Accepted Manuscript

A Convenient and Efficient Mass-Production Strategy to Fabricate Sustainable

Yuanguo Wu, Xingbao Zhu, Weihua Wan, Yu Wang, Xin Ji, Xingyu Pan, Zhe Lü

PII: S0013-4686(18)32709-9

DOI: 10.1016/j.electacta.2018.12.011

Reference: EA 33226

To appear in: Electrochimica Acta

Received Date: 25 July 2018

Accepted Date: 02 December 2018

Please cite this article as: Yuanguo Wu, Xingbao Zhu, Weihua Wan, Yu Wang, Xin Ji, Xingyu Pan,
Zhe Lü, A Convenient and Efficient Mass-Production Strategy to Fabricate Sustainable Cathodes
for Lithium–Oxygen Batteries: Sucrose-Derived Active Carbon Coating Technology, Electrochimica
Acta (2018), doi: 10.1016/j.electacta.2018.12.011

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form.
Please note that during the production process errors may be discovered which could affect the
content, and all legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT

A Convenient and Efficient Mass-Production Strategy to

Lüa

a Department of Physics, Harbin Institute of Technology, Harbin 150080, People’s Republic of China

b School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150000, China

c State Key Laboratory of Advanced Chemical Power Sources, Zunyi 563000, China

Abstract

In this study, we report an eco-friendly and cost-efficient cathode based on

sucrose-derived active carbon (SDAC). Ni(NO3)2 is then co-impregnated into the

cathode, which is designed to form a hierarchical pore architecture inside the SDAC

that takes into account both the mass transport process of O2/Li+ and the

accommodation of discharge product (Li2O2). Another feature of the cathode is binder-

free that circumvents the aggregation of the cathodic active materials and the three-

phase boundaries loss. This study is aimed to provide a feasible reference plan to give

common cathode substrates an additional capability to catalyze electrochemical

reactions without destroying its pristine structure and mission. A lithium–oxygen

battery with the cathode delivers a high capacity of 24500 mAh g-1 at 200 mA g-1 in a

1 M LiTFSI/TEGDME electrolyte system. Moreover, the cathode exhibits a pretty good

Corresponding author. Tel.: +86 451 86418420; fax: +86 451 86418420

E-mail addresses: [email protected] (X. Zhu)

1
 ACCEPTED MANUSCRIPT

stability in a long-term round-trip test of 1000 cycles. These results suggest that the

SDAC with a hierarchical pore structure has the potential to be used in next-generation

lithium–oxygen batteries in a facile and cost-efficient manner, moreover, the proposed

convenient method is worth applying and popularizing as it can transform even the most

mundane into the spectacular.

Key words: Lithium–air battery; Substrate optimizing; Sucrose; Carbon material; bimodal pore

structure

1. Introduction

With the rapid advancement of portable electric devices, especially electric-

vehicle industry, the demand for new electric energy storage system has dramatically

increased. However, the conventional lithium–ion batteries (LIBs) have fallen short of

power and energy because of its theoretical limitation [1]. Therefore, a new generation

of battery system has been proposed to alternate LIBs. As one of the most promising

candidates, lithium–oxygen batteries (LOBs) have been receiving world-wide attention,

due to its remarkable theoretical energy density (11400 Wh kg-1 excluded and 5200 Wh

kg-1 included O2) [2] which is 10-100 times larger than LIBs. Although the energy

density of LOBs is still lower than gasoline of 11860 Wh kg-1 [3], the operation

efficiency of the former is not limited by the maximum efficiency of the heat engine.

The ideal cathode reaction in LOBs can be described as 2Li﹢+ 2e﹣+ O2 ↔ Li2O2, at

this stage the reactant O2 was usually provided by an pure O2 carrier, so commonly

known as LOBs, but for the final target the battery can initiatively derive O2 from

ambient air. In this case, LOBs can also be called lithium–air batteries. In spite of these

great prospects, the development of LOBs is still in its infant stage with many obstacles

and unknown factors need to be identified and addressed [1,4,5]. (i) In the cathode, the

eletro-catalytically active points are prone to be passivated by insoluble discharge

2
 ACCEPTED MANUSCRIPT

product (Li2O2). (ii) The charge/discharge processes are always accompanied by side

reactions that cause the decomposition of cathode and electrolyte components, leading

to irreversible products like Li2CO3 and LiOH. (iii) Unlike conventional LIBs, the

LOBs are open systems in which the inevitable evaporation and leakage of liquid

electrolytes are guaranteed to accelerate the decay of batteries. (iv) Together with O2,

the CO2 and H2O from ambient air will dissolve in electrolyte solutions and thus

corrode the Li-metal surface [6-8].

Recent years, a great deal of researchers have focused on understanding the

mechanisms and improving the performance of LOBs and made some progress [9,10].

For electrolyte, the initial one is proposed based on carbonate solvent, which was

demonstrated to suffer from significant decomposition after several cycles, resulting in

an unsatisfactory cycleability [1]. Later, various kinds of electrolyte including DMSO,

DMC and TEGDME were reported continuously [10-12]. To now, the most popular

one is lithium triflate (LiTFSI) dissolved into TEGDME, which achieves a massive

improvement in stability. It can still maintain good and stable performance

characteristics even at relative high charge potential ~4.3 V [10]. In addition, solid-state

electrolyte is another majority category in LOBs. It was first reported by Kumar et al.

in 2009, and showed a high discharge potential and a low charge potential

corresponding to 2.8 V and 3.6 V [13]. Several new solid-state electrolyte materials like

LATP, LLZO and LLTO were successfully prepared and reported in these years [14,15].

As for cathode, researchers commonly focus on the catalytic activity, microstructure

and stability. Carbon-based materials with different morphologies, such as porous

carbon [16], graphene nanosheet (GN) [17], carbon nanotubes (CNTs) [18], carbon

nanofibers (CNFs) [19] and carbon powders (CP) [20], were investigated

systematically. In order to further accelerate the oxygen reduction reaction (ORR) and

3
 ACCEPTED MANUSCRIPT

oxygen evolution reaction (OER) of the cathodes, many kinds of catalyst were added

into these carbon-based materials, including transition metal oxides (FeOx, CoOx, NiOx)

[21-23], noble metal (Pt, Ru, Pd) [24-26] and other metal oxides (ZrO2, α-MnO2)

[27,28]. The results proved that the introduction of catalysts is an efficient way to

increase ORR activity during electrochemical reaction. Unfortunately, it may catalyze

side reaction at the same time, which aggravates the decomposition of cathode and

electrolyte. Actually, in order to avoid the inescapable oxidization of active carbon

materials owing to the present of O2﹣during discharge process, some researchers

attempted to develop non-carbon materials such as perovskite oxides [29,30]. Even so,

carbonaceous air cathodes are still advantageous because of their low cost, low weight,

good conductivity and quite high specific surface areas.

From previous literatures [31-33], we note that vast majority of cathodes are not

able to be free-standing, in other words, the substrates are often indispensable for

cathode preparation and operation. To the best of our knowledge, traditional substrates

are used merely as cathode support and current collector. It means that the substrate

occupies majority weight of cathode (>95 wt%), but it does not contribute any catalytic

activity for ORR and OER, which is unreasonable for practical utilization. In addition,

the prices of cathode substrates are usually quite expensive, for example, the price for

a carbon paper from Japan Toray Company is about $800 m-2, roughly accounting for

90% of whole cathode cost. Therefore, we herein report a novel step forward the

realization of commercial LOBs by one step of pretreatment of carbon paper substrate

with sucrose. A cathode substrate was first soaked in a sucrose solution and then

carbonized, merely through which the availability of carbon paper can be improved

substantially. The hierarchical pore architecture derived from Ni/NiO inorganic pore-

former, not only enables effective O2 and electrolyte transfer, but also provides
4
 ACCEPTED MANUSCRIPT

comfortable accommodation for solid-state products. In addition, this method can also

avoid some inherent issues for conventional cathodes prepared by spraying-coating,

slurry-paste, particle deposition, etc. For example, the pore spaces of the cathodes

prepared by a spraying-coating method were easily blocked up during the preparation

process due to the closed-packing nano-particles [34]. And the active materials will

deposit onto the upper surface of the substrate only, resulting in considerable un-coated

area at the opposite surface. Moreover, in these cathodes, the utilization of binder is

inevitable and it tends to cause the aggregation of material particles, limiting the

diffusion of O2 and Li+ and reducing space for discharge product storage [35]. In this

study the structural and chemical properties of the cathode were characterized by means

of BET, SEM and XRD. And the electrochemical properties of the cathode were

characterized via the behaviors of discharge-charge, rate capability, cycle stability,

cyclic voltammetric (CV) and electrochemical impedance spectroscopy (EIS)

measurements. All the results demonstrated a substantially enhanced performance. In a

word, this method will provide an accessible novel strategy for cathode substrate

pretreatment, and it is simple to operate with a low cost and has the potential to

popularize in mass-production.

2. Experimental

Commercial analytical grade sucrose and Ni(NO3)2·6H2O (99%, Aladdin) was

used as received without further purification. The synthetic procedure for impregnating

solution is as follows: a sucrose was dissolved into a mixed solution in which the mass

ratio was adjusted to sucrose : deionized water : ethanol = 4 : 10 : 4. A commercial

carbon paper (Toray Company, Japan) was punched into wafer with a diameter of 15

mm, and the wafer was then soaked into the solution above prepared for 2 min followed

by drying at 150 °C in air. After that, the impregnated carbon paper was carbonized at

5
 ACCEPTED MANUSCRIPT

700 °C under 15% H2+Ar (99.999%) atmosphere. In order to form a hieratical pore

structure into carbon coating over carbon fibers, Ni/NiO was chosen as an inorganic

pore-former which is based on the fact that the volume change is about 74% for the

oxidation of Ni to NiO and about 41% for the reduction of NiO to Ni [36]. So, Ni(NO3)2

precursor was mixed with the impregnating solution, i.e., sucrose solution. In order to

utilize the pore to the best advantage, Ni species were removed via an acid etch process.

We named the Ni/NiO co-impregnated SDAC as N-SDAC, and the acid etch N-SDAC

as P-SDAC. Finally, the batteries with a configuration of the cathodes with/without Ni

| glass-fiber separator infiltrated with liquid electrolyte (1 M LiTFSI/TEGDME) | Li

foil, were assembled in an Ar-filled glove box (Braun, Germany) with O2 and H2O

levels below 0.05 ppm.

The microstructures of the three kinds of cathodes were observed using a field-

emission scanning electron microscopy (SEM, Hitachi S-4700). The discharge product

was confirmed by a Rigaku X-ray diffractometer (XRD, D/max-Ultima IV). The mass

loadings of SDAC, N-SDAC and P-SDAC was firstly calculated by weighting the

difference between the blank carbon paper and the coated carbon paper, and further

confirmed by a thermo-gravimetric analysis (TG, TA SDT2960, USA). And the

specific surface area of SDAC and N-SDAC were analyzed by liquid nitrogen sorption

measurements based on the Brunauer-Emmett-Teller (BET, JW-BK112).

The electrochemical impedance spectroscopy (EIS) measurement was performed

on batteries with CHI604C in frequency range of 0.1-105 Hz under an ac voltage

amplitude of 5 mV, and the cyclic voltammetric (CV) measurements were also carried

out with the electrochemical workstation at a scan rate of 50 mV s −1 in the range of 2-

5 V. The discharge-charge behaviors were studied by the battery cycling system

(Neware, CT-3008W) with a cut-off voltage of 2 V. The cycling stability was also

6
 ACCEPTED MANUSCRIPT

tested and compared at different current densities.

3. Results and Discussion

Fig. 1 compares the galvanostatic discharge curves of batteries with two different

kinds of cathodes at the same current density of 200 mA g-1. One is a blank carbon

paper and the other is a SDAC coated carbon paper. It indicates that the surface coating

has the ability to improve the discharge capacity from almost zero to 4100 mAh g-1.

Comparing to other reported cathodes that also chose carbon paper as its substrate, the

SDAC coated carbon paper exhibited a quite good performance and showed a great

potential to be a novel active cathode material. Wang et al. fabricated a perovskite

cathode (La0.8Sr0.2MnO3) by coating catalyst ink onto carbon paper substrate. The

cathode delivered a discharge capacity of 4400 mAh g-1, however, the current density

was only 25% of the SDAC coated carbon paper [37]. And Sevim et al. prepared a

cathode with carbon paper as substrate by a brushing-painting method. The cathodes

with precious metal catalyst exhibited behaviors of 3200 (reduced graphene oxide-

Co3Pd7) and 2500 (reduced graphene oxide-Ni3Pd7) mAh g-1 at a current density of 100

mA g-1. Their capacities were 78% and 61% of the SDAC coated carbon paper, while

current density was 50% [38]. Under a current density of 200 mA g-1, the cathode

prepared by spraying Super P onto carbon paper shows a discharge capacity of 1400

mAh g-1, while another kind of cathode consisted of Vulcan XC-72 shows about 2000

mAh g-1, 34% and 49% of the SDAC coated carbon paper, respectively [33,39].

Furthermore, in order to confirm the most appropriate carbonized temperature for

sucrose, the impregnated carbon papers were treated at different temperatures changed

from 700 °C to 850 °C, and the test results were evaluated and compared in Fig. 2a and

b. It can be observed that the capacity achieved the highest value of 8200 mAh g-1 when

the impregnated carbon paper was carbonized at 800 °C. The reason is probably that

7
 ACCEPTED MANUSCRIPT

the pore volume of SDAC increased with the increasing temperature, resulting in a

more efficient transfer of Li+ and O2 (from 700 °C to 800 °C) [40]. And the surface area

has the same order as that of variation of pore volume, which provided a more reaction

area for ORR and OER. However, the lower capacity at 850 °C may be ascribed to the

partial collapses of the micropores at the high carbonization temperature of 850 °C, and

this result was consistent with the previous report [40]. Please note that in this work the

optimal carbonized temperature of N-SDAC and P-SDAC is as same as that of SDAC,

because the carbonized temperature influences the catalytic activity rather than porosity

of these materials.

Meanwhile, the electrochemical performances of the pure SDAC coated, the N-

SDAC coated and the P-SDAC coated carbon papers were compared in Fig. 3. When

they were carbonized at 700 °C, the N-SDAC coated carbon paper displayed a quite

good discharge capacity of 11100 mAh g-1 at a current density of 200 mA g-1, 43%

higher than that of P-SDAC coated carbon paper and almost two times higher than that

of pure SDAC coated carbon paper. Besides, a stable discharge plateau for the N-SDAC

coated carbon paper can be observed at 2.75 V, the number of which is similar to that

of P-SDAC coated carbon paper and 0.5 V higher than that of pure SDAC coated carbon

paper. According to previous reports [41,42], the solid-type and nonconductive

discharge product Li2O2 can accumulate in the pores of cathode structure, causing

blockage of the available surface area for further Li2O2 accommodation and the transfer

pathway for O2, Li+ and electrolyte, which resulted in a sharply increased polarization

of the cathode. The previous literature has reported that the micro-pores (<2 nm) easily

becomes blocked [1], resulting in poor capacity despite the large surface area [16]. The

porous structure cannot be seen clearly in the pure SDAC even under a high

magnification of 90 thousand, which means that if there are any pores existence in
8
 ACCEPTED MANUSCRIPT

SDAC layer, the diameter of them will less than about 2 nm. However, as for the P-

SDAC and the N-SDAC layer, the diameter of their hierarchical pores is from 10 nm

to 50 nm, which has been proved to show the best performance [43]. Therefore, the

lower voltage plateau can be mainly attributed to the porous structure though many

factors affected in capacity and interplayed with each other complexly [44]. The

specific area of the SDAC and N-SDAC was 15 and 243 m2 g-1 from the results of BET

test, respectively. The structure analysis was directly carried out by SEM. Fig. 4a-b

shows the surface morphology of pure SDAC. From the images, no porous structure

can be observed directly, suggesting the pure SDAC formed a tight carbon layer. While

Ni(NO3)2 was added as a pore-former, as displayed in Fig. 4c-d, a plenty of pores were

found to evenly distribute across all the area of the coating layer. The diameter of the

small pore structure was ~10 nm and that of the large pore was ~50 nm. In addition, a

great deal of Ni particles dispersed on the surface, which can take part in reaction as a

catalyst, producing a much higher capacity. Fig. 4e-f presented the morphology of the

P-SDAC. After the Ni particles (pore-former) were removed through an acid etch

process, the bimodal pore structure of the carbon layer was displayed clearly. Besides,

Fig. 4f shows the fracture surface of P-SDAC and demonstrates that the inside of the

coating layer is microporous as well. With the help of BET and SEM test results, we

can clearly understand the reasons for the difference between the aforementioned three

kinds of cathodes. It was generally believed that the pore volume is the most critical

factor which determined the power capability and rate performance for the LOBs [45-

47], therefore, the porous cathodes exhibited much better behaviors. Furthermore, it has

been proved that electro-catalysts played a key role in ORR (2Li+ + O2 + 2e- → Li2O2)

and OER (Li2O2 → O2 + 2Li+ + 2e-) processes for enhancing the capacity and power

density, so we cannot ignore the effect of Ni particles herein. Wittmaier et al. proved
9
 ACCEPTED MANUSCRIPT

that Ni is a suitable catalyst for cathodic reactions and is prone to favor catalyzing OER

rather than ORR [48]. As suggested, carbon is a kind of ORR catalyst, so N-SDAC can

be thought as a bifunctional catalyst for electrochemical reaction. The termination of

the battery discharge process is due to rapid build-up of discharge product covering the

active sites, rather than the blockage of pores [44], thus keeping a stable level of active

site is significant. The mechanism of electro-catalysts has not been verified clearly

because of its complexity, but Ren et al. offered an explanation in their work [49]. His

argument was that the catalysts can provide higher level of catalytically active site, so

they can maintain a longer reaction, namely getting a better capacity. Nevertheless, the

higher discharge capacity of the N-SDAC cathode can be ascribed to the existence of

the OER catalyst Ni particles. The CV curves of the pure SDAC coated, the N-SDAC

coated and the P-SDAC coated cathodes at the same scan rate of 50 mV s-1 were

displayed in Fig. 4g, and the test results were consistent with the previous

electrochemical test well.

In non-aqueous LOBs, electrolyte will permeate into porous structure of cathode,

which is necessary to provide Li+ for ORR, yet once the pore volume was occupied by

the electrolyte completely, the O2 diffusion channels will be blocked. In this state,

electrochemical reaction will be solely based on the little dissolved O2 in organic

electrolyte, which limited much to the capacity of LOBs. The electrochemical

interfacial reaction only takes place when electrolyte and O2 molecules co-exist at the

same cathode interfaced, thus it is critical to establish a high efficient 3-phase

electrochemical interface in non-aqueous LOBs. The side of the cathode facing

electrolyte should be wetted totally, but in order to provide sufficient channels for O2

molecules to migrate to the liquid-solid interface, the side facing O2 would be better not

immersed by electrolyte [50]. Fig. 5a-b exhibited the process of establishing the optimal

10
 ACCEPTED MANUSCRIPT

3-phase electrochemical interface. The capacity first improved with the increasing

electrolyte volume, and reached a maximum at 60 μL, then dropped down. The reason

for ascent portion of the curve shown in Fig. 5b was believed to be that the electrolyte

not only wetted the side of the cathode facing electrolyte, but also diffused into the

internal surface of the N-SDAC layer due to capillary action, which extended the 3-

phase electrochemical interface and enhanced the capacity. However, when the cathode

immersed in electrolyte totally the kinetics of reaction was limited by mass transfer

rate, so the performance dropped with further increasing electrolyte amount.

As we emphasized above, the pore volume largely influenced the capacity, and the

concentration of the Ni pore-former affect the aperture of the coating layer as well, so

it is also worth knowing the optimal concentration of Ni(NO3)2. The discharge curves

of the carbon papers soaked in different Ni(NO3)2+sucrose solutions were show in Fig.

6a, and the 0.05 M solution (Ni2+ concentration) impregnated carbon paper delivered

the highest capacity of 20600 mAh g-1 at 500 mA g-1. In contrast, the cathode constitutes

of RuO2/Co3O4 composite nanowires reported by Kim et al. showed the discharge

capacity of 10900 mAh g-1 at a current density of 200 mA g-1 [51]. The capacity is 52.9%

of the N-SDAC coated carbon paper, while the current density is 40%. The enhanced

electrochemical performance demonstrated that the N-SDAC was a pretty good cathode

material with a high activity.

The full discharge-charge curves of the batteries with the N-SDAC coated carbon

paper were summarized in Fig. 7, and as one step of pretreatment of carbon paper

substrate, the value of 24500 mAh g-1 was satisfactory. For comparison, Wang et al.

synthesized MnO2/graphene composite as a cathode material, which delivered a

capacity of 5600 mAh g-1 under 200 mA g-1, 22.9% of the N-SDAC coated carbon paper

[52]. The cathode reported by Jiang et al. (CeO2 nanoparticles on N-doped reduced

11
 ACCEPTED MANUSCRIPT

graphene oxide) achieved a value of 18900 mAh g-1 (77% of N-SDAC) under the same

current density [53]. And the cathode (flower-like NiCo2O4 –nitrogen doped graphene

oxide composite) reported by Moni et al. showed 15000 mAh g-1 under the same current

density of the N-SDAC one, but the capacity was 61% of the N-SDAC [54]. The

morphology of cathode during the whole cycle process was characterized by SEM as

shown in Fig. 8a-e. As shown in Fig. 8a, the N-SDAC coated on the surface of

commercial carbon paper uniformly, like a film enwrapped on the carbon fiber. After a

full discharge behavior, the cell-like discharge products evenly deposited on the

cathode surface, and the characteristic of this shape suggested the formation of Li2O2,

which has been widely reported in LOBs system [55-59]. This result was also be

confirmed by XRD image shown in Fig. 8g. The peaks related to Li2O2 were clearly

revealed in the XRD discharge pattern, and vanished again after a full charge process,

which indicated that the cathode was reversible for the duration of discharge-charge

cycle. In addition, the XRD pattern also proved the present of Ni particle catalyst,

further demonstrated our previous analysis.

The optimized N-SDAC coated carbon paper was further characterized under

different current densities. Fig. 9 displayed the discharge curves at current densities

changed from 200 mA g-1 to 1000 mA g-1. A high capacity of 10600 mAh g-1 can still

be achieved even at a high current density of 1000 mA g-1. Some of recent reported

electrodes employed as cathode for LOBs are summarized in Tab. 1 and from the

comparison, the N-SDAC coated carbon paper exhibited an increased rate performance.

12
 ACCEPTED MANUSCRIPT

Table 1. Comparison of some recently reported cathodes for LOBs

Current collector Cathode constitution Electrolyte Current density (capacity) Reference

Ti mesh RuO2@CNT LiTFSI 400 mA g-1 (4400 mAh g-1) [18]

Carbon paper CeO2@N-doped reduced 1M LiTFSI in DMSO 500 mA g-1 (10500 mAh g-1) [53]

graphene oxide

PTFE plant CNT array LiTFSI in acetonitrile 500 mA g-1 (12000 mAh g-1) [60]

Carbon paper MnO2@graphene 1M LiCF3SO3 in TEGDME 600 mA g-1 (3600 mAh g-1) [52]

Free standing Ru@nanoporous DMSO 1000 mA g-1 (12000 mAh -1) [61]

graphene

Carbon paper MnCoO@CNT 0.5M LiTFSI+0.5M 1000 mA g-1 (12700 mAh g-1) [62]

LiNO3+0.05M LiI in

TEGDME

Carbon paper Ni@Sucrose derived 1 M LiTFSI in TEGDME 500 mA g-1 (20600 mAh g-1) This work

active carbon 1000 mA g-1 (10600 mAh g-1)

The cycleability of N-SDAC coated carbon paper was studied as the cathode in

LOB as well. Fig. 10a presented the long-term cycle curves of the batteries cycled at

different current densities of 100 mA g-1 and 200 mA g-1 for 1 h. The batteries showed

remarkable performances during 1000 cycling. The first and the last 20 cycles of the

cycling behaviors were shown in Fig. 10b, which illustrated that during the cycle

behaviors, the cathode did not vary with time seriously, indicating a superior stability.

In addition, at the beginning of cycling test, the charge voltage increased gradually, but

after the 4th cycle, it decreased with time and finally lower than the initial voltage. The

decrease can be attributed to the decomposition of active carbon materiel because of

the present of the intermediate product LiO2. From previous reports [63,64], during the

reaction, LiO2 can desorb by solvation and undergo direct reduction with Li+/e﹣ to

form Li2O2 (LiO2 + e﹣+ Li+ → Li2O2). Therefore, with the reaction of LiO2, it etched

the surface of carbon layer and more surface area was exposed, resulting in a better

13
 ACCEPTED MANUSCRIPT

performance of the batteries. Moreover, short-term behaviors were also tested. The

batteries were operated to cycle at 200 mA g-1 for 2 h (Fig. 11a) and 400 mA g-1 for 1

h (Fig. 11b), respectively. Under the same capacity limitation, the cathode decayed

more seriously at a higher current density. As presented in Fig. 11b, after 150 cycles,

the discharge voltage decreased 0.38 V and the charge voltage increased 0.16 V, 65%

and 60% higher than those of the battery cycled at 200 mA g-1, which suggested that

current density was a vital factor of cycle stability.

The EIS can provide dynamic impedance changes in LOBs, and the EIS curves of

the battery before discharge and after a full cycle were shown in Fig. 12. The equivalent

circuit model used in test was shown in the inset of Fig. 12a. The analysis of the

equivalent circuit model was given as follows: (I) the ohmic resistant R0 was related to

Li+ transport in the electrolyte; (II) the resistant R1 and constant phase element CPE1

were related to Li+ migration through the surface layers; (III) the resistant R2 and CPE2

were associated with the charge transfer between the electrode and electrolyte interfaces

[65] and the number of the resistances were displayed in Tab. 2. It is obviously

displayed that R1 and R2 decreased after a full cycle, which can be attributed to the

erosion of the carbon layer. When the intermediate product LiO2 resolved, it etched the

carbon layer, leading to an expanded surface area as well as a lower resistant. This result

was also well consistent with previous cycleability test.

Table 2. The results of EIS test

Element R0 R1 R2

OCV 10.63 37.01 83.09

After one cycle 14.30 34.87 43.13

Based on the analysis above, the origin of the enhanced electrochemical

performance can be attributed to the flowing: (I) the present of Ni particle drastically
14
 ACCEPTED MANUSCRIPT

improved ORR kinetics during the reaction; (II) the bimodal pore architecture not only

enabled effective O2 diffusion without clogging the pores, but also provides enough

volume for discharge product accommodation and (III) the N-SDAC layer great

interfaced with the surface of carbon paper.

4. Conclusions

In this study, we reported a novel way to prepare a battery cathode incorporating

the simple operation process and the low cost. The cathode showed a capacity of 10600

mAh g-1 at a high current density of 1000 mA g-1, and established the maximum

capacity of 24500 mAh g-1 at 200 mA g-1. In particular, the N-SDAC coated cathode

achieved a long-term cycle behavior of 1000 cycles at 200 mA g-1, and had an

appropriate cyclic performance in short-term tests at 400 mA g-1. These results

suggested the potential of this coating materials to be used in LOBs as a cathode.

Acknowledgements

We gratefully acknowledge the financial support of Natural Science Foundation of

China (21673063), Harbin Institute of Technology (PIRS OF HIT 201616,

HIT.BRETIII.201505), the Postdoctoral Fund (2013M531031), and Natural Science

Foundation of Heilongjiang Province (B2017005).

References

[1] L. Grande, E. Paillard, J. Hassoun, J.B. Park, Y.J. Lee, Y.K. Sun, S. Passerini, B. Scrosati, The

lithium–air battery: still an emerging system or a practical reality? Adv. Mater. 27 (2015) 784-800.

[2] T. Ogasawara, A. Débart, M. Holzapfel, A.P. Novák, P.G. Bruce, Rechargeable Li2O2 electrode for

lithium batteries, J. Am. Chem. Soc. 128 (2006) 1390-1393.

[3] S.S. Sandhu, J.P. Fellner, G.W. Brutchen, Diffusion-limited model for a lithium–air battery with an

organic electrolyte, J. Power Sources 164 (2007) 365-371.

15
 ACCEPTED MANUSCRIPT

[4] D.S. Geng, N. Ding, T.S.A. Hor, S.W. Chien, Z.L. Liu, D. Wuu, X.L. Sun, Y. Zong, From lithium–

oxygen to lithium–air batteries: challenges and opportunities, Adv. Energy Mater. 6 (2016) 1502164.

[5] W.B. Luo, X.W. Gao, S.L. Chou, Y.M. Kang, J.Z. Wang, H.K. Liu, S.H. Dou, Investigation of

promising air electrode for realizing ultimate lithium oxygen battery, Adv. Energy Mater. 7 (2017)

1700234.

[6] H.K. Lim, H.D. Lim, K.Y. Park, D.H. Seo, H. Gwon, J. Hong, W.A. Goddard, H. Kim, K. Kang,

Toward a lithium–"air" battery: the effect of CO2 on the chemistry of a lithium–oxygen cell, J. Am. Chem.

Soc. 135 (2013) 9733-9742.

[7] G.Q. Wei, L.L. Huang, S.Y. Liu, J. Xie, S.C. Zhang, P.Y. Zhu, G.S. Cao, X.B. Zhao, Understanding

moisture and carbon dioxide involved interfacial reactions on electrochemical performance of lithium–

air batteries catalyzed by gold/manganese-dioxide, Acs Appl. Mater. Interfaces 7 (2015) 23876-23884.

[8] P. Tan, W. Shyy, T.S. Zhao, R.H. Zhang, X.B. Zhu, J. Yan, Effects of moist air on the cycling

performance of non-aqueous lithium–air batteries, Appl. Energy 182 (2016) 569-575.

[9] D. Aurbach, B.D. Mccloskey, L.F. Nazar, P.G. Bruce, Advances in understanding mechanisms

underpinning lithium–air batteries, Nat. Energy 1 (2016) 16128.

[10] H.G. Jung, J. Hassoun, J.B. Park, Y.K. Sun, B. Scrosati, An improved high-performance lithium–

air battery, Nat. Chem. 4 (2012) 579-585.

[11] C.O. Laoire, S. Mukerjee, K.M. Abraham, E.J. Plichta, M.A. Hendrickson, Influence of nonaqueous

solvents on the electrochemistry of oxygen in the rechargeable lithium–air battery, J. Phys. Chem. C 114

(2010) 9178-9186.

[12] S.A. Freunberger, Y.H. Chen, Z.Q. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novak, P.G.

Bruce, Reactions in the rechargeable lithium–O2 battery with alkyl carbonate electrolytes, J. Am. Chem.

16
 ACCEPTED MANUSCRIPT

Soc. 133 (2011) 8040-8047.

[13] P. Kichambare, J. Kumar, S. Rodrigues, B. Kumar, Electrochemical performance of highly

mesoporous nitrogen doped carbon cathode in lithium–oxygen batteries, J. Power Sources 196 (2011)

3310-3316.

[14] T. Zhang, H.S. Zhou. A reversible long-life lithium–air battery in ambient air, Nat. Commun. 4

(2013) 1817.

[15] M. Kotobuki, H. Munakata, K. Kanamura, Y. Sato, T. Yoshida, Compatibility of Li7La3Zr2O12 solid

electrolyte to all-solid-state battery using Li metal anode, J. Electrochem. Soc. 157 (2010) A1076-A1079.

[16] X.H. Yang, P. He, Y.Y. Xia, Preparation of mesocellular carbon foam and its application for

lithium–oxygen battery, Electrochem. Commun. 11 (2009) 1127-1130.

[17] Y.L. Li, J.J. Wang, X.F. Li, D.S. Geng, R.Y. Li, X.L. Sun, Superior energy capacity of graphene

nanosheets for a nonaqueous lithium–oxygen battery, Chem. Commun. 47 (2011) 9438-9440.

[18] Z.L. Jian, P. Liu, F.J. Li, P. He, X.W. Guo, M.W. Chen, H.S. Zhou, Core-shell-structured

CNT@RuO2 composite as a high-performance cathode catalyst for rechargeable Li–O2 batteries, Angew.

Chem. Int. Ed. 53 (2014) 442-446.

[19] J.L. Shui, F. Du, C.M. Xue, Q. Li, L.M. Dai, Vertically aligned N-doped coral-like carbon fiber

arrays as efficient air electrodes for high-performance nonaqueous Li–O2 batteries, Acs Nano 8 (2014)

3015-3022.

[20] Y.L. Li, X.F. Li, D.S. Geng, Y.J. Tang, R.Y. Li, J.P. Dodelet, M. Lefevre, X.L. Sun, Carbon black

cathodes for lithium oxygen batteries: Influence of porosity and heteroatom-doping, Carbon 64 (2013)

170-177.

[21] Y. Liu, Y. Liu, H.H. Shi, M. Wang, S.H.S. Cheng, H.D. Bian, M. Kamruzzaman, L.J. Cao, C.Y.

17
 ACCEPTED MANUSCRIPT

Chung, Z.G. Lu, Cobalt-copper layered double hydroxide nanosheets as high performance bifunctional

catalysts for rechargeable lithium–air batteries, J. Alloys Compounds 688 (2016) 380-387.

[22] J.L. Shui, N.K. Karan, M. Balasubramanian, S.Y. Li, D.J. Liu, Fe/N/C composite in Li–O2 battery:

studies of catalytic structure and activity toward oxygen evolution reaction, J. Am. Chem. Soc. 134 (2012)

16654-16661.

[23] H.S. Jadhav, R.S. Kalubarme, A.H. Jadhav, J.G. Seo, Iron-nickel spinel oxide as an electrocatalyst

for non-aqueous rechargeable lithium–oxygen batteries, J. Alloys Compounds 666 (2016) 476-481.

[24] Y.S. Jeong, J.B. Park, H.G. Jung, J. Kim, X.Y. Luo, J. Lu, L. Curtiss, K. Amine, Y.K. Sun, B.

Scrosati, Y.J. Lee, Study on the catalytic activity of noble metal nanoparticles on reduced graphene oxide

for oxygen evolution reactions in lithium–air batteries, Nano Lett. 15 (2015) 4261-4268.

[25] B. Sun, P. Munroe, G. Wang, Ruthenium nanocrystals as cathode catalysts for lithium–oxygen

batteries with a superior performance, Sci. Report 3 (2013) 2247.

[26] L.J. Wang, J. Zhang, X. Zhao, L.L. Xu, Z.Y. Lyu, M. Lai, W. Chen, Palladium nanoparticle

functionalized graphene nanosheets for Li–O2 batteries: enhanced performance by tailoring the

morphology of the discharge product, Rsc Adv. 5 (2015) 73451-73456.

[27] S. Bae, Y.G. Yoo, J. Par, S. Park, I. Nam, J.W. Han, J. Yi, A platinum catalyst deposited on a

zirconia support for the design of lithium–oxygen batteries with enhanced cycling ability, Chem.

Commun. 53 (2017) 11767-11770.

[28] A. Debart, A.J. Paterson, J.L. Bao, P.G. Bruce, α-MnO2 nanowires: a catalyst for the O2 electrode

in rechargeable lithium batterie, Angew. Chem. 120 (2008) 4597-4600.

[29] X.J. Lin, Y.S. Shang, L.Y. Li, A.S. Yu, Sea-urchin-like cobalt oxide grown on nickel foam as a

carbon-free electrode for lithium–oxygen batteries, Acs Sustainable Chem. Eng. 3 (2015) 903-908.

18
 ACCEPTED MANUSCRIPT

[30] T.V. Pham, H. Guo, W. Luo, S. Chou, J. Wang, H. Liu, Carbon and binder-free 3D porous perovskite

oxide air electrode for rechargeable lithium–oxygen batteries, J. Mat. Chem. A 5 (2017) 5283-5289.

[31] E. Yoo, H.S. Zhou, Carbon cathodes in rechargeable lithium–oxygen batteries based on double-

lithium-salt electrolytes, Chemsuschem 9 (2016) 1249-1254.

[32] J. Park, J. Jeong, S. Lee, C. Jo, J. Lee, Effect of mesoporous structured cathode materials on charging

potentials and rate capability of lithium–oxygen batteries, Chemsuschem 8 (2015) 3146-3152.

[33] M.C. Wu, T.S. Zhao, P. Tan, H.R. Jiang, X.B. Zhu, Cost-effective carbon supported Fe2O3

nanoparticles as an efficient catalyst for non-aqueous lithium–oxygen batteries, Electrochim. Acta 211

(2016) 545-551.

[34] M. Balaish, Y. Eineli, Enhancing oxygen adsorption capabilities in Li–O2 battery cathodes through

solid perfluorocarbons, J. Mat. Chem. A 5 (2017) 14152-14164.

[35] A.A. Franco, K.H. Xue, Carbon-based electrodes for lithium–air batteries: scientific and

technological challenges from a modeling perspective, Ecs J. Solid State Sc. 2 (2013) M3084-M3100.

[36] S. Zha, P. Tsang, Z. Cheng, M. Liu, Electrical properties and sulfur tolerance of La0.75Sr0.25Cr1-

xMnxO3 under anodic conditions, J. Solid State Chem. 178 (2005) 1844-1850.

[37] Z.D. Wang, Y. You, J. Yuan, Y.X. Yin, Y.T. Li, S. Xin, D.W. Zhang, Nickel-doped La0.8Sr0.2Mn1-

xNixO3 nanoparticles containing abundant oxygen vacancies as an optimized bifunctional catalyst for

oxygen cathode in rechargeable lithium–air batteries, Acs Appl. Mater. Interfaces 8 (2016) 6520-6528.

[38] M. Sevim, T. Şener, Ö. Metin, Monodisperse MPd (M: Co, Ni, Cu) alloy nanoparticles supported

on reduced graphene oxide as cathode catalysts for the lithium–air battery, Int. J. Hydrogen Energy 40

(2015) 10876-10882.

[39] Z. Ma, X. Yuan, Z. Zhang, D. Mei, L. Li, Z.F. Ma, L. Zhang, J. Yang, J.J. Zhang, Novel flower-like

19
 ACCEPTED MANUSCRIPT

nickel sulfide as an efficient electrocatalyst for non-aqueous lithium–air batteries, Sci. Rep. 5 (2015)

18199.

[40] P.A. Guo, Y. Gu, Z.B. Lei, Y.Q. Cui, X.S. Zhao, Preparation of sucrose-based microporous carbons

and their application as electrode materials for supercapacitors, Micropor. Mesopor. Mat. 156 (2012)

176-180.

[41] A. Kraytsberg, Y. Ein-Eli, Review on Li–air batteries—opportunities, limitations and perspective,

J. Power Sources 196 (2011) 886-893.

[42] M. Eswaran, N. Munichandraiah, L.G. Scanlon, High capacity Li–O2 cell and electrochemical

impedance spectroscopy study, Electrochem. Solid-State Lett. 13 (2010) A121-A124.

[43] F. Soavi, S. Monaco, M. Mastragostino., Catalyst-free porous carbon cathode and ionic liquid for

high efficiency, rechargeable Li–O2 battery, J. Power Sources 224 (2013) 115-119.

[44] Y. Shao, S. Park, J. Xiao, J.G. Zhang, Y. Wang, J. Liu, Electrocatalysts for nonaqueous lithium–air

batteries: status, challenges, and perspective, Acs Catal. 2 (2012) 844-857.

[45] J.J. Read, Characterization of the lithium–oxygen organic electrolyte battery, J. Electrochem. Soc.

149 (2002) A1190-A1195.

[46] J. Xiao, D.H. Wang, W. Xu, D.Y. Wang, R.E. Williford, J. Liu, J.G. Zhang, Optimization of air

electrode for Li–air batteries, J. Electrochem. Soc. 157 (2010) A487-A492.

[47] M. Mirzaeian, P.J. Hall, Characterizing capacity loss of lithium–oxygen batteries by impedance

spectroscopy, J. Power Sources 195 (2010) 6817-6824.

[48] D. Wittmaier, S. Aisenbrey, N. Wagner, K.A. Friedrich, Carbon-free nickel/cobalt-oxide cathodes

for lithium–air batteries with an aqueous alkaline electrolyte, Electrochim. Acta 149 (2014) 355-363.

[49] X.M. Ren, S.S. Zhang, D.T. Tran, J. Read. Oxygen reduction reaction catalyst on lithium–air battery

20
 ACCEPTED MANUSCRIPT

discharge performance, J. Mater. Chem. 21 (2011) 10118-10125.

[50] C. Tran, X.Q. Yang, D. Qu, Investigation of the gas-diffusion-electrode used as lithium–air cathode

in non-aqueous electrolyte and the importance of carbon material porosity, J. Power Sources 195 (2010)

2057-2063.

[51] Y. Kim, J.H. Park, J.G. Kim, Y. Noh, Y. Kim, H. Han, W.B. Kim, Ruthenium oxide incorporated

one-dimensional cobalt oxide composite nanowires as lithium–oxygen battery cathode catalysts,

Chemcatchem 9 (2017) 3554-3562.

[52] J. Wang, L. Liu, C.M. Subramaniyam, S. Chou, H. Liu, J. Wang, A microwave autoclave

synthesized MnO2/graphene composite as a cathode material for lithium–oxygen batteries, J. Appl.

Electrochem. 46 (2016) 869-878.

[53] Y.X. Jiang, J.F. Cheng, L. Zou, X.Y. Li, Y.P. Gong, B. Chi, J. Pu, J. Li, In-situ growth of CeO2

nanoparticles on N-doped reduced graphene oxide for anchoring Li2O2 formation in lithium–oxygen

batteries, Electrochim. Acta 210 (2016) 712-719.

[54] P. Moni, S. Hyun, A. Vignesh, S. Shanmugam, Chrysanthemum flower-like NiCo2O4-nitrogen

doped graphene oxide composite: an efficient electrocatalyst for lithium–oxygen and zinc–air batteries,

Chem. Commun. 53 (2017) 7836-7839.

[55] B.M. Gallant, D.G. Kwabi, R.R. Mitchell, J. Zhou, C.V. Thompson, S.H. Yang, Influence of Li2O2

morphology on oxygen reduction and evolution kinetics in Li–O2 batteries, Energy Environ. Sci. 6 (2013)

2518-2528.

[56] S.M. Cho, J.H. Yom, S.W. Hwang, I.W. Seong, J. Kim, S.H. Cho, W.Y. Yoon, Morphology control

of lithium peroxide using Pd3Co as an additive in aprotic Li–O2 batteries, J. Power Sources 342 (2017)

427-434.

21
 ACCEPTED MANUSCRIPT

[57] J.J. Xu, Z.L. Wang, D. Xu, L.L. Zhang, X.B. Zhang, Tailoring deposition and morphology of

discharge products towards high-rate and long-life lithium–oxygen batteries, Nat. Commun. 4 (2013)

2438.

[58] X.B. Zhu, T.S. Zhao, Z.H. Wei, P. Tan, G. Zhao, A novel solid-state Li–O2 battery with an integrated

electrolyte and cathode structure, Energy Environ. Sci. 8 (2015) 2782-2790.

[59] X.B. Zhu, T.S. Zhao, Z.H. Wei, P. Tan, L. An, A high-rate and long cycle life solid-state lithium–

air battery, Energy Environ. Sci. 8 (2015) 3745-3754.

[60] J. Pan, H.P. Li, H. Sun, Y. Zhang, L. Wang, M. Liao, X.M. Sun, H.S. Peng, A lithium–air battery

stably working at high temperature with high rate performance, Small 14 (2018) 1703454.

[61] B. Sun, X. Huang, S. Chen, P. Munroe, G. Wang, Porous graphene nanoarchitectures: an efficient

catalyst for low charge-overpotential, long life, and high capacity lithium–oxygen batteries, Nano Lett.

14 (2014) 3145-3152.

[62] J.H. Kim, Y.J. Oh, Y.C. Kang. Design and synthesis of macroporous (Mn1/3Co2/3)O-carbon

nanotubes composite microspheres as efficient catalysts for rechargeable Li–O2 batteries, Carbon 128

(2017) 125-133.

[63] J. Hassoun, F. Croce, M. Armand, B. Scrosati, Investigation of the O2 electrochemistry in a polymer

electrolyte solid-state cell, Angew. Chem. 50 (2011) 2999-3002.

[64] X.B. Zhu, T.S. Zhao, P. Tan, Z.H. Wei, M.C. Wu, A high-performance solid-state lithium–oxygen

battery with a ceramic-carbon nanostructured electrode, Nano Energy 26 (2016) 565-576

[65] I. Landa-Medrano, I.R.D. Larramendi, N. Ortiz-Vitoriano, R. Pinedo, J.I.R.D. Larramendi, T. Rojo,

In situ monitoring of discharge/charge processes in Li–O2 batteries by electrochemical impedance

spectroscopy, J. Power Sources 249 (2014) 110-117.

22
 ACCEPTED MANUSCRIPT

Figure captions
Fig. 1. The comparison of discharge capacities between pure carbon paper and SDAC coated carbon paper.

Fig. 2. (a) The comparison of discharge capacities between the SDAC coated carbon papers carbonized at different

temperatures. (b) Bode plots of the dependence of discharge capacity on carbonized temperature.

Fig. 3. The comparison of the discharge capacities between the SDAC coated, the P-SDAC coated and the N-SDAC

coated carbon papers.

Fig. 4. SEM images of (a, b) the SDAC, (c, d) the N-SDAC and (e, f) the P-SDAC. (g) CV curves of the SDAC

coated, the N-SDAC coated and the P-SDAC coated carbon papers.

Fig. 5. (a) The comparison of the discharge capacities of N-SDAC coated carbon papers with different electrolyte

volumes. (b) Bode plots of the dependence of discharge capacity on electrolyte volume.

Fig. 6. (a) The comparison of the discharge capacities between the N-SDAC with different content of Ni catalyst.

Scatter plot of (b) the dependence of capacity on Ni catalyst content and (c) the dependence of voltage on Ni catalyst

content.

Fig. 7. Discharge-charge curves of the N-SDAC coated carbon paper.

Fig. 8. SEM images of the cathode (a) before discharge, after (b, c) full discharge and (d, e) full recharge. (g) XRD

patterns of the N-SDAC coated carbon papers, i.e., pristine, full discharge, and full recharge.

Fig. 9. Rate performance of the N-SDAC coated carbon papers.

Fig. 10. (a) Long-term stability of the N-SDAC coated carbon paper at different current densities. (b) The first and

the last 20 cycles of the long-term behaviors.

Fig. 11. Short-term cycling stability of the cathodes under the same capacity limitation of 400 mAh g-1 with different

current densities of (a) 200 mA g-1 and (b) 400 mA g-1.

Fig. 12. Nyquist plots and fitting curves of EIS of the N-SDAC coated carbon paper (insert: equivalent circuit).

23
 ACCEPTED MANUSCRIPT

Figures

Fig. 1

24
 ACCEPTED MANUSCRIPT

Fig. 2

(a) (b)

25
 ACCEPTED MANUSCRIPT

Fig. 3

Fig. 4
26
 ACCEPTED MANUSCRIPT

(g)

Fig. 5

27
 ACCEPTED MANUSCRIPT

(a) (b)

Fig. 6

28
 ACCEPTED MANUSCRIPT

(a) (b)

(c)

Fig. 7

29
 ACCEPTED MANUSCRIPT

Fig. 8

30
 ACCEPTED MANUSCRIPT

(f)

Fig. 9

31
 ACCEPTED MANUSCRIPT

Fig. 10

32
 ACCEPTED MANUSCRIPT

(a) (b)

Fig. 11

33
 ACCEPTED MANUSCRIPT

(a) (b)

Fig. 12

34