CN109216686B - Silicon-carbon composite material of lithium ion battery and preparation method thereof - Google Patents
Silicon-carbon composite material of lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon-carbon composite material of a lithium ion battery and a preparation method thereof, belonging to the technical field of lithium ion batteries. The composite material comprises: the composite material is a porous secondary structure with micron size, and is prepared by mixing nano silicon, a carbon material, a metal salt and an organic carbon source solution, and performing spray pyrolysis and sintering carbonization. The composite material can fully exert the synergistic effect of silicon, carbon and metal materials, the electrochemical capacity of the silicon material is high, the carbon material increases the conductivity, and the inert metal or metal silicide can further increase the conductivity and reduce the volume change; the porous secondary structure effectively increases tap density and accommodates the volume expansion of silicon to relieve mechanical stress.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery silicon-carbon composite material and a preparation method thereof.
Background
Graphite-based carbon negative electrode materials are still widely used in commercial lithium ion batteries due to good charge-discharge cycle stability, but their theoretical capacity is very limited (372 mAh/g). With the development of consumer electronics and electric automobiles, people have higher and higher requirements on the energy density of lithium ion batteries, and the development of new high-capacity lithium ion battery cathode materials is urgently needed. Among various novel lithium storage anode materials, silicon has the highest theoretical capacity (4212 mAh/g); meanwhile, the silicon-based negative electrode material also has the advantages of wide source, low price, low lithium intercalation potential, no toxicity and the like. Silicon is therefore considered as the most promising next-generation anode material for commercial applications.
However, silicon undergoes severe volume expansion and contraction during charge and discharge, which causes continuous pulverization of silicon, resulting in gradual detachment between an electrode active material and a current collector and loss of electrical contact with the current collector, resulting in rapid degradation of electrode cycle performance. Meanwhile, with the damage of the electrode structure, a new solid electrolyte film (SEI) is continuously formed on the newly exposed silicon surface in the contact process with the electrolyte, so that a stable SEI is difficult to form, the charge and discharge efficiency is reduced, and the capacity attenuation is increased. In addition, silicon itself is a semiconductor material, and has low conductivity, and a conductive agent needs to be added to improve the electronic conductivity of the electrode. In order to effectively apply silicon materials to lithium ion batteries, the first charge-discharge coulombic efficiency and the electrochemical cycle stability of the silicon materials need to be improved.
At present, in order to reduce the volume expansion of silicon in the lithium ion deintercalation process and obtain a silicon-based negative electrode material with higher capacity and more stable cyclicity, research works at home and abroad mainly focus on the nanocrystallization of silicon materials and the preparation of silicon-based composite materials with various shapes and structures based on nano silicon.
For example, CN102208636A discloses a method for preparing porous silicon/carbon composite material by using diatomite as raw material and its application, specifically discloses: firstly, diatomite is used as a silicon source to prepare porous silicon, and then the porous silicon and a carbon material are compounded to prepare the porous silicon/carbon composite material, so that the preparation cost is reduced and the volume effect of silicon is relieved.
Nian Liu et al reported a Si @ C of yolk-shell structure. The Si is completely encapsulated by a thin carbon layer, with an intermediate interstitial layer that allows the Si particles to freely expand without damaging the carbon layer. Under 0.1C, the Si @ C discharge capacity can reach 2800 mAh/g; after 1000 cycles, the capacity remains 74% (Nian Liu et al. A yolk-shell design for stabilized and scalable Li-ion battery alloys [ J ]. Nano Lett,2012,12(6): 3315).
Sujong Chae et al prepared Fe-Cu-Si ternary composites by spray pyrolysis method, reversible capacity of 1287mAh/g, coulombic efficiency of 91% (Sujong Chae al. micron-sized Fe-Cu-Si ternary composites for high Energy Li-ion batteries [ J ]. Energy environ. Sci.,2016,9, 1251-1257).
CN102790204A discloses a preparation method of a silicon-carbon lithium ion battery cathode material, which specifically discloses: firstly, mixing a polymer solution with silicon powder and graphite to obtain a mixed solution; and then freeze-drying to remove the solvent, and finally sintering at high temperature to obtain the silicon-carbon lithium ion battery cathode material.
CN104332594A discloses a silicon-based negative electrode material, and a preparation method and an application thereof, the silicon-based negative electrode material includes graphene having a layered structure, nano silicon particles and nano metal particles, and the nano silicon particles and the nano metal particles are both embedded in the layered structure of the graphene.
Although the silicon-based negative electrode materials relieve the volume expansion and contraction effect generated when the silicon materials insert and remove lithium to a certain extent, because the silicon-based negative electrode materials have larger specific surface area, a large amount of lithium ions can be consumed in the circulation process and the contact with electrolyte, so that the increase of side reaction and the reduction of coulombic efficiency are caused, and the circulation performance and the capacity retention rate are further reduced; on the other hand, the single silicon-carbon, silicon-metal and other composite materials cannot completely solve the problems of silicon materials, either the volume expansion effect cannot be completely solved, or the conductivity is still to be improved, or the preparation cost is high, so that the practical application of the composite materials is influenced.
Disclosure of Invention
The invention aims to provide a silicon-carbon composite material which has the advantages of low cost, high specific capacity, low volume expansion effect, high conductivity and good compatibility with a battery electrolyte.
In order to achieve the above object, the present invention provides a lithium ion battery silicon carbon composite material, which comprises: the composite particle comprises nano silicon, carbon materials, nano inert metal or metal silicide and a carbon layer coated on the surface of the composite particle; the silicon-carbon composite material of the lithium ion battery is a porous secondary structure with micron size.
The composite material provided by the invention is a porous secondary structure with micron size, wherein a plurality of nano-sized silicon, carbon, inert metal or metal silicide particles are embedded, and meanwhile, the outer layer is uniformly coated with pyrolytic carbon, so that the synergistic effect of silicon, carbon and metal materials can be fully exerted; and the porous secondary structure effectively improves the tap density and adapts to the volume expansion of silicon to relieve mechanical stress.
Preferably, the particle size of the nano silicon is 50-900nm, the particle size of the carbon material is 10nm-100 μm, the particle size of the nano inert metal or the metal silicide is 10-100nm, and the thickness of the carbon layer is 10-50 nm.
Preferably, the lithium ion battery silicon-carbon composite material comprises, by mass, 10-60% of nano silicon, 30-80% of a carbon material, 5-20% of a nano inert metal or metal silicide and 5-20% of a carbon layer. By adjusting the silicon, carbon material and inactive metal base material, the volume expansion, coulombic efficiency and specific capacity of the composite material can be controlled, thereby regulating and controlling the capacity and cycle life of the electrode material.
Preferably, the lithium ion battery silicon-carbon composite material has the micropore size of 30-l00nm and the porosity of 10-100%. The pores facilitate electrolyte wetting and accelerate ion conduction.
The invention also provides a method for preparing the silicon-carbon composite material of the lithium ion battery, which comprises the following steps:
(1) mixing nano silicon, a carbon material, a metal salt and an organic carbon source solution to obtain a precursor solution;
(2) spray drying the precursor solution to obtain a primary Si-C-M composite material product;
(3) dispersing the Si-C-M composite material primary product in an organic carbon source solution, removing the solvent, and then sintering and carbonizing in an inert atmosphere to obtain the lithium ion battery silicon-carbon composite material.
Preferably, the nano silicon is prepared by mixing and ball-milling a silicon dioxide raw material and a metal reducing agent, then soaking in acid to remove impurities, and separating. And (3) initiating a reduction reaction of the silicon dioxide raw material in the mechanical ball milling process to obtain the nano silicon particles. More preferably, the particle size of the prepared nano silicon is 50-200 nm.
The invention starts from low-cost silicon dioxide raw materials, adopts a mechanical ball milling method to prepare the nano silicon, greatly saves the production cost, and optimally, the silicon dioxide raw materials and the metal reducing agent are ball milled on a ball mill according to the molar ratio of 1: 2.
Preferably, the raw material of the silicon dioxide is diatomite, mesoporous silicon dioxide, porous molecular sieve, quartz stone or artificially synthesized silicon dioxide; the metal reducing agent is magnesium, calcium, lithium, sodium or potassium metal powder. The acid is hydrochloric acid or sulfuric acid.
Preferably, the carbon material is at least one of natural graphite, artificial graphite, expanded graphite, graphene, carbon black, activated carbon and carbon nanotubes. The particle size of the carbon material is 10nm-100 mu m.
Preferably, the metal salt is at least one of iron, copper, zinc, manganese, cobalt and nickel salt. More preferably, the metal salt is iron nitrate, copper nitrate or manganese nitrate.
More preferably, in the step (1), the ratio of nano-silicon: carbon material: the mass ratio of the metal salt is 1:1: 0.5.
Preferably, in the steps (1) and (3), the organic carbon source is at least one of sucrose, glucose, fructose, citric acid, starch, cellulose, pitch, coal tar, styrene butadiene rubber, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl chloride, polystyrene, polyacrylonitrile, furfural resin, phenolic resin, and epoxy resin.
The organic carbon source can be water, ethanol, butanol, methanol, acetone, ethyl acetate, tetrahydrofuran, N-methylpyrrolidone, drive, chloroform or cyclohexane.
More preferably, in the step (1), the organic carbon source solution is an aqueous glucose solution, an aqueous citric acid solution or an aqueous sucrose solution; in the step (3), the organic carbon source solution is a pitch-tetrahydrofuran solution, a polyacrylonitrile-ethanol solution or an epoxy resin-ethanol solution.
In the step (2), the precursor solution is atomized by a spray drying method, and a microporous structure is formed along with solvent volatilization and precursor decomposition. According to the invention, nano silicon, carbon materials and metal particles are uniformly distributed in the porous microspheres coated by the carbon source through atomization. Preferably, after the precursor solution is atomized, the precursor solution is carried into the reaction furnace by a carrier gas and is subjected to in-situ spray pyrolysis at the temperature of 200-900 ℃.
In the step (3), a carbon source is further carbonized and wrapped, which is beneficial to increasing the structural stability and the conductivity of the composite material. The carbon layer is amorphous carbon. The temperature of the sintering carbonization is 600-1200 ℃. In the step, the pores and the structure of the composite material can be regulated and controlled through carbon source coating. Preferably, the mass ratio of the Si-C-M composite material primary product to the organic carbon source is 4: 1.
In the heating carbonization process, the metal salt generates inert metal or metal silicide particles, further increases the conductivity and reduces the volume change, thereby reducing the side effect and improving the coulombic efficiency.
The invention has the following beneficial effects:
(1) the silicon-carbon composite material provided by the invention is a porous secondary structure with micron size and composed of nano crystals, the material can fully exert the synergistic effect of silicon, carbon and metal materials, the electrochemical capacity of the silicon material is high, the carbon material increases the conductivity, and the inert metal or metal silicide can further increase the conductivity and reduce the volume change; the porous secondary structure effectively increases tap density and accommodates the volume expansion of silicon to relieve mechanical stress.
(2) The invention starts from low-cost silicon dioxide raw materials, adopts a mechanical ball milling method to prepare nano silicon, and then prepares the micron silicon-carbon composite material consisting of nano crystals by mixing with carbon materials, metal salts and organic carbon sources, spray pyrolysis and pyrolysis carbonization.
Drawings
Fig. 1 is a first charge-discharge curve diagram of a silicon-carbon composite-based battery prepared in example 1;
fig. 2 is a graph showing the cycle of the silicon-carbon composite-based battery prepared in example 1.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be purely exemplary of the invention and are not intended to limit its scope. In addition, it should be understood that the modification of the non-essential modification made by the person skilled in the art according to the above summary of the invention should fall within the protection scope of the present invention.
Example 1
Firstly, ball-milling silicon dioxide raw materials of diatomite and magnesium powder on a ball mill according to the molar ratio of 1:2, then soaking the ball-milled mixture in hydrochloric acid, then washing with deionized water, ethanol and the like, separating and drying to obtain the nano silicon.
Then, 0.2g of synthesized nano silicon powder particles with the particle size of 50nm, 0.2g of graphite and 0.1g of ferric nitrate are respectively and independently added into a glucose aqueous solution with the concentration of 0.2M, and ultrasonic dispersion is carried out for 30min to form a uniformly-hooked suspension or solution; then the three solutions are put together and mixed evenly.
Secondly, carrying out spray pyrolysis on the obtained mixed solution at 200 ℃ by adopting a spray drying method to prepare a primary Si-C-M composite material;
then, 0.2g of the above Si-C composite and 0.05g of pitch were dispersed in tetrahydrofuran by sonication for 90min to form a uniform suspension, which was then dried under vacuum at 80 ℃ to obtain a mixture of Si-C-M composite particles and pitch.
And finally, putting the mixture of the dried Si-C-M composite particles and the asphalt into a tubular furnace, and roasting and carbonizing at 900 ℃ under the protection of argon to obtain the final Si-C-M composite material.
Example 2
Firstly, a silicon dioxide raw material porous molecular sieve and lithium blocks are ball-milled on a ball mill according to the mol ratio of 1:2, then the ball-milled mixture is soaked in sulfuric acid, and then the mixture is washed by deionized water, ethanol and the like, separated and dried to obtain the nano silicon.
Then, 0.2g of synthesized nano silicon powder particles with the particle size of 100nm, 0.2g of graphite and 0.1g of copper nitrate are respectively and independently added into a citric acid aqueous solution with the concentration of 0.2M, and ultrasonic dispersion is carried out for 30min to form a uniformly-hooked suspension or solution; then the three solutions are put together and mixed evenly.
Secondly, carrying out spray pyrolysis on the obtained mixed solution at 500 ℃ by adopting a spray drying method to prepare a primary Si-C-M composite material;
then, 0.2g of the Si-C-M composite material primary product and 0.05g of polyacrylonitrile are ultrasonically dispersed in ethanol for 90min to form uniform suspension, and then vacuum drying is carried out at 80 ℃ to obtain a mixture of Si-C-M composite particles and polyacrylonitrile.
And finally, putting the dried mixture of the Si-C-M composite particles and polyacrylonitrile into a tubular furnace, and roasting and carbonizing at 1000 ℃ under the protection of argon to obtain the final Si-C-M composite material.
Example 3
Firstly, silica raw material quartz stone and sodium blocks are ball-milled on a ball mill according to the molar ratio of 1:2, then the ball-milled mixture is soaked in hydrochloric acid, and then the mixture is washed by deionized water, ethanol and the like, separated and dried to obtain the nano silicon.
Then, 0.2g of synthesized nano silicon powder particles with the particle size of 200nm, 0.2g of graphite and 0.1g of manganese nitrate are respectively and independently added into a sucrose aqueous solution with the concentration of 0.2M, and ultrasonic dispersion is carried out for 30min to form a uniformly-hooked suspension or solution; then the three solutions are put together and mixed evenly.
Secondly, carrying out spray pyrolysis on the obtained mixed solution at 700 ℃ by adopting a spray drying method to prepare a primary Si-C-M composite material;
then, 0.2g of the above Si-C composite material primary product and 0.05g of epoxy resin were ultrasonically dispersed in ethanol for 90min to form a uniform suspension, which was then vacuum-dried at 80 ℃ to obtain a mixture of Si-C-M composite particles and epoxy resin.
And finally, putting the mixture of the dried Si-C-M composite particles and the epoxy resin into a tubular furnace, and roasting and carbonizing at 1200 ℃ under the protection of argon to obtain the final Si-C-M composite material.
Example 4
Firstly, ball-milling silicon dioxide raw materials of diatomite and magnesium powder on a ball mill according to the molar ratio of 1:2, then soaking the ball-milled mixture in hydrochloric acid, then washing with deionized water, ethanol and the like, separating and drying to obtain the nano silicon.
Then, 0.2g of synthesized nano silicon powder particles with the particle size of 50nm, 0.2g of graphite, 0.05g of carbon nano tubes and 0.1g of ferric nitrate are respectively and independently added into a 0.2M glucose aqueous solution, and are subjected to ultrasonic dispersion for 30min to form uniformly-hooked suspension or solution; then the four solutions are put together and mixed evenly.
Secondly, carrying out spray pyrolysis on the obtained mixed solution at 200 ℃ by adopting a spray drying method to prepare a primary Si-C-M composite material;
then, 0.2g of the above Si-C composite primary product and 0.05g of pitch were dispersed in tetrahydrofuran by ultrasonic for 90min to form a uniform suspension, followed by vacuum drying at 80 ℃ to obtain a mixture of Si-C-M composite particles and pitch.
And finally, putting the mixture of the dried Si-C-M composite particles and the asphalt into a tubular furnace, and roasting and carbonizing at 900 ℃ under the protection of argon to obtain the final Si-C-M composite material.
Application example
Taking the silicon-carbon composite material prepared in the examples 1-4 as a negative electrode active substance, taking carbon black (SP) as a conductive agent, taking carboxymethylcellulose sodium (CMC) and Styrene Butadiene Rubber (SBR) as an adhesive, mixing the SP, the CMC and the SBR in a mass ratio of 90:5:2:3, taking deionized water as a dispersing agent, stirring to prepare slurry with solid content of about 50% and viscosity of 2000-4000mPa.s, coating the slurry on a copper foil, drying, cold pressing, cutting into pieces and slitting to prepare a negative electrode plate of a button cell or a flexible package cell; the electrolyte is prepared into LiPF with the concentration of l M6A lithium salt, a mixture of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio EC: EMC: DEC ═ 1:1:1 as a nonaqueous organic solvent.
The button cell prepared by the method with the silicon-carbon composite material prepared in the example 1 as the negative active material is subjected to an initial capacity test and a cycle performance test under the conditions that the current density is 200mA/g and the voltage interval is 0.01-2.5V, and the results shown in the figure 1 and the figure 2 are respectively obtained.
As can be seen from fig. 1 and 2, this material has excellent discharge capacity. Under the current density of 200mA/g, the specific discharge capacity of the first circle of the Si-C-M electrode is 1113mAh/g, and the coulomb efficiency of the first circle is 87%. The capacity is still kept at 970mAh/g after 80 cycles, and the coulomb efficiency is maintained at 100% in 80 cycles. This indicates that the porous secondary microcomposite exhibits superior structural advantages and can effectively provide sufficient space to accommodate the expansion and pulverization of Si. The silicon-carbon composite material has excellent electrochemical performance and can be used as a good cathode material of a lithium ion battery.
Claims (4)
1. A silicon-carbon composite material for a lithium ion battery, comprising: the composite particle comprises nano silicon, carbon materials, nano inert metal or metal silicide and a carbon layer coated on the surface of the composite particle; the silicon-carbon composite material of the lithium ion battery is a porous secondary structure with micron size;
the grain size of the nano silicon is 50-900nm, the grain size of the carbon material is 10nm-100 mu m, the grain size of the nano inert metal or the metal silicide is 10-100nm, and the thickness of the carbon layer is 10-50 nm;
the lithium ion battery silicon-carbon composite material comprises, by mass, 10-60% of nano silicon, 30-80% of carbon material, 5-20% of nano inert metal or metal silicide and 5-20% of carbon layer;
the preparation method of the silicon-carbon composite material of the lithium ion battery comprises the following steps:
(1) mixing nano silicon, a carbon material, a metal salt and an organic carbon source solution to obtain a precursor solution;
(2) after the precursor solution is atomized, the precursor solution is carried into a reaction furnace by carrier gas and is subjected to in-situ spray pyrolysis at the temperature of 200-900 ℃ to obtain an initial product of the Si-C-M composite material;
(3) dispersing the Si-C-M composite material primary product in an organic carbon source solution, removing the solvent, and then sintering and carbonizing in an inert atmosphere to prepare the silicon-carbon composite material of the lithium ion battery;
the carbon material is at least one of natural graphite, artificial graphite, expanded graphite, graphene, carbon black, activated carbon and carbon nanotubes;
the metal salt is ferric nitrate, cupric nitrate or manganese nitrate;
in the step (1), the organic carbon source solution is a glucose aqueous solution, a citric acid aqueous solution or a sucrose aqueous solution; in the step (3), the organic carbon source solution is a pitch-tetrahydrofuran solution, a polyacrylonitrile-ethanol solution or an epoxy resin-ethanol solution.
2. The silicon-carbon composite material for lithium ion batteries according to claim 1, wherein the silicon-carbon composite material for lithium ion batteries has a pore size of 30 to 100nm and a porosity of 10 to 100%.
3. The silicon-carbon composite material for the lithium ion battery of claim 1, wherein the nano-silicon is prepared by mixing and ball-milling a silicon dioxide raw material and a metal reducing agent, then soaking in acid to remove impurities, and separating.
4. The silicon-carbon composite material for lithium ion batteries according to claim 3, wherein the silica raw material is diatomaceous earth, mesoporous silica, porous molecular sieve, quartz stone, or synthetic silica; the metal reducing agent is magnesium, calcium, lithium, sodium or potassium metal powder.
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| CN115072697B (en) * | 2022-05-05 | 2023-08-11 | 广东邦普循环科技有限公司 | Preparation method and application of silicon-carbon composite anode material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007627A (en) * | 2008-04-18 | 2011-04-06 | 株式会社丰田自动织机 | Negative electrode for lithium ion secondary battery, and method for production thereof |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007627A (en) * | 2008-04-18 | 2011-04-06 | 株式会社丰田自动织机 | Negative electrode for lithium ion secondary battery, and method for production thereof |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN104332621A (en) * | 2014-09-27 | 2015-02-04 | 奇瑞汽车股份有限公司 | Method for preparing hollow nano silicon microsphere through metal thermal reduction and lithium ion battery |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
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