CN105226251A - A kind of pure carbon compound cathode materials and preparation method thereof - Google Patents
A kind of pure carbon compound cathode materials and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001722 carbon compounds Chemical class 0.000 title claims 9
- 239000010406 cathode material Substances 0.000 title claims 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000013530 defoamer Substances 0.000 claims abstract description 7
- 239000007921 spray Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 10
- 230000002441 reversible effect Effects 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 239000013081 microcrystal Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 21
- 238000009830 intercalation Methods 0.000 abstract description 20
- 230000002687 intercalation Effects 0.000 abstract description 19
- 239000007773 negative electrode material Substances 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 239000002612 dispersion medium Substances 0.000 abstract description 7
- 238000004299 exfoliation Methods 0.000 abstract description 3
- 238000005562 fading Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 2
- 238000000889 atomisation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- -1 Lithium transition metal Chemical class 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- H01M4/366—Composites as layered products
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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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Abstract
本发明提供一种纯碳复合负极材料，该复合负极材料以球形天然石墨为核心，经包裹厚度为10-15nm的包覆层而成，所述的包覆层由次外层为无定形碳及最外层的微晶石墨组成。同时本发明还提供了一种制备方法，具体是将无定形碳溶于分散介质中，加入球形天然石墨，添加消泡剂；再将其置于混浆机中搅拌均匀，得到的浆料在喷雾干燥机中进行雾化、干燥和造粒得到粉体物料；最后将得到的粉体物料置于炉中进行氮气气氛热处理，经过处理的粉体冷却至室温后即为纯碳复合负极材料。本发明的纯碳复合负极材料纯碳材料的比容量超高、循环稳定性好；微晶石墨和无定形碳同时存在，能有效地分散深度嵌锂累积的应力，从而抑制因石墨层片剥落引起的容量衰减现象。
The invention provides a pure carbon composite negative electrode material. The composite negative electrode material takes spherical natural graphite as the core and is formed by wrapping a cladding layer with a thickness of 10-15nm. The cladding layer is composed of amorphous carbon as the second outer layer and the outermost layer of microcrystalline graphite. At the same time, the present invention also provides a preparation method, specifically dissolving amorphous carbon in the dispersion medium, adding spherical natural graphite, and adding a defoamer; then placing it in a mixer and stirring evenly, and the obtained slurry is in Atomization, drying and granulation are carried out in a spray dryer to obtain powder materials; finally, the obtained powder materials are placed in a furnace for heat treatment in a nitrogen atmosphere, and the treated powder is cooled to room temperature to become a pure carbon composite negative electrode material. The pure carbon composite negative electrode material of the present invention has ultra-high specific capacity and good cycle stability; the simultaneous presence of microcrystalline graphite and amorphous carbon can effectively disperse the accumulated stress of deep lithium intercalation, thereby inhibiting the exfoliation of graphite sheets caused by capacity fading.
Description
技术领域 technical field
本发明涉及一种高能量密度纯碳复合负极材料及其制备方法，属于电化学电源技术领域。 The invention relates to a high energy density pure carbon composite negative electrode material and a preparation method thereof, belonging to the technical field of electrochemical power sources.
背景技术 Background technique
锂离子电池因具有能量密度大、开路电压高、循环寿命长、自放电小、无记忆效应及无污染等优点，已成为便携式电子产品中最广泛采用的二次电池。但是，随着便携式电子产品小型化发展及锂离子电池在航空、军事及汽车产业中的需求日益旺盛，电池的容量和能量密度均亟待大幅度提高。目前，商品化锂离子电池主要采用具有优异循环性能的改性天然石墨和人造石墨作为负极材料。但是该类材料也存在着循环性能差、与电解液相容性差、倍率性能不好等缺点。就人造石墨材料而言，其可逆比容量维持在330mAhg-1（石墨的理论容量为372mAhg-1），其循环性能不理想，且原材料（沥青类芳烃化合物）价格波动大。 Lithium-ion batteries have become the most widely used secondary batteries in portable electronic products due to their advantages such as high energy density, high open circuit voltage, long cycle life, small self-discharge, no memory effect and no pollution. However, with the miniaturization of portable electronic products and the increasing demand for lithium-ion batteries in aviation, military and automotive industries, the capacity and energy density of batteries need to be greatly improved. At present, commercial lithium-ion batteries mainly use modified natural graphite and artificial graphite with excellent cycle performance as anode materials. However, this type of material also has disadvantages such as poor cycle performance, poor compatibility with electrolyte, and poor rate performance. As far as the artificial graphite material is concerned, its reversible specific capacity is maintained at 330mAhg -1 (the theoretical capacity of graphite is 372mAhg -1 ), its cycle performance is not ideal, and the price of raw materials (pitch aromatic compounds) fluctuates greatly.
近年来，针对可逆的嵌/脱锂负极材料的研究十分活跃，除了改性石墨和人造石墨外，许多研究瞄准新型高比容量负极材料：储锂金属及其氧化物（如Sn，Si）和锂过渡金属磷化物，这些材料在嵌/脱锂时存在巨大的体积效应，易发生破裂和粉化，从而丧失与集流体的接触，造成循环性能急剧下降；同时这些新型负极材料的嵌/脱锂电压平台偏高（大于0.5V），对于材料的能量密度提高不利。 In recent years, research on reversible intercalation/delithiation anode materials has been very active. In addition to modified graphite and artificial graphite, many studies have aimed at new types of high specific capacity anode materials: lithium storage metals and their oxides (such as Sn, Si) and Lithium transition metal phosphides, these materials have a huge volume effect when intercalating/extracting lithium, and are prone to cracking and pulverization, thus losing contact with the current collector, resulting in a sharp decline in cycle performance; at the same time, the intercalation/extraction of these new negative electrode materials The lithium voltage platform is too high (greater than 0.5V), which is not conducive to the improvement of the energy density of the material.
目前，改性天然石墨负极材料由于循环稳定性好，工作电位低（约为0.2V）、可逆容量较高（＞350mAhg-1）、制备成本低和制备工艺简单等优点，占领了大部分商业化锂离子电池负极材料市场。针对石墨负极的改性工作已将材料比容量提高到360mAhg-1左右，在现有材料结构基础上继续提升容量的空间不大（纯石墨理论容量极限372mAhg-1）。因此，本发明通过制备一种结构新颖的高能量密度纯碳复合负极材料，在大幅提升材料比容量（420mAhg-1）的基础上，保持石墨负极材料优异的嵌/脱锂特性（嵌/脱锂电压平台小于0.2V），最终大幅提升材料的能量密度。 At present, due to the advantages of good cycle stability, low working potential (about 0.2V), high reversible capacity (>350mAhg -1 ), low preparation cost and simple preparation process, modified natural graphite anode materials occupy most of the commercial Lithium-ion battery anode material market. The modification of graphite negative electrode has increased the specific capacity of the material to about 360mAhg -1 , and there is not much room to continue to increase the capacity on the basis of the existing material structure (the theoretical capacity limit of pure graphite is 372mAhg -1 ). Therefore, the present invention maintains the excellent intercalation/ delithiation characteristics (intercalation/extraction Lithium voltage platform is less than 0.2V), which ultimately greatly improves the energy density of the material.
发明内容 Contents of the invention
本发明的目的在于提供一种纯碳复合负极材料及其制备方法，其中纯碳复合负极材料具有高能量高密度性，该复合负极材料以球形天然石墨为核心，经包裹厚度为10-15nm的包覆层而成，所述的包覆层由次外层为无定形碳及最外层的微晶石墨组成，按重量份计，无定形碳为5%-15%，球形天然石墨为85%-95%。微晶石墨的“有序化”有利于充放电过程中电荷的传输，改善其循环性能；微晶石墨和无定形碳的存在不仅有效地避免了天然石墨与电解液的直接接触，而且也有效地分散了深度嵌锂累积的应力，从而抑制了因石墨层片剥落引起的容量衰减现象；微晶石墨和无定形碳存在的缺陷能提供额外的储锂空间，这使得材料在保持石墨负极低嵌/脱锂电压平台的同时，还可释放出的远高于现有石墨负极材料的比容量。 The object of the present invention is to provide a pure carbon composite negative electrode material and a preparation method thereof, wherein the pure carbon composite negative electrode material has high energy and high density, and the composite negative electrode material takes spherical natural graphite as the core, and is wrapped with a carbon fiber with a thickness of 10-15nm Formed from a coating layer, the coating layer is composed of amorphous carbon and the outermost microcrystalline graphite as the second outer layer. In parts by weight, the amorphous carbon is 5%-15%, and the spherical natural graphite is 85% %-95%. The "ordering" of microcrystalline graphite is beneficial to the transmission of charges during charging and discharging, and improves its cycle performance; the existence of microcrystalline graphite and amorphous carbon not only effectively avoids the direct contact between natural graphite and electrolyte, but also effectively The stress accumulated by deep lithium intercalation is effectively dispersed, thereby suppressing the capacity fading phenomenon caused by the exfoliation of graphite sheets; the defects in microcrystalline graphite and amorphous carbon can provide additional lithium storage space, which makes the material keep the graphite negative electrode low. At the same time as the intercalation/delithiation voltage platform, it can also release a specific capacity much higher than that of the existing graphite anode materials.
本发明所得的负极材料在大幅提高可逆容量的同时，能够保持石墨负极的电压曲线特征，且充放电反应发生0.2伏以下。 The negative electrode material obtained by the invention can greatly improve the reversible capacity, and can maintain the voltage curve characteristics of the graphite negative electrode, and the charging and discharging reaction occurs below 0.2 volts.
所述的无定形碳包括柠檬酸、葡萄糖、蔗糖中的任一种，其纯度均大于99%。 The amorphous carbon includes any one of citric acid, glucose, and sucrose, and its purity is greater than 99%.
所述的球形天然石墨的粒径为10~25μm，其纯度均大于99%。 The particle size of the spherical natural graphite is 10-25 μm, and its purity is greater than 99%.
所述的次外层至少是一层，优选为2-3层。 The second outer layer is at least one layer, preferably 2-3 layers.
所述的最外层至少是一层，优选为3-5层。 The outermost layer is at least one layer, preferably 3-5 layers.
本发明的高能量密度纯碳复合负极材料的制备方法：先将无定形碳、球形天然石墨和分散介质混合，添加消泡剂后搅拌均匀，所得浆料在喷雾干燥机中进行雾化、干燥和造粒得到粉体物料；将得到的粉体物料置于氮气保护的高温石墨化炉中进行热处理，粉体冷却至室温后，研磨、过筛，即得到高能量密度纯碳复合负极材料。将得到的负极材料与乙炔黑、聚偏氟乙烯（PVdF）按一定质量比在N-甲基吡咯烷酮（NMP）介质中搅拌成浆料，涂布于铜箔上，经过干燥、压膜制成高能量密度纯碳复合负极电极。 The preparation method of the high-energy-density pure carbon composite negative electrode material of the present invention: first mix amorphous carbon, spherical natural graphite and dispersion medium, add defoamer and stir evenly, and the obtained slurry is atomized and dried in a spray dryer and granulation to obtain a powder material; the obtained powder material is placed in a nitrogen-protected high-temperature graphitization furnace for heat treatment, and after the powder is cooled to room temperature, it is ground and sieved to obtain a high-energy-density pure carbon composite negative electrode material. Stir the obtained negative electrode material with acetylene black and polyvinylidene fluoride (PVdF) in a certain mass ratio in N-methylpyrrolidone (NMP) medium to form a slurry, coat it on a copper foil, dry it, and press it into a film. High energy density pure carbon composite negative electrode.
所述的分散介质为水或酒精。 The dispersion medium is water or alcohol.
所述的热处理分两步进行：600~800°C保温2~4h后，900~2900°C保温3~7h。 The heat treatment is carried out in two steps: 600-800°C for 2-4h, and 900-2900°C for 3-7h.
本发明所述的高能量密度纯碳复合负极材料与现有的石墨负极材料相比有以下优势：（1）纯碳材料的比容量超高、循环稳定性好；（2）微晶石墨和无定形碳同时存在，能有效地分散深度嵌锂累积的应力，从而抑制因石墨层片剥落引起的容量衰减现象；（3）微晶石墨和无定形碳存在大量的缺陷，能提供额外的储锂空间；（4）嵌脱锂电压平台低（低于0.2V）；（5）合成工艺简单，易于工业化；（6）材料制备成本低廉，污染小；（7）制备过程无有害气体排放。 Compared with the existing graphite negative electrode materials, the high energy density pure carbon composite negative electrode material of the present invention has the following advantages: (1) The specific capacity of pure carbon materials is super high and the cycle stability is good; (2) Microcrystalline graphite and The presence of amorphous carbon at the same time can effectively disperse the stress accumulated by deep lithium intercalation, thereby inhibiting the capacity fading phenomenon caused by the exfoliation of graphite sheets; (3) There are a large number of defects in microcrystalline graphite and amorphous carbon, which can provide additional storage capacity. Lithium space; (4) Low voltage platform for lithium intercalation and extraction (less than 0.2V); (5) Simple synthesis process, easy to industrialize; (6) Low cost of material preparation and less pollution; (7) No harmful gas emissions during the preparation process.
附图说明 Description of drawings
图1为实施例4样品的扫描电子显微镜照片。 Fig. 1 is the scanning electron micrograph of the sample of embodiment 4.
图2为实施例4样品的高分辨率透射电子显微镜照片。 Figure 2 is a high-resolution transmission electron micrograph of the sample of Example 4.
图3为实施例4样品的电化学性能曲线。 Fig. 3 is the electrochemical performance curve of the sample of embodiment 4.
具体实施方式 detailed description
下面通过实施例和比较例的描述，进一步阐述本发明的实质性特点和优势。为描述方便，首先对比较例加以叙述，然后再描述实施例，与之比较，显示出本发明的效果。 The substantive features and advantages of the present invention will be further set forth below through the description of examples and comparative examples. For the convenience of description, firstly, the comparative example is described, and then the embodiment is described, and compared with it, the effect of the present invention is shown.
比较例1Comparative example 1
将天然球形石墨微粉与聚偏氟乙烯（PVdF）按9:1的质量比在N-甲基吡咯烷酮（NMP）介质中调成浆料，涂布于铜箔上，经过干燥、压膜制成工作电极。以金属锂箔为对电极，Celgard2400为隔膜，1MLiPF6/(EC+DMC)(1:1)为电解液组装成电池进行恒流充放电测试，电流密度为0.15mA/cm2，电压范围在0~1.5V之间。首次嵌锂容量为395.6mAhg-1，脱锂容量为317.8mAhg-1，库伦效率为80.35%；第100次循环嵌锂容量为192.6mAhg-1，脱锂容量为192.4mAhg-1。循环稳定性不好说明直接以天然球形石墨微粉为活性物质制备电极时会因石墨与电解液直接接触，使得溶剂化锂离子嵌入石墨片层，导致石墨在深度充放电时发生剥离失效。 The natural spherical graphite powder and polyvinylidene fluoride (PVdF) are adjusted into a slurry in N-methylpyrrolidone (NMP) medium at a mass ratio of 9:1, coated on copper foil, dried and pressed into a film. working electrode. A battery was assembled with lithium metal foil as the counter electrode, Celgard2400 as the diaphragm, and 1MLiPF 6 /(EC+DMC) (1:1) as the electrolyte for constant current charge and discharge tests. The current density was 0.15mA/cm 2 , and the voltage range was Between 0~1.5V. The first lithium intercalation capacity is 395.6mAhg -1 , the delithiation capacity is 317.8mAhg -1 , and the Coulombic efficiency is 80.35%; the 100th cycle lithium intercalation capacity is 192.6mAhg -1 , and the delithiation capacity is 192.4mAhg -1 . The poor cycle stability shows that when the electrode is directly prepared with natural spherical graphite powder as the active material, the direct contact between the graphite and the electrolyte will cause the solvated lithium ions to intercalate into the graphite sheet, resulting in the peeling failure of the graphite during deep charge and discharge.
实施例1Example 1
将柠檬酸、球形天然石墨和分散介质混合，添加消泡剂搅拌均匀，得到的浆料在喷雾干燥机中进行雾化、干燥和造粒得到粉体物料。将得到的粉体物料置于氮气保护高温石墨化炉中，先在800°C保温2h，再在900°C下烧结3h，冷却至室温后，研磨、过筛，得到的材料标记为G/C-900。将G/C-900与聚偏氟乙烯（PVdF）按9:1的质量比在N-甲基吡咯烷酮（NMP）介质中调成浆料，涂布于铜箔上，经过干燥、压膜制成工作电极。以金属锂箔为对电极，Celgard2400为隔膜，1MLiPF6/(EC+DMC)(1:1)为电解液组装成电池进行恒流充放电测试，电流密度为0.15mA/cm2，电压范围在0~1.5V之间。首次嵌锂容量为432.5mAhg-1，脱锂容量为356.5mAhg-1，库伦效率为82.43%；第100次循环嵌锂容量为288.9mAhg-1，脱锂容量为288.7mAhg-1，材料的循环稳定性得到改善。 Mix citric acid, spherical natural graphite and a dispersion medium, add a defoamer and stir evenly, and the obtained slurry is atomized, dried and granulated in a spray dryer to obtain a powder material. The obtained powder material is placed in a nitrogen-protected high-temperature graphitization furnace, first kept at 800°C for 2h, then sintered at 900°C for 3h, cooled to room temperature, ground and sieved, and the obtained material is marked as G/ C-900. G/C-900 and polyvinylidene fluoride (PVdF) are adjusted into a slurry in N-methylpyrrolidone (NMP) medium at a mass ratio of 9:1, coated on copper foil, dried and pressed into a film into the working electrode. A battery was assembled with lithium metal foil as the counter electrode, Celgard2400 as the diaphragm, and 1MLiPF 6 /(EC+DMC) (1:1) as the electrolyte for constant current charge and discharge tests. The current density was 0.15mA/cm 2 , and the voltage range was Between 0~1.5V. The first lithium intercalation capacity is 432.5mAhg -1 , the delithiation capacity is 356.5mAhg -1 , and the Coulombic efficiency is 82.43%; the 100th cycle lithium intercalation capacity is 288.9mAhg -1 , the delithiation capacity is 288.7mAhg -1 , the cycle of the material Stability has been improved.
实施例2Example 2
将柠檬酸、球形天然石墨和分散介质混合，添加消泡剂搅拌均匀，得到的浆料在喷雾干燥机中进行雾化、干燥和造粒得到粉体物料。将得到的粉体物料置于氮气保护高温石墨化炉中，先在800°C保温2h，再在1200°C下烧结3h，冷却至室温后，研磨、过筛，得到的材料标记为G/C-1200。将G/C-1200与聚偏氟乙烯（PVdF）按9:1的质量比在N-甲基吡咯烷酮（NMP）介质中调成浆料，涂布于铜箔上，经过干燥、压膜制成工作电极。以金属锂箔为对电极，Celgard2400为隔膜，1MLiPF6/(EC+DMC)(1:1)为电解液组装成电池进行恒流充放电测试，电流密度为0.15mA/cm2，电压范围在0~1.5V之间。首次嵌锂容量为453.9mAhg-1，脱锂容量为398.2mAhg-1，库伦效率为87.73%；第100次循环嵌锂容量为364.4mAhg-1，脱锂容量为363.8mAhg-1，材料循环稳定性得到明显改善，且可逆容量接近石墨的理论容量（372mAhg-1）。 Mix citric acid, spherical natural graphite and a dispersion medium, add a defoamer and stir evenly, and the obtained slurry is atomized, dried and granulated in a spray dryer to obtain a powder material. The obtained powder material is placed in a nitrogen-protected high-temperature graphitization furnace, first kept at 800°C for 2h, then sintered at 1200°C for 3h, cooled to room temperature, ground and sieved, and the obtained material is marked as G/ C-1200. G/C-1200 and polyvinylidene fluoride (PVdF) are adjusted into a slurry in N-methylpyrrolidone (NMP) medium at a mass ratio of 9:1, coated on copper foil, dried and pressed into a film into the working electrode. A battery was assembled with lithium metal foil as the counter electrode, Celgard2400 as the diaphragm, and 1MLiPF 6 /(EC+DMC) (1:1) as the electrolyte for constant current charge and discharge tests. The current density was 0.15mA/cm 2 , and the voltage range was Between 0~1.5V. The first lithium intercalation capacity is 453.9mAhg -1 , the delithiation capacity is 398.2mAhg -1 , and the Coulombic efficiency is 87.73%; the 100th cycle lithium intercalation capacity is 364.4mAhg -1 , the delithiation capacity is 363.8mAhg -1 , and the material cycle is stable The properties are obviously improved, and the reversible capacity is close to the theoretical capacity of graphite (372mAhg -1 ).
实施例3Example 3
将柠檬酸、球形天然石墨和分散介质混合，添加消泡剂搅拌均匀，得到的浆料在喷雾干燥机中进行雾化、干燥和造粒得到粉体物料。将得到的粉体物料置于氮气保护高温石墨化炉中，先在800°C保温2h，再在1500°C下烧结3h，冷却至室温后，研磨、过筛，得到的材料标记为G/C-1500。将G/C-1500与聚偏氟乙烯（PVdF）按9:1的质量比在N-甲基吡咯烷酮（NMP）介质中调成浆料，涂布于铜箔上，经过干燥、压膜制成工作电极。以金属锂箔为对电极，Celgard2400为隔膜，1MLiPF6/(EC+DMC)(1:1)为电解液组装成电池进行恒流充放电测试，电流密度为0.15mA/cm2，电压范围在0~1.5V之间。首次嵌锂容量为482.4mAhg-1，脱锂容量为410.8mAhg-1，库伦效率为85.16%；第100次循环嵌锂容量为385.4mAhg-1，脱锂容量为385.4mAhg-1，材料的循环稳定性得到进一步改善，且可逆容量大于石墨的理论容量。 Mix citric acid, spherical natural graphite and a dispersion medium, add a defoamer and stir evenly, and the obtained slurry is atomized, dried and granulated in a spray dryer to obtain a powder material. The obtained powder material is placed in a nitrogen-protected high-temperature graphitization furnace, first kept at 800°C for 2h, then sintered at 1500°C for 3h, cooled to room temperature, ground and sieved, and the obtained material is marked as G/ C-1500. G/C-1500 and polyvinylidene fluoride (PVdF) are adjusted into a slurry in N-methylpyrrolidone (NMP) medium at a mass ratio of 9:1, coated on copper foil, dried and pressed into a film into the working electrode. A battery was assembled with lithium metal foil as the counter electrode, Celgard2400 as the diaphragm, and 1MLiPF 6 /(EC+DMC) (1:1) as the electrolyte for constant current charge and discharge tests. The current density was 0.15mA/cm 2 , and the voltage range was Between 0~1.5V. The first lithium intercalation capacity is 482.4mAhg -1 , the lithium delithiation capacity is 410.8mAhg -1 , and the Coulombic efficiency is 85.16%; the 100th cycle lithium intercalation capacity is 385.4mAhg -1 , the delithiation capacity is 385.4mAhg -1 , the cycle of the material The stability is further improved, and the reversible capacity is larger than the theoretical capacity of graphite.
实施例4Example 4
将柠檬酸、球形天然石墨和分散介质混合，添加消泡剂搅拌均匀，得到的浆料在喷雾干燥机中进行雾化、干燥和造粒得到粉体物料。将得到的粉体物料置于氮气保护高温石墨化炉中，先在800°C保温2h，再在2900°C下烧结3h，冷却至室温后，研磨、过筛，得到的材料标记为G/C-2900。将G/C-2900与聚偏氟乙烯（PVdF）按9:1的质量比在N-甲基吡咯烷酮（NMP）介质中调成浆料，涂布于铜箔上，经过干燥、压膜制成工作电极。以金属锂箔为对电极，Celgard2400为隔膜，1MLiPF6/(EC+DMC)(1:1)为电解液组装成电池进行恒流充放电测试，电流密度为0.15mA/cm2，电压范围在0~1.5V之间。首次嵌锂容量为470.8mAhg-1，脱锂容量为403.1mAhg-1，库伦效率为85.63%；第100次循环嵌锂容量为421.8mAhg-1，脱锂容量为421.3mAhg-1。循环稳定性得到显著改善，且可逆容量远高于石墨的理论容量。 Mix citric acid, spherical natural graphite and a dispersion medium, add a defoamer and stir evenly, and the obtained slurry is atomized, dried and granulated in a spray dryer to obtain a powder material. The obtained powder material is placed in a nitrogen-protected high-temperature graphitization furnace, first kept at 800°C for 2h, then sintered at 2900°C for 3h, cooled to room temperature, ground and sieved, and the obtained material is marked as G/ C-2900. Prepare G/C-2900 and polyvinylidene fluoride (PVdF) at a mass ratio of 9:1 in N-methylpyrrolidone (NMP) medium to make a slurry, coat it on a copper foil, dry it, and press it into a film into the working electrode. A battery was assembled with lithium metal foil as the counter electrode, Celgard2400 as the diaphragm, and 1MLiPF 6 /(EC+DMC) (1:1) as the electrolyte for constant current charge and discharge tests. The current density was 0.15mA/cm 2 , and the voltage range was Between 0~1.5V. The first lithium intercalation capacity is 470.8mAhg -1 , the delithiation capacity is 403.1mAhg -1 , and the Coulombic efficiency is 85.63%; the 100th cycle lithium intercalation capacity is 421.8mAhg -1 , and the delithiation capacity is 421.3mAhg -1 . The cycle stability is significantly improved, and the reversible capacity is much higher than the theoretical capacity of graphite.
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