Journal of Electroanalytical Chemistry 957 (2024) 118122

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Red phosphorus confined in porous structures formed by PVDF-Derived

carbon as superior anode material for sodium-ion batteries
Yu’an Lin a, Dongping Yang a, Deping Xiong a, Li Chen a, Zuyong Feng a, Kunhua Wen a,
Miao He a, b, *
a
School of Physics and Optoelectronic Engineering, Guangdong University of Technology, Guangzhou Guangdong 510006, China
b
The State Key Laboratory of Precision Electronic Manufacturing Technology and Equipment, School of Electromechanical Engineering, Guangdong University of
Technology, Guangzhou 510006, China

A R T I C L E I N F O A B S T R A C T

Keywords: Given the widespread availability of sodium on our planet, sodium-ion batteries (SIBs) hold substantial promise
Polyvinylidene fluoride (PVDF) as cost-effective energy storage solutions. Red Phosphorus (red P) has emerged as a promising candidate for SIBs
Ultrasonic dispersion anodes due to its impressive theoretical capacity of 2596mAh g− 1. However, red P faces inherent challenges,
Porous structure
mainly due to its insulating nature and significant volume changes during cycling, which adversely affect its
Anode materials
cycling and rate performance. To overcome these challenges, we have developed a novel material called P@C,
Sodium-ion batteries
composed of carbon-coated and porous carbon structures. The synthesis of P@C involves integrating red P with
PVDF and a series of carefully controlled steps, including ultrasonic dispersion, magnetic stirring, centrifugation,
and high-temperature calcination. This well-designed composite material facilitates electron transfer and pro­
vides ample space within its porous carbon structure to accommodate the substantial volume changes associated
with phosphorus during sodium insertion/extraction. The use of PVDF as a carbon source contributes to the
creation of a defined porous carbon framework, enhancing the material’s flexibility, mechanical strength, and
ease of processing. As a result, when employed as an anode material for SIBs, the P@C composite material ex­
hibits exceptional cycling stability and remarkable rate performance. Notably, it demonstrates superior capacity
retention, maintaining 336.7mAh g− 1 after 200 cycles at 0.2 A/g, and excellent cycling durability, with minimal
capacity degradation even after 500 cycles at 1 A/g.This innovative work, characterized by its strategic carbon-
coating approach that effectively encapsulates the active material within porous structures, provides valuable
insights into the development of high-performance electrode materials for metal-ion batteries and other energy
storage applications.

1. Introduction rising costs in the near future [11–15]. This scenario has instigated the
quest for alternatives to LIBs, ones that offer both resource abundance
In today’s dynamic energy landscape, battery technology plays a and cost-effectiveness.
vital role in meeting the ever-increasing demand for efficient and sus­ In light of this context, sodium-ion batteries (SIBs) have emerged as
tainable energy storage solutions. As the use of portable electronic de­ prospective candidates to supplant LIBs. This shift is attributed to the
vices, electric vehicles, and grid-scale energy storage systems continues abundant availability of sodium resources and the electrochemical
to expand, the demand for reliable and cost-effective battery solutions parallels shared with conventional LIBs [16–18]. SIBs provide a poten­
has become increasingly critical [1–5]. tial solution to the issues of lithium scarcity and cost, rendering them
For a substantial duration, lithium-ion batteries (LIBs) have held a attractive for large-scale energy storage systems [19–22]. The critical
prominent position in energy storage technology, primarily due to their advantage of SIBs lies in their ability to tap into the ample reservoirs of
exceptional energy density and robust rechargeability [6–10]. However, sodium resources, enabling the development of cost-efficient battery
the sustainability of LIBs is currently challenged by global lithium sup­ technology that can be readily scaled for widespread deployment.
ply constraints and uneven distribution, factors expected to result in While investigating diverse anode materials suitable for Sodium-ion

* Corresponding author.
E-mail address: herofate666@126.com (M. He).

https://doi.org/10.1016/j.jelechem.2024.118122
Received 4 December 2023; Received in revised form 25 January 2024; Accepted 12 February 2024
Available online 15 February 2024
1572-6657/© 2024 Elsevier B.V. All rights reserved.
Y. Lin et al. Journal of Electroanalytical Chemistry 957 (2024) 118122

batteries (SIBs), phosphorus-based compounds have surfaced as excep­ layer enhances electrical conductivity and ensures intimate contact be­
tionally promising options. Their appeal stems from their impressive tween red P and the conductive substrate. Reducing particle size
theoretical capacity and cost-efficiency [23–25]. Three primary phos­ through grinding and ultrasonic dispersion while achieving a more
phorus allotropes are notable: white phosphorus, black phosphorus, and uniform distribution of red P effectively governs its volume fluctuations
red P. White phosphorus, due to its extreme instability, is unsuitable for and shortens ion diffusion pathways. Ultimately, this confines red P
electrochemical energy storage. In contrast, black phosphorus, charac­ primarily within the carbon coating, curtailing its volume variations
terized by its high electrical conductivity (102 S/m) and stable ther­ within the carbon pores.
modynamic properties stemming from its layered structure, has found
utility in sodium-ion batteries. For instance, Xu and colleagues utilized 2. Experimental section
nanostructured composites combining black phosphorus with multi-
walled carbon nanotubes, demonstrating their efficacy as high- 2.1. Preparation of P@C
performance anode materials for sodium-ion batteries [26]. However,
synthesizing black phosphorus poses exceptional challenges, requiring For the synthesis of P@C, 1 g of red P (P) particles underwent manual
high-temperature and high-pressure conditions. Considering overall grinding to form a powder. This powder was then introduced into 100
performance and production costs, red P, distinguished by its non- mL of deionized water and subjected to one hour of ultrasonic dispersion
toxicity, chemical stability, low-cost synthesis potential, high theoret­ within an ultrasonic cleaner, maintaining a temperature below 50 ◦ C.
ical capacity, and substantial theoretical specific capacity (2596mAh Subsequently, 1.75 g of polyvinylidene fluoride (PVDF) were added, and
g− 1), has gained prominence in the realm of new energy batteries. magnetic stirring was applied for one hour. The resulting mixture un­
Nevertheless, red P encounters intrinsic challenges tied to its low derwent three rounds of centrifugation, accompanied by deionized
electrical conductivity and considerable volume fluctuations during water rinsing. The resulting suspension was then transferred to a drying
cycling, compromising its electrochemical performance. Thus, to fully oven and subjected to a 24-hour drying period at 80 ◦ C, yielding a
exploit the potential of red P materials in SIBs, innovative strategies are powdered substance. This dried powder was then placed onto a ceramic
being pursued to enhance their electrochemical performance and facil­ vessel and calcined in a nitrogen atmosphere: 500 ◦ C for 3 h followed by
itate practical implementation in energy storage applications. For 300 ◦ C for 1 h, resulting in the P@C sample.
instance, doping with various atoms such as B, N, S, P, etc., can generate
abundant active sites and enhance conductivity [27]. Furthermore, 2.2. Preparation of P@Graphite
straightforward methods such as ball-milling and vaporization-
condensation have been employed. For instance, one study utilized The synthesis process for P@Graphite closely mirrored that of P@C,
ball-milling to make a conductive P/graphene composite anode material differing only in the substitution of PVDF with graphite.
for SIBs [28]. Another investigation described the incorporation of red
phosphorus into a single-walled carbon nanotube network using an 2.3. Preparation of red P
improved vaporization-condensation technique, thus extending the
cycling life of the phosphorus anode [29]. Yu et al. observed that during The treatment procedure for Red P matched that of P@C, except that
sodium insertion/extraction, surface red P particles experienced sub­ PVDF is not added.
stantial volume fluctuations (>300 %), whereas carbon particles loaded
with red P exhibited minimal overall volume alterations (10 %) [30]. 2.4. Preparation of the pristine carbon
This observation strongly emphasizes the significant role of surface red
phosphorus in influencing the volume dynamics of the P/C anode. This The treatment procedure for the pristine carbon matched that of
influence leads to the instability of the solid electrolyte interface (SEI) P@C, except that the material is only the pristine carbon.
film, subsequent electrode pulverization or layering, and, ultimately,
rapid battery degradation. Therefore, the use of carbon’s porous struc­ 2.5. Material characterization
tures to confine the volume fluctuations of red P appears to be a practical
approach to improve its cycling performance. For instance, the Please refer to the appendix for details.
vaporization-condensation transformation method primarily confines
red P within nanoscale particles or clusters, constraining its volume 2.6. Electrochemical evaluation
fluctuations within carbon nanocavities [31]. Despite these promising
strides, considerable challenges persist in optimizing the electro­ Please refer to the appendix for details.
chemical performance of phosphorus-based materials.
Simply mixing phosphorus with carbon substrates often leads to 3. Results and discussion
uneven particle sizes, incomplete coverage, and inadequate electrical
contact, which can be suboptimal for the desired performance. These 3.1. Physical characterizations
issues lead to rapid capacity degradation and, in severe cases, electrode
damage. Additionally, conventional vaporization-condensation tech­ Fig. 1 outlines the schematic representation of the P@C composite
niques face challenges in precisely controlling the distribution of red P material synthesis process. Initially, manual grinding was employed to.
within the carbon framework, thus constraining the overall electro­ reduce red P particles to a powdered form. This powder was subse­
chemical performance of the electrode. To tackle these challenges, we quently introduced into deionized water and subjected to one hour of
propose an innovative porous carbon structure incorporating phos­ ultrasonic dispersion within an ultrasonic cleaner. This step reduced
phorus. Given the underwhelming electrochemical performance of prior particle size and ensured a more even distribution of red P. Following
phosphorus-based materials, we have adopted polyvinylidene fluoride this, PVDF was added, and magnetic stirring was applied for one hour to
(PVDF) as a carbon source to address this limitation. Notably, PVDF not ensure thorough mixing of red P and PVDF. Subsequently, centrifuga­
only generates a porous architecture but also enhances material flexi­ tion was performed, followed by rinsing with deionized water and
bility, bending strength, and processability, all of which are advanta­ subsequent drying. The resulting dry powder was transferred onto a
geous for practical applications [32,33]. Furthermore, this approach ceramic vessel and calcined under a nitrogen atmosphere at 500 ◦ C for 3
lends itself well to scalable production on manufacturing lines, elimi­ h and then at 300 ◦ C for 1 h. The 500 ◦ C calcining process removed
nating the previous constraints associated with shaping processes. This impurities such as fluorine through the thermal decomposition of PVDF,
scalability significantly reduces processing costs. The resultant carbon generating HF gas in the process. In conjunction with the 300 ◦ C

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Y. Lin et al. Journal of Electroanalytical Chemistry 957 (2024) 118122

Fig. 1. Schematic preparation of the synthesis of P@C.

calcining process, it facilitated the carbon coating of red P within PVDF, 1576 cm− 1, corresponding to characteristic carbon features, specifically
resulting in the formation of a porous structure. This effectively miti­ sp3-type disordered carbon and sp2-type graphitic carbon, often
gated the volume deformation of red P during cycling, significantly referred to as the D-band and G-band. The lower ID/IG ratio in P@C
enhancing the material’s overall stability and conductivity. indicated a higher degree of graphitization, which subsequently
Fig. 2a illustrates the X-ray diffraction (XRD) patterns of red P and improved the conductivity of the P-based material [35].
the P@C composite materials. Characteristic peaks for red P were X-ray photoelectron spectroscopy (XPS) was utilized to delve deeper
observed at approximately 15.4◦ and 21◦ , and corresponding features into the analysis of P@C composite material. Fig. 2c presents the XPS
were also evident in the XRD pattern of P@C. An additional peak spectra for the C and P elements in P@C. The XPS spectrum of P2p in
appeared in the XRD pattern of P@C at ~ 26◦ , corresponding to the P@C is depicted in Fig. 2d, revealing two peaks at 130 and 131 eV,
carbon standard card. This indicates the successful synthesis of the red P corresponding to the splitting of the 2p3/2 and 2p1/2 spin–orbit orbitals
and carbon composite. of the P–P bond [36]. Additionally, a characteristic peak of red phos­
material. The slightly reduced intensity of this peak in P@C can be phorus at 133.7 eV, attributed to the P–O bond, indicated a slight
attributed to the uniform mixing of red P and carbon, resulting in a oxidation due to exposure to air [37]. As illustrated in Fig. 2e, the
decrease in the carbon peak’s intensity [34]. dominant sp2-C peak appeared at 284.8 eV, accompanied by other
Raman spectrum was employed to analyze the chemical composition weaker bands, including sp3-C at 285.5 eV. Additionally, a C– –O peak
of red phosphorus and carbon. Distinctive Raman peaks attributed to red emerged at 287.1 eV, analogous to the presence of P–O bonds.
phosphorus were readily detected within the 300–500 cm− 1 range The red P content in the P@C composite material was quantified
(Fig. 2b), indicating a relatively weak interaction between red phos­ using thermal gravimetric analysis (TGA) under an argon atmosphere, as
phorus and carbon. In contrast to the red phosphorus Raman spectrum, depicted in Fig. 2f. Within the temperature range of 400 ◦ C to 500 ◦ C, a
the P@C composite material exhibited two distinctive peaks at 1332 and significant mass loss of 53.3 % was recorded, primarily attributed to the

Fig. 2. (a) XRD patterns; (b) Raman spectra of P@C, C, and Red P; (c) X-ray photoelectron spectroscopy (XPS) full-scan spectrum; (d-e) High-resolution XPS spectra
of P2p,C1s of P@C, respectively;(f) TGA curves of P@C composites in Ar atmosphere. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

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Y. Lin et al. Journal of Electroanalytical Chemistry 957 (2024) 118122

sublimation of red P [38]. These findings point to a notably high con­ representing the stepwise de-sodiation reaction. Notably, the redox
centration of red P, surpassing that which has been previously reported peaks appeared relatively weak, possibly due to irreversible electrolyte
for the majority of P@C composite materials [26,39–41]. This elevated decomposition and SEI formation [42]. Furthermore, the anodic peak at
content positions the material advantageously for capitalizing on the 0.09 V corresponds to the N+ insertion and extraction within the carbon
impressive high-capacity performance inherent to red P. layers. [43].In the second and third cycles, the reduction broad peak
The morphology and microstructure of the prepared P@C composite remained stable at 0.6 V, and the oxidation broad peak persisted be­
material were scrutinized using scanning electron microscopy (SEM). As tween 0.3 and 0.7 V. The conspicuous overlap between these two cyclic
portrayed in Fig. 3a, the P@C composite material exhibited a distinct curves indicates a reversible electrochemical reaction between P and
porous structure, characterized by a significantly enlarged surface area. Na3P, underscoring the excellent cycling stability of the P@C composite
This architectural attribute not only accommodates the volumetric material electrode [39–41,44–47]. As a contrast, the CV curves of the
fluctuations experienced by red P during charge and discharge cycles first three circles of the Red P electrode material are shown in Figure S1.
but also effectively constrains these fluctuations within the carbona­ Fig. 4c depicts the capacity and efficiency evolution of the P@C
ceous pores. Consequently, it facilitates the facile insertion and extrac­ electrode at a current density of 0.2 A g− 1, while the capacity of
tion of sodium ions during the cycling process. To gain further insights, P@Graphite and Red P electrodes at the same current density is included
transmission electron microscopy (TEM) was employed to investigate for comparative analysis. Notably, the P@C electrode exhibits remark­
the P@C composite material in finer detail. The resultant images clearly able cyclic stability in contrast to the control group electrodes. The P@C
demonstrated the uniform encapsulation of red P within a carbonaceous electrode exhibits an initial capacity of 407.9mAh g− 1, and after 200
shell (Fig. 3c). High-resolution TEM (HRTEM) images (Fig. 3d) provided cycles, it retains 336.7mAh g− 1, translating to an impressive capacity
a more intricate depiction of the material’s morphological characteris­ retention rate of 82.5 %. The minor capacity decay per cycle is merely
tics, highlighting the crystallographic planes. This encapsulation struc­ 0.087 %, with the Coulombic efficiency stabilizing at around 98 % after
ture, typical of red P, featured a carbonaceous envelope enveloping the 80 cycles. These findings certificate the effective utilization of the active
red P. Furthermore, energy-dispersive X-ray spectroscopy (EDS) analysis material and the stability of the electrode material. In stark contrast,
substantiated the even distribution of carbon and phosphorus elements P@Graphite displays a lower capacity and a noticeable declining trend,
throughout the composite material (Fig. 3e). reaching only 157.2mAh g− 1 after 200 cycles. The RP electrode exhibits
erratic capacity behavior with significantly lower values, especially after
3.2. Electrochemical performance 124 cycles, when further testing becomes unfeasible, possibly due to the
substantial expansion of red P resulting in electrode failure. The elec­
To investigate the electrochemical behavior of the synthesized P@C trochemical property of the pristine carbon is also examined, as shown
material, we constructed a half-cell for sodium-ion batteries. As depicted in Figure S2, revealing a significantly low capacity. In summary, red P
in Fig. 4a, we conducted cyclic voltammetry (CV) tests on the P@C exhibits promise as an electrode material. However, it grapples with
composite material electrode within the voltage range of 0.01 ~ 3 V. notable capacity decay and volume expansion issues. In summary, the
During the initial cathodic scan, two distinctive peaks were observed at introduction of carbon coating and a porous structure through PVDF
0.21 V and 0.47 V. However, these peaks vanished in subsequent cycles, demonstrates significant enhancement in electrode performance,
corresponding to the formation of a solid electrolyte interphase (SEI) resulting in a high capacity and exceptional cycling stability.
and the reduction of red Phosphide to Na3P. This is in line with the Subsequent rate performance tests were conducted, as illustrated in
noticeable variation, as observed in the initial galvanostatic discharge Fig. 4d. At various current densities of 0.1, 0.2, 0.5, 1.0, and 2.0 A/g, the
curve (Fig. 4b). As the voltage further approached 0.01 V, a rapid surge P@C electrode exhibited corresponding capacities of 414.2, 392.6,
in current became evident, likely associated with ongoing reactions 340.2, 306.3, and 280.6mAh g− 1, respectively. Upon returning the
between carbon and sodium ions [37]. Following the positive scan, a current density to 0.1 A g− 1, the P@C electrode demonstrated a capacity
broad peak spanning approximately 0.3–0.7 V was detected, recovery to 392.1mAh g− 1, equivalent to a capacity retention rate of

Fig. 3. (a, b) SEM of P@C; (c) TEM of P@C; (d) HRTEM of P@C; (e) Elemental mapping of P@C.

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Y. Lin et al. Journal of Electroanalytical Chemistry 957 (2024) 118122

Fig. 4. (a) CV curves of P@C at scan rate of 0.1 mV/s;(b) Charge discharge voltage profiles for selected cycles of P@C composite at a current density of 0.1 A/g;(c)
Cycling performance of P@C, P@Graphite and Red P electrodes at 0.2 A/g;(d) Rate performance of the P@C electrodes; e) Long-term cycling performance of P@C at
1 A/g for 500 cycles. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

94.7 %. These results underscore its remarkable rate performance. The controlled and capacitive processes, as represented by the b-values in
curves remained stable throughout, a consequence of the synergistic Eq. (1) [48,49]:
benefits from carbon coating and the porous structure. In addition,
i = avb (1)
prolonged cycling under high current density conditions was performed.
As depicted in Fig. 4e, the P@C electrode, cycled at 1 A g− 1, maintained
Here, ’i’ represents the peak current, and ’v’ is the scan rate of the
a capacity of 242mAh g− 1 after 500 cycles, with a capacity decay of
voltage. After taking logarithms on both sides, Eq. (1) can be rewritten
0.036 % per cycle and no observed anomalous charge–discharge
as follows:
behavior during extended cycling.
To delve deeper into the electrochemical kinetics of the P@C elec­ log(i) = blog(v) + log(a) (2)
trode, we conducted cyclic voltammetry (CV) tests over a range of scan
rates, from 0.1 to 2 mV/s, as depicted in Fig. 5a. The CV curves, corre­ where the ’b’ value can be obtained from the relationship between log(i)
sponding to varying scan rates, displayed consistent shapes and relative and log(v). Notably, the ’b’ value ranges from 0.5 to 1.0, where 0.5
positions, signifying the exceptional rate capability and reversibility of signifies a purely diffusion-controlled process, and 1.0 indicates com­
the synthesized composite electrode. For comparison, CV curves of Red plete capacitive contributions [50]. As depicted in Fig. 5b, the ’b’ values
P electrode materials at various scan rate are shown in Figure S3. for the cathodic and anodic peaks are 0.52 and 0.69, respectively, sug­
Furthermore, the overall charge storage can be delineated into diffusion- gesting that the dynamic behavior of the P@C composite electrode en­
compasses both diffusion-controlled processes and surface capacitive

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Y. Lin et al. Journal of Electroanalytical Chemistry 957 (2024) 118122

Fig. 5. (a) CV profles of P@C at various scan rate; (b) The b value of P@C; (c) CV profle and contribution of pseudocapacitive at a scan rate of 0.7 mV s− 1; (d) and
pseudocapacitive contribution rate of P@C at various scan rate.

contributions. Utilizing the method proposed by Dunn et al., the pro­ Fig. 5d reveals that with increasing scan rates, the proportion of pseu­
portion of pseudocapacitive contribution can be quantitatively analyzed docapacitive contribution rises from 38.5 % to 93.31 %. This demon­
[51]. The theoretical expression can be written as follows: strates that pseudocapacitive behavior plays a crucial role in the high-
rate Na+ storage. The substantial pseudocapacitive contribution of
i = k1 v + k2 v1/2 (3) P@C is advantageous for achieving superior rate performance. In
addition, the pseudocapacitive contribution for the Red P rises from
where ’k1′ and ’k2′ are constants, ’v’ is the scan rate, and ’i’ is the fixed
21.78 % to 53.69 % with increasing scan rates, as shown in Figure S4.
potential [52–55]. As shown in Fig. 5c, at a given scan rate (0.7 mV/s),
To investigate material changes during cycling, electrochemical
77.5 % of the total capacity stems from pseudocapacitive contribution.

Fig. 6. (a) Electrochemical impedance spectra of the P@C composite measured before and after 300th cycles at 200mAh g− 1; (b) SEM image of the P@C composite at
0.2 A/g after 300 cycles.

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