Journal of Colloid and Interface Science 662 (2024) 1086–1095

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Journal of Colloid And Interface Science

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

Regular Article

A quantitative analysis method of complex sulfide components for

understanding initial capacity degradation mechanism in
lithium-sulfur batteries
Zhaoyang Li a, Mengran Wang a, b, c, *, Jiewei Yang a, Bo Hong a, b, c, *, Yanqing Lai a, b, c, Jie Li a, b, c
a
School of Metallurgy and Environment, Central South University, Changsha, Hunan 410083, China
b
Engineering Research Centre of Advanced Battery Materials, The Ministry of Education, Changsha 410083, Hunan, China
c
Hunan Provincial Key Laboratory of Nonferrous Value-added Metallurgy, Changsha 410083, Hunan, China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A highly effective approach for the

graded leaching and precise quantitative
detection techniques of sulfur-
containing components within Li-S bat­
teries has been successfully developed.
The total detection rate of this method
for sulfur-containing components in Li-S
batteries exceeds 99 %.
• Clarify that the presence of lithium
polysulfide in the electrolyte after
discharge is the main factor for
restricting the full utilization of Li-S
batteries’ capacity, and propose tar­
geted improvement measures.
• This study offers a considerably refined
and comprehensive methodology for the
capacity fading and failure mechanisms
assessment of high-energy-density Li-S
batteries.

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

Keywords: Lithium-sulfur (Li-S) batteries are a strong contender for the new-generation battery system to meet the growing
Lithium-sulfur batteries energy demand due to their significantly high energy density (2600 Wh/kg) and cost-effectiveness. However, the
Capacity loss practical operating conditions yield an initial capacity of less than 80 % of the theoretical capacity, resulting in a
Potentiometric titration
limited lifespan and hindering broader application. What’s worse, current mechanism, especially the evolution
High sulfur loading
process of sulfides for the initial capacity degradation is not clear due to the practical difficulties of effective
separation and detection of sulfur-containing components. Herein, we have developed an instrumental analysis
method enabling graded leaching and quantitative determination of sulfur-containing components. This tech­
nology achieves a detection precision surpassing 99.11 %, addressing the inherent deficiency in calculating
sulfur-containing components using the decrement method. Applying this method reveals that the presence of
lithium polysulfides in the electrolyte (26.34 wt%) after discharging is the primary factor causing insufficient
capacity utilization in Li-S batteries. This work not only demonstrates the unique behavior of Li-S batteries at

* Corresponding authors at: School of Metallurgy and Environment, Central South University, Changsha, Hunan 410083, China.
E-mail addresses: mengranwang93@163.com (M. Wang), bop_hong@163.com (B. Hong).

https://doi.org/10.1016/j.jcis.2024.02.017
Received 29 November 2023; Received in revised form 21 January 2024; Accepted 2 February 2024
Available online 5 February 2024
0021-9797/© 2024 Elsevier Inc. All rights reserved.
Z. Li et al.
high sulfur loading but also provides a systematic evaluation method to guide further research on high-energy-
density batteries, and provides theoretical and technical support to promote the development of high-energy,
long-life Li-S batteries.
1. Introduction
Li-S batteries are at the cutting edge of electrochemical energy
storage devices due to their high specific capacity, greenness, and low
cost[1–3]. In recent years, plenty of researches have been carried out on
the optimization the cathode materials of Li-S batteries[4–7]. Com­
pounding sulfur with porous carbon materials with high specific surface
area[8–10]and high conductivity[11,12] is reported to be an effective
strategy to improve the conductivity of electrodes and increase the
utilization rate of active material[13]. Besides, the heterostructure can
integrate the benefits of various components to achieve a synergistic
effect on the electrostatic sulfur redox[14–16]. Another effective
method to improve Li-S battery performance is to introduce catalysts
into cathode[17–22] to improve the electrochemical activity and con­
version efficiency of sulfur[23]. While significant progress has been
achieved in the mentioned material preparation and modification
methods for Li-S battery research, with many high specific capacity and
high stability material systems reported[24–26], but the commercial
application of Li-S batteries is still struggling[27,28].
To push on the large-scale application of Li-S batteries, high sulfur
loading is essential[29–31]. However, in batteries with high sulfur
loading, the capacity loss during the first discharge is approximately 30
%. The detailed mechanism for capacity degradation is still unclear,
restricting the further targeted improvement for advanced Li-S batteries.
Exploring capacity deterioration and battery failure mechanisms is of
significant importance, as it aids in formulating appropriate remedies
for enhancing battery performance. Huang and co-workers employed
the EIS-GITT method to analyze the kinetic limiting steps in the
discharge process of Li-S batteries, revealing that activation polarization
during lithium sulfide nucleation emerges as the dominant polarization
as the electrolyte-to-sulfur ratio (E/S ratio) decreases, and the sluggish
interfacial charge transfer kinetics is identified as the main reason for
degraded cell performances under lean-electrolyte conditions[32].
Similarly, Lu and colleagues utilized XRF with XAS revealed that cata­
strophic failure of high-energy Li-S pouch cell results from uneven sul­
fur/polysulfide reactions and electrolyte depletion for the first tens of
cycles[33]. Zhang also found similar conclusions in his study, with the
help of SEM he concluded that the non-uniformity distribution of sulfur
and lithium upon cycling is probed as one of the origins for the rapid
capacity fading in a Li–S pouch cell[34]. However, the aforementioned
work uses electrochemical and spectral characteristics to qualitatively
analyze the related failure behavior of Li-S batteries. It is challenging to
quantitatively and continuously monitor the change process of sulfur-
containing components during discharge. Simultaneously, the quanti­
tative analysis of sulfur-containing components allows for a continuous
exploration of the operational characteristics of Li–S batteries. Li used
EDX to examine sulfur changes at the cathode during battery operation,
the results showing that the formation and accumulation of noncon­
ductive Li2S2/Li2S films were the main reason of rapid capacity fade in
liquid-type Li–S batteries[35]. Quantitative analysis by Wang employed
the XPS technique pointed out that the reduction of Li2S4 to a Li2S2-Li2S
solid, with an almost constant ratio of 1:4, is the potential-limiting step
under lean electrolyte conditions[36]. Unfortunately, EDX and XPS can
only provide semi-quantitative analysis in the microscopic region, and
the results are significantly influenced by the material’s microscopic
region, hindering the acquisition of effective information on a macro
scale and impeding horizontal comparisons. This limitation restricts the
generalizability of this method. Meanwhile, Huang determined the
distribution of different sulfur-containing components in the cell using
inductively coupled plasma emission spectrometer (ICP) thermal
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gravimetric analysis (TGA) and elemental analyzer (EA), the sulfur
content in the electrolyte and cathode side of Li-S batteries after
charging and discharging was studied, showing the unique behavior of
high energy density lithium-sulfur batteries[37]. However, due to sys­
tematic errors in the experimental design, such as the inability to
exclude the interference of elemental sulfur in lithium salts in the
electrolyte by testing the total sulfur concentration in the electrolyte via
ICP, then, since sulfur is difficult to fully combust during ICP testing, it is
difficult to obtain stable and valid test results, and the accuracy of the
total sulfur content in the electrode tested by elemental analysis, as well
as the accuracy of the calculation of Li2S via the subtraction method is
difficult to be guaranteed, therefore, the applicability of this method is
limited. To sum up, since the capacity loss of the battery is entirely
linked to sulfur changes, which vary during operation and move be­
tween different parts of the cell under the influence of concentration
gradients and electric potential[34,38–40], this complex process makes
it difficult to model the corresponding distribution evolution of sulfur-
containing components. There is still a lack of systematic analysis
method for the distribution and content of sulfur-containing compo­
nents in batteries. The in-depth analysis of this problem is helpful to
further explore the working and failure mechanism of high energy
density Li-S batteries.
In this paper, we propose a graded leaching and quantitative deter­
mination method for complex sulfur components in Li-S batteries. This
method achieves a detection accuracy of over 99.11 % for sulfur-
containing components across all cell components, representing a sig­
nificant advancement over reported methods. Concurrently, we delve
into the underlying causes behind the initial capacity degradation
observed in Li-S batteries. Following the initial discharge, the presence
of lithium polysulfides (LPS) in the electrolyte emerges as the primary
factor hindering the full utilization of batteries capacity. This work not
only accounts for the initial capacity degradation of Li-S batteries, but
also provides a systematic evaluation method for investigating Li-S
batteries with high energy densities.
2. Materials and methods
2.1. Materials
The commercial ether electrolyte was obtained from DoDoChem.
The experimental manganese dioxide (98.8 %), barium chloride (99.5
%), toluene (99.5 %), benzene (99.8 %), and 25 %-28 % Ammonia liquor
were procured from Sinopharm reagent. Sublimed sulfur (99.95 %), 1,2-
Dimethoxyethane (99.5 %), lithium sulfide, and carbon disulfide (99.5
%) were purchased from Aladdin. All raw materials were used without
additional purification, sourced from commercial suppliers.
2.2. Preparation of sulfur/carbon cathodes
The mesoporous carbon materials in our experiment were prepared
based on our previously reported work. The 25 wt% mesoporous carbon
material and 75 wt% sulfur powder was weighed accurately using a
balance, and the appropriate amount of CS2 was added and ground
thoroughly in a fume hood. The well-mixed materials were transferred
to a sealed stainless steel tank and then held in a muffle furnace at 160 ◦ C
for 2 h. After cooling, the sulfur/mesoporous carbon composites were
obtained.
The sulfur/mesoporous carbon composite, acetylene black, and
polyvinylidene fluoride (PVDF) were mixed well by dry grinding in a
mortar and pestle at a mass ratio of 90:5:5 for 8–10 min. The mixture
Z. Li et al.
was then transferred to a small beaker, added dropwise with an appro­
priate amount of NMP, and stirred for 10–12 min using a homogenizer
(knife head speed set to 12.5–14 kr min− 1). The stirred slurry was evenly
coated on the clean aluminum foil by a squeegee and then dried in an
oven at 45 ◦ C for 12 h until the NMP evaporated completely. The sulfur-
carbon cathode was subsequently cut into disks with a diameter of 13
mm by a tablet press. The areal loading of active sulfur was around 5.2
mg cm− 2.
2.3. Assembly and electrochemical test of Li–S cells
The Li-S coin cells (CR2032) were assembled by the sulfur-carbon
composite cathode, lithium anode, and separator (Celgard 2320). The
electrolyte was composed of 1 M lithium bis (trifluoromethane sulfonyl)
imide (LiTFSI) in a solvent made up of 1,3-dioxolane (DOL) and ethylene
glycol dimethyl ether (DME) (volume ratio, 1:1), with 1 wt% LiNO3. The
electrolyte amount was approximately 8 μL mg−s 1. The cells were dis­
charged to different DOD on the LAND test system (Wuhan, China) at
0.01C. The electrochemical impedance spectroscopy (EIS) was tested in
the frequency range 0.01 Hz-100 kHz.
2.4. Detection of sulfur-containing components
The cell disassembly and separation of sulfur components were
carried out in a glove box under Ar gas atmosphere with the partial
pressure of H2O and O2 less than 0.01 ppm. The cells were disassembled
into cathode, anode, separators and coin shell.
Initially, the three distinct battery components were introduced into
three glass container and subsequently treated with a predetermined
quantity of DME for a duration of 30 min, the bottle is soluble inter­
mediate product of lithium polysulfide (Li2Sn, 2 < n ≤ 8). The three
types of battery components were individually dried and subsequently
placed in separate glass containers containing a specific amount of
toluene for one hour. The solution in the bottle was the toluene solution
of the S8. The final battery components are placed in an empty glass
bottle and sealed, marking the completion of sulfur-containing compo­
nent dissolution and separation.
Each sulfur-containing component was oxidized under alkaline
conditions with hydrogen peroxide, followed by the addition of an
appropriate amount of manganese dioxide to scavenge any residual
hydrogen peroxide. The resulting oxidized solution was then adjusted to
a volume of 100 mL using a volumetric flask and reserved for future use.
The sample was filtered with a 0.45 um filter membrane before
titration. Potentiometric titration calibrates the instrument with a 1000
ppm standard solution before each test to minimize unnecessary errors.
The addition rate during titration is 0.5 mL/min, and the signal drift is
set to 50 mV/min.
The specific test procedure was as follows:
(1) Introduce 2 mL of BaCl2 solution into a beaker and then add a
suitable quantity of distilled water into the mixture, followed by
the addition of 5 mL of pH 10 ammonia-chloride buffer solution.
Initiate stirring for a duration of 3 min to ensure proper homog­
enization. Subsequently, employ potentiometric titration utiliz­
ing an EGTA solution as the titrant.
Blank(mL) = EP1
(2) Accurately transfer a certain volume of the 1000 ppm standard
solution using a precision pipette and transfer tube. Add an
appropriate amount of deionized water to the solution, followed
by adjusting the pH of the sample to below 4 using a 2 M HCl
solution. Subsequently, introduce 2 mL of BaCl2 solution and
initiate stirring for a duration of 3 min to ensure complete pre­
cipitation. Following this, incorporate 5 mL of ammonia-chloride
buffer solution with a pH of 10 into the mixture and continue
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Journal of Colloid And Interface Science 662 (2024) 1086–1095
stirring for an additional minute. Finally, conduct potentiometric
titration using an EGTA solution as the titrant.
SO2−
4 (g/L) = (Blank-EP2) * CEGTA * Titer * M(SO4)/Sample size
EP2———————————— equivalence point volume, mL
Blank———————————— EP1, mL
Titer———————————— Titration coefficients, including so­
lution configuration errors as well as systematic errors
CEGTA ———————————— Theoretical concentration of
EGTA
M(SO4) ———————————— Molar mass of SO2− 4 , 96.0626 g/
mol
In this process, the titration coefficient is obtained by titrating the
standard solution and used for subsequent detection.
(3) The procedure is the same as 2, replace the standard solution with
the sample to be tested.
SO2−
4 (g/L) = (Blank-EP3) * CEGTA * Titer * M(SO4)/Sample size
2.5. Material characterization
The treated electrodes are characterized by the Scanning electron
microscope (SEM, MIRA4 LMH), X-ray photoelectron spectroscopy
(XPS, Thermo Scientific K-Alpha), X-ray diffraction (XRD, PANalytical
Empyren). Determination of sulfur content in electrode by Inductively
coupled plasma spectrometer (ICP-OES SPECTRO BLUE SOP), Elemental
Analyzer (EA, Vario EL III, German) in CHNS mode. The concentration
of SO2−
4 was tested by potentiometric titration (Metrohm 905).
3. Results and discussion
This work categorizes sulfur-containing components in Li-S batteries
into three groups: (1) The initial active material: this group comprises
the S8 molecules that serve as the starting active material in the Li-S
battery; (2) The intermediate product: a soluble compound Lithium
Polysulfide (LPS) that formed during the battery operation, which per­
forms as a transitional state between the initial S8 and the final Li2S; (3)
The final product: The insoluble final product Li2S generated during
discharge process.
The cell components are categorized into three main parts: cathode,
anode, separators and coin shell. The comprehensive procedural over­
view is depicted in Fig. 1, the process entails the following streamlined
steps: (1) Selective solvent extraction: optimization of solvent is made to
individually extract S8, LPS, and Li2S from distinct parts of the cell. (2)
Oxidation to Sulfate (SO2− 4 ): Subsequently, the extracted sulfur-
containing components (S8, LPS, and Li2S) undergo oxidation, result­
ing in the formation of SO2−
4 . This oxidation process is carried out under
alkaline conditions using hydrogen peroxide. (3) Accurate SO2− 4 con­
centration analysis: The process of precipitating SO2− 4 is meticulously
carried out by introducing a precise quantity of Ba2+, subsequently, the
remaining Ba2+ within the system were meticulously quantified through
potentiometric titration using EGTA, enabling the accurate calculation
and derivation of the sulfate ion concentration (SO2− 4 ) in the system.
Following these steps, we have successfully achieved the graded leach­
ing and precise quantitative detection of distinct sulfur-containing
components within various cell subassemblies.
A suitable leaching solvent is meticulously chosen based on its
physicochemical attributes to enable selective leaching. In the experi­
ments, the concentration of LPS in DME can reach 0.2 M or even higher,
while the solubility of S8 and Li2S in DME is less than 10 ppm
(Figure S1), a difference of nearly four orders of magnitude, i indicating
the feasibility of employing DME to leach LPS, while the large solubility
difference avoids the premature precipitation of other sulfur-containing
Z. Li et al. Journal of Colloid And Interface Science 662 (2024) 1086–1095

Fig. 1. Schematic diagram of working principle of the whole process of separation, oxidation and detection.

components during LPS leaching. The efficacy of extracting S8 from the
cathode was assessed through a systematic exploration involving diverse
solvents, varying leaching durations, and temperatures. This investiga­
tive process is visually presented in Fig. 2a-e. The leaching efficiency of
S8 using methylbenzene, benzene, and carbon disulfide (CS2) displayed
minor reduction at 25℃, 35℃, and 45℃. Notably, an extended leaching
duration led to gradual fluctuations in leaching efficiency, nevertheless,
all measurements consistently remained above 98 %. Consequently,
methylbenzene, benzene, and CS2 emerge as prime candidates, repre­
senting optimal selections for achieving exceptionally efficient leaching
of S8 from the cathode.
To eliminate possible interference from Li2S during S8 leaching, the
selected organic solvent must have low solubility towards Li2S, ensuring
selective leaching of 8. CS2 was excluded due to its potential
introduction of sulfur atoms, which could disrupt with subsequent de­
terminations. This exclusion is detailed in Figure S2, illustrating the
visual dissolution behavior of Li2S in the remaining two organic sol­
vents. Li2S demonstrates minimal solubility in both benzene and meth­
ylbenzene, precipitating at the solution’s bottom after a 1 h soaking
period. The sulfur content of surface solution was quantified as shown
Fig. 2f. The findings revealed an exceedingly low sulfur content. At the
same time, the solubility of S8 in both solutions was examined, and the
three orders of magnitude difference in solubility between S8 and Li2S
affirming that the leaching S8 process with benzene and methylbenzene
does not result in Li2S loss. So benzene and methylbenzene are a
favorable candidate for leaching S8.
Considering both toxicity and separation efficiency, it was concluded
that a temperature of 25 ◦ C and a duration of 1 h constitute an optimal

Fig. 2. The leaching efficiency of S8 in different polar solvents at different temperatures (a) 25℃, (b) 35℃, (c) 45℃ during 1 h; The leaching efficiency of S8 in (d)
Methylbenzene and (e) Benzene under different leaching time; (f) Saturated sulfur concentrations of S8/Li2S in methylbenzene and benzene, respectively. The
experiment was repeated three times to determine the mean value and the corresponding error bar.

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Z. Li et al.
combination for effectively distinguishing S8 from Li2S. As a result, the
combination of DME with methylbenzene emerges as a viable approach
to achieve efficient separation of sulfur-containing components.
The following specific reaction equation[41] were utilized to oxidize
the sulfur-containing components to SO2− 4 for the next step of accurate
testing. By examining the oxidation process and the oxidation efficiency
at different temperatures (Figure S3), it was found that the oxidation
efficiency depends on the degree of contact between sulfur and the
oxidizing agent and the vigor of the reaction. Lower temperatures make
it difficult for sulfur to dissolve in alkaline solutions, resulting in
insufficient contact with the oxidizing agent, leading to lower oxidation
efficiencies. Higher temperature makes the oxidant decompose prema­
turely, resulting in insufficient oxidation efficiency to meet the experi­
mental requirements, and is difficult to repeat on a large scale, which is
not conducive to subsequent testing. Therefore, ethanol was used as the
mixed solvent, the sulfur-containing components dissolved in DME or
methylbenzene and the alkaline solution were in liquid–liquid contact in
an ethanol-rich environment to complete the high-efficiency oxidation.
S2− + 4H2O2 = SO2−
4 + 4H2O (1)
S + 3H2O2 + 2OH− = SO2−
4 + 4H2O (2)
S2−
x
−
+ (3x + 1) H2O2 + (2x-2) OH = xSO2−
4 + 4xH2O (3)
In the meticulous quantitative evaluation of the overall sulfur con­
tent within cathodes, prevalent methodologies heretofore encompass
Elemental Analysis (EA), Inductively Coupled Plasma (ICP), turbidi­
metric technique and X-ray photoelectron spectroscopy (XPS). The
turbidimetric approach, being unduly reliant on the subjective expertise
of the examiner, and XPS, fraught with substantial constraints in liquid
sample detection, are hereby excluded from consideration. Fig. 3a il­
lustrates the total sulfur content within the cathode as determined by the
EA, ICP, and PT methods, respectively. It’s noticeable that the measured
values tend to be elevated, potentially attributed to quality deviations
stemming from the non-uniformity of the aluminum foil and the
inherent bias of the detection method. Intriguingly, the EA, ICP method
exhibits a notably greater margin of error compared to PT, reaching up
Fig. 3. (a) Comparison of different detection methods for accurate detection of sulfur content in cathodes. (b) The response of the standard SO2−
different concentrations was detected by ICP and PT, respectively. (c) Typical potentiometric titration curves and (d) Measurement of detection accuracy. The
experiment was repeated three times to determine the mean value and the corresponding error bar.
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Journal of Colloid And Interface Science 662 (2024) 1086–1095
to 8.24 %, 3.24 %. Not only that, they are larger data fluctuation, in
comparison Potentiometric Titration offers superior precision and sta­
bility. Subsequently, the precise assessment of distinct different con­
centrations of SO2−
4 standard solution, depicted in Fig. 3b, in comparison
to ICP, PT exhibit a notably closer alignment with theoretical values.
This method enables the meticulous quantitative analysis of samples
spanning the range of 10–1000 ppm. The detection curve, established
based on the outcomes of sample tests, showcases an impressive con­
sistency at 99.71 %, signifying an exceptional level of reliability. Lastly,
the presence of Li2S within the cathode after cycling posed significant
challenges for EA testing (Li2S requiring an oxygen-free environment),
the low sensitivity and detection of elemental sulfur by ICP depends on
the standardization of the inspector and the accuracy of the instrument,
neither EA nor ICP can distinguish the sulfur in the lithium salt from the
target sulfur-containing components efficiently, therefore, precise
determination of SO2− 4 was performed by potentiometric titration.
A representative potentiometric titration graph is depicted in Fig. 3c.
As the titrant (EGTA) is gradually introduced, the Ba2+ within the so­
lution are progressively utilized, leading to a gradual decrease in po­
tential. A sudden and distinct change in potential occurs upon complete
consumption of Ba2+, at this juncture, the volume of consumed EGTA is
known as the equivalence point. The concentration of SO2− 4 can be
deduced from the difference between the equivalent points before and
after the addition of SO2− 4 to the system. In addition, the sensitivity of
the method was detected by titration of different volumes of BaCl2 (0.02
M/L). Equivalent points obtained by titrating 1.9, 1.95, 1.975, 1.99, 2
mL of BaCl2 solution are shown in Fig. 3d. Notably, the response values
showcasing a robust linear correlation across each concentration. the
achieved consistency level stood at an impressive 99.90 %. This degree
of accuracy aptly fulfills the specified testing requisites. Therefore, the
synergistic application of oxidative separation and potentiometric
titration emerges as an exceedingly efficient approach for the quanti­
tative detection of sulfur-containing components.
Hence, employing a systematic approach involving graded leaching,
high-efficiency oxidation, and potentiometric titration for the quanti­
tative detection of sulfur-containing components in cells can be outlined
as follows: Initially, cells are meticulously disassembled within a glove
4 samples with
Z. Li et al.
box, and the LPS in the cathode, anode, separators, and coin shell are
dissolved by soaking three times in a specific amount of DME for 30 min.
The three subassemblies are then separately immersed in methyl­
benzene for 1 h, ensuring the complete dissolution of S8, leaving solely
insoluble Li2S. The next step involves the oxidation of these sulfur-
containing components using hydrogen peroxide (H2O2) in an alkaline
environment. Then, the oxidized solution containing SO2− 4 was metic­
ulously adjusted to a fixed volume. Ultimately, the oxidation solution
undergoes meticulous potentiometric titration, enabling the precise
determination of equivalent SO2− 4 quantities corresponding to distinct
sulfur-containing components present in various cell components.
The accuracy of the separation and detection of each sulfur-
containing component of the whole process was systematically evalu­
ated. First, the post-cycled electrode underwent three washes with DME
to ensure complete leaching of LPS. The sulfur content in the washing
solution and the DME of the fourth rinsed electrode was then separately
detected, as depicted in Fig. 4a, the significant difference of two orders
of magnitude in the sulfur content indicated that the LPS could be
completely leached out after three times of washing with DME. Subse­
quently, different ratios of S8:Li2S electrode were prepared, separately,
and the sulfur content was detected by oxidation after leaching with
methylbenzene, as shown in Fig. 4b-d. When compared with the theo­
retical values, the detected values were found to be lower. Upon careful
analysis observed that the ratio of the loss of S8 to Li2S was close to 3.5,
this loss of sulfur was attributed to a part of the spontaneous reaction of
S8 and Li2S to generate L2S6. Despite this, the total detection accuracy
remained objective. Finally, the detection rate of sulfur-containing
components reached an astonishing 99.11 % when testing the post-
cycling cell using this method, as demonstrated in Table S1. The inno­
vative approach adeptly achieves the graded leaching and quantitative
detection of active materials within cells. By establishing a robust
theoretical and methodological foundation, this novel technique offers
invaluable support for subsequent research endeavors.
The cells were discharged to different states at 0.01C, as illustrated in
Fig. 5a, which presents a typical discharge profile of a Li-S battery.
Specifically, certain parts of the cell were discharged until the end of the
first plateau (point E), while others reached the middle of the second
Fig. 4. (a) Sulfur Concentration in LPS Leachate and Post-leaching DME. (b) Detected values of elemental sulfur in electrodes with a mass ratio of S8 to Li2S of 6:2. (c)
Detected values of elemental sulfur in electrodes with a mass ratio of S8 to Li2S of 3:3 and (d) Detected values of elemental sulfur in electrodes with a mass ratio of S8
to Li2S of 2:6. The experiment was repeated three times to determine the mean value and the corresponding error bar.
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Journal of Colloid And Interface Science 662 (2024) 1086–1095
plateau (point F), the remaining portion was discharged until reaching a
cut-off voltage of 1.7 V (point H). Concurrently, a comprehensive
disassembly of cells at different states was performed, seeking to unravel
the intricate operational mechanisms of Li-S batteries. This investigation
scrutinized electrode macro-morphology, spatial distribution variations
and analysis of sulfur species, as well as the ultimate states of lithium
polysulfides.
Initially, the macroscopic and qualitative components change within
cells in different states were examined. The cathode surface, discharged
to the end of the first plateau in Fig. 5b, exhibited a coating of red-brown
liquid resembling prepared LPS in color. This occurrence may be
attributed to S8 reduced to LPS and becoming soluble in electrolyte. The
middle section of the cathode on the second platform did not exhibit the
same red-brown liquid, and the color of the separators became signifi­
cantly lighter due to LPS reduction and shuttle. Additionally, a portion
of yellowish solid was deposited onto the separator surface, presumed to
be Li2S, while non-uniform distribution of yellowish particles could also
be observed on the cathode surface. At the end of discharge, the sepa­
rators’ color was even lighter, replaced by a layer of yellowish deposits,
and similar yellowish solid deposits are present on the surface of the
cathode. The transformation of active materials on the cathode surface
during discharge was subjected to an extensive analysis utilizing quasi-
in situ X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy
(XPS). In the initial discharge phase, sulfur primarily exists in the form of
S8. As the discharge progresses to the terminus of the first plateau,
conventional XRD observations struggle to discern any identifiable form
of sulfur. At this juncture, S8 undergoes reduction, transforming into LPS
and dispersing freely within the electrolyte. As a result, the sulfur con­
tent becomes insufficient to register above the detection threshold of the
XRD. The XPS spectrum captured at point E corroborates the substantial
reduction of the S8 component, accompanied by the emergence of Li2S2.
As the discharge proceeds deeper, a discernible peak corresponding to
Li2S gradually becomes apparent within the XRD pattern. Concurrently,
the XPS analysis indicates a progressive rise in the Li2S content. These
collective observations strongly imply that LPS undergoes gradual
reduction and deposition onto the cathode surface throughout this
evolving process. At the same time, the yellowish deposits on the
Z. Li et al. Journal of Colloid And Interface Science 662 (2024) 1086–1095

Fig. 5. (a) Discharge curve of Li-S battery and (b) optical photos, (c) XRD and (d) XPS spectra of cathode under different discharge stages.

separators during the discharge also caught our attention. The
morphology and composition of the particle are further studied.
Figure S4 shows that some of the holes on the surface of the separators
are covered by a layer of lumpy material. After further confirmation by
XPS (Figure S5), part of the substance is Li2S2 and the rest is mainly due
to the oxidation of polysulfide lithium by lithium nitrate and the
decomposition of lithium salt LiTFSI. Li2S2 on the separators indicates
that some LPS was not deposited at the cathode during the reduction
process. Since the separators are not conductive, it is difficult for Li2S2 to
participate in the subsequent reaction, resulting in the loss of active
material. The accumulation of by-products on the surface of the sepa­
rators may lead to the blockage of ionic transport, affecting the opera­
tion of the battery.
Next, the microcosmic morphology of the cathode in varying states
was meticulously examined through scanning electron microscopy, as
illustrated in Fig. 6. In the initial discharge phase, a noteworthy trans­
formation unfolds, marked by the reduction of sulfur within the meso­
porous carbon framework, as depicted in Fig. 6a. This discharge process
leaves behind solely the intricate, honeycomb-like mesoporous carbon
hosts, characterized by a thickness measuring 129 μm (Fig. 6i, 6d). Thus,
as previously understood that S8 is rapidly reduced to LPS from the
beginning of discharge, resulting in the formation of a highly concen­
trated LPS solution, visibly manifesting as reddish-brown. Upon dis­
charging to the midpoint of the second plateau, the honeycomb porous
morphology disappears and a layer of solids is deposited on some parts
of the mesoporous carbon surface, as shown in Fig. 6b. This discernible
layer is primarily composed of insoluble Li2S, aligning with the over­
arching macroscopic scenario. Importantly, this observation suggests

Fig. 6. Microscopic morphology of the cathode at different discharge stages. (a) plane and (d) cross-sectional view of the cathode at the end of the first platform, (i)
partially enlarged the plane; (b) plane and (e) cross-sectional view of the cathode at the middle of the second platform; (c) plane and (f) cross-sectional view of the
cathode at the end of the first discharge.

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Z. Li et al.
that the reduction of LPS is non-uniform, a phenomenon likely influ­
enced by host surface morphology and conductivity. The conducting
framework gradually fades from view as the discharge completed.
Simultaneously, the porous carbon structure undergoes a comprehen­
sive coverage and cross-linkage, unifying into a cohesive and integrated
entity, vividly captured in Fig. 6c. This compelling observation indicates
that LPS experiences reduction and subsequent deposition onto the
cathode surface, as opposed to being generated in the porous carbon as
previously speculated. Moreover, the discharge process is accompanied
by a noticeable thickening of the cathode, attributed to Li2S deposition.
This transformation is accompanied by the emergence of microcracks,
depicted in Fig. 6e-f. These structural alterations may potentially
contribute to a decrease in cell stability over time. Simultaneously, the
discharged lithium anode assumes a conventional de-lithiation state
morphology, as visually captured in Figure S6.
Thirdly, with the help of previously established methods for graded
leaching and quantitative detection, we systematically ascertain the
diverse types and precise concentrations of sulfur-containing compo­
nents within the cathode, anode, electrolyte, separators, and cell shells.
Following the above method, a substantial portion of S8 experiences
reduction and transitioning into LPS, which disperses freely within the
electrolyte upon reaching the end of the first plateau. As the discharge
progresses, this LPS undergoes further reduction, ultimately converting
into insoluble Li2S, this gradual transformation manifests as an incre­
mental accumulation of sulfur within the cathode. Consequently, by the
end of the discharge, a substantial 70.85 wt% of the original sulfur
content remains within the cathode. while 27.55 wt% is distributed
Fig. 7. Under different discharge states (a) Sulfur spatial distribution in cathode, anode, and others; (b) Variation in the content of different sulfur species; (c) The
changes of sulfur components and content in the cathode; (d) the discharge and charge profiles of the discharged electrolyte.
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Journal of Colloid And Interface Science 662 (2024) 1086–1095
elsewhere, encompassing non-conductive regions and the electrolyte.
Only a minor 1.6 wt% of the sulfur content persists within the anode, as
visually demonstrated in Fig. 7a. XPS also shows that the anode side
sulfur content is very small and the vast majority originate from the
decomposition of lithium salt LiTFSI (Figure S7). The presence of a small
amount of sulfur in the anode indicates that the active sulfur consumed
in the initial stage of discharge is very limited due to the shuttle effect.
However, it cannot be ignored that there is a large amount of sulfur in
the electrolyte and non-conductive parts, which is not completely
reduced and is the main factor leading to the loss of discharge capacity.
Several factors contribute to the presence of large amounts of sulfur at
these sites, such as insufficient electrical contact of the discharge in­
termediates with the conducting substrate, diffusion of the LPS under
the concentration gradient, slow reduction kinetics and high reduction
energy barriers[32] and so on.
Fig. 7b presents a comprehensive analysis of the sulfur-containing
components, elucidating their specific species and concentrations. At
the end of the first plateau, only 2.05 wt% of sulfur remains as S8,
indicating a significant 97.95 wt% reduction from the initial active
material state. In this context, 96.66 wt% of sulfur exists as LPS, while a
minor proportion in the form of Li2S. This intriguing distribution sug­
gests a multifaceted reaction scenario during discharge, as opposed to a
gradual reduction process occurring progressively over time. With
further reduction in voltage, a discernible trend emerged: the LPS con­
tent exhibited a gradual decline, diminishing from 96.66 wt% at the first
plateau’s culmination to 43.05 wt% at the midpoint of the second
plateau, ultimately, the LPS content reduced to 26.34 wt% after
Z. Li et al.
discharged. This dynamic shift occurred concomitantly with a steady
increment in Li2S concentration. By the end of the discharge, Li2S
constituted 71.12 wt% of the total sulfur content. This pattern of
transformation is in harmony with the earlier qualitative observations
derived from optical photographs and SEM. At the termination of
discharge, it is noteworthy that 26.34 wt% of sulfur remained dissoci­
ated in the electrolyte as LPS. The result underscores that more than a
quarter of the sulfur did not undergo complete discharge trans­
formation, remaining in the form of long-chain lithium polysulfide and
keep free after discharge. This phenomenon is likely attributed to mul­
tiple factors, encompassing concentration gradients and the possible
migration of LPS to regions distant from the conductive network, or
potentially hindered by sluggish reduction kinetics. The theoretical
specific capacity of 1675 mAh g− 1 translates to approximately 1200
mAh g− 1 during the initial discharge. The observed actual specific ca­
pacity, approximately 71.64 % of the theoretical value, harmoniously
corresponds to the Li2S content, which is 71.12 wt% during the first
discharge. Therefore, the main reason for the loss of the first discharge
capacity of the battery is that approximately 26.34 wt% of the sulfur
remains in the electrolyte in the form of LPS and not living up to their
potential.
Fig. 7c illustrates the evolution of various sulfur species within the
cathode. Importantly, S8 undergoes rapid reduction, resulting in a
minimal presence of both S8 and Li2S on the cathode at the end of the
first plateau. With further reduction in potential, LPS was gradually
reduced and the content of Li2S was gradually increased, aligning
harmoniously with the macroscopic and microscopic observations pre­
sented earlier. To discern the specific nature of LPS at discharge’s
termination, quantitative LPS solutions were subjected to charge and
discharge measurements, as illustrated in Fig. 7d. The particular sulfur
species can be deduced by comparing discharge and charge capacities.
In this context, LPS exhibits a discharge capacity of 6 μAh and a charge
capacity of 3 μAh, the discharge-to-charge capacity ratio is 2. This cor­
respondence corresponds to the attributes of Li2S3. Therefore, it can be
concluded that the remaining LPS within the cells at the discharge’s
conclusion is indeed Li2S3.
Fourthly, during the discharge process, there are continuous fluctu­
ations in the internal impedance of the cell. While various conjectures
have been proposed to explain these variations, none have been sup­
ported by substantiated evidence. In this section, a detailed evaluation
of sulfur-containing components within each cell part is conducted, and
this systematic approach can establish a discernible connection between
the evolving impedance and the internal material transformations
transpiring within the battery.
Semi-in situ Electrochemical Impedance Spectroscopy (EIS) was
conducted at varying discharge depths and subsequently analyzed using
a correlated equivalent circuit, as depicted in Fig. 8. As the reaction
Fig. 8. (a) Nyquist plots of a Li-S battery at various states of discharge during the first cycle; (b) Plots depicting the electrolyte resistance (Re), interphase contact
resistance (Rint), and charge-transfer resistance (Rct) as functions of depth of discharge in the first cycle.
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Journal of Colloid And Interface Science 662 (2024) 1086–1095
progresses from point A to H, involving the reduction of S8 to LPS and
then to Li2S, the generation and consumption of LPS (decreasing from
96.66 wt% to 26.34 wt%) cause an initial surge followed by a gradual
decline in electrolyte viscosity. This dynamic viscosity shift is mirrored
by the corresponding ascent and descent in electrolyte resistance (Re).
Furthermore, the alterations in contact resistance (Rint) are intrinsically
connected to the transformations occurring within the electrode. The
upsurge in Rint can be attributed to initial particle rearrangements
during the discharge. As the S8 diminishes and evolves into LPS, the
proportion of poorly conductive S8 dwindles to 2.05 wt%, thereby
reducing the Rint. The content of Li2S on the cathode experiences a
gradual ascent from 1.04 wt% at the first plateau’s conclusion (point E)
to 69.29 wt% upon discharge’s culmination (point H), as vividly
depicted in Fig. 7c. The charge transfer reaction (Rct) takes place at the
interface between the conductive additive and the electrolyte. Hence,
the notable upsurge in Rct is likely intertwined with the accumulation
and agglomeration of Li2S, due to its insulating nature, consumption of
S8 and deposition of Li2S on the cathode leads to fluctuate in Rct,
contributing to the reduction of the conductive surface area on the
cathode. This phenomenon subsequently hinders ion transport towards
the cathode interior, thereby impeding the kinetics of the transfer re­
action. This trend is consistent with the quantitative analysis of Li2S
changes and the optical images captured by SEM, ultimately, the cath­
ode’s surface is completely covered by insulating precipitates.
The insights gleaned from the preceding analyses demonstrate the
efficacy of the devised graded leaching technique for sulfur-containing
components and the precision of quantitative detection techniques in
comprehending the operational nuances of Li-S batteries. At the end of
the discharge, in addition to the significant presence of Li2S in the
cathode, a notable portion (26.34 wt%) of sulfur persists in the elec­
trolyte as LPS, indicating incomplete discharge, electrical contact dis­
ruptions, slow kinetics, and the release of LPS can potentially exacerbate
this phenomenon. Notably, the operational and failure mechanisms of
high-sulfur-loading batteries markedly diverge from those of conven­
tional batteries, requiring more credible characterization and analysis
approaches. This study proffers a comprehensive analytical framework
for appraising Li-S batteries, aiming to inspire future research endeavors
in this field.
4. Conclusions
In this study, we devised a graded leaching approach for sulfur-
containing components, coupled with precise quantitative detection
techniques, achieving an impressive 99.11 % detection rate for sulfur-
containing components in the battery. This overcomes the limitations
of low precision and poor repeatability found in previous methods[37].
Essentially, this approach distinguishes various sulfur-containing
Z. Li et al.
components and quantifies their concentrations, when combined with
the specific electrochemical state, we can get more information about
the working process of Li-S batteries. By employing this method, we
determined that 26.34 wt% of sulfur persisted in the electrolyte after
discharge, indicating an incomplete discharge process. This finding
identified the factor contributing to the initial capacity degradation of
Li-S batteries. Building on this understanding, potential improvements
can be identified, such as optimizing the structure and polarity of the
host to restrict the LPS, enhancing overall conductivity, and introducing
catalysts to expedite LPS reduction kinetics. In the future, we can
quantitatively evaluate the catalytic performance of various catalytic
materials by this method. It allows for the study of the operation and
failure mechanism of Li-S batteries in different systems under practical
conditions. This effort provides new insights into the operational in­
tricacies of Li-S batteries, carrying significant practical implications.
CRediT authorship contribution statement
Zhaoyang Li: Writing – review & editing, Writing – original draft,
Visualization, Methodology, Investigation, Data curation, Conceptuali­
zation. Mengran Wang: Writing – review & editing, Supervision,
Formal analysis. Jiewei Yang: Validation, Investigation, Data curation.
Bo Hong: Writing – review & editing, Methodology, Funding acquisi­
tion. Yanqing Lai: Writing – review & editing, Supervision, Funding
acquisition. Jie Li: Writing – review & editing, Supervision.
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
The data that has been used is confidential.
Acknowledgments
This work is supported from the National Natural Science Founda­
tion of China (No. 52174287), the National Natural Science Foundation
of China (52034011 and 52101278).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jcis.2024.02.017.
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