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Based on N, F, and P co-doping biomass carbon to construct 3D porous car-

bon coated LiFePO4 for preparing lithium-ion batteries

Jian Liu, Shijie Wang, Junfeng He, Kang Liang, Jianbin Li, Xiaobing Huang,
Yurong Ren

PII: S1226-086X(24)00188-6
DOI: https://doi.org/10.1016/j.jiec.2024.03.023
Reference: JIEC 7327

To appear in: Journal of Industrial and Engineering Chemistry

Received Date: 12 January 2024

Revised Date: 7 March 2024
Accepted Date: 14 March 2024

Please cite this article as: J. Liu, S. Wang, J. He, K. Liang, J. Li, X. Huang, Y. Ren, Based on N, F, and P co-
doping biomass carbon to construct 3D porous carbon coated LiFePO4 for preparing lithium-ion batteries,
Journal of Industrial and Engineering Chemistry (2024), doi: https://doi.org/10.1016/j.jiec.2024.03.023

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Based on N, F, and P co-doping biomass carbon to construct 3D porous

carbon coated LiFePO4 for preparing lithium-ion batteries

Jian Liu1, Shijie Wang1, Junfeng He1, Kang Liang1, Jianbin Li1, Xiaobing Huang2,
Yurong Ren1,*

1 School of Materials Science and Engineering, Jiangsu Province Engineering

Research Center of Intelligent Manufacturing Technology for the New Energy Vehicle

Power Battery, Changzhou High Technology Key Laboratory of Intelligent

Manufacturing for Power Battery, Changzhou University, Changzhou 213164,

People’s Republic of China.

2 College of Chemistry and Materials Engineering, Hunan University of Arts and

Science, Changde 415000, People’s Republic of China.

*Corresponding author

Yurong Ren: ryrchem@cczu.edu.cn (Y. Ren)

Abstract: Because of its superior structural stability, high level of safety,

and low cost, the olivine-type LiFePO4 (LFP) is a prevailing cathode

material in lithium-ion batteries. However, its development is constrained

to inferior electronic conductivity and sluggish diffusion kinetic. In this

work, a biomass carbon source derived from microbial residue was

introduced to modify LiFePO4 (LFP@NFPC). LFP@NFPC composite

with three-dimensional (3D) porous structure was synthesized via a facile

wet ball milling and high-temperature calcination. Through well-

designed experiment and feasible data analysis, a high conductive 3D

network structure is constructed by N, F, and P co-doped carbon coating

 in the surface of LiFePO4, facilitating fast electron transport and rapid

reaction kinetics bewteen intercrystalline. Meanwhile, the LFP@NFPC

with three-dimensional (3D) porous structure can also improve the

accessibility of Li+ over a protrcated cycle. The as-prepared LFP@NFPC

shows discharge specific capacities of 168.2, 138.4, and 103.8 mAh g-1 at

1, 10, and 50 C, respectively. Simultaneously, the LFP@NFPC||Graphite

full battery indicates a specific capacity of 161.2 mAh g-1 at 1 C, thus

exhibiting superior rate capacity and outstanding cycle stability. This

work provides a sustainable and economical approach to modify the

cathode material of LIBs.

Keywords: Lithium-ion batteries, LiFePO4, Carbon source, Porous

structure.

1. Introduction

As fossil energy is gradually replaced by new clean energy, lithium-

ion batteries, which are highly representative and efficient energy storage

devices, are increasingly attracting close attention in the energy market[1,2].

Thereinto, high energy density, long cycle life, and environmental

friendliness, lithium-ion batteries have widely used in the filed of electric

vehicles (Evs) and portable electronic devices[3,4]. Due to LiFePO4 possess

low price, abundant raw materials, high safety and good thermal stability,

which has been regared as a great practical cathode material in LIBs[5-7].

However, LiFePO4 is affected by the inherent defects, such as low

electronic conductivity (10−9 ~ 10−10 S·cm−1)[8] and sluggish lithium-ion

diffusion kinetics (10−14 ~ 10−16 cm2·s−1)[9], resulting in inferior rates

capacity and cycle performance. To make matters worse, the intercalation

and de-intercalation of lithium ions are severely affected at high rates. As

is well-known, LiFePO4 is an olivine structure, composed of ferroxide-

octahedrons [FeO6], lithium-oxygen octahedrons [LiO6], and phosphorus-

oxygen tetrahedron [PO4][10,11]. Ferroxide octahedrons are connected by

common vertices and do not construct common-edge network to

continuously form electronic conductive channels, causeing a low

electronic conductivity in entire LiFePO4 material[12]. Besides, because the

phosphorus-oxygen tetrahedron is located between the ferro-oxygen

octahedrons and the lithium-oxygen octahedrons, hindering the migration

and diffusion of Li+ and resulting in a sluggish ion diffusion kinetics

throughout the LiFePO4 material[13]. Although a mass of research works

have been implemented on surface coating[14-16], ion doping[17-19], and

morphological control of LiFePO4[20-23]. The relevant methods had caused

a series of problems such as complex process, high cost and unstable

performance, so further research and breakthrough are still needed.

Biomass carbon sources have the advantages of sustainability, low

cost and high carbon content, so are widely used in the structural

modification of multi-functional carbon materials related to energy storage,

sensing and environmental fields[24,25]. In this work, introducing the waste

microbial bacteria residue and via a series of pre-treatments, including acid

impregnation and alkali leaching. As a result, the bacteria residue can be

transformed into a biomass carbon source (called as: NFPC) rich in N, F,

and P elements. And the NFPC can be used to coat LiFePO4 through a

facile synthesis process by wet ball milling and high-temperature sintering.

Simultaneously, N doping could provide fast charge transmission networks,

contribute to electron transport[26,27], F doping can improve the accessibility

of Li+ and maintain the stability of LiFePO4 crystal structure during the

long cycle[28,29], and P doping can construct defect structures in carbon

materials and low ionization energies[30], as well as can be conducive to

reducing charge tranfer impedance.

Based on experimental investigation and feasibility analysis, N, F, and

P co-doping carbon coating layer with a three-dimensional (3D) porous

structure can establish an ultra-high electronic conductive network, which

can facilicate fast electron transmission throughout the entire electrode and

promote rapid reaction kinetics. As expected, the LFP@NFPC exhibits

impressive electrochemical perfoemance, especially outstanding

cyclability and superior rates performance.

2. Experimental

2.1 Preparation of 3D porous carbon derived from bacterial residue

First, a certain amount of bacterial residues were placed in a blast

drying oven under 100 ℃ for 12 h. Then, 10 g of dried bacterial residue

were uniformly dispersed in 30 mL HF (20 wt.%) acid solution and stirinng

for 4 h. After filtration and washing, added the bacterial residues to 30 mL

HCl (18.5 wt.%) acid solution and continue to stir for 4 h, as well as filtered

and washed to neutral, then dryed at 90 °C for 12 h in a vacuum oven. 2 g

of pretreated bacterial residue and 8 g KOH were added to the nickel

crucible with containing 40 mL of ethanol and water (ethanol to water

volume ratio is 1:1), fully saturated and dried at 110 °C for 16 h. Finally,

the mixture was calcined at 450 °C for 4h and maintained at 800 °C for 4

h, then naturally cooled to room twmperature. The N, F and P co-doped

porous carbon coatings (NFPC) was obtained by means of washing to

neutral and dried at 80 °C.

2.2 Synthesis of LiFePO4@NFPC

LFP@NFPC was prepared using wet ball milling and high-

temperature sintering. First, 0.02 mol ammonium dihydrogen phosphate

(99.99% NH4H2PO4), 0.02 mol lithium carbonate (99.99% Li2CO3) and

0.02 mol ferrous oxalate dihydrate (99.7% FeC2O4·2H2O) were added to

the ball mill tank. Besides, adding the biomass carbon (NFPC) serve as

carbon source (0.5 g, 1 g, and 1.5 g for LFP@NFPC-1, LFP@NFPC-2, and

LFP@NFPC-3) and absolute ethanol (30mL) as solvent. The above

material weighed in a certain proportion and the ball mill ratio is 15:1, and

the same quality of calcium carbonate (CaCO3) is added to the another tank

and the solvent is still absolute ethanol. The ball milling time is 12 hours
and rotate speed is 500 r/min. Then the precursor was obtained via drying

at 85 °C for 6 h in a vacuum oven. After that, the synthesized precursor

was calcined in Ar atmosphere at 700 °C for 12 h and the LFP@NFPC was

synthesized.

By comparation, the reference LFP/C was synthesized as following:

0.02 mol ammonium dihydrogen phosphate (99.99% NH4H2PO4), 0.02

mol lithium carbonate (99.99% Li2CO3) and 0.02 mol ferrous oxalate

dihydrate (99.7% FeC2O4·2H2O) and asphalt powder (1g for LFP/C) as

carbon source, absolute ethanol (30mL) as solvent were added to the ball

mill tank. The previous experimental operation steps were repeated,

without changing the other parameters.

3. Results and discussion

Scheme 1. Schematic of the preperation processes for LFP@NFPC.

Scheme 1 shows the synthesis procedure of LFP@NFPC. Firstly, the

raw materials are thoroughly mixed to prepare the precursors using the wet

ball milling process. Subsequently, the as-prepared precursors are annealed

at a high temperature in an atmosphere of argon. After that the pretreated

biomass carbon source produces the porous structure and coats around

LiFePO4. This porous strcture could enhance the the infiltrability of

electrolyte and mlti-ions doping carbon coating layer could elevate the

conducivity and construct continuous ion migration channels, resulting in

high rate performance cathode in LIBs[31,32]. The XRD patterns of

LFP@NFPC-1, LFP@NFPC-2, LFP@NFPC-3, and LFP/C samples are

presented in Figure 1(a). It can be observed that all characteristic peaks can

be indexed as peridot-type structures with orthogonal Pnma space groups.

The characteristic peaks positions of LFP@NFPC-1, LFP@NFPC-2,

LFP@NFPC-3, and LFP/C are consistent with the LFP phase (JCPDS Card
No. 81-1173). Figure 1(b) indicates the Ball-and-stick model of LiFePO4,

which is composed of ferroxide-octahedrons [FeO6], lithium-oxygen

octahedrons [LiO6], and phosphorus-oxygen tetrahedron [PO4].

Meanwhile, Figure 1(c) and Figure S1 also exhibit the Rietveld refinement

results of LFP@NFPC-1 ， LFP@NFPC-2, and LFP@NFPC-3.

Furthermore, the refined parameters of LFP@NFPC-2 of orthorhombic

space group pmna including a = 10.332 Å, b = 6.010 Å, c = 4.692 Å, and

V = 291.35 Å3, are in accordance with previous reports in Table S1[33].

Figure. 1(d) exhibits the Fourier transform infrared (FT-IR) of LFP/C,

LFP@NFPC-1 ， LFP@NFPC-2, and LFP@NFPC-3 samples. The

observed peak at 3400 cm-1 near is commonly associated with the

stretching vibration of the hydroxyl goups (—OH). The characteristic peak

observed around 2096 cm-1 is related to the C—H bending and stretching

vibrations of methylene group (—CH2). The C=O stretching peak at 1642

cm-1 is connected with the carboxylic group. In addition, the boradband

observed in the range of 900-1150 cm-1 corresponds to the asymmetric

stretching virbration of the phosphate ion (PO43-)[34]. The Raman spectra of

LFP/C, LFP@NFPC-1, LFP@NFPC-2, and LFP@NFPC-3 are displayed

in Figure. 1(e), the four samples exhibit the characteristic peaks of PO43- in

LiFePO4 appears around 900-1100 cm-1[35]. Besides, the characteristic peak

of LFP@NFPC-1 is strogner than that of LFP@NFPC-2 and LFP@NFPC-

3. Because LFP@NFPC-2 and LFP@NFPC-3 both are uniformly coated

with carbon that attenuates the intensity of Raman signal, the LFP@NFPC-

1 is not fully covered by the carbon layer. In addition, the two broad

characteristic peaks of the LFP@NFPC-1, LFP@NFPC-2, and

LFP@NFPC-3 are around 1360 and 1586 cm-1, where corresponding to

disordered graphite (D-band) and crystalline graphite (G-band)[36],

respectively. In Figure 1(e), the ID/IG (the intensity ratio of the D-band and

G-band) of LFP@NFPC-1, LFP@NFPC-2 and LFP@NFPC-3 is

calculated as 0.901, 0.936, and 0.933, respectively, indicating the high

degree of graphitization. Simultaneously, the N, F, and P co-doping in

carbon coating can enhance electric conductivity of material and be

beneficial to electron migration and ion transport. Figure S2 displays the

thermogravimetric (TG) curves of LFP/C, LFP@NFPC-1, LFP@NFPC-2,

and LFP@NFPC-3 samples, the carbon contents of four samples are

calculated to 5.086, 1.682, 4.914 and 6.312 wt%, respectively. The weight

loss at 400~600 ℃ is associated with the conversion of carbon into carbon

dioxide. The XPS is performed to determine the elemental composition and

valence of LFP@NFPC-2[37]. According to Figure 1(f), the characteristic

peaks of Li 1s, P 2p, C 1s, N 1s, O 1s, F 1s, and Fe 2p are corresponding

to 55.8, 133.8, 284.8, 400.7, 531.8, 687.6, and 710.8 eV in the LFP/C and

LFP@NFPC-2Error! Reference source not found., respectively. Moreover, Figure

1(g) displayed the high-resolution C 1s spectra of LFP@NFPC-2. The

peaks at 284.8, 286.5, 287.6, 289.1, and 291.0 eV, are associated with the
C—C, C—N, C—P, O=C—O, and C—F bonds. Figure 1(h) exhibits the

N 1s spectrum of the LFP@NFPC-2, the deconvoluted peaks at 398.5,

399.9, and 402 eV are corresponding to pyridinic N, pyrrolic N, and

graphite N, respectively. In Figure 1(i), the two peaks at 685.4 and 687.8

eV can be connected with C—F and CF2 in the high-resolution F 1s spectra

of LFP@NFPC-2. Simultaneously, Figure 1(j) presents the P 2p spectrum

of the LFP@NFPC-2, two characteristic peak at 132.7 and 133.1 eV

confirms the existance of P-O and P-C bonds. And the N 1s, F 1s, and P 2p

peaks of NFPC can also be observed in Figure S3. The above results

demonstrate N, F, and P co-doping carbon layer is sucessful. According to

Figure 1(k), the porous structure feature of LFP@NFPC-2 is explored by

means of N2 absorption/desorption isothermal. The result manifests the

produce of mesoporous structure main attributed to high temperature

sintering[38,39]. The specific surface area of LFP@NFPC-2 and LFP/C are

88.367, 19.682 m2·g-1, respectively. Moreover, the inset from Figure 1(k)

indicates the pore distribution of LFP@NFPC-2 and LFP/C. The pore of

LFP@NFPC-2 centered at 3.7 nm can enhance the infiltration between the

cathode and the electrolyte, thus facilitate the electrochemical reaction

activity. The above results indicate that LFP@NFPC-2 with porous

characteristic can be conducive to electrolyte infiltration, provide more

insertion sites of Li+, enhance the diffusivity of lithium-ion, and facilitate

the electrochemical reactivity[40]. Figure 1(l) illustrates the schematic of Li+

and electron transmission of LFP@NFPC. The structural stability of the

LFP@NFPC is greatly enhanced through the structural regulation on the

3D porous carbon matrix, thus has a significant implications for improving

the practical application of LIBs.

Fig. 1. (a) XRD patterns of the LFP/C and the LFP@NFPC-X (X=1, 2, 3). (b) the structural model of the LiFePO4.
(c) Rietveld refinement result of the LFP@NFPC-2. (d) FT-IR spectra of the as-obtained LFP/C and LFP@NFPC-
X (X=1, 2, 3) samples. (e) Ranman spectra of the LFP/C and LFP@NFPC-X (X=1, 2, 3) samples. (f) X-ray
photoelectron spectroscopy (XPS) survey spectra of the LFP/C and LFP@NFPC-2. High-resolution XPS spectra for
LFP@NFPC-2: (g) C 1s, (h) N 1s, and (i) F 1s, (j) P 2p, (k) Nitrogen adsorption-desorption isotherms of LFP/C and
LFP@NFPC-2. The inset shows the pore-size distribution of two samples. (l) Schematic of Li+ and electron
transmission.
Fig. 2. (a) SEM image of the LFP/C. (b-d) SEM images of LFP@NFPC-2. (e) TEM image of the LFP@NFPC-2. (f)
HRTEM image of LFP@NFPC-2 corresponding to the yellow dashed rectangle in (c). The images (g1, g2) are the
regions within the yellow dashed rectangle in (f). (h) The SAED image of LFP@NFPC-2. (i) SEM-EDS mapping
of LFP@NFPC-2 powder and Elemental distribution of C, O, Fe, N, F, and P, respectively.

The surface morphology, micro-structure characterizations, and

lattice fringes are analyzed by scanning electron microscopy (SEM) and

transmission electron microscopy(TEM). In Figure 2(a), the SEM image

of LFP/C reveals an irregular block and sheet structure, along with the large

particle morphology, resulting in poor infiltration of electrolyte[41]. Figure

2(b-d) exhibit the SEM images of LFP@NFPC-2. The porous structures

on the surface can promote the penetration of electrolytes and alleviate the
structural stress generated during lithiation and delithiation processes,

accelerates electrochemical reactions kinetic, and improves the rate of

charge diffusivity[42]. High-resolution TEM (HR-TEM) is conducted to

analysis the crystal facets of LFP@NFPC-2. Figure 2(e) and Figure S5(a)

exhibits the general situation of random distribution of partial

LFP@NFPC-2 particles. Figure 2(f) is the enlarged image of the selected

yellow dashed rectangle in the figure above. The out layer of LiFePO4 is

coated with the size around 2 nm uniform amorphous carbon layer, which

could promote the charge diffusivity and void erosion of the electrolyte as

well as reduce polarization. The selected two regions display the clearly

continuous lattice fringes from Figure. 2(g1) and (g2). Simultaneously,

Region 1 and Region 2 exhibit the lattice fringe distances of 0.301 and

0.348 nm, matching to the (211) and (111) crystal plane of LiFePO4.

Besides, Figure S5(b) also indicates the different lattice fringe distances of

0.276 and 0.213 nm, which represent the (301) and (112) crystal plane of

LiFePO4. According to Figure 2(h), the selected area electron diffraction

(SAED) pattern exhibits a host of clearly diffraction rings, belonging to

(112), (121), (301), (211), and (111) crystal plane of LFP@NFPC-2, which

can verify the pure crystalline phase in LFP@NFPC-2. In Figure 2(i), the

EDS elemental mappings exhibit the morphology and elemental

distribution of LFP@NFPC-2. It could be seen that the C, O, Fe, N, F, and

P was evenly distributed throughout the region, which demonstrated that

these elements have been uniformly dispersed in the well-designed three-

dimensional porous LFP@NFPC-2.

Fig. 3. (a) In-situ XRD pattern for LFP@NFPC-2 at 0.2 C rate. the left figure of diffraction pattern
shows the time-voltage curve. (b) Corresponding the contour map of the diffraction peak. (c)
Schematic diagram of phase transition structure of lithium iron phosphate during charging and
discharging.

To prove the completeness of the phase transition of LiFePO4 during

charging and discharging (provided sufficient lithium ions are supplied),

In-situ XRD test was conducted on the half battery assembled with

LFP@NFPC-2. The charging and discharging profile at a current density

of 0.2 C and the occurring phase change of the LFP@NFPC-2 is monitored

in-situ and indicated in Figure 3(a-b). Figure 3(a) shows the relationship

between the time-voltage curve and the XRD pattern in the charge-

discharge process, the battery underwent two charges and discharges over

the course of test. When the battery is charged to 4.2 V, the characteristic

peaks of LiFePO4 disappear and the characteristic peak of FePO4 appears.

In addition, the diffraction peak of the (211) crystal plane of LiFePO4 is

transformed into the FePO4 corresponding to the (131) crystal plane,

indicating the complete phase transformation from LiFePO4 to FePO4.

When the discharge voltage reaches to 2.5 V, Li+ gradually embeds into

the lattice of FePO4, leading to the presence of both LiFePO4 and FePO4

phases once again[45]. And it is observed that the position of the diffraction

peak of the LiFePO4 changes continuously, which is related to the

delithiation and lithiation behavior during the charge and discharge. Figure

3(b) indicates the contour map of the diffraction peak at 29~34 degrees.

The diffraction peaks of LFP@NFPC-2 shifted twice at 29.7 and 32.2

degrees, corresponding to the (211) and (301) crystal plane. It has been

reported that the formation of FePO4 phase in the charge-discharge process

is caused by the removal of Li+ from the lattice of LiFePO4 phase. After

the transition from LiFePO4 phase to FePO4 phase, it can still change back

to LiFePO4 phase, which fully proves the excellent structural stability and

good phase transition reversibility of the LFP@NFPC-2 material[43]. Figure

3(c) illustrates this fundamental reason that the conversion of LiFePO4 into
FePO4 phase during the process of charging and discharging. The existance

of both LiFePO4 and FePO4 phases can be observed successively during

the charging and discharging platform, suggesting the continous

detachment of Li+ from the LiFePO4 lattice to form the FePO4 phase[44].

The above results are consistent with previous findings, it can be proved

that the phase transition between LiFePO4 phase and FePO4 phase is stable

and controllable through the continuous insertion and extraction of Li+ in

the process of charge and discharge, and the modifoed biomass carbon will

not destroy the stability of the crystal structure of LiFePO4. Which

intuitively and strongly confirmed the structural stability and

electrochemical reversibility of the LFP@NFPC-2 electrodes in the charge

and discharge.
Fig. 4. (a) the GCD profiles of the LFP/C and the LFP@NFPC-X (X=1, 2, 3) at 1 C (the inset displays part of
amplified region of voltage plateau). (b) Cycling capacity of LFP@NFPC-2 at 1 C and the inset displays GCD curves
at different cycles. (c) GCD curves of LFP@NFPC-2 samples at 1, 2, 5, 10, 20, 30, 40 and 50 C. (d) Rate capacity
of the LFP/C and the LFP@NFPC-X (X=1, 2, 3). (e) Cycling capacity of the LFP/C and the LFP@NFPC-X (X=1,
2, 3) at 10 C.

In order to investigate the presence of carbon coating how impacts the

electrochemical properties of LiFePO4, The four samples were assembled

into batteries and various electrochemical performance tests were

conducted. Figure 4(a) displays the normal galvanostatic charge-discharge

(GCD) profiles of four samples at 1 C. The four samples exhibit similar

smooth charging and discharging plateau near 3.45 V that can be associated

with the reversible phase transition between LiFePO4 with FePO4[46].

Meanwhile, according to the inset from Figure 4(a), the charging and

discharging voltage plateau of LFP@NFPC-2 exhibits a flatter and smaller

profile compared to other samples. This indicates that LFP@NFPC-2

provides a convenient and faster pathway for lithium ion diffusion, which

can induce a slighter polarization compared to the other samples[47,48]. The

above results can be attributed to N, F, and P co-doping combine with the

structural regulation of carbon matrix. Not only does it suppresses further

the growth of LiFePO4 crystal grain and minimizes the distance of lithium-

ions diffusion, but it also improves the kinetics of Li+ diffusion and

facilitates charge diffusivity[49]. Figure 4(b) depicts the cycle capability of

the LFP@NFPC-2 at 1 C. The discharge capacity of LFP@NFPC-2

maintains at 160.32 mAh g−1 after 600 cycles and the capacity retention is

sustained on 95.88%. Figure 4(c) and Figure S7 display the charging and

discharging curves of the LFP@NFPC-2 and others samples at 1-50 C.

LFP@NFPC-2 exhibits a significant and consistent charge-discharge

voltage plateau, particularly at the current density of 50 C, a stable

discharge voltage platform of 3.012 V can still be maintained. Figure 4(d)

and Table S2 illustrate the rate capacity of LFP/C, LFP@NFFPC-1,

LFP@NFPC-2, and LFP@NFPC-3 at different current density.

Simultaneously, the relationship between middle working potential (Vm)

with rate at 1-50 C is revealed, as illustrated in Figure S8. The

LFP@NFPC-2 electrode exhibits discharge capacity of 168.2, 162.3, 159.6,

150.1, 138.8, 130.5, 120.4, and 103.8 mAh g−1 at various rate of 1, 2, 5, 10,

20, 30, 40, and 50 C, respectively. LFP@NFPC-2 can provide a higher

reversible discharge capacity than other samples, exhibiting an outstanding

electrochemical performance compared to previously reported carbon-

coated LiFePO4 cathodes materials. Furthermore, as shown in Figure 4(e),

it can be seen that the LFP@NFPC-2 sustains a significantly larger

discharge capacity of 131.93 mAh g−1 after 1000 cycles, and the capacity

retention rate is 86.93% compared to that of LFP@NFPC-3 (120.54 mAh

g−1, 82.80%), LFP@NFFPC-1 (112.06 mAh g−1, 54.85%), and LFP/C

(105.42 mAh g−1, 69.95%) even at 10 C. The result manifests that the

LFP@NFPC-2 material exhibits the exceptional fast charge-discharge

capability. This is mainly attributed to N, F, and P co-doping carbon

coating with 3D porous structure constructs a highly conductive network

that can be conducive to active material sufficient contact with the

electrolyte, remedy charge diffusivity, and promote the diffusion kinetics

of LiFePO4 material[50,51]. Moreover, LFP@NFPC-2 exhibited excellent

electrochemical performance compared with previously reported LiFePO4

material in Table S4.

Fig. 5. (a) CV curves of the LFP/C and the LFP@NFPC-X (X=1, 2, 3) at 0.5 mv/s. (b) LFP@NSPC-
2 Cyclic voltammetry curves at different sacnning rates. (c) Nyquist plots of the LFP/C and the
LFP@NFPC-X (X=1, 2, 3). (d) The linear relationship between the Ip and ν1/2 in the charging and
discharging process. (e) DLi+ of the LFP/C and the LFP@NFPC-X (X=1, 2, 3) electrodes was
calculated by Randles-Sevcik equation. (f) The relationship for Z’ and -1/2 of the LFP/C and the
LFP@NFPC-X (X=1, 2, 3). (g-i) Lithium-ion-diffusion coefficients of the LFP@NFPC-X (X=1, 2,
3) during charge and discharge processes calculated by GITT.

With the purpose of further studying the diffusion kinetics of lithium-

ions of LFP@NFPC. Cyclic voltammetry (CV) profiles of four samples

were tested, as illustrated in Figure 5(a). LFP@NFPC-2 shows minimal

voltage intervial (0.33 V) of the redox peaks, which is much smaller than

that of LFP@NFPC-3 (0.48 V), LFP@NFPC-1 (0.50 V), and LFP/C (0.44

V). The smaller voltage gaps of the redox peak indicate a lower degree of

polarization[52,53]. Moreover, LFP@NFPC-2 exhibits the sharpest and most

symmetrical redox peaks, indicating stronger lithium ion diffusion kinetics

compared to LFP/C, LFP@NFPC-1, and LFP@NFPC-3. In Figure 5(b)

and Figure S9, CV profiles can be used to analyze the primary cause of
exceptional rate capability and long-term cycle life span of LFP@NFPC-

2. The observed redox peaks are relevant to the phase-transition occurring

in LiFePO4 and FePO4, during the process of intercalation and

deintercalation of lithium-ion[54,55]. Following the scanning rates increases,

the interval between the oxidation peaks and the reduction peaks as well as

the peaks area also increase, indicating that the polarization intensity of the

electrode is larger at the higher scanning rate[56]. Figure 5(c) shows the

electrochemical impedance spectroscopy (EIS) of four samples. Based on

the equivalent circuit model, all plots have been fitted and calculated. And

the fitted data for the EIS and the lithium-ion diffusion coefficient (DLi+)

of four samples are presented in Table S3. The Rct values of 4 samples

increased in the following order: LFP@NFPC-2 < LFP@NFPC-3 <

LFP@NFPC-1 < LFP/C. Figure 5(d) and Figure S10 show the relation

between the peak current (Ip) and the square root of sweep rate (v1/2). The

DLi+ can be calculated from the Randles-Sevcik equation (Equation S1).

Figure 5(e) exhibited the DLi+ for four samples, and the results illustrated

that the DLi+ of LFP@NFPC-2 are higher compared to LFP/C,

LFP@NFPC-1, and LFP@NFPC-3. Figure 5(f) indicates the relationship

between Z’ with ω−1/2. According to Equation (S2) and (S3), LFP@NFPC-

2 shows the lowest  value (10.6) and the highest DLi+, which confirms the

superior charge diffusivity and great lithium-ion diffusion knietics in the

LFP@NFPC-2. As shown in Figure 5(g-i) and Figure S11, the

galvanostatic intermittent titration technique (GITT) (Equation S4) can be

used to evaluate the DLi+ in LFP/C, LFP@NFPC-1, LFP@NFPC-2, and

LFP@NFPC-3 during charging and discharging processes. According to

the obtained calculation results exhibit that the DLi+ for LFP@NFPC-2 are

larger than LFP/C, LFP@NFPC-1, and LFP@NFPC-3, revealing that N,

F, and P co-doping carbon coating can reduce the energy barrier for charge

transfer and facilitate the kinetics of ion diffusion.

Fig. 6. (a) Shematic of the LFP@NFPC-2||Gr lithium-ion full battery. (b) Cycle performance of
LFP@NFPC-2||Gr at 1C and the assembly structure of full battery. (c) Rate performance of the
LFP@NFPC-2||Gr full battery. (d) GCD curves of LFP@NFPC-2||Gr full battery at 1, 2, 5, 10, 20,
and 30 C. (e) Use of the LFP@NFPC-2||Gr full battery to light this LED lamp. (f) Cycle performance
of LFP@NFPC-2||Gr full battery at 10 C.

The LFP@NFPC-2 and graphite (Gr) are used to construct full battery
and investigate their practical application potential (Figure 6(a)). The Gr is

used as the anode in the lithium-ion battery, and LFP@NFPC-2 is used as

the cathode, in accordance with the N/P ratio (1:1.18) of active substances

to assemble the full battery. Before assembling the lithium-ion battery, the

pre-lithium procedure was used to activate the Gr anode for five cycles at

a current density of 0.1 C, which can decrease the occurrence of side

reaction and keep that in a stable state, as illustrated in Figure S12. The

internal structure component of battery and the cycling stability of the

LFP@NFPC-2||Gr full battery is presented in Figure 6(b). After 200 cycles,

the battery displays a capacity of 161.2 mAh g-1 with a retention of 96.5%

at 1 C. Figure 6(c-d) analyzes the rate capabilities of the LFP@NFPC-2||Gr

full battery at various rates. The full battery shows a discharge capacity of

165.2, 158.6, 151.3, 138.9, 118.6, and 93.5 mAh g-1 at 1-30 C, respectively.

After testing different rates, the LFP@NFPC-2||Gr full battery can regain

its discharge capacity to 163.2 mAh g-1, when the rate recovers to 1 C,

revealing the outstanding reversibility over the course of charging and

discharging. In addition, as shown in Figure 6(e), the fully charged

LFP@NFPC-2||Gr full battery can lighten the small LED lamp, confirming

its promising practical application. Figure 6(f) indicates the cycling

capability of the LFP@NFPC-2||Gr full battery at 10 C. This battery

exhibits exceptional cyclability, maintaining 82.8% of capacity after 1000

cycles.
Fig. 7 (a) Cycled electrode. (b) electrolyte decomposition. (c) C 1s, (d) N 1s, (e) F 1s, (f) P 2p (g) Fe 2p, and (h) O
1s High-resolution XPS spectra of the LFP@NFPC-2 electrode and the LFP@NFPC-2 electrode after cycled 500 th
at 1 C.

To further explore the mechanism of electrochemical performance

degradation of batteries, the impact of electrolyte decomposition on the

battery’s electrochemical performance was thoroughly analyzed. The

electrolyte decomposition products of LiPF6 are primarily phosphorus

pentafluoride (PF5), phosphorus oxide trifluoride (POF3), and lithium

fluoride (LiF) in Figure 7(a-b). As reported, the deposition of electrolyte

by-products on the LiFePO4 surface can hinder the migration of Li+ and

electron transport, resulting in inferior electrochemical performance of

batteries[57]. In addition, XPS was used to analyze the chemical valence and

elemental composition of the LFP@NFPC-2 material surface after cycling.

The deconvoluted C 1s spectra of LFP@NFPC-2 in Figure 7(c) shows the

binding energy at 284.8, 286.3, 287.9, 289.2 and 291 eV, which are

associated with C—C, C—N, C—P, O—C=O and C—F bond[29],

respectively. After 500 cycles, the peak intensity and content of C—F bond

has increased, because the decomposition products of LiPF6 in the

electrolyte are deposited in the carbon layer over the charging and

discharging process[58]. For N 1s spectra of LFP@NFPC-2 in Figure 7(d),

the existance of Pyridinic N, Pyrrolic N and Graphitic N is confirmed.

After 500 cycles, the bottom four different diffraction peaks at the binder

energy values of 398.3, 399.8, 400.9, and 402.8 eV, which are associated

with Pyridinic N, Pyrrolic N, Graphitic N, and oxidation of N atoms[27,30].

The oxidation of N atoms may be related to the Oxidative decomposition

of Pyridinic N during the long-term charging and discharging process[59].

As presented in Figure 7(e), the characteristic peak at 688.1 and 685.9 eV

can be correlated to C—F bond and LiF[60], respectively. After 500 cycles,

the increased LiF content was primarily attributed to the decomposition

products of the electrolyte LiPF6[57]. According to Figure 7(f), the P 2p XPS

spectrum of LFP@NFPC-2 can be deconvoluted into two characteristic

peaks with the bindering energy at 133.1 and 136.8 eV, demonstratng the

existance of P—O and P—C bonds[27]. After 500 cycles, the peak intensity
has weakened, which can be connected with the oxidative decomposition

of P—C bond. As illustrated in Figure 7(g), the Fe 2p spectrum can be

divided into 4 characteristic peaks. The main peaks located at 711.4 and

724.4 eV corresponded to the Fe 2p3/2 and Fe 2p1/2, the two satellite peaks

located at 715.2 and 729.3 eV, which indicated the Fe is present divalent

in LiFePO4[60]. After 500 cycles, the two peaks located at 712.6 and 726.3

eV can be attributed to the trivalent Fe3 +. It is resulted from the phase

conversion between LiFePO4 and FePO4 phase[43]. In Figure 7(h), the

deconvoluted O 1s spectra of the LFP@NFPC-2 shows the characteristic

peaks at 530.17 and 532.31 eV, demonstrating the existence of P-O and O-

C=O[60]. After 500 cycles, it can be observed that the content of O-C=O is

elevated slightly, attributed to the residual ether compounds in electrolytes.

The above results demonstrated that the chemical composition of

LFP@NFPC-2 electrode did not undergo significant changes before and

after cycling, reflecting its extraordinary structural stability. In addition,

because the construction of co-doped conductive carbon coating and the

design of three-dimensional porous structure can effectively restrain the

negative effects of electrolyte deposition on the electrode material surface.

Therefore, facilitating the diffusion and transport of Li+, and resulting in

electrochemical performance of the battery improves.

4. Conclusion

In this study, a biomass carbon source derived from microbial residue

was introduced to modify LiFePO4 (LFP@NFPC), via a facile wet ball

milling and high-temperature sintering. The conductive network of N, F,

and P co-doped carbon coating was constructed and the 3D porous

structure was designed on the surface of LiFePO4, which can contribute to

electron transport, facilitate the accessibility of Li+ and keep the stability

of LiFePO4 crystal structure throughout the long cycle. In addition, the

porous structure can also enhance electrolyte permeability and alleviate

structural stress resulting from lithiation and delithiation processes, thus

can improve the rates performance and cycle capability. The results

demonstrated that LFP@NFPC-2 shows discharge capacities of 168.3,

138.1 and 103.8 mAh g-1 at 1, 10 and 50 C. Moreover, the LFP@NFPC-

2||Gr full battery also exhibited great rates and cycle performance,

confirming good practical application prospects. This work provids a

sustainable and economical method to design and utilization LiFePO4

cathode material.

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence the

work reported in this paper.

Data availability

Data will be made available on request.

Acknowledgements

This work was financially supported by the National Natural Science

Foundation of China (No. U22A20420). The author thank to Aid Program

for Science and Technology Innovative Research Team in Higher

Educational Institutions of Hunan Province. In addition, the authors would

like to thank Zhengyun Bian from Shiyanjia Lab(www.shiyanjia.com) for

the XPS and TEM measurements.

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Hightlight:

a. LFP-based carbon coated nanocomposite can remarkable improve the

electrochemical performance of LIBs.

b. The conductivity and ion diffusion rate of LFP were improved through

the construction of co-doped conductive carbon coating and the design of

three-dimensional porous structure.

c. The rate performance and long cycle stability of LFP under 10C high

current density are improved.

d. The electrochemical performance of full batteries has proved LFP good

practical applications.

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests: