CN109659548B - Co-SiO with core-shell structure2Preparation method of/C negative electrode material - Google Patents
Co-SiO with core-shell structure2Preparation method of/C negative electrode material Download PDFInfo
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Abstract
The invention provides Co-SiO with a core-shell structure2The preparation method of the/C negative electrode material comprises the steps of dissolving cobalt salt and a surfactant in dilute hydrochloric acid, then adding silicate, stirring and heating, standing, cooling, washing with water, and carrying out suction filtration to prepare the cobalt-doped nano SiO2Sol, calcining, washing and drying to obtain cobalt-doped nano SiO2Powder, then cobalt-doped nano SiO2Adding the powder into an organic solvent, adding a silanization reagent, refluxing, filtering, washing, drying and carbonizing to obtain Co-SiO2a/C composite material. The invention solves the problem of poor cycle performance caused by cracking and pulverization due to huge volume change generated in the process of lithium intercalation and deintercalation.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, relates to a lithium ion battery cathode material and a preparation method thereof, and particularly relates to a core-shell silicon-carbon cathode material for a lithium ion battery.
Background
The demand of society for energy sources is increasing due to continuous progress and development, and the main energy stone fuel (coal, petroleum and natural gas) resources in the world are gradually exhausted. The lithium ion battery is clean and pollution-free due to the high energy conversion efficiency, and becomes an ideal energy storage and conversion device, and is widely applied to daily life of people. However, the lithium ion batteries commercialized at present have failed to satisfy the demand for high energy density and high power sources. In the aspect of lithium ion battery cathode materials, the theoretical specific capacity of the graphite materials widely used at present is 372mAh/g, and the further improvement of the specific capacity of the lithium ion battery is limited, so that the development and research of novel high-specific-capacity and high-safety cathode materials are urgent.
Silicon is considered as an ideal negative electrode material for the new generation of lithium ion batteries due to high theoretical specific lithium storage capacity (4200mAh/g) and moderate lithium intercalation and deintercalation potential. However, during lithium deintercalation, silicon expands up to 300% in volume, severely affecting the cycling stability of the electrode. Li formed during the first discharge of a siloxane material compared to elemental silicon2O and a series of lithium silicates (Li)2SiO3，Li2SiO4And Li2Si2O5) The silicon compound electrode has relatively better cycling stability because the silicon has a certain buffer effect on the volume expansion during the subsequent cycling process. For the silicon dioxide with good crystal form, because the Si-O bond is very stable, the silicon dioxide hardly shows electrochemical activity, a patent (CN 201610130175.3) reports that the theoretical specific capacity of an amorphous silicon dioxide negative electrode material reaches 1965 mAh.g-1, which is far higher than that of the conventional graphite negative electrode material, the content of the silicon dioxide in the nature is higher, a charge and discharge platform is lower, but the silicon dioxide with a micron structure is difficult to realize lithium storage activity, and the silicon dioxide cannot be practically used in a lithium ion battery. The silica/hard carbon composite material is prepared by a research group of Mega-Xiang professor Wang of the institute of Physics of Chinese academy of sciences by using TEOS as a silicon source and adopting a hydrothermal method. The first reversible specific capacity of the electrode prepared by the material is up to 630 mAh/g (B.K. Guo, J. Shu, et al. Electrochemistry Communications 10 (2008): 1876-. It should be due to the fact that the silicon-oxygen compound is accompanied by a large volume change during the lithium deintercalation, causing cracking and powdering, thereby affecting the cycle performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the core-shell nano SiO2A negative electrode material and a preparation method thereof. The method is characterized in that: the core is cobalt-doped nano SiO2(SiO generated by silicate and hydrochloric acid2And SiO produced by hydrolysis of silylation agent2) The shell is an organic carbon layer formed by carbonizing a silylation agent. The cathode active material has the advantages of good conductivity, cycle performance, high first effect and the like.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
Co-SiO with core-shell structure2The preparation method of the/C negative electrode material is characterized by comprising the following steps of:
b1, dissolving cobalt salt and surfactant in dilute hydrochloric acid, mixing uniformly to form a mixed solution, then adding silicate into the mixed solution, stirring and heating at the temperature of 150-200 ℃ for 6-8 hours, standing, cooling, washing with water, and carrying out suction filtration to prepare the cobalt-doped nano SiO2Sol is calcined for 3 to 5 hours at the temperature of 550-700 ℃, and then is washed and dried to obtain the cobalt-doped nano SiO2Powder, Co-SiO for short2。
B2, mixing the cobalt prepared in the step B1 with the nano SiO2Adding the powder into a three-neck flask filled with an organic solvent, adding a silanization reagent, refluxing for 8-12h at a reflux temperature above the boiling point of the organic solvent, performing suction filtration, washing with water, drying, and carbonizing in a carbonization furnace to obtain Co-SiO2a/C composite material.
Preferably, the mass ratio of the cobalt salt, the surfactant and the dilute hydrochloric acid is (1-2.5): (5-12.5):24, and the concentration of the dilute hydrochloric acid is 0.01-0.5 mol/L.
Preferably, in the step B1, the silicate is added into the mixed solution according to the mass ratio of 1 (6-9).
Preferably, in step B1, the surfactant is an ionic surfactant or a nonionic surfactant.
Preferably, in step B1, the surfactant is one of polyvinylpyrrolidone (PVP), sodium dodecylbenzenesulfonate and sodium hexadecylbromide.
Preferably, in step B2, the cobalt is doped with nano SiO2The powder was added to a three-necked flask of an organic solvent at 0.8 to 0.4g/ml based on the volume of the organic solvent.
Preferably, in the step B2, the silanization reagent is added according to the cobalt-doped nano SiO2The amount of the powder is determined, and preferably, the addition amount of the silanization reagent is equal to that of the cobalt-doped nano SiO2The mass ratio of the powder is 1 (2-4).
Preferably, in the step B2, the carbonization is performed under an inert atmosphere, the carbonization temperature is 800-1100 ℃, and the carbonization time is 4-8 h.
Preferably, in step B2, the organic solvent is one of ethanol, benzene and toluene; the silanization reagent comprises a molecular formula of CnH(2n+1)Si(OCH3)3、CnH(2n-1)Si(OCH3)3Long chain silylation agents of (4).
Co-SiO with core-shell structure2The preparation method of the/C negative electrode material is characterized by comprising the following steps of:
b1: preparation of cobalt-doped nano SiO2Powder: respectively weighing 2-5g of cobalt salt and 10-25g of surfactant, dissolving in 120g of dilute hydrochloric acid with the concentration of 0.01-0.5mol/L, uniformly mixing to form a mixed solution, then adding 15-24g of silicate into the mixed solution, stirring and heating at the temperature of 150-200 ℃ for 6-8 hours, standing, cooling, washing with water, and carrying out suction filtration to prepare the cobalt-doped nano SiO2Sol, calcining at 550-700 deg.c for 3-5 hr, water washing and drying to prepare nanometer SiO doped with Co2Powder, Co-SiO for short2；
B2: preparation of Co-SiO2the/C composite material: taking 100g of cobalt-doped nano SiO prepared in step B12Adding the powder into a three-neck flask containing 120-300ml of organic solvent, adding 25-35g of silanization reagent, refluxing for 8-12h at a reflux temperature above the boiling point of the organic solvent, performing suction filtration, water washing, drying, and carbonizing in a carbonization furnace under an inert atmosphere at a carbonization temperature of 800-1100 DEG CCarbonizing for 4-8h to prepare Co-SiO2a/C composite material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts the principle of preparing weak acid by strong acid to prepare the precursor material, has simple process, easy operation, no organic volatile component and environmental protection.
(2) The invention is to nano SiO2Doping with Co to SiO2Coordinate bond formation in the skeleton (Co oxide mainly based on cobalt3O4Etc. exist, and Co3O4Is an important transition metal oxide semiconductor), the conductivity of the material is improved.
(3) According to the invention, a silane reagent is grafted on the surface of a precursor, a layer of organic compound is formed in a chemical bond form, and a coating layer is formed after carbonization. And the induction effect of the cobalt element is utilized, so that the coating formed by carbonization is more uniform and ordered, the graphitization degree of the subsequent carbon coating is favorably improved, the conductivity of the material is improved, the first effect of the cathode material is improved, and the reversible capacity of the cathode material is improved.
(4) Co-SiO prepared by the method of the invention2the/C negative electrode material has good cycle performance and high coulombic efficiency, the capacity of the composite material after 100 cycles is 85% of the initial capacity, and the first coulombic efficiency is about 73%. The problem of poor cycle performance caused by cracking and pulverization due to huge volume change generated in the process of lithium desorption and insertion is solved, and the lithium storage activity of micron-sized silicon dioxide and the practical application in lithium ion batteries are realized.
Drawings
FIG. 1 shows the preparation of Co-SiO according to the present invention2Scanning electron microscope images of the/C composite material.
FIG. 2 shows the Co-SiO prepared by the present invention2XRD pattern of the/C composite material.
FIG. 3 is a diagram of SiO material2(a) And composite Co-SiO2UV spectrogram of/C (b).
FIG. 4 shows the preparation of Co-SiO according to the present invention2Raman spectrum of/C composite material.
FIG. 5 shows the preparation of Co-SiO according to the present invention2Cycle performance profile of the/C composite.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to these examples.
Example 1
Co-SiO with core-shell structure2The preparation method and the application of the/C negative electrode material specifically comprise the following steps:
(1) 5g of CoCl was weighed out separately2•6(H2O) and 25g of hexadecyl sodium bromide are dissolved in 120g of dilute hydrochloric acid (the concentration is 0.01 mol/L), the mixture is uniformly mixed, then 24g of sodium silicate is added into the mixed solution, the mixed solution is heated and stirred in water bath at 150 ℃ for 6 hours, and the mixture is stood, cooled, washed and filtered to prepare the cobalt-doped nano SiO2Sol, calcining at 550 deg.c for 3 hr, water washing and drying to prepare nanometer Co-doped SiO2Powder, Co-SiO for short2。
(2) The preparation process of the composite material is as follows: 100g of the Co-SiO prepared in step 1 are taken2Adding into a three-neck flask containing 300ml of toluene, adding 35g of hexadecyl trimethoxy silane, refluxing for 12h at 120 ℃, filtering, washing with water, drying, taking out, placing into a crucible, and then putting into a carbonization furnace, wherein N is2Carbonizing for 4 hours at the temperature of 800 ℃ in atmosphere to prepare Co-SiO2a/C composite material. In the research, a button cell consisting of a working electrode and a metal lithium electrode is adopted to test the electrochemical performance of the electrode material. When the electrode pole piece is manufactured, a negative active material, SBR, CMC and SP (mixed according to the mass ratio of 80: 6: 4: 10) are added with a proper amount of methyl pyrrolidone as a solvent, uniformly dispersed, coated on copper foil, dried in vacuum for 24 hours, finally, a wafer with the diameter of being cut out from the manufactured pole piece is used as a material, a button cell is assembled in a glove box in an argon atmosphere, and the cell is subjected to constant current charging and discharging tests.
Example 2
Co-SiO with core-shell structure2The preparation method and the application of the/C negative electrode material specifically comprise the following steps:
(1) respectively weighing 2g of CoAc2Dissolving 10g sodium dodecyl benzene sulfonate in 120g dilute hydrochloric acid (the concentration is 0.5 mol/L), mixing uniformly, then adding 15g sodium silicate into the mixed solution, stirring and heating in a water bath at 200 ℃ for 8 hours, standing, cooling, washing with water, and filtering to prepare the cobalt-doped nano SiO2Sol, calcining at 700 deg.C for 5 hr, washing with water, and drying to obtain cobalt-doped nano SiO2Powder, Co-SiO for short2。
(2) The preparation process of the composite material is as follows: 100g of the Co-SiO prepared in step 1 are taken2Adding into a three-neck flask containing 120ml of toluene, adding 25g of N-dodecyl trimethyl silane, refluxing for 8h at 120 ℃, filtering, washing with water, drying, taking out, placing into a crucible, and then placing into a carbonization furnace, wherein N is2Carbonizing for 8 hours at the temperature of 1100 ℃ in atmosphere to prepare Co-SiO2a/C composite material. And then assembling the button cell, and carrying out constant current charge and discharge test on the cell.
The electrochemical properties of the materials prepared in examples 1 and 2 at a current density of 0.1A/g are shown in the following table:
for the Co-SiO prepared in example 12the/C composite material is subjected to electron microscope scanning, spectral analysis and performance measurement, and the result characterization analysis is as follows:
core-shell structure Co-SiO prepared in embodiment 1 of the invention2The scanning electron microscope image of the/C composite material is shown in figure 1, and the electron microscope image shows that the composite material has a pore structure.
Core-shell structure Co-SiO prepared in embodiment 1 of the invention2The XRD pattern of the/C composite material is shown in figure 2, and the figure shows that: a wide diffraction peak appears at about 20 degrees, which indicates that the composite material is in an amorphous state.
SiO material in EXAMPLE 1 of the invention2(a) And composite Co-SiO2The UV spectrum of/C (b) is shown in FIG. 3, from which it can be seen that three absorption peaks appear in the wavelength range 449nm to 694nm, 518nm, 581nm and661nm, it belongs to the characteristic absorption peak of cobalt ion coordination bond, which indicates that Co is successfully doped.
Core-shell structure Co-SiO prepared in embodiment 1 of the invention2The Raman spectrum of the/C composite is shown in FIG. 4, from which it can be seen that the composite is 1360cm-1And 1590cm-1Two peaks appear at the position of the carbon coating, which respectively correspond to amorphous carbon and graphitized carbon, and the coated carbon layer on the surface of the precursor has higher graphitization degree as seen from the peak area ratio.
Core-shell structure Co-SiO prepared in embodiment 1 of the invention2The cycle performance graph of the/C composite material is shown in FIG. 5, and it can be seen from the graph that: the material has good cycle performance and high coulombic efficiency, the capacity of the composite material after 100 cycles is 85% of the initial capacity, and the first coulombic efficiency is about 73%.
Claims (9)
1. Co-SiO with core-shell structure2The preparation method of the/C negative electrode material is characterized by comprising the following steps of:
b1, dissolving cobalt salt and surfactant in dilute hydrochloric acid, mixing uniformly to form a mixed solution, then adding silicate into the mixed solution, stirring and heating at the temperature of 150-200 ℃ for 6-8 hours, standing, cooling, washing with water, and carrying out suction filtration to prepare the cobalt-doped nano SiO2Sol is calcined for 3 to 5 hours at the temperature of 550-700 ℃, and then is washed and dried to obtain the cobalt-doped nano SiO2Powder, Co-SiO for short2；
B2, mixing the cobalt prepared in the step B1 with nano SiO2Adding the powder into a three-neck flask filled with an organic solvent, adding a silanization reagent, refluxing for 8-12h at a reflux temperature above the boiling point of the organic solvent, performing suction filtration, washing with water, drying, and carbonizing in a carbonization furnace to obtain Co-SiO2a/C composite material.
2. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in the step B1, the mass ratio of the cobalt salt, the surfactant and the dilute hydrochloric acid is (1-2.5): (5-12.5):24, and the concentration of the dilute hydrochloric acid is 0.01-0.5mol/L。
3. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in step B1, the surfactant is an ionic surfactant or a nonionic surfactant.
4. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in step B1, the surfactant is one of polyvinylpyrrolidone (PVP), sodium dodecylbenzenesulfonate, and sodium hexadecylbromide.
5. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in step B2, the cobalt is doped with nano SiO2The powder was added to a three-necked flask of an organic solvent at 0.8 to 0.4g/ml based on the volume of the organic solvent.
6. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in the step B2, the addition amount of the silanization reagent and the cobalt-doped nano SiO2The mass ratio of the powder is 1 (2-4).
7. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in the step B2, the carbonization is carried out under an inert atmosphere, the carbonization temperature is 800-1100 ℃, and the carbonization time is 4-8 h.
8. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps: in the step B2, the organic solvent is one of ethanol, benzene and toluene; the silanization reagent comprises a molecular formula of CnH(2n+1)Si(OCH3)3、CnH(2n-1)Si(OCH3)3Long chain silicon ofAn alkylating agent.
9. Core-shell structure Co-SiO according to claim 12The preparation method of the/C negative electrode material is characterized by comprising the following steps of:
b1: preparation of cobalt-doped nano SiO2Powder: respectively weighing 2-5g of cobalt salt and 10-25g of surfactant, dissolving in 120g of dilute hydrochloric acid with the concentration of 0.01-0.5mol/L, uniformly mixing to form a mixed solution, then adding 15-24g of silicate into the mixed solution, stirring and heating at the temperature of 150-200 ℃ for 6-8 hours, standing, cooling, washing with water, and carrying out suction filtration to prepare the cobalt-doped nano SiO2Sol, calcining at 550-700 deg.c for 3-5 hr, water washing and drying to prepare nanometer SiO doped with Co2Powder, Co-SiO for short2；
B2: preparation of Co-SiO2the/C composite material: taking 100g of cobalt-doped nano SiO prepared in step B12Adding the powder into a three-neck flask filled with 120-inch-siltation 300ml of organic solvent, then adding 25-35g of silanization reagent, refluxing for 8-12h, setting the reflux temperature above the boiling point of the organic solvent, performing suction filtration, washing with water, drying, then putting into a carbonization furnace for carbonization under the inert atmosphere, wherein the carbonization temperature is 800-inch-siltation 1100 ℃, and carbonizing for 4-8h to prepare the Co-SiO2a/C composite material.
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| CN102169996A (en) * | 2011-03-31 | 2011-08-31 | 湖南工业大学 | Micro-sphere compound anode material with core-shell structure and preparation method thereof |
| CN104694081A (en) * | 2015-03-23 | 2015-06-10 | 江苏天恒纳米科技股份有限公司 | Cobalt-containing doped silicon dioxide nano-composite abrasive grain sol and preparation method thereof, and polishing solution and preparation method thereof |
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