CN106571451A - Lithium ion battery anode material, and preparation method thereof - Google Patents
Lithium ion battery anode material, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery anode material, and a preparation method thereof. The preparation method comprises following steps: 1, a carbon source is mixed with an organic solvent so as to obtain a sol A; 2, nano silicon monoxide, a surfactant, the carbon source, and the organic solvent are mixed so as to obtain a sol B; 3, the sol A and the sol B are taken as raw materials for electrostatic spinning so as to obtain a composite fiber with a double-layer structure, wherein a shell layer is formed by the sol A, and a core layer is formed by the sol B; and 4, the composite fiber is dried, is subjected to pre-oxidation, and then is subjected to calcination at an insert atmosphere. The process of the preparation method is simple and controllable; large-scale production is easy to realize; an obtained composite material is a carbon-coated flexible self-supported silicon monoxide/amorphous carbon composite fiber anode material; in charging-discharging process of lithium ion batteries prepared from the composite material, the volume change of silicon-based oxide anode materials is controlled effectively, electrode structures are maintained to be complete, first time coulombic efficiency is increased obviously, cycling life is prolonged, and electrochemical performance is excellent.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of lithium ion battery negative material and its preparation
Method.
Background technology
Silicon is because content is high, theoretical capacity is high in the earth's crust, the low numerous advantages such as superior with security performance of discharge voltage into
For the study hotspot of lithium ion battery negative material.But, silicon bulk effect in depth removal lithium embedded is peeled off greatly, easily with collector
Caused cycle performance is poor, first coulombic efficiency it is low, in addition silicon materials itself low conductivity etc. also limit it in lithium-ion electric
Commercial applications in pond.
Research shows (Zhou W, Upreti S, Whittingham M S.High performance Si/MgO/
graphite composite as the anode for lithium-ion batteries[J].Electrochemistry
Communications,2011,13(10):1102-1104), silicon monoxide equally has as lithium ion battery negative material
Reversible embedding de- lithium performance, the Li that its electrode reaction is generated2O can effectively suppress it in removal lithium embedded process as buffer medium
In the change in volume brought, improve the cycle performance of electrode.In addition, the nano Si that reaction is produced can be uniformly distributed in Li2O and silicon
In the substrate that hydrochlorate is formed, the structure of this Dispersed precipitate had both buffered the change in volume produced during active Si granules removal lithium embedded,
The reunion of nano Si is prevented again, shows preferable chemical property.But in fact, produced by material electrode reaction itself
Buffer medium to improve silica-base material cycle performance effect it is limited.Research shows, in silicon grain outer wrapping carbon-coating, can improve
The volumetric expansion of Si granules can also be suppressed between granule while electrical conductivity.Using the cooperative effect between composite each component,
The purpose of mutual supplement with each other's advantages is can reach, the method is widely used in the study on the modification of lithium ion battery negative material.
Wherein, agraphitic carbon prepares the extensive concern that simple, embedding lithium capacity height receives researcher due to having.It holds very much
Easily silicon grain is coated by methods such as high-temperature decomposition, chemical vapour deposition technique and ball-milling methods, form nucleocapsid structure, play volume
Cushioning effect, so being the first-selection for preparing silico-carbo composite.The preparation method of all silicon-agraphitic carbon composite, be all
Amorphous carbon is wished while combining closely with silicon, and imporous can be coated on silicon grain surface, sink surface SEI is reduced
Silicon electrode holding structure integrity in charge and discharge process, the expansion of volume is set to be effectively suppressed while product, so as to increase
The coulombic efficiency of electrode simultaneously reduces its irreversible capacity.But existing method is difficult to allow silicon equably closely to be coated or be distributed in
Among carbon, silicon slow destruction of structure in reversible charge and discharge process still can not be avoided completely.Deng(Deng J,Ji H,
Yan C,et al.Naturally Rolled‐Up C/Si/C TrilayerNanomembranes as Stable Anodes
for Lithium‐Ion Batteries with Remarkable Cycling Performance[J]
.AngewandteChemie,2013,125(8):2382-2386.) et al. report and a kind of to be rolled into by C/Si/C three-deckers
Composite, the material has the specific capacity of 2000mAh/g under the electric current density of 50mA/g, and close in the electric current of 500mA/g
Afterwards capacity is held essentially constant for the lower circulation of degree 300 times.It can be seen that, double carbon-coating sandwich structures can effectively improve silicon-carbon cathode material
Chemical property, but its complicated process of preparation, high cost, it is difficult to industrialization.(Wu H, the Cui Y.Designing such as Hui Wu
nanostructured Si anodes for high energy lithium ion batteries[J].Nano Today,
2012,7(5):414-429.) mixed with silicon dioxide precursor solution by nano silicon particles, electrostatic spinning is carried out, by height
The heat carbonization of molecule polystyrene one layer of thin carbon layer of cladding on nanofiber, and the fiber of this carbon coating HF solution etches
To remove SiO2And leave Si.To finally give be sealed in hollow carbon pipe nano silicon particles to prepare and have each other neutral gear
Nano silicon particles.The method complicated process of preparation, although and the addition of carbon nano-fiber and multi-walled carbon nano-tubes can improve
Conductance, but the regularity of material is destroyed, make cycle performance undesirable on the contrary.
Authorization Notice No. discloses a kind of nano-silicon agraphitic carbon complex lithium for the Chinese invention patent of CN101527357B
Ion battery cathode material and preparation method thereof, its by by silicon nanoparticle and can electrospinning Organic substance stir mixing in a solvent
After uniform, high-pressure electrostatic electrospinning becomes fibrous composite, causes solvent volatilization complete in 80～200 DEG C of insulations, then 400～
It is carbonized in the range of 1000 DEG C.Although the method can well obtain nano-silicone wire/carbon composite material, in preparation process, employing
Composite cellulosic membrane obtained by single shaft electrostatic spinning process, its amorphous carbon layer is difficult to envelope active particle completely, it is impossible to effectively
Suppress the volumetric expansion problem of silicon, and target product grinding coating is assembled into into button cell, complex process, processing procedure is difficult to control
System, industrialization high cost, and cycle performance is poor.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of simple controllable, the easy large-scale production of technical process, gained
Composite is carbon coating flexible self-supporting silicon monoxide/agraphitic carbon composite fibre negative material, using the lithium of this material
In charge and discharge process, the change in volume of silicon-base oxide negative material is effectively controlled ion battery, and electrode structure keeps
Completely, first coulombic efficiency is improved obviously, and has extended cycle life, electrochemical performance.
A kind of preparation method of lithium ion battery negative material, comprises the steps：
(1) carbon source and organic solvent are mixed to get into Sol A；
(2) mixing of nanometer silicon monoxide, surfactant, carbon source and organic solvent is obtained into sol B；
(3) electrostatic spinning is carried out as raw material with Sol A and sol B, obtains double-deck composite fibre, wherein Sol A
Shell is formed, sol B forms stratum nucleare；
(4) composite fibre be dried after Jing pre-oxidation, be subsequently placed under inert gas atmosphere and calcined, be obtained the lithium from
Sub- cell negative electrode material；
The carbon source is polyvinyl alcohol, polyacrylonitrile, polyurethane, polrvinyl chloride, polyethylene glycol oxide, polyacrylate, poly-
One or more in vinylpyrrolidone, polymethyl methacrylate.
Preferably, the mass ratio of carbon source and organic solvent is 1: 5～10 in step (1) and (2), nanometer one in step (2)
Silicon oxide, surfactant, the mass ratio of carbon source are 1: 0.2～1: 1.2～4.5.
Preferably, the organic solvent is N ' dinethylformamide solution, N ' N- dimethylacetamide solutions or ethanol.
Preferably, the surfactant is benzyl sodium sulfonate.
Preferably, the parameter of spinning-drawing machine is during electrostatic spinning：20～25kV of spinning voltage, receives 10～30cm of distance, pushes away
Enter 0.6～1.0mL/h of pump speed.Experimental researches prove that, the product property of last gained is preferable in these parameter areas.
Preferably, the noble gases are nitrogen, helium or argon.Carry out calcining under inert gas atmosphere to avoid in height
Silicon monoxide is oxidized to silicon dioxide under the conditions of temperature.
Preferably, the calcining heat is 750 DEG C～900 DEG C, and calcination time is 5～10h.In the calcining heat and time
In the range of, the carbon that can guarantee that generation is that undefined structure and remaining carbon are held essentially constant, can be with the addition of raw material come near
Seemingly characterize the proportionate relationship of final product.
Invention further provides lithium ion battery negative material prepared by the preparation method.By the method prepare lithium from
Sub- cell negative electrode material constitutes composite fibre by the nano-particle centre stratum nucleare outside cladding amorphous carbon layer that continuously-directional is distributed
Stratum nucleare is inlayed silicon monoxide nano-particle and is constituted by carbon-based skeleton in the middle of structure, wherein nano-particle.Due to nanometer silicon monoxide
With the loss very little of amorphous carbon, according to the amount of added raw material, the quality of silicon monoxide in the lithium ion battery negative material
Percentage ratio is about 10%～30%, and the mass percent of amorphous carbon is about 90%～70%.
Preferably, the lithium ion battery negative material is complex structure of filament, middle stratum nucleare outside cladding amorphous carbon
Layer, wherein a diameter of 100～350nm of complex structure of filament, the thickness of amorphous carbon layer are 20～80nm.
Present invention also offers lithium ion battery prepared by the lithium ion battery negative material.The lithium ion battery negative
The corresponding positive plate slitting lamination assembling of material fit into soft-package battery, without the need for copper foil current collector, the change in volume of silicon electrode material
It is effectively controlled, electrode structure flexible self-supporting, the electric conductivity and good rate capability of flexible packaging products.
Compared with prior art, it is an advantage of the current invention that：
(1) composite fibre negative material of the invention compares conventional Si-C composite material, and the polymer for using not only can
As carbon source, it is often more important that being also used as the carrier of fiber carries out spinning, and the agraphitic carbon for preparing have it is more
Embedding lithium it is vacant, it is easier in its surface attachment nano active particle and form the strong chemical bonding of adhesion, interface resistance is more
It is low, effectively improve the coulombic efficiency first and cycle performance of Si oxide negative material；
(2) preparation technology of the coaxial electrical spinning that the present invention is adopted, can orient to form accurate one-dimensional agraphitic carbon/mono- oxidation
The composite cellulosic membrane of silicon clad structure, while material nano is realized, it is easier to form three-dimensional conductive network, compare silicon-carbon
Batch mixing coated film, with more preferable electric conductivity and mechanical property, and without the need for collector, it is to avoid silicon materials due to volumetric expansion with
The problem that collector comes off；
(3) present invention has obtained the smooth composite fibre negative plate of more consolidation, effectively using unique heat pressing process
Improve by the different caused sintering cracking phenomenas of thermal coefficient of expansion, interfibrous interface resistance is reduced conscientiously, improve multiple
The monolithic conductive of condensating fiber negative plate simultaneously maintains good machinability；
(4) the composite cellulosic membrane structural flexibility self-supporting for preparing, lamination winding is directly used in the negative pole of soft-package battery
Main material, the selection for soft-package battery provides new approaches；
(5) preparation method of the invention is simple, controllable, and preparation temperature is low, technical process non-pollutant discharge, low cost
It is honest and clean, it is suitable for scale production.
Description of the drawings
Fig. 1 is the gained composite fibre negative material of embodiment 1 flexibility testing result figure；
Fig. 2 is the gained composite fibre negative material TEM testing result figures of embodiment 2；
Fig. 3 is the gained composite fibre negative material cycle performance testing result figure of embodiment 3.
Specific embodiment
Embodiment 1
(1) 4.5g polyacrylonitrile is dissolved in 22.5g N ' dinethylformamide solution and is made into Sol A；By 4.5g poly- third
Alkene nitrile, 1g nanometer silicon monoxide powder, the surfactant benzyl sodium sulfonate of 1g and 22.5g N ' dinethylformamide solution
It is made into sol B；Wherein, Sol A is using 25 DEG C of stirring in water bath 10 hours, and sol B first passes through 1 hour magnetic agitation, little through 1 again
Shi Chaosheng, is finally stirred for 2 hours, and the Sol A and sol B of certain viscosity is respectively obtained Jing after being sufficiently stirred for；
(2) Sol A obtained above and sol B are poured into two syringes respectively, wherein filling the syringe connection of Sol A
The shell of electrostatic spinning machine coaxial nozzle, the syringe for filling sol B connects the stratum nucleare of electrostatic spinning machine coaxial nozzle, using quiet
Electrospun machine carries out spinning；Spinning voltage is controlled to 20kV, and the distance of nozzle distance reception device is 30cm；Reception device is roller
Cylinder；
(3) spun silk is put in drying baker and is dried, temperature when being dried is 120 DEG C, and drying time is 24 hours, is obtained
To Precursors of Fibers；
(4) pretreatment is carried out 4 hours in the air atmosphere by the Precursors of Fibers of gained at 260 DEG C；
(5) above-mentioned pretreated Precursors of Fibers is put in nitrogen atmosphere stove, programming rate controls 1 DEG C/min heating
To 750 DEG C and 10 hours are incubated, obtain composite fibre of the top layer agraphitic carbon with stratum nucleare silicon monoxide fiber quality than about 9: 1 and bear
Pole material.
(SiO/C composite fibres), silicon monoxide are formed by nanometer silicon monoxide active substance and agraphitic carbon fiber composite
Used as the kernel of composite fibre negative material, outer surface coats agraphitic carbon fiber forming nucleocapsid structure to fiber.Jing transmission electricity
Microscopy is surveyed, and composite fibre diameter is about 100nm～150nm, agraphitic carbon silicon monoxide fibrous outer surfaces cladding thickness about
For 20nm～50nm.
As shown in figure 1, the composite fibre negative material of gained is bent into 180 degree, the composite fibre negative material has soft
Property self-supporting, with good folding properties.
The composite fibre negative material is directly cut into into flexible electrical pole piece, with the common lithium band in market, polypropylene film,
LiPF6 solution, steel mesh make respectively negative pole, barrier film, electrolyte and lug and draw body, and aluminum plastic film Vacuum Package is entered into simple soft-package battery
Row test, discharge and recharge 100 times under 1C, capacity is maintained at 552mAh/g.
Embodiment 2
(1) the pure polyvinyl alcohol of 2g (molecular weight is 80000) is dissolved in 16g N ' N- dimethylacetamide solutions be made into it is molten
Glue A；By the pure polyvinyl alcohol of 2g, 1g nanometer silicon monoxide powder, the surfactant benzyl sodium sulfonate of 0.5g and 16g N ' N- bis-
Methyl vinyl amine aqueous solution is made into sol B；Wherein, using 40 DEG C of stirring in water bath 8 hours, sol B first passed through 2 hours magnetic force to Sol A
Stirring, again through 1 hour ultrasound, be finally stirred for 2 hours, the Sol A of certain viscosity and molten is respectively obtained Jing after being sufficiently stirred for
Glue B；
(2) Sol A obtained above and sol B are poured into two syringes respectively, wherein filling the syringe connection of Sol A
The shell of electrostatic spinning machine coaxial nozzle, the syringe for filling sol B connects the stratum nucleare of electrostatic spinning machine coaxial nozzle, using quiet
Electrospun machine carries out spinning；Spinning voltage is controlled to 22kV, and the distance of nozzle distance reception device is 20cm；Reception device is flat
Plate；
(3) spun silk is put in drying baker and is dried, temperature when being dried is 130 DEG C, and drying time is 16 hours, is obtained
To Precursors of Fibers；
(4) pretreatment is carried out 3 hours in the air atmosphere by the Precursors of Fibers of gained at 280 DEG C；
(5) above-mentioned pretreated Precursors of Fibers is put in nitrogen atmosphere stove, programming rate controls 1.5 DEG C/min and adds
Heat is to 800 DEG C and is incubated 8 hours, obtains composite fibre of the top layer agraphitic carbon with stratum nucleare silicon monoxide fiber quality than about 4: 1
Negative material.
Gained composite fibre negative material is can be seen that by Fig. 2 TEM (transmission electron microscope) detection photos to present significantly
Nucleocapsid structure, the diameter about 300nm～350nm of fiber, silicon monoxide continuous fiber integrated distribution is distributed with nothing in stratum nucleare, both sides
Sizing carbon, carbon-coating cladding thickness about 50nm～80nm.
The composite fibre negative material is directly cut into into flexible electrical pole piece, with the common lithium band in market, polypropylene film,
LiPF6 solution, steel mesh make respectively negative pole, barrier film, electrolyte and lug and draw body, and aluminum plastic film Vacuum Package is entered into simple soft-package battery
Row test, discharge and recharge 100 times under 1C, capacity is maintained at 548mAh/g.
Embodiment 3
(1) 1.75g polyvinylpyrrolidones are dissolved in 17.5g ethanol solution and are made into Sol A；By 1.75g polyethylene pyrroles
Pyrrolidone, 1.5g nanometer silicon monoxide powder, the surfactant benzyl sodium sulfonate of 0.3g and 17.5g ethanol solution are made into colloidal sol
B；Wherein, Sol A is using 60 DEG C of stirring in water bath 6 hours, and sol B first passes through 3 hours magnetic agitation, again through 1 hour ultrasound, most
After be stirred for 3 hours, the Sol A and sol B of certain viscosity is respectively obtained Jing after being sufficiently stirred for；
(2) Sol A obtained above and sol B are poured into two syringes respectively, wherein filling the syringe connection of Sol A
The shell of electrostatic spinning machine coaxial nozzle, the syringe for filling sol B connects the shell of electrostatic spinning machine coaxial nozzle, using quiet
Electrospun machine carries out spinning；Spinning voltage is controlled to 25kV, and the distance of nozzle distance reception device is 10cm；Reception device is roller
Cylinder；
(3) spun silk is put in drying baker and is dried, temperature when being dried is 140 DEG C, and drying time is 12 hours, is obtained
To Precursors of Fibers；
(4) pretreatment is carried out 2 hours in the air atmosphere by the Precursors of Fibers of gained at 310 DEG C；
(5) above-mentioned pretreated Precursors of Fibers is put in nitrogen atmosphere stove, programming rate controls 1 DEG C/min heating
To 900 DEG C and 5 hours are incubated, obtain composite fibre of the top layer agraphitic carbon with stratum nucleare silicon monoxide fiber quality than about 7: 3 and bear
Pole material.
TEM detection discoveries, a diameter of 100nm～150nm of composite fibre, agraphitic carbon is in silicon monoxide fibrous outer surfaces
Cladding thickness is 20nm～50nm.
The composite fibre negative material is directly cut into into flexible electrical pole piece, with the common lithium band in market, polypropylene film,
LiPF6 solution, steel mesh make respectively negative pole, barrier film, electrolyte and lug and draw body, and aluminum plastic film Vacuum Package is entered into simple soft-package battery
Row test, as shown in the cycle performance figure of Fig. 3, discharge and recharge 153 times under 1C, capacity is maintained at 553mAh/g.
Claims (10)
1. a kind of preparation method of lithium ion battery negative material, it is characterised in that comprise the steps：
(1) carbon source and organic solvent are mixed to get into Sol A；
(2) mixing of nanometer silicon monoxide, surfactant, carbon source and organic solvent is obtained into sol B；
(3) electrostatic spinning is carried out as raw material with Sol A and sol B, obtains double-deck composite fibre, wherein Sol A is formed
Shell, sol B forms stratum nucleare；
(4) Jing pre-oxidation, is subsequently placed under inert gas atmosphere and is calcined after composite fibre is dried, and the lithium-ion electric is obtained
Pond negative material；
The carbon source is polyvinyl alcohol, polyacrylonitrile, polyurethane, polrvinyl chloride, polyethylene glycol oxide, polyacrylate, polyethylene
One or more in ketopyrrolidine, polymethyl methacrylate.
2. preparation method as claimed in claim 1, it is characterised in that the quality of carbon source and organic solvent in step (1) and (2)
Than for 1: 5～10, nanometer silicon monoxide, surfactant, the mass ratio of carbon source are 1: 0.2～1: 1.2～4.5 in step (2).
3. preparation method as claimed in claim 1, it is characterised in that the organic solvent is that N ' dinethylformamides are molten
Liquid, N ' N- dimethylacetamide solutions or ethanol.
4. preparation method as claimed in claim 1, it is characterised in that the surfactant is benzyl sodium sulfonate.
5. preparation method as claimed in claim 1, it is characterised in that the parameter of spinning-drawing machine is during electrostatic spinning：Spinning voltage
20～25kV, receives 10～30cm of distance, advances 0.6～1.0mL/h of pump speed.
6. preparation method as claimed in claim 1, it is characterised in that the noble gases are nitrogen, helium or argon.
7. preparation method as claimed in claim 1, it is characterised in that the calcining heat is 750 DEG C～900 DEG C, during calcining
Between be 5～10h.
8. the lithium ion battery negative material that prepared by preparation method described in claim 1～7.
9. lithium ion battery negative material as claimed in claim 8, it is characterised in that the lithium ion battery negative material is
Complex structure of filament, middle stratum nucleare outside cladding amorphous carbon layer, a diameter of 100～350nm of complex structure of filament, wherein without
The thickness of amorphous carbon layer is 20～80nm.
10. the lithium ion battery that prepared by lithium ion battery negative material as claimed in claim 8.
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| CN108417808A (en) * | 2018-03-21 | 2018-08-17 | 南京工业大学 | Carbon fiber-silicon-graphene oxide composite material and preparation method thereof |
| CN108682805A (en) * | 2018-04-25 | 2018-10-19 | 福建翔丰华新能源材料有限公司 | A kind of method that electrostatic spinning combination sol-gel method prepares porous nano-fibre |
| CN108923035A (en) * | 2018-07-16 | 2018-11-30 | 四川理工学院 | A kind of preparation method of lithium ion battery nano-silicone wire/carbon composite negative pole material |
| CN109524648A (en) * | 2018-11-08 | 2019-03-26 | 华南理工大学 | A kind of porous carbon nanotube flexible battery material and preparation method thereof containing nano-silicon |
| CN109585808A (en) * | 2018-11-08 | 2019-04-05 | 华南理工大学 | A kind of nanotube-shaped silica-base material and preparation and application with core-shell structure |
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| CN111403741A (en) * | 2020-03-24 | 2020-07-10 | 华鼎国联四川动力电池有限公司 | Nano SiO-C composite material and application thereof in preparation of lithium ion battery cathode material |
| CN111769274A (en) * | 2020-07-17 | 2020-10-13 | 昆山宝创新能源科技有限公司 | SiOx-C composite fiber felt negative electrode material and preparation method and application thereof |
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| CN112289983B (en) * | 2020-09-18 | 2022-09-06 | 合肥国轩高科动力能源有限公司 | SiO (silicon dioxide) x -MWCNTs/C core-shell composite anode material and preparation method and application thereof |
| CN113540444A (en) * | 2021-06-03 | 2021-10-22 | 南方电网电动汽车服务有限公司 | Carbon-coated nanofiber material, preparation method thereof and battery |
| CN114284479A (en) * | 2021-12-22 | 2022-04-05 | 博路天成新能源科技有限公司 | Preparation method of novel carbon-silicon negative electrode material |
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