CN103247803B - 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 coated structure, tool
Body refers to graphene coated Ge composite and one one step preparation method and application, belongs to new forms of energy and nano-functional material skill
Art field.
Background technology
Graphene, as individual layer or thin layer graphite, has a specific surface area of super large, the specific strength of superelevation, outstanding electric conductivity
Etc. outstanding performance so as to lithium ion battery, solar energy, ultracapacitor, semiconductor, nano electron device, high intensity material
There is great application space in the field such as material and Novel noise reduction radiating.But its preparation and synthesis technique are greatly all in laboratory stage
Or minimum batch production, the technique of large-scale production Graphene or its composite need to improve.
Lithium ion battery has high voltage, high power capacity, has extended cycle life, has a safety feature and environmentally friendly etc. significantly excellent
Point is so as to having a extensive future in fields such as mancarried electronic aid, electric automobile, national defence space flight.But it is commercialized due to current
Graphite as anode material for lithium-ion battery theoretical capacity low（372mAhg-1）, limit the raising of capacity of lithium ion battery.For
Meet the demand to high power capacity excellent cycle stability lithium ion battery such as ever-increasing civilian, industrial or national defence.Research people
Member is in the continuous carbon alternative materials exploring other high power capacity.In numerous non-carbon negative material systems studied, metal Ge
System capacity is high, lithium ion diffusion coefficient is big, good conductivity, disclosure satisfy that at present for high power capacity, high magnification, eco-friendly
Lithium ion battery growth requirement.But during the meeting similar with materials such as other Si, Sn of pure germanium electrode material is due to embedding and removing
There are larger Volume Changes, and gradually efflorescence, depart from the phenomenon that collector leads to active material to lose efficacy.
Graphene is combined the safeguard structure forming graphene coated Ge, Graphene network with Ge particle
High-specific surface area and high intensity can for pure germanium electrode in charge and discharge cyclic process Volume Changes provide protective effect, make activity
While material keeps high power capacity, there is stable cycle performance and high rate performance.But this composite wood that current document is delivered
The building-up process of material is complicated, typically passes through electronation graphene oxide, then reacts gained further with the compound of germanium, synthesis
Amount is few and process parameter control is cumbersome it is impossible to industrial volume production.
Content of the invention
An object of the present invention is to provide a kind of graphene coated Ge particulate composite of process is simple.
The second object of the present invention is to provide the preparation method of above-mentioned composite.
The third object of the present invention is to provide the application of above-mentioned composite.
A kind of preparation method of graphene coated nanometer pure germanium composite, comprises the following steps that：
Method one：The expanded graphite of germanium powder and graphite powder or heat treatment is adopted dielectric barrier discharge plasma auxiliary high
Ball milling can be carried out by ball-milling method；
Method two：First germanium powder is carried out dielectric barrier discharge plasma auxiliary high-energy ball milling, then by the germanium after ball milling
Powder is carried out using dielectric barrier discharge plasma auxiliary high-energy ball-milling method after being mixed with the expanded graphite of graphite powder or heat treatment
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 adopting in described ball milling is argon gas.
Preferably, described Ball-milling Time is 3～15h.
Preferably, 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, by the iron core in front shroud and electrode bar respectively with plasma
The positive and negative two-stage of body power supply is connected, and wherein, the iron core in electrode bar connects the positive pole of plasma electrical source, and front shroud connects plasma
The negative pole of power supply；
（2）Abrading-ball and the good starting powder of proportioning is loaded in ball grinder；
（3）By vacuum valve, ball grinder is vacuumized, be then charged with discharge gas medium A r gas, make the pressure in ball grinder
Value reaches 0.10～0.12MPa；
（4）Connect plasma electrical source, setting plasma electrical source voltage is 15KV, electric current is 1.5A, discharge frequency
60KHz, starts motor and drives exciting block, makes frame and the ball grinder that is fixed in frame vibrates simultaneously, carry out medium resistance
Gear discharge plasma auxiliary high-energy ball milling.
Preferably, described exciting block adopts double-amplitude 5mm～10mm, motor speed 930～1400r/min.
Preferably, the heat treatment method of described expanded graphite：Expansible graphite piece is placed in tube furnace, is continually fed into Ar
Air-flow, quickly heats up to 1000 DEG C, the cold taking-up of stove after being incubated 30 minutes.
The graphene coated Ge particulate composite of present invention preparation, by the germanium particle of 100nm～200nm, individual layer
Or the Graphene of multilayer is composited, wherein, Ge particle is distributed evenly in graphene sheet layer, is formed by graphene mesh
The safeguard structure that network is coated.
Above-mentioned graphene coated nanometer pure germanium composite is as the application of lithium ion battery negative material.
The present invention compared with prior art, has the advantages that：
（1）The preparation method of gained individual layer or thin graphene cladding Ge particulate composite is simple.Adopt first
Plasma medium stops that auxiliary high-energy ball-milling method prepares graphene coated Ge particulate composite.The germanium carbon unit of the present invention
Plain proportioning is easy to control, preparation process process is simple, and power consumption is few, and yield is high, state modulator is simple, pollution-free, easily realizes industrialization
Produce.
（2）Gained graphene coated Ge particulate composite as lithium ion battery negative material, have capacity high,
The advantages of good rate capability and good cycling stability.
Brief description
Fig. 1 is the graphene coated Ge particulate composite XRD spectra of the embodiment of the present invention 4 preparation（With Ge-
77wt%EG, as a example ball milling 10h）.
Fig. 2 is the Raman figure of the graphene coated Ge particulate composite of the embodiment of the present invention 8 preparation（With Ge-
20wt% graphite, as a example ball milling 15h）.
Fig. 3 is the SEM figure of the graphene coated Ge particulate composite of the embodiment of the present invention 2 preparation method preparation
（With Ge-50wt%EG, as a example Ball-milling Time 5h）.
Fig. 4 is the SEM figure of the graphene coated Ge particulate composite of the embodiment of the present invention 6 preparation（With Ge-
50wt% native graphite, as a example ball milling 8h）.
Fig. 5 is filling under the different circulations of the graphene coated Ge particulate composite of the embodiment of the present invention 2 preparation
Discharge curve（With Ge-50wt%EG, as a example Ball-milling Time 5h）.
Fig. 6 is the cycle performance curve of the graphene coated Ge particulate composite of the embodiment of the present invention 4 preparation（With
Ge-77wt%EG, as a example Ball-milling Time 10h）.
Fig. 7 is the cycle performance curve of the graphene coated Ge particulate composite of the embodiment of the present invention 1 preparation（With
Ge-50wt%EG, as a example Ball-milling Time 3h）.
Fig. 8 is the cycle performance curve of the graphene coated Ge particulate composite of the embodiment of the present invention 5 preparation（With
Ge-77wt%EG, as a example Ball-milling Time 15h）.
Fig. 9 is the cycle performance curve of the graphene coated Ge particulate composite of the embodiment of the present invention 7 preparation（With
Ge-50wt% native graphite, as a example Ball-milling Time 10h）.
Figure 10 is plasma auxiliary high-energy mechanical milling process effect 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 the present invention adopts.
Figure 12 is the structural representation of ball grinder shown in Figure 11.
Figure 13 is the side view of ball grinder shown in Figure 12.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Various embodiments of the present invention preparation is high using the dielectric barrier discharge plasma auxiliary disclosed in patent ZL200510036231.9
Can ball mill.
As shown in figure 11, realize the plasma auxiliary high-energy ball mill device of the present invention, including motor l, ball grinder
2nd, frame 3, base 4, ball grinder 2 is arranged in frame 3, is placed with abrading-ball 5 inside it, and frame 3 is arranged on base by spring 6
On 4, outside it, be provided with exciting block 7, motor 1 is arranged on base 4, and by elastic coupling 8 respectively with frame 3,
Exciting block 7 connects.
As shown in Figure 12,13, abrading-ball 5 is placed in ball grinder 2, and ball grinder 2 is also associated with electrode bar 9, plasma electricity
Source 10, ball grinder 2 includes cylinder 2-1, front shroud 2-1, back shroud 2-3, and the flange at cylinder 2-1 two ends passes through sealing ring 2-4, spiral shell
Bolt 2-5 is tightly connected with front shroud 2-2, back shroud 2-3 respectively, any one bolt 2-5 of front shroud 2-2 and plasma electrical source
10 pole connects, and front shroud 2-2 is provided with electrode perforations 2-2-1, and the inner side of electrode perforations 2-2-1 is provided with concave station, back shroud 2-3
Medial surface is provided with blind hole 2-3-1.
The outer surface of electrode bar 9 is provided with clad 11, and the concave station of clad 11 respective electrode perforation is provided with shoulder, concave station
It is provided with gasket seal 12 and shoulder between, electrode bar 9 front end 9-1 is exposed and another pole of with plasma electrical source 10 is connected,
And front end 9-1 threaded with nut 13, nut 13 is close to the lateral surface of protecgulum 2-2, and electrode bar 9 rear end 9-2 penetrates protecgulum
In blind hole 2-3-1 of electrode perforations 2-2-1 of plate 2-2 embedded back shroud 2-3.
Front shroud 2-2 is additionally provided with vacuum valve 2-2-2, can take out negative pressure by vacuum valve 2-2-2 it is also possible to be passed through electric discharge gas
Body medium argon gas, nitrogen, ammonia or organic gas（As methane）To realize milling atmosphere in ball grinder.
Cylinder 2-1, abrading-ball 5 material are stainless steel or hard alloy, and the material of electrode bar 9 is stainless steel, front shroud 2-2,
Back shroud 2-3, the material of electrode bar clad 11 are polytetrafluoroethylene (PTFE).The output voltage range of plasma electrical source 10 be 1～
30kv, frequency range is 1～40kHz.
Embodiment 1
The comprising the concrete steps that of dielectric barrier discharge plasma auxiliary high-energy ball grinding method：
（1）Install front shroud and the electrode bar of ball grinder, by the iron core in front shroud and electrode bar respectively with plasma
The positive and negative two-stage of body power supply is connected, and wherein, the iron core in electrode bar connects the positive pole of plasma electrical source, and front shroud connects plasma
The negative pole of power supply；
（2）Hard alloy abrading-ball is loaded in ball grinder（Differ in size）The good starting powder with proportioning（Ball powder ratio 50:
1）；
（3）By vacuum valve, ball grinder is vacuumized, be then charged with discharge gas medium A r gas, make the pressure in ball grinder
Value reaches 0.12MPa；
（4）Connect plasma electrical source, setting plasma electrical source voltage is 15KV, electric current is 1.5A, discharge frequency
60KHz, starts motor and drives exciting block, makes frame and the ball grinder that is fixed in frame vibrates simultaneously, carry out medium resistance
Gear discharge plasma auxiliary high-energy ball milling.Described exciting block adopts double-amplitude 8mm, motor speed 1000r/min.
The heat treatment method of expanded graphite：Expansible graphite piece is placed in tube furnace, is continually fed into Ar air-flow, quickly add
Heat to 1000 DEG C, insulation 30 minutes after the cold taking-up of stove.
Germanium raw material is carried out pre- ball milling 5h according to the method described above, it is swollen that expansible graphite is processed as vermiform according to the method described above
Swollen graphite；Vermiform EG after the germanium of pre-grinding 5h and 1000 DEG C of heat treatments is pressed 1:1（wt%）Mixing carries out dielectric barrier discharge etc.
Gas ions auxiliary high-energy ball milling 3h, discharge medium is argon gas.
By the composite powder after ball milling, conductive agent super-p（Acetylene black）With binding agent SBR（Butadiene-styrene rubber）By matter
Amount compares 8：1：1 mixes to be coated on Copper Foil and is fabricated to electrode slice.In argon gas atmosphere glove box, using lithium metal as to electricity
Pole, ethylene carbonate（EC）+ dimethyl carbonate（DMC）+1MLiPF6For electrolyte, it is assembled into button cell and is tested.Test
Condition is：Charging and discharging currents density be 0.2C, 4.5C and 0.03C～6C multiplying power test, discharge and recharge by voltage for 0.01V～
1.5V(vs.Li+/Li).
Carry out charge-discharge test according to above-mentioned battery testing condition and step, the graphene coated Ge obtaining preparing is multiple
Condensation material its first discharge specific capacity under 0.2C is 1785.5mAhg-1, initial charge specific capacity is 1142.4, first charge-discharge
Efficiency is 64%；After 50 circulations, discharge capacity is 1019.9mAhg-1(Fig. 7).
Embodiment 2
The present embodiment is with the difference of embodiment 1：
Described germanium raw material is 5h with the time of expansible graphite mixing and ball milling.Above-mentioned powder is made lithium ion battery negative
Carry out charge-discharge test after electrode slice assembled battery.
Embodiment 3
The present embodiment is with the difference of embodiment 1：
Described germanium raw material is 10h with the time of expansible graphite mixing and ball milling.And above-mentioned powder is made lithium ion battery
Carry out charge-discharge test under the conditions of 0.2C charge-discharge magnification after negative electricity pole piece assembled battery.Its first discharge capacity be
1313mAhg-1, after 40 circulations, capacity is maintained at 845mAhg-1.
Embodiment 4
The present embodiment is with the difference of embodiment 1：
Vermiform EG after the germanium of pre-grinding 5h and 1000 DEG C of heat treatments is according to mass ratio 0.3：1 carries out proportioning, Ball-milling Time
For 10h.Above-mentioned powder is made and after lithium ion battery negative electrode slice assembled battery, carries out charge-discharge test.
Embodiment 5
The present embodiment is with the difference of embodiment 4：
Described germanium raw material is 15h with the time of expansible graphite mixing and ball milling.And above-mentioned powder is made lithium ion battery
Carry out the charge-discharge test under high current density under the conditions of 4.5C after negative electricity pole piece assembled battery.After its 2nd time circulation
Specific discharge capacity is 624mAhg-1, after 100 circulations, capacity is maintained at 436.2mAhg-1（Fig. 8）.
Embodiment 6
Original pure germanium powder is pressed 1 with native graphite reagent powder:1（wt%）Mixing, the dielectric impedance using embodiment 1 is put
Electro-plasma auxiliary high-energy ball grinding method, high-energy ball milling 8h, discharge medium is argon gas（Fig. 4）.
Embodiment 7
The present embodiment is with the difference of embodiment 6：
Described Ball-milling Time is 10h.Then according to above-mentioned battery testing condition and step carry out charge-discharge test, made
Standby graphene coated Ge composite its first discharge specific capacity under 2C is 1546mAhg-1, initial charge specific capacity
For 1039mAhg-1, first charge-discharge efficiency is 67%；After 100 circulations, discharge capacity is 645mAhg-1 (Fig. 9).
Embodiment 8
The present embodiment is with the difference of embodiment 6：
Described original germanium powder presses 5 with native graphite reagent powder:1（wt%）, Ball-milling Time is 15h.
As described above, just can preferably realize the present invention, above-described embodiment is only the section Example of the present invention, not uses
To limit the practical range of the present invention；I.e. all impartial changes made according to present invention and modification, all will for right of the present invention
Scope required for protection is asked to be covered.
Claims (8)
1. a kind of preparation method of graphene coated nanometer pure germanium composite it is characterised in that
The expanded graphite of germanium powder and graphite powder or heat treatment is entered using dielectric barrier discharge plasma auxiliary high-energy ball-milling method
Row ball milling；
Or first germanium powder is carried out dielectric barrier discharge plasma auxiliary high-energy ball milling, then by the germanium powder after ball milling and graphite
After the expanded graphite mixing of powder or heat treatment, ball milling is carried out using dielectric barrier discharge plasma auxiliary high-energy ball-milling method；
The discharge gas medium adopting in described ball milling is argon gas；
The method of described dielectric barrier discharge plasma auxiliary high-energy ball milling is as follows：
(1) front shroud and the electrode bar of ball grinder are installed, the iron core in front shroud and electrode bar is electric with plasma respectively
The positive and negative two-stage in source is connected, and wherein, the iron core in electrode bar connects the positive pole of plasma electrical source, and front shroud connects plasma electrical source
Negative pole；
(2) abrading-ball and the good starting powder of proportioning are loaded in ball grinder；
(3) by vacuum valve, ball grinder is vacuumized, be then charged with discharge gas medium A r gas, so that the pressure value in ball grinder is reached
To 0.10～0.12MPa；
(4) connect plasma electrical source, setting plasma electrical source voltage is 15KV, electric current is 1.5A, discharge frequency 60KHz,
Start motor and drive exciting block, make frame and the ball grinder that is fixed in frame vibrates simultaneously, carry out dielectric barrier discharge
Plasma auxiliary high-energy ball milling.
2. preparation method according to claim 1, its feature exists, and described germanium powder and graphite powder or expanded graphite are according to quality
Compare Ge：C=(0.3～8)：1 carries out proportioning.
3. preparation method according to claim 1 is it is characterised in that described Ball-milling Time is 3～15h.
4. preparation method according to claim 3 is it is characterised in that described Ball-milling Time is 5h.
5. the preparation method according to claim 1 or 2 or 3 or 4 is it is characterised in that the heat treatment side of described expanded graphite
Method：Expansible graphite piece is placed in tube furnace, is continually fed into Ar air-flow, quickly heat up to 1000 DEG C, stove after being incubated 30 minutes
Cold taking-up.
6. the graphene coated nanometer pure germanium composite of Claims 1 to 5 any one method preparation.
7. composite according to claim 6 it is characterised in that this composite by 100nm～200nm germanium
Grain, the Graphene of single or multiple lift are composited, and wherein, Ge particle is distributed evenly in graphene sheet layer, form quilt
The safeguard structure that Graphene network is coated.
8. the graphene coated nanometer pure germanium composite according to claim 6 or 7 is as lithium ion battery negative material
Application.
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| US10944101B2 (en) * | 2014-02-28 | 2021-03-09 | University Of South Carolina | Superior lithium ion battery electrode and methods for fabricating such |
| CN103943836B (en) * | 2014-04-01 | 2016-09-21 | 太原理工大学 | Lithium ion battery negative material hollow Ge nano-tube array electrode and preparation method thereof |
| CN104979533B (en) * | 2015-04-17 | 2020-12-08 | 重庆大学 | Preparation method of graphene nanoribbon wound germanium nanoparticle composite material |
| CN105006351B (en) * | 2015-07-15 | 2017-05-10 | 宁波仁栋电气有限公司 | Transformer iron core and manufacture method thereof |
| US9899672B2 (en) * | 2016-05-17 | 2018-02-20 | Nanotek Instruments, Inc. | Chemical-free production of graphene-encapsulated electrode active material particles for battery applications |
| CN107673307A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery |
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| CN107546387B (en) * | 2017-08-10 | 2019-12-03 | 北京工业大学 | A kind of molten-salt electrolysis prepares vermiform germanium base nano-wire and application |
| CN107720740A (en) * | 2017-11-14 | 2018-02-23 | 郴州国盛新材科技有限公司 | A kind of preparation method that graphene nanometer sheet is prepared based on crystalline flake graphite |
| CN107601485A (en) * | 2017-11-14 | 2018-01-19 | 郴州国盛新材科技有限公司 | The preparation method of graphene nanometer sheet is prepared based on micro crystal graphite |
| CN108281627B (en) * | 2018-01-03 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN108580885B (en) * | 2018-04-09 | 2021-03-16 | 西安交通大学 | Preparation method of graphene coated powder with core-shell structure |
| CN109273702B (en) * | 2018-11-28 | 2020-10-27 | 西安交通大学 | All-solid-state preparation method for uniformly coating graphene on surface of irregular micro-nano particle |
| CN110364706B (en) * | 2019-06-27 | 2021-07-20 | 华南理工大学 | Antimony oxide-based negative electrode material with high reversible capacity and preparation method thereof |
| CN110518188A (en) * | 2019-07-18 | 2019-11-29 | 华南理工大学 | A kind of selenium-phosphorus-carbon composite and the preparation method and application thereof |
| CN110556525B (en) * | 2019-08-21 | 2022-03-29 | 华南理工大学 | Lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN110643407A (en) * | 2019-09-30 | 2020-01-03 | 集美大学 | Preparation method of graphene-coated spherical metal |
| CN110666179B (en) * | 2019-11-11 | 2022-11-29 | 沈阳航空航天大学 | Graphene aluminum-based composite powder for laser deposition manufacturing, and preparation method and application thereof |
| CN113122186A (en) * | 2021-04-21 | 2021-07-16 | 广东工业大学 | Nano-metal composite phase-change material and preparation method thereof |
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| WO2007136046A1 (en) * | 2006-05-23 | 2007-11-29 | Sony Corporation | Negative electrode and its manufacturing method, and battery and its manufacturing method |
| US7745047B2 (en) * | 2007-11-05 | 2010-06-29 | Nanotek Instruments, Inc. | Nano graphene platelet-base composite anode compositions for lithium ion batteries |
| CN102427127A (en) * | 2011-12-02 | 2012-04-25 | 华南理工大学 | Stannum oxide/stannum-carbon composite material, and preparation method and application thereof |
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