WO2023071337A1 - 石墨烯基钠离子电池负极材料的制备方法 - Google Patents

石墨烯基钠离子电池负极材料的制备方法 Download PDF

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WO2023071337A1
WO2023071337A1 PCT/CN2022/108657 CN2022108657W WO2023071337A1 WO 2023071337 A1 WO2023071337 A1 WO 2023071337A1 CN 2022108657 W CN2022108657 W CN 2022108657W WO 2023071337 A1 WO2023071337 A1 WO 2023071337A1
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graphene oxide
solid
solution
sodium
preparation
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French (fr)
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余海军
谢英豪
李爱霞
张学梅
李长东
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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 DE112022000863.6T priority Critical patent/DE112022000863T5/de
Priority to GB2309439.4A priority patent/GB2616231A/en
Priority to HU2400086A priority patent/HUP2400086A1/hu
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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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  • the invention belongs to the technical field of sodium ion batteries, and in particular relates to a preparation method of a graphene-based sodium ion battery negative electrode material.
  • Sodium and lithium belong to the same main group and have many similar chemical properties. Lithium-ion batteries have developed rapidly because of their high specific energy, which is superior to sodium-ion batteries. The research on sodium-ion batteries is quite slow. In recent years, with the development of large-scale energy storage and electric vehicles, sodium-ion batteries have received renewed attention due to their abundant raw materials and low cost, and have become one of the options to replace lithium-ion batteries. The positive electrode material of the sodium-ion battery draws lessons from the research results of the lithium-ion battery, and has made great progress.
  • graphene is mainly used in supercapacitors and lithium-ion batteries in electrochemical aspects.
  • Traditional lithium-ion batteries usually use graphite as the negative electrode material.
  • the theoretical specific capacity of graphite is low (372mAh/g), which is no longer suitable for the requirements of energy power and emerging electronic products. Therefore, as the most potential carbon source material, graphene has been extensively studied.
  • the perfect two-dimensional structure of graphene has a larger specific surface area, which makes it easier to insert and extract lithium ions, thus ensuring a higher capacity of lithium-ion batteries (theoretical capacity 740-780mAh/ g) and energy density.
  • the rate performance of the battery is also improved to a certain extent.
  • Graphite has excellent cycle performance and high specific capacity as the anode material of lithium-ion batteries, but when used as the anode of sodium-ion batteries, the specific capacity is only 35mAh/g, which cannot be used as the anode of sodium-ion batteries.
  • the anode material of the sodium ion battery is used as the sodium storage body of the sodium ion battery, and the insertion/extraction of sodium ions is realized during the charging and discharging process. Therefore, the choice of anode materials plays a decisive role in the development of Na-ion batteries.
  • sodium-ion batteries As a lithium-ion battery, sodium-ion batteries have many similarities with lithium-ion batteries, which makes sodium-ion batteries have a lot to learn from in the selection of negative electrode materials. However, since the radius of sodium ions (0.102nm) is greater than that of lithium ions (0.069nm), graphite-based materials, commercialized anode materials for lithium-ion batteries, are not suitable as anode materials for sodium-ion batteries. Carbon materials can become a new choice of anode materials for sodium-ion batteries.
  • the sodium storage anode materials with intercalation mechanism have received more attention due to their high cycle stability, mainly including hard carbon, Na 2 Ti 3 O 7 and Li 4 Ti 5 O 12 , etc.
  • the specific capacity of Na 2 Ti 3 O 7 and Li 4 Ti 5 O 12 is usually less than 200mAh/g, which is difficult to meet the requirements of large-capacity energy storage batteries.
  • the sodium storage capacity of hard carbon can reach 300mAh/g, its rate performance is poor, and most of its capacity is realized in the region where the discharge voltage is lower than 0.1V (vs.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. Therefore, the present invention proposes a preparation method of a graphene-based sodium ion battery negative electrode material.
  • the material is composed of cobalt monoxide and nitrogen-doped graphene oxide, the mass fraction of graphene oxide is 30-90%, and the rest is cobalt monoxide.
  • the ultrasonic treatment is carried out at 30-60° C.; the time of the ultrasonic treatment is 30-240 min.
  • the liquid-solid ratio of the absolute ethanol to graphene oxide is 1 mL: (0.05-0.2) g.
  • the concentration of cobalt ions in the solution A is 1-2 mol/L, and the concentration of sodium nitrite is 8-12 mol/L.
  • the mass concentration of the acetic acid is 50-60%, and the volume ratio of the added amount of acetic acid to the solution A is (1-2):5.
  • the mass concentration of hydrogen peroxide is 25-35%, and the volume ratio of hydrogen peroxide added to solution A is (1-2):5.
  • the solid is washed with absolute ethanol before being calcined.
  • the times of washing are 2-5 times.
  • the ratio of the volume of the graphene oxide alcohol dispersion to the volume of solution B is (1.5-4):1.
  • the calcination temperature is 500-800°C; the calcination time is 2-8h.
  • the solid-liquid separation adopts centrifugal separation.
  • sodium hexanitrocobaltate and graphene oxide achieve the purpose of uniform mixing, which is beneficial to the next step of sintering.
  • the present invention first disperses graphene oxide in absolute ethanol to obtain a graphene oxide alcohol dispersion, and then prepares sodium hexanitrocobaltate through a synthesis reaction, and the hexanitrocobaltate is synthesized by the graphene oxide alcohol dispersion.
  • Sodium cobaltate is subjected to alcohol analysis, and the next step of sintering is used to prepare the target product; the reaction equation for preparing sodium hexanitrocobaltate is as follows:
  • sodium hexanitrocobaltate contains a large amount of nitro groups, and graphene oxide is doped with nitrogen by using sodium hexanitrocobaltate; on the other hand, sodium hexanitrocobaltate Cobalt is a trivalent ion with strong oxidizing properties, which further improves the efficiency of nitrogen doping, thereby expanding the interlayer spacing of graphene oxide and facilitating the deintercalation of sodium ions.
  • graphene oxide is doped with nitrogen and cobalt monoxide, which improves the specific capacity and cycle performance of the material.
  • Figure 1 is a TEM image of the graphene-based sodium ion battery negative electrode material prepared in Example 2 of the present invention.
  • a graphene-based sodium ion battery negative electrode material is prepared, and the specific process is as follows:
  • step (1) After adding the graphene oxide alcohol dispersion in step (1) to the solution B, centrifuge to obtain a solid, and wash the solid with absolute ethanol for 2-5 times;
  • the total mass of the graphene-based sodium ion battery negative electrode material is 9.37g, of which cobalt monoxide is 3.16g.
  • a graphene-based sodium ion battery negative electrode material is prepared, and the specific process is as follows:
  • step (1) After adding the graphene oxide alcohol dispersion in step (1) to the solution B, centrifuge to obtain a solid, and wash the solid with absolute ethanol for 2-5 times;
  • the total mass of the graphene-based sodium-ion battery negative electrode material is 15.42g, of which cobalt monoxide is 3.66g.
  • a graphene-based sodium ion battery negative electrode material is prepared, and the specific process is as follows:
  • step (1) After adding the graphene oxide alcohol dispersion in step (1) to the solution B, centrifuge to obtain a solid, and wash the solid with absolute ethanol for 2-5 times;

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Abstract

本发明公开了一种石墨烯基钠离子电池负极材料的制备方法，包括将氧化石墨烯加入到无水乙醇中，在一定温度下超声处理，得到氧化石墨烯醇分散液，再配制六硝基合钴酸钠溶液，向六硝基合钴酸钠溶液中加入氧化石墨烯醇分散液，固液分离得到固体物，将固体物隔绝氧气进行煅烧，经洗涤和干燥即得石墨烯基钠离子电池负极材料。本发明通过氧化石墨烯醇分散液对六硝基合钴酸钠进行醇析，再利用下一步的烧结，制备目标产物，六硝基合钴酸钠中含有大量的硝基，通过六硝基合钴酸钠对氧化石墨烯进行掺杂氮，同时又混入了一氧化钴，提升了材料的比容量和循环性能。

Description

石墨烯基钠离子电池负极材料的制备方法 技术领域
本发明属于钠离子电池技术领域，具体涉及一种石墨烯基钠离子电池负极材料的制备方法。
背景技术
钠与锂属于同一主族，具有很多相似的化学性质，锂离子电池以其高比能的特点优于钠离子电池而迅速发展起来，钠离子电池的研究相当缓慢。近年来，随着大规模储能和电动汽车的发展，钠离子电池由于其原料丰富、成本低的特点，重新受到关注，成为替代锂离子电池的选择之一。钠离子电池的正极材料借鉴了锂离子电池的研究成果，取得了很大的进展。
目前石墨烯在电化学方面主要用于超级电容器和锂离子电池。传统的锂离子电池通常采用石墨作为负极材料，石墨的理论比容量较低(372mAh/g)，已经不再适用于能源动力和新兴电子产品的要求。因此，作为最具有潜力的碳源材料，石墨烯得到了大量的研究。与传统石墨相比，石墨烯的完美二维结构具有更大的比表面积，这使得锂离子的嵌入和脱出变得更加容易，从而保证了锂离子电池更高的容量(理论容量740～780mAh/g)和能量密度。另外，由于石墨烯较高的电导率及较短的锂离子扩散路径，因此在一定程度上同时提高了电池的倍率性能。
石墨作为锂离子电池负极材料具有优异的循环性能和较高的比容量，但是作为钠离子电池负极时比容量仅为35mAh/g，无法作为钠离子电池负极。
钠离子电池负极材料作为钠离子电池的储钠主体，在充放电的过程中，实现钠离子的嵌入/脱出。因此，负极材料的选择对钠离子电池的发展有决定性的作用。
作为类锂离子电池，钠离子电池与锂离子电池有许多的相似之处，这使钠离子电池在负极材料的选择上有很多可借鉴之处。然而，由于钠离子的半径(0.102nm)大于锂离子的半径(0.069nm)，锂离子电池商业化的负极材料石墨类材料，并不适合作为钠离 子电池负极材料，而具有更大层间距的碳材料才能成为钠离子电池负极材料的新选择。
目前，插层机制的储钠负极材料由于其较高的循环稳定性受到较多关注，主要包括硬碳、Na 2Ti 3O 7和Li 4Ti 5O 12等。在这些储钠负极材料中，Na 2Ti 3O 7和Li 4Ti 5O 12的比容量通常小于200mAh/g，难以满足大容量储能电池的要求。硬碳的储钠容量虽然可以达到300mAh/g，但是其倍率性能较差，并且其大部分的容量是在放电电压低于0.1V(vs.Na/Na +)的区域内实现的，该电位非常接近金属钠的析出电位，可能导致电极表面形成钠枝晶，带来严峻的安全隐患。因此，寻找具有高比容量、较好的倍率性能和循环稳定性及高安全性的新型钠电负极材料具有重要意义。
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，本发明提出一种石墨烯基钠离子电池负极材料的制备方法。
根据本发明的一个方面，提出了一种石墨烯基钠离子电池负极材料的制备方法，包括以下步骤：
将氧化石墨烯加入到无水乙醇中，在一定温度下超声处理，得到氧化石墨烯醇分散液；
将硝酸钴和亚硝酸钠加入水中溶解，得到溶液A；
向所述溶液A中加入乙酸，再加入过氧化氢进行反应，反应后固液分离得到溶液B；
向所述溶液B中加入所述氧化石墨烯醇分散液，固液分离得到固体物，将所述固体物隔绝氧气进行煅烧，经洗涤和干燥即得所述石墨烯基钠离子电池负极材料。该材料由一氧化钴和掺杂氮的氧化石墨烯组成，氧化石墨烯的质量分数为30-90％，其余为一氧化钴。
在本发明的一些实施方式中，所述超声处理在30-60℃下进行；所述超声处理的时间为30-240min。
在本发明的一些实施方式中，所述无水乙醇与氧化石墨烯的液固比为1mL：(0.05-0.2)g。
在本发明的一些实施方式中，所述溶液A中钴离子的浓度为1-2mol/L，亚硝酸钠的浓度为8-12mol/L。
在本发明的一些实施方式中，所述乙酸的质量浓度为50-60％，乙酸加入量与溶液A的体积比为(1-2)：5。
在本发明的一些实施方式中，所述过氧化氢的质量浓度为25-35％，过氧化氢加入量与溶液A的体积比为(1-2)：5。
在本发明的一些实施方式中，所述固体物在煅烧前，还采用无水乙醇进行洗涤。优选的，洗涤的次数为2-5次。
在本发明的一些实施方式中，所述氧化石墨烯醇分散液的体积与溶液B的体积之比为(1.5-4)：1。
在本发明的一些实施方式中，所述煅烧的温度为500-800℃；煅烧的时间为2-8h。
在本发明的一些实施方式中，所述固液分离采用离心分离。在离心分离的作用下，六硝基合钴酸钠与氧化石墨烯达到了均匀混合的目的，利于下一步的烧结。
在本发明的一些实施方式中，所述煅烧后，采用质量份数≥95％的乙醇洗涤，将无用的钠离子除去。
根据本发明的一种优选的实施方式，至少具有以下有益效果：
1、本发明首先将氧化石墨烯分散于无水乙醇中，制得氧化石墨烯醇分散液，再经合成反应制备六硝基合钴酸钠，通过氧化石墨烯醇分散液对六硝基合钴酸钠进行醇析，利用下一步的烧结，制备目标产物；制备六硝基合钴酸钠的反应方程式如下：
24NaNO 2+4Co(NO 3) 2+4HAc+2H 2O 2＝4Na 3[Co(NO 2) 6]+8NaNO 3+4NaAc+4H 2O。
2、一方面，六硝基合钴酸钠中含有大量的硝基，通过利用六硝基合钴酸钠对氧化石墨烯进行掺杂氮；另一方面，六硝基合钴酸钠中的钴为三价离子，具有较强的氧化性，进一步提升氮掺杂的效率，从而扩大了氧化石墨烯的层间距，利于钠离子的脱嵌。
3、煅烧后，钴以一氧化钴的形式均匀分散在石墨烯表面，有效抑制了石墨烯在充放电过程中的破碎。
4、本发明通过一步烧结，在氧化石墨烯中即掺杂了氮，又混入了一氧化钴，提升了材料的比容量和循环性能。
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制备的石墨烯基钠离子电池负极材料TEM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
本实施例制备了一种石墨烯基钠离子电池负极材料，具体过程如下：
(1)将5g氧化石墨烯加入到100mL无水乙醇中，在30℃下恒温超声处理30min，得到氧化石墨烯醇分散液；
(2)制备50mL的1mol/L硝酸钴和8mol/L亚硝酸钠混合溶液A；
(3)在不断搅拌下缓慢向溶液A中缓慢加入10mL质量浓度为50％的乙酸后，再加入10mL质量浓度为30％的过氧化氢，反应结束后固液分离，除去可能析出的杂质盐类，得到溶液B；
(4)向溶液B中加入步骤(1)中的氧化石墨烯醇分散液后，离心分离，得到固体物，采用无水乙醇洗涤固体物2-5次；
(5)将洗涤后的固体物在500℃条件下隔绝氧气煅烧8h，冷却后，采用95％的乙醇洗涤2-5次，再经干燥后即可得到石墨烯基钠离子电池负极材料。
经检测，石墨烯基钠离子电池负极材料总质量为9.37g，其中一氧化钴为3.16g。
实施例2
本实施例制备了一种石墨烯基钠离子电池负极材料，具体过程如下：
(1)将10g氧化石墨烯加入到120mL无水乙醇中，在45℃下恒温超声处理120min，得到氧化石墨烯醇分散液；
(2)制备50mL的1.2mol/L硝酸钴和10mol/L亚硝酸钠混合溶液A；
(3)在不断搅拌下缓慢向溶液A中缓慢加入15mL质量浓度为50％的乙酸后，再加入15mL质量浓度为30％的过氧化氢，反应结束后固液分离，除去可能析出的杂质盐类，得到溶液B；
(4)向溶液B中加入步骤(1)中的氧化石墨烯醇分散液后，离心分离，得到固体物，采用无水乙醇洗涤固体物2-5次；
(5)将洗涤后的固体物在600℃条件下隔绝氧气煅烧5h，冷却后，采用95％的乙醇洗涤2-5次，再经干燥后即可得到石墨烯基钠离子电池负极材料。
经检测，石墨烯基钠离子电池负极材料总质量为15.42g，其中一氧化钴为3.66g。
实施例3
本实施例制备了一种石墨烯基钠离子电池负极材料，具体过程如下：
(1)将20g氧化石墨烯加入到200mL无水乙醇中，在30℃下恒温超声处理100min，得到氧化石墨烯醇分散液；
(2)制备50mL的2mol/L硝酸钴和12mol/L亚硝酸钠混合溶液A；
(3)在不断搅拌下缓慢向溶液A中缓慢加入20mL质量浓度为50％的乙酸后，再加入20mL质量浓度为30％的过氧化氢，反应结束后固液分离，除去可能析出的杂质盐类，得到溶液B；
(4)向溶液B中加入步骤(1)中的氧化石墨烯醇分散液后，离心分离，得到固体物，采用无水乙醇洗涤固体物2-5次；
(5)将洗涤后的固体物在800℃条件下隔绝氧气煅烧2h，冷却后，采用95％的乙醇洗涤2-5次，再经干燥后即可得到石墨烯基钠离子电池负极材料。
经检测，石墨烯基钠离子电池负极材料总质量为28.76g，其中一氧化钴为6.33g。试验例
取实施例1-3制得的钠离子电池负极材料和未改性的氧化石墨烯分别制备钠离子电池负极极片，并组装成扣式电池在电流密度为100mA/g、电压范围0.001-2.0V下进行测试，结果如表1所示。
表1石墨烯基钠离子电池负极材料性能测试结果
  首次充放电克容量mAh/g 50次充放电后的克容量mAh/g
实施例1 632.7 628.3
实施例2 642.4 640.3
实施例3 613.3 607.6
未改性的氧化石墨烯 352.9 177.32
由表1可见，与未改性的氧化石墨烯相比，实施例1-3的比容量和循环性能明显更高，这是由于在氧化石墨烯中掺杂氮，扩大了氧化石墨烯的层间距，利于钠离子的脱嵌，提高了比容量，同时钴以一氧化钴的形式均匀分散在氧化石墨烯表面，有效抑制了石墨烯在充放电过程中的破碎，提升了循环性能。
上面结合附图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. 一种石墨烯基钠离子电池负极材料的制备方法，其特征在于，包括以下步骤：
    将氧化石墨烯加入到无水乙醇中，在一定温度下超声处理，得到氧化石墨烯醇分散液；
    将硝酸钴和亚硝酸钠加入水中溶解，得到溶液A；
    向所述溶液A中加入乙酸，再加入过氧化氢进行反应，反应后固液分离得到溶液B；
    向所述溶液B中加入所述氧化石墨烯醇分散液，固液分离得到固体物，将所述固体物隔绝氧气进行煅烧，经洗涤和干燥即得所述石墨烯基钠离子电池负极材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述超声处理在30-60℃下进行；所述超声处理的时间为30-240min。
  3. 根据权利要求1所述的制备方法，其特征在于，所述无水乙醇与氧化石墨烯的液固比为1mL：(0.05-0.2)g。
  4. 根据权利要求1所述的制备方法，其特征在于，所述溶液A中钴离子的浓度为1-2mol/L，亚硝酸钠的浓度为8-12mol/L。
  5. 根据权利要求1所述的制备方法，其特征在于，所述乙酸的质量浓度为50-60％，乙酸加入量与溶液A的体积比为(1-2)：5。
  6. 根据权利要求1所述的制备方法，其特征在于，所述过氧化氢的质量浓度为25-35％，过氧化氢加入量与溶液A的体积比为(1-2)：5。
  7. 根据权利要求1所述的制备方法，其特征在于，所述固体物在煅烧前，还采用无水乙醇进行洗涤。
  8. 根据权利要求1所述的制备方法，其特征在于，所述氧化石墨烯醇分散液的体积与溶液B的体积之比为(1.5-4)：1。
  9. 根据权利要求1所述的制备方法，其特征在于，所述煅烧的温度为500-800℃；煅烧的时间为2-8h。
  10. 根据权利要求1所述的制备方法，其特征在于，所述固液分离采用离心分离。
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