CN115714172A - Preparation method of hollow graphene @ IVA group oxide composite material, product and application thereof - Google Patents
Preparation method of hollow graphene @ IVA group oxide composite material, product and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000000034 method Methods 0.000 claims abstract description 35
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 239000013078 crystal Substances 0.000 claims description 20
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- 238000010438 heat treatment Methods 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
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- 239000010703 silicon Substances 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- -1 tin alkoxide Chemical class 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 53
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 10
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000012296 anti-solvent Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
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- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 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 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a hollow graphene group IVA oxide composite material, which comprises the following steps: s1: mixing a template agent and phthalocyanine; s2: carrying out pyrolysis on the material obtained in the step S1, and then cooling to room temperature; s3: adding the material obtained in the step S2 into an alcohol solvent and a surfactant, uniformly mixing, then adding a carbon group element source, stirring, adding water for hydrolysis reaction, washing a reaction product with an organic solvent, and drying to obtain composite powder; s4: and (4) performing high-temperature treatment on the composite powder in the step S3, and then washing and drying to obtain the hollow graphene @ IVA oxide composite material. The composite material can be used for preparing a porous cathode material of a lithium ion battery, has good electrochemical performance in a half-cell, and can effectively relieve the volume expansion of tin dioxide and silicon monoxide in the charge-discharge process.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a preparation method of a hollow graphene @ IVA family oxide composite material, and a product and application thereof.
Background
With the rapid development of electric vehicles, a clean energy storage system with high safety and higher energy storage capacity and power output is urgently needed for the next generation of lithium ion batteries.
Tin and silicon of group IVA and derivatives thereof (e.g. tin-based alloys, tin oxide/sulphides, silicon, silica, silicon carbon materials, etc.) due to their high theoretical capacity, e.g. SnO 2 The theoretical capacity of the silicon can reach 1494mAh/g, the simple substance silicon can reach 4200mAh/g, and the silicon oxide has 1965mAh/g, which has received much attention. However, the volume of the materials of IVA varies up to 300% during cycling, and the active materials tend to agglomerate, resulting in a rapid capacity fade.
Graphene has a large specific surface area, high conductivity and good flexibility, and is generally considered to beSnO 2 An ideal composite matrix. However, snO at graphene (rGO) sheet surface 2 The particles are easy to agglomerate and fall off in the electrochemical circulation process, so that SnO is caused 2 The circulation performance of the @ graphene composite material is quickly attenuated. Cubic graphene is a stable structure and generally exhibits excellent electrochemical performance in energy storage devices such as batteries due to its efficient ion transport channels and relatively stable framework. However, the lithium precipitation potential of the traditional carbon material is low, and lithium dendrite is easy to generate, so that the safety of the lithium ion battery is harmed. Therefore, there is a need to perform composite modification on carbon materials to obtain a safer electrode material with higher energy storage capacity and power output.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a hollow graphene group IVA oxide composite material, a product and application of the hollow graphene group IVA oxide composite material as a porous negative electrode of a lithium ion battery, so as to at least achieve the effect of improving the cycle stability and specific capacity of the battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a hollow graphene group IVA oxide composite material is characterized by comprising the following steps:
s1: mixing a template agent and phthalocyanine (CAS number: 574-93-6);
s2: carrying out pyrolysis on the material obtained in the step S1, and then cooling to room temperature;
s3: adding the material obtained in the step S2 into an alcohol solvent and a surfactant, uniformly mixing, then adding a carbon group element source, stirring, adding water for hydrolysis reaction, washing a reaction product with an organic solvent, and drying to obtain composite powder;
the stirring time is 30-40 minutes, and the hydrolysis reaction time is 12-96 hours. The hydrolysis reaction is carried out at normal temperature, and stirring is continuously carried out during the reaction.
S4: and (4) performing high-temperature treatment on the composite powder in the step S3, and then washing and drying to obtain the hollow graphene @ IVA oxide composite material.
Further, the template is a salt crystal with a melting point of more than 500 ℃ (the decomposition temperature of the phthalocyanine is about 500 ℃), and preferably, the template comprises a sodium chloride crystal, a potassium chloride crystal or a magnesium chloride crystal.
Further, the particle size of the salt crystal is 1-30 μm.
Further, in the step S1, the template agent is 5-20 parts by weight, and the phthalocyanine is 0.01-2 parts by weight.
Further, in step S2, the specific pyrolysis method is as follows: heating to 300-400 deg.C at a rate of 5 deg.C/min from room temperature, heating to 600-1200 deg.C at 2 deg.C/min, and maintaining for 0.5-36h.
Preferably, the pyrolysis method comprises the following steps: the temperature is raised from room temperature to 350 ℃ at a heating rate of 5 ℃/min, and then raised to 700 ℃ at a heating rate of 2 ℃/min and kept for 8h.
Further, in step S3, by weight, 1 to 2 parts of the material obtained in step S2, 150 parts of the alcohol solvent, 0.1 to 0.2 part of the surfactant, 1 to 10 parts of the carbon group element source, and 0.1 to 10 parts of water.
Preferably, the alcohol solvent is ethanol.
The surfactant comprises hexadecylamine, n-tetradecylamine and tween. Preferably, the surfactant is hexadecylamine.
Further, in step S3, the organic solvent includes ethanol, toluene, hexane, acetone, and carbon tetrachloride. Preferably, the organic solvent is ethanol,
further, in step S3, the carbon group element source includes a tin source, a silicon source, and a titanium source; preferably a tin source and a silicon source.
The tin source includes: at least one of stannous isooctanoate, stannic chloride, organic tin alkoxide, stannic iodide, stannic chloride pentahydrate, stannic acetate and stannous chloride; preferably, the tin source is stannous isooctanoate.
The silicon source comprises at least one of tetraethyl silicate, vinyl triethoxysilane and trimethylchlorosilane; preferably, the silicon source is tetraethyl silicate.
The titanium source includes tetrabutyl titanate and isopropyl titanate.
Further, when the carbon group element is a tin source, in step S4, the high temperature treatment method is: and reacting the composite powder in inert gas at 300-1200 ℃ for 0.5-35h.
Preferably, the high-temperature treatment method comprises the following steps: the composite powder was reacted for 2h at 450 ℃ in an inert gas.
Further, when the carbon group element is a silicon source, in step S4, the high temperature treatment method includes: according to the weight portion, 1 portion of the composite powder is added with 10 to 20 portions of heat conducting agent, 1 to 2 portions of metal magnesium powder and 0.1 to 2 portions of silicon powder to react for 0.5 to 12 hours in inert gas at the temperature of 500 to 1200 ℃.
Preferably, the high-temperature treatment method comprises the following steps: according to the weight portion, 10 to 20 portions of heat conducting agent, 1 to 2 portions of metal magnesium powder and 0.1 to 2 portions of silicon powder are added into 1 portion of the composite powder, and the mixture reacts for 3 hours in inert gas at 1000 ℃.
The second object of the present invention is to provide a hollow graphene group IVA oxide composite material prepared by the preparation method.
The third object of the present invention is to provide an application of the hollow graphene group IVA oxide composite material, which is used as a porous negative electrode material for preparing a lithium ion battery.
The invention has the beneficial effects that:
1. the process and raw materials for preparing the cubic graphene by the quasi-CVD method are simple, and large-scale production is facilitated.
2. The hydrolysis and pyrolysis process is also very simple. Through the hollow structure of the cubic graphene, the volume expansion of the tin dioxide and the silicon monoxide in the charge and discharge process is effectively relieved. Meanwhile, the porous electrode is expected to be constructed by utilizing the hollow structure, so that the lithium ion transmission efficiency is improved, and the composite material has good electrochemical performance in a half cell.
Drawings
Fig. 1 is an SEM and elemental distribution plot of tin dioxide coated hollow cubic graphene prepared in example 1;
fig. 2 is an SEM image of silica-coated hollow cubic graphene prepared in example 2;
fig. 3 is a CV curve graph obtained from cyclic voltammetry tests of the tin dioxide-coated hollow cubic graphene prepared in example 1 and its comparative pure silica. (the test voltage range is 0.01-3.0V, the test voltage sweep rate is 1mV/s, and the number of test turns is 3 turns);
FIG. 4 is an electrochemical impedance spectrum of tin dioxide coated hollow cubic graphene prepared in example 1 and its comparative sample pure tin dioxide;
fig. 5 is a graph of the cycling performance of tin dioxide coated hollow cubic graphene prepared in example 1 and its comparative pure tin dioxide under high rate (2A/g) charge and discharge.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The manufacturing process of the electrode slice comprises the following steps: the active material was physically mixed with a conductive agent (Super P) and a binder, polyvinylidene-dipropyleneboron difluoride (PVDF), and N-methyl-2-pyrrolidone (NMP) was used as a solvent in a mixing weight ratio of 8. A CR2032 button-type half cell was assembled with lithium sheets in a glove box using Celgard2500 membrane as the cell separator and 1M LiPF6 as the electrolyte (ethylene carbonate: diethyl carbonate =1:1, volume ratio).
Electrochemical impedance and cyclic voltammetry tests were performed using the Chenghua electrochemical workstation CH 760E. The charge-discharge curve was measured in a voltage range of 0.01V to 3.0V using a blue CT2001A battery system.
Example 1
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
step (1): the potassium chloride crystal with the grain diameter of 1-30 mu m is prepared by an anti-solvent method.
Step (2): 14 parts of potassium chloride crystals are physically mixed with 0.1 part of metal-free phthalocyanine.
And (3): and (3) carrying out pyrolysis treatment on the mixture obtained in the step (2). The reaction temperature treatment procedure is that the temperature is raised from room temperature to 350 ℃ at the heating rate of 5 ℃/min, then raised to 700 ℃ at the heating rate of 2 ℃/min and kept for 8 hours, and finally naturally cooled, and the SALT-Gr is marked.
And (4): weighing 1 g of SALT-Gr in the step (3), adding 150 ml of ethanol, carrying out ultrasonic treatment, adding 0.1 g of hexadecylamine, and stirring for 10 minutes. Then adding 1 ml of stannous isooctanoate, stirring for 30 minutes, slowly dropwise adding one ml of water, finally stirring for 24 hours at normal temperature, and washing with ethanol to obtain the SALT-Gr coated with the tin hydroxide.
And (5): and (4) carrying out pyrolysis treatment on the sample obtained in the step (4) to obtain the SALT-Gr coated by the tin dioxide, wherein the pyrolysis procedure is that argon gas is treated for two hours at 450 ℃. Finally, deionized water is used for washing off salt to obtain the SnO2 @ graphene compound with a hollow core-shell structure (shown in figure 1), and tin dioxide uniformly coats the surface of a cube, wherein the side length is 20-25 mu m as shown in figure 1.
The manufacturing process of the SnO2 @ graphene composite negative electrode slice comprises the following steps: the active material was physically mixed with a conductive agent (Super P) and a binder, polyvinylidene-dipropyleneboron difluoride (PVDF), and N-methyl-2-pyrrolidone (NMP) was used as a solvent in a mixing weight ratio of 8. A CR2032 button-type half cell was assembled with lithium sheets in a glove box using Celgard2500 membrane as the cell separator and 1M LiPF6 as the electrolyte (ethylene carbonate: diethyl carbonate =1:1, volume ratio). Electrochemical impedance and cyclic voltammetry tests were performed using the chenhua electrochemical workstation CH 760E. The electrochemical AC impedance value of the stannic oxide @ graphene complex is 48 Ω (shown in figure 4), and the cyclic voltammogram of the stannic oxide @ graphene is shown in figure 3.
The charging and discharging curve was measured in a voltage range of 0.01V to 3.0V using a blue CT2001A battery system. Under the condition of 2A/g, the discharge capacity of 2307.4mAh/g in the first circle of large-rate charge and discharge is 450.0mAh/g after 200 circles of charge and discharge cycles (see attached figure 5).
Example 2
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
step (1): sodium chloride crystals with the grain diameter of 1-30 mu m are prepared by an anti-solvent method.
Step (2): 14 parts of sodium chloride crystals are physically mixed with 0.1 part of metal-free phthalocyanine.
And (3): and (3) carrying out pyrolysis treatment on the mixture obtained in the step (2). The reaction temperature treatment procedure is that the temperature is raised from room temperature to 350 ℃ at the heating rate of 5 ℃/min, then raised to 700 ℃ at the heating rate of 2 ℃/min and kept for 8 hours, and finally naturally cooled, and the SALT-Gr is marked.
And (4): weighing 1 g of SALT-Gr in the step (3), adding 150 ml of ethanol, carrying out ultrasonic treatment, adding 0.1 g of hexadecylamine, and stirring for 10 minutes. Then adding 1 ml of stannous isooctanoate, stirring for 30 minutes, slowly dropwise adding one ml of water, finally stirring for 24 hours at normal temperature, and washing with ethanol to obtain the SALT-Gr coated with the tin hydroxide.
And (5): and (4) carrying out pyrolysis treatment on the sample obtained in the step (4) to obtain the SALT-Gr coated by the tin dioxide, wherein the pyrolysis procedure is that argon gas is treated for two hours at 450 ℃. Finally, washing off salt by using deionized water to obtain the SnO2 @ graphene compound with a hollow core-shell structure.
Example 3
A porous negative electrode material of a lithium ion battery is prepared, and the specific method refers to example 1, except that the step (2) is changed into: 1 part of potassium chloride crystal is physically mixed with 1 part of metal-free phthalocyanine. The other steps are the same as the example 1, and the composites of graphene and SnO2 with different thicknesses are obtained.
Example 4
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
step (1): the potassium chloride crystal with the grain diameter of 1-30 mu m is prepared by an anti-solvent method.
Step (2): 14 parts of potassium chloride crystals are physically mixed with 0.1 part of metal-free phthalocyanine.
And (3): and (3) carrying out pyrolysis treatment on the mixture obtained in the step (2). The reaction temperature treatment procedure is that the temperature is raised from room temperature to 350 ℃ at the heating rate of 5 ℃/min, then raised to 700 ℃ at the heating rate of 2 ℃/min and kept for 8 hours, and finally naturally cooled, and the SALT-Gr is marked.
And (4): weighing 1 g of SALT-Gr in the step (3), adding 150 ml of ethanol, carrying out ultrasonic treatment, adding 0.1 g of hexadecylamine, and stirring for 10 minutes. Then 1 ml of tetraethyl silicate is added, stirred for 30 minutes, then one ml of water is slowly dropped, finally stirred for 24 hours at normal temperature, washed by ethanol and dried.
And (5): and (3) taking 2g of the sample obtained in the step (4), adding 2g of sodium chloride serving as a heat conducting agent, adding 2g of metal magnesium powder and 0.12g of silicon powder, and finally treating for three hours at 1000 ℃ by argon. Finally, washing off the salt by using deionized water to obtain the hollow graphene @ SiOx compound (shown in figure 2). As can be seen from fig. 2, the whole cubic structure is retained after the template is removed, the side length of the cube is 4-5 μm, and the porous graphene @ SiOx electrode can be effectively constructed by utilizing the hollow cubic structure with certain rigidity.
Example 5
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
step (1): the potassium chloride crystal with the grain diameter of 1-30 mu m is prepared by an anti-solvent method.
Step (2): 1 part of potassium chloride crystal is physically mixed with 1 part of metal-free phthalocyanine.
And (3): and D, carrying out pyrolysis treatment on the mixture obtained in the step II. The reaction temperature treatment procedure is that the temperature is raised from room temperature to 350 ℃ at the heating rate of 5 ℃/min, then raised to 700 ℃ at the heating rate of 2 ℃/min and kept for 8 hours, and finally naturally cooled, and the SALT-Gr is marked.
And (4): weighing 1 g of SALT-Gr in the third step, adding 150 ml of ethanol, carrying out ultrasonic treatment, adding 0.1 g of hexadecylamine, and stirring for 10 minutes. Then 1 ml of tetraethyl silicate is added, stirred for 30 minutes, then one ml of water is slowly dropped, finally stirred for 24 hours at normal temperature, washed by ethanol and dried.
And (5): taking 2g of the sample obtained in the fourth step, adding 2g of sodium chloride as a heat conducting agent, adding 2g of metal magnesium powder and 0.12g of silicon powder, and finally processing for three hours at 1000 ℃ by argon. Finally, washing off the salt by using deionized water to obtain the hollow graphene SiOx complex.
Comparative example 1
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
0.1 g of hexadecylamine was added to 150 ml of ethanol and stirred for 10 minutes. Then 1 ml of stannous isooctanoate is added, after stirring for 30 minutes, one ml of water is slowly dropped, finally stirring is carried out for 24 hours at normal temperature, and washing is carried out by ethanol, thus obtaining the stannic hydroxide. Argon treatment at 450 ℃ for two hours removed the organic solvent while the tin hydroxide decomposed to white SnO2 particles.
Comparative example 2
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
weighing 1 g of graphene oxide powder, and adding the graphene oxide powder into 150 ml of ethanol for ultrasonic dispersion for 30 minutes. And then adding 0.1 g of hexadecylamine, stirring for 10 minutes, adding 1 ml of stannous isooctanoate, stirring for 30 minutes, slowly dropwise adding one ml of water, finally stirring for 24 hours at normal temperature, washing with ethanol to obtain a compound of tin hydroxide and graphene oxide, filtering, and drying in an oven at 80 ℃ for 24 hours to obtain a powder sample of the compound.
And carrying out heat treatment on the obtained powder sample at 800 ℃ for two hours under the argon gas condition to obtain the SnO2 @ graphene compound.
Comparative example 3
The preparation method of the porous negative electrode material of the lithium ion battery comprises the following steps:
0.1 g of hexadecylamine was added to 150 ml of ethanol and stirred for 10 minutes. Then adding 1 ml of tetraethyl silicate, stirring for 30 minutes, slowly dropping one ml of water, finally stirring for 24 hours at normal temperature to obtain a nano-scale hydrolysate, washing with absolute ethyl alcohol, and then drying for 24 hours at 80 ℃.
And taking 2g of the sample in the previous step, adding 2g of metal magnesium powder and 0.12g of silicon powder, and then carrying out heat treatment for 3 hours in an argon atmosphere environment at the temperature of 1000 ℃ to obtain SiOx white particles.
Examples of the experiments
The composite materials of examples 2-6 and comparative examples 1-3 were used as negative active materials of lithium ion batteries, and assembled into CR2032 button type half cells separately in a glove box and a lithium sheet according to the method of example 1. Electrochemical performance analysis is performed by using a Chenghua electrochemical workstation CH760E and a blue CT2001A battery system, electrochemical alternating current impedance values, first-circle discharge capacity of high-magnification charge and discharge under the condition of 2A/g and capacity after circulation for 200 circles are obtained, and experimental results are counted in a table 1.
TABLE 1
As can be seen from Table 1, in comparative example 1 and example 2, the potassium chloride crystal is used as a heat conducting agent and a template agent, and has better electrochemical performance than the sodium chloride crystal; comparing example 1 with example 3, the larger the ratio of potassium chloride crystal to metal-free phthalocyanine, the smaller the thickness of the prepared graphene, the better the electrochemical performance of the corresponding lithium ion battery, i.e. the electrochemical performance of example 1 is better than that of example 3; in contrast, comparative examples 1 and 4, graphene @ SnO was present in a complex of a group IVA oxide and graphene 2 The electrochemical performance of the composite material is better than that of graphene @ SiOx composite, and particularly, the graphene @ SnO2 composite (example 1) is better in improving the lithium ion migration rate and restraining the volume expansion of the electrode material.
FIG. 3 is a graphene @ SnO of example 1 2 CV curves of the composite and the comparative sample (comparative example 1) pure tin dioxide after assembly into a CR2032 cell. The voltage sweep rate was 1mV/s, with test voltages ranging from 0.01 to 3.0V (vs Li/Li +). The cathodic peak at 0.7 volts in round 1 disappeared after round 2, corresponding to the non-decomposability of the tin dioxide, while the area of the curve decreased, corresponding to the formation of an irreversible Solid Electrolyte Interface (SEI). Two anodic peaks of 0.5V, 1.2V and three cathodic peaks of 0.01V, 0.16V, 1.0V correspond to the intercalation and deintercalation process of lithium ions. At the same time, it can be seen that graphene @ SnO 2 The CV integrated area is far larger than that of a pure tin dioxide material, and the graphene @ SnO can be inferred 2 Compared with a pure tin dioxide material, the composite material has larger specific capacity. FIG. 4 is graphene @ SnO of example 1 2 Composite material and comparative sample (comparative example 1) pure tin dioxide (pure-SnO) 2 ) Electrochemical impedance after assembly into a CR2032 cell. Compared with the prior art, the charge transfer impedance of the tin dioxide graphene composite material with the hollow structure in a high-frequency region is far smaller than that of pure tin dioxide; simultaneously in the low frequency region, graphene @ SnO 2 The slope of (a) is much greater than that of pure tin dioxide, indicating rapid conduction of lithium ions. FIG. 5 shows the graphene @ SnO2 composite material obtained in example 1 and SnO of a comparative sample (comparative example 1) 2 Long cycle plot at high current density. Since irreversible capacity exists, the capacity decreases after the first cycle and is maintained at about 500 mAh/g. It can be seen that the graphene @ SnO is not only the initial discharge capacity but also the capacity after 200 cycles (450 mAh/g) 2 The performance of the composite is better than that of pure stannic oxide.
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and is not to be construed as limited to the exclusion of other embodiments, and that various other combinations, modifications, and environments may be used and modifications may be made within the scope of the concepts described herein, either by the above teachings or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a hollow graphene group IVA oxide composite material is characterized by comprising the following steps:
s1: mixing a template agent and phthalocyanine;
s2: carrying out pyrolysis on the material obtained in the step S1, and then cooling to room temperature;
s3: adding the material obtained in the step S2 into an alcohol solvent and a surfactant, uniformly mixing, then adding a carbon group element source, stirring, adding water for hydrolysis reaction, washing a reaction product with an organic solvent, and drying to obtain composite powder;
s4: and (4) performing high-temperature treatment on the composite powder in the step S3, and then washing and drying to obtain the hollow graphene @ IVA oxide composite material.
2. The method of claim 1, wherein: the template agent comprises at least one of sodium chloride crystals, potassium chloride crystals or magnesium chloride crystals.
3. The method of claim 1, wherein: in the step S1, the template agent is 5-20 parts by weight, and the phthalocyanine is 0.01-2 parts by weight.
4. The production method according to claim 1, characterized in that: in step S2, the pyrolysis method specifically includes: heating to 300-400 deg.C at a rate of 5 deg.C/min from room temperature, heating to 600-1200 deg.C at 2 deg.C/min, and maintaining for 0.5-36h.
5. The method of claim 1, wherein: in the step S3, the material obtained in the step S2 is 1-2 parts by weight, the alcohol solvent is 150 parts by weight, the surfactant is 0.1-0.2 part by weight, the carbon group element source is 1-10 parts by weight, and the water is 0.1-10 parts by weight.
6. The method of claim 1, wherein: in step S3, the carbon group element source comprises a tin source and a silicon source;
the tin source comprises at least one of stannous isooctanoate, stannic chloride, organic tin alkoxide, stannic iodide, stannic chloride pentahydrate, stannic acetate and stannous chloride;
the silicon source comprises at least one of tetraethyl silicate, vinyltriethoxysilane, and trimethylchlorosilane.
7. The method of claim 6, wherein: when the carbon group element is a tin source, in step S4, the high-temperature treatment method includes: and reacting the composite powder in inert gas at 300-1200 ℃ for 0.5-36h.
8. The method of claim 6, wherein: when the carbon group element is a silicon source, in step S4, the high-temperature treatment method includes: according to the weight portion, 10 to 20 portions of heat conducting agent, 1 to 2 portions of metal magnesium powder and 0.1 to 2 portions of silicon powder are added into 1 portion of the composite powder, and the mixture reacts for 0.5 to 12 hours in inert gas at the temperature of 500 to 1200 ℃.
9. A hollow graphene group IVA oxide composite prepared by the process for preparation according to claims 1-9.
10. The use of the hollow graphene group IVA oxide composite material according to claim 9, characterized in that: the porous anode material is used for preparing a lithium ion battery.
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