CN103247803A - Graphene-cladding nano germanium composite material as well as preparation method and application thereof - Google Patents
Graphene-cladding nano germanium composite material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene-cladding nano germanium composite material. The preparation method is characterized in that germanium powder and graphite powder or the expanded graphite after being thermally treated are ball-milled by adopting a dielectric barrier discharge plasma assistant high-energy ball milling method; or the germanium powder is firstly under the dielectric barrier discharge plasma assistant high-energy ball milling, and the ball-milled germanium powder is mixed with the graphite powder or the expanded graphite after being thermally treated to be ball-milled by adopting the dielectric barrier discharge plasma assistant high-energy ball milling method. The structure of the composite material prepared through the technological steps is that the nano germanium particles are uniformly coated by a single layer or multiple layers of graphene networks; and due to the high capacity and excellent lithium-ion dispersion speed of the germanium and the high strength, high specific area, high conductivity and the like of the graphene, when being used as a negative electrode material of the lithium-ion battery, the composite material has high capacity, high multiplying factor and excellent cycling performance. The preparation method is simple in process, little in energy consumption, high in yield and environment-friendly.
Description
Technical field
The present invention relates to lithium ion battery negative material and other need the nano-functional material of Graphene clad structure, specifically refer to Graphene clad nano germanium composite material and one one step preparation method and application, belong to new forms of energy and nano-functional material technical field.
Background technology
Graphene is as individual layer or thin layer graphite, specific area with super large, the specific strength of superelevation, outstanding outstanding performances such as conductivity, make its lithium ion battery,, there is great application space in field such as solar energy, ultracapacitor, semiconductor, nano electron device, high-strength material and novel noise abatement heat radiation.But its preparation and synthesis technique mostly are in laboratory stage or minimum batch process, and the technology of large-scale production Graphene or its composite material is badly in need of improving.
Lithium ion battery has high voltage, high power capacity, has extended cycle life, security performance reaches remarkable advantages such as environmentally friendly well, makes its having a extensive future in fields such as mancarried electronic aid, electric automobile, national defence space flight.But because the low (372mAhg of theoretical capacity of present business-like lithium ion battery negative material graphite
-1), limited the raising of capacity of lithium ion battery.For satisfying ever-increasing civilian, industry or national defence etc. to the demand of high power capacity excellent cycle stability lithium ion battery.The researcher is in the carbon substitution material of constantly exploring other high power capacity.In numerous non-carbon negative pole material systems after deliberation, metal Ge system capacity height, big, the good conductivity of lithium ion diffusion coefficient can satisfy at present for high power capacity, high magnification, eco-friendly lithium ion battery growth requirement.But materials similar such as pure germanium electrode material and other Si, Sn can and be taken off the change in volume that existence is bigger in the lithium process owing to the embedding lithium, and efflorescence gradually breaks away from collector and causes the active material failure phenomenon.
Graphene and nanometer germanium particle are combined the safeguard structure that forms Graphene clad nano germanium; the high-specific surface area of Graphene network and high strength can provide protective effect for pure germanium electrode change in volume in charging and discharging cyclic process; when making active material keep high power capacity, have stable cycle performance and high rate performance.But the building-up process complexity of this composite material that present document is delivered, generally by the electronation graphene oxide, the compound with germanium further reacts gained again, and synthetic quantity is few and technological parameter control is more loaded down with trivial details, can't the industrialization volume production.
Summary of the invention
One of purpose of the present invention is to provide the simple Graphene clad nano of a kind of technology germanium particulate composite.
Two of purpose of the present invention is to provide the preparation method of above-mentioned composite material.
Three of purpose of the present invention is to provide the application of above-mentioned composite material.
A kind of preparation method of Graphene clad nano pure germanium composite material, concrete steps are as follows:
Method one: adopt dielectric barrier discharge plasma auxiliary high-energy ball-milling method to carry out ball milling germanium powder and graphite powder or heat treated expanded graphite;
Method two: earlier the germanium powder is carried out dielectric barrier discharge plasma auxiliary high-energy ball milling, then the germanium powder behind the ball milling is mixed the back with graphite powder or heat treated expanded graphite and adopt dielectric barrier discharge plasma auxiliary high-energy ball-milling method to carry out ball milling.
Preferably, described germanium powder and graphite powder or expanded graphite are according to mass ratio Ge:C=(0.3～8): 1 carries out proportioning.
Preferably, the discharge gas medium that adopts in the described ball milling is argon gas.
Preferably, the described ball milling time is 3～15h.
Preferably, the described ball milling time is 5h.
Preferably, the method for described dielectric barrier discharge plasma auxiliary high-energy ball milling is as follows:
(1) install front shroud and the electrode bar of ball grinder, front shroud is linked to each other with the positive and negative two-stage of plasma electrical source respectively with iron core in the electrode bar, wherein, the iron core in the electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) the good starting powder of abrading-ball and proportioning of in ball grinder, packing into;
(3) by vacuum valve ball grinder is vacuumized, charge into discharge gas medium A r gas then, make the force value in the ball grinder reach 0.10～0.12MPa;
(4) connect plasma electrical source, it is 15KV that plasma electrical source voltage is set, and electric current is 1.5A, discharge frequency 60KHz, start drive motors and drive the exciting piece, make frame and the ball grinder that is fixed on the frame vibrates simultaneously, carry out dielectric barrier discharge plasma auxiliary high-energy ball milling.
Preferably, described exciting piece adopts double-amplitude 5mm～10mm, motor speed 930～1400r/min.
Preferably, the heat treatment method of described expanded graphite: the expansible graphite sheet is placed in the tube furnace, continues to feed the Ar air-flow, quickly heat up to 1000 ℃, be incubated the cold taking-up of stove after 30 minutes.
The Graphene clad nano germanium particulate composite of the present invention's preparation, be composited by the germanium particle of 100nm～200nm, the Graphene of single or multiple lift, wherein, be distributed in the Graphene lamella to nanometer germanium uniform particles, form the safeguard structure that is coated by the Graphene network.
Above-mentioned Graphene clad nano pure germanium composite material is as the application of lithium ion battery negative material.
The present invention has following beneficial effect compared with prior art:
(1) preparation method of gained individual layer or thin layer Graphene clad nano germanium particulate composite is simple.Using plasma dielectric impedance auxiliary high-energy Prepared by Ball Milling Graphene clad nano germanium particulate composite first.Germanium carbon proportioning of the present invention is easy to control, and preparation process technology is simple, and power consumption is few, and output height, parameter are controlled simple, pollution-free, easily realize suitability for industrialized production.
(2) gained Graphene clad nano germanium particulate composite has advantages such as capacity height, good rate capability and good cycling stability as lithium ion battery negative material.
Description of drawings
Fig. 1 is the Graphene clad nano germanium particulate composite XRD spectra (with Ge-77wt%EG, ball milling 10h is example) of the embodiment of the invention 4 preparations.
Fig. 2 is the Raman figure (with Ge-20wt% graphite, ball milling 15h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 8 preparations.
Fig. 3 is the SEM figure (with Ge-50wt%EG, ball milling time 5h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 2 preparation methods preparation.
Fig. 4 is the SEM figure (with the Ge-50wt% native graphite, ball milling 8h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 6 preparations.
Fig. 5 is the charging and discharging curve (with Ge-50wt%EG, ball milling time 5h is example) under the difference of the Graphene clad nano germanium particulate composite of the embodiment of the invention 2 preparations circulates.
Fig. 6 is the cycle performance curve (with Ge-77wt%EG, ball milling time 10h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 4 preparations.
Fig. 7 is the cycle performance curve (with Ge-50wt%EG, ball milling time 3h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 1 preparation.
Fig. 8 is the cycle performance curve (with Ge-77wt%EG, ball milling time 15h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 5 preparations.
Fig. 9 is the cycle performance curve (with the Ge-50wt% native graphite, ball milling time 10h is example) of the Graphene clad nano germanium particulate composite of the embodiment of the invention 7 preparations.
Figure 10 is plasma auxiliary high-energy mechanical milling process effect schematic diagram used in the present invention.
Figure 11 is the external structure schematic diagram of the dielectric barrier discharge plasma auxiliary high-energy ball mill that adopts of the present invention.
Figure 12 is the structural representation of ball grinder shown in Figure 11.
Figure 13 is the end view of ball grinder shown in Figure 12.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.Disclosed dielectric barrier discharge plasma auxiliary high-energy ball mill among the patent ZL200510036231.9 is adopted in the various embodiments of the present invention preparation.
As shown in figure 11, realize plasma auxiliary high-energy ball mill device of the present invention, comprise drive motors l, ball grinder 2, frame 3, base 4, ball grinder 2 is installed on the frame 3, its inside is placed with abrading-ball 5, and frame 3 is installed on the base 4 by spring 6, and its arranged outside has exciting piece 7, drive motors 1 is installed on the base 4, and is connected with frame 3, exciting piece 7 respectively by elastic coupling 8.
Shown in Figure 12,13, abrading-ball 5 is placed in the ball grinder 2, ball grinder 2 also is connected with electrode bar 9, plasma electrical source 10, ball grinder 2 comprises cylindrical shell 2-1, front shroud 2-1, back shroud 2-3, the flange at cylindrical shell 2-1 two ends is tightly connected with front shroud 2-2, back shroud 2-3 respectively by sealing ring 2-4, bolt 2-5, any bolt 2-5 of front shroud 2-2 is connected with a utmost point of plasma electrical source 10, front shroud 2-2 is provided with electrode perforations 2-2-1, the inboard of electrode perforations 2-2-1 is provided with concave station, and back shroud 2-3 medial surface is provided with blind hole 2-3-1.
The outer surface of electrode bar 9 is provided with coating layer 11, the concave station of coating layer 11 respective electrode perforation is provided with shoulder, be provided with gasket seal 12 between concave station and the shoulder, electrode bar 9 front end 9-1 expose and are connected with another utmost point of plasma electrical source 10, and front end 9-1 is threaded and nut 13, nut 13 is close to the lateral surface of protecgulum 2-2, and electrode bar 9 rear end 9-2 penetrate the electrode perforations 2-2-1 of front shroud 2-2 and embed in the blind hole 2-3-1 of back shroud 2-3.
Front shroud 2-2 also is provided with vacuum valve 2-2-2, can take out negative pressure by vacuum valve 2-2-2, also can feed discharge gas medium argon gas, nitrogen, ammonia or organic gas (as methane) and realize milling atmosphere in the ball grinder.
Cylindrical shell 2-1, abrading-ball 5 materials are stainless steel or carbide alloy, and the material of electrode bar 9 is stainless steels, and the material of front shroud 2-2, back shroud 2-3, electrode bar coating layer 11 is polytetrafluoroethylene.The output voltage range of plasma electrical source 10 is 1～30kv, and frequency range is 1～40kHz.
Embodiment 1
The concrete steps of dielectric barrier discharge plasma auxiliary high-energy ball grinding method are:
(1) install front shroud and the electrode bar of ball grinder, front shroud is linked to each other with the positive and negative two-stage of plasma electrical source respectively with iron core in the electrode bar, wherein, the iron core in the electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) the good starting powder of carbide alloy abrading-ball (differing in size) and proportioning (ball powder ratio 50:1) of in ball grinder, packing into;
(3) by vacuum valve ball grinder is vacuumized, charge into discharge gas medium A r gas then, make the force value in the ball grinder reach 0.12MPa;
(4) connect plasma electrical source, it is 15KV that plasma electrical source voltage is set, and electric current is 1.5A, discharge frequency 60KHz, start drive motors and drive the exciting piece, make frame and the ball grinder that is fixed on the frame vibrates simultaneously, carry out dielectric barrier discharge plasma auxiliary high-energy ball milling.Described exciting piece adopts double-amplitude 8mm, motor speed 1000r/min.
The heat treatment method of expanded graphite: the expansible graphite sheet is placed in the tube furnace, continues to feed the Ar air-flow, quickly heat up to 1000 ℃, be incubated the cold taking-up of stove after 30 minutes.
The germanium raw material is carried out pre-ball milling 5h according to the method described above, and expansible graphite is treated to the vermiform expanded graphite according to the method described above; With the vermiform EG after the germanium of pre-grinding 5h and the 1000 ℃ of heat treatments by 1:1(wt%) mix and carry out dielectric barrier discharge plasma auxiliary high-energy ball milling 3h, discharge medium is argon gas.
With the composite powder behind the ball milling, conductive agent super-p(acetylene black) and binding agent SBR(butadiene-styrene rubber) mix to be coated on by mass ratio 8:1:1 and be made into electrode slice on the Copper Foil.In the argon gas atmosphere glove box, with lithium metal as to electrode, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF
6Be electrolyte, be assembled into button cell and test.Test condition is: charging and discharging currents density is the multiplying power test of 0.2C, 4.5C and 0.03C～6C, and discharging and recharging by voltage is 0.01V～1.5V (vs.Li
+/ Li).
Carry out charge-discharge test according to above-mentioned battery testing condition and step, Graphene clad nano germanium composite material its first discharge specific capacity under 0.2C that obtains preparing is 1785.5mAhg
-1, the initial charge specific capacity is 1142.4, first charge-discharge efficiency is 64%; 50 times circulation back discharge capacity is 1019.9mAhg
-1(Fig. 7).
The difference of present embodiment and embodiment 1 is:
The time of described germanium raw material and expansible graphite mixing and ball milling is 5h.Carry out charge-discharge test after above-mentioned powder made lithium ion battery negative electrode slice and assembled battery.
The difference of present embodiment and embodiment 1 is:
The time of described germanium raw material and expansible graphite mixing and ball milling is 10h.And under 0.2C charge-discharge magnification condition, carry out charge-discharge test after above-mentioned powder made lithium ion battery negative electrode slice and assembled battery.Its first discharge capacity be 1313mAhg
-1, 40 times circulation back capacity remains on 845mAhg
-1
The difference of present embodiment and embodiment 1 is:
Vermiform EG after the germanium of pre-grinding 5h and the 1000 ℃ of heat treatment carries out proportioning according to mass ratio 0.3:1, and the ball milling time is 10h.Carry out charge-discharge test after above-mentioned powder made lithium ion battery negative electrode slice and assembled battery.
The difference of present embodiment and embodiment 4 is:
The time of described germanium raw material and expansible graphite mixing and ball milling is 15h.And above-mentioned powder made after lithium ion battery negative electrode slice and the assembled battery at the charge-discharge test that carries out under the 4.5C condition under the high current density.Its 2nd time circulation back specific discharge capacity is 624mAhg
-1, 100 times circulation back capacity remains on 436.2mAhg
-1(Fig. 8).
With original pure germanium powder and native graphite reagent powder by 1:1(wt%) mix, adopt the dielectric barrier discharge plasma auxiliary high-energy ball grinding method of embodiment 1, high-energy ball milling 8h, discharge medium are argon gas (Fig. 4).
The difference of present embodiment and embodiment 6 is:
The described ball milling time is 10h.Carry out charge-discharge test according to above-mentioned battery testing condition and step then, Graphene clad nano germanium composite material its first discharge specific capacity under 2C that obtains preparing is 1546mAhg
-1, the initial charge specific capacity is 1039mAhg
-1, first charge-discharge efficiency is 67%; 100 times circulation back discharge capacity is 645mAhg-1 (Fig. 9).
The difference of present embodiment and embodiment 6 is:
Described original germanium powder and native graphite reagent powder are pressed 5:1(wt%), the ball milling time is 15h.
As mentioned above, just can realize the present invention preferably, above-described embodiment is part embodiment of the present invention only, is not to limit practical range of the present invention; Be that all equalizations of doing according to content of the present invention change and modification, all contained by claim of the present invention scope required for protection.
Claims (10)
1. the preparation method of a Graphene clad nano pure germanium composite material is characterized in that,
Adopt dielectric barrier discharge plasma auxiliary high-energy ball-milling method to carry out ball milling germanium powder and graphite powder or heat treated expanded graphite;
Perhaps earlier the germanium powder is carried out dielectric barrier discharge plasma auxiliary high-energy ball milling, then the germanium powder behind the ball milling is mixed the back with graphite powder or heat treated expanded graphite and adopt dielectric barrier discharge plasma auxiliary high-energy ball-milling method to carry out ball milling.
2. preparation method according to claim 1, its feature exists, described germanium powder and graphite powder or expanded graphite are according to mass ratio Ge:C=(0.3～8): 1 carries out proportioning.
3. preparation method according to claim 1 is characterized in that, the discharge gas medium that adopts in the described ball milling is argon gas.
4. preparation method according to claim 1 is characterized in that, the described ball milling time is 3～15h.
5. preparation method according to claim 4 is characterized in that, the described ball milling time is 5h.
6. according to claim 1 or 2 or 3 or 4 or 5 described preparation methods, it is characterized in that the method for described dielectric barrier discharge plasma auxiliary high-energy ball milling is as follows:
(1) install front shroud and the electrode bar of ball grinder, front shroud is linked to each other with the positive and negative two-stage of plasma electrical source respectively with iron core in the electrode bar, wherein, the iron core in the electrode bar connects the positive pole of plasma electrical source, and front shroud connects the negative pole of plasma electrical source;
(2) the good starting powder of abrading-ball and proportioning of in ball grinder, packing into;
(3) by vacuum valve ball grinder is vacuumized, charge into discharge gas medium A r gas then, make the force value in the ball grinder reach 0.10～0.12MPa;
(4) connect plasma electrical source, it is 15KV that plasma electrical source voltage is set, and electric current is 1.5A, discharge frequency 60KHz, start drive motors and drive the exciting piece, make frame and the ball grinder that is fixed on the frame vibrates simultaneously, carry out dielectric barrier discharge plasma auxiliary high-energy ball milling.
7. according to claim 1 or 2 or 3 or 4 or 5 described preparation methods, it is characterized in that the heat treatment method of described expanded graphite: the expansible graphite sheet is placed in the tube furnace, continues to feed the Ar air-flow, quickly heat up to 1000 ℃, be incubated the cold taking-up of stove after 30 minutes.
8. the Graphene clad nano pure germanium composite material of any method preparation of claim 1～7.
9. composite material according to claim 8, it is characterized in that this composite material is composited by the germanium particle of 100nm～200nm, the Graphene of single or multiple lift, wherein, be distributed in the Graphene lamella to nanometer germanium uniform particles, form the safeguard structure that is coated by the Graphene network.
According to Claim 8 or 9 described Graphene clad nano pure germanium composite materials as the application of lithium ion battery negative material.
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