CN101944596A - Preparation method of silicon and carbon composite microspheres and application thereof - Google Patents
Preparation method of silicon and carbon composite microspheres and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of silicon and carbon composite microspheres and an application thereof as a negative electrode material of a lithium ion battery. The preparation method of the silicon and carbon composite microspheres comprises the following steps: 1) spray drying is carried out on solution containing a silicon source and a carbon source, thus obtaining spherical particles, wherein the carbon source is carbon-containing high molecular polymer; and 2) the spherical particles are sintered under non-oxidizing atmosphere, thus obtaining the silicon and carbon composite microspheres. The preparation method is simple and practicable, can realize large-scale production and has high practicality degree, and the obtained silicon and carbon composite microspheres integrate the advantages of a silicon and carbon composite material and a porous material and improve the problems of poor cyclicity and low coulomb efficiency of a silicon-based material as the negative electrode material of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-carbon complex microsphere and as the application of lithium ion battery negative material.
Background technology
Lithium ion battery is because of it has operating voltage height, specific energy height, capacity is big, self discharge is little, cyclicity is good, the ideal source of long service life, in light weight, outstanding advantage becomes portable electric appts such as mobile phone, notebook computer such as volume is little.In order to satisfy instructions for use, high power capacity, extended-life lithium ion battery become an important research direction of lithium ion battery development.Because the specific capacity of positive electrode is relatively low, the room for promotion of capacity is little, so the development work of high-capacity lithium ion cell mainly concentrates on negative material.The existing commercial negative material that uses is material with carbon element, and its theoretical specific capacity only has 372mAh/g, and therefore seeking the high power capacity negative material that substitutes carbon becomes an important research direction.
Because silicon has high theoretical specific capacity (4200mAh/g) and lower embedding lithium current potential, and in the earth abundant, lower, the environmental sound of cost of reserves, be a kind of promising negative material.Yet in charge and discharge process, the removal lithium embedded process of silicon is followed 310% change in volume, causes that electrode cracking and active material come off from collector, and structure is destroyed gradually, and capacity constantly descends in cyclic process repeatedly.At this shortcoming, mainly improve the cyclicity of silicon materials in recent years by the following aspects:
1, nano silicon material
In order to improve the cycle performance of elemental silicon, the silicon nanometer can be reduced the change in volume of silicon to a certain extent, reduce electrode interior stress.The contraction although silicon nanowires, nano-tube volume in charge and discharge process can expand, length and diameter also can change, but the variation that the space that silicon nanowires or pipe oldered array exist can buffer volumes, make that structure is not broken in the repeated charge process, electronics can flow to nano wire or pipe from collector effectively simultaneously, and the electrolyte that permeates between nano wire or pipe array has shortened the path of lithium ion diffusion, makes it have good cyclicity and high-multiplying power discharge.Although the cyclicity of silicon nanowires, nano-tube is better, but its preparation process complexity, yield poorly, be difficult to satisfy the needs that large-scale industrialization is produced, degree of being practical is low, and the electrode material of therefore seeking a kind of suitability for mass industrialized production is an important directions of lithium ion battery electrode material development.
Spray drying technology is widely used in the suitability for industrialized production as a very ripe granulating technique, the solution that will contain embedded material during spray drying is dispersed into minimum drop by atomizer, and spray into drop is shunk rapidly, hardened in the past at the arrival chamber wall, and carried out drying at last and collect.Spray drying can one the step balling-up, the preparation method is simple and efficient, is one of most promising approach of preparation microballoon industrialization.
2, silicon based composite material
Study more silicon based composite material and mainly contain the silico-carbo composite material, flexibility, good electron conductivity, less density, smaller volume expand (10%) because carbon has preferably, therefore become the active matrix of silicon-based anode material.Carry out after carbon coats at silicon face, help contacting of isolated silicon and electrolyte, reduce surface area, reduce irreversible capacity, also prevent the reunion and the growth of silicon grain in the charge and discharge process simultaneously, thereby improve the capacity maintenance performance of silicon-based anode material.But also there are some problems in Si-C composite material, adopts pyrolysismethod, ball-milling method, vapour deposition process and polymerization-pyrolysismethod etc. during preparation, and the material homogeneity that these methods obtain is relatively poor, and silicon is dispersed bad in carbon matrix, and the interface contact of silicon-carbon is relatively poor.
Except adopting above-mentioned composite material, discover recently, a large amount of hole and the electron channels of design in silicon based composite material, can alleviate the destruction that the silicon materials change in volume causes the electrode material structure in charge and discharge process, keep the good electron migrating channels, make silicon based composite material have good capacity hold facility and high-multiplying power discharge.
Summary of the invention
The purpose of this invention is to provide a kind of silicon-carbon complex microsphere and preparation method thereof.
Silicon-carbon complex microsphere provided by the present invention is to prepare according to the method that comprises the steps:
1) solution that will contain silicon source, carbon source carries out spray drying, obtains spheric granules; Wherein, described carbon source is the high molecular polymer of carbon containing;
2) described spheric granules is carried out sintering under non-oxidizing atmosphere, obtain described silicon-carbon complex microsphere.
Wherein, the source of silicon described in the step 1) can be selected from following at least a: silicon quantum dot, silica flour and silicon monoxide.Described carbon source can be the synthesising macromolecule copolymer and/or the natural polymers of carbon containing; Described synthesising macromolecule copolymer specifically can be at least a in the following substances: phenolic resins, polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC), polyacrylonitrile (PAN); Described natural polymers specifically can be at least a in the following substances: glucan, starch, gelatin, shitosan, sodium carboxymethylcellulose and alginic acid.
The mass ratio of source of silicon described in the step 1) and carbon source can be (0.1～20): (1～50) is preferably (0.1-1): (1～50) specifically can be 0.1: 50,0.1: 20,0.1: 1,1: 1; The mass concentration sum of silicon source and carbon source can be 1～50% in the described solution.
Spray-dired condition is in the step 1): inlet temperature can be 120～200 ℃, and preferred 150～180 ℃, outlet temperature can be 105～150 ℃, preferred 105～120 ℃.
Step 2) non-oxidizing atmosphere described in is provided by following at least a gas: nitrogen, argon gas, hydrogen, helium and carbon dioxide.
The condition of sintering step 2) is: be warming up to 300～1000 ℃ of sintering temperatures by room temperature, keep described sintering temperature 1～30h, be cooled to room temperature; The speed of described intensification is 1～20 ℃/min.
The particle diameter of silicon-carbon complex microsphere provided by the present invention is a micron order, is 1～50 micron as the particle diameter of silicon-carbon complex microsphere; Carbon in the described silicon-carbon complex microsphere exists with the form of amorphous carbon and/or graphitized carbon, and microballoon inside is the porous carbon skeleton structure.
Further object of the present invention provides the application of described silicon-carbon complex microsphere.
Application provided by the present invention is the application of silicon-carbon complex microsphere as battery electrode material, particularly as the application of lithium ion battery negative material.
The present invention also provides a kind of energy storage elements, and described energy storage elements contains described silicon-carbon complex microsphere, this energy storage elements preferred lithium ion battery.
The present invention also provides a kind of portable electric appts, and this electronic equipment uses above-mentioned energy storage elements, the preferred mobile phone of this portable electric appts, camera, video camera, MP3, MP4, notebook computer.
Compared with prior art, preparation method provided by the invention is simple, suitable for mass production, the degree of being practical height, and the advantage of the silicon-carbon complex microsphere that obtains is integrated Si-C composite material and porous material has improved that silica-base material is poor as the cyclicity that lithium ion battery negative material exists, the inefficient problem of enclosed pasture.
Description of drawings
The electron scanning micrograph of the silicon-carbon complex microsphere that Fig. 1 obtains for embodiment 1.
X-ray diffraction (XRD) collection of illustrative plates of the silicon-carbon complex microsphere that Fig. 2 obtains for embodiment 1.
Fig. 3 is a negative material for the silicon-carbon complex microsphere that obtains with embodiment 1, the charging and discharging curve under 50mA/g constant current charge-discharge condition.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Experimental technique described in the following embodiment if no special instructions, is conventional method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, silicon-carbon complex microsphere and electrochemical property test thereof
In shitosan (weight average molecular weight is 89000): the ratio (mass ratio) of silicon quantum dot=50: 0.1 is mixed, with water is solvent, at room temperature stir more than the 24h, the mass concentration sum that obtains shitosan and silicon quantum dot is 1% solution, spray drying, inlet temperature is 120 ℃, and outlet temperature is 110 ℃.The microballoon speed with 10 ℃/min under nitrogen protection that obtains is risen to 800 ℃ by room temperature, naturally cool to room temperature behind the constant temperature 6h, obtain the silicon-carbon complex microsphere.
The sign of silicon-carbon complex microsphere:
With the particle diameter and the particle size distribution of the silicon-carbon complex microsphere that obtains under the above-mentioned condition of NEC ESEM (JEOL-6700F) detection, the result shows that the particle size distribution of silicon-carbon complex microsphere is more even, and particle diameter is (see figure 1) between 1～50 micron.
With powder x-ray diffraction (Rigaku DmaxrB, CuK
αRay) as can be seen from Figure 2, there is not impurity peaks in the crystal structure (see figure 2) of analysis silicon-carbon complex microsphere in the spectrogram, and the product purity height is described; Because the carbon of gained is noncrystalline structure, so there is not its diffraction maximum.
The chemical property of silicon-carbon complex microsphere characterizes:
The silicon-carbon complex microsphere, acetylene black and the Kynoar binding agent that prepare among the embodiment 1 are made into slurry with mass ratio mixing in 80: 10: 10, are coated to equably on the Copper Foil collector and obtain cathode membrane.As collection, microporous polypropylene membrane (Celgard 2400) is as barrier film with metal lithium sheet, 1mol/L LiPF
6(solvent is that volume ratio is 1: 1 ethylene carbonate and a dimethyl carbonate mixed liquor) is assembled into the Swagelok pattern and intends battery as electrolyte in the glove box of argon shield.
The battery of above-mentioned assembling is carried out the constant current charge-discharge test on Arbin BT2000 charge-discharge test instrument, charge-discharge magnification is 50mA/g, and the charging/discharging voltage interval is 0～2.0V, and charging and discharging curve is seen Fig. 3.The composition and the simulated battery test result of the silicon-carbon complex microsphere for preparing in the present embodiment are listed in table 1.
The preparation of embodiment 2, silicon-carbon complex microsphere and electrochemical property test thereof
In shitosan (weight average molecular weight is 89000): the ratio (mass ratio) of silica flour=20: 0.1 is mixed, and is solvent with water, at room temperature stirs more than the 24h, and the mass concentration sum that obtains shitosan and silica flour is 5% solution.Polymer solution is carried out spray drying, and inlet temperature is 150 ℃, and outlet temperature is 120 ℃.The microballoon that obtains rises to 300 ℃ with 15 ℃/min) speed by room temperature under nitrogen protection, reduce to room temperature with the speed of 10 ℃/min behind the constant temperature 6h, obtains the silicon-carbon complex microsphere.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained silicon-carbon complex microsphere reaches and lists in table 1 in the test result of simulated battery.
The preparation of embodiment 3, silicon-carbon complex microsphere and electrochemical property test thereof
In sodium carboxymethylcellulose (weight average molecular weight is 250000): the ratio (mass ratio) of silicon monoxide=1: 0.1 is mixed, with water is solvent, at room temperature stir more than the 24h, the mass concentration sum that obtains sodium carboxymethylcellulose and silicon monoxide is 50% solution.Polymer solution is carried out spray drying, and inlet temperature is 180 ℃, and outlet temperature is 105 ℃.The microballoon that obtains speed with 20 ℃/min under nitrogen protection rises to 1000 ℃ by room temperature, reduces to room temperature with the speed of 10 ℃/min behind the constant temperature 6h, obtains the silicon-carbon complex microsphere.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained silicon-carbon complex microsphere reaches and lists in table 1 in the test result of simulated battery.
The preparation of embodiment 4, silicon-carbon complex microsphere and electrochemical property test thereof
In starch (weight average molecular weight is 300000): the ratio (mass ratio) of silicon monoxide=1: 1 is mixed, and is solvent with water, at room temperature stirs more than the 24h, obtains starch and silicon monoxide mass concentration sum and be 20% solution.Polymer solution is carried out spray drying, and inlet temperature is 125 ℃, and outlet temperature is 120 ℃.The microballoon that obtains speed with 10 ℃/min under nitrogen protection rises to 1000 ℃ by room temperature, reduces to room temperature with the speed of 10 ℃/min behind the constant temperature 6h, obtains the silicon-carbon complex microsphere.
The positive pole of simulated battery, negative pole, electrolyte and battery assembling are identical with embodiment 1, and the composition of gained silicon-carbon complex microsphere reaches and lists in table 1 in the test result of simulated battery.
The composition of table 1, silicon-carbon complex microsphere reaches the test result of constant current charge-discharge under the 50mA/g condition
According to the result of table 1 as can be seen, the silicon-carbon complex microsphere discharge capacity of the present invention's preparation can reach 1000mAh/g, enclosed pasture efficient can reach more than 90%, has improved poor, the inefficient problem of enclosed pasture of cycle performance that the silicon-based anode material exists to a great extent.
Claims (10)
1. method for preparing the silicon-carbon complex microsphere may further comprise the steps:
1) solution that will contain silicon source, carbon source carries out spray drying, obtains particle; Wherein, described carbon source is the high molecular polymer of carbon containing;
2) described particle is carried out sintering under non-oxidizing atmosphere, obtain described silicon-carbon complex microsphere.
2. method according to claim 1 is characterized in that: the source of silicon described in the step 1) is selected from following at least a: silicon quantum dot, silica flour and silicon monoxide.
3. method according to claim 1 and 2 is characterized in that: carbon source described in the step 1) is the synthesising macromolecule copolymer and/or the natural polymers of carbon containing; Described synthesising macromolecule copolymer is preferably at least a in the following substances: phenolic resins, polyvinylidene fluoride, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol oxide, polyvinyl chloride and polyacrylonitrile; Described natural polymers is preferably at least a in the following substances: glucan, starch, gelatin, shitosan, sodium carboxymethylcellulose and alginic acid.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: the mass ratio of source of silicon described in the step 1) and carbon source is (0.1～20): (1～50); The mass concentration sum of silicon source and carbon source is 1～50% in the described solution.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: spray-dired condition is described in the step 1): inlet temperature is 120～200 ℃, preferred 150～180 ℃; Outlet temperature is 105～150 ℃, preferred 105～120 ℃.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: step 2) described in non-oxidizing atmosphere provide by following at least a gas: nitrogen, argon gas, hydrogen, helium and carbon dioxide;
The condition of sintering step 2) is: rise to 300～1000 ℃ of sintering temperatures by room temperature, keep described sintering temperature 1～30h, be cooled to room temperature; Heating rate is 1～20 ℃/min.
7. the silicon-carbon complex microsphere that arbitrary described method prepares among the claim 1-6.
8. the described silicon-carbon complex microsphere of claim 7 is as the application of battery electrode material, particularly as the application of lithium ion battery negative material.
9. an energy storage elements is characterized in that: contain the described silicon-carbon complex microsphere of claim 7.
10. a portable electric appts is characterized in that: use the described energy storage elements of claim 9.
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN102593418A (en) * | 2012-02-24 | 2012-07-18 | 奇瑞汽车股份有限公司 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
| CN102694155A (en) * | 2012-05-31 | 2012-09-26 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same |
| CN103000901A (en) * | 2012-11-20 | 2013-03-27 | 江苏科捷锂电池有限公司 | Preparation method of high-capacity SiC negative electrode material |
| CN103311522A (en) * | 2013-05-31 | 2013-09-18 | 中国科学院过程工程研究所 | Silicon/carbon composite microsphere negative electrode material as well as preparation method and application for same |
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| CN104953092A (en) * | 2015-05-12 | 2015-09-30 | 浙江天能能源科技有限公司 | Lithium ion battery negative material and preparation method thereof |
| CN105280894A (en) * | 2014-07-17 | 2016-01-27 | Oci有限公司 | Manufacturing method of carbon-silicon composite |
| CN105304882A (en) * | 2014-07-25 | 2016-02-03 | 中国科学院物理研究所 | Preparation method of lithium-sulfur battery cathode material, lithium-sulfur battery cathode material and battery |
| CN105609711A (en) * | 2014-11-21 | 2016-05-25 | 国家纳米科学中心 | Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof |
| CN105742611A (en) * | 2016-05-06 | 2016-07-06 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery negative material, preparation method thereof and lithium ion battery |
| CN106159213A (en) * | 2015-03-24 | 2016-11-23 | 南京安普瑞斯有限公司 | A kind of Si-C composite material and preparation method thereof and the application on lithium ion battery |
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| CN102593418A (en) * | 2012-02-24 | 2012-07-18 | 奇瑞汽车股份有限公司 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
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| CN109004188B (en) * | 2018-07-09 | 2022-03-25 | 绍兴文理学院 | Green preparation method of porous carbon-silicon composite material |
| CN109817908A (en) * | 2019-01-03 | 2019-05-28 | 欣旺达电子股份有限公司 | Si-C composite material and preparation method thereof, lithium ion battery |
| CN109817966B (en) * | 2019-01-07 | 2022-01-04 | 宁波维科电池有限公司 | Preparation method of lithium ion battery cathode composite material |
| CN109817966A (en) * | 2019-01-07 | 2019-05-28 | 宁波维科电池有限公司 | A kind of preparation method of composite cathode material of lithium ion battery |
| CN117117159A (en) * | 2023-10-24 | 2023-11-24 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
| CN117117159B (en) * | 2023-10-24 | 2023-12-26 | 琥崧智能装备(太仓)有限公司 | Silicon-carbon negative electrode material and preparation method and application thereof |
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