CN108336346A - A kind of application of germanium gallium nano wire as lithium ion battery electrode material - Google Patents
A kind of application of germanium gallium nano wire as lithium ion battery electrode material Download PDFInfo
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- CN108336346A CN108336346A CN201810124313.6A CN201810124313A CN108336346A CN 108336346 A CN108336346 A CN 108336346A CN 201810124313 A CN201810124313 A CN 201810124313A CN 108336346 A CN108336346 A CN 108336346A
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Abstract
A kind of application the present invention provides germanium gallium nano wire as lithium ion battery electrode material, includes elemental Germanium and Metallic Gallium in the germanium gallium nano wire chemical composition, and the atomic ratio of elemental Germanium and Metallic Gallium is (4~9) in the germanium gallium nano wire：1.Electrode material of the present invention using germanium gallium nano wire as lithium ion battery, can improve the cycle performance of battery and high rate performance of lithium ion battery.
Description
Technical field
The present invention relates to electrode material technical fields more particularly to a kind of germanium gallium nano wire as lithium ion cell electrode material
The application of material.
Background technology
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 most important energy in industrial energy-storage system.However, the low energy densities of about 150Wh/kg are to meeting the following mobile device
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
Have become worldwide one big hot spot for graphite to develop the lithium alloy anode of high power capacity.Wherein, silicon and germanium Yin Qili
It is up to 4200mAh/g and 1600mAh/g respectively by capacity and becomes very promising material.But silicon and germanium are as electrode
The common drawback of material is the very big (Si of volume expansion during lithium is inserted into deintercalation：400%, Ge：370%), this is being recycled
Crushing and the cracking that can lead to electrode material in the process, influence the using effect of lithium ion battery.
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 there is higher interfacial area when being contacted 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 less 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, electric using liquid metal nano-liquid droplet as ultra micro
The seed of pole and crystal growth；But the electro-deposition nano wire obtained in this way is when as electrode material, chemical property
It is bad.
Invention content
In view of this, the purpose of the present invention is to provide a kind of germanium gallium nano wire answering as lithium ion battery electrode material
With improving the cycle performance of battery and high rate performance of lithium ion battery.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of application the present invention provides germanium gallium nano wire as lithium ion battery electrode material, the germanium gallium nano wire
Include elemental Germanium and Metallic Gallium in chemical composition, the atomic ratio of elemental Germanium and Metallic Gallium is (4~9) in the germanium gallium nano wire：
1。
Preferably, a diameter of 50~100nm of the germanium gallium nano wire, length are 500~1000nm.
Preferably, the preparation method of the germanium gallium nano wire, includes the following steps：
In environment of the water oxygen content less than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；
Using the three-electrode electro Chemical system including working electrode, to electrode and reference electrode by the electrolyte 55~
65 DEG C, constant pressure electro-deposition gallium under conditions of -1.0~-1.5V, gallium deposit is obtained on the surface of the working electrode；Continue
55~65 DEG C, constant pressure electro-deposition germanium under conditions of -1.8~-2.2V, germanium gallium nano wire is obtained on the surface of the working electrode.
Preferably, the ionic liquid includes bis- (trimethyl fluoride sulfonyl) inferior amine salts of 1- ethyl-3-methylimidazoles, 1- fourths
Bis- (trimethyl fluoride sulfonyl) inferior amine salts of base -3- methylimidazoles or bis- (fluoroform sulphonyl) inferior amine salts of N- butyl-N- methyl piperidines.
Preferably, GaCl in the electrolyte3A concentration of 0.09~0.11mol/L；GeCl4A concentration of 0.09~
0.11mol/L。
Preferably, the method for required deposition voltage includes when obtaining the constant pressure electro-deposition gallium and the constant pressure electro-deposition germanium
Following steps：
In environment of the water oxygen content less than 2ppm, by GaCl3It is mixed with ionic liquid, obtains GaCl3Electrolyte；It will
GeCl4It is mixed with ionic liquid, obtains GeCl4Electrolyte；
Using the three-electrode electro Chemical system including working electrode, to 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
Voltage when gallium is deposited, the voltage when recovery voltage of germanium is constant pressure electro-deposition germanium in gained cyclic voltammetry curve.
Preferably, the time of gallium described in constant pressure electro-deposition is 30~60s.
Preferably, the gallium deposit is liquid microballoon, and the grain size of the gallium deposit is 30~60nm.
Preferably, the time of germanium described in constant pressure electro-deposition is 150~300s.
Preferably, in the lithium ion battery using germanium gallium nano wire as working electrode, lithium piece as to electrode, polyethylene
Microporous barrier is as diaphragm, the LiPF of 1mol/L6The mixed solution of ethylene carbonate-ethylene carbonate is dissolved in as electrolyte.
A kind of application the present invention provides germanium gallium nano wire as lithium ion battery electrode material, the germanium gallium nano wire
Include elemental Germanium and Metallic Gallium in chemical composition, the atomic ratio of elemental Germanium and Metallic Gallium is (4~9) in the germanium gallium nano wire：
1.Electrode material of the present invention using germanium gallium nano wire as lithium ion battery, can improve the cycle performance of battery of lithium ion battery
With high rate performance.The experimental results showed that, using the germanium gallium nano wire as working electrode (negative material), it is assembled in embodiment
Half-cell is made in CR2025 button cell shells, under experimental conditions, the first time electric discharge of germanium gallium nano wire and charge specific capacity
Respectively 1730 and 1537mAh/g, initial coulombic efficiency are 89%；And since the second circle cycle, coulombic efficiency can be kept
95% or more；Discharge capacity after 50 cycles is 1414mAh/g, after 150 cycles, Ge-Ga nano wire electricity
Pole remains to keep the capacity of 1146mAh/g.By germanium gallium nano line electrode half-cell under different current densities test loop specific volume
Amount, discharge capacity of the germanium gallium nano wire 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 arrives
1422mAh/g, capacity retention ratio reach 87%.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is GaCl on Cu substrates in embodiment 13The cyclic voltammetry curve (a) and GeCl of electrolyte4The cycle of electrolyte
Volt-ampere curve (b)；
Fig. 2 is the schematic diagram of electro-deposition germanium gallium nano wire in embodiment 2；
Fig. 3 be embodiment 2 on Cu substrates after constant pressure electro-deposition 60s gallium deposit scanning electron image, times magnification
20,000 times of number；
Fig. 4 be embodiment 2 on Cu substrates after constant pressure electro-deposition 300s germanium gallium nano wire scanning electron image, amplification
20,000 times of multiple；
Fig. 5 is the transmission electron microscope image of single germanium gallium nano wire in embodiment 2；
Fig. 6 is the selective electron diffraction image of germanium gallium nano wire in embodiment 2；
Fig. 7 is not have the x-ray photoelectron spectroscopy of argon ion etching and germanium gallium nano wire after etching 120s bent in embodiment 2
Line；
Fig. 8 is the optical photograph of germanium gallium nano wire and the CR2025 half-cell optics being assembled on Cu substrates in embodiment 3
Photo；
Fig. 9 is germanium gallium nano line electrode half-cell test loop stability and coulombic efficiency figure in embodiment 3；
Figure 10 is that germanium gallium nano line electrode half-cell tests the cycle figure under different current densities in embodiment 3；
Figure 11 is the scanning electron microscope image that germanium gallium nano wire cycle surveys after 150 circles in embodiment 3.
Specific implementation mode
A kind of application the present invention provides germanium gallium nano wire as lithium ion battery electrode material, the germanium gallium nano wire
Include elemental Germanium and Metallic Gallium in chemical composition, the atomic ratio of elemental Germanium and Metallic Gallium is (4~9) in the germanium gallium nano wire：
1.In the present invention, the diameter of the germanium gallium nano wire is preferably 50~100nm, and length is preferably 500~1000nm.
In the present invention, the preparation method of the germanium gallium nano wire preferably includes following steps：
In environment of the water oxygen content less than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；
Using the three-electrode electro Chemical system including working electrode, to electrode and reference electrode by the electrolyte 55~
65 DEG C, constant pressure electro-deposition gallium under conditions of -1.0~-1.5V, gallium deposit is obtained on the surface of the working electrode；Continue
55~65 DEG C, constant pressure electro-deposition germanium under conditions of -1.8~-2.2V, germanium gallium nano wire is obtained on the surface of the working electrode.
The present invention preferably prepares the germanium gallium nano wire in environment of the water oxygen content less than 2ppm.The present invention is preferably in hand
The germanium gallium nano wire is prepared in casing；The glove box can control water oxygen content and be less than 2ppm.
The present invention is preferably in environment of the water oxygen content less than 2ppm, by GaCl3、GeCl4It mixes, obtains with ionic liquid
Electrolyte.In the present invention, GaCl in the electrolyte3Concentration be preferably 0.09~0.11mol/L, more preferably
0.1mol/L；GeCl4A concentration of 0.09~0.11mol/L, more preferably 0.1mol/L.In the present invention, the GaCl3's
Purity is preferably 99.999%；The GeCl4Purity be preferably 99.9999%.The present invention is for the GaCl3And GeCl4's
Source does not have special restriction, using commercial goods well known to those skilled in the art.In an embodiment of the present invention, institute
State GaCl3(99.999%) it buys from AlfaAesar companies；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-methylimidazoles
Salt ([EMIm] Tf2N), bis- (trimethyl fluoride sulfonyl) inferior amine salt ([BMIm] Tf of 1- butyl -3- methylimidazoles2) 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 less than 2ppm.The present invention goes to remove water described in water process and progress for described
Equipment does not have special restriction used by processing, 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 less than 2ppm
In casing, at 100 DEG C for 24 hours to ionic liquid vacuum distillation.The present invention is for the no spy in 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 of section in Io-Li-Tec companies of 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, keep the nano wire that deposition obtains 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 that material known to personnel mixes.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, i.e., need not additionally be heated or cooled.In the present invention,
The mixing preferably carries out under agitation, and the rotating 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 less than 2ppm.
After obtaining electrolyte, present invention preferably employs including working electrode, to three electrode electrochemicals of electrode and reference electrode
System constant pressure electro-deposition gallium under conditions of 55~65 DEG C, -1.0~-1.5V by the electrolyte, in the working electrode
Surface obtains gallium deposit；Continue constant pressure electro-deposition germanium under conditions of 55~65 DEG C, -1.8~-2.2V, in work electricity
The surface of pole obtains germanium gallium nano wire (Ge-Ga nano wires).
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 copper base as working electrode, using filamentary silver as reference electrode, with platinized platinum.In the present invention, filamentary silver
It is capable of providing sufficiently stable electrode voltage.In the present invention, the copper base is preferably washed using preceding, the washing
It preferably includes to carry out acetone successively to wash and be washed with isopropanol；Number and every time washing used washing of the present invention for the washing
The amount of reagent does not have special restriction, using the technical solution of washing well known to those skilled in the art.The present invention's
In embodiment, the copper base is after washing, it is also necessary to use the salt acid soak 1min that mass content is 10% to remove surface layer
Oxide.
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 that can carry out cyclic voltammetry curve scanning and 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 softwares carry 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 deposition
Object is liquid microballoon, and the grain size of the gallium deposit is preferably 30~60nm.
In the present invention, the time of germanium described in constant pressure electro-deposition is preferably 150~300s.
In the present invention, the method for obtaining required voltage when the constant pressure electro-deposition gallium and the constant pressure electro-deposition germanium is preferred
Include the following steps：
In environment of the water oxygen content less than 2ppm, by GaCl3It is mixed with ionic liquid, obtains GaCl3Electrolyte；It will
GeCl4It is mixed with ionic liquid, obtains GeCl4Electrolyte；
Using the three-electrode electro Chemical system including working electrode, to 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
Voltage when gallium is deposited, the voltage when recovery voltage of germanium is constant pressure electro-deposition 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、GeCl4Reagent is consistent used by preferably preparing germanium gallium nano wire 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 -2.0
~0V；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
~0V；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 preferably prepares germanium gallium nano wire with the application above-mentioned technical proposal used by the scanning of ring volt-ampere curve
Used three-electrode electro Chemical system is consistent.
After the completion of constant pressure electro-deposition germanium, the present invention, which preferably immerses gained print in isopropanol, to be cleaned to remove ionic liquid
Residue obtains germanium gallium nano wire.In the present invention, the gallium Ge nanoline need not be detached with the working 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 deposit be liquid condition, and under the action of surface tension keep spherical droplets state (i.e. Ga nanospheres)；Then
At 55~65 DEG C, the constant pressure electro-deposition germanium on the Ga nanospheres.According to theory of electrodeposition, metal ion can preferentially work
It discharges the position of electrode protrusion.On the deposited substrate for having Ga nanospheres, Ga nanospheres are protrusions relative to working electrode
Point, so germanium ion can preferentially enter within Ga nanospheres, and working electrode is reached by Ga nanospheres, in Ga nanospheres
Germanium deposit is formed with the interface of working electrode.With the progress of constant pressure electro-deposition, germanium deposit is on the increase, in this process
Middle gallium is doped in the deposit of germanium, and final gallium deposit forms nano thread structure with germanium deposit, obtains germanium gallium nano wire.
The present invention is not special as application process of the electrode material in lithium ion battery for the germanium gallium nano wire
Restriction, using method well known to those skilled in the art.In the present invention, preferably with germanium gallium in the lithium ion battery
Nano wire as working electrode, lithium piece as to electrode, polyethene microporous membrane as diaphragm, the LiPF of 1mol/L6It is dissolved in carbon
The mixed solution of sour ethyl ester-ethylene carbonate (EC-DEC) is as electrolyte；Wherein, in the electrolyte EC and DEC body
Product is than preferably 1：1.
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 the glove box full of argon gas and water oxygen content less than 2ppm, by the bis- (trifluoromethyls of 1- ethyl-3-methylimidazoles
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；
Clean Cu substrates with acetone and isopropanol successively, then mass content be 10% salt acid soak 1min to remove
Surface oxides utilize polytetrafluoroethyl-ne using Cu substrates as working electrode, filamentary silver as reference electrode, platinized platinum as to electrode
It is 1.5cm that alkene electrolytic cell, which limits depositional area,2, using 2273 electrochemical workstations (PrincetonApplied Research)
It will warm up 60 DEG C of GaCl respectively3Electrolyte and GeCl4Electrolyte carries out cyclic voltammetry curve scanning, and gained cyclic voltammetric is bent
The voltage when recovery voltage of gallium is constant pressure electro-deposition gallium in line, the recovery voltage of germanium is constant pressure electricity in gained cyclic voltammetry curve
Voltage when deposit Germanium；Wherein, by the GaCl3Electrolyte carry out cyclic voltammetry curve scanning when, scanning range be -2.0~
0V；Sweep speed is 50mV/s；Equilibration time is 15s；By the GeCl4When electrolyte carries out cyclic voltammetry curve scanning, sweep
Retouch ranging from -2.5~0V；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；Two of negative potential region go back in Fig. 1 (b)
Parent peak is respectively Ge4+→Ge2+With Ge2+The reduction peak of → Ge.According to Fig. 1, the present invention selects under conditions of -1.0~-1.5V
Constant pressure electro-deposition gallium, constant pressure electro-deposition germanium under conditions of -1.8~-2.2V.
Embodiment 2
Fig. 2 is the process schematic in Cu deposition on substrate germanium gallium nano wires, is as follows：
In the glove box full of argon gas and water oxygen content less than 2ppm, by the bis- (trifluoromethyls of 1- ethyl-3-methylimidazoles
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；
Clean Cu substrates with acetone and isopropanol successively, then mass content be 10% salt acid soak 1min to remove
Surface oxides utilize polytetrafluoroethyl-ne using Cu substrates as working electrode, filamentary silver as reference electrode, platinized platinum as to electrode
It is 1.5cm that alkene electrolytic cell, which limits depositional area,2, will using 2273 electrochemical workstations (PrincetonAppliedResearch)
It is heavy to obtain gallium on the surface of the working electrode by electrolyte constant pressure electro-deposition gallium 60s under 60 DEG C of temperature, -1.5V voltages
Product object；Continue constant pressure electro-deposition germanium 300s under conditions of 60 DEG C, -2.0V, obtains germanium gallium on the surface of the working electrode and receive
Rice noodles.
The gallium deposit and final gained germanium gallium nano wire that are obtained in constant pressure electrodeposition process are characterized, as a result such as
Under：
Fig. 3 is the scanning electron image of the gallium deposit after constant pressure electro-deposition 60s on Cu substrates, 20,000 times of amplification factor；By
For Fig. 3 it is found that gallium deposit is presented spherical (Ga nanospheres), particle size range is 30~60nm.
Fig. 4 is the scanning electron image of the germanium gallium nano wire after constant pressure electro-deposition 300s on Cu substrates, amplification factor 20,000
Times；As shown in Figure 4, the deposit finally obtained is nano wire, and a diameter of 50~100nm of the nano wire largely receives
Rice noodles are in twisting contour and obviously attenuate in an axial direction.
Fig. 5 is the transmission electron microscope image of single germanium gallium nano wire, it can be seen from the figure that the length of germanium gallium nano wire
Degree is more than 700nm.
Fig. 6 is the selective electron diffraction image of germanium gallium nano wire, does not have the diffraction spot of regular lattice in figure, whole to present
Go out polycrystalline diffraction ring, illustrates that germanium gallium nano wire is polycrystalline state.
Fig. 7 is the x-ray photoelectron spectroscopy curve of no argon ion etching and germanium gallium nano wire after etching 120s.There is no argon
When ion etching, peak-fit processing is carried out to initial data, can observe appearance of the chromium oxide with gallium oxide, this is because will
Sample is put into inevitably air contact during test equipment；After etching 120s, the peak position of oxide is said close to disappearing
Bright germanium gallium nano wire is surface oxidation.Also, after etching 120s, the content of germanium and gallium is respectively 77% and 8.7%, thus
Show that the atom content ratio of germanium and gallium is about 9：1.This also illustrates that gallium has been doped into inside nano wire, is not to be merely present in nanometer
The surface of line.
Embodiment 3
Using the germanium gallium nano wire as working electrode, it is assembled in CR2025 button cell shells 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) as electrolyte, (wherein, the volume ratio of EC and DEC is 1 to mixed solution：1), with new prestige battery test system (in
State Shenzhen) battery charging and discharging performance is tested, it is as a result as follows：
Fig. 8 is the optical photograph of germanium gallium nano wire and the CR2025 half-cell optical photographs being assembled on Cu substrates.
Fig. 9 is germanium gallium nano line electrode half-cell test loop stability and coulombic efficiency figure, circulating current density are
0.32A/g；As shown in Figure 9, the first time electric discharge of Ge-Ga nano wires 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 prepared by the ionic liquid electrodeposition reported before comparison
Pipe and Ge nano wires (initial coulombic efficiency is respectively 58%, 77% and 81%), the first coulombic efficiency of Ge-Ga nano wires is
It improves；And since the second circle cycle, coulombic efficiency can be maintained at 95% or more；50 times cycle after discharge capacity be
1414mAh/g, after 150 cycles, Ge-Ga nano line electrodes remain to keep the capacity of 1146mAh/g.There is document
(YUAN et al,ACS Nano,2012,6(11):9932-9942) report, Ge nanoline recycled at 100 times after reversible ratio
Capacity is 1130mAh/g, and the nano wire in the present invention is apparently higher than document report.
Figure 10 is that germanium gallium nano line electrode half-cell tests the recycle ratio Capacity Plan under different current densities；It can by Figure 10
Know, 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 often recycling 5 times,
Then 0.16A/g is again returned to.Discharge capacity of the Ge-Ga nano wires 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 respectively；Also, when current density again returns to 0.16A/g
When, capacity restoration to 1422mAh/g, capacity retention ratio reaches 87%.This illustrates Ge-Ga nanometers prepared by ionic liquid electrodeposition
Line can improve the cycle performance of battery and high rate performance of pure germanium anode.
Figure 11 is the scanning electron microscope image after 150 circle of germanium gallium nano wire cycle survey, can be found out from figure, Ge-
Ga nano wires are still retaining its basic configuration after 150 charge and discharge cycles and be not crushed, but Ge-Ga nano wires is straight
Diameter has become larger a bit, shows that volume expansion has occurred in Ge-Ga nano wires in charging-discharging cycle.In addition, the table of Ge-Ga nano wires
Face becomes coarse, there is aperture and groove, and significant texture is formd in Ge-Ga nanowire surfaces.On germanium gallium Ge-Ga nano wires
Porous structure can provide continuous conductive and ion transport path, to improve the diffusivity of lithium ion, and can release
The stress for putting volume expansion, makes structure become stable.
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 (10)
1. a kind of application of germanium gallium nano wire as lithium ion battery electrode material, include in the germanium gallium nano wire chemical composition
Elemental Germanium and Metallic Gallium, the atomic ratio of elemental Germanium and Metallic Gallium is (4~9) in the germanium gallium nano wire：1.
2. application according to claim 1, which is characterized in that a diameter of 50~100nm of the germanium gallium nano wire, length
For 500~1000nm.
3. application according to claim 2, which is characterized in that the preparation method of the germanium gallium nano wire, including following step
Suddenly：
In environment of the water oxygen content less than 2ppm, by GaCl3、GeCl4It is mixed with ionic liquid, obtains electrolyte；
Using the three-electrode electro Chemical system including working electrode, to electrode and reference electrode by the electrolyte 55~65
DEG C, constant pressure electro-deposition gallium under conditions of -1.0~-1.5V, obtain gallium deposit on the surface of the working electrode；Continue 55
~65 DEG C, constant pressure electro-deposition germanium under conditions of -1.8~-2.2V, germanium gallium nano wire is obtained on the surface of the working electrode.
4. application according to claim 3, which is characterized in that the ionic liquid includes that 1- ethyl-3-methylimidazoles are double
(trimethyl fluoride sulfonyl) inferior amine salt, bis- (trimethyl fluoride sulfonyl) inferior amine salts of 1- butyl -3- methylimidazoles or N- butyl-N- methyl piperazines
Bis- (fluoroform sulphonyl) inferior amine salts of pyridine.
5. application according to claim 3, which is characterized in that GaCl in the electrolyte3A concentration of 0.09~
0.11mol/L；GeCl4A concentration of 0.09~0.11mol/L.
6. application according to claim 3, which is characterized in that obtain the constant pressure electro-deposition gallium and the constant pressure electro-deposition
The method of required deposition voltage includes the following steps when germanium：
In environment of the water oxygen content less than 2ppm, by GaCl3It is mixed with ionic liquid, obtains GaCl3Electrolyte；By GeCl4With
Ionic liquid mixes, and obtains GeCl4Electrolyte；
Using the three-electrode electro Chemical system including working electrode, to 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
Voltage when product gallium, the voltage when recovery voltage of germanium is constant pressure electro-deposition germanium in gained cyclic voltammetry curve.
7. application according to claim 3, which is characterized in that the time of gallium described in constant pressure electro-deposition is 30~60s.
8. application according to claim 3, which is characterized in that the gallium deposit is liquid microballoon, the gallium deposit
Grain size be 30~60nm.
9. application according to claim 3, which is characterized in that the time of germanium described in constant pressure electro-deposition is 150~300s.
10. according to claim 1~9 any one of them application, which is characterized in that with germanium gallium nanometer in the lithium ion battery
Line as working electrode, lithium piece as to electrode, polyethene microporous membrane as diaphragm, the LiPF of 1mol/L6It is dissolved in carbonic acid
The mixed solution of ethyl ester-ethylene carbonate is as electrolyte.
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| CN102934264A (en) * | 2010-06-07 | 2013-02-13 | 奈克松有限公司 | Additive for lithium ion rechargeable battery cells |
| CN103606683A (en) * | 2013-11-26 | 2014-02-26 | 哈尔滨工业大学 | Coiling-type germanium nanomaterial and preparation method thereof |
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|---|---|---|---|---|
| CN1966779A (en) * | 2005-11-17 | 2007-05-23 | 中国科学院兰州化学物理研究所 | Process for making Ni-Cu-Ag multilayer film |
| WO2009125504A1 (en) * | 2008-04-09 | 2009-10-15 | Ma Xiaodong | Nanowire and method of forming the same |
| CN102934264A (en) * | 2010-06-07 | 2013-02-13 | 奈克松有限公司 | Additive for lithium ion rechargeable battery cells |
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