CN107673307A - Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery - Google Patents
Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery Download PDFInfo
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- CN107673307A CN107673307A CN201610621900.7A CN201610621900A CN107673307A CN 107673307 A CN107673307 A CN 107673307A CN 201610621900 A CN201610621900 A CN 201610621900A CN 107673307 A CN107673307 A CN 107673307A
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Abstract
The invention discloses germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and metal ion battery, wherein, it the described method comprises the following steps：Germanium/graphene nano fiber is prepared using method of electrostatic spinning；Titanium dioxide is prepared using atomic layer deposition method on germanium/graphene；Subsequent treatment is carried out to obtained germanium/graphene/titanium dioxide nanofiber composite.Titanium deoxid film of the present invention covers germanium/graphene kernel nanofiber, it is ensured that the integrality of structure；Graphene and titanium dioxide can be with duplicate protection germanium nanofibers, so as to avoid germanium from being damaged in charge and discharge process caused by volumetric expansion.Therefore, the nano composite material that prepared by the present invention has excellent electrochemical performance, high power capacity, excellent cycling stability and good high rate performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery, anode material of lithium-ion battery, more particularly to germanium/graphene/titanium dioxide
Titanium nano-fiber composite material preparation method and metal ion battery.
Background technology
With the increase of non-renewable fossil fuel consumption, the whole world is faced with the energy challenge of sternness.This is asked
Inscribe the exploratory development for accelerating people to meeting the energy-storage system of economic benefit.Rechargeable lithium ion battery and sodium ion electricity
Pond has proven to that the energy storage device for solving the problem can be used for.However, for following development and in electronic vapour
Application in car, capacity, stability and the high rate performance of the rechargeable battery still need further to be lifted.Furthermore it is worth mentioning
, can further lift these performances of battery by finding suitable electrode material and electrode protection method.
Silicon and germanium cause the extensive concern of people because of its great theoretical capacity value, it is considered to be follow-on lithium-ion electric
Pond and the most promising negative material of sodium-ion battery.Compared with silicon, germanium has bigger electric conductivity (100 times that are more than silicon),
It has preferable ion diffusivity (about higher than silicon 400 times) simultaneously, and these advantages of germanium make it in high-performance energy storage device
With bigger potential.However, the volumetric expansion of its super large can cause structure degradation and unstable solid electrolyte interface (SEI)
Formation, this will seriously limit its application in practice.So far, it is huge to overcome this problem people to pay
Big effort, such as prepare various nanostructured germanium (nanotube, loose structure, very thin film), Ge alloy material, carbon or graphene
Coat germanium mixture etc..However, these methods are generally all extremely complex, while battery cycle life still has much room for improvement.
The content of the invention
It is an object of the invention to provide germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery,
It has capacity height, good cycling stability, high rate performance good.
To achieve the above object, the present invention uses following technical scheme：
Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof, the described method comprises the following steps：1) adopt
Germanium/graphene nano fiber is prepared with method of electrostatic spinning；2) titanium dioxide is prepared using atomic layer deposition method on germanium/graphene
Titanium；3) subsequent treatment is carried out to obtained germanium/graphene/titanium dioxide nanofiber composite.
Preferably, the step 1) prepares germanium/graphene nano fiber using method of electrostatic spinning, and its is specific as follows：A) make
Standby electrostatic spinning liquid
It is 1 in mass ratio by graphene and dispersion solvent：200-1：250 mix, and are then ultrasonically treated 30-
120min, form uniform graphene dispersing solution；Then will be 1 with the mass ratio of graphene：25-1：15 germanium tetrachloride adds super
Graphene mixed liquor after sound, then magnetic agitation 20-90min at room temperature；Being eventually adding will be 1 with graphene mass ratio：
60-1：30 PVP, then stirs 2-8h, obtains electrostatic spinning solution；
B) electrostatic spinning
In the syringe of stainless steel nozzle for being first 0.3-0.8mm by above-mentioned electrostatic spinning liquid injection internal diameter, then will
Nozzle and reception device connect two electrodes of high voltage power supply respectively, and it is multiple that progress electrostatic spinning obtains germanium/graphene nano fiber
Condensation material.
Preferably, the dispersion solvent in the step a) is N, N- dimethylformamides acid amides (DMF), N- methyl -2- pyrroles
At least one of alkanone (NMP), tetrahydrofuran (THF), ethylene glycol.
Preferably, the germanium tetrachloride purity in the step a) is 99.999%.
Preferably, the high voltage power supply in the step b) between two electrodes is 10-25KV.
Preferably, the step 2) prepares titanium dioxide, specific steps on germanium/graphene using atomic layer deposition method
For：Germanium/graphene nano fiber that step 1) is obtained is put into reative cell, with isopropyl titanate (Ti (OCH (CH3)2) and H2O makees
For reactant, respectively toward introducing isopropyl titanate and H in reative cell2O, adjust isopropyl titanate and H2O dosage to be accurately controlled
One atomic layer deposition cycles of titanium dioxide, then using each atomic layer deposition cycles thickness as 1nm's at 170 DEG C -210 DEG C
Growth rate deposition of titanium oxide film.
Preferably, the Ti (OCH (CH3)2Purity is 97%, the H2O is the H of high pressure liquid level2O。
Preferably, the titanium deoxid film thickness of deposition is 1-20nm in the step 2).
Preferably, the step 3) comprises the following steps that to germanium/graphene/titanium dioxide progress subsequent treatment：
A) dry：By germanium/graphene/titanium dioxide nanofiber composite that step 2) obtains in the roasting of vacuum environment
In case, 20-30h is dried using temperature as 40-80 DEG C；
B) calcine：Dried germanium/graphene/titania composite material is put into air ambient, at 400-600 DEG C
At a temperature of be calcined 1-5h；
C) anneal：Then germanium/graphene/titania composite material is placed on H2It is 5% with Ar volume ratios：95% it is mixed
Close in gaseous environment, further anneal 1-5h at 500-800 DEG C, and it is multiple to finally give germanium/graphene/titanium dioxide nanofiber
Condensation material.
The invention also discloses a metal ion species battery, the negative material of the metal ion battery is any of the above-described institute
State obtained germanium/graphene/titanium dioxide nanofiber composite.
The present invention uses above technical scheme：Titanium deoxid film covers germanium/graphene kernel nanofiber, it is ensured that
The integrality of structure；Graphene and titanium dioxide can be with duplicate protection germanium nanofibers, so as to avoid germanium in charge and discharge process
Damaged caused by volumetric expansion.Therefore, the nano-fiber composite material prepared by the present invention has excellent chemical property, height
Capacity, excellent cyclical stability and good high rate performance.Using its lithium ion battery first time as negative material
Cyclic discharge capacity reaches 1701mAh/g, and after 100 circulations, capacity remains at 1050mAh/g, sodium-ion battery the
One time discharge capacity reaches 368mAh/g, and 182mAh/g is remained at by 250 circulation volumes；Lithium ion battery and sodium ion
For battery since the second circle circulation, its capacity attenuation rate for often enclosing circulation only has 0.13% and 0.04%；Lithium ion battery and sodium
Even if ion battery discharge and recharge under conditions of high current, electrode remains to keep stable circulation, shows good high rate performance.
Brief description of the drawings
Fig. 1 is the flow chart of germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof of the present invention；
Fig. 2 is the structural representation of germanium/graphene/titanium dioxide nanofiber composite of the present invention；
Fig. 3 is the Morphological Characterization figure of germanium/graphene/titanium dioxide nanofiber composite of the present invention：Wherein a
For the TEM that SEM figures, b are low range TEM figures, c is Ge/G schemes, d is distribution diagram of element；
Fig. 4 is the structural characterization figure of germanium/graphene/titanium dioxide nanofiber composite of the present invention：Wherein a
For XRD case, b Ge/G/TiO2The HRTEM that Raman spectrum, c with Ge/G are Ge schemes, d is corresponding SAED patterns；
Fig. 5 is Ge/G/TiO2, Ge/G, Ge electrode lithium ion storage characteristics：Wherein a is Ge/G/TiO2In voltage range
0.01-3V scans obtained cyclic voltammetry curve, b Ge/G/TiO using 0.2mV/s sweep speed2In 100mA/g charge and discharge
Electric curve map, c Ge/G/TiO2, cycle characteristics, d Ge/G/ of the tri- kinds of materials of Ge/G, Ge under current density 100mA/g
TiO2, high rate performance of the tri- kinds of materials of Ge/G, Ge under different current densities；
Fig. 6 is Ge/G/TiO2, Ge/G, Ge electrode sodium ion storage characteristics：Wherein a is Ge/G/TiO2In voltage range
0.01-2.7V scans obtained cyclic voltammetry curve, b Ge/G/TiO using 0.2mV/s sweep speed2In filling for 100mA/g
Discharge curve, c are cycle characteristics, d Ge/G/TiO of three kinds of materials under current density 100mA/g2, tri- kinds of Ge/G, Ge
High rate performance of the material under different current densities；
Fig. 7 be germanium/graphene/titanium dioxide nanofiber for preparing of the present invention as cell negative electrode material when discharge and recharge
The schematic diagram that material structure changes in journey；
Fig. 8 is traditional nanofiber schematic diagram that material structure changes in charge and discharge process.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Germanium/graphene/titanium dioxide nanofiber composite prepared by the present invention, form core shell structure, the nucleocapsid
Structure is can to strengthen one of successful guard method of battery performance.Generally, a suitable electrode protection measure can not only
Electrical conductivity is lifted, resistance in reduction, and cyclical stability and high rate performance can be dramatically increased, extend the longevity of rechargeable battery
Life.Graphene, due to the electric conductivity of its protrusion, remarkable mechanical strength, great specific surface area, makes it as two-dimentional carbon material
With wider application.Graphene can prevent the solid between graphite and electrode in lithium ion battery or sodium-ion battery
The formation of electrolyte interface.
Generally germanium nanofiber can be because of its larger body in the transition process of embedding lithium/embedding sodium and de- lithium/removing sodium
Product expansion easily causes the efflorescence and cracking of electrode, and is peeled off from nanofiber surface, so as to cause capacity in cyclic process
Rapid decay and irreversible；Furthermore SEI films can be deformed or ruptured when germanium expansion or shrinkage, this will be formed on new surface
New SEI films, the gradual accumulation of SEI films will finally prevent the transmission of lithium/sodium ion, so as to cause low coulombic efficiency.
As shown in figure 1, the invention discloses germanium/graphene/titanium dioxide (Ge/G/ titanium dioxide) nanofiber composite wood
Preparation method for material, it the described method comprises the following steps：
S101：Germanium/graphene nano fiber is prepared using method of electrostatic spinning；
S102：Titanium dioxide is prepared using atomic layer deposition method (ALD) on germanium/graphene (Ge/G)；
S103：Subsequent treatment is carried out to obtained germanium/graphene/titanium dioxide nanofiber composite.
The specific present invention can be implemented by the following method：
Embodiment 1:
1) electrostatic spinning prepares germanium/graphene nano fiber；
A) electrostatic spinning liquid is prepared
0.01g graphenes and 2.2gDMF (N, N- dimethylformamide acid amides) are mixed first, then carry out ultrasound
60min, form uniform graphene dispersing solution；Secondly by 0.214g purity be 99.999% germanium tetrachloride (GeCl4) add it is super
In graphene mixed liquor after sound, magnetic agitation 30min at room temperature；Finally 0.4g polyvinylpyrrolidones (PVP) are added
Above-mentioned solution, then persistently stirs 3h, obtains electrostatic spinning solution；
B) electrostatic spinning
In the syringe for the stainless steel nozzle for being about 0.5mm by above-mentioned electrostatic spinning liquid injection internal diameter, then by nozzle and
Reception device is connected on two electrodes of 20KV high voltage power supplies, is carried out electrostatic spinning and is obtained germanium/graphene nano fiber
Composite；
2) titanium dioxide is prepared using technique for atomic layer deposition on germanium/graphene；
Germanium/graphene nano fiber that step 1) is obtained is put into reative cell, using purity as 97% isopropyl titanate (Ti
(OCH(CH3)2) and high pressure liquid level (HPLC-grade) H2O is sequentially introduced isopropyl titanate and H as reactant2O, adjust
Both whole dosages cause an ALD cycle for being accurately controlled titanium dioxide, then at 180 DEG C with each ALD cycle thickness about
ForGrowth rate deposition, obtain the titanium deoxid film that thickness is about 5nm.
3) subsequent treatment of germanium/graphene/titanium dioxide nanofiber；
A) dry：Germanium/graphene/titania composite material that step 2) is obtained is put into the baking box of vacuum environment,
60 DEG C of dry 24h；
B) calcine：Dried germanium/graphene/titania composite material is put into air ambient, in 450 DEG C of temperature
Lower calcination 2h, to remove PVP organic principles；
C) further annealing：Then germanium/graphene/titania composite material is put into H2：Ar volume ratios are for 5%：
In 95% mixed-gas environment, further annealed 3h at 600 DEG C, and germanium oxide is reduced into germanium；Finally give germanium/graphite
Alkene/titanium dioxide nanofiber composite.
Embodiment 2
1) electrostatic spinning prepares germanium/graphene nano fiber；
A) electrostatic spinning liquid is prepared
0.01g graphenes and 2.5gNMP (METHYLPYRROLIDONE) are mixed first, then ultrasonic 90min,
Form uniform graphene dispersing solution；Secondly by 0.2g purity be 99.999% germanium tetrachloride (GeCl4) add ultrasound after stone
In black alkene mixed liquor, then magnetic agitation 60min at room temperature；Finally 0.5g polyvinylpyrrolidones (PVP) are added above-mentioned
Solution, 5h is then persistently stirred, obtain electrostatic spinning solution.
B) electrostatic spinning
In the syringe for the stainless steel nozzle for being about 0.5mm by above-mentioned electrostatic spinning liquid injection internal diameter, then by nozzle and
Reception device is connected on two electrodes of 20KV high voltage power supplies, is carried out electrostatic spinning and is obtained germanium/graphene nano fiber
Composite；
2) titanium dioxide is prepared using atomic layer deposition method (ALD) on germanium/graphene；
Germanium/graphene nano fiber that step 1) is obtained is put into reative cell, using purity as 97% isopropyl titanate (Ti
(OCH(CH3)2) and high pressure liquid level (HPLC-grade) H2O is sequentially introduced isopropyl titanate and H as reactant2O, adjust
Whole dosage causes an ALD cycle for being accurately controlled titanium dioxide, is then about with each ALD cycle thickness at 180 DEG C
Growth rate deposit to obtain the titanium deoxid film that thickness is about 8nm.
3) subsequent treatment of germanium/graphene/titanium dioxide nanofiber；
A) dry：Germanium/graphene/titania composite material that step 2) is obtained is put into the baking box of vacuum environment,
50 DEG C of dry 28h；
B) calcine：Dried germanium/graphene/titania composite material is put into air ambient, in 480 DEG C of temperature
Lower calcination 2h, to remove PVP organic principles；
C) further annealing：Then germanium/graphene/titania composite material is placed on volume ratio for 5%：95%
In H2/Ar mixed-gas environments, further annealed 3h at 650 DEG C, and germanium oxide is reduced into germanium；Finally give germanium/graphene/
Titanium dioxide nanofiber composite.
It is as shown in Fig. 2 compound for germanium/graphene/titanium dioxide (Ge/G/ titanium dioxide) nanofiber prepared by the present invention
Material, it includes shell 1 and kernel 2, and shell 1 coats kernel 2, and the shell 1 is titanium deoxid film layer 11, the kernel 2
It is thin for the nanofiber of 21/ graphene of germanium 22, the titanium deoxid film layer cladding germanium/graphene nano fiber formation titanium dioxide
The core shell structure of film layer and graphene duplicate protection germanium.The thickness of the titanium deoxid film layer 11 is 1-20nm；The present invention's
Nanofiber includes graphene in core shell structure, on the one hand, graphene due to its good bending machinery performance and stable heat/
Chemical property can accommodate and alleviate the pressure that germanium fragment is brought in embedding lithium/volumetric expansion caused by sodium process；On the other hand, stone
Black alkene is as conductive mesh, and lithium/sodium ion can provide transport effective passage of more electronics and ion when inserting, so as to obtain
One high reversible capacity.Meanwhile during germanium/graphene provided by the invention/titanium dioxide work, more SEI films are in dioxy
The outer surface for changing titanium film is formed, and is limited SEI films quantity and is increased its stability.
Here is the performance measurement of the nano-fiber composite material prepared to the present invention：
Comparative example 1
Germanium/graphene (Ge/G) nanofiber is synthesized by the same preparation technology, but is not covered with titanium dioxide.Specifically
Step 1) with embodiment 1 directly carries out step 3) without step 2) after step 1), contrast material is prepared with 3)
1Ge/G nano-fiber composite materials；
Comparative example 2
Germanium nanofiber is synthesized by the same preparation technology, but without addition graphene and covering titanium dioxide.Specifically
For by 2.2g DMF (N, N- dimethylformamide acid amides) and germanium tetrachloride (GeCl that 0.214g purity is 99.999%4) mixed
Close, at room temperature magnetic agitation 30min；Then 0.4g polyvinylpyrrolidones (PVP) are added into above-mentioned solution, then persistently stirred
3h is mixed, obtains electrostatic spinning solution.The syringe for the stainless steel nozzle for being about 0.5mm by obtained electrostatic spinning liquid injection internal diameter
In, then nozzle and reception device are connected on two electrodes of 20KV high voltage power supplies, electrostatic spinning is carried out and obtains germanium
(Ge) nanofiber；Then the subsequent treatment of the same step 3) of embodiment 1 equally is carried out, obtains contrast material 2Ge nanofibers；
Electro-chemical test detailed process is as follows：By active material germanium/graphene/titanium dioxide nanofiber：Acetylene black：Carboxylic
Ylmethyl cellulose (CMC) is using mass ratio as 8：1：1 is mixed, then by mixed-powder be dissolved in 1.0g deionized water and
8h is persistently stirred in 2.5g ethanol；Then obtained slurry is coated on thin copper foil, and in vacuum oven 80 DEG C it is dry
To electrode strip；Wherein, in the case where deducting copper foil quality, the average quality of electrode strip is about in 0.8mg/cm2；Lithium metal and gold
Belong to sodium respectively as lithium ion battery and sodium-ion battery to electrode；1M LiPF6Ethylene carbonate (EC):Carbonic acid diethyl
Ester (DEC) (volume ratio 1：1) and 1M NaClO4Ethylene carbonate (EC):Dimethyl carbonate (DMC) (volume ratio 6：4)
The respectively electrolyte of lithium ion battery and sodium-ion battery.
As shown in figure 3, the Morphological Characterization figure of the germanium/graphene/titanium dioxide nanofiber prepared for the present invention：, wherein
The average diameter of the nanofiber of germanium/graphene/titanium dioxide is about 10nm, as in Fig. 3 a figures be enlargement ratio SEM figure, its
Show that nanofiber surface is unsmooth, include many nanoparticles；As shown in Figure 3 b, germanium/graphene/titanium dioxide is shown
Low range TEM figures, it shows complete structure, and is observed that week of the titanium dioxide layer around nanofiber
Enclose；As shown in Figure 3c, it shows single Ge/G nanofibers, it can be seen that the attachment of graphene, as shown in Figure 3d,
Being uniformly distributed for the element of germanium/graphene/titanium dioxide illustrates germanium (Ge), and titanium (Ti) and oxygen (O's) is evenly distributed.
As shown in figure 4, the structural characterization figure of the germanium/graphene/titanium dioxide nanofiber prepared for the present invention：Such as Fig. 4
Be the XRD case of germanium/graphene/titanium dioxide shown in middle a figures, it can be seen that at 27.28 °, 45.30 °, 53.68 °, 66.01 ° and
72.8 ° of 2 θ peaks are attributed to (111) of diamond cubic phase germanium respectively, (220), (311), (400) and (331) lattice layer；Such as
In Fig. 4 shown in b figures, Raman spectrogram is in about 1332.5 and 1585.8cm-1Two peaks accord with the D bands and G bands of carbon；Meanwhile
In 530cm-1Peak meet the non-crystalline of titanium dioxide, further confirm the presence of graphene and titanium dioxide；Such as c in Fig. 4
Shown in figure, HRTEM is used for studying the microstructure of germanium/graphene/titanium dioxide, and image shows that possesses a 0.32nm lattices
The nanocrystal germanium of the high-sequential of striped, equivalent to (111) face；As shown in d figures in Fig. 4, at SEAD (SAED)
Faint crystal and polycrystalline ring under pattern further demonstrate the presence of crystal germanium.
As shown in figure 5, germanium/graphene/the titanium dioxide nanofiber of the invention prepared and contrast material 1Ge/G and contrast
The chemical property contrast that material 2Ge is applied in lithium ion battery：It is germanium/graphene/titanium dioxide as shown in a figures in Fig. 5
Titanium potential range be 00.1-3V with 0.2mV/s sweep speed under obtained cyclic voltammetry curve.First lap circulation is obvious not
With circulation later, particularly discharge process.This is not both as caused by first lap circulation being formed of SEI films.In about 0.12V
Peak accord with graphene and Li+Reaction (C (graphene)+xLi++xe-→LixC).At 0.55V and 1.25V two peaks
Germanium is attributed to LixGe alloy conversion processAfterwards
Circulation in, cathode flowpath and anode flowpath have good plyability, illustrate that it has high invertibity and good entirety
Cyclical stability.As shown in the b figures in Fig. 5, it is shown that germanium/graphene/titanium dioxide (Ge/G/ titanium dioxide) is in current density
Charge/discharge cycle curve of the 100mA/g voltage ranges under 0.01-3V.Plateau potential of the first time discharge regime in about 0.55V
It is consistent with CV Dependence Results.The initial coulomb efficiency of lithium ion battery is about 74%, due to the formation of SEI films, it may be said that and bright germanium/
Graphene/titanium dioxide electrodes have lost about 26% irreversible capacity in first time discharge process.As the c in Fig. 5 schemes institute
Show, be the cycle characteristics curve of germanium/graphene/titanium dioxide, Ge/G and Ge threes in the case where current density is for 100mA/g.Three
Person's, the discharge capacity of first lap is respectively 1701mAh/g, 1766mAh/g, 1789mAh/g.However, under Ge reversible capacity
Drop is very fast, drops to the 495mAh/g of the 100th circle from the 1174mAh/g of the 2nd circle.Ge/G electrodes are shown more compared with Ge
Good cycle performance, it remains to the specific capacity for keeping 804mAh/g after 100 circulations.When Ge/G titanium dioxide is further
Protection, germanium/graphene/titania composite material show best cycle performance and still kept after 100 circulations
1050mAh/g capacity.This suffice to show that graphene on germanium and germanium/graphene and titanium dioxide layer to increase its circulation special
Property.Its excellent cyclical stability is further confirmed at higher current densities.It is shown as shown in the d figures in Fig. 5, germanium/graphite
Alkene/titanium dioxide is respectively to have higher specific capacity under 100,200,400,600,800,1000mA/g in current density, point
Wei 1050,921,850,750,627,550mAh/g.When current density returns to 100mA/g, it still has 1000mAh/g's
Reversible capacity, almost without capacitance loss.However, when current density returns to 100mA/g, Ge or Ge/G suffer from larger appearance
Amount loss.The high power capacity return rate of germanium/graphene/titanium dioxide is primarily due to its special double-layered protecting structure.
As shown in fig. 6, germanium/graphene/the titanium dioxide nanofiber of the invention prepared and contrast material 1Ge/G and contrast
The chemical property contrast that material 2Ge is applied in lithium ion battery：It is germanium/graphene/titanium dioxide as shown in a figures in Fig. 6
CV curve map of the Ti electrode in sodium-ion battery, without redox peaks are found during anode and cathodic scan, this is just
It is the Surface Creation in compound to demonstrate SEI films.It is that germanium/graphene/titanium dioxide is close in electric current as shown in the b figures in Fig. 6
The charging and discharging curve figure spent under 100mA/g.Have a longer discharge voltage plateau on 0.4V position, with Ge Na it is embedding
Enter reaction to be consistent.Illustrate that sodium reaction is reversible in the little by little difference of the 5th circle and the 10th circle charge and discharge cycles process.Such as
Shown in c figures in Fig. 6, it is shown that in current density 100mA/g, voltage range 0.01-2.7V cycle characteristics.Although germanium/stone
The first lap coulombic efficiency of black alkene/titanium dioxide is relatively low, but it is still having 190mAh/g specific capacity after 100 circulations
Up to 99% coulombic efficiency.Compared with Ge/G and Ge quick special capacity fade, germanium/graphene/titanium dioxide electrodes table
Reveal superior cycle characteristics, be primarily due to its double-layered protecting structure.As shown in the d figures in Fig. 6,3 kinds of electrode materials are shown
High rate performance under different current densities.The specific discharge capacity of germanium/graphene/titanium dioxide is in electric current 100, and 200,400,
200,164,135,115,102,88mAh/g are maintained at well under 600,800,1000mA/g electric currents.Meanwhile return to 100mA/
Specific capacity returns to 190mAh/g well during g, and this has sufficed to show that germanium/graphene/titanium dioxide has fine high rate performance.
Illustrate that the method for double-layered protecting structure equally can apply in sodium-ion battery.
As shown in Figure 7 and Figure 8, core shell structure germanium/graphene/titanium dioxide nanofiber composite that prepared by the present invention
It can effectively alleviate germanium body as presence of the GND because of shell titanium deoxid film layer and graphene in charge and discharge process
The pressure that product expansion is brought, the integrality of holding structure；And traditional nanofiber in charge and discharge process because of the large volume of germanium
Expansion causes structural damage.
Present invention doped graphene on germanium can improve battery behavior, while be covered in ultra-thin outside germanium/graphene
Titanium deoxid film layer can more enter any enhancing cyclical stability and high rate performance.Furthermore lithium ion battery or sodium ion
Germanium/graphene/titanium dioxide electrodes of battery are keeping 1050 and 194mAh/g specific capacity respectively after 100 circulations,
Show high and stable specific capacity.(higher than germanium or germanium/graphene is more) are in addition, germanium/graphene/titanium dioxide electrodes
High current density can be born, after the charge and discharge process under different current densities (100,200,400,600,800,
1000mAh/g), it still can return to the 194mAh/g of the 1000mAh/g of lithium ion battery and sodium-ion battery, almost not have
There is capacitance loss.Its unique double-layered protecting structure of present invention offer germanium/graphene/titanium dioxide nanofiber can extend
Other application is in the manufacture of various other function nano materials of energy storage.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof, it is characterised in that methods described includes following
Step：
1) germanium/graphene nano fiber is prepared using method of electrostatic spinning；
2) titanium dioxide is prepared using atomic layer deposition method in germanium/graphene nano fiber；
3) subsequent treatment is carried out to obtained germanium/graphene/titanium dioxide nanofiber composite.
2. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 1, its feature
It is：The step 1) prepares germanium/graphene nano fiber using method of electrostatic spinning, and its is specific as follows：
A) electrostatic spinning liquid is prepared
It is 1 in mass ratio by graphene and dispersion solvent：200-1：250 mix, and are then ultrasonically treated 30-120min,
Form uniform graphene dispersing solution；Then will be 1 with the mass ratio of graphene：25-1：After 15 germanium tetrachloride adds ultrasound
Graphene mixed liquor, then magnetic agitation 20-90min at room temperature；Being eventually adding will be 1 with graphene mass ratio：60-1：30
PVP, then stir 2-8h, obtain electrostatic spinning solution；
B) electrostatic spinning
In the syringe of stainless steel nozzle for being first 0.3-0.8mm by above-mentioned electrostatic spinning liquid injection internal diameter, then by nozzle
Connect two electrodes of high voltage power supply respectively with reception device, carry out electrostatic spinning and obtain germanium/graphene nano fiber composite wood
Material.
3. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 2, its feature
It is：Dispersion solvent in the step a) is N, N- dimethylformamides acid amides (DMF), METHYLPYRROLIDONE (NMP),
At least one of tetrahydrofuran (THF), ethylene glycol.
4. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 2, its feature
It is：Germanium tetrachloride purity in the step a) is 99.999%.
5. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 2, its feature
It is：High voltage power supply in the step b) between two electrodes is 10-25KV.
6. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 1, its feature
It is：The step 2) prepares titanium dioxide on germanium/graphene using atomic layer deposition method, concretely comprises the following steps：By step 1)
Obtained germanium/graphene nano fiber is put into reative cell, with isopropyl titanate (Ti (OCH (CH3)2) and H2O divides as reactant
Not toward introducing isopropyl titanate and H in reative cell2O, adjust isopropyl titanate and H2O dosage to be accurately controlled titanium dioxide
One atomic layer deposition cycles, then the growth rate using each atomic layer deposition cycles thickness as 1nm at 170 DEG C -210 DEG C sink
Product titanium deoxid film.
7. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 6, its feature
It is：Ti (OCH (the CH3)2Purity is 97%, the H2O is the H of high pressure liquid level2O。
8. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 6, its feature
It is：The titanium deoxid film thickness of deposition is 1-20nm in the step 2).
9. the preparation method of germanium/graphene/titanium dioxide nanofiber composite according to claim 1, its feature
It is：The step 3) carries out subsequent treatment to germanium/graphene/titanium dioxide and comprised the following steps that：
A) dry：By germanium/graphene/titanium dioxide nanofiber composite that step 2) obtains vacuum environment baking box
In, 20-30h is dried using temperature as 40-80 DEG C；
B) calcine：Dried germanium/graphene/titania composite material is put into air ambient, in 400-600 DEG C of temperature
Lower calcination 1-5h；
C) anneal：Then germanium/graphene/titania composite material is placed on H2It is 5% with Ar volume ratios：95% gaseous mixture
In body environment, further anneal 1-5h at 500-800 DEG C, finally gives germanium/graphene/titanium dioxide nanofiber composite wood
Material.
A kind of 10. battery, it is characterised in that：The negative material of the battery is any obtained germanium/stones of claim 1-9
Black alkene/titanium dioxide nanofiber composite.
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| PCT/CN2017/095366 WO2018024184A1 (en) | 2016-08-01 | 2017-08-01 | Method for preparing germanium/graphene/titanium dioxide nanofiber composite material, and battery |
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| CN109616615B (en) * | 2018-12-10 | 2021-10-15 | 合肥国轩高科动力能源有限公司 | Method for preparing graphene composite nanofiber material through electrostatic spinning |
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