CN108565403A - A kind of lithium battery graphene silicium cathode material and its preparation method and application - Google Patents
A kind of lithium battery graphene silicium cathode material and its preparation method and application Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/00—Electrodes
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention belongs to field of new energy technologies, a kind of lithium battery graphene silicium cathode material and its preparation method and application is disclosed.This method uses Lithium hydroxide monohydrate and polyacrylic acid for binder, specifically according to the following steps：Ball milling, the then drying in drying box in high energy ball mill by micron silica flour；The silica flour that graphene addition ball milling is crossed continues ball milling in high energy ball mill；To ball milling, processing is dried in good substance；Weigh polyacrylic acid：One hydronium(ion) lithia mass ratio is 1:2.0‑1:1.5 are dissolved in deionized water, obtain homogeneous transparent binder；Weigh the active material, the 10 20 mass parts part binders of 80 90 mass parts；For even application on copper foil, drying obtains graphene silicium cathode material after binder grinding uniformly.The novel binders that the present invention uses can be effectively improved the cycle performance of graphene silicium cathode material, extend the cycle life of negative material, improve the cycle life of estimation material.
Description
Technical field
The invention belongs to field of new energy technologies, and in particular to a kind of lithium battery graphene silicium cathode material and its preparation side
Method and application.
Background technology
Since lithium ion battery in 1992 realizes product commercialization, the application range of lithium ion is gradually expanded, from portable
Formula electronic product has the figure of lithium battery invariably to military equipment, then to the utilization of new energy.With the development of science and technology and energy
The exacerbation of source crisis, people more favor the lithium battery of high power capacity, high-energy density, and weight of the negative material as lithium battery
Want component part, it has also become the emphasis of various countries' research.Traditional cathode of lithium battery is Carbon materials, and theoretical specific capacity is
372mAh/g, lithium storage content is relatively low, and intercalation potential is close to the deposition potential of lithium metal, hidden in the presence of safety when high magnification charges
Suffer from.
Silicon is because the theoretical of silicon holds as a kind of object that can become people's research with the metal of lithium alloyage and pay close attention to
Amount is 4200mAh/g (Li22Si5), 11 times than Carbon materials are more, and its intercalation potential is less than the deposition potential of lithium, carries
Safety under high high magnification charging.But during removal lithium embedded, the variation of silicon meeting recurring structure forms serious volume
Expansion and contraction (reaching as high as 300% or more) cause active material to be easy to be in electrical contact deterioration between dusting, with collector, into
And cause irreversible capacity, the problems such as cyclical stability is poor for the first time.It is mainly two silicon to solve the thinking of silicon bulk effect at present
Nanosizing and silicon Composite.Silicon nanosizing includes mainly using nano silica fume and silicon nanowire, using magnetically controlled sputter method or change
The method for learning vapor deposition directly deposits one layer of nano silicon film on a current collector, and uses high-energy ball milling method by silica flour nanosizing
Deng.The cyclical stability for improving silicon using this kind of thinking is relatively high to equipment requirement, and production cost is higher, is existed using nano silicone
The phenomenon that reunion and electrochemistry ablation are easy to happen in cyclic process, it is limited to silicium cathode performance improvement.Silicon Composite mainly wraps
Include silicon and metallic alloying, such as silicon-nickel alloy, silicon-copper alloy, silicon-cobalt alloy, silicon-tin alloy, silicon-aluminum alloy, silicon and carbon
Composite such as prepares silicon-carbon cathode composite material using thermal reduction, and does carbon source coating modification etc. using pitch.Silicon is compound
Change can introduce buffer medium, slow down the bulk effect of silicon to a certain extent, improve the cycle performance of silicium cathode, but effect according to
It is so less desirable, it is unable to meet demand.Other researcher sets about from electrode structure and binder, by changing electrode
Structure and binder improve the cycle performance of silicium cathode, but effect is not very significantly.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of lithium battery stone
The preparation method of black alkene silicium cathode material；It can effectively extend the rate of decay of silicon-carbon cathode material the process employs a kind of, change
The binder of the lithium ion battery silicon-carbon cathode material of kind silicon-carbon cathode material cycle performance
Another object of the present invention is to provide a kind of lithium battery graphene silicium cathode material that above-mentioned preparation method is prepared
Material.
Still a further object of the present invention is to provide a kind of application of above-mentioned lithium battery graphene silicium cathode material.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of lithium battery graphene silicium cathode material, includes the following steps：
(1) by micron silica flour, high-energy ball milling, the then drying in drying box obtain nano-silicon in high energy ball mill
Grain；
(2) graphene is added in silicon nanoparticle obtained by step (1), the mass ratio of graphene and silicon nanoparticle is
35:65, continue ball milling in high energy ball mill；
(3) processing is dried by the substance of ball milling to step (2), obtains graphene silicon composite；
(4) it is 1 to take mass ratio:2.0-1:1.5 polyacrylic acid and a hydronium(ion) lithia, are dissolved in deionized water,
Obtain homogeneous transparent binder；
(5) it weighs binder obtained by graphene silicon composite and step (4) obtained by step (3) to be mixed, graphene
The mass ratio of composite material and binder is 1：9-2：8, it grinds 10 minutes；
(6) by the mixture even application after grinding on copper foil, drying obtains lithium battery graphene silicium cathode material.
Preferably, the grain size of the micron silica flour described in step (1) is 1-3 μm, and ball material mass ratio when ball milling is 10:
1-20:1, ball milling speed 450-600r/min, Ball-milling Time 20-80min.
The speed for continuing ball milling described in step (2) is 450-600r/min, Ball-milling Time 10-100min.
The viscosity 1.0-1.2PaS of homogeneous transparent binder described in step (4).
Drying described in step (6) is placed in drying box in 80 DEG C of dry 3h, is transferred in vacuum drying chamber in 80
DEG C dry 12h.
A kind of lithium battery graphene silicium cathode material being prepared by above-mentioned preparation method.
Application of the above-mentioned lithium battery graphene silicium cathode material in preparing lithium battery.
The present invention compared with the existing technology, has the following advantages and advantageous effect：
(1) present invention puts graphene and nano silica fume into high energy ball mill high-energy ball milling, is provided in ball mill moment
Huge energy make nano-silicon and graphene form the three-decker of nano-silicon-graphene-nano-silicon, because of high-energy ball milling energy
There is provided the huge energy of up time, moreover it is possible to make silicon and carbon in one layer of thin silicon carbide (SiC) of Surface Creation, to improve leading for material
Electrically, to improve the high rate performance of material.
(2) silica flour employed in the present invention is micron order, simple and easy to get, reduces production cost, passes through high-energy ball milling
Its granularity can be made to reduce, even particle size distribution, and realize part amorphization, the body of silicon can be improved to a certain extent
Product effect additionally incorporates graphene as buffer medium, can effectively inhibit volume effect of silicon during embedding lithium, de- lithium
It answers, while improving the electrical contact between silicon and collector.
(3) using the caking property effectively increased after novel binders between active material and collector, silicon-carbon is avoided
The rate of decay of material, so as to improve the cycle performance of silicon-carbon cathode material.
Description of the drawings
Fig. 1 is the SEM figures of silicon nanoparticle after high-energy ball milling.
Fig. 2 is the XRD diagram of nano-silicon after high-energy ball milling.
Fig. 3 is that the SEM of graphene schemes.
Fig. 4 is the SEM figures of graphene/nanometer silicon prepared by the embodiment of the present invention 1.
Fig. 5 is the XRD diagram of graphene/nanometer silicon prepared by the embodiment of the present invention 1.
Fig. 6 is that graphene/nanometer silicon materials prepared by the embodiment of the present invention 1 are bent as the charge and discharge of negative electrode of lithium ion battery
Line.
Fig. 7 is cycle performance of the graphene/nanometer silicon materials of the preparation of the embodiment of the present invention 1 as negative electrode of lithium ion battery
Curve and coulombic efficiency curve.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
By 2 μm of silica flour high-energy ball milling 50min in high energy ball mill, ball material mass ratio is 15：1, rotational speed of ball-mill 550r/
Then min is dried to obtain silicon nanoparticle in drying box；Taking graphene, (mass ratio of graphene and silicon nanoparticle is 35：
65) it is added in the silica flour by ball milling, is added in ball grinder in an inert atmosphere, ratio of grinding media to material 15：1, high-energy ball milling
The good material of ball milling is taken out drying after waiting ball grinders to cool down, obtains graphene silicon by 60min, rotational speed of ball-mill 550r/min
Composite material.
Fig. 1 is that the SEM of silicon nanoparticle schemes, and the size of silicon is probably differed in hundreds of nanometers nanometer after high-energy ball milling,
It is the XRD diagram of nano-silicon shown in Fig. 2, the characteristic peak of silicon is fairly obvious as seen from the figure, and does not have dephasign, shown in Fig. 3 to be
The SEM of graphene schemes, as seen from the figure graphene be in layer structure, and lamella is in uneven thickness, it is shown in Fig. 4 be through
The SEM figures of the graphene silicon composite of high-energy ball milling method preparation are crossed, as can be seen from the figure nano-silicon particle is dispersed in graphite
On alkene lamella, the larger particle of grain size is graphene, and the smaller particle of grain size is silica flour, and silica flour is substantially attached to graphene film
On layer so that the three-decker of nano-silicon and graphene formation nano-silicon-graphene-nano-silicon, such structure are conducive to delay
The convergent-divergent of solution silicon particle in charge and discharge process improves the cyclical stability and high rate performance of material, and shown in fig. 5 is high
The XRD diagram of graphene silicon composite prepared by energy ball-milling method, the characteristic peak of silicon obviously weakens as seen from the figure, and is in 2 θ
Occur the peak of SiC when 38 °, illustrate during high-energy ball milling because high-energy ball milling can provide the huge energy of up time,
Make silicon and carbon in one layer of thin silicon carbide of Surface Creation, to improve the electric conductivity of material, to improve the forthright again of material
Energy.
It weighs polyacrylic acid 0.9g to be dissolved in the deionized water of 20ml, weighs hydronium(ion) lithia 0.5g and be dissolved in 10ml
Deionized water in, polyacrylic acid solution will be formed by and hydronium(ion) lithia solution is sufficiently mixed uniformly, obtain uniformly thoroughly
Bright binder；The binder for obtaining 85 parts and 15 parts quality of graphene silicon composite is fully ground, and is coated on copper foil,
80 DEG C of dry 3h in being placed in drying box, slice, 8Mpa pressure tablettings transfer to the dry 12h of 80 DEG C of vacuum drying chamber.More than
It is anode to state negative material obtained, and lithium piece is to electrode, and electrolyte is the EC/DMC (Vol of the LiPF6 of 1mol/L：Vol=1:
1), diaphragm is polyethylene diagrams, is processed into button cell, and test charging and discharging currents are 200mA/g, and cut-off charging/discharging voltage is
0.01-2.00V, charge and discharge cycles curve is shown in Fig. 6, it can be seen from the figure that reversible capacity reaches 2671mAh/g for the first time, the electricity
The cycle performance curve and coulombic efficiency curve coulombic efficiency as shown in Figure 7 of pole material are 88.31%, illustrate to use high-energy ball milling
Method as the method for preparing graphene silicium cathode material improve carbon silicium cathode material for the first time can reverse efficiency, using a water hydrogen-oxygen
Words lithium and polyacrylic acid as binder also improve carbon silicium cathode material for the first time can reverse efficiency.After being recycled to 100 times, capacity
For 1236mAh/g, efficiency 98% illustrates that the silicon-carbon cathode material being prepared has than the good cycling stability of pure silicon material
There is preferable cyclical stability.
Embodiment 2
By 1 μm of silica flour high-energy ball milling 20min in high energy ball mill, ball material mass ratio is 10：1, rotational speed of ball-mill 450r/
Then min is dried to obtain silicon nanoparticle in drying box；Taking graphene, (mass ratio of graphene and silicon nanoparticle is 35：
65) it is added in the silica flour by ball milling, is added in ball grinder in an inert atmosphere, ratio of grinding media to material 10：1, high-energy ball milling
The good material of ball milling is taken out drying after waiting ball grinders to cool down, obtains graphene silicon by 100min, rotational speed of ball-mill 450r/min
Composite material.
It weighs polyacrylic acid 0.9g to be dissolved in the deionized water of 20ml, weighs hydronium(ion) lithia 0.5g and be dissolved in
Polyacrylic acid solution and hydronium(ion) lithia solution are sufficiently mixed uniformly by 10ml, take 90 parts of graphene silicon composite and 10
The binder of part quality is fully ground, and coated on copper foil, 80 DEG C of dry 3h in being placed in drying box are sliced, 8Mpa pressure
Tabletting is being transferred to the dry 12h of 80 DEG C of vacuum drying chamber, and silicon-carbon cathode material is made.It is just with negative material obtained above
Pole, lithium piece are to electrode, and electrolyte is the EC/DMC (Vol of the LiPF6 of 1mol/L：Vol=1:1), diaphragm is polyethylene diagrams,
It is processed into button cell, test charging and discharging currents are 200mA/g, and cut-off charging/discharging voltage is 0.01-2.00V, for the first time reversible appearance
Amount reaches 2468mAh/g, coulombic efficiency 84%.
Embodiment 3
By 3 μm of silica flour high-energy ball milling 20min in high energy ball mill, ball material mass ratio is 20：1, rotational speed of ball-mill 600r/
Then min is dried to obtain silicon nanoparticle in drying box；Taking graphene, (graphene and silicon nanoparticle mass ratio are 35：
65) it is added in the silica flour by ball milling, is added in ball grinder in an inert atmosphere, ratio of grinding media to material 20：1, high-energy ball milling
The good material of ball milling is taken out drying after waiting ball grinders to cool down, obtains graphene silicon by 10min, rotational speed of ball-mill 600r/min
Composite material.
It weighs polyacrylic acid 0.8g to be dissolved in the deionized water of 20ml, weighs hydronium(ion) lithia 0.4g and be dissolved in
Polyacrylic acid solution and hydronium(ion) lithia solution are sufficiently mixed uniformly by 10ml, take 90 parts of graphene silicon composite and 10
The binder of part quality is fully ground, and coated on copper foil, 80 DEG C of dry 3h in being placed in drying box are sliced, 8Mpa pressure
Tabletting is being transferred to the dry 12h of 80 DEG C of vacuum drying chamber, and silicon-carbon cathode material is made.It is just with negative material obtained above
Pole, lithium piece are to electrode, and electrolyte is the EC/DMC (Vol of the LiPF6 of 1mol/L：Vol=1:1), diaphragm is polyethylene diagrams,
It is processed into button cell, test charging and discharging currents are 200mA/g, and cut-off charging/discharging voltage is 0.01-2.00V, for the first time reversible appearance
Amount reaches 3479mAh/g, coulombic efficiency 86%.
Embodiment 4
By 3 μm of silica flour high-energy ball milling 80min in high energy ball mill, ball material mass ratio is 15：1, rotational speed of ball-mill 450r/
Then min is dried to obtain silicon nanoparticle in drying box；Taking graphene, (mass ratio of graphene and silicon nanoparticle is 35：
65) it is added in the silica flour by ball milling, is added in ball grinder in an inert atmosphere, ratio of grinding media to material 20：1, high-energy ball milling
The good material of ball milling is taken out drying after waiting ball grinders to cool down, ball grinders is waited to cool down by 40min, rotational speed of ball-mill 550r/min
The good material of ball milling is taken out into drying afterwards, obtains graphene silicon composite.
It weighs polyacrylic acid 0.9g to be dissolved in the deionized water of 20ml, weighs hydronium(ion) lithia 0.5g and be dissolved in
Polyacrylic acid solution and hydronium(ion) lithia solution are sufficiently mixed uniformly by 10ml, take 90 parts of graphene silicon composite and 10
The binder of part quality is fully ground, and coated on copper foil, 80 DEG C of dry 3h in being placed in drying box are sliced, 8Mpa pressure
Tabletting is being transferred to the dry 12h of 80 DEG C of vacuum drying chamber, and silicon-carbon cathode material is made.It is just with negative material obtained above
Pole, lithium piece are to electrode, and electrolyte is the EC/DMC (Vol of the LiPF6 of 1mol/L：Vol=1:1), diaphragm is polyethylene diagrams,
It is processed into button cell, test charging and discharging currents are 200mA/g, and cut-off charging/discharging voltage is 0.01-2.00V, for the first time reversible appearance
Amount reaches 2694mAh/g, coulombic efficiency 87%.
Embodiment 5
By 1 μm of silica flour high-energy ball milling 60min in high energy ball mill, ball material mass ratio is 20：1, rotational speed of ball-mill 600r/
Then min is dried to obtain silicon nanoparticle in drying box；Take graphene (the ratio mass ratio of graphene and silicon nanoparticle
It is 35：65) it is added in the silica flour by ball milling, is added in ball grinder in an inert atmosphere, ratio of grinding media to material 15：1, high-energy ball milling
The good material of ball milling is taken out drying after waiting ball grinders to cool down, ball grinders is waited to cool down by 30min, rotational speed of ball-mill 500r/min
The good material of ball milling is taken out into drying afterwards, obtains graphene silicon composite.
It weighs polyacrylic acid 0.9g to be dissolved in the deionized water of 20ml, weighs hydronium(ion) lithia 0.5g and be dissolved in
Polyacrylic acid solution and hydronium(ion) lithia solution are sufficiently mixed uniformly by 10ml, take 90 parts of graphene silicon composite and 10
The binder of part quality is fully ground, and coated on copper foil, 80 DEG C of dry 3h in being placed in drying box are sliced, 8Mpa pressure
Tabletting is being transferred to the dry 12h of 80 DEG C of vacuum drying chamber, and silicon-carbon cathode material is made.It is just with negative material obtained above
Pole, lithium piece are to electrode, and electrolyte is the EC/DMC (Vol of the LiPF6 of 1mol/L：Vol=1:1), diaphragm is polyethylene diagrams,
It is processed into button cell, test charging and discharging currents are 200mA/g, and cut-off charging/discharging voltage is 0.01-2.00V, for the first time reversible appearance
Amount reaches 2655mAh/g, coulombic efficiency 85%.
Embodiment 6
By 3 μm of silica flour high-energy ball milling 60min in high energy ball mill, ratio of grinding media to material 10：1, rotational speed of ball-mill 500r/min,
Then silicon nanoparticle is dried to obtain in drying box；Taking graphene, (mass ratio of graphene and silicon nanoparticle is 35：65)
It is added in the silica flour by ball milling, is added in ball grinder in an inert atmosphere, ratio of grinding media to material 10：1, high-energy ball milling 80min, ball
Mill rotating speed is 450r/min, and the good material of ball milling is taken out drying after waiting ball grinders to cool down, by ball milling after waiting ball grinders to cool down
Good material takes out drying, obtains graphene silicon composite.
It weighs polyacrylic acid 0.8g to be dissolved in the deionized water of 20ml, weighs hydronium(ion) lithia 0.4g and be dissolved in
Polyacrylic acid solution and hydronium(ion) lithia solution are sufficiently mixed uniformly by 10ml, take 90 parts of graphene silicon composite and 10
The binder of part quality is fully ground, and coated on copper foil, 80 DEG C of dry 3h in being placed in drying box are sliced, 8Mpa pressure
Tabletting is being transferred to the dry 12h of 80 DEG C of vacuum drying chamber, and silicon-carbon cathode material is made.It is just with negative material obtained above
Pole, lithium piece are to electrode, and electrolyte is the EC/DMC (Vol of the LiPF6 of 1mol/L：Vol=1:1), diaphragm is polyethylene diagrams,
It is processed into button cell, test charging and discharging currents are 200mA/g, and cut-off charging/discharging voltage is 0.01-2.00V, for the first time reversible appearance
Amount reaches 2478mAh/g, coulombic efficiency 87%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of lithium battery graphene silicium cathode material, it is characterised in that include the following steps：
(1) by micron silica flour, high-energy ball milling, the then drying in drying box obtain silicon nanoparticle in high energy ball mill；
(2) graphene is added in silicon nanoparticle obtained by step (1), the mass ratio of graphene and silicon nanoparticle is 35:65,
Continue ball milling in high energy ball mill；
(3) processing is dried by the substance of ball milling to step (2), obtains graphene silicon composite；
(4) it is 1 to take mass ratio:2.0-1:1.5 polyacrylic acid and a hydronium(ion) lithia, are dissolved in deionized water, obtain
Homogeneous transparent binder；
(5) it weighs binder obtained by graphene silicon composite and step (4) obtained by step (3) to be mixed, graphene is compound
The mass ratio of material and binder is 1：9-2：8, it grinds 10 minutes；
(6) by the mixture even application after grinding on copper foil, drying obtains lithium battery graphene silicium cathode material.
2. preparation method according to claim 1, it is characterised in that：The grain size of micron silica flour described in step (1) is 1-3
μm, ball material mass ratio when ball milling is 10:1-20:1, ball milling speed 450-600r/min, Ball-milling Time 20-80min.
3. preparation method according to claim 1, it is characterised in that：Described in step (2) continue ball milling speed be
4500-600r/min, Ball-milling Time 10-100min.
4. preparation method according to claim 1, it is characterised in that：Homogeneous transparent binder described in step (4) glues
Spend 1.0-1.2PaS.
5. preparation method according to claim 1, it is characterised in that：It dries and is placed in drying box described in step (6)
In 80 DEG C of dry 3h, transfer in vacuum drying chamber in 80 DEG C of dry 12h.
6. a kind of lithium battery graphene silicium cathode material being prepared by any one of the claim 1-5 preparation methods.
7. application of the lithium battery graphene silicium cathode material according to claim 6 in preparing lithium battery.
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| CN109879286A (en) * | 2019-02-28 | 2019-06-14 | 湖南九华碳素高科有限公司 | A kind of preparation method of lithium battery silicon-carbon cathode composite material |
| CN109950490A (en) * | 2019-03-21 | 2019-06-28 | 柯良节 | A kind of negative electrode material and preparation method thereof, lithium battery |
| CN110148738A (en) * | 2019-06-13 | 2019-08-20 | 深圳市中金岭南科技有限公司 | A kind of preparation method of silicon-carbon composite powder material |
| CN111366853A (en) * | 2018-12-25 | 2020-07-03 | 微宏动力***（湖州）有限公司 | Method for testing cycle performance of negative electrode material and application thereof |
| CN111446431A (en) * | 2020-04-14 | 2020-07-24 | 南京宁智高新材料研究院有限公司 | Method for enhancing interface contact of silicon-oxygen-carbon cathode material of lithium ion battery through oxygen transfer reaction |
| CN112635762A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Lithium ion battery cathode material, preparation method and application thereof, and lithium ion battery |
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