Home Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
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Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery

  • Gaobang Chen , Feng Cao , Zexiao Li , Jianan Fu , Baoshan Wu EMAIL logo , Yifan Liu EMAIL logo and Xian Jian EMAIL logo
Published/Copyright: August 21, 2023
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Nanotechnology Reviews
From the journal Nanotechnology Reviews Volume 12 Issue 1

Abstract

Lithium/fluorinated carbon (Li/CF x ) primary battery is a promising energy supply device with high energy density. However, poor electrochemical capabilities such as the initial voltage delay phenomenon and the large polarization have obstructed their applications. The electrochemical performance of CF x primarily depends on the feature of the carbon source and the corresponding fluorination technique. Herein, we developed a high energy density Li/CF x battery by employing helical carbon nanotubes (HCNTs) as the carbon source. In detail, the precise control of the fluorination temperature was designed at the range of 250–400°C to tune the F/C ratio of CF x . Furthermore, the high F/C ratio of fluorinated HCNTs (F-HCNTs) reaches about 1.43, which surpasses the highest theoretical value in fluorinated crystalline carbon materials. Due to the active rich fluorination sites provided by the periodical insertion of the carbon pentacyclic (C5) and heptacyclic (C7) rings, HCNTs exhibited a defect-rich feature and F-HCNTs have a nodular shape. These features favor to enhance the transport of lithium ions and allow more C–F bonds to react with lithium ions, leading to a high energy density of 2133.13 W h/kg. This novel material offers an alternative approach for lithium primary battery being great potential in actual applications.

Keywords: lithium primary battery; fluorinated carbon materials; helical carbon nanotube; multichannel effect

1 Introduction

With the growing demand for energy storage devices [1], pursuing batteries that possess both high energy and power density has become a significant issue [2]. Li/CF x primary battery, commercialized by Matsushita Electric Co., is well known for its highest theoretical energy density and specific capacity (2,180 W h/kg and 865 mA h/g for carbon monofluoride, respectively) among typical lithium primary batteries like Li/MnO2 [3], Li/S, and Li/SOCl2 battery [4]. Furthermore, superior properties of carbon fluorinate such as high discharge voltage plateau (∼2.5 V) [5], open circuit potential (around 3–4 V vs Li/Li+) [6], low self-discharge characteristic, wide operating temperature range [7,8], and high reliability [9] have grabbed extensive attention.

However, increasing the F/C ratio, the insulating groups including CF2 and CF3 are formed at the edges and vacancies [6], resulting in the large polarization [10]. The slow formation of conductive carbon from insulating CF x during the discharge process according to the reaction mechanism leads to a significant initial voltage delay phenomenon [11].

Recently, considerable effort has been made to improve the performance of Li/CF x battery. Among them, one of the key points to determine the performance is the carbon source and adjustment of its microstructure. Generally, fluorination carbon sources are divided into two main species, namely, the crystalline type and the noncrystalline type. In depth, the crystalline-type carbon materials, known by the graphite [12] and multiwalled carbon nanotubes [8], whose carbon atoms are mainly combined through the sp2 hybridization. Commonly, carbon materials with a high crystalline degree show a sharp reflection peak of its (002) lattice plane, which shows its highly ordered structure [13]. Besides, carbon materials possess a more disordered structure with a considerable number of sp3 hybridized bonds [8,14]. Biomass-derived carbon [6], nanostructured carbon [15], and hard carbon materials [16] are classified into this type of carbon material. Typically, the crystalline carbon has a higher intrinsic in-plane conductivity due to its conductive π bonds formed by the sp2 hybridization [17] and the noncrystalline type materials are less conductive than the former ones because of its sp3 hybridization, where all four outermost electrons of carbon atoms are occupied to form the C–C covalent bonds, inducing its poor conductivity. However, fluoridated carbon materials derived from the noncrystalline carbon are prone to exhibit higher specific capacity than the ones synthesized by crystalline-type carbon materials under similar fluorination conditions. For example, there are three types of fluorination structures in graphite fluoride, (C2F) n , C x F, and (CF) n , among which the (CF) n holds the highest F/C ratio [18]. These structures limit the F/C ratio of crystalline carbon materials to 1 (x = 1 in CF x ). Meanwhile, noncrystalline-type carbon materials have the potential to surpass the theoretical restriction of the F/C ratio in crystalline-type carbon materials. Prof. Feng Wei’s group developed an ultra-high energy density CF x compound with the highest x = 1.17 using the amorphous carbon source derived from a calcinated macadamia nutshell. The ability to surpass the theoretical limit of the F/C ratio of the noncrystalline carbon comes from its high curvature morphology and enhances the electrochemical activity of C–F covalent bonds [10]. Above all, each type of carbon source has its own privileges. Combining these benefits through designing the structure of the carbon source makes the principal of a high-performance cathode material of Li/CF x battery. What’s more, due to the existence of various types of C–F bonds [19] (covalent C–F bonds, semi-ionic C–F bonds, and ionic C–F bonds), a high-performance Li/CF x battery could be also realized by increasing the content of ionic and semi-ionic C–F bonds [20] that have better electrochemical properties [21,22,23] or limit the formation of insulating groups mentioned earlier. In a word, the structure of the carbon source serves as a vital role in electrochemical performance of Li/CF x batteries [24].

Helical carbon materials have been extensively explored owing to their outstanding properties and potential applications [25,26,27]. Generally speaking, helical structures of helical carbon nanotubes (HCNTs) are formed by catalytic anisotropies of the precursor [28]. As a result, unique carbon pentacyclic (C5) and heptacyclic (C7) rings are formed on the surface of the HCNTs to maintain the helical structure [29]. Typical catalyst materials such as transition metals (Fe, Co, Ni, Cu, etc.) [27,30] are widely applied in the synthesis of HCNTs. For instance, Vardhan et al. utilized the co-pyrolysis reaction of Fe(CO)5 and pyridine to gain the vertically aligned HCNTs. Meng et al. realized a large-scale synthesis of HCNTs by adding trace water to the growing process of HCNTs. Qing, et al. obtained HCNTs by using ferrous tartrate (C4H4O6Fe) as the catalyst precursor for electrical double-layer capacitors [26]. The growth mechanisms, synthesis, properties, and applications are broadly examined throughout the years. However, fluorinated HCNTs (F-HCNTs) and their potential to be high-performance electrode materials are rarely investigated.

In this work, we developed a simple method of catalytic chemical vapor deposition (CCVD) in the preparation of HCNTs. The gas flow was carefully adjusted so that the high-purity HCNTs were formed on a large scale. HCNTs were further fluorinated to obtain F-HCNTs. The role that the helical structure plays in the fluorination process and the structural properties of F-HCNTs would be thoroughly discussed. Furthermore, F-HCNTs were further modified to be cathode electrodes and then assembled into the lithium primary battery. Electrochemical performance of F-HCNTs was then tested. Thanks to the unique structure of F-HCNTs, this newly developed material exhibited extraordinary capacity and specific energy, with a high specific capacity of 794.42 mA h/g, showing the great potential of being a possible candidate among lithium primary batteries in low-power applications.

2 Experimental section

2.1 Preparation of the catalyst and HCNTs

HCNTs were synthesized according to the previous literature [26] with minor modifications. First, catalyst precursors of C4H4O6Fe were synthesized by dropping 100 mL of 1 M C4H4O6Na2 into 100 mL FeCl2 solutions at a stirring state for 20–40 min. Then the aforementioned solution was filtered and washed thoroughly with deionized water. Then the residue was dried for 24 h to obtain C4H4O6Fe as the catalyst precursor. The as-obtained precursors with a mass of 0.25 g were put into a tube furnace and heated up to 550°C with a rate of 10°C/min under H2 at the flow of 80 mL/min, and then, H2 was replaced by C2H2 reacting for 1 h to obtain HCNTs. In addition, a quartz boat with a small amount of water was placed on the inlet of the CCVD furnace aiming to increase the yield as well as the high purity according to ref. [31].

2.2 Preparation of F-HCNTs

F-HCNTs were prepared by the direct-fluorinate method under the F2 flow (100 mL/min) in the tube furnace. The fluorination processes were implemented at 250, 300, 350, and 400°C to adjust the F/C ratio. The products as well as the assembled cells were defined as F-HCNT-250, F-HCNT-300, F-HCNT-350, and F-HCNT-400.

2.3 Characterization of as-synthesized materials

By using an Ultima IV X-ray diffractometry (XRD) with a Cu Kα 426 radiation source (40 kV, 40 mA), XRD of F-HCNTs was carried out. A Sigma500 scanning electron microscope (SEM) and a JEOL-JEM 2,100 F transmission electron microscope (TEM) were used to examine the micromorphology of as-prepared materials. In addition, the elemental distribution of the F-HCNT-300 was determined through an energy-dispersive X-ray spectrometer (EDX) in combination with a TEM. The nitrogen adsorption–desorption isotherms and pore size distributions of HCNTs and F-HCNT-300 were measured in a Micrometrics automated surface area and porosity analyzer (BET). The Raman spectra were measured with a Raman shift of 500–4,000 cm−1 on the HORIBA LabRAM HR Evolution Raman system. A thermal system, thermogravimetric analysis (TGA)/DSC (SDT Q600), was applied to perform the TGA of F-HCNTs. X-ray photoelectron spectroscopy (XPS) spectra with an Al Kα source were recorded to confirm chemical compositions of F-HCNTs and iron fluoride (FeF3).

2.4 Electrochemical measurements

The electrochemical measurements were conducted through galvanostatic discharges. The working electrode was manufactured by combining F-HCNTs with carbon black as a conductive additive and polyvinylidene difluoride as a binder in a weight proportion of 8:1:1. N-Methyl-2-pyrrolidone was added into the mixed powder so as to gain a slurry in good dispersion. The slurry was coated on the aluminum foil, which served as the current collector subsequently. The aluminum foil with the coating was dried in the vacuum oven at a temperature of 80°C for 2 h, and the resulting electrode film was cut into small discs with a diameter of 12 mm, which were further dried under vacuum at 80°C for 24 h. The cut discs were then transferred into a dry glove box filled with argon gas for the assembling of the button coin cells (CR2032). Li discs functioned as the anode, 1.0 M LiPF4 in propylene carbonate/dimethoxy ethane (PC/DME, 1:1 vol) was employed as the electrolyte, and a Celgard 2034 membrane was used to separate the anode and cathode. The cells were taken out of the glove box and held overnight for the electrochemical measurements. Electrochemical impedance spectroscopy (EIS) was recorded from 0.01 to 100 kHz using the CHI760D equipment. Coin cells were discharged on a battery test system under the temperature of 25°C, and the cut-off voltage was set to 1.5 V (vs Li/Li+) to simulate the actual working condition of the lithium primary cells as possible.

3 Results and discussion

The synthesis process of HCNTs and F-HCNTs is schematically illustrated in Figure 1a, which shows them a unique helical structure. The helical structure of HCNTs was originated from the periodic embedding C5 and C7 rings. As discussed earlier, this unusual feature is considered as the combination of the crystalline and noncrystalline carbon materials since the introduction of C5 and C7 rings has broken the sp2 hybridization and altered the electron distribution, eventually creating localized uncrystallized area inside the well-arranged hexagonal plane. Based on this characteristic, F-HCNTs are able to retain the conductivity of the crystalline carbon while exceeding the theoretical boundary of the crystalline carbon. Thus, during the preparation of HCNTs, temperature and gas flow control are extremely crucial to HCNTs, which determine the helix purity and the degree of noncrystallinity. Likewise, the fluorination temperature is associated with the F/C ratio of the CF x cathode materials regardless of the fluorination method [32,33]. Then precise control of the fluorination temperature is important for tuning the electrochemical performance of the CF x cathode materials.

Figure 1 (a) The related flowchart of the synthesis process of F-HCNTs and (b) schematic illustration of a Li/F-HCNTs primary battery.
Figure 1

(a) The related flowchart of the synthesis process of F-HCNTs and (b) schematic illustration of a Li/F-HCNTs primary battery.

Figure 1b provides an overview of a complete Li/CF x battery, showing that the transportation of Li+ also matters in actual working batteries. Through the widespread curvature of HCNTs, the etching of F2 is capable of creating substantial vacancies and cracks on the surface of F-HCNTs, promoting ion transport during the discharging process. Furthermore, particles with Fe in HCNTs react with F2 to form FeF3 during the fluorination [34], which functions as an additive electrode material to reinforce the batteries’ capability.

3.1 Morphological and structural characterization

The morphologies of HCNTs produced by CCVD and F-HCNTs were observed by SEM and HRTEM (Figure 2). Figure 2a shows that most of HCNTs exhibit obvious helical structures and impurities are hardly found. The average outer diameter of HCNTs is about 92.5 nm, and the coil distance is 170 nm. The average outer diameter of F-HCNT-300 is 70 nm, which is smaller than HCNTs. This result indicates that carbon nanotubes with helical shapes are successfully synthesized with high purity. The excellent properties of materials are obtained by nanoscale materials [35]. The typical morphology of F-HCNT-300 shown in Figure 2b demonstrates that the helical structure of these tubes is still maintained after the fluorination at 300°C, and small cracks are observed in F-HCNTs because some C–C sp2 bonds are broken and transformed into the C–F bonds. Hence, the cracked structure of F-HCNT-300 probably originated from the appearance of vacancies and micropores arose from the broken C–C bonds [8]. However, there is no noticeable change in the diameter of the HCNTs and F-HCNT-300, suggesting that the additionally attached fluorine atoms in F-HCNT-300 are mostly located on the surface of the nanotubes, which potentially accelerates the reaction rate between the Li+ and the fluorine atoms. The uniform tube diameter of HCNTs and F-HCNT-300 also proves that the stacked carbon layers are not detached from each other preserving a certain degree of crystallinity. The cracked and nodular morphology of fluorinated carbon materials provides an enlarged surface area and a multichannel transport pathway for Li+ diffusion during the discharge [36], contributing to the better performance of the lithium primary battery.

Figure 2 SEM images of (a) HCNTs and (b) F-HCNT-300; (c), (e), and (g) TEM images of HCNTs, F-HCNT-300, and FeF3; (d), (f), and (h) HRTEM images of HCNTs, F-HCNT-300, and FeF3; and (i)–(l) EDS mapping of F-HCNT-300.
Figure 2

SEM images of (a) HCNTs and (b) F-HCNT-300; (c), (e), and (g) TEM images of HCNTs, F-HCNT-300, and FeF3; (d), (f), and (h) HRTEM images of HCNTs, F-HCNT-300, and FeF3; and (i)–(l) EDS mapping of F-HCNT-300.

Detailed information for the morphology and nanostructures of HCNTs that fluorinated at high temperatures is given by the TEM images in Figure 2c–f. The typical morphology of HCNTs shown in Figure 2c demonstrates that the helical structure of these tubes is perfect, which is consistent with the SEM observation. The C (002) facet of HCNTs corresponded to the lattice fringe spacing is measured at 0.35 nm in Figure 2d. Basically, the helical shape of F-HCNT-300 remains well. A relatively low contrast in the middle parts of the nanotubes in Figure 2e indicates the hollow and few-walled helical structures are present in F-HCNT-300. Figure 2f shows that the amorphous nanostructure is a common nature of CF x [6,37,38]. It is initiated by the large-scale alteration from sp2 to sp3 hybridization caused by the noncrystallinity of HCNTs [8,14]. Furthermore, Figure 2g shows the microstructure of FeF3. The corresponding enlarged view of a selection area was marked by the dotted line to confirm the substance category as shown in Figure 2h. The lattice fringe spacing is determined to be about 0.56 nm, which corresponds to the (110) facet of FeF3 [39]. The existence of the catalyst particle located inside of HCNTs can be confirmed directly by its color contrast. FeF3 has a high specific capacity and high operating voltage, while improving the ion storage capacity of the electrode materials. As the cathode materials of lithium ion battery, the performance and service life of lithium ion battery is improved by FeF3. A well-defined boundary between the crystallized catalyst particle and apparently disordered HCNTs is shown in the bottom right corner of Figure 2h.

The distribution of the element of F-HCNT-300 is shown in EDX elemental mapping images in Figure 2i–l, which indicates the existence of carbon, fluorine, and a small quantity of iron. The uniform distribution of fluorine in F-HCNT-300 indicates the good fluorination effect of HCNTs. Figure 2j and k shows that the elemental content is clearly comparable. When fluorinated, HCNTs with Fe form a small number of FeF3 particles, which can be seen from the distribution of iron elements in the elemental mapping image in Figure 2l. It is also evident from the color contrast that the content of iron is significantly lower than that of carbon and fluorine.

The N2 adsorption–desorption isotherm measurement is applied to evaluate the surface feature of HCNTs and F-HCNT-300. The N2 adsorption–desorption isotherm of HCNTs and F-HCNT-300 shown in Figure 3a is classified as type IV, which reveals a large amount of micropores and mesoporous in the materials. On the basis of the isotherm, the BET surface areas of HCNTs and F-HCNT-300 are 60.94 and 197.32 m2/g, respectively. Compared with HCNTs, the BET surface areas of F-HCNT-300 increase, and the increase is due to the etching of the HCNTs by F2 during fluorination. The etching of F2 changes part of the ordered structure of HCNTs into the disordered structure. The pore sizes of HCNTs and F-HCNT-300 shown in Figure 3b and c are analyzed based on the nonlocalized density functional theory. The average pore sizes of HCNTs and F-HCNT-300 are 14.84 and 6.79 nm. After high-temperature fluorination, F-HCNT-300 retains the porous structure of pristine HCNTs, which is beneficial for lithium ion transfer. A great deal of micropores are generated in F-HCNT-300, which increases the specific surface area of the electrode reaction, thus improving the electrochemical reaction rate and efficiency of the battery.

Figure 3 (a) Nitrogen adsorption–desorption isotherms of HCNTs and F-HCNT-300, and (b) and (c) pore size distributions of HCNTs and F-HCNT-300.
Figure 3

(a) Nitrogen adsorption–desorption isotherms of HCNTs and F-HCNT-300, and (b) and (c) pore size distributions of HCNTs and F-HCNT-300.

Thermal parameters of F-HCNTs are also investigated by TGA under N2 flow at a heating rate of 10°C/min, and the F/C ratios are then calculated as shown in Figure 4a. The TGA results denote that all CF x samples exhibit an obvious weight loss when being heated under N2 since that the fluorine atom is prone to be removed from the CF x [40,41]. F-HCNT-400 shows the best thermal stability since its weight begins to drop at about 450°C, which possesses the highest stability among all samples. The F/C ratio is carried out using the formula as follows (including the existence of FeF3, the F/C ratio estimated by the TGA curve would suffer a decrease in accuracy):

(1) R F / C = ( 1 − W R ) / A r ( F ) W R / A r ( C ) ,

Figure 4 (a) TGA curves of F-HCNT-250, 300, 350, and 400; (b) Raman spectra of F-HCNT-250, 300, 350, and 400; (c) XRD patterns of F-HCNT-250, 300, 350, and 400; (d) XPS survey spectrum of F-HCNT-300; (e) high-resolution XPS spectra in C 1s of F-HCNT-300; and (f) high-resolution XPS spectra in F 1s of F-HCNT-300.
Figure 4

(a) TGA curves of F-HCNT-250, 300, 350, and 400; (b) Raman spectra of F-HCNT-250, 300, 350, and 400; (c) XRD patterns of F-HCNT-250, 300, 350, and 400; (d) XPS survey spectrum of F-HCNT-300; (e) high-resolution XPS spectra in C 1s of F-HCNT-300; and (f) high-resolution XPS spectra in F 1s of F-HCNT-300.

Here, W R is the remaining mass at the end of weightlessness, and A r(F) and A r(C) are the atomic weight of fluorine and carbon, respectively [42]. The F/C ratio of F-HCNTs goes up as the fluorination temperature rises consecutively, and a dramatic increase of the fluorine content took place for F-HCNT-300, F-HCNT-350, and F-HCNT-400. Besides, the curves of F-HCNT-350 and F-HCNT-400 show more similarity than any other samples, indicating their intrinsic structural similarity. The F/C ratio of F-HCNT-400 is about 1.43, which is a relatively high value compared to other CF x materials fluorinated under similar temperatures [8]. This may be the consequence of the large number of defects caused by the high curvature feature and the noncrystalline defect caused by C5 and C7 rings of HCNTs, resulting in the instability of C–C bonds and tendency to be broken and generating C–F bonds.

The Raman spectrum is used to provide the structural information of F-HCNTs. Two main peaks located at about 1,310 and 1,590 cm−1 are attributed to the D band and G band of carbon materials shown in Figure 4b [43]. The D band is the defect-induced peak, which reflects the degree of the defect and distorted carbon atoms like sp3 hybridized carbon and the edge carbon atoms [6,44,45]. The G band is attached to the sp2 hybridized carbon stemming from the E2g mode [8]. The ratio of the integral intensity of the two bands could be utilized to determine the degree of the disordered carbon [46,47]. The value of I D/I G of raw HCNTs is 0.92, which is higher than typical carbon materials such as graphene [48] and carbon nanotubes [49] due to the enrichment of C5 and C7 defects in raw HCNTs. The upsurge of the disordered carbon shows that the formation of C–F bonds has broken the original crystal-like structure of HCNTs. Higher fluorine content results in a more disordered structure and hence, more sp2 hybridized graphite-like C–C bonds are broken, leaving a higher I D/I G ratio [15]. For F-HCNT-300, the D and G bands have been suppressed owing to the presence of strong luminescence in deeply fluorinated materials [50]. F-HCNT-300 possesses a trend of increasing I D/I G values compared with F-HCNT-250, indicating a decrease in the order of the carbon layer structure due to the formation of fluorocarbon bonds. As increasing fluorination temperature up to 350 and 400°C, the disintegration of the carbon layer in the helical carbon leads to the disappearance of I D and I G . In this way, the adsorption site of Li+ is increased, which is conducive to the transport of ions in the electrode materials and the improvement of the electrochemical performance of the battery. The disappearance of D and G bands in F-HCNT-400 showed the trace existence of sp2 hybridized carbon in this sample. The values of I D/I G, fluorine content, the F/C ratio, and theoretical capacity are summarized in Table 1. The TGA results demonstrate the high fluorine content in F-HCNT-350 and F-HCNT-400, and the dramatic increase of the F/C ratio in these two samples is due to the structure destruction brought by the highly activated F2 at high temperatures. The high F/C ratio caused by the noncrystalline feature is beneficial to create more active reaction sites favoring inserting Li+. The theoretical capacity of CF x is determined by the F/C ratio. Based on relevant literature [51], the theoretical capacities of F-HCNT-250, F-HCNT-300, F-HCNT-350, and F-HCNT-400 are calculated as 709.97, 880.80, 967.71, and 978.45 mA h/g, respectively (Supporting information S1).

Table 1

The list of I D/I G value, F/C ratio, fluorine content, and theoretical capacity of raw HCNTs and CF x including F-HCNT-250, 300, 350, and 400

Name I D/I G F/C ratio Fluorine content (%) Theoretical capacity (mA h/g)
HCNTs 0.92 0 0 —
F-HCNT-250 1.22 0.64 30 709.97
F-HCNT-300 1.32 1.05 51 880.80
F-HCNT-350 1.17 1.38 57 967.71
F-HCNT-400 — 1.43 59 978.45

XRD patterns of F-HCNTs are shown in Figure 4c. Broad (001) and (100) reflection peaks of the fluorinated carbon phase are observed around 14° and 42°, respectively [52]. The peak intensity rises as the fluorination temperature consecutively, reflecting the increases of the fluorine content. Meanwhile, the (001) and (100) reflection peaks have shifted to lower angles with the rising fluorination temperature, corresponding to a larger C–C in-plane length of the CF x lattice. The broad shape of these peaks implies the amorphous structure and the defect-rich feature of F-HCNTs materials. The peak of graphite (002) lattice planar centered around 26° gets weaker as the fluorination temperature grows, and this property also signifies the damage that fluorination caused to the original structure of HCNTs. However, the presence of (100) reflection provides evidence that a partial hexagonal system of graphite carbon is preserved during the fluorination [6]. XRD analyses have shown the primarily disordered structure of F-HCNTs and the presence of FeF3, which are in good agreement with the TEM images, Raman spectrum, and the TGA results.

XPS serves as a powerful approach to evaluating the surface element and the bonding types. The survey of F-HCNT-300 is shown in Figure 4d, and the high-resolution spectrums of C 1s and F 1s are presented in Figure 4e and f. From the survey spectrum, it confirms the peak of iron, fluorine, oxygen, and carbon, which is positioned at about 710.7, 689.1, 532.4, and 290.3 eV, respectively. The existence of iron matches the results of XRD and TEM images. According to previous researches, the C 1s spectrum is fitted to six different carbon bonds, which are sp3 C–C bond (284.8 eV), sp2 C═C bond (285.8 eV), semi-ionic C–F bond (288.4 eV), covalent C–F bond (290.0 eV), perfluorinated C–F2 (290.9 eV), and C–F3 (292.0 eV) groups [8,15,23,42]. The uniform integral intensity of C–C and C═C bonds proves the coexistence of the crystal and noncrystal properties of HCNTs. The presence of C═C sp2 hybridized bonds related to the graphite hexagonal system is also in accordance with the result of XRD analyses. However, the ionic C–F bonds are not found in the C 1s spectrum because the high fluorine content alters the electron distribution and then hinders the development of ionic type C–F bonds [23]. By fitting the C 1s spectrum, the relative contents of these chemical bonds were obtained. The contents of covalent C–F bond and semi-ionic C–F bond in F-HCNT-300 are 34.45% and 14.28%, respectively, as shown in Table S1. By comparison, the ionic C–F bond is supposed to be found in CF x (x < 0.05) [53], which is almost of no practical value in Li/CF x working batteries by virtue of its extremely low specific capacity and no-plateau characteristic discharging curve. The appearance of the semi-ionic C–F bond is crucial to the performance of lithium primary batteries because of their low binding energy compared with the main C–F species [42]. This enables it to be broken and advances the formation of Li–F bonds. The semi-ionic nature also promotes the transport of electrons so as to enhance the conductivity of CF x materials. In the F 1s spectrum, the binding energies at 688.2, 689, and 689.5 eV are assigned to be semi-ionic C–F bond, covalent C–F bond, and perfluorinated C–F2/C–F3 as labeled inside the plot, respectively [14,16,42]. The results of the F 1s fitting also confirms the semi-ionic C–F bonds in F-HCNT-300. The peak that corresponds to Fe–F, which is supposed to be around 285 eV, however, could barely be observed in the spectrum. A possible explanation for the difference between XPS and XRD in the observation of FeF3 is that the FeF3 is highly crystallized as illustrated in TEM images; thus, a sharp (110) diffraction peak is found in XRD patterns. On the other hand, the catalyst particles are affirmed to be covered by the amorphous F-HCNTs layers shown in TEM images, that is, there are nearly no FeF3 particles located on the surface of F-HCNTs, which leads to the poor detection of Fe–F bonds in the XPS spectrum.

3.2 Electrochemical performance

The electrochemical performance of F-HCNTs cells was measured by the galvanostatic discharge method. The results are shown in Figure 5. All samples were assembled into CR2032 cells and tested under the same circumstance. What is interesting about the data in these curves is that all samples exhibit no clear initial voltage delay despite the destroyed structures caused by the F2. Special structural design and treatment processes for the materials make materials with unique properties [54]. According to previous articles, the initial voltage delay might be reduced or eliminated by adding a small number of second cathode materials, which do not have this delaying effect [55–58]. FeF3 is also applied in lithium batteries as cathode materials [39] and possesses nearly no initial voltage delay. Taking those factors discussed earlier, this result is explained by the fact that the synergistic effect caused by F-HCNTs/FeF3 has diminished the initial voltage delay although this might cause a decrease in the specific capacity.

Figure 5 (a–d) Galvanostatic discharge curves of F-HCNT-250, 300, 350, and 400 at 0.01–1 C discharge rates; (e) relationships between F/C ratio, energy density, and fluorination temperature of F-HCNT-250, 300, 350, and 400; and (f) EIS plots of F-HCNT-250, 300, 350, and 400. The inset is the equivalent circuit.
Figure 5

(a–d) Galvanostatic discharge curves of F-HCNT-250, 300, 350, and 400 at 0.01–1 C discharge rates; (e) relationships between F/C ratio, energy density, and fluorination temperature of F-HCNT-250, 300, 350, and 400; and (f) EIS plots of F-HCNT-250, 300, 350, and 400. The inset is the equivalent circuit.

The galvanostatic discharge curves, including specific capacity–voltage curve and specific capacity-C rate curve, are shown in Figure 5a–d. It is a typical phenomenon that all CF x -specific capacities drop, while the rate increases because of the electrochemical and concentration polarization. Evidently, the specific capacity of each cell is proportional to the F/C ratio of each CF x sample. F-HCNT-250, F-HCNT-300, F-HCNT-350, and F-HCNT-400, whose F/C ratios are 0.64, 1.05, 1.38, and 1.43, respectively, have delivered a specific capacity of 704.2, 794.4, 807.1, and 819.8 mA h/g under 0.01 C, respectively (Table S2). A sloping discharge profile is shown in Figure 5a and b. Because of the low fluorine content in these samples, the discharge characteristic is close to the one in FeF3/C [39], eventually causing the slope–shape curve in F-HCNT-250 and F-HCNT-300. F-HCNT-300, F-HCNT-350, and F-HCNT-400 exhibit a stable plateau in their discharge curves, and F-HCNT-300 possesses the highest discharge plateau (2.9 V@0.01 C). Although the discharge plateau of F-HCNT-300 is about 2.9 V, it holds a high specific capacity of 794.4 mA h/g with a high energy density of 2133.13 W h/kg, which is close to the theoretical value. At a cut-off voltage of 1.0 V, the F-HCNT-300 reaches a discharge-specific capacity of 949.7 mA h/g and a maximum energy density of 2302.8 W h/kg (Table S3). Plentiful available C–F bonds provided by the vast-spread curvature and noncrystalline structure of HCNTs have contributed to the high capacity of F-HCNT-300. Meanwhile, a drop of the discharge voltage plateau can be seen in the discharge curves of F-HCNT-350 and F-HCNT-400 at higher rates, which is due to the insulate groups formed at higher fluorination temperature, bringing about large ohm polarization [8,9]. Notably, there is a slight decrease of specific capacity in F-HCNT-400 as the discharge rate increases, implying that the multichannel effect brought by the defect-rich structure in F-HCNTs has a considerable impact on its electrochemical capability. Compared to F-HCNT-300, a relatively low capacity was found for F-HCNT-250, which might be due to the low F/C ratio. Despite the large polarization, F-HCNT-300 still possesses the highest energy density and high specific capacity. The semi-ionic C–F bonds are found in F-HCNT-300, which are easier to react with Li+ to form lithium fluoride (LiF) and eventually stimulate more abundant use of active C–F bonds. In addition, the intrinsic crystallinity of HCNTs has also made it possible for efficient electron conduction. What is more, the patterns of curves of F-HCNT-350 and F-HCNT-400 are relatively similar, suggesting the commonalities in their structures and fluorine contents, which are confirmed by the TGA, XRD, and Raman spectra.

The particular helical stacking structure, the adequate specific surface area, and the proper amount of semi-ionic C–F bonds are all responsible for the exceptional electrochemical performance of F-HCNT-300. F-HCNT-300 has the largest I D/I G value, indicating a high level of defects inside the materials. These decrease the Li+ diffusion paths and increase the active sites of electrode materials by enhancing the contact surface area between the electrolyte and the electrode materials. Li+ reacts with the C–F compounds during discharge to generate conductive carbon and LiF. LiF forms and attaches to the electrode surface to create a LiF surface layer as the discharge reaction process. As a result of the LiF surface layer, Li2F+ occurs to enhance the electrochemical performance and produce more capacity of F-HCNT-300 materials. Multilevel transportation channels and rich active sites greatly improve the performance of the F-HCNTs. The F/C ratio and the energy density of the as-designed CF x are summarized in the histogram of Figure 5e. Generally, a positive correlation between specific capacity and F/C ratio is confirmed. As raising fluorination temperature from 250 to 400°C, the F/C ratio of the materials gradually increases. The F-HCNT-300 possesses the F/C ratio of 1.05, with a high energy density of 2133.13 W h/kg.

To further investigate the difference among F-HCNTs, the electrochemical performance is measured. The EIS in Figure 5f is formed of a semicircle in the high frequency and a sloped straight line in the low frequency. The semicircle and the sloped straight line are responsible for the charge transfer resistance (Rct) and the Warburg resistance (W), respectively [59]. In accordance with the EIS plots, the value of Rct also increases with the increase of fluorination temperature, which is consistent with the relationship between carbon materials and fluorination temperature. Resistance of F-HCNT-300 is only less than F-HCNT-250, indicating that it has good electrical conductivity. The diffusion of Li+ in the electrode is mainly related to W. The W of F-HCNT-350 and F-HCNT-400 is slightly less than F-HCNT-250 and F-HCNT-300. This is mainly due to the fact that more C5 and C7 rings appear in fluoridation at higher temperatures, forming more reaction sites and facilitating the transport of Li+. But the Rct values of F-HCNT-350 and F-HCNT-400 are much larger than F-HCNT-250 and F-HCNT-300, respectively, resulting in a decrease in energy density.

4 Conclusion

HCNTs with crystal and noncrystal properties were synthesized by the CCVD method and then fluorinated directly at the temperature range of 250–400°C. The morphological features of the as-obtained HCNTs and F-HCNTs were observed via SEM and TEM, and the tube diameters of HCNTs and F-HCNT-300 are 92.5 and 70 nm, respectively. F-HCNTs/FeF3 hybrid is confirmed with a F/C ratio of 1.05 at the fluorination temperature of 300°C, which exceeds the theoretical constrain in typical crystalline carbon owing to its noncrystalline property brought by the insertion of the C5 and C7 rings. Multiple types of C–F bonds are found in F-HCNT-300, including covalent and semi-ionic C–F bonds and per-fluorinated groups like C–F2 and C–F3 by XPS. Furthermore, high-performance lithium primary batteries with zero initial voltage delay are realized by utilizing F-HCNTs as cathode materials among which F-HCNT-300 has delivered specific capacity of 794.4 mA h/g and an energy density of 2133.13 W h/kg due to the stimulation of the defect-rich nature of F-HCNTs and the stimulation of semi-ionic C–F bonds. The capacity loss due to the large polarization triggered by the high fluorine content is also minimized on account of the quasi-crystalline feature of HCNTs. For the first time, F-HCNTs are adopted in the lithium primary battery as the carbon source cathode materials possessing a great potential for their future applications. Also, the attempt to utilizing a carbon source material with crystalline and noncrystalline properties presents a new strategy for the design of Li/CF x cathode materials.

Acknowledgments

The authors would like to appreciate the financial support for the above funding and the contributions of each author. This work was financially supported by National Natural Science Foundation of China (No. 51972045), Fundamental Research Funds for the Chinese Central Universities, China (No. ZYGX2019J025). Besides, the authors would like to thank all the reviewers who participated in the review.

  1. Funding information: The present work was financially supported by National Natural Science Foundation of China (No. 51972045) and the Fundamental Research Funds for the Chinese Central Universities, China (No. ZYGX2019J025).

  2. Authors contribution: Gaobang Chen conceived the concept, designed the experiments, carried out the TEM and SEM observations, and conducted the XRD tests; Feng Cao, Zexiao Li, and Jianan Fu performed the materials preparation, characterization, and electrochemical measurements; Baoshan Wu and Yifan Liu conducted the experimental guidance; and Xian Jian conducted the experimental guidance and revised the article. All authors discussed the results and reviewed the manuscript. All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

  4. Data availability statement: All data generated or analyzed during this study are included in this published article [and its supplementary information files].

References

[1] Huang S, Du XF, Ma MB, Xiong LL. Recent progress in the synthesis and applications of vertically aligned carbon nanotube materials. Nanotechnol Rev. 2021;10(1):1592–623.10.1515/ntrev-2021-0102Search in Google Scholar

[2] Wang CY, Yang CP, Zheng ZJ. Toward practical high-energy and high-power lithium battery anodes: present and future. Adv Sci. 2022;9(9):e2105213.10.1002/advs.202105213Search in Google Scholar PubMed PubMed Central

[3] Dose WM, Donne SW. Optimizing Li/MnO2 batteries: Relating manganese dioxide properties and electrochemical performance. J Power Source. 2013;221:261–5.10.1016/j.jpowsour.2012.08.043Search in Google Scholar

[4] Zabara MA, Ulgut B. Electrochemical impedance spectroscopy based voltage modeling of lithium thionyl chloride (Li∖SOCl2) primary battery at arbitrary discharge. Electrochim Acta. 2020;334:135584.10.1016/j.electacta.2019.135584Search in Google Scholar

[5] Peng SK, Yan SJ, Wang N, Nan WZ, Wang JX, Chen X, et al. Fluorinated graphene/sulfur hybrid cathode for high energy and high power density lithium primary batteries. Rsc Adv. 2018;8(23):12701–7.10.1039/C8RA00226FSearch in Google Scholar PubMed PubMed Central

[6] Peng C, Li Y, Yao FN, Fu HY, Zhou RX, Feng YY, et al. Ultrahigh-energy-density fluorinated calcinated macadamia nut shell cathodes for lithium/fluorinated carbon batteries. Carbon. 2019;153:783–91.10.1016/j.carbon.2019.07.065Search in Google Scholar

[7] Groult H, Tressaud A. Use of inorganic fluorinated materials in lithium batteries and in energy conversion systems. Chem Commun (Camb). 2018;54(81):11375–82.10.1039/C8CC05549ASearch in Google Scholar

[8] Li YY, Wu XZ, Liu C, Wang S, Zhou PF, Zhou T, et al. Fluorinated multi-walled carbon nanotubes as cathode materials of lithium and sodium primary batteries: effect of graphitization of carbon nanotubes. J Mater Chem A. 2019;7(12):7128–37.10.1039/C8TA12074ASearch in Google Scholar

[9] Zhong GM, Chen HX, Huang XK, Yue HJ, Lu CZ. High-power-density, High-energy-density fluorinated graphene for primary lithium batteries. Front Chem. 2018;6:50.10.3389/fchem.2018.00050Search in Google Scholar PubMed PubMed Central

[10] Ahmad Y, Dubois M, Guerin K, Hamwi A, Zhang W. Pushing the theoretical limit of Li-CFx batteries using fluorinated nanostructured carbon nanodiscs. Carbon. 2015;94:1061–70.10.1016/j.carbon.2015.07.073Search in Google Scholar

[11] Liu YF, Jiang LY, Wang HN, Wang H, Jiao W, Chen GZ, et al. A brief review for fluorinated carbon: synthesis, properties and applications. Nanotechnol Rev. 2019;8(1):573–86.10.1515/ntrev-2019-0051Search in Google Scholar

[12] Chung DDL. Review graphite. J Mater Sci. 2002;37(8):1475–89.10.1023/A:1014915307738Search in Google Scholar

[13] Li R, Sun XG, Zou JY, He Q. Improvement of electrochemical performance by fluorinated multiwall carbon nanotubes interlayer in lithium-sulfur battery. J Mater Sci Mater Electron. 2021;32(7):8265–74.10.1007/s10854-020-05233-2Search in Google Scholar

[14] Li Y, Feng YY, Feng W. Deeply fluorinated multi-wall carbon nanotubes for high energy and power densities lithium/carbon fluorides battery. Electrochim Acta. 2013;107:343–9.10.1016/j.electacta.2013.06.086Search in Google Scholar

[15] Yang XX, Zhang GJ, Bai BS, Li Y, Li YX, Yang Y, et al. Fluorinated graphite nanosheets for ultrahigh-capacity lithium primary batteries. Rare Met. 2021;40(7):1708–18.10.1007/s12598-020-01692-ySearch in Google Scholar

[16] Zhou RX, Li Y, Feng YY, Peng C, Feng W. The electrochemical performances of fluorinated hard carbon as the cathode of lithium primary batteries. Compos Commun. 2020;21:100396.10.1016/j.coco.2020.100396Search in Google Scholar

[17] Yang SW, Yang YC, He P, Wang G, Ding GQ, Xie XM. Insights into the Oxidation Mechanism of sp2-sp3 Hybrid Carbon Materials: Preparation of a Water-Soluble 2D Porous Conductive Network and Detectable Molecule Separation. Langmuir. 2017;33(4):913–9.10.1021/acs.langmuir.6b03937Search in Google Scholar PubMed

[18] Yoshida K, Sugawara Y, Saitoh M, Matsumoto K, Hagiwara R, Matsuo Y, et al. Microscopic characterization of the C-F bonds in fluorine-graphite intercalation compounds. J Power Source. 2020;445:227320.10.1016/j.jpowsour.2019.227320Search in Google Scholar

[19] Murakami M, Matsumoto K, Hagiwara R, Matsuo Y. 13C/19F high-resolution solid-state NMR studies on layered carbon-fluorine compounds. Carbon. 2018;138:179–87.10.1016/j.carbon.2018.06.004Search in Google Scholar

[20] Fulvio PF, Veith GM, Adcock JL, Brown SS, Mayes RT, Wang XQ, et al. Fluorination of “brick and mortar” soft-templated graphitic ordered mesoporous carbons for high power lithium-ion battery. J Mater Chem A. 2013;1(33):9414–7.10.1039/c3ta10710hSearch in Google Scholar

[21] Fulvio PF, Brown SS, Adcock J, Mayes RT, Guo BK, Sun XG, et al. Low-temperature fluorination of soft-templated mesoporous carbons for a high-power lithium/carbon fluoride battery. Chem Mater. 2011;23(20):4420–7.10.1021/cm2012395Search in Google Scholar

[22] Sato Y, Itoh K, Hagiwara R, Fukunaga T, Ito Y. On the so-called “semi-ionic” C-F bond character in fluorine-GIC. Carbon. 2004;42(15):3243–9.10.1016/j.carbon.2004.08.012Search in Google Scholar

[23] Kim J, Zhou R, Murakoshi K, Yasuda S. Advantage of semi-ionic bonding in fluorine-doped carbon materials for the oxygen evolution reaction in alkaline media. Rsc Adv. 2018;8(26):14152–6.10.1039/C8RA01636DSearch in Google Scholar

[24] Yang ZB, Ren J, Zhang ZT, Chen XL, Guan GZ, Qiu LB, et al. Recent advancement of nanostructured carbon for energy applications. Chem Rev. 2015;115(11):5159–223.10.1021/cr5006217Search in Google Scholar PubMed

[25] Wang DC, Lei Y, Jiao W, Liu YF, Mu CH, Jian X. A review of helical carbon materials structure, synthesis and applications. Rare Met. 2021;40(1):3–19.10.1007/s12598-020-01622-ySearch in Google Scholar

[26] Zeng Q, Tian HQ, Jiang J, Ji XB, Gao DJ, Wang C. High-purity helical carbon nanotubes with enhanced electrochemical properties for supercapacitors. Rsc Adv. 2017;7(12):7375–81.10.1039/C6RA27459ESearch in Google Scholar

[27] Tang H, Jian X, Wu B, Liu SY, Jiang ZC, Chen XN, et al. Fe3C/helical carbon nanotube hybrid: Facile synthesis and spin-induced enhancement in microwave-absorbing properties. Compos Part B-Eng. 2016;107:51–8.10.1016/j.compositesb.2016.09.003Search in Google Scholar

[28] Amelinckx S, Zhang XB, Bernaerts D, Zhang XF, Ivanov V, Nagy JB. A formation mechanism for catalytically grown helix-shaped graphite nanotubes. Science. 1994;265(5172):635–9.10.1126/science.265.5172.635Search in Google Scholar PubMed

[29] Hou HQ, Jun Z, Weller F, Greiner A. Large-scale synthesis and characterization of helically coiled carbon nanotubes by use of Fe(CO)5 as floating catalyst precursor. Chem Mater. 2003;15(16):3170–5.10.1021/cm021290gSearch in Google Scholar

[30] Jian X, Jiang M, Zhou ZW, Zeng Q, Lu J, Wang DC, et al. Gas-induced formation of cu nanoparticle as catalyst for high-purity straight and helical carbon nanofibers. ACS Nano. 2012;6(10):8611–9.10.1021/nn301880wSearch in Google Scholar PubMed

[31] Meng FB, Wang Y, Wang Q, Xu XL, Jiang M, Zhou XS, et al. High-purity helical carbon nanotubes by trace-water-assisted chemical vapor deposition: Large-scale synthesis and growth mechanism. Nano Res. 2018;11(6):3327–39.10.1007/s12274-017-1897-4Search in Google Scholar

[32] Zhang W, Guerin K, Dubois M, El Fawal Z, Ivanov DA, Vidal L, et al. Carbon nanofibres fluorinated using TbF4 as fluorinating agent. Part I: Structural properties. Carbon. 2008;46(7):1010–6.10.1016/j.carbon.2008.02.029Search in Google Scholar

[33] Ahmad Y, Guerin K, Dubois M, Zhang W, Hamwi A. Enhanced performances in primary lithium batteries of fluorinated carbon nanofibers through static fluorination. Electrochim Acta. 2013;114:142–51.10.1016/j.electacta.2013.09.140Search in Google Scholar

[34] Jiang QT, Li XF, Li J, Wang JJ, Cao GQ, Duan RX, et al. 3D conductive iron fluoride (III) cathode with high loading for lithium-ion batteries. J Phys D-Appl Phys. 2023;56(5):055501.10.1088/1361-6463/acab0fSearch in Google Scholar

[35] Zhou Y, Zheng HY, Kravchenko II, Valentine J. Flat optics for image differentiation. Nat Photonics. 2020;14(5):316.10.1038/s41566-020-0591-3Search in Google Scholar

[36] Cui LF, Qi HY, Wang NN, Gao X, Song CY, Yang JH, et al. N/S co-doped CoSe/C nanocubes as anode materials for Li-ion batteries. Nanotechnol Rev. 2021;11(1):244–51.10.1515/ntrev-2022-0018Search in Google Scholar

[37] Jiang C, Wang BJ, Wu ZR, Qiu JL, Ding ZP, Zou J, et al. Electrolyte-assisted dissolution-recrystallization mechanism towards high energy density and power density CF cathodes in potassium cell. Nano Energy. 2020;70:104552.10.1016/j.nanoen.2020.104552Search in Google Scholar

[38] Bi X, Li YY, Qiu ZP, Liu C, Zhou T, Zhuo SP, et al. Fluorinated graphene prepared by direct fluorination of N, O-doped graphene aerogel at different temperatures for lithium primary batteries. Materials. 2018;11(7):1072.10.3390/ma11071072Search in Google Scholar PubMed PubMed Central

[39] Ma RG, Wang M, Tao PP, Wang Y, Cao CW, Shan GC, et al. Fabrication of FeF3 nanocrystals dispersed into a porous carbon matrix as a high performance cathode material for lithium ion batteries. J Mater Chem A. 2013;1(47):15060–7.10.1039/c3ta13086jSearch in Google Scholar

[40] Gong PW, Wang ZF, Wang JQ, Wang HG, Li ZP, Fan ZJ, et al. One-pot sonochemical preparation of fluorographene and selective tuning of its fluorine coverage. J Mater Chem. 2012;22(33):16950–6.10.1039/c2jm32294cSearch in Google Scholar

[41] Whitacre J, Yazami R, Hamwi A, Smart MC, Bennett W, Prakash GKS, et al. Low operational temperature Li-CFx batteries using cathodes containing sub-fluorinated graphitic materials. J Power Source. 2006;160(1):577–84.10.1016/j.jpowsour.2006.01.045Search in Google Scholar

[42] Sun C, Feng Y, Li Y, Qin C, Zhang Q, Feng W. Solvothermally exfoliated fluorographene for high-performance lithium primary batteries. Nanoscale. 2014;6(5):2634–41.10.1039/C3NR04609ESearch in Google Scholar

[43] Wu XF, Li ZJ, Liu JX, Luo W, Gaumet JJ, Mai LQ. Defect engineering of hierarchical porous carbon microspheres for potassium-ion storage. Rare Met. 2022;41(10):3446–55.10.1007/s12598-022-02100-3Search in Google Scholar

[44] Huang SZ, Li Y, Feng YY, An HR, Long P, Qin CQ, et al. Nitrogen and fluorine co-doped graphene as a high-performance anode material for lithium-ion batteries. J Mater Chem A. 2015;3(46):23095–105.10.1039/C5TA06012ESearch in Google Scholar

[45] Li XT, Zhang HC, Liu C, Qiao JY, Zhou XM. A MOF-derived multifunctional nano-porous fluorinated carbon for high performance lithium/fluorinated carbon primary batteries. Micropor Mesopor Mater. 2021;310:110650.10.1016/j.micromeso.2020.110650Search in Google Scholar

[46] Zhang S, Zeng XT, Xie H, Hing P. A phenomenological approach for the Id/Ig ratio and sp3 fraction of magnetron sputtered a-C films. Surf Coat Technol. 2000;123(2–3):256–60.10.1016/S0257-8972(99)00523-XSearch in Google Scholar

[47] Tai FC, Lee SC, Wei CH, Tyan SL. Correlation between ID/IG ratio from visible raman spectra and sp2/sp3 Ratio from XPS spectra of annealed hydrogenated DLC film. Mater Trans. 2006;47(7):1847–52.10.2320/matertrans.47.1847Search in Google Scholar

[48] Lin YM, Huang JT, Shi LD, Cong GT, Zhu CZ, Xu J. Combining Zn0.76Co0.24S with S-doped graphene as high-performance anode materials for lithium-and sodium-ion batteries. Nanotechnol Rev. 2020;9(1):1227–36.10.1515/ntrev-2020-0091Search in Google Scholar

[49] Dresselhaus MS, Dresselhaus G, Saito R, Jorio A. Raman spectroscopy of carbon nanotubes. Phys Rep. 2005;409(2):47–99.10.1016/j.physrep.2004.10.006Search in Google Scholar

[50] Li YY, Liu C, Chen L, Wu XZ, Zhou PF, Shen XY, et al. Multi-layered fluorinated graphene cathode materials for lithium and sodium primary batteries. Rare Met. 2022;42(3):940–53.10.1007/s12598-022-02155-2Search in Google Scholar

[51] Lam P, Yazami R. Physical characteristics and rate performance of (CFx)n (0.33<x<0.66) in lithium batteries. J Power Sources. 2006;153(2):354–9.10.1016/j.jpowsour.2005.05.022Search in Google Scholar

[52] Qin AM, Ji JY, Du R, Tian N, Liao L, Zhang KY, et al. Hydrothermal synthesis and electrochemical performance of CuS@Sisal fiber carbon composite Lithium- ion battery anodes. Compos Commun. 2018;7:47–50.10.1016/j.coco.2017.12.008Search in Google Scholar

[53] Amine K, Nakajima T. A new stage-2 graphite-intercalation compound - C2F with nestled fluorine-atoms. Carbon. 1993;31(4):553–6.10.1016/0008-6223(93)90108-MSearch in Google Scholar

[54] Zhou Y, Kravchenko II, Wang H, Nolen JR, Gu G, Valentine J. Multilayer noninteracting dielectric metasurfaces for multiwavelength metaoptics. Nano Lett. 2018;18(12):7529–37.10.1021/acs.nanolett.8b03017Search in Google Scholar PubMed

[55] Kozawa A. Lithium ‐ MnO2 Cells Containing  CFx or  C2F  in the Cathode. J Electrochem Soc. 2019;134(4):780–2.10.1149/1.2100572Search in Google Scholar

[56] Gan H, Rubino RS, Takeuchi ES. Dual-chemistry cathode system for high-rate pulse applications. J Power Sources. 2005;146(1–2):101–6.10.1016/j.jpowsour.2005.03.203Search in Google Scholar

[57] Zhang SS, Foster D, Read J. Carbothermal treatment for the improved discharge performance of primary Li/CFx battery. J Power Sources. 2009;191(2):648–52.10.1016/j.jpowsour.2009.02.007Search in Google Scholar

[58] Li Y, Feng W. The tunable electrochemical performances of carbon fluorides/manganese dioxide hybrid cathodes by their arrangements. J Power Sources. 2015;274:1292–9.10.1016/j.jpowsour.2014.10.150Search in Google Scholar

[59] Wang FF, Hong RY, Lu XS, Liu HY, Zhu Y, Zheng Y, et al. Improvement of long-term cycling performance of high-nickel cathode materials by ZnO coating. Nanotechnol Rev. 2021;10(1):210–20.10.1515/ntrev-2021-0020Search in Google Scholar
Received: 2023-05-11
Revised: 2023-06-28
Accepted: 2023-07-26
Published Online: 2023-08-21

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  53. Mechanical properties and frost resistance of recycled brick aggregate concrete modified by nano-SiO2
  54. Self-template synthesis of hollow flower-like NiCo2O4 nanoparticles as an efficient bifunctional catalyst for oxygen reduction and oxygen evolution in alkaline media
  55. High-performance wearable flexible strain sensors based on an AgNWs/rGO/TPU electrospun nanofiber film for monitoring human activities
  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
https://doi.org/10.1515/ntrev-2023-0108
Keywords for this article
lithium primary battery; fluorinated carbon materials; helical carbon nanotube; multichannel effect
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Preparation of CdS–Ag2S nanocomposites by ultrasound-assisted UV photolysis treatment and its visible light photocatalysis activity
  3. Significance of nanoparticle radius and inter-particle spacing toward the radiative water-based alumina nanofluid flow over a rotating disk
  4. Aptamer-based detection of serotonin based on the rapid in situ synthesis of colorimetric gold nanoparticles
  5. Investigation of the nucleation and growth behavior of Ti2AlC and Ti3AlC nano-precipitates in TiAl alloys
  6. Dynamic recrystallization behavior and nucleation mechanism of dual-scale SiCp/A356 composites processed by P/M method
  7. High mechanical performance of 3-aminopropyl triethoxy silane/epoxy cured in a sandwich construction of 3D carbon felts foam and woven basalt fibers
  8. Applying solution of spray polyurea elastomer in asphalt binder: Feasibility analysis and DSR study based on the MSCR and LAS tests
  9. Study on the chronic toxicity and carcinogenicity of iron-based bioabsorbable stents
  10. Influence of microalloying with B on the microstructure and properties of brazed joints with Ag–Cu–Zn–Sn filler metal
  11. Thermohydraulic performance of thermal system integrated with twisted turbulator inserts using ternary hybrid nanofluids
  12. Study of mechanical properties of epoxy/graphene and epoxy/halloysite nanocomposites
  13. Effects of CaO addition on the CuW composite containing micro- and nano-sized tungsten particles synthesized via aluminothermic coupling with silicothermic reduction
  14. Cu and Al2O3-based hybrid nanofluid flow through a porous cavity
  15. Design of functional vancomycin-embedded bio-derived extracellular matrix hydrogels for repairing infectious bone defects
  16. Study on nanocrystalline coating prepared by electro-spraying 316L metal wire and its corrosion performance
  17. Axial compression performance of CFST columns reinforced by ultra-high-performance nano-concrete under long-term loading
  18. Tungsten trioxide nanocomposite for conventional soliton and noise-like pulse generation in anomalous dispersion laser cavity
  19. Microstructure and electrical contact behavior of the nano-yttria-modified Cu-Al2O3/30Mo/3SiC composite
  20. Melting rheology in thermally stratified graphene-mineral oil reservoir (third-grade nanofluid) with slip condition
  21. Re-examination of nonlinear vibration and nonlinear bending of porous sandwich cylindrical panels reinforced by graphene platelets
  22. Parametric simulation of hybrid nanofluid flow consisting of cobalt ferrite nanoparticles with second-order slip and variable viscosity over an extending surface
  23. Chitosan-capped silver nanoparticles with potent and selective intrinsic activity against the breast cancer cells
  24. Multi-core/shell SiO2@Al2O3 nanostructures deposited on Ti3AlC2 to enhance high-temperature stability and microwave absorption properties
  25. Solution-processed Bi2S3/BiVO4/TiO2 ternary heterojunction photoanode with enhanced photoelectrochemical performance
  26. Electroporation effect of ZnO nanoarrays under low voltage for water disinfection
  27. NIR-II window absorbing graphene oxide-coated gold nanorods and graphene quantum dot-coupled gold nanorods for photothermal cancer therapy
  28. Nonlinear three-dimensional stability characteristics of geometrically imperfect nanoshells under axial compression and surface residual stress
  29. Investigation of different nanoparticles properties on the thermal conductivity and viscosity of nanofluids by molecular dynamics simulation
  30. Optimized Cu2O-{100} facet for generation of different reactive oxidative species via peroxymonosulfate activation at specific pH values to efficient acetaminophen removal
  31. Brownian and thermal diffusivity impact due to the Maxwell nanofluid (graphene/engine oil) flow with motile microorganisms and Joule heating
  32. Appraising the dielectric properties and the effectiveness of electromagnetic shielding of graphene reinforced silicone rubber nanocomposite
  33. Synthesis of Ag and Cu nanoparticles by plasma discharge in inorganic salt solutions
  34. Low-cost and large-scale preparation of ultrafine TiO2@C hybrids for high-performance degradation of methyl orange and formaldehyde under visible light
  35. Utilization of waste glass with natural pozzolan in the production of self-glazed glass-ceramic materials
  36. Mechanical performance of date palm fiber-reinforced concrete modified with nano-activated carbon
  37. Melting point of dried gold nanoparticles prepared with ultrasonic spray pyrolysis and lyophilisation
  38. Graphene nanofibers: A modern approach towards tailored gypsum composites
  39. Role of localized magnetic field in vortex generation in tri-hybrid nanofluid flow: A numerical approach
  40. Intelligent computing for the double-diffusive peristaltic rheology of magneto couple stress nanomaterials
  41. Bioconvection transport of upper convected Maxwell nanoliquid with gyrotactic microorganism, nonlinear thermal radiation, and chemical reaction
  42. 3D printing of porous Ti6Al4V bone tissue engineering scaffold and surface anodization preparation of nanotubes to enhance its biological property
  43. Bioinspired ferromagnetic CoFe2O4 nanoparticles: Potential pharmaceutical and medical applications
  44. Significance of gyrotactic microorganisms on the MHD tangent hyperbolic nanofluid flow across an elastic slender surface: Numerical analysis
  45. Performance of polycarboxylate superplasticisers in seawater-blended cement: Effect from chemical structure and nano modification
  46. Entropy minimization of GO–Ag/KO cross-hybrid nanofluid over a convectively heated surface
  47. Oxygen plasma assisted room temperature bonding for manufacturing SU-8 polymer micro/nanoscale nozzle
  48. Performance and mechanism of CO2 reduction by DBD-coupled mesoporous SiO2
  49. Polyarylene ether nitrile dielectric films modified by HNTs@PDA hybrids for high-temperature resistant organic electronics field
  50. Exploration of generalized two-phase free convection magnetohydrodynamic flow of dusty tetra-hybrid Casson nanofluid between parallel microplates
  51. Hygrothermal bending analysis of sandwich nanoplates with FG porous core and piezomagnetic faces via nonlocal strain gradient theory
  52. Design and optimization of a TiO2/RGO-supported epoxy multilayer microwave absorber by the modified local best particle swarm optimization algorithm
  53. Mechanical properties and frost resistance of recycled brick aggregate concrete modified by nano-SiO2
  54. Self-template synthesis of hollow flower-like NiCo2O4 nanoparticles as an efficient bifunctional catalyst for oxygen reduction and oxygen evolution in alkaline media
  55. High-performance wearable flexible strain sensors based on an AgNWs/rGO/TPU electrospun nanofiber film for monitoring human activities
  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
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