CN108039465A - Combination electrode material and its preparation method and application - Google Patents
Combination electrode material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of combination electrode material, comprises the following steps：Carbon nanotubes, silicon grain and water soluble organic substance are uniformly dispersed in water, sodium alginate is added and is crosslinked to form hydrogel, and the product after crosslinking is freeze-dried；Above-mentioned product is carbonized under protective atmosphere at 350 600 DEG C, has obtained combination electrode material.The microstructure of combination electrode material prepared by the present invention is three-dimensional mesh, and silicon grain and carbon nanotubes are embedded in multi-layer sheet structure.Present invention also offers application of the above-mentioned combination electrode material in standby lithium ion battery.The present invention prepares combination electrode material with good conductivity, its pattern is adjustable, and has good cyclical stability using the skeleton structure of Sodium Alginate Hydrogel Films as template using simple, efficient method.
Description
Technical field
The present invention relates to battery technology field, more particularly to a kind of combination electrode material and its preparation method and application.
Background technology
Current conventional energy resource is increasingly deficient, develops that the secondary cell of high-energy-density is extremely urgent, and wherein silicium cathode is due to height
Specific capacity attracted great concern.However, due in charge and discharge process have larger volumetric expansion (400%) this
So as to limit its application in actual production.
The main method for solving silicium cathode Problem of Failure at present is to provide expansion space for the expansion of silicon, but the prior art
Not only complex process is difficult to realize, but also easily pollutes environment, it is difficult to realizes large-scale industrial production.In addition, there is research
It was found that when silicon grain size reaches below 150nm, stress effect be not influence performance of lithium ion battery it is main because
Element.But up to the present, in large capacity, high-performance, long-life, low-cost silicon base lithium ion charging battery electrode developmental achievement
In there is no also one kind extensive, low cost, industrialized technology of preparing.Therefore, preparation process is found simply and with good
The negative material of lithium ion storge quality becomes the key of development lithium ion battery.
The content of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of combination electrode material and preparation method thereof and answer
With the present invention prepares combination electrode material, this is compound using Sodium Alginate Hydrogel Films as skeleton using simple, efficient method
Electrode material pattern is adjustable, and has good cyclical stability.
To achieve these goals, present invention employs following technical solution：
On the one hand, the present invention provides a kind of preparation method of combination electrode material, comprise the following steps：
(1) carbon nanotubes, silicon grain, water soluble organic substance are uniformly mixed in water, then add sodium alginate mixing
Uniformly, mixed solution is obtained；
(2) metallic compound is added in the mixed solution obtained to step (1) to be uniformly mixed, then add sustained release agent, it is quiet
Put and be freeze-dried；
(3) under protective atmosphere, the product heats obtained in step (2) are obtained into the compound electric to high temperature to be carbonized
Pole material.
Further, in step (1), the particle diameter of silicon grain is 50nm-1 μm, preferably 50-100nm.That is, silicon grain is
Silicon nanoparticle or micron silicon grain.
Further, in step (1), water soluble organic substance is polyvinylpyrrolidone, it is as dispersant.
Further, in step (1), the mass ratio of carbon nanotubes, silicon grain and water soluble organic substance is 0.5-2:1:
1.By adjusting the ratio and both ratios with sodium alginate of carbon nanotubes and silicon grain, mixed solution, i.e. forerunner are formed
Liquid solution.
Further, in step (2), metallic compound is selected from calcium carbonate, basic copper carbonate, Kocide SD, nickel nitrate
With the one or more in ferric nitrate.By adjusting the ratio of material in metallic compound, sustained release agent and step (1), formed not
With the gel of the degree of cross linking.
Further, in step (1), the mass ratio of sodium alginate and carbon nanotubes and silicon grain is 5-50：3.
Further, in step (2), the mass ratio of metallic compound and silicon grain is 5-60:4.
Further, in step (2), the mass ratio of sustained release agent and the solute in the mixed solution in step (1) is 3:
1-15。
Preferably, in step (2), sustained release agent is glucolactone and/or acetic acid.
Further, in step (3), protective atmosphere is the one or more in nitrogen, helium and argon gas.
In step (2), after sustained release agent is added, sustained release agent slowly discharges hydrogen ion, hydrogen ion and metal compound
Thing, which reacts, discharges corresponding metal ion, and metal ion is crosslinked with sodium alginate, so that hydrogel is formed, in shape
Into among the process of hydrogel, carbon nanotubes and silicon grain are wrapped in Sodium Alginate Hydrogel Films.During gelation,
Solid-solid interface between different amounts of carbon nanotubes and silicon grain has differences, by adjust the material containing metal ion with
The addition of sustained release agent, can adjust the microstructure of composite material and finally influence the performance of combination electrode.
Further, in step (2), product is placed in room temperature environment standing, and gelation reaction can occur for sodium alginate, molten
Liquid is gradually solidified into hydrogel.
Further, product time of repose step (2) obtained is 6-24h.Preferably, time of repose 12-24h,
More preferably 24 it is small when.
Further, when product freeze-drying 12-24 step (2) obtained is small.Preferably, drying time 24h.
Further, in step (3), by the product heats obtained in step (2) to 350-600 under protective atmosphere
DEG C, material is carbonized, and forms silicon carbon compound.Preferably, 400 DEG C are heated in step (3), under protective atmosphere, it is compound
Hydrogel carbonization is complete.
On the other hand, a kind of above method is additionally provided present invention also offers a kind of method of the invention to be prepared
Combination electrode material, the wherein microstructure of the combination electrode material is three-dimensional mesh, and inside configuration is by silicon grain and carbon
Nanotube supports to form skeleton.
It yet still another aspect, the application present invention also offers above-mentioned combination electrode material in lithium ion battery is prepared.
According to the above aspect of the present invention, the present invention has the following advantages：
The present invention provides a kind of method for preparing combination electrode material, this method is prepared with rule using sodium alginate
The combination electrode material that then structure and property are stablized, its size adjustable, can mass produce.This method is made using carbon nanotubes
For conductive network, the electric conductivity of whole combination electrode on the one hand can be improved, still further aspect is since carbon nanotubes is with certain
Toughness, the volumetric expansion problem of silicon can be alleviated by forming network.In addition, the present invention uses sodium alginate as water-setting collagen
Material, nano-metal particle has been obtained after carbonization treatment, has improved the electric conductivity of electrode material.Therefore, method of the invention
The combination electrode material of preparation, it is possible to increase the cyclical stability of electrode, can be widely used for electroplating, is electrolysed, the neck such as solidification and crystallization
Domain.
Brief Description Of Drawings
Fig. 1 is the SEM figures that product is freeze-dried in the embodiment of the present invention 1；
Fig. 2 is the part-structure enlarged drawing in Fig. 1；
Fig. 3 is the SEM figures of product after being carbonized in the embodiment of the present invention 1；
Fig. 4 is the XRD diagram of combination electrode material in the embodiment of the present invention 1；
Fig. 5 is combination electrode material chemical property figure in the embodiment of the present invention 1
Fig. 6 is the SEM figures that product is freeze-dried in the embodiment of the present invention 2；
Fig. 7 is the SEM figures of product after being carbonized in the embodiment of the present invention 2；
Fig. 8 is the part-structure enlarged drawing in Fig. 7；
Fig. 9 is the SEM figures that product is freeze-dried in the embodiment of the present invention 3；
Figure 10 is the SEM figures of product after being carbonized in the embodiment of the present invention 3；
Figure 11 is the part-structure enlarged drawing in Figure 10；
Figure 12 is the SEM figures of product after freeze-drying when sodium alginate quality is 0.5g in the embodiment of the present invention 4；
Figure 13 is the SEM figures of product after carbonization when sodium alginate quality is 0.5g in the embodiment of the present invention 4；
Figure 14 is the part-structure enlarged drawing in Figure 13；
Figure 15 is the SEM figures of product after freeze-drying when sodium alginate quality is 5g in the embodiment of the present invention 4；
Figure 16 is the SEM figures of product after carbonization when sodium alginate quality is 5g in the embodiment of the present invention 4；
Figure 17 is the part-structure enlarged drawing in Figure 16；
Figure 18 is the SEM figures of product after being freeze-dried in the embodiment of the present invention 5；
Figure 19 is the SEM figures of product after being carbonized in the embodiment of the present invention 5；
Figure 20 is the part-structure enlarged drawing in Figure 19；
Figure 21 is the SEM figures of product after being freeze-dried in the embodiment of the present invention 6；
Figure 22 is the SEM figures of product after being carbonized in the embodiment of the present invention 6；
Figure 23 is the part-structure enlarged drawing in Figure 22；
Figure 24 is pictorial diagram after the embodiment of the present invention 7 is crosslinked；
Figure 25 is pictorial diagram after being carbonized in the embodiment of the present invention 7；
Figure 26 is XRD diagram after being carbonized in the embodiment of the present invention 7；
Figure 27 is pictorial diagram after the embodiment of the present invention 8 is crosslinked；
Figure 28 is pictorial diagram after being carbonized in the embodiment of the present invention 8；
Figure 29 is XRD diagram after being carbonized in the embodiment of the present invention 8；
Figure 30 is that material SEM schemes after being carbonized in the embodiment of the present invention 9；
Figure 31 is that material SEM schemes after being carbonized in the embodiment of the present invention 9；
Figure 32 is that material figure SEM schemes after being carbonized in the embodiment of the present invention 9.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.It should be understood that
, following embodiments are merely to illustrate the purpose of the present invention, but are not limited to the scope of the present invention.
Embodiment 1
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:100mg:
After the mass ratio of 100mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 2g sodium alginates and continue
After mechanical agitation 2h, 3g glucolactones are added after adding 1.5g Kocide SD mechanical agitations 30min, are stirred evenly rear quiet
24h is put, is then freeze-dried 24h.Product after freeze-drying is heated to 400 DEG C in tube furnace to be carbonized, during heating
Between be 2h, with nitrogen as protection gas in tube furnace.Taken out after stove is cooled to room temperature and obtain silicon-carbon composite electrode material.Figure
1st, Fig. 2 schemes for its material SEM, it can be seen from the figure that three-dimensional mesh is presented in the material after freeze-drying, and synusia thickness is put down
It is 8-10 μm.Fig. 3 is the SEM figures of material after 400 DEG C of carbonizations, it is recognised that the material after carbonization still can be preferable from figure
Maintenance three-dimensional mesh structure.Fig. 4 is XRD diagram, and the material after being as can be seen from the figure carbonized is mainly by Si+Cu+Cu2O groups
Into.Fig. 5 is its Electrochemical Characterization figure, and left side ordinate represents specific discharge capacity, and abscissa represents the circulation number of turns, from figure
As can be seen that under the current density of C/2 (1C=4200mA/g), still there is the electric discharge specific volume of 623mAh/g after the circle of circulation 45
Amount.
Embodiment 2
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 200mg:100mg:
After the mass ratio of 100mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 2g sodium alginates after
After continuous mechanical agitation 2h, 3g glucolactones are added after adding 1.5g Kocide SD mechanical agitations 30min, after stirring evenly
24h is stood, is then freeze-dried 24h.Product after freeze-drying is heated to 400 DEG C in tube furnace to be carbonized, is heated
Time is 2h, with nitrogen as protection gas in tube furnace.Taken out after stove is cooled to room temperature and obtain silicon-carbon composite electrode material.
Fig. 6 -- 8 is obtain material SEM characterization results, compared to embodiment 1, with the increase of nano silica fume quality, three-dimensional mesh
Structure does not change, and occurs copper simple substance particle after being carbonized on synusia, and particle size is 1-10 μm, is still maintained after carbonization
Relatively good three-dimensional mesh structure.
Embodiment 3
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:200mg:
After the mass ratio of 200mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 2g sodium alginates after
After continuous mechanical agitation 2h, 3g glucolactones are added after adding 1.5g Kocide SD mechanical agitations 30min, after stirring evenly
24h is stood, is then freeze-dried 24h.Product after freeze-drying is heated to 400 DEG C in tube furnace to be carbonized, is heated
Time is 2h, with nitrogen as protection gas in tube furnace.Taken out after stove is cooled to room temperature and obtain silicon-carbon composite electrode material.
Fig. 9 -- the 11 material SEM characterization results to obtain, with the increase of carbon nanotube mass, the three-dimensional grid of combination electrode material
Shape structure is changed into honeycomb structure, and the diameter of hole is 2-20 μm, and body structure surface and hole surface are uniformly dispersed with copper
Simple substance particle, particle size are 1-3 μm.
Embodiment 4
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:200mg:
After the mass ratio of 200mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, 0.5g sodium alginates are added
Obtain mixed solution.In addition by nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:
200mg:After the mass ratio of 200mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, 5g seaweed are added
Sour sodium, obtains mixed solution.Following handle is made respectively to above two mixed solution：After continuing mechanical agitation 2h, 1.5g is added
Kocide SD mechanical agitation, takes out after 30min and adds 3g glucolactones, 24h is stood after stirring evenly, is then freeze-dried
24h.Product after freeze-drying is heated to 400 DEG C in tube furnace to be carbonized, heating time 2h, with nitrogen in tube furnace
Gas is as protection gas.Taken out after stove is cooled to room temperature and obtain silicon-carbon composite electrode material.Figure 12-14 is for sodium alginate
Material SEM characterization results during 0.5g, Figure 15 -- 17 be material SEM characterization results when sodium alginate is 5g, works as sodium alginate
For 0.5g when, do not occur hole in structure, body structure surface is uniformly dispersed with the copper simple substance particle that particle size is 1-2 μm.
When sodium alginate quality increases to 5g, there is hole in structure, and hole size is distributed in structure and hole surface for 2-20 μm
Copper simple substance particle reduce, particle diameter becomes larger, and particle size is 1-6 μm.
Embodiment 5
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:200mg:
After the mass ratio of 200mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, 2g sodium alginates are added,
After continuing mechanical agitation 2h, after adding 1.5g Kocide SD mechanical agitations 30min, take out and add 3g acetic acid, stir evenly rear quiet
24h is put, is then freeze-dried 24h.Product after freeze-drying is heated to 400 DEG C in tube furnace to be carbonized, during heating
Between be 2h, with nitrogen as protection gas in tube furnace.Taken out after stove is cooled to room temperature and obtain silicon-carbon composite electrode material.Figure
18-20 to obtain material SEM characterization results, using acetic acid as sustained release agent after, the copper of hole and body structure surface in structure
Simple substance particle disappears substantially.
Embodiment 6
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:200mg:
After the mass ratio of 200mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 2g sodium alginates after
After continuous mechanical agitation 2h, after adding 0.5g calcium carbonate mechanical agitations 30min, take out and add 1g glucolactones, stir evenly
After stand 24h, be then freeze-dried 24h.Product after freeze-drying is heated to 400 DEG C in tube furnace to be carbonized, is added
The hot time is 2h, with nitrogen as protection gas in tube furnace.Taken out after stove is cooled to room temperature and obtain silicon-carbon combination electrode material
Material.Figure 21 -- 23 is obtain material SEM characterization results, and during using calcium carbonate as crosslinking agent, microstructure is three-dimensional mesh
Structure, synusia spacing are 1-2 μm, short texture and synusia surface is smooth.
Embodiment 7---Ni (NO3)2
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:100mg:
After the mass ratio of 100mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 1g sodium alginates and continue
Added after mechanical agitation 2h after 0.25g nickel nitrates stir evenly and stand 24h, be then freeze-dried 24h.After freeze-drying
Product is heated to 400 DEG C in tube furnace and is carbonized, heating time 2h, with nitrogen as protection gas in tube furnace.Treat stove
Taking-up obtains silicon-carbon composite electrode material after son is cooled to room temperature.Figure 24 is material pictorial diagram after crosslinking, and presentation is learnt from figure
Block feature.Figure 25 is the pictorial diagram after carbonization, it is recognised that material still can macroscopically maintain bulk material from figure
Overall structure.Figure 26 is the XRD diagram for taking out metal after material is carbonized using nitric acid, is as can be seen from the figure silicon grain, meets
Requirement of the lithium ion battery to electrode material.
Embodiment 8---Fe (NO3)3
By nano silica fume (particle diameter 50-100nm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:100mg:
After the mass ratio of 100mg mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 1g sodium alginates and continue
0.25g ferric nitrate mechanical agitations are added after mechanical agitation 2h and uniformly stand 24h afterwards, are then freeze-dried 24h.Will freeze-drying
Product afterwards is heated to 400 DEG C in tube furnace and is carbonized, heating time 2h, with nitrogen as protection gas in tube furnace.
Taken out after stove is cooled to room temperature and obtain silicon-carbon composite electrode material.Figure 27 is material pictorial diagram after crosslinking, is learnt from figure
Block feature is presented.Figure 28 is the pictorial diagram after carbonization, it is recognised that material still can macroscopically maintain block-shaped material from figure
The overall structure of material.Figure 29 is the XRD diagram after material carbonization and main thing is mutually Si+Fe-C.
Embodiment 9--- micron silicons
By micron silica flour (particle diameter is 1 μm), carbon nanotubes, polyvinylpyrrolidone is according to 100mg:100mg:100mg's
After mass ratio mixes in 100ml water, using Ultrasonic Cell Disruptor ultrasonic disperse 30min, add 1g sodium alginates and continue machinery
After stirring 2h, after adding 0.25g Kocide SD mechanical agitations 30min, take out and add 0.5g glucolactones, after stirring evenly
24h is stood, is then freeze-dried 24h.Figure 30-32 is obtains material SEM characterization results, using Kocide SD as crosslinking agent
When, microstructure is layer pea shape, and short texture has order and synusia surface is smooth.
Claims (10)
1. a kind of preparation method of combination electrode material, it is characterised in that comprise the following steps：
(1) carbon nanotubes, silicon grain, water soluble organic substance are uniformly dispersed in water, then add sodium alginate and be uniformly mixed,
Obtain mixed solution；
(2) metallic compound is added in the mixed solution obtained to step (1) to be uniformly mixed, then add sustained release agent, stand simultaneously
Freeze-drying；
(3) under protective atmosphere, by the product heats obtained in step (2) to being carbonized, the combination electrode material is obtained.
2. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the silicon
The particle diameter of particle is 50nm-1 μm.
3. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the water
Soluble organism is polyvinylpyrrolidone.
4. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the gold
Belong to one or more of the compound in calcium carbonate, basic copper carbonate, Kocide SD, nickel nitrate and ferric nitrate.
5. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the carbon
The mass ratio of nanotube, silicon grain and water soluble organic substance is 0.5-2:1:1.
6. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the sea
Mosanom and the ratio of carbon nanotubes and the quality sum of silicon grain are 5-50：3.
7. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (2), the gold
The mass ratio for belonging to compound and silicon grain is 5-60:4.
8. the preparation method of combination electrode material according to claim 1, it is characterised in that：It is described slow in step (2)
It is glucolactone and/or acetic acid to release agent.
A kind of 9. combination electrode material being prepared according to any one of claim 1-8 method.
10. the combination electrode material prepared by the method any one of claim 1-9 is in lithium ion battery is prepared
Application.
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| CN109830668A (en) * | 2019-02-28 | 2019-05-31 | 昆明理工大学 | The method that lithium ion battery silicon-carbon cathode material is prepared using carbon nanotube |
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| CN111146424A (en) * | 2019-12-30 | 2020-05-12 | 上海交通大学 | Metal sulfide/carbon composite material and preparation method and application thereof |
| CN113943158A (en) * | 2021-12-20 | 2022-01-18 | 杭州德海艾科能源科技有限公司 | Preparation method of graphite felt for flow battery |
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| CN113943158A (en) * | 2021-12-20 | 2022-01-18 | 杭州德海艾科能源科技有限公司 | Preparation method of graphite felt for flow battery |
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