CN118117080A - Preparation method of graphene composite material for lithium battery - Google Patents
Preparation method of graphene composite material for lithium battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 20
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims abstract description 18
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- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000010981 drying operation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000003993 interaction Effects 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- -1 TPP compound Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
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- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a graphene composite material for a lithium battery, which comprises the following steps: and (3) taking graphene oxide, nano silicon powder and TPP modifier as raw materials, adding an organic solvent and water, ultrasonically stirring for 20-60 min at 50-100 ℃, centrifuging, washing, drying, transferring the product into a tube furnace, and preserving heat for 5-12 h at 150-300 ℃ to obtain the graphene composite material. The graphene composite material prepared by the method is used as a battery cathode material, and has higher specific capacity and cycle stability.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a graphene composite material for a lithium battery.
Background
The rechargeable lithium ion battery is widely applied to the national strategic emerging industries such as new energy automobile power batteries, high-end 3C lithium batteries, energy storage batteries and the like due to the advantages of light weight, high energy density, long cycle life, no memory effect and the like. In order to increase the energy density of lithium ion batteries, researchers have conducted intensive studies on a large number of electrode materials including carbon materials, silicon-based materials, and alloy materials. The silicon-based material has the advantages of safety, no toxicity, high theoretical specific capacity and the like, is considered as one of candidate materials hopefully commercialized in a large scale in the lithium ion battery cathode material, however, the electron conductivity of the silicon cathode material is relatively poor, and the silicon cathode material has a volume expansion effect in the charge and discharge processes. The carbon material is mainly based on graphene, and the graphene and the derivatives thereof show good physical properties including but not limited to excellent electrical conductivity, high specific surface area, fast carrier mobility, high thermal conductivity, high strength, high transparency and low preparation cost. Graphene has been found in increasingly wide application in various fields since 2004 due to its unique properties. Graphene, as an emerging two-dimensional material, has a high specific surface area, good mechanical properties, and incomparable electronic and physical properties, and has a wide application prospect in various fields. Graphene is a dense, cellular two-dimensional lattice consisting of sheets of mono-or minority atomic thickness bonded to carbon atoms in the form of sp 2, including pristine graphene (p-G), graphene Oxide (GO), and reduced graphene oxide (rGO). The prior research shows that the graphene has larger initial discharge capacity, but the charge storage capacity and the cycle holding capacity of the graphene cannot meet the requirements. In addition, interlayer stacking occurs between graphene sheets under the induction of van der waals force, thereby resulting in reduction of specific surface area and active sites, which may result in non-ideal specific capacitance.
In addition, the improvement of the silicon electrode performance by using graphene is widely focused and a better research result is obtained, and the reason is mainly that: ① The graphene has a certain mechanical strength and flexibility, can buffer the volume expansion of silicon in the lithiation process, and is beneficial to improving the conductivity of the silicon, so that the silicon/graphene composite electrode material with more excellent performance is obtained; ② The doping of the graphene enables the silicon nano particles to be dispersed more uniformly, and is beneficial to the improvement of the material cycle performance and specific capacity.
It can be seen that the selection of different materials is closely related to the performance and application requirements of the battery, and the use of different materials can affect the indexes such as energy density, cycle life and safety performance of the battery. With the wide application of lithium ion batteries in various fields, the performance requirements of the lithium ion batteries are also improved, and based on the performance requirements, development of a negative electrode material for improving the specific capacity and the cycling stability of the batteries is needed.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene composite material for a lithium battery, which can be used as a negative electrode material of the lithium battery to improve the specific capacity and the cycling stability of the battery. In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the graphene composite material for the lithium battery comprises the following steps:
Taking graphene oxide, nano silicon powder and TPP modifier as raw materials, adding an organic solvent and water, ultrasonically stirring for 20-60 min at 50-100 ℃, centrifuging, washing, drying, transferring the product into a tube furnace, and preserving heat for 5-12 h at 150-300 ℃ to obtain a graphene composite material;
The TPP modifier has the structure that:
，
In some embodiments, the TPP modifier is prepared using the following method:
，
And (3) reacting the compound I, the compound II and the Na 2CO3、Pd(PPh3)4 in a nitrogen environment to obtain the TPP compound.
In some embodiments, graphene oxide is preferably prepared by the following method:
adding original graphite powder and concentrated sulfuric acid into a reactor, adding KMnO 4 under ice bath condition, stirring for a period of time, sequentially adding deionized water and H 2O2 until the mixture turns from purple to yellow, and standing. And adding HCl, stirring, centrifuging, washing and drying to obtain graphene oxide.
In some embodiments, the organic solvent is selected from one or more of THF, toluene, ethanol.
In some embodiments, the mass ratio of graphene oxide to TPP modifier is (1-5): 1.
In some embodiments, the mass ratio of the graphene oxide to the nano silicon powder is (1-3): 1.
In some embodiments, the volume ratio of the organic solvent to deionized water is 1 (5-10).
In some embodiments, the conditions of centrifugation are: centrifuging for 1-10 minutes at 1000-3000 rpm.
In some embodiments, the conditions of the washing operation are: the washing solvent is ethanol.
In some embodiments, the conditions of the drying operation are: and (5) drying in vacuum at the temperature of 60-100 ℃ for 5-15 h.
Compared with the prior art, the invention has the following beneficial effects:
1) The graphene composite material prepared by the method is used as a battery cathode material, and has higher specific capacity and cycle stability;
2) The invention utilizes strong D-A interaction to construct the highly conjugated organic micromolecular modifier Which can enhance intramolecular charge transfer and facilitate formation of pi-pi stacking of molecules. When the TPP modifier is used for modifying the molecular level of graphene, the TPP modifier can prop open the graphene sheet layer through pi-pi stacking interaction, and the completely conjugated structure of the graphene can not be damaged due to pi-pi stacking interaction, so that the modified graphene shows excellent conductivity, and the specific capacity and the cycling stability of the battery are improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1: preparation of TPP modifier
，
Compound I (0.3 mol), compound II (0.1 mol), na 2CO3（0.8 mol）、Pd(PPh3)4 (0.02 mol) were added to a 100mL double neck round bottom flask under nitrogen. Then, a mixed solvent of THF (200 mL)/water (50 mL) after oxygen removal was added to the reactor, and the temperature was raised to 100℃and the reaction was stirred for 12 hours. After the reaction, the mixture was filtered, the filtrate was washed 3 times with deionized water (100 ml x 3), the organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure to give a crude product, and the crude product was purified by column chromatography (eluent petroleum ether/dichloromethane=3/1) to give TPP compound in a yield of 81.2% and an HPLC purity of 99.2%.
LC-MS (ESI): [M+H]+ =803.3。
1H-NMR (500 MHz, CDCl3)：δ(ppm): 7.85-7.74 (m,4H),7.53-7.45 (m,4H),7.32-7.11 (m,24H), 6.90 -6.78 (m,6H).
Preparation example 2: preparation of graphene oxide
Raw graphite powder (50 g) and 98% by mass concentrated sulfuric acid (600 mL) were added to the reactor, KMnO 4 (50 g) was added under ice bath conditions and stirred for 30min, then 1000mL deionized water and a certain amount of 30% by mass H 2O2 were added in sequence until the mixture turned from purple to yellow, and left to stand for 24H. Then adding HCl (500 mL) with the mass fraction of 10% and stirring for 30min, centrifuging at 5000 rpm for 10min, washing the product to be neutral by deionized water, and then drying in vacuum at 90 ℃ to obtain graphene oxide.
Example 1: preparation of graphene composite material
TPP modifier (5.0 g) obtained in preparation example 1, graphene oxide (20.0 g) obtained in preparation example 2, and nano silicon powder (15.0 g) were added to a reactor, THF (50 mL) and deionized water (300 mL) were then added, ultrasonic stirring was performed at 50℃for 30min, centrifugation was performed at 2000 rpm for 5min, the composite was washed 3 times with ethanol, and vacuum drying was performed at 80℃for 10h. And after drying, transferring the product into a tube furnace, and preserving heat for 12 hours at 180 ℃ under nitrogen to obtain the graphene composite material.
Example 2: preparation of graphene composite material
TPP modifier (8.0 g) obtained in preparation example 1, graphene oxide (20.0 g g) obtained in preparation example 2, and nano silicon powder (20.0 g) were added to a reactor, toluene (50 mL) and deionized water (300 mL) were then added, ultrasonic stirring was performed at 60℃for 30min, centrifugation was performed at 2000 rpm for 5min, the composite was washed 3 times with ethanol, and vacuum drying was performed at 80℃for 10h. And transferring the product into a tube furnace after drying, and preserving the temperature at 200 ℃ for 12 hours under nitrogen to obtain the graphene composite material.
Example 3: preparation of graphene composite material
TPP modifier (10.0 g) obtained in preparation example 1, graphene oxide (20.0 g g) obtained in preparation example 2, and nano silicon powder (20.0 g) were added to a reactor, ethanol (50 mL) and deionized water (300 mL) were then added, ultrasonic stirring was performed at 80℃for 30min, centrifugation was performed at 2000 rpm for 5min, the composite was washed 3 times with ethanol, and vacuum drying was performed at 80℃for 10h. And transferring the product into a tube furnace after drying, and preserving the temperature at 250 ℃ for 12 hours under nitrogen to obtain the graphene composite material.
Comparative example 1: omitting TPP modifier on the basis of example 1
Graphene oxide (20.0 g) and nano silicon powder (15.0 g) obtained in preparation example 2 were added to a reactor, THF (50 mL) and deionized water (300 mL) were then added, ultrasonic stirring was performed at 50 ℃ for 30min, centrifugation was performed at 2000 rpm for 5 min, the composite was washed 3 times with ethanol, and vacuum drying was performed at 80 ℃ for 10h. And after drying, transferring the product into a tube furnace, and preserving heat for 12 hours at 180 ℃ under nitrogen to obtain the graphene composite material.
Performance testing
The graphene composite materials prepared in the examples 1-3 and the comparative example 1, acetylene black and sodium alginate are mixed according to the mass ratio of 6:2:2, adding a proper amount of deionized water, then carrying out ball milling and mixing, wherein the revolution of the ball mill is 600 revolutions per minute, the ball milling time is 4 hours, uniformly coating 50 mu m on a copper foil, carrying out vacuum drying at 100 ℃, compacting and cutting into electrode slices, taking a lithium slice as a counter electrode, taking an electrolyte solution of LiPF 6/EC+DMC+ECM (volume ratio is 1:1:1), taking a membrane as a microporous polypropylene membrane, carrying out performance test on a battery by using a battery tester, and measuring the current density used by the test to be 100mA/g.
The results are shown in Table 1:
，
as can be seen from the data in table 1, the graphene composite material prepared by the method provided by the invention has higher specific capacity and cycle stability when being used as a battery anode material.
As can be seen from example 1 and comparative example 1, TPP modifierPlays a very important role in the capacitance performance of the graphene composite material. The reason for this is that: the invention utilizes strong D-A interaction to construct a highly conjugated organic small molecule modifier which can enhance intramolecular charge transfer and is beneficial to the formation of pi-pi accumulation of molecules. When the TPP modifier is used for modifying the molecular level of graphene, the TPP modifier can prop open the graphene sheet layer through pi-pi stacking interaction, and the completely conjugated structure of the graphene can not be damaged due to pi-pi stacking interaction, so that the modified graphene shows excellent conductivity, and the specific capacity and the cycling stability of the battery are improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the graphene composite material for the lithium battery is characterized by comprising the following steps of: taking graphene oxide, nano silicon powder and TPP modifier as raw materials, adding an organic solvent and water, ultrasonically stirring for 20-60 min at 50-100 ℃, centrifuging, washing, drying, transferring the product into a tube furnace, and preserving heat for 5-12 h at 150-300 ℃ to obtain a graphene composite material;
The TPP modifier has the structure that:
。
2. The method for preparing a graphene composite material for a lithium battery according to claim 1, wherein the organic solvent is one or more selected from THF, toluene and ethanol.
3. The method for preparing a graphene composite material for a lithium battery according to claim 1, wherein the mass ratio of the graphene oxide to the TPP modifier is (1-5): 1.
4. The preparation method of the graphene composite material for the lithium battery, which is disclosed in claim 1, is characterized in that the mass ratio of graphene oxide to nano silicon powder is (1-3): 1.
5. The preparation method of the graphene composite material for the lithium battery, which is disclosed in claim 1, is characterized in that the volume ratio of the organic solvent to deionized water is 1 (5-10).
6. The method for preparing a graphene composite material for a lithium battery according to claim 1, wherein the centrifugation conditions are as follows: centrifuging for 1-10 minutes at 1000-3000 rpm.
7. The method for preparing a graphene composite material for a lithium battery according to claim 1, wherein the conditions of the washing operation are: the washing solvent is ethanol.
8. The method for preparing a graphene composite material for a lithium battery according to claim 1, wherein the conditions of the drying operation are: and (5) drying in vacuum at the temperature of 60-100 ℃ for 5-15 h.
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| CN202410528602.8A CN118117080B (en) | 2024-04-29 | 2024-04-29 | Preparation method of graphene composite material for lithium battery |
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| CN102292374A (en) * | 2008-11-26 | 2011-12-21 | 佛罗里达大学研究基金公司 | Black soluble conjugated polymers with high charge carrier mobilities |
| WO2015097197A1 (en) * | 2013-12-23 | 2015-07-02 | Solvay Sa | Electrodes for energy storage devices |
| JP2016134570A (en) * | 2015-01-21 | 2016-07-25 | パナソニックＩｐマネジメント株式会社 | Organic photoelectric conversion material, photoelectric conversion element and imaging apparatus |
| US20200362098A1 (en) * | 2018-05-05 | 2020-11-19 | Jason D. Azoulay | Open-Shell Conjugated Polymer Conductors, Composites, and Compositions |
| CN114361560A (en) * | 2021-12-17 | 2022-04-15 | 温州大学 | Tetrakis (triphenylphosphine) palladium modified graphene composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102292374A (en) * | 2008-11-26 | 2011-12-21 | 佛罗里达大学研究基金公司 | Black soluble conjugated polymers with high charge carrier mobilities |
| WO2015097197A1 (en) * | 2013-12-23 | 2015-07-02 | Solvay Sa | Electrodes for energy storage devices |
| JP2016134570A (en) * | 2015-01-21 | 2016-07-25 | パナソニックＩｐマネジメント株式会社 | Organic photoelectric conversion material, photoelectric conversion element and imaging apparatus |
| US20200362098A1 (en) * | 2018-05-05 | 2020-11-19 | Jason D. Azoulay | Open-Shell Conjugated Polymer Conductors, Composites, and Compositions |
| CN114361560A (en) * | 2021-12-17 | 2022-04-15 | 温州大学 | Tetrakis (triphenylphosphine) palladium modified graphene composite material and preparation method and application thereof |
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