GB2590340A - A preparation method for anode materials of lithium-ion batteries - Google Patents

A preparation method for anode materials of lithium-ion batteries Download PDF

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GB2590340A
GB2590340A GB2105534.8A GB202105534A GB2590340A GB 2590340 A GB2590340 A GB 2590340A GB 202105534 A GB202105534 A GB 202105534A GB 2590340 A GB2590340 A GB 2590340A
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lithium
anode materials
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cyclodextrin
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Wen Huahui
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Hangzhou Jingshu New Mat Co Ltd
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H01M10/052—Li-accumulators
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    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

An anode material for Li-ion batteries is prepared using the following steps: (a) 2,2-Bis[4-(4-aminophenoxy) phenyl] hexafluoropropane, 3,3',4,4'-Biphenyltetracarboxylic dianhydride and graphene oxide are mixed to prepare PAA/GO, and then acetic anhydride and triethylamine are added to prepare concentrate; (b) PI-rGO composite is obtained by high-temperature firing; (c) N-Methylpyrrolidone, Pyralene, Polyvinylidene fluoride, Nanoscale silicon particles, Carbon nano tubes (CNT) and Beta-Cyclodextrin are added to obtain conductive paste; and (d) after being dried and cooled, the required anode materials are obtained by slicing on a manual microtome. The resulting anode materials have good lithium-ion conductivity and capacity retention. The cyclodextrin is stated to be used for pore formation and the combination of pyralene and PVDF as binder coats the Si particles effectively and prevents silicon falling off surfaces during charging and discharging. The pores created in the material also ensure effective mixing of the reduced graphene oxide and CNTs in the binder.

Description

A PREPARATION 71 HOD FOR ANODE MATERIALS OF LITHIUM-ION BATTERIES
TECHNICAL FIELD
[0001] The present invention relates to the field of lithium-ion batteries preparation, in particular to a preparation method for anode materials of lithium-ion batteries.
BACKGROUND OF THE INVENTION
100021 The first research on lithium batteries dates back to the 1950s and entered practical use in the 1970s. It is based on lithium metal as the negative electrode, some kind of solid material that can make lithium ions embedded and di sembedded as the positive electrode, and salts or solid salts dissolved in organic solvents as the electrolyte. However; during the charging arid discharging process of lithium batteries, lithium metal will be deposited on the negative electrode to form lithium dendrites, which will penetrate the diaphragm and cause short circuit and easily form an explosion. In order to overcome this shortcoming and improve the safety of the use of batteries, lithium-ion batteries were born. 1991; Sony Japan released the birth of the first commercial lithium-ion batten-, the battery with graphite as the negative electrode, lithium cobaltate as the cathode material, the batten" to overcome the shortcomings of the lithium secondary battery cycle life, poor safety" marking a revolution in the battery industry. Since its commercialization, lithium-ion batteries have been widely used not only in the field of new energy electric vehicles, but also in consumer electronics.
[0003] The anode material of lithium-ion batten' plays the role of "lithium storage" in the battery, ensuring that lithium ions can be freely embedded and discharged during the re discharge process. From the perspective of the development of lithium-ion batteries, the research and selection of anode materials play a decisive role in the widespread use of lithium-ion batteries. The earliest anode material is lithium metal, but due to the safety of the battery; lithium metal has not been used in lithium batteries; lithium alloy research to a certain extent to solve the safety risks of lithium metal anode, but it is accompanied by the problem of volume expansion during the cycle, so it has not been successful. Through continuous exploration., scientists believe that the anode material should meet the following requirements: (1) the embedded lithium-delithium potential of the material should be as low as possible, preferably similar to the lithium metal point lithium ions can be embedded in a large number of materials to ensure battery capacity; (3) in the battery charging and discharging process, the electrode should retain an intact structure, stable cycle performance, (4) lithium ions in the material has a good diffusion (5) high electronic conductivity; (6) stable chemical and electrochemical performance, no electrolyte reaction; (7) stable charge and discharge platform;inexpensive and environmentally friendly materials to meet the requirements of green and sustainable development. With the emergence of carbon materials, solving the problem of safety in the use of lithium metal electrodes, thus directly affecting the commercialization of lithium-ion batteries, the current anode materials for lithium-ion batteries are still graphite materials, the rest of the anode materials, including non-carbon materials, organic materials, etc., have not been put into market use. Non-carbon materials are mainly tin-based materials and silicon-based materials, and transition metal oxides; etc. [0004] Graphite materials are most widely used in lithium-ion batteries and have the advantages of stable cycling performance, but there are disadvantages such as low first coulomb efficiency, material stripping and shedding in the process, resulting in capacity decay; and poor low temperature resistance. Tin-based materials mainly include silicon, silicon oxide, carbon-silicon composites and silicon alloys, which are by far the highest specific capacity anode materials, but are prone to serious and volume expansion, which can easily lead to structural collapse, material differentiation, poor cycling stability and other problems.
BRIEF SUMMARY OF THE INVENTION
[0005] This invention discloses a preparation method for anode materials of h um-ion batteries, wherein specific technical proposal is listed as follows: [0006] A suitable amount of 2,2-Bis[4-(4-am nophenoxy) phenyl] hexafluoropropane, 3,3',4,4'-Biphenyltetracarboxylic dianhydride and graphene oxide are mixed to prepare PAA/GO, and then acetic anhydride and triethylamine are added to prepare concentrate, and then PI-rGO composite is obtained by a high-temperature firing, and then a suitable amount of N-Methylpyrrolidone, Pyralene, Polyvinylidene fluoride, Nanometer silicon particle, Carbon nano tube(CNT) and Beta-Cyclodextrin are added to obtain conductive paste, and furthermore, after being dried and cooled, the required anode materials are obtained by slicing on a manual microtome.
[0007] The preparation method comprises the following specific steps: [0008] Sl: the graphene oxide are added into DN4Ac solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride are added to be reacted for 10-14h by stirring at -3-0°C, and then Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride is 1:1.
[0009] S2: the acetic anhydride and the triethylamine dissolve in the DMAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PA/A/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 8-10h at 65-100°C, and then the concentrate is obtained.
[0010] S3: the concentrate obtained in S2 is put into a tube furnace under nitrogen atmosphere to be burnt for 30 min at 150-250°C, and then the temperature is raised to 500600°C to maintain for 40 min, and then the PI-rGO composite is obtained.
[0011] 54: the PI-rGO composite obtained in S3 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyvinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.1-0.65, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.3-0.5:0.13-0.23, and then the conductive paste is obtained.
[0012] S5. the conductive paste obtained in S4 is uniformly coated on a flat copper foil, and then put into an oven at 80°Cto be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained.
[0013] As an optimized technical proposal, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride added in above-stated S4 is 1:0.1-0.35.
[0014] As an optimized technical proposal, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin added in above-stated S4 is 1:0.3-0.45:0.13-0.2.
[0015] Compared with other electrolyte composite materials, this invention patent has the following advantages: (I) for the present invention, when in a preparation process, a certain amount of the Beta-Cyclodextrin are required to be added to achieve a pore-forming by using cyclodextrin, and moreover, such a preparation method is able to provide rich binding sites for lithium-ion and more ion diffusion channels; (2) the binder used in the present invention is a mixture of the Pyralene and the Polyvinylidene fluoride, and the binder coats the silicon particles tightly, which is effectively preventing the silicon particles falling down from surfaces in a charge-discharge process and a sharp drop in capacity; (3) after the pore-forming with the cyclodextrin, the graphene oxide and the Carbon nano tube(CNT) are able to completely inserted into the binder of the Pyralene and the Polyvinylidene fluoride, when a reduction temperature is continuously increased, with an increase of cycle number, the capacity of the anode materials is on a tendency of slowly rising.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 is a SEM pattern of anode materials of lithium-ion batteries prepared with a preparation method in embodiment I of the present invention; [0017] Figure 2 is an impedance spectroscopy of the anode materials of lithium-ion batteries prepared with a preparation method in embodiment I of the present invention; [0018] Figure 3 is a comparative pattern for cycle performances of the anode materials of lithium-ion batteries prepared with a preparation method in embodiment I of the present invention in an ampere density of zoomA [0019] Figure 4 is a comparative pattern for rate capacities of the anode materials of lithium-ion batteries prepared with a preparation method in embodiment 1 of the present invention in different ampere densities;
DETAILED DESCRIPTION OF THE INVENTION
[0020] The detailed description and process are provided for the implementation of the technical scheme of the invention according to the specific implementation, but the scope of protection of the invention is not limited in the following embodiments: [0021] Embodiment 1: [0022] A preparation method for anode materials of lithium-ion batteries specifically comprises the following specific steps: [0023] Si: graphene oxide are added into DMAc solvent to be stirred sufficiently and uniformly, and then 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and 3,3',4,4'-Biphenyltetracarboxylic dianhydride are added to be reacted for 10h by stirring at -3°C, and then Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride is 1:1; [0024] S2: acetic anhydride and triethylamine dissolve in the DIVIAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 8h at 65°C, and then concentrate is obtained, [0025] S3: the concentrate obtained in S2 is put into a tube furnace under nitrogen atmosphere to be burnt for 30 min at 150°C, and then the temperature is raised to 500°C to maintain for 40 min, and then PI-rGO composite is obtained, [0026] S4: the PI-rGO composite obtained in S3 is added into N-NIethylpyrrolidone, and then Pyralene and Polyvinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.1, and then Nanometer silicon particle, Carbon nano tube(CNT) and Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.3:0.13, and then conductive paste is obtained; [0027] SS: the conductive paste obtained in S4 is uniformly coated on a flat copper foil, and then put into an oven at 80°C to be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with a manual microtome, and then the required anode materials are obtained.
[0028] Embodiment 2 [0029] The preparation method for anode materials of lithium-ion batteries specifically comprises the following specific steps [0030] Si: the graphene oxide are added into the DMAc solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4i-Biphenyltetracarboxylic dianhydride are added to be reacted for 14h by stirring at 0°C, and then the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4i-Biphenyltetracarboxylic dianhydride is 1:1; [0031] S2: the acetic anhydride and the triethylamine dissolve in the DMAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:], after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 10h at 100°C, and then the concentrate is obtained; [0032] S3: the concentrate obtained in S2 is put into the tube furnace under nitrogen atmosphere to be burnt for 30 min at 250°C, and then the temperature is raised to 600°C to maintain for 40 mm, and then the PI-rGO composite is obtained; [0033] S4: the PI-rGO composite obtained in S3 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyvinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.65, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.5:0.23, and then the conductive paste is obtained; [0034] S5: the conductive paste obtained in S4 is uniformly coated on the flat copper foil, and then put into the oven at 80°Cto be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained.
[0035] Embodiment 3 [0036] The preparation method for anode materials of lithium-ion batteries specifically comprises the following specific steps [0037] Si: the graphene oxide are added into the DMAc solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4i-Biphenyltetracarboxylic dianhydride are added to be reacted for 11h by stirring at -2°C, and then the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4i-Biphenyltetracarboxylic dianhydride is 1:1; [0038] S2: the acetic anhydride and the triethylamine dissolve in the DMAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 8-10h at 70°C, and then the concentrate is obtained; [0039] S3: the concentrate obtained in S2 is put into the tube furnace under nitrogen atmosphere to be burnt for 30 min at 200°C, and then the temperature is raised to 550°C to maintain for 40 mm, and then the PI-rGO composite is obtained; [0040] S4: the PI-rGO composite obtained in S3 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyvinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.15, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.35:0.15, and then the conductive paste is obtained; [0041] 55. the conductive paste obtained in 54 is uniformly coated on the flat copper foil, and then put into the oven at 80°Cto be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained [0042] Embodiment 4 [0043] The preparation method for anode materials of lithium-ion batteries specifically comprises the following specific steps: [0044] Sl: the graphene oxide are added into the DMAc solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride are added to be reacted for 12h by stirring at -1°C, and then the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4!-Biphenyltetracarboxylic dianhydride is 1:1; [0045] S2: the acetic anhydride and the triethylam ne dissolve in the DNIAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 10h at 80°C, and then the concentrate is obtained; [0046] S3: the concentrate obtained in S2 is put into the tube furnace under nitrogen atmosphere to be burnt for 30 min at 150°C, and then the temperature is raised to 500°C to maintain for 40 mm, and then the PI-rGO composite is obtained, [0047] 54: the P1-rGO composite obtained in 53 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyyinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.45, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.4:0.16, and then the conductive paste is obtained; [0048] 55. the conductive paste obtained in 54 is uniformly coated on the flat copper foil, and then put into the oven at 80°Cto be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained [0049] Embodiment 5 [0050] The preparation method for anode materials of lithium-ion batteries specifically comprises the following specific steps: [0051] Sl: the graphene oxide are added into the DMAc solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride are added to be reacted for 10h by stirring at -3°C, and then the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4!-Biphenyltetracarboxylic dianhydride is 1:1; [0052] S2: the acetic anhydride and the triethylam ne dissolve in the DNIAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 10h at 90°C, and then the concentrate is obtained; [0053] S3: the concentrate obtained in S2 is put into the tube furnace under nitrogen atmosphere to be burnt for 30 min at 250°C, and then the temperature is raised to 550°C to maintain for 40 min, and then the PI-rGO composite is obtained, [0054] 54: the P1-rGO composite obtained in 53 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyyinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.55, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.43:0.19, and then the conductive paste is obtained; [0055] 55. the conductive paste obtained in 54 is uniformly coated on the flat copper foil, and then put into the oven at 80°Cto be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained [0056] Embodiment 6 [0057] The preparation method for anode materials of lithium-ion batteries specifically comprises the following specific steps: [0058] Sl: the graphene oxide are added into the DMAc solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride are added to be reacted for 14h by stirring at -3°C, and then the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4!-Biphenyltetracarboxylic dianhydride is 1:1; [0059] S2: the acetic anhydride and the triethylam ne dissolve in the DNIAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 10h at 95°C, and then the concentrate is obtained; [0060] S3: the concentrate obtained in S2 is put into the tube furnace under nitrogen atmosphere to be burnt for 30 min at 150°C, and then the temperature is raised to 500°C to maintain for 40 min, and then the PI-rGO composite is obtained, [0061] 54: the P1-rGO composite obtained in 53 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyvinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.6, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.48:0.21, and then the conductive paste is obtained; [0062] S5. the conductive paste obtained in S4 is uniformly coated on the flat copper foil, and then put into the oven at 80°Cto be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained [0063] Performance test [0064] SEM Test is performed to the anode materials prepared in embodiment 1, and the morphology is observed as figure 1, particles are relatively loose, the slurry is mixed evenly, no adhesion phenomenon exists; [0065] An electrochemical AC impedance test is performed by using an electrochemical workstation with a testing frequency range of 0.01-100KHz, an amplitude of.±.5mV, resistance Rst=80.260; referring to figure 2, the anode materials have a relative small resistance which is benefit for lithium-ion to perform a shuttle movements with a relative fast speed, as a relative resistance, thereby battery performance is able to be further improved.
[0066] A cycle performance and a coulombic efficiency are tested to the battery with a testing ampere density of 100mA 8-1, after cycling for 100 times, a capacity retention ratio is 90.6% and a coulombic efficiency is 85.5%, referring to figure 3, the present battery has a relative good cycle stability and a nice lithium-ion conductivity.
[0067] For testing the rate capacity, the present invention performs 5 cycles under different ampere densities; referring to figure 4, the present invention is basically resetting to original specific capacity, which demonstrates the anode materials has a reEative good rate capacity; above all, the anode materials have a less chance of adverse reactions in a cycling process, and moreover, the lithium-ion has a relative fast shuttle speed with a good conductivity and cycle stability.

Claims (4)

  2. I. A preparation method for anode materials of lithium-ion batteries, wherein technical proposal is listed as follows: a suitable amount of 2,2-Bis[4-(4-aminophenoxy) phenyl] hexafluoropropane, 3,3',4,4'-Biphenyltetracarboxylic dianhydride and graphene oxide are mixed to prepare PAA/GO, and then acetic anhydride and triethylamine are added to prepare concentrate, and then P1-rGO composite is obtained by a high-temperature firing, and then a suitable amount of N-Methylpyrrolidone, Pyralene, Polyvinylidene fluoride, Nanometer silicon particle, Carbon nano tube(CNT) and Beta-Cyclodextrin are added to obtain conductive paste, and furthermore, after being dried and cooled, the required anode materials are obtained by slicing on a manual microtome 2. The preparation method for anode materials of lithium-ion batteries defined in claim 1, wherein the preparation methods comprise the following specific steps: Sl: the graphene oxide are added into DMAc solvent to be stirred sufficiently and uniformly, and then the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4'-Biphenyltetracarboxylic dianhydride are added to be reacted for 10-14h by stirring at -3-0°C, and then Polyamic acid/ graphene oxide (PAA/GO) mixing liquid are obtained, wherein a mass ratio of the 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane monomer and the 3,3',4,4!-Biphenyltetracarboxylic dianhydride is 1:1; S2: the acetic anhydride and the triethylamine dissolve in the DMAc solvent for being stirred sufficiently and uniformly, wherein a mass ratio of the acetic anhydride and the triethylamine is 1:1, after being dissolved sufficiently by stirring, the Polyamic acid/ graphene oxide (PAA/GO) mixing liquid in Si is added slowly to be stirred more quickly and reacted for 8-10h at 65-100°C, and then the concentrate is obtained; S3: the concentrate obtained in S2 is put into a tube furnace under nitrogen atmosphere to be burnt for 30 min at 150-250°C, and then the temperature is raised to 500-600°C to maintain for 40 min, and then the PI-rGO composite is obtained; S4. the PI-rGO composite obtained in S3 is added into the N-Methylpyrrolidone, and then the Pyralene and the Polyvinylidene fluoride are added to be stirred, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride is 1:0.1-0.65, and then the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin are added for being stirred continuously, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin is 1:0.3-0.5:0.13-0.23, and then the conductive paste is obtained; S5. the conductive paste obtained in S4 is uniformly coated on a flat copper foil, and then put into an oven at 80°C to be dried for 15h, and then after taking out and being cooled, the coated copper foil is sliced into wafers with the manual microtome, and then the required anode materials are obtained.
  3. 3. The preparation method for anode materials of lithium-ion batteries defined in claim 1 or 2, wherein a mass ratio of the Pyralene and the Polyvinylidene fluoride added in above-stated S4 is 1:0.1-0.35.
  4. 4. The preparation method for anode materials of lithium-ion batteries defined in claim 1 or 2, wherein a mass ratio of the Nanometer silicon particle, the Carbon nano tube(CNT) and the Beta-Cyclodextrin added in above-stated S4 is 1:0.3-0.45:013-0.2.
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