CN102790204B - Preparation method of silicon carbon lithium ion battery cathode material - Google Patents
Preparation method of silicon carbon lithium ion battery cathode material Download PDFInfo
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Abstract
The invention provides a preparation method of a silicon carbon lithium ion battery cathode material, which comprises the following steps: a) mixing a polymer solution, silicon powder and graphite to obtain a mixed solution; b) performing freeze drying of the mixed solution to obtain a solid mixture; c) sintering the solid mixture to obtain the silicon carbon lithium ion battery cathode material. The invention adopts freeze drying instead of a common drying method; the freeze drying means freezing the material, allowing the solvent component to rapidly become a solid state and to directly sublime under a vacuum condition so as to reach the drying purpose. With the process, the composite material and a carbon source can rapid coagulate within a short period, which avoids the problems of surface oxidation of the silicon material caused by normal temperature drying or high temperature drying, and non-uniform coating caused by settlement of the composite material powder. The obtained carbon-coated material has improved recycle performance and capacity when compared with materials obtained by common drying.
Description
Technical field
The present invention relates to electrode material preparation method field, particularly relate to a kind of preparation method of silicon carbon lithium ion battery cathode.
Background technology
In lithium ion battery negative material field, the negative material of main flow is graphite, and its theoretical capacity is only 372mAh/g, greatly limit the volumetric properties of lithium ion battery.In order to improve the reversible capacity of negative material further, be necessary the exploration exploitation carrying out Novel anode material.Wherein especially obtain the extensive concern of researcher with the capacity advantage (theoretical specific capacity is for 4200mAh/g) that other material is incomparable with Si.But the greatest problem of Si is the insertion of lithium and deviates from process the efflorescence that huge change in volume itself causes material, and cause electrode structure unstability, make material structure avalanche, active material peels off and loses electrical contact, thus cycle performance is undesirable simultaneously.
In order to avoid the shortcomings of silicon-based anode, researcher takes numerous schemes, the main Research Thinking of each class methods all have followed the material efflorescence adopting cushioning frame to slow down silicon volumetric expansion to cause, and adopts the coated suppression volumetric expansion of carbon and strengthen conductive effect.At present, no matter silicon based anode material is and Ni, Cu on preparation method, Ti, Mg, Ag, Fe, Al, Cr, Mg etc. make alloy type composite material, or with some as inertial base compounds such as TiN, TiC, direct and graphite-like even, carbon nano-tube, the material with carbon element compounds such as carbonaceous mesophase spherules, the composite material obtained uses as negative material, and its cycle performance and specific capacity can not reach practical requirement completely.And as starting point, it is coated silicon or silicon alloys material to be carried out carbon-coating, can alleviate the bulk effect of silicon to a great extent, thus play the high capacity characteristics of silicon to greatest extent.
In the method that numerous carbon is coated, the people such as A.Magasinski by CVD at silicon grain outer cladding amorphous carbon layer, compound system is formed with silicon, this approach improves structure and the electric conductivity of silicon materials, alleviate the bulk effect that lithium embeds and deviates to a certain extent, cycle performance is improved significantly.Adopt this mode can make the coated Si of carbon-coating uniform close, inhibit the expansion of silicon, meanwhile, repeatedly CVD can reach the effect of granulation, and nano-silicon is dispersed in particle uniformly, reversible capacity is to greatest extent close to theoretical value, but the maximum defect of these class methods is that preparation process is complicated, and governing factor is more, and production efficiency is low, high cost, is difficult to batch production.Therefore, wide variety of conventional carbon method for coating all selects pyrolysis high score subclass carbon source to carry out coated, and these class methods comparatively CVD process are simple, and with low cost, practical application foreground is obvious.But common coated generally select silica flour or silicon-base alloy composite material to be dispersed in be dissolved with high score subclass carbon source, as pitch, PVC, in sucrose solution, after solvent evaporates, obtains the coated material of carbon by pyrolysis.The specific capacity of this type of material all can reach about 600mAh/g-1000mAh/g, and the purer nano-silicon of cycle performance has significant improvement.This kind of method for coating is simple to operate, process easily controls, but in the process that solvent evaporates is namely dry, inevitably there will be the sedimentation of silicon grain, thus cause composite material granular can not be uniformly distributed in organic carbon source, cause carbon coated uneven, affect the chemical property of whole composite material.
Chinese patent CN101710617A discloses pitch that Dalian Greentech Advanced Materials Co., Ltd. adopts, and to carry out RESEARCH OF PYROCARBON as pyrolysis carbon source to silicon and graphite powder coated, silicon after using traditional drying mode coated to carbon and graphite powder drying, and through mist projection granulating, the processes such as high magnetic carbonization, the silicon carbon material specific capacity obtained is at 1000mAh/g, cycle performance is good, but these class methods are for making the even clad material of pitch, adopt and nanoprocessing is carried out to mesophase pitch, and use the devices such as spray injection, technological process is complicated, and running cost is higher.Chinese patent CN101339987A discloses Changsha Hai Rong Electron Material Co., Ltd and have employed silicon and graphite carries out high-energy ball milling, then with pitch ball milling after prepare silicon carbon material, simple traditional drying mode still makes the performance of material be affected.
Summary of the invention
The technical problem to be solved in the present invention is the preparation method providing a kind of silicon carbon lithium ion battery cathode, and negative material prepared by the cycle characteristics of the battery using described negative material to prepare and the common drying mode of Capacity Ratio is higher.
In order to prior art problem, the invention provides a kind of preparation method of silicon carbon lithium ion battery cathode, comprising:
A) Polymer Solution and silica flour, graphite are mixed to get mixed liquor;
B) described mixed liquor is carried out freeze drying, obtain solid mixture;
C) described solid mixture is sintered, obtain silicon carbon lithium ion battery cathode.
Preferably, described Polymer Solution is: the one in aqueous citric acid solution, D/W, aqueous sucrose solution, Aqueous Solutions of Polyethylene Glycol, polyvinyl alcohol water solution.
Preferably, described silica flour and graphite are (1 ~ 9) in mass ratio: (1 ~ 9).
Preferably, the quality of the RESEARCH OF PYROCARBON obtained after described Polymer Solution sintering is 5 ~ 20 times of silica flour and graphite quality summation.
Preferably, step b) be specially:
B1) by described mixed liquor liquid nitrogen frozen;
B2) by the solid that obtains after freezing in vacuumize, obtain solid mixture.
Preferably, the described vacuum drying time is 10 ~ 30h.
Preferably, described vacuum drying temperature is-30 DEG C.
Preferably, the temperature of described sintering is 600 DEG C ~ 1000 DEG C.
Preferably, silica flour purity need be greater than 99%, and granularity is 100 ~ 500nm.
Preferably, described graphite is native graphite or artificial stone ink sheet, and lamella size is 1-50 μm.
The preparation method of a kind of silicon carbon lithium ion battery cathode provided by the invention, employ freeze drying and substitute common drying means, so-called freeze drying is exactly that material is freezing, solvent composition is wherein become rapidly solid-state, and directly distils under vacuum and reach dry object.Adopt this process that composite material and carbon source can be made to condense rapidly at short notice, avoid the surface oxidation of the silicon materials that air drying or hyperthermia drying cause, and the coated uneven problem that composite material powder sedimentation produces.Negative material prepared by the carbon encapsulated material cycle performance obtained and the more common drying mode of capacity all increases.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph before the negative material sintering prepared by the embodiment of the present invention 4.
Fig. 2 is the scanning electron microscope (SEM) photograph before the negative material sintering prepared by comparative example 2 of the present invention.
Fig. 3 is the XRD figure of the negative material prepared by the embodiment of the present invention 4.
Fig. 4 is the negative material 100mA/g current density first charge-discharge curve after making button cell prepared by the embodiment of the present invention 4.
Fig. 5 is that the negative material 500mA/g current density charge and discharge cycles after making button cell prepared by the embodiment of the present invention 4 takes off lithium capacity curve.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
The invention provides a kind of preparation method of silicon carbon lithium ion battery cathode, comprising:
A) Polymer Solution and silica flour, graphite are mixed to get mixed liquor;
B) described mixed liquor is carried out freeze drying, obtain solid mixture;
C) described solid mixture is sintered, obtain silicon carbon lithium ion battery cathode.
According to the present invention, described Polymer Solution can be called again macromolecule carbon source solution, and preferably use water-soluble high-molecular material to be dissolved in the aqueous solution obtained in water, described water-soluble high-molecular material is preferably polyethylene glycol, polyvinyl alcohol, glucose, citric acid, sucrose.Be (1 ~ 9) with silica flour according to weight ratio by graphite again: (1 ~ 9) mixes, obtain composite powder, described composite powder is mixed with described Polymer Solution and is uniformly dispersed, mixing dispersion mode used is preferably one or more in mechanical agitation, high energy milling, ultrasonic disperse, to ensure that material is dispersed in water-soluble polymers.
According to the present invention, graphite used is preferably native graphite or artificial stone ink sheet, and the size of described graphite flake is preferably 1 ~ 50 μm, is more preferably 20 ~ 50 μm.The purity of described silica flour is preferably more than 99%.The particle diameter of silica flour is 100 ~ 500nm, and described silica flour is pulverized grinding preferably by silico briquette and prepared.According to the present invention, the quality of described macromolecular material is 5 ~ 20 times of graphite and silica flour quality summation.
To compare prior art, the present invention uses freeze-drying, the mixed liquor quick freeze that graphite, silica flour and Polymer Solution are formed, cryogenic temperature should below-150 DEG C, and quick freeze can by finely dispersed mixed liquor rapid solidification, and aqueous solvent is frozen, solute is still evenly distributed in solid ice, and then the solid obtained after mixed liquor is freezed be placed in-30 ~-40 DEG C at vacuumize, under vacuum degree is 5 ~ 20Pa, described freezing after solid in ice constantly distil.According to the present invention, the described vacuum drying time is preferably 10 ~ 30h, is more preferably 15 ~ 25h.After vacuumize, obtain solid mixture.
The solid mixture obtained after freeze drying is started at 5 ~ 20 DEG C heat up, 2 ~ 6h is incubated after being heated to 600 ~ 1000 DEG C, macromolecular material in described solid mixture is by pyrolysis carbonization gradually, the carbon obtained after carbonization and graphite are coated on the surface of silicon powder particle uniformly, silicon carbon lithium ion battery cathode.
Below will describe the present invention in detail with specific embodiment: it should be noted that, the material that the present invention uses is selected from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
(1) preparation of silicon/graphite composite particles
10g citric acid is dissolved in 50mL deionized water, by silica flour (200 orders, purity 99.9%) 0.6g and graphite flake (2 μm) 0.4g, be dispersed in above-mentioned solution, pour in 100ml stainless steel jar mill together, adopt zirconium oxide balls, grind 10h with in the impact grinding of vibrating type nanometer with 300 turns beats/min.In the composite granule obtained, silicon granularity is at 200-300nm.
(2) freeze drying
By mill after mixed solution ultrasonic half an hour, further by material dispersion in solvent.Use liquid nitrogen frozen at once after ultrasonic, treat that solution coagulates Cheng Binghou proceeds in freeze drier, vacuumize.Freeze drier condenser temperature is-30 DEG C, and vacuum degree remains on 10Pa.After 20 hours, material becomes dry foaming solid.
(3) pyrolysis organic carbon
Solid product step 2 obtained, under Ar protection, is warming up to 600 DEG C with 5 DEG C/min in tube furnace, insulation 2h, then naturally cools to room temperature, then takes out, grinding, crosses 200 mesh sieves.Obtain negative material.
The negative material prepared by the present embodiment and carbon black and Kynoar (PVDF) make slurry by the mass ratio of 75: 15: 10 in 1-METHYLPYRROLIDONE (NMP) medium, Copper Foil is coated with, makes electrode after drying.Be to electrode with metallic lithium foil, being prepared into model is CR-2032 button cell, its first embedding lithium capacity be 1054.3mAh/g, de-lithium capacity is 875.2mAh/g first, adopt 100mAh/g current density after 30 charge and discharges circulation, de-lithium capacity is 587mAh/g.Relative to pure silicon powder (i.e. comparative example 1), performance improves a lot, and simultaneously relative to the drying mode (i.e. comparative example 2) of common oven dry, first charge-discharge efficiency is increased to 83%, and cycle performance also has a more substantial increase.
Embodiment 2
By 0.4g silica flour (200 orders; purity 99.9%) with 0.6g graphite flake (20 μm) according to the ball milling 20h in the deionized water being dissolved with 20g glucose of the mode described in embodiment 1; the powdery pulp obtained is ultrasonic 30min again; freeze drying is carried out by mode described in embodiment 1; the foaming solid obtained after drying is warming up to 800 DEG C with the heating rate of 5 DEG C/min under Ar protective atmosphere in tube furnace; naturally cool after insulation 4h, obtain negative material.
The negative material prepared by the present embodiment and carbon black and Kynoar (PVDF) make slurry by the mass ratio of 75: 15: 10 in 1-METHYLPYRROLIDONE (NMP) medium, Copper Foil is coated with, makes electrode after drying.Be to electrode with metallic lithium foil, being prepared into model is CR-2032 button cell, adopts the charge and discharge of 100mA/g current density, its first embedding lithium capacity be 780.8mAh/g, de-lithium capacity 640.3mAh/g first.After 30 circulations, de-lithium capacity attenuation is to 570.5mAh/g, and capability retention is 89%, and its cycle performance comparatively embodiment 1 improves a lot, and the visible amount increasing graphite enhances the cycle performance of composite material, but reduces the specific capacity of material simultaneously.The increase of carbon source amount also contributes to strengthening cycle performance.
Embodiment 3
0.8g silica flour (200 orders, purity 99.9%) and 0.2g graphite flake (30 μm) are mixed according to the 40h that dry grinds under atmosphere protection of the mode described in embodiment 2, then by the powder ultrasonic disperse that obtains in the deionized water being dissolved with 5g sucrose.Freeze drying, the foaming solid obtained sinters under Ar gas shielded with the heating rate of 10 DEG C/min in tube furnace, and 900 DEG C of insulation 4h obtain negative material.
The negative material prepared by the present embodiment and carbon black and Kynoar (PVDF) make slurry by the mass ratio of 75: 15: 10 in 1-METHYLPYRROLIDONE (NMP) medium, Copper Foil is coated with, makes electrode after drying.Be to electrode with metallic lithium foil, being prepared into model is CR-2032 button cell, adopts the charge and discharge of 100mA/g current density, its first embedding lithium capacity be 1468.5mAh/g, de-lithium capacity is 1174.8mAh/g first.Depart from capacity attenuation after 30 circulations to 675.4mAh/g, capability retention is 57%, and capacity comparatively embodiment 2 improves a lot, but cycle performance is slightly poor.The content of silicon raises the capacity contributing to improving integral composite, but is reduction of cycle performance.
Embodiment 4
0.7g silica flour (200 orders, purity 99.9%) and 0.3g graphite flake (50 μm) are prepared according to mode described in embodiment 2.Polyethylene glycol (PEG) is carried out freeze drying as carbon source.The foaming solid obtained after drying is warming up to 1000 DEG C with the heating rate of 5 DEG C/min in tube furnace under argon shield, and insulation 6h, obtains negative material.
The negative material prepared by the present embodiment and carbon black and Kynoar (PVDF) make slurry by the mass ratio of 75: 15: 10 in 1-METHYLPYRROLIDONE (NMP) medium, Copper Foil is coated with, makes electrode after drying.Be to electrode with metallic lithium foil, being prepared into model is CR-2032 button cell, and when adopting 100mA/g current density discharge and recharge, it is embedding lithium capacity 1702.2mAh/g first, and de-lithium capacity is 1410.3mAh/g, and efficiency is 83% first.When adopting larger current density 500mAh/g charge and discharge cycles, de-lithium capacity is 720.8mAh/g first, and circulate and still have the capacity of about 540mAh/g after 40 times, conservation rate is 75%, higher than similar composite material.
Embodiment 5
0.6g silica flour (200 orders, purity 99.9%) and 0.4g graphite flake (1 μm) are prepared according to mode described in embodiment 2.Glucose (PEG) is carried out freeze drying as carbon source.The foaming solid obtained after drying is warming up to 700 DEG C with the heating rate of 5 DEG C/min in tube furnace under argon shield, and insulation 6h, obtains negative material.
The negative material prepared by the present embodiment and carbon black and Kynoar (PVDF) make slurry by the mass ratio of 75: 15: 10 in 1-METHYLPYRROLIDONE (NMP) medium, Copper Foil is coated with, makes electrode after drying.Be to electrode with metallic lithium foil, being prepared into model is CR-2032 button cell, and when adopting 100mA/g current density discharge and recharge, it is embedding lithium capacity 1250.4mAh/h first, and de-lithium capacity is 1000.3mAh/g, and efficiency is 80% first.Circulate and still have the capacity of about 850mAh/g after 40 times, conservation rate is 85%.
Comparative example 1
Silica flour (200 orders, purity 99.9%) is scattered in alcohol, is placed in stainless steel jar mill, adopt ZrO
2abrading-ball, the ratio of grinding media to material with 15: 1 is placed in the impact grinding of vibrating type nanometer and grinds 10h under Ar gas shielded, and the silicon grain obtained is at about 100-200nm, and 80 degree of oven dry afterwards, grinding is sieved.The elemental silicon powder obtained and carbon black and Kynoar (PVDF) make slurry by the mass ratio of 75: 15: 10 in 1-METHYLPYRROLIDONE (NMP) medium, Copper Foil is coated with, makes electrode after drying.Be to electrode with metallic lithium foil, being prepared into model is CR-2032 button cell, under the current density of 100mA/g, carries out charge and discharge circulation between 0.01V-2V.Embedding lithium capacity is 1834.1mAh/g first, and de-lithium capacity is 1086.4mAh/g, and circulate after 10 times, capacity attenuation is to below 10mAh/g.
Comparative example 2
10g citric acid is dissolved in 50mL alcohol, by silica flour (200 orders, purity 99.9%) 0.6g be scattered in above-mentioned solution with graphite flake (2 μm) 0.4g together be placed in 100mL stainless steel jar mill, adopt ZrO2 abrading-ball with 15: 1 ratio of grinding media to material under Ar gas shielded, be placed in the impact grinding of vibrating type nanometer grind 10h, obtain silicon and graphite composite particles, wherein silicon grain size is at about 200-300nm, afterwards the slurry obtained directly is dried, the powder that oven dry obtains is under Ar protection, 600 DEG C are warming up to 5 DEG C/min in tube furnace, insulation 2h, then screening is ground, button cell is made according to the mode described in comparative example 1.With 100mAh/g charge and discharge cycles, embedding lithium capacity 1018.5mAh/g first, de-lithium capacity is 631.2mAh/g, and efficiency is 61.9%, and the capacity attenuation that to circulate after 30 times is to 237.1mAh/g.
By the contrast of embodiment and comparative example, be not difficult to find out and adopt freeze drying that composite material and carbon source are condensed rapidly at short notice, avoid the surface oxidation of the silicon materials that air drying or hyperthermia drying cause, and the coated uneven problem that composite material powder sedimentation produces.Negative material prepared by the carbon encapsulated material cycle performance obtained and the more common drying mode of capacity all increases.
Above the preparation method of a kind of silicon carbon lithium ion battery cathode provided by the invention is described in detail; apply specific case herein to set forth principle of the present invention and execution mode; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (8)
1. a preparation method for silicon carbon lithium ion battery cathode, is characterized in that, comprising:
A) Polymer Solution and silica flour, graphite are mixed to get mixed liquor;
B) described mixed liquor is carried out freeze drying, obtain solid mixture;
C) sintered by described solid mixture, obtain silicon carbon lithium ion battery cathode, the temperature of described sintering is 600 ~ 1000 DEG C, and the time is 2 ~ 6h;
Step b) be specially:
B1) by described mixed liquor liquid nitrogen frozen, cryogenic temperature is below-150 DEG C;
B2) by the solid that obtains after freezing in vacuumize, described vacuum drying temperature is-30 ~-40 DEG C, and vacuum degree is 5 ~ 20Pa, obtains solid mixture.
2. preparation method according to claim 1, is characterized in that, described Polymer Solution is: the one in aqueous citric acid solution, D/W, aqueous sucrose solution, Aqueous Solutions of Polyethylene Glycol, polyvinyl alcohol water solution.
3. preparation method according to claim 1, is characterized in that, described silica flour and graphite are (1 ~ 9) in mass ratio: (1 ~ 9).
4. preparation method according to claim 1, is characterized in that, the quality of the RESEARCH OF PYROCARBON obtained after described Polymer Solution sintering is 5 ~ 20 times of silica flour and graphite quality summation.
5. preparation method according to claim 1, is characterized in that, the described vacuum drying time is 10 ~ 30h.
6. preparation method according to claim 1, is characterized in that, described vacuum drying temperature is-30 DEG C.
7. preparation method according to claim 1, is characterized in that, silica flour purity need be greater than 99%, and granularity is 100 ~ 500nm.
8. preparation method according to claim 1, is characterized in that, described graphite is native graphite or artificial stone ink sheet, and lamella size is 1-50 μm.
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| CN104752699B (en) * | 2013-12-31 | 2018-10-26 | 西北大学 | A kind of preparation method of Si-C composite material |
| CN103956459B (en) * | 2014-03-13 | 2016-11-02 | 清华大学 | A kind of eco-friendly method for manufacturing lithium battery negative electrode plate |
| CN105742589B (en) * | 2016-02-29 | 2018-09-18 | 中国有色桂林矿产地质研究院有限公司 | A kind of negative electrode of lithium ion battery silicon-cobalt-carbon composite and preparation method thereof |
| CN111384370B (en) * | 2018-12-29 | 2022-02-25 | 安普瑞斯（南京）有限公司 | High-capacity density lithium ion battery cathode |
| CN109830668B (en) * | 2019-02-28 | 2021-09-03 | 昆明理工大学 | Method for preparing lithium ion battery silicon-carbon negative electrode material by adopting carbon nano tube |
| CN112652755B (en) * | 2019-10-09 | 2022-07-12 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode material, preparation method and application thereof, and lithium ion battery |
| CN111146421B (en) * | 2019-12-26 | 2022-03-18 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
| CN111170364A (en) * | 2019-12-30 | 2020-05-19 | 北方奥钛纳米技术有限公司 | Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery |
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