the LiPF of 1mol/L6It is dissolved in ethylene carbonate-ethylene carbonate (EC-DEC) mixed solution as electrolyte (wherein, the volume ratio of EC and DEC be 1:1), with new prestige battery test system (in State Shenzhen) battery charge and discharge performance is tested, as a result as follows:
Figure 11 is germanium gallium nano line electrode half-cell test loop stability and coulombic efficiency figure, and circulating current density is 0.32A/g；As shown in Figure 8, the first time electric discharge of Ge-Ga nano wire and charge specific capacity are respectively 1730 and 1537mAh/g, just Beginning coulombic efficiency is 89%.Ge, Ge nanometers of There-dimensional ordered macroporous materials of the ionic liquid electrodeposition preparation reported before comparison Pipe and Ge nano wire (initial coulombic efficiency is respectively 58%, 77% and 81%), the first coulombic efficiency of Ge-Ga nano wire is It improves；And since the second circle circulation, coulombic efficiency is able to maintain 95% or more；50 times circulation after discharge capacity be 1414mAh/g, after 150 circulations, Ge-Ga nano line electrode is still able to maintain the capacity of 1146mAh/g.
Figure 12 is that germanium gallium nano line electrode half-cell tests the cyclic specific capacity figure under different current densities；As shown in Figure 9, Test is by 0.16A/g, increase to the current density of 0.32,0.8,1.6,3.2,8 and 16A/g after every circulation 5 times, then Again return to 0.16A/g.Discharge capacity difference of the Ge-Ga nano wire in 0.16,0.32,0.8,1.6,3.2,8 and 16A/g It is 1621,1506,1409,1331,1242,977 and 687mAh/g；Also, when current density again returns to 0.16A/g, hold Amount is restored to 1422mAh/g, and capacity retention ratio reaches 87%.This illustrates the Ge-Ga nano wire energy of ionic liquid electrodeposition preparation Improve the cycle performance of battery and high rate performance of pure germanium anode.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (9)

1. a kind of growth in situ method of germanium gallium nano wire, comprising the following steps:
In environment of the water oxygen content lower than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；The ion Liquid is selected from bis- (trimethyl fluoride sulfonyl) inferior amine salts of 1- ethyl-3-methylimidazole, the bis- (trifluoromethyls of 1- butyl -3- methylimidazole Sulphonyl) inferior amine salt or bis- (fluoroform sulphonyl) inferior amine salts of N- butyl-N- methyl piperidine；
Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the electrolyte 55~65 DEG C, constant pressure electro-deposition gallium under conditions of -1.4~-1.6V, obtain gallium nanosphere on the surface of the working electrode；Continue 55 ~65 DEG C, constant pressure deposition growth germanium under conditions of -2~-2.3V grow germanium gallium nanometer in the surface in situ of the working electrode Line.
2. growth in situ method according to claim 1, which is characterized in that GaCl in the electrolyte3Concentration be 0.09 ~0.11mol/L；GeCl4Concentration be 0.09~0.11mol/L.
3. growth in situ method according to claim 1, which is characterized in that the working electrode is ITO substrate or copper-based Piece, the reference electrode are filamentary silver, and described is platinized platinum to electrode.
4. growth in situ method according to claim 1, which is characterized in that obtain the constant pressure electro-deposition gallium and the perseverance When piezo deposition grows germanium required voltage method the following steps are included:
In environment of the water oxygen content lower than 2ppm, by GaCl3It is mixed with ionic liquid, obtains GaCl3Electrolyte；By GeCl4With Ionic liquid mixing, obtains GeCl4Electrolyte；
Using include working electrode, to the three-electrode electro Chemical system of electrode and reference electrode by the GaCl3Electrolyte and GeCl4Electrolyte carries out cyclic voltammetry curve scanning respectively, and the recovery voltage of gallium is heavy for constant pressure electricity in gained cyclic voltammetry curve Accumulate voltage when gallium, the voltage when recovery voltage of germanium is constant pressure deposition growth germanium in gained cyclic voltammetry curve.
5. growth in situ method according to claim 1, which is characterized in that the time of gallium described in constant pressure electro-deposition be 30~ 60s；The time of germanium described in constant pressure deposition growth is 150~300s.
6. growth in situ method according to claim 1 or 5, which is characterized in that the gallium nanosphere is liquid nanometer ball, The partial size of the gallium nanosphere is 50~200nm.
7. the germanium gallium nano wire that any one of the claim 1~6 growth in situ method obtains, which is characterized in that chemical composition Upper includes elemental Germanium and Metallic Gallium.
8. germanium gallium nano wire according to claim 7, which is characterized in that elemental Germanium and Metallic Gallium in the germanium gallium nano wire Atomic ratio be (4~9): 1.
9. germanium gallium nano wire according to claim 7 or 8, which is characterized in that the diameter of the germanium gallium nano wire be 100~ 200nm, length are 2.2~2.5 μm.
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