CN116960317A - Preparation method of ZIF-8 derived carbon coated modified silicon nanoparticle material and lithium ion battery pack - Google Patents
Preparation method of ZIF-8 derived carbon coated modified silicon nanoparticle material and lithium ion battery pack Download PDFInfo
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- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 82
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000003376 silicon Chemical class 0.000 claims abstract description 40
- 239000002153 silicon-carbon composite material Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000005576 amination reaction Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000017525 heat dissipation Effects 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 239000011856 silicon-based particle Substances 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006183 anode active material Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002243 precursor Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material and a lithium ion battery pack, wherein the preparation method comprises the following steps: adding an amination agent and silicon nano-particles into deionized water, stirring to aminate the silicon nano-particles, and centrifuging, washing and drying to obtain aminated silicon nano-particles; adding aminated silicon nano particles, zinc salt and dimethyl imidazole into deionized water, stirring for reaction, and centrifugally washing and drying to obtain a solid sample; and carbonizing the solid sample at high temperature to obtain the silicon-carbon composite material. When the material is used as a lithium ion battery anode active material, the material has high capacity, high capacity retention rate, excellent multiplying power performance and cycle stability. According to the invention, the ZIF-8 derived carbon is coated on the surface of the silicon nano particle to synthesize the silicon-carbon anode material through simple amination treatment, and the carbon layer is still stably coated on the surface of the silicon particle even under high-temperature treatment. Has the advantages of simple operation, high safety, high reaction efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material and a lithium ion battery pack.
Background
With the emerging market for portable electronics and electric vehicles creating a great demand for advanced Lithium Ion Batteries (LIBs), there is an increasing interest in developing battery electrodes with high weight and volumetric capacity to exceed the energy density of current lithium ion batteries. The rechargeable lithium ion battery mainly comprises four parts: two electrodes, a separator and an electrolyte. The negative electrode material is one of key components in the lithium ion battery, and plays a role in storing and releasing sodium ions in the charge and discharge process.
As a conventional lithium ion battery anode material, graphite is commercially used as an electrode material due to its high conductivity, good reversibility, and relatively low cost. However, graphite has a limited energy density because only one lithium atom can be accommodated per six carbon atoms. Silicon is widely recognized as one of the most promising anode materials due to its high capacity. Each silicon atom can be combined with four lithium ions, which makes its capacity smaller than that of graphite anode Gao Shibei (Li at high temperature 4.4 Si is 4212 mAh g −1 Li observed in ambient electrochemical cells 15 Si 4 3579 mAh g −1 372 mAh g to graphite anode −1 Compared to the prior art). In addition, silicon is the second most abundant element in the crust, is environmentally friendly, and has a lower electrochemical potential. Unfortunately, during lithiation and delithiation, the silicon bulkThe product changes by about 300%, resulting in severe particle pulverization, unstable Solid Electrolyte Interface (SEI) formation, and extremely easy electrical contact loss, resulting in capacity fade and limited cycle life.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material and a lithium ion battery pack. According to the invention, the silicon nano-particles are aminated, so that ZIF-8 can be stably coated on the surfaces of the silicon nano-particles, and even under high-temperature treatment, the carbon layer is stable and the structure is not damaged; has the advantages of simple operation, high safety, high reaction efficiency and the like.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material comprises the following steps:
s1, adding an amination agent and silicon nanoparticles into deionized water, stirring to aminate the silicon nanoparticles, and centrifuging, washing and drying to obtain aminated silicon nanoparticles;
s2, adding aminated silicon nano particles, zinc salt and dimethyl imidazole into methanol, stirring for reaction, and obtaining a solid sample after centrifugal washing and drying;
and S3, carbonizing the solid sample at high temperature to obtain the silicon-carbon composite material.
Preferably, in the step S1, the amination agent is 3-aminopropyl trimethoxysilane (APTMS), and the silicon nano-particles are spherical particles of 100-150 nm.
Preferably, in the step S1, the ratio of the amination agent to the silicon nanoparticles is 200mg of silicon nanoparticles per 0.6-1 ml of amination agent.
Further preferably, the ratio of amination agent to silicon nanoparticles is 200mg silicon nanoparticles per 0.8ml amination agent.
Preferably, in the step S1, the mass concentration of the silicon nano particles in the deionized water is 0.05-0.2 wt%, the stirring reaction time is 12-24 h, and the drying temperature is 60-100 ℃.
Further preferably, the mass concentration of the silicon nano particles in deionized water is 0.1 and wt%, the stirring time is 18 hours, and the drying temperature of the sample obtained by centrifugation and filtration is 80 ℃.
Preferably, in the step S2, the zinc salt is one of zinc nitrate hexahydrate, zinc acetate dihydrate and zinc chloride.
Further preferably, the zinc salt is zinc nitrate hexahydrate.
Preferably, in the step S2, the molar ratio of the aminated silicon nanoparticle to the zinc salt to the dimethylimidazole is 7: 4-10: 30-80.
It is further preferred that the mole ratio of aminated silicon nanoparticles, zinc salt, and dimethylimidazole is 7:10:40.
Preferably, in the step S2, the mass concentration of the aminated silicon nano particles in the methanol is 0.1-0.4wt%, the stirring reaction time is 6-24 h, and the drying temperature is 60-100 ℃.
Further preferably, the mass concentration of the aminated silicon nanoparticles in methanol is 0.2wt%, the stirring reaction time is 12 hours, and the drying temperature is 80 ℃.
Preferably, in the step S3, the high-temperature carbonization temperature is 700-950 ℃ and the carbonization time is 1-4 hours.
Further preferably, the high temperature carbonization temperature is 900 ℃ and the carbonization time is 2 hours.
Preferably, the particle size of the silicon-carbon composite material obtained in the step S3 is 0.5-1 μm.
The battery pack comprises a plurality of batteries, an insulating plate, a heat dissipation plate and a protection circuit board, and is characterized in that the batteries are lithium ion batteries, and the cathode raw material of the lithium ion batteries comprises a silicon-carbon composite material prepared by the preparation method of the ZIF-8 derived carbon coated modified silicon nano particle material.
The action mechanism of the invention is as follows: amination of silicon nanoparticles with 3-aminopropyl trimethoxysilane (APTMS) to give ammonium groups (NH) on the surface of the silicon nanoparticles 2 - ). NH during stirring of aminated silicon nanoparticles with zinc nitrate hexahydrate in methanol 2 - Will be combined with Zn 2+ The coordination reaction takes place to lead the surface of the silicon to capture Zn 2+ . Simultaneously with the dimethylRadical imidazole and Zn 2+ Coordination occurs to produce ZIF-8. Leading ZIF-8 to be uniformly and completely coated on the surface of the silicon nano-particles. At the same time due to NH 2 - And Zn 2+ The strong coordination effect between the two components ensures that the synthesized precursor can still keep stable structure at high temperature. The simple and easy synthesis method can be widely applied to a system with ZIF-8 coated on the surfaces of various core matrixes.
Compared with the prior art, the invention has the following beneficial effects:
1) The product of the invention has high shape consistency: the synthesized ZIF-8 coated silicon nano particles and the carbonized ZIF-8 derived carbon coated silicon nano particles have uniform particle sizes, and the problem of poor carbon and silicon coating property of the traditional lithium ion battery silicon-carbon negative electrode material is solved.
2) The invention has simple operation: dissolving, stirring, centrifugally drying and finally carbonizing the raw materials in a tube furnace; amination is completed by simple stirring, so that the silicon nano particles can be firmly combined with ZIF-8.
3) The invention has high safety: the synthesis process is not needed to be performed in a closed way, so that the problem of overhigh autogenous pressure generated in the reaction is avoided, and the green chemical principle that potential safety hazards should be minimized in the chemical production process is satisfied.
4) The invention has high reaction efficiency: the reaction is easy to occur, the amination and the coating of the silicon nano-particles can be completed in a short time, and the reaction efficiency is improved.
5) The invention has low cost: the silicon-carbon composite material produced by adopting the cheap and easily available raw materials has good performance and high capacity, and reduces the production cost.
In summary, the invention carries out amination on the silicon nano particles through simple solution stirring, and self-assembles the ZIF-8 coated on the silicon nano particles in the solution to obtain the silicon-carbon composite material with the core-shell structure, and the method can be widely used for coating different core matrixes with the ZIF-8, and can keep the coating structure stably existing at high temperature.
Drawings
FIG. 1 is an aminated silicon nanoparticle prepared in example 1 (denoted asNH 2 -SEM image of Si);
FIG. 2 shows aminated silicon nanoparticles (NH. RTM.) prepared in example 1 2 -FTIR plot of Si);
FIG. 3 is a silicon carbon composite precursor (NH) prepared in example 1 2 -SEM images of si@zif);
FIG. 4 shows a silicon carbon composite (NH) prepared in example 1 2 -SEM images of si@c);
FIG. 5 is an SEM image of a silicon carbon composite precursor (noted Si@ZIF) prepared in comparative example 1;
FIG. 6 is an SEM image of a silicon carbon composite (designated Si@ZIF) prepared in comparative example 1;
FIG. 7 shows a silicon carbon composite (NH) prepared in example 1 2 -a TEM image of si@c);
fig. 8 is a graph of the first charge and discharge of the silicon-carbon composite material prepared in example 1 and comparative example 1 as a negative electrode active material of a lithium ion battery in a half cell;
FIG. 9 is a graph showing the cycle performance of the silicon-carbon composite material prepared in example 1 and comparative example 1 as a negative electrode active material of a lithium ion battery in a half cell (200 mA g -1 ）；
FIG. 10 is a graph showing the cycle performance of the silicon-carbon composite material prepared in example 1 and comparative example 1 as a negative electrode active material for a lithium ion battery in a half cell (1A g -1 )；
Fig. 11 is a graph showing the performance magnification of the silicon-carbon composite material prepared in example 1 and comparative example 1 as a negative electrode active material of a lithium ion battery in a half cell.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, preferred embodiments of the present invention will be described below with reference to specific examples, but the present invention should not be construed as being limited thereto, but only by way of example.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are obtained from conventional commercial sources or prepared in conventional manner.
Example 1
The invention provides a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material, which comprises the following steps:
(1) 200mg silicon nanoparticles are weighed, dispersed in 200 ml deionized water, sonicated for 1h and then added with 0.8ml of APTMS. After intense stirring for 18h, the mixture was centrifuged three times with ethanol and dried in an oven at 80℃to give aminated silicon nanoparticles (designated NH) 2 -Si）；
(2) 2.97g of zinc nitrate hexahydrate was weighed out, and the solid obtained in the step (1) was dissolved and dispersed in 75 ml methanol to obtain a solution A. 3.284g of dimethylimidazole was weighed and dissolved in 25: 25 ml methanol to give solution B. The solution A and the solution B are mixed and stirred for reaction for 12h. And (3) centrifuging for three times by using ethanol, and drying in an oven at 80 ℃ to obtain the precursor of the silicon-carbon composite material. (denoted as NH) 2 -Si@ZIF）；
(3) Placing the silicon-carbon composite material precursor obtained in the step (2) into a tube furnace, and carbonizing for 2h at 900 ℃ to obtain a silicon-carbon composite material (NH) 2 -Si@C）。
Example 2
The invention provides a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material, which comprises the following steps:
(1) 200mg silicon nanoparticles are weighed, dispersed in 200 ml deionized water, sonicated for 1h and then added with 0.8ml of APTMS. After intense stirring for 18h, the mixture was centrifuged three times with ethanol and dried in an oven at 80℃to give aminated silicon nanoparticles (designated NH) 2 -Si）；
(2) 2.19g of zinc acetate dihydrate was weighed out, and the solid obtained in step (1) was dissolved and dispersed in 75 ml methanol to obtain solution A. 3.284g of dimethylimidazole was weighed and dissolved in 25: 25 ml methanol to give solution B. The solution A and the solution B are mixed and stirred for reaction for 12h. And (3) centrifuging for three times by using ethanol, and drying in an oven at 80 ℃ to obtain the precursor of the silicon-carbon composite material. (denoted as NH) 2 -Si@ZIF-2）；
(3) Placing the silicon-carbon composite material precursor obtained in the step (2) into a tube furnace, and carbonizing for 2h at 900 ℃ to obtain a silicon-carbon composite material (NH) 2 -Si@C-2）。
Example 3
The invention provides a preparation method of a ZIF-8 derived carbon coated modified silicon nanoparticle material, which comprises the following steps:
(1) 200mg silicon nanoparticles are weighed, dispersed in 200 ml deionized water, sonicated for 1h and then added with 0.8ml of APTMS. After intense stirring for 18h, the mixture was centrifuged three times with ethanol and dried in an oven at 80℃to give aminated silicon nanoparticles (designated NH) 2 -Si）；
(2) 1.36g of zinc chloride was weighed out, and the solid obtained in the step (1) was dissolved and dispersed in 75 ml methanol to obtain a solution A. 3.284g of dimethylimidazole was weighed and dissolved in 25: 25 ml methanol to give solution B. The solution A and the solution B are mixed and stirred for reaction for 12h. And (3) centrifuging for three times by using ethanol, and drying in an oven at 80 ℃ to obtain the precursor of the silicon-carbon composite material. (denoted as NH) 2 -Si@ZIF-3）；
(3) Placing the silicon-carbon composite material precursor obtained in the step (2) into a tube furnace, and carbonizing for 2h at 900 ℃ to obtain a silicon-carbon composite material (NH) 2 -Si@C-3）。
The invention will be described with reference to the silicon carbon composite material (NH) prepared in example 1 2 -si@c) as an example, the preparation results are characterized:
aminated silicon nanoparticles prepared in example 1 (denoted as NH 2 SEM image of Si) as shown in fig. 1, the morphology is seen as nano-silicon particles with a diameter of about 150 nm.
Aminated silicon nanoparticles prepared in example 1 (denoted as NH 2 FTIR image of-Si) as shown in fig. 2, at 3500 cm compared to untreated silicon nanoparticles -1 At the place, a stretching band of N-H bond appears, which indicates that NH exists on the surface of the aminated silicon nano-particle 2 - 。
The silicon carbon composite precursor prepared in example 1 (denoted as NH 2 As shown in FIG. 3, the SEM image of-Si@ZIF) shows that the regular-shape ZIF-8 is outside, and silicon particles are coated in a cube, and the particle size is about 0.6-1 μm.
The silicon carbon composite material prepared in example 1 (denoted as NH 2 SEM image of-Si@C) as shown in FIG. 4, it can be seen that ZIF-8 remains after carbonization at high temperatureThe surface of the silicon particles is regularly coated with the shape, and the particle size is about 0.6-1 mu m.
The silicon carbon composite material prepared in example 1 (denoted as NH 2 HRTEM image of-si@c) as shown in fig. 7, dark colored silicon nanoparticles were seen to be encapsulated in light colored ZIF-8 derived carbon shells.
Example 2 and example 3 were successfully synthesized, and the invention will not be described in detail.
Comparative example 1
The invention provides a preparation method of a ZIF-8 derived carbon-coated silicon nanoparticle material, which comprises the following steps:
(1) 0.2 g g silicon nano-particles and 2.97g zinc nitrate hexahydrate are weighed, dissolved and dispersed in 75 ml methanol to obtain solution A. 3.284g of dimethylimidazole was weighed and dissolved in 25: 25 ml methanol to give solution B. The solution A and the solution B are mixed and stirred for reaction for 12h. And (3) centrifuging for three times by using ethanol, and drying in an oven at 80 ℃ to obtain the precursor of the silicon-carbon composite material. (noted Si@ZIF);
(2) And (3) placing the silicon-carbon composite precursor obtained in the step (1) into a tube furnace, and carbonizing for 2 hours at 900 ℃ to obtain the silicon-carbon composite (Si@C).
An SEM image of the silicon carbon composite precursor prepared in comparative example 1 (noted Si@ZIF) is shown in FIG. 5, in which regular-shaped ZIF-8 and silicon nanoparticles are mixed, and it is seen that most of the silicon particles are not encapsulated in ZIF-8.
SEM images of the silicon carbon composite material (noted si@c) prepared in comparative example 1 are shown in fig. 6, and it can be seen that the ZIF-8 structure collapses after high temperature carbonization, and a large amount of silicon nanoparticles are exposed outside the ZIF-8-derived carbon due to no force between the ZIF-8 and the silicon nanoparticles.
Example 4
The silicon carbon composite material prepared in example 1 (denoted as NH 2 -si@c) as negative active material in a lithium ion battery.
The silicon carbon composite material (denoted as si@c) prepared in comparative example 1 was assembled as a negative electrode active material in a lithium ion battery.
First charge-discharge curve graph (200)mA g -1 ) As shown in FIG. 8, it can be seen that NH 2 Si@C is improved in initial coulombic efficiency compared with Si@C.
Cycling performance graph of both in half cell (200 mA g -1 ) As shown in FIG. 9, it can be seen that NH 2 Si@C is excellent in cycling stability at small current densities.
Cycling performance graph of both in half cell (1A g -1 ) As shown in FIG. 10, it can be seen that NH 2 Si@C is excellent in cycling stability at high current densities.
The ratio performance of the two in half cells is shown in FIG. 11, which shows NH 2 Excellent kinetic properties and structural stability of si@c.
Introduction of NH on silicon nanoparticle surface 2 - The ZIF-8 can realize more complete and firm coating on the surface of the silicon particles, and can also keep the structure stable and not collapse at high temperature.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (10)
1. The preparation method of the ZIF-8 derivative carbon coated modified silicon nanoparticle material is characterized by comprising the following steps of:
s1, adding an amination agent and silicon nanoparticles into deionized water, stirring to aminate the silicon nanoparticles, and centrifuging, washing and drying to obtain aminated silicon nanoparticles;
s2, adding aminated silicon nano particles, zinc salt and dimethyl imidazole into methanol, stirring for reaction, and obtaining a solid sample after centrifugal washing and drying; the zinc salt is one of zinc nitrate hexahydrate, zinc acetate dihydrate and zinc chloride;
and S3, carbonizing the solid sample at high temperature to obtain the silicon-carbon composite material.
2. The method for preparing the ZIF-8 derivative carbon-coated modified silicon nanoparticle material according to claim 1, wherein in the step S1, the amination agent is 3-aminopropyl trimethoxysilane.
3. The method for preparing the ZIF-8 derivative carbon coated modified silicon nanoparticle material according to claim 1, wherein in the step S1, the silicon nanoparticles are spherical particles of 100-150 nm.
4. The method for preparing the ZIF-8-derived carbon-coated modified silicon nanoparticle material according to claim 1, wherein in the step S1, the ratio of the amination agent to the silicon nanoparticles is 200mg of silicon nanoparticles per 0.6-1 ml of amination agent.
5. The preparation method of the ZIF-8-derived carbon-coated modified silicon nanoparticle material according to claim 1, wherein in the step S1, the mass concentration of the silicon nanoparticles in deionized water is 0.05-0.2 wt%, the stirring reaction time is 12-24 h, and the drying temperature is 60-100 ℃.
6. The method for preparing the ZIF-8 derivative carbon-coated modified silicon nanoparticle material according to claim 1, wherein in the step S2, the molar ratio of the aminated silicon nanoparticle to the zinc salt to the dimethylimidazole is 7: 4-10: 30-80.
7. The preparation method of the ZIF-8-derived carbon-coated modified silicon nanoparticle material according to claim 1, wherein in the step S2, the mass concentration of the aminated silicon nanoparticles in methanol is 0.1-0.4wt%, the stirring reaction time is 6-24 h, and the drying temperature is 60-100 ℃.
8. The preparation method of the ZIF-8-derived carbon-coated modified silicon nanoparticle material according to claim 1, wherein in the step S3, the high-temperature carbonization temperature is 700-950 ℃ and the carbonization time is 1-4 hours.
9. The method for preparing the ZIF-8 derivative carbon coated modified silicon nanoparticle material according to claim 1, wherein the particle size of the silicon-carbon composite material obtained in the step S3 is 0.5-1 μm.
10. A battery pack comprising a plurality of batteries, an insulating plate, a heat dissipation plate and a protection circuit board, wherein the batteries are lithium ion batteries, and the cathode raw material of the lithium ion batteries comprises a silicon-carbon composite material prepared by the preparation method of the ZIF-8 derived carbon coated modified silicon nanoparticle material according to any one of claims 1 to 9.
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| CN107359326A (en) * | 2017-06-26 | 2017-11-17 | 江苏师范大学 | A kind of Si@C lithium ion battery negative materials with core shell structure and preparation method thereof |
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