CN107195879A - A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery - Google Patents
A kind of preparation method of the graphite oxide negative material of high performance lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 32
- 239000010439 graphite Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 20
- 239000007772 electrode material Substances 0.000 abstract description 4
- 229910021382 natural graphite Inorganic materials 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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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
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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
- 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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明提供了一种高性能锂离子电池的氧化石墨负极材料的制备方法，用强酸和氧化剂对天然石墨粉进行氧化，然后在零度进行低温发应，再在水浴中中温反应，加入去离子水高温处理，冷却至室温后加入一定量的过氧化氢，待反应完成后加入温水搅拌抽滤，再用稀盐酸清洗多次，在干燥箱中干燥，制得氧化石墨负极材料。所得电极材料相比传统锂离子电池的石墨负极，表现出非常高的性能，在1.875Ag‑1的放电电流下容量仍然有261.4mAhg‑1，远高于石墨粉的43.7mAhg‑1。该制备工艺简单、可控，成本较低，安全性较高，能有效满足现有锂离子电池的发展和需求。
The invention provides a preparation method of graphite oxide negative electrode material of high-performance lithium-ion battery. The natural graphite powder is oxidized with strong acid and oxidant, and then reacted at zero temperature at low temperature, then reacted at medium temperature in a water bath, and added deionized water. High temperature treatment, after cooling to room temperature, add a certain amount of hydrogen peroxide, after the reaction is completed, add warm water, stir and suction filter, then wash with dilute hydrochloric acid for several times, and dry in a drying oven to obtain graphite oxide negative electrode material. Compared with the graphite negative electrode of the traditional lithium-ion battery, the obtained electrode material shows very high performance, and the capacity is still 261.4mAhg ‑1 at a discharge current of 1.875Ag ‑1 , which is much higher than the 43.7mAhg ‑1 of graphite powder. The preparation process is simple, controllable, low in cost and high in safety, and can effectively meet the development and demand of existing lithium ion batteries.
Description
技术领域technical field
本发明涉及一种纳米材料制备技术，属于高性能锂离子电池负极材料制造的技术领域。The invention relates to a nanometer material preparation technology, which belongs to the technical field of high-performance lithium ion battery negative electrode material production.
背景技术Background technique
在可持续发展的当今社会，能源问题和环境问题日益突出。而采用清洁能源电动汽车代替原有的高污染的燃油动力汽车已势在必行。锂离子电池由于能量密度高、环境相容性好、安全可靠、无记忆效应、工作性能稳定等优点，已成为新一代动力电源的候选之一。In today's sustainable society, energy issues and environmental issues are becoming increasingly prominent. It is imperative to use clean energy electric vehicles to replace the original high-pollution fuel-powered vehicles. Due to the advantages of high energy density, good environmental compatibility, safety and reliability, no memory effect, and stable working performance, lithium-ion batteries have become one of the candidates for a new generation of power sources.
近年来，随着科技的进步，对锂离子电池体积比能量及充电时间等性能要求的不断提高，电动自行车及电动汽车对锂离子电池的续航里程、循环寿命等提出了更高的要求。电极材料作为锂离子电池的核心和关键技术，电池性能要求直接关联在正、负极材料的各项性能指标上，而负极材料对锂离子电池性能的发挥具有更大的影响；锂离子电池的负极材料有碳材料、金属间化合物等，目前，工业化的锂离子电池负极材料主要为碳材料(石墨、硬碳、软碳等)和钛酸锂，这其中石墨类碳材料，具有较低的锂嵌入/脱嵌电位、合适的可逆容量且资源丰富、价格低廉等优点，同时技术最成熟、应用最广泛；尽管石墨材料应用广泛，但没有经过改性的天然石墨负极材料首次不可逆容量损失很高，高倍率充放电时容量下降较快，对电解液的选择性较高，大电流充放电性能不好，在循环过程中溶剂化的锂离子会插入到石墨层间，其理论比容量只有372mAh/g，因而限制了锂离子电池比能量的进一步提高，不能满足日益发展的高能量便携式移动电源的需求。In recent years, with the advancement of science and technology, the performance requirements of lithium-ion batteries such as volume specific energy and charging time have been continuously improved. Electric bicycles and electric vehicles have put forward higher requirements for the cruising range and cycle life of lithium-ion batteries. As the core and key technology of lithium-ion batteries, electrode materials are directly related to the performance indicators of positive and negative electrode materials, while negative electrode materials have a greater impact on the performance of lithium-ion batteries; the negative electrodes of lithium-ion batteries Materials include carbon materials, intermetallic compounds, etc. At present, the anode materials of industrialized lithium-ion batteries are mainly carbon materials (graphite, hard carbon, soft carbon, etc.) and lithium titanate, among which graphite carbon materials have lower lithium Intercalation/deintercalation potential, suitable reversible capacity, rich resources, low price, etc., and the most mature technology and the most widely used; although graphite materials are widely used, the first irreversible capacity loss of unmodified natural graphite anode materials is very high , the capacity drops rapidly when charging and discharging at a high rate, the selectivity to the electrolyte is high, the performance of charging and discharging at a high current is not good, and the solvated lithium ions will be inserted into the graphite layer during the cycle, and its theoretical specific capacity is only 372mAh /g, which limits the further improvement of the specific energy of lithium-ion batteries, and cannot meet the needs of the growing high-energy portable mobile power supply.
针对这一问题，目前研究主要采用表面处理、表面包覆、和元素掺杂等方法来改进其电导率。其中，对石墨进行氧化还原处理所得的石墨烯研究最多，石墨烯具有优良的电传导性、较高的比表面积(2600m2/g)、优异的热学性能和机械性能，被认为是理想的锂电池电极材料，作为锂离子电池负极材料具有巨大的应用空间。单纯的石墨烯理论比容量为744mAh/g，虽然优于石墨，但在循环稳定性上不如原始石墨，不适合直接作为锂离子电池的负极材料。通常需要再次对石墨烯进行复杂的改性、掺杂或者与其他材料进行复合。In response to this problem, current research mainly uses methods such as surface treatment, surface coating, and element doping to improve its conductivity. Among them, graphene obtained by redox treatment of graphite has been studied the most. Graphene has excellent electrical conductivity, high specific surface area (2600m 2 /g), excellent thermal properties and mechanical properties, and is considered to be an ideal lithium Battery electrode materials have huge application space as anode materials for lithium-ion batteries. Pure graphene has a theoretical specific capacity of 744mAh/g. Although it is worse than graphite, its cycle stability is not as good as that of original graphite, so it is not suitable to be directly used as the negative electrode material of lithium-ion batteries. It is usually necessary to carry out complex modification, doping or compounding with other materials on graphene again.
目前，表面改性、表面包覆虽然在一定程度上改善了天然石墨的表面结构和化学性能，降低了电解液对石墨片层的腐蚀，有效改善负极材料首次充放电效率，但对石墨负极材料性能的提高，特别是大电流充放电性能的改善不是很特别显著，以至石墨负极材料在高端锂离子电池的应用受到一定限制，无法满足当前快速充放电性能的要求。At present, although surface modification and surface coating have improved the surface structure and chemical properties of natural graphite to a certain extent, reduced the corrosion of graphite sheets by the electrolyte, and effectively improved the first charge and discharge efficiency of negative electrode materials, but the graphite negative electrode materials The improvement of performance, especially the improvement of high-current charge-discharge performance is not very significant, so that the application of graphite anode materials in high-end lithium-ion batteries is limited to a certain extent, and cannot meet the current requirements of fast charge-discharge performance.
发明内容Contents of the invention
技术问题：为了克服上述现有技术的不足，通过研究不同氧化程度的石墨直接作为负极材料，提供出一种工艺简单，成本低，易于工业化生产且电化学性质优异、稳定的材料制备，具体是提供一种高性能锂离子电池的氧化石墨负极材料的制备方法。Technical problem: In order to overcome the deficiencies of the above-mentioned prior art, by studying graphite with different degrees of oxidation directly as the negative electrode material, a material preparation with simple process, low cost, easy industrial production, excellent electrochemical properties and stability is provided, specifically Provided is a method for preparing a graphite oxide negative electrode material for a high-performance lithium ion battery.
技术方案：本发明的一种高性能锂离子电池的氧化石墨负极材料的制备方法包括以下步骤：Technical scheme: the preparation method of the graphite oxide negative electrode material of a kind of high-performance lithium-ion battery of the present invention comprises the following steps:
步骤1)将石墨粉与强酸配料进行低温反应，然后边搅拌边缓慢加入氧化剂，在低温反应一段时间；Step 1) react graphite powder and strong acid ingredients at low temperature, then slowly add an oxidant while stirring, and react at low temperature for a period of time;
步骤2)将步骤1)的反应物进行中温反应，之后加入去离子水进行高温反应；Step 2) The reactant in step 1) is subjected to a medium-temperature reaction, and then deionized water is added to perform a high-temperature reaction;
步骤3)步骤2)的反应产物冷却至室温后，加入过氧化氢，待反应完成后加入温水抽滤，并用稀盐酸洗涤多次后真空干燥，即得氧化石墨负极材料。Step 3) After the reaction product in step 2) is cooled to room temperature, hydrogen peroxide is added, after the reaction is completed, warm water is added for suction filtration, washed with dilute hydrochloric acid for several times, and then vacuum-dried to obtain graphite oxide negative electrode material.
其中：in:
在步骤1)中，所述强酸为浓硫酸，氧化剂为高锰酸钾。In step 1), the strong acid is concentrated sulfuric acid, and the oxidizing agent is potassium permanganate.
步骤1)中，所述强酸和氧化剂与石墨的质量比为：23x:3.5x:1，其中0.5<x<4。In step 1), the mass ratio of the strong acid and the oxidant to the graphite is: 23x:3.5x:1, wherein 0.5<x<4.
步骤1)中，低温反应搅拌温度为0-10℃，与硫酸反应时间2-30分钟，加入氧化剂后反应时间为0.5-6小时。In step 1), the low-temperature reaction stirring temperature is 0-10° C., the reaction time with sulfuric acid is 2-30 minutes, and the reaction time after adding the oxidant is 0.5-6 hours.
步骤2)中，中温反应温度为20-50度，反应时间为0.5-6小时。In step 2), the medium temperature reaction temperature is 20-50 degrees, and the reaction time is 0.5-6 hours.
高温反应温度为70-98℃，时间为0.5-5小时。The high temperature reaction temperature is 70-98° C., and the time is 0.5-5 hours.
有益效果：本发明提供的长循环高倍率电化学性能优异的锂离子电池负极材料氧化石墨的制备方法通过调节强酸和氧化剂与石墨比例，控制反应条件来实现最优化电极材料电化学性能的目的，方法简单、工艺可控，获得的负极材料具有良好的电化学性能、长循环稳定性高、倍率性能佳、安全可靠，能有效满足锂离子电池的需要。目前很少有人研究不同氧化程度的氧化石墨直接作为负极材料应用到锂电池中，获得最优高倍率充放电性能的负极材料。Beneficial effects: the preparation method of the lithium ion battery negative electrode material graphite oxide with excellent long-cycle high-rate electrochemical performance provided by the present invention realizes the purpose of optimizing the electrochemical performance of the electrode material by adjusting the ratio of strong acid and oxidant to graphite and controlling the reaction conditions. The method is simple and the process is controllable, and the obtained negative electrode material has good electrochemical performance, high long-term cycle stability, good rate performance, safety and reliability, and can effectively meet the needs of lithium-ion batteries. At present, few people have studied graphite oxide with different oxidation degrees to be directly used as negative electrode materials in lithium batteries to obtain negative electrode materials with optimal high-rate charge-discharge performance.
附图说明Description of drawings
图1为以下实施例2中制备出产品与石墨粉的循环性能比较。Fig. 1 is the cycle performance comparison of the product prepared in the following example 2 and graphite powder.
图2为以下实施例2中制备出产品与石墨粉的倍率性能比较。Fig. 2 is the rate performance comparison of the product prepared in the following example 2 and graphite powder.
图3为以下实施例2中制备出产品与石墨粉的高倍率循环性能比较。Fig. 3 is the high-rate cycle performance comparison of the product prepared in the following example 2 and graphite powder.
具体实施方式detailed description
根据权利要求所包含的内容举例说明Examples of what is included in the claims
实施例1：Example 1:
1)将石墨粉与浓硫酸配料在0度进行低温反应2分钟，然后边搅拌边缓慢加入高锰酸钾，在低温0度反应0.5小时。浓硫酸与高锰酸钾以及石墨粉的质量比为11.5:1.75:1。1) React graphite powder and concentrated sulfuric acid ingredients at 0°C for 2 minutes at a low temperature, then slowly add potassium permanganate while stirring, and react at a low temperature of 0°C for 0.5 hours. The mass ratio of concentrated sulfuric acid to potassium permanganate and graphite powder is 11.5:1.75:1.
2)步骤1)反应完成后，将反应物升温到20度进行中温反应0.5小时，之后加入去离子水升温到70度进行高温发应，反应时间0.5小时。2) Step 1) After the reaction is completed, the temperature of the reactant is raised to 20 degrees for a medium temperature reaction for 0.5 hours, and then deionized water is added and the temperature is raised to 70 degrees for a high temperature reaction, and the reaction time is 0.5 hours.
3)步骤2)产物冷却至室温后，加入过氧化氢，待反应完成后加入温水抽滤，并用稀盐酸洗涤多次后真空干燥。即得氧化石墨负极材料。3) After the product in step 2) is cooled to room temperature, hydrogen peroxide is added, after the reaction is completed, warm water is added for suction filtration, washed with dilute hydrochloric acid for several times, and then vacuum-dried. That is, the graphite oxide negative electrode material is obtained.
实施例2：Example 2:
1)将石墨粉与浓硫酸配料在0度进行低温反应10分钟，然后边搅拌边40.25:6.125:1。1) React graphite powder and concentrated sulfuric acid ingredients at 0°C for 10 minutes at low temperature, and then stir at 40.25:6.125:1.
2)步骤1)反应完成后，将反应物升温到35度进行中温反应2小时，之后加入去离子水升温到90度进行高温发应，反应时间1小时。2) Step 1) After the reaction is completed, raise the temperature of the reactant to 35°C for medium temperature reaction for 2 hours, then add deionized water and raise the temperature to 90°C for high temperature reaction, the reaction time is 1 hour.
3)步骤2)产物冷却至室温后，加入过氧化氢，待反应完成后加入温水抽滤，并用稀盐酸洗涤多次后真空干燥。即得氧化石墨负极材料。3) After the product in step 2) is cooled to room temperature, hydrogen peroxide is added, after the reaction is completed, warm water is added for suction filtration, washed with dilute hydrochloric acid for several times, and then vacuum-dried. That is, the graphite oxide negative electrode material is obtained.
实施例3：Example 3:
1)将石墨粉与浓硫酸配料在10度进行低温反应30分钟，然后边搅拌边92:14:1。1) React graphite powder and concentrated sulfuric acid ingredients at a low temperature of 10 degrees for 30 minutes, and then stir at 92:14:1.
2)步骤1)反应完成后，将反应物升温到50度进行中温反应6小时，之后加入去离子水升温到98度进行高温发应，反应时间5小时。2) Step 1) After the reaction is completed, raise the temperature of the reactant to 50°C for medium temperature reaction for 6 hours, then add deionized water and raise the temperature to 98°C for high temperature reaction, the reaction time is 5 hours.
3)步骤2)产物冷却至室温后，加入过氧化氢，待反应完成后加入温水抽滤，并用稀盐酸洗涤多次后真空干燥。即得氧化石墨负极材料。3) After the product in step 2) is cooled to room temperature, hydrogen peroxide is added, after the reaction is completed, warm water is added for suction filtration, washed with dilute hydrochloric acid for several times, and then vacuum-dried. That is, the graphite oxide negative electrode material is obtained.
实施例3：Example 3:
1)将石墨粉与浓硫酸配料在6度进行低温反应20分钟，然后边搅拌边46:7:1。1) React graphite powder and concentrated sulfuric acid ingredients at 6 degrees for 20 minutes at low temperature, and then stir at 46:7:1.
2)步骤1)反应完成后，将反应物升温到40度进行中温反应3小时，之后加入去离子水升温到85度进行高温发应，反应时间3小时。2) Step 1) After the reaction is completed, the temperature of the reactant is raised to 40 degrees for a medium-temperature reaction for 3 hours, and then deionized water is added and the temperature is raised to 85 degrees for a high-temperature reaction. The reaction time is 3 hours.
3)步骤2)产物冷却至室温后，加入过氧化氢，待反应完成后加入温水抽滤，并用稀盐酸洗涤多次后真空干燥。即得氧化石墨负极材料。3) After the product in step 2) is cooled to room temperature, hydrogen peroxide is added, after the reaction is completed, warm water is added for suction filtration, washed with dilute hydrochloric acid for several times, and then vacuum-dried. That is, the graphite oxide negative electrode material is obtained.
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