CN104362311A - Silicon-carbon composite microsphere anode material and preparation method thereof - Google Patents
Silicon-carbon composite microsphere anode material and preparation method thereof Download PDFInfo
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a silicon-carbon composite microsphere anode material and its preparation method. the preparation method comprises the following steps: firstly, nano-silicon particles and a first macromolecular solution are mixed, and first composite microspheres are formed after spray drying; then, the first composite microspheres and a second macromolecular solution are mixed to carry out surface coating on the first composite microspheres, and second composite microspheres with a core-shell structure are formed after solvent evaporation; and finally, the second composite microspheres undergo oxidation and carbonization treatments to form the silicon-carbon composite microsphere anode material. By the preparation method which has a simple technology, is low-cost and is easy to operate, the silicon-carbon composite microsphere anode material is prepared. In addition, no etching operation for pore-forming is required by the preparation method. Raw materials used in the preparation method can be selected from a number of sources. According to the silicon-carbon composite microsphere anode material obtained, advantages of nano-silicon and a carbon substrate are combined effectively. Thus, electrochemical performance of the silicon-carbon composite microsphere anode material used as a negative electrode of a lithium ion battery is enhanced.
Description
Technical field
The present invention relates to a kind of silicon-carbon composite microsphere negative electrode material for lithium ion battery and preparation method thereof.
Background technology
The negative material of lithium ion battery is generally material with carbon element, the theoretical lithium storage content of the existing graphite cathode be widely used is 372mAh/g, be difficult to meet the high-capacity lithium ion cell requirement more and more higher to electrode material, therefore the negative material of research and development high power capacity has become the key factor improving performance of lithium ion battery.The theoretical lithium storage content of silicon materials is 4200mAh/g, is a kind of ideal material improving capacity of negative plates.But, the structural instability of silicon materials, volumetric expansion in embedding lithium process can reach 400%, during de-lithium, volume can shrink again, in continuous cyclic process, to destruction and the mechanical crushing of material structure be caused, and make silicon materials and conductive network and collector lose electrical contact simultaneously, and finally cause the capacity rapid decay of electrode, cycle performance to be deteriorated.
In order to alleviate the change in volume in doff lithium alloying process, improving the cyclical stability of silicon based electrode material, by using nano level silicon to obtain Si-C composite material with carbon base body in conjunction with compound, is the effective ways overcome the above problems.
The people such as Liu (Nature Nanotechnology 9 (2014) 187.) are based on water in oil liquid phase self-assembling method, and the step such as subsequent heat treatment, template etching, prepare the silicon/carbon complex microsphere of pomegranate shape structure, this complex microsphere has multilayered structure, outermost layer is carbon shell, inside is cellular porous carbon network, silicon nanoparticle is encapsulated in internal porous carbon network, when the composite material of this kind of structure is used as lithium ion battery negative, show very excellent chemical property.Can under the capacity of 1200mAh/g stable circulation 1000 weeks.Silicon grain is first carried out incomplete oxidation by the people such as Yue (Electrochimica Acta 125 (2014) 206.), forms SiO outward at particle
2layer, and then by the silicon grain of this incomplete oxidation, SiO
2particle mixes with phenolic resins, high temperature cabonization, the Si/SiO obtained
2/ C composite; After HF etching, obtain silicon/porous carbon composite, and show good chemical property, reversible capacity is 1100mAh/g first, and after 80 circulations, capability retention is 86%.The people such as Jung (Nano Letters 13 (2013) 2092.) are by the method for high temperature spray-drying, obtain the complex microsphere of Si/SiO2/ sucrose, after carbonization, HF etching, obtain the Si@po-C type complex microsphere of porous carbon clad nano silicon grain, and show excellent chemical property, circulate 150 weeks under the electric current of 4A/g, reversible capacity still remains on about 1200mAh/g.Based on the basis of above research, can find out that the exploitation volumetric expansion had for silicon provides the Si-C composite material of cushion space, to the development of high power capacity silicon based anode material lithium ion battery, there is very large impetus.But in these researchs, providing of the cushion space of silicon materials, majority adopts the method removing hard template to obtain, and namely first introduces SiO in the preparation process of composite material
2around layer to silicon, formed after Si-C composite material through heat treatment, then remove template by HF etching, thus obtain the cushion space for holding silicon change in volume.This follow-up etching operation not only adds preparation cost, also has larger danger and the unfriendly property of environment.
The people such as Magasinski (Nature Materials 9 (2010) 353.) pass through chemical vapour deposition technique, by high conductivity carbon black and silicon nanoparticle compound, self-assembled growth is the Si/C compound micron ball of concrete dynamic modulus, this kind of composite material has good electrical conductance and porousness, porous High-conductivity carbon network can improve the service efficiency of silicon on the one hand, makes the maximum performance of reversible capacity first of silicon to 3670mAh/g; Can hold on the other hand the volumetric expansion of silicon, the structural intergrity of holding electrode material, improves the cyclical stability of silicon-carbon cathode, can under the capacity of 1400mAh/g stable circulation 100 weeks.But the porous carbon matrix of this Si-C composite material is unenclosed construction, and electrolyte infiltrates into composite inner by hole, and preparation cost is high, is unfavorable for large-scale production.The people such as Li (Journal of Power Sources 248 (2014) 721.) carry out spraying dry at the mixed liquor of graphite, silicon nanoparticle and citric acid, obtain with graphite is kernel, with the granular composite material that the compound of Si and porous carbon is shell, during as lithium ion battery negative, show good chemical property, reach the reversible capacity of 600mAh/g, and Absorbable organic halogens circulates 100 weeks, but capacity is on the low side, and silicon grain is exposed to composite material outside, cause the structural instability of material.In these researchs, the carbon base body of the porous silicon carbon composite of preparation is open type system, fully can not play the effect of isolated electrolyte, make electrolyte easily be infiltrated into the inside of composite material by hole, thus cause the structural instability of negative material.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of silicon-carbon composite microsphere negative electrode material and preparation method thereof, based on spraying dry and follow-up surface coating technology, obtain the silicon-carbon complex microsphere with multi-level nucleocapsid structure, and use it for the negative material of lithium ion, show good chemical property, comprise higher reversible specific capacity, longer cycle life and good high rate performance; Preparation method's technique of the present invention is simple, cost is low, workable, there is boundless application prospect.
For achieving the above object, the present invention by the following technical solutions:
The invention discloses a kind of preparation method of silicon-carbon composite microsphere negative electrode material, comprise the following steps:
S1: mixing silicon nanoparticle and the first Polymer Solution, form the first complex microsphere after spraying dry;
S2: mixed with the second Polymer Solution by described first complex microsphere, carries out Surface coating to described first complex microsphere, after solvent evaporates, forms second complex microsphere with nucleocapsid structure;
S3: to be oxidized described second complex microsphere, carbonization, forms silicon-carbon composite microsphere negative electrode material.
Preferably, described first Polymer Solution comprises poly-vinyl alcohol solution, and described second Polymer Solution comprises polyacrylonitrile solution.
Preferably, described first Polymer Solution comprises the poly-vinyl alcohol solution that mass percent is 0.1-6%, and described second Polymer Solution comprises the polyacrylonitrile solution that mass percent is 1-10%.
Preferably, the mass ratio of the polyvinyl alcohol in described silicon nanoparticle and described poly-vinyl alcohol solution is 0.01-0.3.
Preferably, the mass ratio of the polyacrylonitrile in described polyacrylonitrile solution and described first complex microsphere is 0.1-1.
Preferably, also comprise in step S2 and carry out ultrasonic disperse, solidification by carrying out in the described first complex microsphere immersion ethanolic solution after Surface coating after evaporation of the solvent, form described second complex microsphere with nucleocapsid structure.
Preferably, the step of described oxidation is progressively warming up to 250-300 DEG C with the programming rate of 1-10 DEG C/min, and constant temperature 0.5-3h.
Preferably, the step of described carbonization is progressively warming up to 500-1000 DEG C with the programming rate of 1-20 DEG C/min in inert gas, and constant temperature 0.5-5h.
Preferably, the diameter of described silicon nanoparticle is less than 150nm.
The present invention also discloses a kind of silicon-carbon composite microsphere negative electrode material in addition, for lithium ion battery, is obtain according to above-described preparation method.
Compared with prior art, the beneficial effect that the present invention has is: the present invention is simple by technique, cost is low, the preparation method being easy to operate prepares silicon-carbon composite microsphere negative electrode material, wherein the first Polymer Solution and the rear spraying dry of silicon nanoparticle mixing form the first complex microsphere that silicon nanoparticle is embedded in porous carbon network, then carrying out Surface coating with the second Polymer Solution to the first complex microsphere makes the first complex microsphere outside form the presoma shell of fine and close carbon, during based on high temperature cabonization, macromolecule cleavable is material with carbon element, and utilize variety classes macromolecule to have the feature of different carbon yield, obtain the silicon-carbon composite microsphere negative electrode material with multi-level nucleocapsid structure.Therefore prepare by preparation method of the present invention the doped structure that inside is porous carbon grid and silicon, outside is dense carbon shell, there is the silicon-carbon composite microsphere negative electrode material of multi-level nucleocapsid structure, and without the need to etching piercing procedure in preparation method, its raw materials used raw material can choosing wide material sources, the silicon-carbon composite microsphere negative electrode material obtained effectively combines the advantage of both nano-silicon and carbon base body: the embedding of silicon improves the entirety storage lithium performance of material, and carbon base body contributes to the efficiency of transmission improving electric charge and ion, and pore structure wherein effectively can hold the volumetric expansion of silicon to reduce the stress rupture to Si-C composite material entirety, outer fine and close carbon shell simultaneously, the contact of electrolyte and silicon can also be completely cut off, and effectively reduce the contact area of active material and electrolyte, contribute to forming stable solid-electrolyte interface, thus improve silicon-carbon composite microsphere negative electrode material as chemical property during lithium ion battery negative.
In preferred scheme, the first macromolecule in the present invention chooses polyvinyl alcohol, carry out being mixed to form suitable presoma with silicon nanoparticle, then surperficial polyacrylonitrile carries out to spray-dired first complex microsphere coated, after oxidation, carbonization, obtain the silicon-carbon composite microsphere negative electrode material with multi-level nucleocapsid structure that chemical property is more excellent.
Accompanying drawing explanation
Fig. 1 a to Fig. 1 d is the scanning electron microscope (SEM) photograph of the different visual angles of the preparation-obtained silicon-carbon composite microsphere negative electrode material of example 1 in the present invention respectively.
Fig. 2 is the scanning electron microscope (SEM) photograph of the preparation-obtained silicon-carbon composite cathode material of comparative example 1 in the present invention.
Embodiment
Below contrast accompanying drawing and combine preferred embodiment the invention will be further described.
Embodiments provide a kind of preparation method of silicon-carbon composite microsphere negative electrode material, comprise the following steps: first mix silicon nanoparticle and the first Polymer Solution, after spraying dry, form the first complex microsphere; Then described first complex microsphere is mixed with the second Polymer Solution, Surface coating is carried out to described first complex microsphere, after solvent evaporates, form second complex microsphere with nucleocapsid structure; Finally described second complex microsphere is oxidized, carbonization treatment, form silicon-carbon composite microsphere negative electrode material.
First Polymer Solution comprises poly-vinyl alcohol solution in a preferred embodiment of the invention, and the second Polymer Solution comprises polyacrylonitrile solution.
Below by way of the silicon-carbon of example explanation more specifically composite microsphere negative electrode material and preparation method thereof, and electrochemical property test is carried out to the silicon-carbon composite microsphere negative electrode material preparing gained.
Example 1:
The first step: prepared by solution.This example adopts molecular weight is about the polyvinyl alcohol (PVA) of 20000g/mol, molecular weight is about 15000g/mol polyacrylonitrile (PAN) and diameter to be less than the silicon nanoparticle (Si) of 100nm.First take a certain amount of PVA, be added in a certain amount of deionized water, stir 2h at 90 DEG C and dissolve, be mixed with the PVA aqueous solution that mass fraction is 1%; Be that 1:10 takes a certain amount of silicon nanoparticle according to the mass ratio of silicon nanoparticle and PVA, be added in the PVA aqueous solution, continue to stir 2h at 80 DEG C, and ultrasonic disperse 2h makes silicon nanoparticle dispersed in the PVA aqueous solution, obtain PVA-Si and disperse mixed liquor.Take a certain amount of PAN, be added in a certain amount of DMF (DMF), stir 5h at 80 DEG C and dissolve, be mixed with the PAN/DMF solution that mass fraction is 5%.
Second step: spraying dry, Surface coating prepare nano-silicon/polymer composite microsphere.Disperse mixed liquor at high temperature to carry out spraying dry PVA-Si obtained for the first step, import and outlet temperature are respectively 220 DEG C and 120 DEG C, and peristaltic pump speed is 60r/min, and after solvent removal, solute is rapidly solidificated into Si/PVA complex microsphere, i.e. the first complex microsphere.Surface coating is carried out to the Si/PVA complex microsphere collected, be that PAN/DMF solution mixes with Si/PVA complex microsphere by 1:3 according to the mass ratio of PAN and Si/PVA complex microsphere, smear evenly, PAN is made evenly to be coated on Si/PVA complex microsphere surface, after solvent evaporates, mixture is immersed ultrasonic disperse in ethanolic solution, solidification, obtain the Si/PVA/PAN complex microsphere with nucleocapsid structure.
3rd step: oxidation processes.The Si/PVA/PAN complex microsphere obtained by second step carries out oxidation processes in atmosphere, is progressively warming up to 250 DEG C with the programming rate of 2 DEG C/min from room temperature, takes out after constant temperature 2h.
4th step: carbonization treatment.Si/PVA/PAN complex microsphere after 3rd step oxidation processes is carried out carbonization treatment in high-temperature atmosphere furnace, under the protection of high-purity argon gas (purity >99.999%), 800 DEG C are progressively warming up to from room temperature with the programming rate of 5 DEG C/min, and constant temperature 2h, take out after being cooled to room temperature, obtaining having multi-level nucleocapsid carbosphere is matrix, silicon nanoparticle is embedded in the silicon-carbon composite microsphere negative electrode material in internal porous carbon, its scanning electron microscope (SEM) photograph is as shown in Fig. 1 a to Fig. 1 d, wherein Fig. 1 a is overall structure, Fig. 1 b is nucleocapsid structure, Fig. 1 c is carbon shell, Fig. 1 d is inner core.
Electrochemical property test: the silicon-carbon composite microsphere negative electrode material prepared is assembled into 2032 type button cells in the glove box being full of high-purity argon gas.Utilize Land battery test system at room temperature to carry out cycle performance test to above-mentioned half-cell, charging and discharging currents is 0.1A/g, and charging/discharging voltage scope is 0.01-1.5V; During high rate performance test, electric current progressively increases 0.2 from 0.1A/g, 0.5,1.0,2.0A/g, circulate 10 weeks under each electric current, charging/discharging voltage scope is 0.01-1.5V.
Test result: according to above-mentioned steps operation obtain silicon-carbon composite microsphere negative electrode material that this example prepares under 0.1A/g electric current, carry out cycle performance test time, reversible capacity is 1015mAh/g first, coulombic efficiency is 65%, the reversible capacity after 100 times that circulates is 924mAh/g, and the conservation rate of capacity is 91%; During high rate performance test, the reversible capacity under 2.0A/g electric current is 660mAh/g.
Comparative example 1:
The first step: prepared by solution.Be wherein not need to prepare PAN/DMF solution with first step difference in example 1.
Second step: spraying dry prepares nano-silicon/polymer composite microsphere.Second step difference in spray drying condition and example 1 is not carry out Surface coating to the Si/PVA complex microsphere collected.
3rd step: oxidation processes.Oxidation processes condition is identical with the 3rd step in example 1.
4th step: carbonization treatment.Carbonization treatment condition is identical with the 4th step in example 1, but in carbonization treatment process, owing to not having the protection of PAN shell, the Si-C composite material obtained does not possess nucleocapsid structure, and spherical structure caves in, as shown in Figure 2.
Electrochemical property test: test condition is identical with the 5th step in example 1.
Test result: when carrying out cycle performance test under 0.1A/g electric current, reversible capacity is 1645mAh/g first, and coulombic efficiency is 58%, the reversible capacity after 100 times that circulates is 481mAh/g, and the conservation rate of capacity is 29%; During high rate performance test, the reversible capacity under 2.0A/g electric current is 369mAh/g.
Example 2:
The mass fraction being the PVA aqueous solution that this example is prepared in this example with the difference in example 1 is 3%.The electrochemical property test as example 1 is carried out by the silicon-carbon composite microsphere negative electrode material prepared this example, test result is: when carrying out cycle performance test under 0.1A/g electric current, reversible capacity is 939mAh/g first, coulombic efficiency is 62%, the reversible capacity after 100 times that circulates is 763mAh/g, and the conservation rate of capacity is 81%; During high rate performance test, the reversible capacity under 2.0A/g electric current is 537mAh/g.
Example 3:
Being with the difference of example 1 in this example that this example is is that 3:10 disperses mixed liquor to prepare PVA-Si according to the mass ratio of silicon nanoparticle and PVA.The electrochemical property test as example 1 is carried out by the silicon-carbon composite microsphere negative electrode material prepared this example, test result is: when carrying out cycle performance test under 0.1A/g electric current, reversible capacity is 1437mAh/g first, coulombic efficiency is 64%, the reversible capacity after 100 times that circulates is 856mAh/g, and the conservation rate of capacity is 58%; During high rate performance test, the reversible capacity under 2.0A/g electric current is 578mAh/g.
Example 4:
This example is with the difference of example 1, and this example selects molecular weight to be about the PVA of 30000g/mol, and diameter is less than the silicon nanoparticle of 150nm, the mass fraction of the PVA aqueous solution of preparation is 0.1%, the mass fraction of PAN/DMF solution is 1%, the mass ratio of silicon nanoparticle and PVA is 1:100, the mass ratio of PAN and Si/PVA complex microsphere is 1:10, the Si/PVA/PAN complex microsphere with nucleocapsid structure is obtained by this proportioning, 300 DEG C are progressively warming up to the programming rate of 1 DEG C/min from room temperature in oxidation processes, carbonization treatment is carried out after constant temperature 3h, 500 DEG C are progressively warming up to the programming rate of 1 DEG C/min from room temperature in carbonization treatment process, be cooled to room temperature after constant temperature 5h and prepare silicon-carbon composite microsphere negative electrode material, electrochemical property test as example 1 is carried out to the silicon-carbon composite microsphere negative electrode material of this example, when carrying out cycle performance test under 0.1A/g electric current, reversible capacity is 537mAh/g first, coulombic efficiency is 54%, the reversible capacity after 100 times that circulates is 456mAh/, the conservation rate of capacity is 85%, during high rate performance test, the reversible capacity under 2.0A/g electric current is 378mAh/g.
Example 5:
This example is with the difference of example 1, this example selects molecular weight to be about the PVA of 10000g/mol, the mass fraction of the PVA aqueous solution of preparation is 6%, the mass fraction of PAN/DMF solution is 10%, the mass ratio of PAN and Si/PVA complex microsphere is 1:1, the Si/PVA/PAN complex microsphere with nucleocapsid structure is obtained by this proportioning, 270 DEG C are progressively warming up to the programming rate of 10 DEG C/min from room temperature in oxidation processes, carbonization treatment is carried out after constant temperature 0.5h, 1000 DEG C are progressively warming up to the programming rate of 20 DEG C/min from room temperature in carbonization treatment process, be cooled to room temperature after constant temperature 0.5h and prepare silicon-carbon composite microsphere negative electrode material, electrochemical property test as example 1 is carried out to the silicon-carbon composite microsphere negative electrode material of this example, when carrying out cycle performance test under 0.1A/g electric current, reversible capacity is 863mAh/g first, coulombic efficiency is 65%, the reversible capacity after 100 times that circulates is 659mAh/, the conservation rate of capacity is 76%, during high rate performance test, the reversible capacity under 2.0A/g electric current is 492mAh/g.
Example 6:
This example is with the difference of example 1, and this example selects molecular weight to be about the PVA of 30000g/mol, and diameter is less than the silicon nanoparticle of 150nm, the mass fraction of the PVA aqueous solution of preparation is 0.5%, the mass fraction of PAN/DMF solution is 2%, the mass ratio of silicon nanoparticle and PVA is 1:20, the mass ratio of PAN and Si/PVA complex microsphere is 1:5, the Si/PVA/PAN complex microsphere with nucleocapsid structure is obtained by this proportioning, 280 DEG C are progressively warming up to the programming rate of 5 DEG C/min from room temperature in oxidation processes, carbonization treatment is carried out after constant temperature 1h, 900 DEG C are progressively warming up to the programming rate of 10 DEG C/min from room temperature in carbonization treatment process, be cooled to room temperature after constant temperature 1h and prepare silicon-carbon composite microsphere negative electrode material, electrochemical property test as example 1 is carried out to the silicon-carbon composite microsphere negative electrode material of this example, when carrying out cycle performance test under 0.1A/g electric current, reversible capacity is 975mAh/g first, coulombic efficiency is 65%, the reversible capacity after 100 times that circulates is 819mAh/, the conservation rate of capacity is 84%, during high rate performance test, the reversible capacity under 2.0A/g electric current is 580mAh/g.
Prepare PAN solution in the present invention also can select to adopt THF, DMSO equal solvent, to employing DMF solvent, there is similar effect.Known by the contrast of example 1 and comparative example 1, the silicon-carbon composite microsphere negative electrode material prepared after carrying out Surface coating to the first complex microsphere in preparation method of the present invention is higher for reversible specific capacity during lithium ion battery, and cycle performance is also more excellent.In conjunction with example 1 to example 6, adopting the preparation method of optimization provided by the present invention to prepare obtained silicon-carbon composite microsphere negative electrode material for showing good chemical property during lithium ion battery, comprising higher reversible specific capacity, compared with long circulation life and good high rate performance.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, some equivalent to substitute or obvious modification can also be made, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a preparation method for silicon-carbon composite microsphere negative electrode material, is characterized in that, comprises the following steps:
S1: mixing silicon nanoparticle and the first Polymer Solution, form the first complex microsphere after spraying dry;
S2: mixed with the second Polymer Solution by described first complex microsphere, carries out Surface coating to described first complex microsphere, after solvent evaporates, forms second complex microsphere with nucleocapsid structure;
S3: to be oxidized described second complex microsphere, carbonization, forms silicon-carbon composite microsphere negative electrode material.
2. preparation method according to claim 1, is characterized in that, described first Polymer Solution comprises poly-vinyl alcohol solution, and described second Polymer Solution comprises polyacrylonitrile solution.
3. preparation method according to claim 2, is characterized in that, described first Polymer Solution comprises the poly-vinyl alcohol solution that mass percent is 0.1-6%, and described second Polymer Solution comprises the polyacrylonitrile solution that mass percent is 1-10%.
4. preparation method according to claim 2, is characterized in that, the mass ratio of the polyvinyl alcohol in described silicon nanoparticle and described poly-vinyl alcohol solution is 0.01-0.3.
5. preparation method according to claim 2, is characterized in that, the mass ratio of the polyacrylonitrile in described polyacrylonitrile solution and described first complex microsphere is 0.1-1.
6. preparation method according to claim 1, it is characterized in that, also comprise in step S2 and carry out ultrasonic disperse, solidification by carrying out in the described first complex microsphere immersion ethanolic solution after Surface coating after evaporation of the solvent, form described second complex microsphere with nucleocapsid structure.
7. preparation method according to claim 1, is characterized in that, the step of described oxidation is progressively warming up to 250-300 DEG C with the programming rate of 1-10 DEG C/min, and constant temperature 0.5-3h.
8. preparation method according to claim 1, is characterized in that, the step of described carbonization is progressively warming up to 500-1000 DEG C with the programming rate of 1-20 DEG C/min in inert gas, and constant temperature 0.5-5h.
9. the preparation method according to any one of claim 1 to 8, is characterized in that, the diameter of described silicon nanoparticle is less than 150nm.
10. a silicon-carbon composite microsphere negative electrode material, for lithium ion battery, is characterized in that, is that the preparation method according to claim 1 to any one of claim 9 obtains.
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Cited By (17)
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| CN112652742A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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| CN112786848A (en) * | 2019-11-18 | 2021-05-11 | 多氟多化工股份有限公司 | Silicon-based negative electrode material |
| CN110844910A (en) * | 2019-11-19 | 2020-02-28 | 北京卫蓝新能源科技有限公司 | Preparation method of silicon-based negative electrode material of lithium ion battery |
| CN111517317A (en) * | 2020-01-21 | 2020-08-11 | 西安隆基锂电新材料有限公司 | Silicon-carbon composite negative electrode material and preparation method thereof |
| CN111517317B (en) * | 2020-01-21 | 2023-02-17 | 西安隆基锂电新材料有限公司 | Silicon-carbon composite negative electrode material and preparation method thereof |
| CN113493194A (en) * | 2020-04-08 | 2021-10-12 | 万文文 | Preparation method of high-conductivity silicon-carbon composite material |
| CN112201787A (en) * | 2020-09-16 | 2021-01-08 | 深圳大学 | High-capacity negative electrode bonding system, negative electrode and lithium ion battery |
| CN112310382A (en) * | 2020-11-23 | 2021-02-02 | 山东硅纳新材料科技有限公司 | SiCO-Si microsphere prepared by coating Si with SiCO and preparation method thereof |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN114447284B (en) * | 2022-01-13 | 2024-04-05 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN114566634A (en) * | 2022-03-04 | 2022-05-31 | 深圳石墨烯创新中心有限公司 | Titanium dioxide coated silicon carbon nanofiber composite material and preparation method and application thereof |
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