Investigations on the Performance of the Blending Natural and Artificial Graphite for Lithium ion Battery

In this work,it was found that the improved battery performance such as thermal stability and cycle performance with the blending of nature and artificial graphite.

Homogeneous distributed natural pyrite-derived composite induced by modified graphite as high-performance lithium-ion batteries anode

Natural minerals-based energy materials have attracted enormous attention because of the advantages of good materials consistency,high production,environmental friendliness,and low cost.The uniform distribution of grains can effectively inhibit the aggregation of active materials,improving lithium storage performance.In this work,natural graphite is modified by polyvinylpyrrolidone to obtain modified graphite with reduced size and better dispersion.Natural pyrite composite polyvinylpyrrolidone-modified graphite(pyrite/PG)material with uniform particle distribution is obtained by the ball milling process.The subsequent calcination process converts pyrite/PG into Fe_(1-x)Scompounded with polyvinylpyrrolidone-modified graphite(Fe_(1-x)S/PG).The homogeneous grain distributions of active material can facilitate the faster transfer of electrons and promote the efficient utilization of active materials.The as-prepared Fe_(1-x)S/PG electrode exhibits a remarkably reversible specific capacity of 613.0 mAh·g^(-1)at 0.2 A·g^(-1)after 80 cycles and an excellent rate capability of 523.0 mAh·g^(-1)at 5 A·g^(-1).Even at a higher current density of 10 A·g^(-1),it can deliver a specific capacity of 348.0 mAh·g^(-1).Moreover,the dominant pseudocapacitance in redox reactions accounts for the impressive rate and cycling stability.This work provides a low-cost and facile method to fabricate natural mineral-based anode materials and apprise readers about the impact of uniform particle distribution on lithium storage performance.

Modified graphite filled natural rubber composites with good thermal conductivity

The rubber composites with good thermal conductivity contribute to heat dissipation of tires. Graphite filled natural rubber composites were developed in this study to provide good thermal conductivity. Graphite was coated with polyacrylate polymerized by monomers including methyl methacrylate, n-butyl acrylate and acrylic acid. The ratios between a filler and acrylate polymerization emulsion and those between monomers were varied. Eight types of surface modification formulas were experimentally investigated. Modification formula can affect coating results and composite properties greatly. The best coating type was achieved by a ratio of1:1 between methyl methacrylate and n-butyl acrylate. The coating of graphite was thermally stable in a running tire. Filled with modified graphite, the tire thermal conductivity reached up to 0.517–0.569 W·m-1·K-1. In addition, the mechanical performance was improved with increased crosslink density, extended scorch time and short vulcanization time.

Carbide derived carbon electrode with natural graphite addition in magnesium electrolyte based cell for supercapacitor enhancements

Herein,we have presented a supercapacitor based on carbide derived carbon（CDC） electrode with natural graphite（NG） addition.The capacitor was analyzed at 22°C by cyclic voltammetry,galvanostatic charge-discharge and impedance techniques using a 0.5 mol/L of magnesium（II）bis（trifluoro methanesulfonyl） imide（Mg TFSI） in ethylene carbonate-propylene carbonate（EC ：PC = 1 ：1,v/v） as electrolyte.The results conclude that the CDC cell enhancements have been proven by the composite electrode（5%–30% NG to CDC） especially on the cell efficiency and voltage i.e.,the CDC cell around 2.5 V limit was improved.An obtainable specific capacitance,real power and energy density are 15 F g-1,1.2 k W kg-1and 15 Wh kg-1,respectively.

A Novel Modification Approach for Natural Graphite Anode of Li-ion Batteries

To improve the rate capability and cyclability of natural graphite anode for Li-ion batteries,a novel modification approach was developed.The modification approach included two steps:(a)high-energy ball milling in a rotary autoclave containing alumina balls,H_3PO_4 and ethanol;(b)coating with pyrolytic carbon from phenlic resin.The treated graphite shows obvious improvement compared with the original natural graphite in electrochemical properties such as cyclability and rate capability,especially at high current density.The primary reasons leading to the improvement in rate capability and cyclability are that the diffusion impedance of Li^+ in graphite is reduced due to the fact that P filtered into graphite layers can mildly increase interlayer distances,and the fact that the structural stability of graphite surface is enhanced since the coated pyrolytic carbon can depress the co-intercalation of solvated lithium ion.

The feasibility for natural graphite to replace artificial graphite in organic electrolyte with different film-forming additives

The feasibility for natural graphite(NG)to replace artificial graphite(AG)in organic electrolytes with different additives are investigated.Although the strong film-forming additives contributes to form robust solid electrolyte interphase(SEI)film on graphite particle surface,great differences in gas evolution,lithium inventory loss and other side reactions are observed.Lithium bis(oxalato)borate(Li BOB)and fluoroethylene carbonate(FEC)are found more effective and the combination shows to be more promising.In the optimized electrolyte,natural graphite anode exhibits excellent long-term cycling capability.After 800 cycles at high temperature,the capacity retention is comparable to that using artificial graphite.The mechanisms for the capacity-fading of the full cells with AG and NG anode are investigated by ICP,SEM and polarization studies.The results shows that NG electrode consumes more active lithium due to the rough surface and larger volume expansion.The rapid capacity-fading in the initial 100 cycles is related to the instability of the SEI film aroused from large volume expansion.The systematic analysis is inspiriting for the development of high performance lithium ion batteries with reduced cost.

Influence of particle structure on electrochemical character of composite graphite

The natural graphite has been used as the anode material for Lithium-Ion batteries, because of its low cost, chemical stability and excellent reversibility for Li+ insertion. However, the slow diffusion rate of lithium ion and poor compatibility with electrolyte solutions make it difficult to use in some conditions. In order to solve these problems, an epoxy-coke/graphite composite has been manufactured. The particle of composite carbonaceous material coated on non-graphitizable (hard) carbon matrix. Due to the disordered structure, the diffusion rate of lithium species in the non-graphitzable carbon is remarkably fast and less anisotropic. The process for preparing a composite carbon powder provides a promising new anode material with superior electrochemical properties for Li-ion batteries. The unique structure of epoxy-coke/graphite composite electrodes results in much better kinetics, also better recharge ability and initial charge/discharge efficiency.

Cost-effective natural graphite reengineering technology for lithium ion batteries

Graphite tailings produced by natural graphite is usually regarded as garbage to be buried underground,which would result in a certain waste of resources.Here,in order to explore the utilization of natural graphite tailings(NGT),a liquid-polyacrylonitrile(LPAN)is used to modify the NGT fragments and aggregate them together to form secondary graphite particles with low surface area and high tap density.Moreover,the modified NGT show much better electrochemical performances than those of original one.When tested in full cells coupled with NMC532 cathode,the material achieves a high rate capability and cycle stability at the cutoff voltage of 4.25 V as well as 4.45 V,which maintains 84.32%capacity retention after 500 cycles at 1 C rate(4.25 V),higher than that of the pristine one(73.65%).The enhanced performances can be attributed to the use of LPAN to create a unique carbon layer upon graphite tailings to reconstruct surface and repair defects,and also to granulate an isotropic structure of secondary graphite particles,which can help to weaken the anisotropy of Li^(+)diffusion pathway and form a uniform,complete and stable solid-electrolyte-interface(SEI)on the surface of primary NGT fragments to promote a fast Li+diffusion and suppress lithium metal dendrites upon charge and discharge.

Synthesis of Alumina-Coated Natural Graphite for Highly Cycling Stability and Safety of Li-Ion Batteries

The natural graphite(NG)urdformly coated with alumina ceramics(Al2O3)was successfully synthesized through sol-gel method.The aluminum plastic film soft-packed battery prepared using Al2O3-coated NG as anode material exhibits excellent cycle performance and safety performance.The cycling retention of AN-1 is 84.95% after 200 cycles at a rate of 1 C in a potential window ranging from 3.0 to 4.35 V,which is much greater than 75.07% of NG under the same test conditions.The result of the nail penetration tests shows that the successful nail penetration rate of the NG used as anode is 0%,while that of Al2O3 coated samples AN-1 is 100%.The test results show that the Al2O3 coating could act as a solid electrolyte to suppress side reactions,improve cycle stability,and prevent a thermal runaway under mechanical abuse.

Preparation and Properties of Ultrathin Flexible Expanded Graphite Film via Adding Natural Rubber

Expanded graphite(EG) films exhibit potential use in a wide field including thermal management, conductive applications,and electromagnetic interference(EMI) shielding. However, their poor tensile strength and brittleness are crucial deficiencies for commercial applications. To address these defects, in our work, natural rubber(NR) is employed to improve EG films for better mechanical strength and flexibility. The origin of the strengthening effect of EG films by the addition of natural rubber mainly arises from the formation of a simulate shell structure. Compared to the neat EG films, the addition of merely 2 wt% NR can give rise to superior ductility. Further, the loading of 10 wt% NR realizes a significant mechanical enhancement of the EG/NR films, i.e., 2.4 and 11.4 times increase in tensile strength and elongation at break, respectively. Besides, EG/NR films containing 10 wt% NR can still sustain excellent thermal and electric conductivities of 173 W·m^-1·K^-1 and 75 S·cm^-1, respectively. Furthermore, a very high EMI of 41.4 dB is achieved as the film thickness reaches 50 μm. Thus, the lightweight EG/NR films with comprehensive performance as well as their virtue of green and simple large-scale preparation endow them with the possibility of designing next-generation flexible electronics.

Comparative tribological behavior of friction composites containing natural graphite and expanded graphite

In this study, expanded graphite and natural graphite were introduced into resin-based friction materials, and the tribological behavior of the composites was investigated. The tribo-performance of the two friction composites was evaluated using a constant speed friction tester. The results showed that the expanded graphite composite (EGC) displayed better lubricity in both the fading and the recovery processes. The wear rate of the EGC decreased by 22.43%more than that of the natural graphite composite (NGC). In the fading process, and the EGC enhanced the stability of the coefficient of friction. The recovery maintenance rate of the NGC was 4.66% higher than that of the EGC. It can be concluded that expanded graphite plays an important role in the formation of a stable contact plateau and can effectively reduce the wear.

Processing Compressed Expanded Natural Graphite for Phase Change Material Composites

Phase change materials(PCMs)are used in various thermal energy storage applications but are limited by their low thermal conductivity.One method to increase conductivity involves impregnating organic PCMs into highly porous conductive matrix materials.Of these materials,compressed expanded natural graphite(CENG)matrices have received the most attention.Despite this attention,the effect that CENG processing has on PCM saturation and overall matrix thermal conductivity has not been fully investigated.Therefore,the effect of the heat treatment process used to expand intercalated graphite flakes is evaluated here.Higher heat treatment temperatures yielded higher saturation rates and overall saturation at similar matrix porosities.For example,increasing temperature from 300℃to 700℃resulted in approximately 60%-70%increase in pore saturation after 100 minutes of soaking.The exposure time to heat treatment had less of an effect on PCM saturation.The exposure time had negligible effect above 30 min and above 500℃heating temperatures.However,because the expanded graphite was found to oxidize around 700℃,the use of longer exposure time in manufacturing applications can be beneficial if a shortened impregnation time is needed.Heat treatment conditions did not impact thermal conductivity.The composite latent heat of fusion was also reduced approximately proportionally to the PCM mass fraction.A local maximum in axial thermal conductivity was observed at around 83%porosity,which is similar to previous studies.The observed conductivity at this maximum was a factor of 81 times greater than the conductivity of the PCM.

The evolution of coal, examining the transitions from anthracite to natural graphite: a spectroscopy and optical microscopy evaluation

Coal-derived natural graphite(CDNG)has multiple industrial applications.Here,ten metamorphic coals from anthracite to CDNG were obtained from Lutang and Xinhua in the Hunan Province and Panshi in the Jilin Province.Bulk characterization(proximate and ultimate analyses,X-Ray powder diffraction(XRD),and powder Raman spectroscopy),along with optical microscopy,scanning electron microscope(SEM)and micro-Raman spectroscopy were utilized to examine the transitions from anthracite to semi-graphite to CDNG.The XRD and Raman spectroscopy data indicate that from anthracite to highly ordered graphite the average crystal diameter(La)and height(Lc)increased from 6.1 and 4.6 nm to 34.8 and 27.5 nm,respectively.The crystalline parameters of the CDNG samples from Panshi and Lutang varied slightly when closer to the intrusive body.Optical microscopy and SEM indicated that in the anthracite samples there were thermoplastic vitrinite,devolatilized vitrinite,and some“normal”macerals.In the meta-anthracite,pyrolytic carbon,mosaic structure,and crystalline tar were present.In the CDNG there were flake graphite,crystalline aggregates,and matrix graphite.The crystalline aggregates show the highest structural ordering degree as determined from Raman spectral parameters(full-width at half maxima(G-FWHM)~20 cm^(−1),D1/(D1+D2+G)area ratio(R2)value<0.5).The flake graphite is less ordered with G-FWHM~28 cm^(−1) and 0.5<R2<1,but a larger grain size(up to 50μm).The mosaic structures were likely the precursors of the matrix graphite through in situ solid-state transformation.The pyrolytic carbon and crystalline tars are the transient phase of gas-state and liquid-state transformations.This study is beneficial to realize the rational utilization of CDNG.

2025-2035年中国天然石墨资源需求预测

天然石墨广泛应用于传统工业和战略性新兴产业,是支撑我国高新技术发展的重要原材料。本文论述了我国天然石墨资源现状,并通过分析天然石墨主要消费部门需求,预测了未来耐火材料、铸造、铅笔、密封材料、摩擦材料、润滑吸附材料、锂电池负极材料等产业对天然石墨的需求。研究发现:我国天然石墨资源丰富,未来需求量将快速增长,预计到2025年、2030年、2035年我国天然石墨的需求量将分别达到109.0万t、188.3万t和278.3万t。全球天然石墨供给侧正在重塑,我国在全球天然石墨产业链供应链中的地位正在下降。我国石墨消费重心正从传统产业向战略性新兴产业转移,高端石墨产业发展面临机遇,为天然石墨产业发展带来新的增长点。通过健全天然石墨产业链和加强天然石墨资源保护力度,使我国从石墨资源大国发展成为石墨资源强国,支撑我国未来在新能源、关键装备密封润滑材料、高温材料等高端领域的石墨产品需求发展。

天然鳞片石墨球形尾料制备柔性电热膜

随着球形石墨在锂离子电池负极材料的应用,天然鳞片石墨球化过程中产生了大量的球形尾料,其利用率及附加值较低。本文将球形石墨(SG8)、球形尾料与羧基化纳米纤维素按不同比例混合,制备了6种柔性电热膜。通过调控球形石墨和球形尾料添加量、电压等参数,研究电热膜的电阻、电阻率和升温速率的演变规律。研究表明,在10V电压下,球形尾料含量为15%的加热膜电阻率为8.57mΩ/mm,达到发热最高温度为59.3℃,前30s的升温速率为0.50℃/s,水洗后球形尾料含量为15%的加热膜电阻率为9.30mΩ/mm,达到发热最高温度为58.6℃,前30s的升温速率为0.46℃/s,表明球形尾料电热膜水洗后仍具备良好的柔性和发热性能,证明了利用天然石墨球形尾料可制备柔性电热膜。相比于球形石墨,球形尾料具有更好的电热性能,为天然石墨球形尾料的高质化利用提供了解决途径。

不同地区天然石墨球形化制备负极材料

天然鳞片石墨是制备锂离子电池负极材料的优质原料,本试验以鸡西、内蒙古、萝北3个地区固定碳含量(质量分数)约为95%的石墨精矿为原料,依次进行球形化整形和化学提纯,制备高纯球形石墨,并对高纯球形石墨进行了电化学性能测试。结果表明,经过球形化后,3个地区球形石墨振实密度分别为0.96 g/cm^(3)、0.94 g/cm^(3)、0.98 g/cm^(3),其中萝北石墨振实密度最高,成球率为41.44%。较优混酸提纯工艺为:混酸与石墨的液固比为3 mL/g,HF体积分数为30%,反应时间为6 h,反应温度为70℃,经混酸提纯处理后,3个地区球形石墨固定碳含量分别提高至99.90%、99.88%、99.97%。电化学性能测试结果表明,3个地区石墨负极材料的首次充放电效率均大于90%,首次放电容量均高于360 mAh/g,是制备天然石墨负极材料的理想原料。

高导热多孔石墨预制体的制备及其性能

以天然鳞片石墨、酚醛树脂以及中间相碳微球为主要原料,制备多孔石墨预制体,经石墨化处理后再与环氧树脂复合,获得高导热石墨/环氧树脂复合材料。研究了素坯成形密度和粉末组成对多孔石墨预制体X-Y方向的导热性能与孔隙率的影响。结果表明:预制体内部石墨片定向排列,酚醛树脂与中间相碳微球连接其间,形成定向多孔网络结构,实现高导热、高孔隙与大孔径的协同。当素坯成形密度为1.4 g/cm^(3),天然鳞片石墨、酚醛树脂、中间相碳微球的含量分别为67.5 mass%、17.5 mass%和15 mass%时,多孔石墨预制体X-Y方向导热性能达到286.97 W/(m·K),气孔率达到44.56%;此时,石墨/环氧树脂复合材料X-Y方向导热性能达到116.81 W/(m·K)、抗压强度为26 MPa,在电子封装领域具有潜在的应用前景。

表面包覆碳层孔隙对石墨负极材料倍率性能的影响

为了研究表面包覆碳层孔隙对石墨负极材料倍率性能的影响,引入少量硼酸,在包覆沥青软化阶段形成硼酸气化逸出效应,再通过碳化工艺在天然石墨尾料表面形成具有一定孔隙的包覆碳层,得到具有不同比例孔隙的石墨负极材料。结果表明,硼酸在材料颗粒表面形成了含有孔隙的碳层,其孔隙类型为介孔和大孔;表面碳层中的介孔比例越高,碳层L_(C)中形成Li^(+)的扩散通道数量越多,Li^(+)的扩散阻抗越低,材料倍率性能及循环性能得以改善。

酚醛⁃不饱和聚酯树脂石墨双极板复合材料研究

以天然鳞片石墨(NG)为导电骨料,酚醛树脂(PF)和不饱和聚酯树脂(UPR)为黏结剂,采用模压成型工艺制备了NG/PF/UPR双极板复合材料。研究了PF与UPR的质量比、树脂含量、成型工艺条件对复合材料电导率和弯曲强度的影响,采用差示扫描量热法进行分析。结果表明,在树脂含量为20%(质量分数,下同)、PF与UPR的质量比为6∶1、施压温度为100℃、模压压力为30 MPa、成型温度为180℃、模压时间为2 h的条件下,NG/PF/UPR双极板复合材料的电导率为336.1 S/cm,弯曲强度为46.5 MPa,对于相同条件下的NG/PF双极板复合材料,样品的电导率提高了134.9%,弯曲强度提高了21.2%。

辉锑矿基Sb_(2)S_(3)/石墨复合材料制备及其电化学性能

以天然辉锑矿和天然石墨为原料,采用辅助球磨法制备具有不同比例的辉锑矿基Sb_(2)S_(3)/石墨复合材料。通过X射线衍射(XRD)、拉曼光谱(Raman)、扫面电子显微镜(SEM)和透射电子显微镜(TEM)等手段分别表征复合材料的结构、组成和形貌。以不同比例的辉锑矿基Sb_(2)S_(3)/石墨复合材料作为锂离子电池负极材料制备纽扣电池,测试该复合材料的电化学性能。结果表明:随着天然石墨的质量分数的增加,辉锑矿基Sb_(2)S_(3)/石墨复合材料的循环稳定性得到提升,在长循环中保持了高可逆性。其中,Sb_(2)S_(3)/石墨(质量比为1∶1)复合材料在1 A·g^(-1)电流密度下经过110次循环后仍可保持351 mA·h·g^(-1)的放电比容量,容量保持率达到52%。