CN105118974A - Silicon-based negative electrode material and preparation method thereof - Google Patents
Silicon-based negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of lithium ion battery negative electrode materials, in particular to a silicon-based negative electrode material and a preparation method thereof. The silicon-based negative electrode material is carbon-wrapped silicon/carbon nanometer fiber and comprises carbon nanometer fiber loaded with silicon nanometer particles, and a carbon wrapping layer having a secondary protection effect on the silicon nanometer particles exposed on the surface of the carbon nanometer fiber. According to the silicon-based negative electrode material, due to the fact that the carbon wrapping layer is introduced to the surface of the fiber, the conductivity of the material and the structural integrity can be effectively improved, the volume expansion of the silicon nanometer particles on the surface of the fiber can be restrained, the phenomena of silicon particle crushing and SEI membrane repeated generation are avoided, and the mechanical strength of the negative electrode material is improved. The electromechanical performance of the obtained material is obviously improved compared with a traditional silicon/carbon composite nanometer fiber negative electrode material.
Description
Technical field
The present invention relates to lithium ion battery negative material field, particularly a kind of silicon based anode material and preparation method thereof.
Background technology
Lithium ion battery is the secondary cell (rechargeable battery) that a kind of main dependence lithium ion moves work between both positive and negative polarity, and general employing lithium-containing compound is the positive electrode of battery.In charge and discharge process, Li
+come and go between two electrodes and embed and deintercalation: during charging, Li
+from positive pole deintercalation, embed negative pole through electrolyte, negative pole is in rich lithium state; Then contrary during electric discharge.The storage lithium performance of negative material is better, then the charging and discharging capacity of battery is higher, and therefore, the performance of negative material on battery has important impact.Commercial li-ion battery many employings material with carbon element makes negative pole, comprises graphitized carbon and agraphitic carbon two kinds.This is because material with carbon element lowly to be put down as having operating voltage during lithium ion battery negative, is had extended cycle life and the advantage such as with low cost.But material with carbon element specific capacity is lower, conventional graphite cathode reversible capacity is only 370mAh/g, can not meet large electrical equipment to the growing energy of lithium ion battery and power density needs.
The content of silicon on the earth's crust is only second to carbon, abundance, and in all known negative materials, Si has the highest theoretical capacity, is about 4200mAh/g.But in charge and discharge process, along with the embedding/deviate from of lithium ion, silicon can produce ~ volumetric expansion of 400%, cause that its efflorescence is cracked to come off, affect the electrical contact between electrode structure integrality, active material on the one hand, be unfavorable for electric transmission, battery capacity is decayed rapidly; On the other hand active material is constantly exposed in the electrolytic solution, cause the continuous decomposition of electrolyte and SEI film repeat formed.
The existing research utilizing carbon coated raising silicon based anode material performance at present.Such as CN102790204A provides and utilizes solution mixing and freeze drying in the coated one deck carbon source of silicon powder surface, and sintering obtains the method for uniform carbon coated Si negative material.CN103346325A openly reports a kind of graphene/carbon/silicium cathode material, and nano silicon particles is distributed between the layer structure of Graphene, is also distributed with netted material with carbon element and improves conductivity between graphene sheet layer and silicon nanoparticle.Outer field graphite can cushion the huge change in volume of silicon grain effectively, improves the cyclical stability of material.Also the report of the one dimension carbon silicium cathode material utilizing material with carbon element to prepare as matrix load silicon grain is had.Such as CN1705148A openly reports the compound of one dimension carbon nano-fiber and silica-base material.This material can directly as the negative pole of lithium ion battery, and is improved as the lithium storage content of material during lithium ion battery negative, cycle characteristics and dynamic performance.
Although said method improves the chemical property of silicon based anode material all to some extent, preparation process more complicated, prepares resulting materials feature performance benefit all not obvious.
Summary of the invention
The invention provides a kind of silicon based anode material, this material conductivity is good, structural integrity, and mechanical strength is high.
The present invention also provides a kind of preparation method of silicon based anode material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of silicon based anode material, this silicon based anode material is a kind of carbon coated Si/carbon nano-fiber, and it comprises: the carbon nano-fiber of load nano silicon particles and the exposed nano silicon particles on carbon nano-fiber surface is had to the carbon coating layer of second protection effect.
As preferably, described nano silicon particles accounts for the 10-50% of described silicon based anode material total weight.Silicon grain content is few, and the capacity of silicon based anode material is lower; Silicon grain content is many, and structure and the stability of silicon based anode material are poor; Therefore, the 10-50% of described silicon based anode material total weight is accounted for as preferred described nano silicon particles.
As preferably, described carbon coated Si/carbon nano-fiber diameter is 160-220nm.Fibre diameter is less, and the specific area of material is larger, high rate performance better; But due to the restriction of spinning equipment and spinning solution performance, the carbon prepared coated Si/carbon nano-fiber diameter is minimum is about 160nm, therefore as preferably, described carbon coated Si/carbon nano-fiber diameter is 160-220nm.
A kind of lithium ion battery, comprising: described silicon based anode material.Relative to the lithium ion battery being negative pole with the silica-base material of similar structures, this lithium ion battery has higher capacity and good cyclical stability.
A kind of preparation method of described silicon based anode material, the method comprises the steps: (1) electrostatic spinning: polyacrylonitrile, nano silicon particles mixing are dissolved in N-N solvent dimethylformamide, finely dispersed electrostatic spinning solution is obtained after stirring, ultrasonic disperse, gained electrostatic spinning solution is carried out electrostatic spinning, obtains silicon/polyacrylonitrile nanofiber; (2) carbonization: by the pre-oxidation in air atmosphere of step (1) gained silicon/polyacrylonitrile nanofiber, carbonization in argon atmosphere subsequently, obtains silicon/carbon nano-fiber; (3) infusion process sucrose is coated: be impregnated in sucrose solution by step (2) gained silicon/carbon nano-fiber, and sucrose coated Si/carbon nano-fiber is dried to obtain in rear taking-up in atmosphere; (4) secondary carbonization: by the carbonization in argon atmosphere of step (3) gained sucrose coated Si/carbon nano-fiber, obtain carbon coated Si/carbon nano-fiber.Method of electrostatic spinning is combined with infusion process by the present invention, is supplied to a kind of simple, easy-operating method preparing carbon coated Si/carbon nano-fiber.Preparation method of the present invention is simple, controlled, after sucrose is coated, carries out secondary carbonization generate one deck carbon coating layer at fiber surface to compound, carry out second protection to the exposed silicon grain at fiber surface.
As preferably, in described step (1), polyacrylonitrile molal weight is 100000 ~ 180000g/mol.The mass percentage of polyacrylonitrile in spinning solution is 5 ~ 8%, and the consumption of nano silicon particles is 10 ~ 30% of polyacrylonitrile quality.In electrostatic spinning process, polyacrylonitrile molal weight and spinning solution concentration larger or littlely all not easily become silk.
As preferably, in described step (1), the process of electrostatic spinning is: the distance of setting shower nozzle and gatherer is 13 ~ 17cm, apply high-pressure electrostatic 10 ~ 20kV, injection rate 0.5 ~ 1.0ml/h, spinnerette diameters 0.3 ~ 0.6mm, when its stable ejection, obtains silicon/polyacrylonitrile nanofiber by aluminium-foil paper gatherer.
As preferably, in described step (2), setting Pre oxidation is 240 ~ 320 DEG C, and heating rate is 3 ~ 7 DEG C/min, and temperature retention time is 1 ~ 5h; Setting carburizing temperature is 600 ~ 800 DEG C, and heating rate is 1 ~ 3 DEG C/min, and temperature retention time is 3 ~ 8h, and rate of temperature fall is 10 DEG C/min.
As preferably, in described step (3), sucrose solution temperature is 30 ~ 80 DEG C, and the mass ratio of sucrose and deionized water is 1 ~ 30:200.
As preferably, in described step (4), setting carburizing temperature is 500 ~ 800 DEG C, and heating rate is 1 ~ 5 DEG C/min, and temperature retention time is 1 ~ 5h, and rate of temperature fall is 10 DEG C/min.
Silicon based anode material of the present invention, because the carbon coating layer introduced at fiber surface can not only improve the conductivity of material effectively, structural intergrity, and the volumetric expansion of fiber surface nano silicon particles can be suppressed, avoid the phenomenon that the broken and SEI film of silicon grain repeats generation, improve the mechanical strength of negative material.Silicon/carbon composite nano-fiber negative material that the chemical property of resulting materials is more traditional is significantly improved.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of carbon coated Si/carbon nano-fiber prepared by the embodiment of the present invention 1;
Fig. 2 is the transmission electron microscope picture of carbon coated Si/carbon nano-fiber prepared by the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope picture of carbon coated Si/carbon nano-fiber prepared by the embodiment of the present invention 2;
Fig. 4 is the cycle performance figure of carbon coated Si/carbon nano-fiber prepared by the embodiment of the present invention 2;
Fig. 5 is the transmission electron microscope picture of carbon coated Si/carbon nano-fiber prepared by the embodiment of the present invention 3.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, percentage are unit of weight, and the equipment adopted and raw material etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1
(1) with the sample bottle that electronic balance takes polyacrylonitrile 0.72g, nano silicon particles 0.16g is placed in 20ml, inject the N-N dimethyl formamide of 7.36g, sample bottle sealed membrane seals, and is heated to 60 DEG C and stirs 24 hours, ultrasonic disperse 1h.Determining area is that the aluminium-foil paper of 40cm × 40cm is close on flat panel collector, get spinning solution sample and put into injection needle, high pressure generator positive pole is connected with spinning nozzle, negative pole is connected with flat panel collector, regulate syringe pump solution flow rate 0.8ml/h, setting spinning head and dash receiver distance 17cm, spinnerette diameters 0.43mm, when its steady extruding, open high pressure generator to setting voltage 18kV, obtain silicon/polyacrylonitrile nanofiber by flat panel collector.
(2) fiber on gatherer is taken off, be close to and lie against load bearing board, load bearing board is lain against in tube furnace, setting Pre oxidation 280 DEG C, heating rate 5 DEG C/min, temperature retention time 5h, setting carburizing temperature 800 DEG C, heating rate 3 DEG C/min, temperature retention time 3h, obtain silicon/carbon nano-fiber negative material.
(3) silicon/carbon nano-fiber is immersed in 60 DEG C of sucrose solutions soaks 1h, take out, in air, dry to obtain sucrose coated Si/carbon nano-fiber.In sucrose solution, the mass ratio of sucrose and water is 10:200.
(4): be close to by sucrose coated Si/carbon nano-fiber and lie against load bearing board, lain against by load bearing board in tube furnace, setting, in argon gas, carburizing temperature is 600 DEG C, and heating rate is 2 DEG C/min, and insulation 1h, rate of temperature fall is 10 DEG C/min.Carbon coated Si/carbon nano-fiber is obtained after carbonization.
The scanning electron microscope (SEM) photograph of carbon coated Si/carbon nano-fiber prepared by the present embodiment is shown in Fig. 1, and the transmission electron microscope picture of carbon coated Si/carbon nano-fiber is shown in Fig. 2.Carbon coated Si/carbon nano-fiber still keeps three-dimensional continuous print fibre structure as seen from Figure 1; There is the obvious unformed layer of one deck on silicon grain surface as seen from Figure 2, proves successfully to introduce one deck carbon-coating by sucrose solution infusion process at fiber surface.
Embodiment 2
(1) with the sample bottle that electronic balance takes polyacrylonitrile 0.72g, nano silicon particles 0.16g is placed in 20ml, inject the N-N dimethyl formamide of 7.36g, sample bottle sealed membrane seals, and is heated to 60 DEG C and stirs 24 hours, ultrasonic disperse 1h.Determining area is that the aluminium-foil paper of 40cm × 40cm is close on flat panel collector, get spinning solution sample and put into injection needle, high pressure generator positive pole is connected with spinning nozzle, negative pole is connected with flat panel collector, regulate syringe pump solution flow rate 0.8ml/h, setting spinning head and dash receiver distance 17cm, spinnerette diameters 0.43mm, when its steady extruding, open high pressure generator to setting voltage 18kV, obtain silicon/polyacrylonitrile nanofiber by flat panel collector.
(2) fiber on gatherer is taken off, be close to and lie against load bearing board, load bearing board is lain against in tube furnace, setting Pre oxidation 280 DEG C, heating rate 5 DEG C/min, temperature retention time 5h, setting carburizing temperature 800 DEG C, heating rate 3 DEG C/min, temperature retention time 3h, obtain silicon/carbon nano-fiber negative material.
(3) silicon/carbon nano-fiber is immersed in 60 DEG C of sucrose solutions soaks 1h, take out, in air, dry to obtain sucrose coated Si/carbon nano-fiber.In sucrose solution, the mass ratio of sucrose and water is 20:200.
(4): be close to by sucrose coated Si/carbon nano-fiber and lie against load bearing board, lain against by load bearing board in tube furnace, setting, in argon gas, carburizing temperature is 600 DEG C, and heating rate is 2 DEG C/min, and insulation 1h, rate of temperature fall is 10 DEG C/min.Carbon coated Si/carbon nano-fiber is obtained after carbonization.
The transmission electron microscope picture of carbon coated Si carbon nano-fiber prepared by the present embodiment is shown in Fig. 3, and the cycle performance figure of carbon coated Si carbon nano-fiber is shown in Fig. 4.
Embodiment 3
(1) with the sample bottle that electronic balance takes polyacrylonitrile 0.72g, nano silicon particles 0.16g is placed in 20ml, inject the N-N dimethyl formamide of 7.36g, sample bottle sealed membrane seals, and is heated to 60 DEG C and stirs 24 hours, ultrasonic disperse 1h.Determining area is that the aluminium-foil paper of 40cm × 40cm is close on flat panel collector, get spinning solution sample and put into injection needle, high pressure generator positive pole is connected with spinning nozzle, negative pole is connected with flat panel collector, regulate syringe pump solution flow rate 0.8ml/h, setting spinning head and dash receiver distance 17cm, spinnerette diameters 0.43mm, when its steady extruding, open high pressure generator to setting voltage 18kV, obtain silicon/polyacrylonitrile nanofiber by flat panel collector.
(2) fiber on gatherer is taken off, be close to and lie against load bearing board, load bearing board is lain against in tube furnace, setting Pre oxidation 280 DEG C, heating rate 5 DEG C/min, temperature retention time 5h, setting carburizing temperature 800 DEG C, heating rate 3 DEG C/min, temperature retention time 3h, obtain silicon/carbon nano-fiber negative material.
(3) silicon/carbon nano-fiber is immersed in 60 DEG C of sucrose solutions soaks 1h, take out, in air, dry to obtain sucrose coated Si/carbon nano-fiber.In sucrose solution, the mass ratio of sucrose and water is 30:200.
(4): be close to by sucrose coated Si/carbon nano-fiber and lie against load bearing board, lain against by load bearing board in tube furnace, setting, in argon gas, carburizing temperature is 600 DEG C, and heating rate is 2 DEG C/min, and insulation 1h, rate of temperature fall is 10 DEG C/min.Carbon coated Si/carbon nano-fiber is obtained after carbonization.
The transmission electron microscope picture of carbon coated Si carbon nano-fiber prepared by the present embodiment is shown in Fig. 5.
In carbon coated Si/carbon nano-fiber that each embodiment prepares above; the silicon grain of sucrose pyrolytic carbon layer to fiber surface provides second protection; effectively can suppress the volumetric expansion of fiber surface silicon grain; alleviate the structure of electrode in cyclic process cracked, improve the cycle performance of silicon based anode material.
Structure and the chemical property information of relevant silicon based anode material is given in table 1.
Table 1
As shown in Table 1, the present invention's three embodiment contrasts, after 50 circulations, the capacity of embodiment 2 resulting materials is higher, is 1215.2mAh/g; This is because silicone content is higher in embodiment 1, outer sucrose RESEARCH OF PYROCARBON can not suppress the volumetric expansion of silicon grain effectively, causes the less stable of material, and capacity declines very fast; In embodiment 3, silicone content is less, and the electrochemical stability of material is better, but capacity is lower; Namely embodiment 2 is prepare the optimal conditions of negative material of the present invention.The embodiment of the present invention 2 is compared with the silicon based anode material of other similar structures, and after 50 circulations, capacity dimension is held in larger value, proves that the capacity of above-mentioned carbon coated Si carbon nano-fiber negative material and cyclical stability are all significantly improved.
Below describe the present invention by way of example, but the invention is not restricted to above-mentioned specific embodiment, all any changes of doing based on the present invention or modification all belong to the scope of protection of present invention.
Claims (10)
1. a silicon based anode material; it is characterized in that; this silicon based anode material is a kind of carbon coated Si/carbon nano-fiber, and it comprises: the carbon nano-fiber of load nano silicon particles and the exposed nano silicon particles on carbon nano-fiber surface is had to the carbon coating layer of second protection effect.
2. silicon based anode material according to claim 1, is characterized in that, described nano silicon particles accounts for the 10-50% of described silicon based anode material total weight.
3. silicon based anode material according to claim 1 and 2, is characterized in that, described carbon coated Si/carbon nano-fiber diameter is 160-220nm.
4. a lithium ion battery, is characterized in that, comprising: the silicon based anode material described in any one of claim 1-3.
5. a preparation method for silicon based anode material described in any one of claim 1-3, it is characterized in that, the method comprises the steps:
(1) electrostatic spinning: polyacrylonitrile, nano silicon particles mixing are dissolved in N-N solvent dimethylformamide, finely dispersed electrostatic spinning solution is obtained after stirring, ultrasonic disperse, gained electrostatic spinning solution is carried out electrostatic spinning, obtains silicon/polyacrylonitrile nanofiber;
(2) carbonization: by the pre-oxidation in air atmosphere of step (1) gained silicon/polyacrylonitrile nanofiber, carbonization in argon atmosphere subsequently, obtains silicon/carbon nano-fiber;
(3) infusion process sucrose is coated: be impregnated in sucrose solution by step (2) gained silicon/carbon nano-fiber, and sucrose coated Si/carbon nano-fiber is dried to obtain in rear taking-up in atmosphere;
(4) secondary carbonization: by the carbonization in argon atmosphere of step (3) gained sucrose coated Si/carbon nano-fiber, obtain carbon coated Si/carbon nano-fiber.
6. the preparation method of silicon based anode material according to claim 5, is characterized in that: in described step (1), and polyacrylonitrile molal weight is 100000 ~ 180000g/mol.
7. the preparation method of silicon based anode material according to claim 5, it is characterized in that: in described step (1), the process of electrostatic spinning is: the distance of setting shower nozzle and gatherer is 13 ~ 17cm, apply high-pressure electrostatic 10 ~ 20kV, injection rate 0.5 ~ 1.0ml/h, spinnerette diameters 0.3 ~ 0.6mm, when its stable ejection, obtains silicon/polyacrylonitrile nanofiber by aluminium-foil paper gatherer.
8. the preparation method of silicon based anode material according to claim 5, is characterized in that: in described step (2), and setting Pre oxidation is 240 ~ 320 DEG C, and heating rate is 3 ~ 7 DEG C/min, and temperature retention time is 1 ~ 5h; Setting carburizing temperature is 600 ~ 800 DEG C, and heating rate is 1 ~ 3 DEG C/min, and temperature retention time is 3 ~ 8h, and rate of temperature fall is 10 DEG C/min.
9. the preparation method of silicon based anode material according to claim 5, is characterized in that: in described step (3), and sucrose solution temperature is 30 ~ 80 DEG C, and the mass ratio of sucrose and deionized water is 1 ~ 30:200.
10. the preparation method of silicon based anode material according to claim 5, is characterized in that: in described step (4), and setting carburizing temperature is 500 ~ 800 DEG C, and heating rate is 1 ~ 5 DEG C/min, and temperature retention time is 1 ~ 5h, and rate of temperature fall is 10 DEG C/min.
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| CN106099073A (en) * | 2016-08-19 | 2016-11-09 | 中航锂电（洛阳）有限公司 | The preparation method of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery |
| CN106129367A (en) * | 2016-08-22 | 2016-11-16 | 浙江理工大学 | A kind of silicon/carbon nano-composite fiber and application thereof |
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| CN111900411A (en) * | 2020-08-14 | 2020-11-06 | 四川轻化工大学 | Self-supporting silicon-carbon negative electrode material and preparation method thereof |
| CN112531144A (en) * | 2019-09-17 | 2021-03-19 | 通用汽车环球科技运作有限责任公司 | Method of preparing silicon-based electrode comprising natural carbonaceous filament and battery cell using the same |
| WO2022193286A1 (en) * | 2021-03-19 | 2022-09-22 | 宁德新能源科技有限公司 | Negative electrode material and preparation method therefor, electrochemical device and electronic device |
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