WO2023273265A1 - 一种预锂化石墨烯及其制备方法和应用 - Google Patents

一种预锂化石墨烯及其制备方法和应用 Download PDF

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WO2023273265A1
WO2023273265A1 PCT/CN2021/142961 CN2021142961W WO2023273265A1 WO 2023273265 A1 WO2023273265 A1 WO 2023273265A1 CN 2021142961 W CN2021142961 W CN 2021142961W WO 2023273265 A1 WO2023273265 A1 WO 2023273265A1
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graphene
lithium
lithiated
preparation
oxide
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PCT/CN2021/142961
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English (en)
French (fr)
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张振华
李长东
范霞
毛林林
阮丁山
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to HU2200225A priority Critical patent/HUP2200225A1/hu
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of battery materials, in particular to a pre-lithiated graphene and its preparation method and application.
  • Graphene nanosheets have a huge impact on energy storage devices due to their unique structure, physical and electrical properties. Especially in terms of battery applications, graphene stands out among many carbon materials due to its ultra-high conductivity and large specific surface area. Although graphene has excellent electrochemical properties, the commercialization of graphene-based lithium-ion batteries has not been fully realized until now, due to the lack of large-scale synthetic methods to synthesize high-quality graphene. The current method of mass production of graphene commonly used is through the redox method.
  • natural graphite is prepared as graphene oxide by the Hummers method.
  • the reduction methods include thermal reduction, hydrothermal method and chemical method.
  • the final graphene electrode leads to capacity fading due to highly irreversible capacity.
  • the irreversible capacity is associated with the large specific surface area of graphene, leading to the consumption of a large amount of lithium ions for SEI film formation during the initial discharge process.
  • the possible method is pre-lithiation, including electrochemical reaction with lithium metal in the half-cell to generate SEI film, or introducing sacrificial lithium to the negative electrode through physical contact with lithium metal.
  • the preformed SEI film reduces the space for the formation of additional SEI films, thus preventing the generation of irreversible capacity.
  • the sacrificial lithium in the electrode makes up for the loss of lithium caused by the formation of the SEI film.
  • the pre-lithiated electrode has a lower voltage, which reduces the voltage difference between the positive and negative electrodes in the full battery, thereby increasing the energy density.
  • the electrochemical pre-lithiation has a large time loss due to the low current density; (2) the electrical overload may cause the battery to catch fire and explode during the process; (3) the use of bulk lithium for pre-lithiation The lithiation efficiency is low.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a kind of pre-lithiated graphene and its preparation method and application, and this pre-lithiated graphene is the compound of graphene and lithium, graphene and lithium-containing compound, and part lithium and graphite Graphene is connected by ionic bonds, and part of lithium will form other lithium-containing compounds evenly distributed on the surface of graphene and lithium film.
  • the prepared pre-lithiated graphene has a large specific surface area and contains more micropores and mesoporous defects, which is conducive to the diffusion and migration of lithium ions. Lithium ions are consumed during charge and discharge, so pre-lithiated graphene has high reversible charge specific capacity, high cycle stability and high rate performance.
  • the present invention adopts the following technical solutions:
  • a pre-lithiated graphene comprising the following components: lithium oxide, lithium carbide; the lithium carbide is Li 2 CO 3 , LiC x and R-Li, wherein R is reduced graphene oxide , 1/6 ⁇ x ⁇ 1.
  • Reduced graphene oxide is graphene oxide, which is the product obtained by the reaction of Li + (C 10 H 14 ) - and graphene oxide.
  • the lithium oxide is lithium oxide.
  • the specific surface area of the pre-lithiated graphene is 79.66-104m 2 g -1
  • the reversible specific capacity of the pre-lithiated graphene is 490-660mAh g -1 .
  • the present invention also provides a kind of preparation method of pre-lithiated graphene, comprising the following steps:
  • Reaction equation Li+C 10 H 14 ⁇ Li + (C 10 H 14 ) - , Li + (C 10 H 14 ) - +R-OH ⁇ LiO 2 +Li 2 CO 3 +LiC x +R-Li.
  • R is reduced graphene oxide.
  • the electron transfer carrier is at least one of tert-butylbenzene, tert-butylbenzo and 4,4-di-tert-butylbenzo.
  • the lithium source is simple lithium.
  • the mass ratio of the lithium element to graphene oxide is (1-5):100.
  • the solvent is N-methylpyrrolidone.
  • the temperature of the reaction is 30-100°C.
  • the reaction atmosphere is argon or nitrogen.
  • the stirring speed of the reaction is 100 rpm to 400 rpm.
  • the drying temperature is 80-90° C.
  • the drying time is 12-18 hours.
  • Lithium metal will first form a compound with the electron transfer carrier, the lithium metal is oxidized to lithium ions, and the electron transfer carrier becomes a negatively charged active group anion, which will react with the oxygen-containing functional group in graphene oxide , the benzene ring in the active group will replace the oxygen-containing functional group, restore the ⁇ - ⁇ structure of graphene, thereby achieve the effect of reducing graphene oxide, and inhibit the generation of structural defects during the reduction process, thereby restoring the electrical conductivity of graphene.
  • lithium is also introduced into graphene to form complexes (lithium carbide, lithium carbonate, lithium oxide, etc.).
  • the formed lithium complex can not only reduce the loss of lithium ions during battery cycling, but also act as a lithium supplement.
  • substances such as lithium carbonate and lithium oxide formed will increase the layer spacing between graphene, thereby promoting the deintercalation of lithium ions, thereby improving the reversible specific capacity and cycle stability.
  • a preparation method of graphene negative electrode comprising the following steps:
  • the mass ratio of the pre-lithiated graphene to the adhesive is (90-95):(5-10).
  • the adhesive is styrene-butadiene rubber.
  • the solvent is N-methylpyrrolidone.
  • the drying temperature is 90-100° C.
  • the drying time is 0.5-2 h
  • the drying atmosphere is argon or nitrogen.
  • the heat treatment temperature is 100-120° C.
  • the heat treatment time is 10-12 hours.
  • a graphene negative electrode is prepared by the preparation method.
  • a battery comprising the following components: lithium metal foil, diaphragm, graphene negative electrode, and electrolyte.
  • the separator is a polypropylene film.
  • the electrolyte is LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • the concentration of LiPF 6 is 1 mol/L.
  • the volume ratio of the ethylene carbonate, dimethyl carbonate and diethyl carbonate is 1:1:1.
  • the pre-lithiated graphene of the present invention is a composite of graphene and lithium, graphene and a lithium-containing compound. In the composite, part of lithium and graphene are connected by ionic bonds, and part of lithium will form other lithium-containing compounds. Distributed on the surface of graphene and lithium films.
  • the prepared pre-lithiated graphene has a large specific surface area and contains more micropores and mesoporous defects, which is conducive to the diffusion and migration of lithium ions.
  • the lithium ions consumed during the charging and discharging process are supplemented, so the pre-lithiated graphene has high reversible charge specific capacity, high cycle stability and high rate performance.
  • the chemical method of the present invention synthesizes pre-lithiated graphene. Compared with the conventional pre-lithiated method of intercalating lithium into the graphene layer, it can more effectively reduce the loss of lithium in the electrolyte, and can complete the production of graphene oxide in one step. Reduction and pre-lithiation are simple and efficient, and provide a direction for the large-scale preparation of graphene for negative electrodes.
  • the present invention selects lithium simple substance instead of lithium salt or other compounds as the lithium source of pre-lithiated graphene, not only because it can effectively react with the electron transfer carrier to further improve the efficiency of reducing graphene oxide, but also can form more Lithium carbide, compared with lithium carbonate or lithium oxide, is more conducive to the improvement of reversible capacity.
  • Fig. 1 is the SEM figure of the pre-lithiated graphene of the embodiment of the present invention 2;
  • Fig. 2 is the high-resolution C1s figure in the X-ray photoelectron energy spectrum analysis of the pre-lithiated graphene of the embodiment of the present invention 2;
  • Fig. 3 is the high-resolution Lis figure in the X-ray photoelectron energy spectrum analysis of the pre-lithiated graphene of the embodiment of the present invention 2;
  • Fig. 4 is the N of the pre-lithiated graphene of embodiment 2 of the present invention Adsorption and desorption constant temperature curve;
  • Fig. 5 is a graph showing the pore size distribution of the pre-lithiated graphene according to Example 2 of the present invention.
  • the pre-lithiated graphene of this embodiment includes the following components: LiO 2 , Li 2 CO 3 , LiC x , R-Li, wherein R is reduced graphene oxide, 1/6 ⁇ x ⁇ 1; pre-lithiated The specific surface area of graphene is 81.18m 2 g -1 , and the reversible specific capacity of pre-lithiated graphene is 540mAh g -1 .
  • Lithium metal will first form a compound with the electron transfer carrier, the lithium metal is oxidized to lithium ions, and the electron transfer carrier becomes a negatively charged active group anion, which will react with the oxygen-containing functional group in graphene oxide , the benzene ring in the active group will replace the oxygen-containing functional group, restore the ⁇ - ⁇ structure of graphene, thereby achieve the effect of reducing graphene oxide, and inhibit the generation of structural defects during the reduction process, thereby restoring the electrical conductivity of graphene.
  • lithium is also introduced into graphene to form complexes (lithium carbide, lithium carbonate, lithium oxide, etc.).
  • the formed lithium complex can not only reduce the loss of lithium ions during battery cycling, but also act as a lithium supplement.
  • substances such as lithium carbonate and lithium oxide formed will increase the layer spacing between graphene, thereby promoting the deintercalation of lithium ions, thereby improving the reversible specific capacity and cycle stability.
  • a preparation method of graphene negative electrode comprising the following steps:
  • the coating process is carried out in a glove box filled with argon , and then dried in an argon atmosphere at 90°C for 1h to obtain a pole piece, put the pole piece under vacuum conditions, heat treatment at 100°C for 12h, remove the remaining solvent and the unreacted electron transfer carrier added before, and obtain graphene
  • the loading capacity of the pre-lithiated graphene is 1.2 mg cm ⁇ 2 .
  • a battery comprising the following components: lithium metal foil, polypropylene film, graphene negative electrode, LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • Preparation of battery Dissolve 1mol/L LiPF 6 in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate with a volume ratio of 1:1:1 to prepare an electrolyte, and then add lithium
  • the metal foil is the positive electrode
  • the polypropylene film is the diaphragm
  • the graphene negative electrode is composed of a coin-shaped half-cell.
  • the electrochemical performance of the coin-shaped half-cell was tested, and the charge-discharge and cycle stability were measured with an electrochemical workstation at a current density of 30mA g -1 and a voltage of 0.01-3.0V (vs. Li/Li + ).
  • the rate performance is measured at a current density of 50-1000mA g -1 .
  • the pre-lithiated graphene of this embodiment includes the following components: LiO 2 , Li 2 CO 3 , LiC x , R-Li, wherein R is reduced graphene oxide, 1/6 ⁇ x ⁇ 1; pre-lithiated
  • the specific surface area of graphene is 103.21m 2 g -1
  • the reversible specific capacity of pre-lithiated graphene is 651mAh g -1 .
  • a preparation method of graphene negative electrode comprising the following steps:
  • the coating process is carried out in a glove box filled with argon , and then dried in an argon atmosphere at 90°C for 1h to obtain a pole piece, put the pole piece under vacuum conditions, heat treatment at 100°C for 12h, remove the remaining solvent and the unreacted electron transfer carrier added before, and obtain graphene
  • the loading capacity of the pre-lithiated graphene is 1.2 mg cm ⁇ 2 .
  • a battery comprising the following components: lithium metal foil, polypropylene film, graphene negative electrode, LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • Preparation of battery Dissolve 1mol/L LiPF 6 in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate with a volume ratio of 1:1:1 to prepare an electrolyte, and then add lithium
  • the metal foil is the positive electrode
  • the polypropylene film is the diaphragm
  • the graphene negative electrode is composed of a coin-shaped half-cell.
  • the electrochemical performance of the coin-shaped half-cell was tested, and the charge-discharge and cycle stability were measured with an electrochemical workstation at a current density of 30mA g -1 and a voltage of 0.01-3.0V (vs. Li/Li + ).
  • the rate performance is measured at a current density of 50-1000mA g -1 .
  • Fig. 1 is the SEM figure of the pre-lithiated graphene of the embodiment 2 of the present invention. From Fig. 1, the lithium compound with uniform distribution on the surface of the graphene film can be obtained.
  • Fig. 2 is the high-resolution C1s figure in the X-ray photoelectron spectroscopy analysis of the pre-lithiated graphene of the embodiment of the present invention 2;
  • Fig. 3 is in the X-ray photoelectron spectroscopy analysis of the pre-lithiated graphene of the embodiment of the present invention 2
  • Figure 2 and Figure 3 prove the existence of LiCO 3 , Li 2 O, and C-Li, indicating that graphene oxide is not only pre-lithiated but also effectively reduced, and the resulting lithium complexes and SEI film components Similarly, it is therefore possible to effectively suppress the formation of the SEI film during charge and discharge.
  • Fig. 4 is the N of the pre-lithiated graphene of the embodiment of the present invention 2 Adsorption and desorption constant temperature curve figure (nitrogen relative pressure);
  • Fig. 5 is the pore size distribution curve figure of the pre-lithiated graphene of the embodiment of the present invention 2;
  • Fig. 4 and Figure 5 show that the pore size in pre-lithiated graphene is mainly distributed in the range of 60-160nm, and these pore structures are conducive to the diffusion of lithium ions on the surface and inside of graphene.
  • the pre-lithiated graphene of this embodiment includes the following components: LiO 2 , Li 2 CO 3 , LiC x , R-Li, wherein R is reduced graphene oxide, 1/6 ⁇ x ⁇ 1; pre-lithiated The specific surface area of graphene is 94.7m 2 g -1 , and the reversible specific capacity of pre-lithiated graphene is 572mAh g -1 .
  • a preparation method of graphene negative electrode comprising the following steps:
  • the coating process is carried out in a glove box filled with argon , and then dried in an argon atmosphere at 90°C for 1h to obtain a pole piece, put the pole piece under vacuum conditions, heat treatment at 100°C for 12h, remove the remaining solvent and the unreacted electron transfer carrier added before, and obtain graphene
  • the loading capacity of the pre-lithiated graphene is 1.2 mg cm ⁇ 2 .
  • a battery comprising the following components: lithium metal foil, polypropylene film, graphene negative electrode, LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • Preparation of battery Dissolve 1mol/L LiPF 6 in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate with a volume ratio of 1:1:1 to prepare an electrolyte, and then add lithium
  • the metal foil is the positive electrode
  • the polypropylene film is the diaphragm
  • the graphene negative electrode is composed of a coin-shaped half-cell.
  • the electrochemical performance of the coin-shaped half-cell was tested, and the charge-discharge and cycle stability were measured with an electrochemical workstation at a current density of 30mA g -1 and a voltage of 0.01-3.0V (vs. Li/Li + ).
  • the rate performance is measured at a current density of 50-1000mA g -1 .
  • the pre-lithiated graphene in this embodiment includes the following components: LiO 2 , Li 2 CO 3 , LiC x , R-Li, wherein R is reduced graphene oxide, 1/6 ⁇ x ⁇ 1; the pre-lithiated The specific surface area of graphene is 79.66m 2 g -1 , and the reversible specific capacity of pre-lithiated graphene is 493mAh g -1 .
  • a preparation method of graphene negative electrode comprising the following steps:
  • the coating process is carried out in a glove box filled with argon , and then dried in an argon atmosphere at 90°C for 1h to obtain a pole piece, put the pole piece under vacuum conditions, heat treatment at 100°C for 12h, remove the remaining solvent and the unreacted electron transfer carrier added before, and obtain graphene
  • the loading capacity of the pre-lithiated graphene is 1.2 mg cm ⁇ 2 .
  • a battery comprising the following components: lithium metal foil, polypropylene film, graphene negative electrode, LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • Preparation of battery Dissolve 1mol/L LiPF 6 in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate with a volume ratio of 1:1:1 to prepare an electrolyte, and then add lithium
  • the metal foil is the positive electrode
  • the polypropylene film is the diaphragm
  • the graphene negative electrode is composed of a coin-shaped half-cell.
  • the electrochemical performance of the coin-shaped half-cell was tested, and the charge-discharge and cycle stability were measured with an electrochemical workstation at a current density of 30mA g -1 and a voltage of 0.01-3.0V (vs. Li/Li + ).
  • the rate performance is measured at a current density of 50-1000mA g -1 .
  • the preparation method of the graphene negative pole of this comparative example comprises the following steps:
  • a battery comprising the following components: lithium metal foil, polypropylene film, graphene negative electrode, LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • Preparation of battery Dissolve 1mol/L LiPF 6 in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate with a volume ratio of 1:1:1 to prepare an electrolyte, and then add lithium
  • the metal foil is the positive electrode
  • the polypropylene film is the diaphragm
  • the graphene negative electrode is composed of a coin-shaped half-cell.
  • the electrochemical performance of the coin-shaped half-cell was tested, and the charge-discharge and cycle stability were measured with an electrochemical workstation at a current density of 30mA g -1 and a voltage of 0.01-3.0V (vs. Li/Li + ).
  • the rate performance is measured at a current density of 50-1000mA g -1 .
  • the preparation method of the reduced graphene oxide of this comparative example comprises the following steps:
  • a preparation method of graphene negative electrode comprising the following steps:
  • a battery comprising the following components: lithium metal foil, polypropylene film, graphene negative electrode, LiPF 6 , ethylene carbonate, dimethyl carbonate and diethyl carbonate.
  • Preparation of battery Dissolve 1mol/L LiPF 6 in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate with a volume ratio of 1:1:1 to prepare an electrolyte, and then add lithium
  • the metal foil is the positive electrode
  • the polypropylene film is the diaphragm
  • the graphene negative electrode is composed of a coin-shaped half-cell.
  • the electrochemical performance of the coin-shaped half-cell was tested, and the charge-discharge and cycle stability were measured with an electrochemical workstation at a current density of 30mA g -1 and a voltage of 0.01-3.0V (vs. Li/Li + ).
  • the rate performance is measured at a current density of 50-1000mA g -1 .
  • Table 1 is a comparison of the specific surface area of the samples prepared in Examples 1, 2, 3, 4 and Comparative Examples 1 and 2. It is found that the specific surface area of pre-lithiated graphene is significantly higher than that of the Comparative Example, especially in Example 2. The specific surface area is the largest.
  • Table 2 is the comparison of the electrochemical properties of the samples prepared in Examples 1, 2, 3, 4 and Comparative Examples 1, 2. It is found that the reversible charge specific capacity, The cycle stability and rate performance are higher than those of Comparative Examples 1 and 2, especially the electrochemical performance of Example 2 is obviously excellent.

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Abstract

提供了一种预锂化石墨烯及其制备方法和应用，预锂化石墨烯包括以下组分：锂的氧化物、锂的碳化物；锂的碳化物为Li 2CO 3、LiC x、R-Li，其中，R为还原氧化石墨烯，1/6≤x≤1。预锂化石墨烯为石墨烯与锂、石墨烯与含锂化合物的复合物，复合物中部分锂与石墨烯是以离子键相连，部分锂会形成其他含锂化合物均匀分布在石墨烯与锂的薄膜表面。

Description

一种预锂化石墨烯及其制备方法和应用 技术领域
本发明电池材料技术领域，具体涉及一种预锂化石墨烯及其制备方法和应用。
背景技术
石墨烯纳米片因为有着独特的结构，物理和电学性能在储能设备方面有着巨大的影响力。尤其，在电池应用方面，超高的导电性和大的比表面积促使石墨烯在众多碳材料中脱颖而出。虽然石墨烯拥有优异的电化学性质，但是直到现在石墨烯基的锂离子电池商业化还没有完全实现，原因则是缺少规模化的合成方法来合成高质量的石墨烯。而目前常用的大量生产石墨烯的方法则是通过氧化还原法。
通常，利用Hummers法将天然石墨制备为氧化石墨烯。而还原方法则包括热还原、水热法和化学方法等。虽然石墨烯的制备方法众多，但最终石墨烯电极由于高度不可逆容量导致容量的衰减。不可逆容量与石墨烯大的比表面积相关，导致在初次放电过程中SEI膜形成消耗了大量的锂离子。为了防止电解液中锂离子浓度降低，可能的方法就是预锂化，包括在半电池中与锂金属产生电化学反应产生SEI膜，或者通过与锂金属物理接触向负极引入牺牲锂。预先形成的SEI膜减少了形成额外SEI膜的空间，因此防止了不可逆容量的产生。同时，电极中的牺牲锂补足了形成SEI膜形成造成的锂损失。另外，预锂化电极拥有更低的电压，减小了全电池中正负极的电压差，从而提高能量密度。然后之前的预锂化方法存在一些缺陷：(1)电化学预锂化由于低电流密度，时间损耗大；(2)过程中电气过载可能产生电池着火爆炸；(3)使用大块锂进行预锂化效率低。
因此，需要一种稳定高效的预锂化石墨烯及其预锂化方法。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种预锂化石墨烯及其制备方法和应用，该预锂化石墨烯为石墨烯与锂、石墨烯与含锂化合物的复合物，该复合物中部分锂与石墨烯是以离子键相连，部分锂会形成其他含锂化合物均匀分布在石墨烯与锂的薄膜表面。所制备的预锂化石墨烯比表面积大，含有较多的微孔和介孔缺陷，有利于锂离子的扩散和迁移，同时较大的比表面积有助于Li的复合， 从而更有效的补充充放电过程中消耗的锂离子，因此预锂化石墨烯具有高可逆充电比容量、高循环稳定性和高倍率性能。
为实现上述目的，本发明采用以下技术方案：
一种预锂化石墨烯，包括以下组分：锂的氧化物、锂的碳化物；所述锂的碳化物为Li 2CO 3、LiC x和R-Li，其中，R为还原氧化石墨烯，1/6≤x≤1。
还原氧化石墨烯是由氧化石墨烯，是由Li +(C 10H 14) -和氧化石墨烯反应得到的产物。
优选地，所述锂的氧化物为氧化锂。
优选地，所述预锂化石墨烯的比表面积为79.66-104m 2g -1，所述预锂化石墨烯的可逆比容量为490-660mAh g -1。
本发明还提供一种预锂化石墨烯的制备方法，包括以下步骤：
将锂源、氧化石墨烯、电子转移载体混合，加入溶剂，反应，干燥，即得预锂化石墨烯。
反应方程式：Li+C 10H 14→Li +(C 10H 14) -，Li +(C 10H 14) -+R-OH→LiO 2+Li 2CO 3+LiC x+R-Li。R为还原氧化石墨烯。
优选地，所述电子转移载体为叔丁基苯、叔丁基苯并和4,4-二叔丁基苯并中的至少一种。
优选地，所述锂源为锂单质。
优选地，所述锂单质、氧化石墨烯的质量比为(1-5):100。
优选地，所述溶剂为N-甲基吡咯烷酮。
优选地，所述反应的温度为30-100℃。
优选地，所述反应的气氛为氩气或氮气。
优选地，所述反应的搅拌转速为100rpm～400rpm。
优选地，所述干燥的温度为80-90℃，干燥的时间为12-18h。
预锂化石墨烯的制备原理：
锂金属会先与电子转移载体形成化合物，锂金属氧化为锂离子，而电子转移载体则变为带负电的活性基团阴离子，该活性基团离子会与氧化石墨烯中的含氧官能团进行反应，活性基团中的苯环会取代含氧官能团，恢复石墨烯的π-π结构，从而达到还原氧化石墨烯的效果，并且抑制还原过程中结构缺陷的产生，从而恢复石墨烯的导电能力。 同时也将锂引入了石墨烯中，形成复合物(碳化锂，碳酸锂，氧化锂等)。形成的锂复合物不仅能减少电池循环过程中锂离子的损耗，同时起到补锂的作用。另外形成的碳酸锂和氧化锂等物质会增大石墨烯之间的层间距，从而促进锂离子的脱嵌，从而提高可逆比容量和循环稳定性。
一种石墨烯负极的制备方法，包括以下步骤：
将所述预锂化石墨烯、胶黏剂、溶剂混合，涂覆在铜箔，干燥，热处理，即得所述石墨烯负极，所述预锂化石墨烯的负载量为1.2-1.5mg cm -2。
优选地，所述预锂化石墨烯、胶黏剂的质量比为(90-95):(5-10)。
优选地，所述胶黏剂为丁苯橡胶。
优选地，所述溶剂为N-甲基吡咯烷酮。
优选地，所述干燥的温度为90-100℃，干燥的时间为0.5-2h，干燥的气氛为氩气气氛或氮气。
优选地，所述热处理的温度为100-120℃，热处理的时间为10～12h。
一种石墨烯负极，由所述的制备方法制备得到。
一种电池，包括以下组分：锂金属箔、隔膜、石墨烯负极、电解液。
优选地，所述隔膜为聚丙烯膜。
优选地，所述电解液为LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
进一步优选地，所述LiPF 6的浓度为1mol/L。
进一步优选地，所述碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的体积比为1:1:1。
相对于现有技术，本发明的有益效果如下：
1、本发明的预锂化石墨烯为石墨烯与锂、石墨烯与含锂化合物的复合物，该复合物中部分锂与石墨烯是以离子键相连，部分锂会形成其他含锂化合物均匀分布在石墨烯与锂的薄膜表面。所制备的预锂化石墨烯的比表面积大，含有较多的微孔和介孔缺陷，有利于锂离子的扩散和迁移，同时较大的比表面积有助于Li的复合，从而更有效的补充充放电过程中消耗的锂离子，因此预锂化石墨烯具有高可逆充电比容量、高循环稳定性和高倍率性能。
2、本发明化学法合成预锂化石墨烯，相比于常规的把锂嵌入到石墨烯层间的预锂化方法，更有效的减少电解液中锂的损耗，可一步完成氧化石墨烯的还原与预锂化，简 单高效，为大规模制备负极用石墨烯提供了方向。
3、本发明选用锂单质而非锂盐或其他化合物作为预锂化石墨烯的锂源，不仅因为它可以与电子转移载体有效反应从而进一步提高还原氧化石墨烯的效率，同时可以形成更多的碳化锂，相比于碳酸锂或氧化锂等，其更有助于可逆容量的提升。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明实施例2的预锂化石墨烯的SEM图；
图2为本发明实施例2的预锂化石墨烯的X射线光电子能谱分析中的高分辨C1s图；
图3为本发明实施例2的预锂化石墨烯的X射线光电子能谱分析中的高分辨Li1s图；
图4为本发明实施例2的预锂化石墨烯的N 2吸脱附恒温曲线图；
图5为本发明实施例2的预锂化石墨烯的孔径分布曲线图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
本实施例的预锂化石墨烯，包括以下组分：LiO 2、Li 2CO 3、LiC x、R-Li，其中，R为还原氧化石墨烯，1/6≤x≤1；预锂化石墨烯的比表面积为81.18m 2g -1，预锂化石墨烯的可逆比容量为540mAh g -1。
锂与氧化石墨烯的质量比不同导致反应生成的碳化锂含量不同，从而导致可逆比容量不同，另外预锂化与还原氧化石墨烯同步完成，不同的Li配比导致还原程度不同，造成缺陷不同，从而比表面积不同。
本实施例的预锂化石墨烯的制备方法，包括以下步骤：
称取质量比为2wt％的锂金属和氧化石墨烯放入容器中，再加入叔丁基苯、叔丁基苯并，得到混合物，向容器内的混合物中倒入N-甲基吡咯烷酮作为溶剂，得到浆料， 通入氮气排除烧杯中的空气，对浆料进行磁力搅拌，转速为300rpm，反应温度为70℃，搅拌2h后，将浆料水洗过滤后置于真空干燥箱中，80℃真空干燥15h，获得预锂化石墨烯。
预锂化石墨烯的制备原理：
锂金属会先与电子转移载体形成化合物，锂金属氧化为锂离子，而电子转移载体则变为带负电的活性基团阴离子，该活性基团离子会与氧化石墨烯中的含氧官能团进行反应，活性基团中的苯环会取代含氧官能团，恢复石墨烯的π-π结构，从而达到还原氧化石墨烯的效果，并且抑制还原过程中结构缺陷的产生，从而恢复石墨烯的导电能力。同时也将锂引入了石墨烯中，形成复合物(碳化锂，碳酸锂，氧化锂等)。形成的锂复合物不仅能减少电池循环过程中锂离子的损耗，同时起到补锂的作用。另外形成的碳酸锂和氧化锂等物质会增大石墨烯之间的层间距，从而促进锂离子的脱嵌，从而提高可逆比容量和循环稳定性。
一种石墨烯负极的制备方法，包括以下步骤：
将90wt％的活性材料与10wt％的丁苯橡胶粘接剂放入N-甲基吡咯烷酮溶剂中搅拌，并将浆料涂覆在铜箔上，涂覆过程在充满氩气的手套箱中进行，然后在氩气气氛和90℃下干燥1h，得到极片，将极片置于真空条件下，100℃热处理12h，除去剩余的溶剂以及之前所添加的未反应的电子转移载体，得到石墨烯负极，其中，预锂化石墨烯的负载量为1.2mg cm -2。
一种电池，包括以下组分：锂金属箔、聚丙烯膜、石墨烯负极、LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
制备电池：将1mol/L的LiPF 6溶解在体积比为1:1:1的碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合混合溶液中制备而成的电解液，再以锂金属箔为正极，聚丙烯膜为隔膜，与石墨烯负极组成为硬币型半电池。
将硬币型半电池进行电化学性能检测，充放电和循环稳定性用电化学工作站在电流密度30mA g -1，电压0.01-3.0V(vs.Li/Li +)下进行测量。倍率性能则是在电流密度50-1000mA g -1下测量。
实施例2
本实施例的预锂化石墨烯，包括以下组分：LiO 2、Li 2CO 3、LiC x、R-Li，其中，R为还原氧化石墨烯，1/6≤x≤1；预锂化石墨烯的比表面积为103.21m 2g -1，预锂化石墨 烯的可逆比容量为651mAh g -1。
本实施例的预锂化石墨烯的制备方法，包括以下步骤：
称取质量比为4wt％的锂金属和氧化石墨烯放入容器中，再加入叔丁基苯、叔丁基苯并，得到混合物，向容器内的混合物中倒入N-甲基吡咯烷酮作为溶剂，得到浆料，通入氮气排除烧杯中的空气，对浆料进行磁力搅拌，转速为300rpm，反应温度为70℃，搅拌2h后，将浆料水洗过滤后置于真空干燥箱中，80℃真空干燥15h，获得预锂化石墨烯。
一种石墨烯负极的制备方法，包括以下步骤：
将90wt％的活性材料与10wt％的丁苯橡胶粘接剂放入N-甲基吡咯烷酮溶剂中搅拌，并将浆料涂覆在铜箔上，涂覆过程在充满氩气的手套箱中进行，然后在氩气气氛和90℃下干燥1h，得到极片，将极片置于真空条件下，100℃热处理12h，除去剩余的溶剂以及之前所添加的未反应的电子转移载体，得到石墨烯负极，其中，预锂化石墨烯的负载量为1.2mg cm -2。
一种电池，包括以下组分：锂金属箔、聚丙烯膜、石墨烯负极、LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
制备电池：将1mol/L的LiPF 6溶解在体积比为1:1:1的碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合混合溶液中制备而成的电解液，再以锂金属箔为正极，聚丙烯膜为隔膜，与石墨烯负极组成为硬币型半电池。
将硬币型半电池进行电化学性能检测，充放电和循环稳定性用电化学工作站在电流密度30mA g -1，电压0.01-3.0V(vs.Li/Li +)下进行测量。倍率性能则是在电流密度50-1000mA g -1下测量。
图1为本发明实施例2的预锂化石墨烯的SEM图；从图1可得石墨烯薄膜表面分布均匀的锂复合物。
图2为本发明实施例2的预锂化石墨烯的X射线光电子能谱分析中的高分辨C1s图；图3为本发明实施例2的预锂化石墨烯的X射线光电子能谱分析中的高分辨Li1s图；图2和图3证明了LiCO 3，Li 2O，C-Li的存在，说明氧化石墨烯不仅被预锂化同时也被有效还原，生成的锂复合物与SEI膜成分类似，因此可以有效抑制充放电过程中SEI膜的形成。
图4为本发明实施例2的预锂化石墨烯的N 2吸脱附恒温曲线图(氮气相对压力)； 图5为本发明实施例2的预锂化石墨烯的孔径分布曲线图；图4和图5说明预锂化石墨烯中孔径主要分布在60-160nm，这些孔结构有助于锂离子在石墨烯表面和内部扩散。
实施例3
本实施例的预锂化石墨烯，包括以下组分：LiO 2、Li 2CO 3、LiC x、R-Li，其中，R为还原氧化石墨烯，1/6≤x≤1；预锂化石墨烯的比表面积为94.7m 2g -1，预锂化石墨烯的可逆比容量为572mAh g -1。
本实施例的预锂化石墨烯的制备方法，包括以下步骤：
称取质量比为6wt％的锂金属和氧化石墨烯放入容器中，再加入叔丁基苯、叔丁基苯并，得到混合物，向容器内的混合物中倒入N-甲基吡咯烷酮作为溶剂，得到浆料，通入氮气排除烧杯中的空气，对浆料进行磁力搅拌，转速为300rpm，反应温度为70℃，搅拌2h后，将浆料水洗过滤后置于真空干燥箱中，80℃真空干燥15h，获得预锂化石墨烯。
一种石墨烯负极的制备方法，包括以下步骤：
将90wt％的活性材料与10wt％的丁苯橡胶粘接剂放入N-甲基吡咯烷酮溶剂中搅拌，并将浆料涂覆在铜箔上，涂覆过程在充满氩气的手套箱中进行，然后在氩气气氛和90℃下干燥1h，得到极片，将极片置于真空条件下，100℃热处理12h，除去剩余的溶剂以及之前所添加的未反应的电子转移载体，得到石墨烯负极，其中，预锂化石墨烯的负载量为1.2mg cm -2。
一种电池，包括以下组分：锂金属箔、聚丙烯膜、石墨烯负极、LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
制备电池：将1mol/L的LiPF 6溶解在体积比为1:1:1的碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合混合溶液中制备而成的电解液，再以锂金属箔为正极，聚丙烯膜为隔膜，与石墨烯负极组成为硬币型半电池。
将硬币型半电池进行电化学性能检测，充放电和循环稳定性用电化学工作站在电流密度30mA g -1，电压0.01-3.0V(vs.Li/Li +)下进行测量。倍率性能则是在电流密度50-1000mA g -1下测量。
实施例4
本实施例的预锂化石墨烯，包括以下组分：LiO 2、Li 2CO 3、LiC x、R-Li，其中，R 为还原氧化石墨烯，1/6≤x≤1；预锂化石墨烯的比表面积为79.66m 2g -1，预锂化石墨烯的可逆比容量为493mAh g -1。
本实施例的预锂化石墨烯的制备方法，包括以下步骤：
称取质量比为8wt％的锂金属和氧化石墨烯放入容器中，再加入叔丁基苯、叔丁基苯并，得到混合物，向容器内的混合物中倒入N-甲基吡咯烷酮作为溶剂，得到浆料，通入氮气排除烧杯中的空气，对浆料进行磁力搅拌，转速为300rpm，反应温度为70℃，搅拌2h后，将浆料水洗过滤后置于真空干燥箱中，80℃真空干燥15h，获得预锂化石墨烯。
一种石墨烯负极的制备方法，包括以下步骤：
将90wt％的活性材料与10wt％的丁苯橡胶粘接剂放入N-甲基吡咯烷酮溶剂中搅拌，并将浆料涂覆在铜箔上，涂覆过程在充满氩气的手套箱中进行，然后在氩气气氛和90℃下干燥1h，得到极片，将极片置于真空条件下，100℃热处理12h，除去剩余的溶剂以及之前所添加的未反应的电子转移载体，得到石墨烯负极，其中，预锂化石墨烯的负载量为1.2mg cm -2。
一种电池，包括以下组分：锂金属箔、聚丙烯膜、石墨烯负极、LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
制备电池：将1mol/L的LiPF 6溶解在体积比为1:1:1的碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合混合溶液中制备而成的电解液，再以锂金属箔为正极，聚丙烯膜为隔膜，与石墨烯负极组成为硬币型半电池。
将硬币型半电池进行电化学性能检测，充放电和循环稳定性用电化学工作站在电流密度30mA g -1，电压0.01-3.0V(vs.Li/Li +)下进行测量。倍率性能则是在电流密度50-1000mA g -1下测量。
对比例1
本对比例的石墨烯负极的制备方法，包括以下步骤：
将90wt％的氧化石墨烯与10wt％的丁苯橡胶粘接剂放入N-甲基吡咯烷酮溶剂中搅拌，并将浆料涂覆在铜箔上，涂覆过程在充满氩气的手套箱中进行，然后在氩气气氛和90℃下干燥1h，得到极片，将极片置于真空条件下，100℃热处理12h，得到石墨烯负极，其中，氧化石墨烯的负载量为1.2mg cm -2。
一种电池，包括以下组分：锂金属箔、聚丙烯膜、石墨烯负极、LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
制备电池：将1mol/L的LiPF 6溶解在体积比为1:1:1的碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合混合溶液中制备而成的电解液，再以锂金属箔为正极，聚丙烯膜为隔膜，与石墨烯负极组成为硬币型半电池。
将硬币型半电池进行电化学性能检测，充放电和循环稳定性用电化学工作站在电流密度30mA g -1，电压0.01-3.0V(vs.Li/Li +)下进行测量。倍率性能则是在电流密度50-1000mA g -1下测量。
对比例2
本对比例的还原氧化石墨烯的制备方法，包括以下步骤：
称取氧化石墨烯放入容器中，加入水合肼，在80℃下磁力搅拌12h，将浆料过滤后90℃真空干燥10h，将干燥后的固体置于管式炉中，在4:1的氩气和氢气混合气体中，150℃热处理6h，获得还原氧化石墨烯。
一种石墨烯负极的制备方法，包括以下步骤：
将90wt％的还原氧化石墨烯与10wt％的丁苯橡胶粘接剂放入N-甲基吡咯烷酮溶剂中搅拌，并将浆料涂覆在铜箔上，涂覆过程在充满氩气的手套箱中进行，然后在氩气气氛和90℃下干燥1h，得到极片，将极片置于真空条件下，100℃热处理12h，除去剩余的溶剂以及之前所添加的未反应的电子转移载体，得到石墨烯负极，其中，还原氧化石墨烯的负载量为1.2mg cm -2。
一种电池，包括以下组分：锂金属箔、聚丙烯膜、石墨烯负极、LiPF 6、碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯。
制备电池：将1mol/L的LiPF 6溶解在体积比为1:1:1的碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合混合溶液中制备而成的电解液，再以锂金属箔为正极，聚丙烯膜为隔膜，与石墨烯负极组成为硬币型半电池。
将硬币型半电池进行电化学性能检测，充放电和循环稳定性用电化学工作站在电流密度30mA g -1，电压0.01-3.0V(vs.Li/Li +)下进行测量。倍率性能则是在电流密度50-1000mA g -1下测量。
理化性能：
表1为实施例1、2、3、4与对比例1、2制备的样品的比表面积对比，发现预锂化石墨烯比表面积明显高于对比例，尤其实施例2的比表面积最大。
表1实施例1-4的预锂化石墨烯与对比例1-2的氧化石墨烯的比表面积
Figure PCTCN2021142961-appb-000001
电化学性能：
表2为实施例1、2、3、4与对比例1、2制备的样品的电化学性能对比，发现本发明实施例1-4所制备的预锂化石墨烯样品中可逆充电比容量、循环稳定性和倍率性能高于对比例1和2，尤其实施例2的电化学性能明显较为优异。
表2预锂化石墨烯与对比样品的电化学性能测试数据
Figure PCTCN2021142961-appb-000002
Figure PCTCN2021142961-appb-000003
上面对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种预锂化石墨烯，其特征在于，包括以下组分：锂的氧化物、锂的碳化物；所述锂的碳化物为Li 2CO 3、LiC x和R-Li，其中，R为还原氧化石墨烯，1/6≤x≤1。
  2. 根据权利要求1所述的预锂化石墨烯，其特征在于，所述锂的氧化物为氧化锂。
  3. 根据权利要求1所述的预锂化石墨烯，其特征在于，所述预锂化石墨烯的比表面积为79.66-104m 2g -1，所述预锂化石墨烯的可逆比容量为490-660mAh g -1。
  4. 权利要求1-3任一项所述的预锂化石墨烯的制备方法，其特征在于，包括以下步骤：
    将锂源、氧化石墨烯、电子转移载体混合，加入溶剂，反应，干燥，即得预锂化石墨烯。
  5. 权利要求4所述的制备方法，其特征在于，所述电子转移载体为叔丁基苯、叔丁基苯并和4,4-二叔丁基苯并中的至少一种。
  6. 权利要求4所述的制备方法，其特征在于，所述锂源为锂单质。
  7. 权利要求4所述的制备方法，其特征在于，所述锂单质、氧化石墨烯的质量比为(1-5):100。
  8. 一种石墨烯负极的制备方法，其特征在于，包括以下步骤：
    将权利要求1-3所述的预锂化石墨烯、胶黏剂、溶剂混合，涂覆在铜箔，干燥，热处理，即得所述石墨烯负极，所述预锂化石墨烯的负载量为1.2-1.5mg cm -2。
  9. 一种石墨烯负极，其特征在于，由权利要求8所述的制备方法制备得到。
  10. 一种电池，其特征在于，包括以下组分：锂金属箔、隔膜、权利要求9所述的石墨烯负极、电解液。
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