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 [UCI]I804:24010-000000060481

Master's Thesis

Effects of Organic Electrolyte Additive on the

Suppression of Li dendrite in Li Metal Based Batteries

Department of Materials Science and Engineering

Graduate School, Chonnam National University

KIM, Hee-Sang

February 2019

i
 CONTENTS

List of Figures ..............................................................................................................................................iiiv

List of Tables..................................................................................................................................................vi

Abstract in English .......................................................................................................................................vii

1. Introduction ......................................................................................................................................... - 1 -

2. Literature survey ............................................................................................................................... - 3 -

2.1 Lithium metal based battery .................................................................... - 3 -

2.2 Solid electrolyte interphase (SEI) layer on Li metal anode .................... - 5 -
2.3 Lithium dendrite growth and related issues ............................................ - 7 -

3. Experimental....................................................................................................................................... - 9 -

3.1. Electrolyte preparations ......................................................................... - 9 -

3.2. Electrochemical measurement of Li metal cells ..................................... - 9 -
3.3. Electrochemical measurement of Li-O2 cells ....................................... - 11 -
3.4. Materials characterization..................................................................... - 12 -

4. Results and discussion .................................................................................................................... - 13 -

4.1 Effects of urea additive in Li/Li symmetric cell .................................... - 13 -

4.2 Surface morphology of the Lithium metal analysis ............................... - 16 -
4.3 Electrochemical performance ................................................................ - 19 -
4.4 Surface chemical composition analysis ................................................. - 23 -
4.5 Effects of urea additive in Li-O2 cell..................................................... - 31 -

5. Conclusion ......................................................................................................................................... - 36 -

6. Reference .......................................................................................................................................... - 37 -

Abstract in Korean.............................................................................................................................. - 46 -

iii
 List of Figures

Fig. 2.1. Comparison of the theoretical specific energy for a variety of batteries. .................. - 3 -

Fig. 2.2. SEI layer formation in a liquid electrolyte. ........................................................................ - 5 -

Fig. 2.3. Scheme of the SEI layer........................................................................................................ - 6 -

Fig. 2.4. The growth of Li dendrite and related issues. . ............................................................... - 7 -

Fig. 3.1. Procedure of assembling the Li/Li symmetric 2032 coin-type cell. ......................... - 10 -

Fig. 3.1. Procedure of assembling the Li-O2 2032 coin-type cell. ............................................ - 10 -

Fig. 4.1. (a) Cell potential profiles and (b) cycle life of Li symmetric cells containing various
concentration of urea. (c) Selected cell potential profiles showing the cycles; the cells
were cycled at a current density of 1.0 mA cm-2 for each discharge and charge intervals
of 2h. ...................................................................................................................................... - 13 -

Fig. 4.2. Cell potential profiles of the Li symmetric cells with and without 0.5 M urea additive.
The cells were cycled at 2 h interval of each discharge and charge step under the applied
current densities of (a) 0.5, (b) 1.0, (c) 1.5 and (d) 2.0 mA cm-2. ................................ - 15 -

Fig. 4.3. Morphologies of Li electrode, obtained from the Li symmetric cells with 0.5 M and
without urea after cyclic tests at a current density of 1 mA cm-2 for each 2h interval; (a
and e) 1 cycle, (b and f) 5 cycles, (c and g) 10 cycles, (d) 50 cycles, (h) pristine Li metal.
................................................................................................................................................. - 16 -

Fig. 4.4. Typical images of components from the Li symmetric cell; (a) pristine Li metal, (b) with,
(c) without 0.5 M urea additive, (d) bare separator, (e) separator of cell with 0.5 M urea
additive, and (f) without urea additive. The cells were cycled after 10 cycles at a current
density of 1.0 mA cm-2 for 2h each of discharge and charge steps........................... - 18 -

Fig. 4.5. Electrochemical impedance spectra of the Li symmetric cells (a) with 0.5 M and (b)
without urea electrolyte additive. The cells were cycled under the limited capacity of
2.0 mA h cm-2 and current density of 1.0 mA cm-2. .................................................... - 19 -

Fig. 4.6. Equivalent circuit for the impedance spectra of the Li symmetric cell. .................... - 20 -

Fig. 4.7. Cyclic voltammograms of 1 M LiTFSI in TEGDME (a) with 0.5 M and (b) without urea
using a glassy carbon working electrode at a scan rate of 0.1 mV s-1 in potential range
of -0.5 ~ 4.5 V vs. Li/Li+................................................................................................... - 22 -
iv
Fig. 4.8. XPS spectra of the Li electrodes, obtained from the cells with and without 0.5 M urea.
The cells were cycled at a current density of 1.0 mA cm-2 for each 2 h interval........-25-

Fig. 4.9. FTIR spectra of the Li electrodes, obtained from the cells (a) with and (b) without 0.5 M
urea additive after cyclic tests at a current density of 1 mA cm-2 for 2h interval. The
reference spectra corresponding to HCOOLi, CH3COOLi, LiOH, Li2CO3, Urea, LiTFSI,
and TEGDME were also indicated..................................................................................... - 26 -

Fig. 4.10. FTIR spectra of the pure LiTFSI and urea.................................................................... - 28 -

Fig. 4.11. XRD patterns of MnO2 catalyst formed on Ni foam (a) after annealing at 450 ℃ for 5 h,
(b) before annealing, and (c) fresh Ni foam. .................................................................. - 31 -

Fig. 4.12. XRD patterns of MnO2 powder obtained by hydrothermal method; (a) after annealing at
450 ℃ for 5 h, and (b) before annealing......................................................................... - 32 -

Fig. 4.13. SEM images of fresh Ni foam, (a) low and (b) high magnification. SEM images of the
MnO2 catalyst formed on Ni foam, (c) low and (d) high magnification..................... - 32 -

Fig. 4.14 (a) Variation of the end cell potential with cycle for the Li-O2 cells without and with the
electrolyte additive, tested under a limited capacity mode of 1000 mAh g-1 at the current
density of 0.1 mA cm-2 in a pure O2 atmosphere: relevant discharge-charge cell
potential profiles in conditions (b) with and (c) without 0.5 M urea ............................ -33-

v
 List of Tables

Table 2.1. Comparison of the theoretical specific energy for a variety of batteries. .............. - 4 -

Table 4.1. Fitted parameters corresponding to equivalent circuit models for the impedance of the
Li symmetric cell with 0.5 M urea additive. ................................................................ - 21 -

Table 4.2. Fitted parameters corresponding to equivalent circuit models for the impedance of the
Li symmetric cell without 0.5 M urea additive............................................................ - 21 -

Table 4.3. Binding energies corresponding to the fitted peaks for the surface of the Li electrode
of the Li symmetric cell. ................................................................................................... -24-

Table 4.4. Vibrational frequencies and assignments for LiTFSI and Urea. ............................. - 30 -

vi
 Effects of Organic Electrolyte Additive on the

Suppression of Li dendrite in Li Metal Based Batteries

Kim, Hee-Sang

Department of Materials Science and Engineering

Graduate School of Chonnam National University

(Directed by Professor Park, Chan-Jin)

(Abstract)

Lithium (Li) metal has been considered to be an ideal anode material for

secondary batteries due to its high theoretical specific capacity (3860 mAh g -1),

low density (0.59 g cm-3), and the lowest standard red-ox potential. However, Li

metal is highly reactive and thermodynamically unstable with organic electrolytes.

It reacts easily with the electrolyte to form a solid electrolyte interphase (SEI) layer.

This layer can prevent the direct contact between Li metal and liquid electrolyte

and further decomposition of the electrolyte, once the stable SEI layer forms.

Nevertheless, due to the non-uniform chemical composition of the SEI layer, lithium

dendrite grows on the side of lithium metal, and accordingly direct contact between

the anode and the cathode occurs. Thus far, approaches to prevent the short circuit

vii
of batteries due to Li dendrite formation have focused on improving the stability

and uniformity of the SEI layer on the Li surface by adjusting electrolyte

components and including electrolyte additives.

In the present work, we suggested the use of an optimum amount of urea

electrolyte additive for suppressing the growth of Li dendrite by forming the

uniform and robust SEI layer on Li surface. In the case of the symmetric cell, the

base electrolyte of 1 M LiTFSI in TEGDME was used for the electrochemical study.

The Li symmetric cell containing the 0.5 M urea electrolyte additive was

galvanostatically cycled over 500 cycles for each charge and discharge time of 2 h

at a current density 1 mA cm-2, which was >50 times longer than that of the Li

symmetric cell without urea additive in the electrolyte. This urea electrolyte

additive helps to make a robust and uniform SEI layer, leading to effectively

suppressing the growth of Li dendrite and helps to improve electrochemical

performance. Furthermore, the urea electrolyte additive can be used in the Li metal

based batteries such as a Li-O2 battery. The Li-O2 cells were assembled with Li

metal, 1 M LiTFSI in TEGDME, and MnO2@Ni foam as an anode, base electrolyte,

and cathode, respectively. The Li-O2 cell containing the 0.5 M urea additive was

cycled for longer than 200 cycles at a current density of 0.1 mA cm-2 under a limited

capacity mode of 1000 mAh g-1, which was >4 times longer than that of the Li-O2

cell without the urea additive in the electrolyte. Urea electrolyte additive helps to

improve the electrochemical performance, especially cyclability of Li-O2 batteries.

viii
1. Introduction

Lithium (Li) metal has been considered as an ideal anode material for

rechargeable Li batteries due to its high theoretical specific capacity (3860 mA h

g-1), low density (0.59 cm-3), and the lowest electrode potential (-3.040 V vs.

standard hydrogen electrode) [1, 2]. However, the Li metal based rechargeable

batteries have not been commercialized yet due to the uncontrollable growth of Li

dendrites and low Coulombic efficiency during repeated Li deposition/stripping

process [3]. Because Li metal is thermodynamically unstable in organic electrolytes,

when Li metal comes in contact with an organic electrolyte, it reacts easily with the

electrolyte to form a solid electrolyte interphase (SEI) layer [4]. This layer can

prevent the direct contact between Li metal and liquid electrolyte and further

decomposition of the electrolyte, once the stable and uniform SEI layer forms [5].

Nevertheless, the non-uniform chemical composition of the SEI layer, which is

cause of lithium dendrite growth leading to the direct contact between the anode

and the cathode [6, 7]. Furthermore, Li dendrites can easily break off and come to

be isolated from the Li metal electrode, forming so-called “dead Li”. Therefore, it

is general for the Li dendrite leads to dead Li; the former can occur the short

circuiting of the battery and latter decrease the Coulombic efficiency [8-10].

Recently, many researchers have focused to stabilize the SEI layer for the suppress

the Li dendrite formation. The strategies of the suppression of the Li dendrite and

dead Li formation have two main categories, such as adjusting the artificial SEI

layer and controlling native SEI layer to use the additive. Concepts of the artificial

-1-
SEI layer have been coated on the surface of Li metal directly and act as SEI layer,

such as Al2O3 particles [11, 12], atomic layer deposition (ALD) of Al2O3 [13, 14],

lithium phosphorous oxynitride (LiPON) [15, 16], tetraethoxysilane (TEOS) [17].

Another strategy is using an additive in electrolyte for the stable and uniform SEI

layer to suppress the Li dendrite and dead Li formation; such as LiI [18], LiNO3

[19, 20], LiBr [21], LiF [22], Cs+ [23]. These electrolyte additive can be

categorized in the inorganic salt additive. Furthermore, organic electrolyte

additives have also been employed to increase the homogeneity of the SEI layer

and suppress the growth of Li dendrite; such as vinylene carbonate (VC) [24],

fluoroethylene carbonate (FEC) [25-27], 2-methylfuran and 2-methylthiophene

[28, 29]. Therefore, Li metal anode with appropriate electrolyte additive for the

stable and uniform SEI layer can exhibit the practical application of the Li metal

batteries (LMBs). Urea has known as dispersant agent and surfactant of

hydrothermal method for the appropriate morphology [30-32]. In addition, urea has

been known as a hydrogen bond donor and has been generally used to diminish the

melting point of the complex system [33, 34]. Herein, we suggest the use of urea

as an electrolyte additive for the first time to stable and uniform SEI layer for the

suppression of the Li dendrite in LMBs. We investigated the SEI layer on the Li

electrode surface employing with and without urea additive in electrolyte for

analyzing the role of the urea additive by monitoring the changes in the morphology,

structure, surface chemistry, and electrochemical characteristics of the Li metal

electrode. In particular, the cyclability of the Li-O2 batteries employing the urea

additive was significantly improved.

-2-
2. Literature survey

2.1 Lithium metal based batteries

Lithium metal based batteries (LMBs) has been considered as next generation

rechargeable batteries. LMBs using Li metal as an anode can be divided into Li-O2

battery with O2 as the cathode, Li-S battery with sulfur as the cathode [35]. These

systems have extremely high theoretical specific energy compared to current

lithium-ion batteries (LIBs). Fig. 2.1 shows the theoretical specific energy for a

variety of batteries.

Fig. 2.1. Comparison of the theoretical specific energy for a variety of batteries

[36].

-3-
Table 2.1. Comparison of the theoretical specific energy for a variety of batteries

[36].

Battery system Specific energy Energy density

(Wh kg-1) (Wh L-1)

Lead Acid 218 929

Ni-MH 216 1386

Li-ion (graphite anode) 385 1168

Li-sulfur (graphite anode) 576 1473

Li-air (graphite anode) 939 2170

Li-ion (lithium anode) 545 1595

Li-sulfur (lithium anode) 2548 3665

Li-air (lithium anode) 5217 5997

Among various batteries, Li-O2 and Li-S battery system exhibit the high specific

energy of 5200 Wh kg-1 and 2600 Wh kg-1, respectively [37].

-4-
 2.2 Solid electrolyte interphase (SEI) layer on Li metal anode

Li metal is thermodynamically unstable in organic electrolytes, when Li metal

comes in contact with an organic electrolyte, it reacts easily with the electrolyte to

form a solid electrolyte interphase (SEI) layer [4]. This layer can prevent the direct

contact between Li metal and liquid electrolyte and further decomposition of the

electrolyte, once the stable and uniform SEI layer forms [5]. Fig. 2.2 shows the SEI

layer formation in a liquid electrolyte.

Fig. 2.2. SEI layer formation in a liquid electrolyte [38].

-5-
 The SEI layer was composed of two part such as inner layer and outer layer. The

inner layer was near to the Li metal surface and composed of low oxidation states,

such as Li2O, LiOH, Li2CO3, LiF, and Li3N referred as inorganic layer. The outer

layer was composed of higher oxidation states, such as RLi, ROLi, RCOOLi, and

RCOO2Li referred as organic layer. R is the hydrocarbon or organic groups.

Accordingly, The SEI layer components was strongly affected by the salts and

solvents used in the electrolytes. The inorganic components of SEI layer were

determined by the reactions with salts and solvents, the organic components of SEI

layer were originated from the solvents. Fig. 2.3 shows the SEI layer, which was a

composed of the complicated mixture of organic and inorganic components

originated from the reduction of organic electrolyte.

Fig. 2.3. Scheme of the SEI layer [39].

-6-
 The SEI layer is the key components which significantly affects the battery

performance. Foremost features of the SEI layer should include [40-42]:

(1) Electronically insulating and a high Li+ conductivity.

(2) Rapidly form on the electrode surface

(3) Mechanically and chemically stable.

(4) Smooth surface morphology and uniform chemical composition.

(5) Good adhesion to the electrode and flexible.

2.3 Lithium dendrite growth and related issues

The high electrochemical reactivity of Li metal results in the corrosion of Li metal

by electrolyte and hence low utilization of Li metal anode. The growth of Li

dendrites has a critical safety issue for LMBs. The formation of Li dendrite can

induce several issues (Fig. 2.4):

Fig. 2.4. The growth of Li dendrite and related issues. [43].

-7-
 (1) Cell short circuit: Li dendrites continuously growth to penetrate the separator

and ultimately reach the cathode, leading to the electrical contact and short-

circuiting of a working cell. The short-circuiting accompanies the cell thermal

runaway, electrolyte combustion, and cell explosion.

(2) Aggravated adverse reactions: Li dendrite growth occurs the increased

surface area of Li metals and parasitic reactions between Li metal and electrolyte.

These side reactions consume the active Li metal materials and electrolyte but do

not contribute to the capacity, hence reducing Coulombic efficiency.

(3) Formation of dead Li from dendrites: Li dendrites can easily break off and

come to be isolated from the Li metal electrode, forming so-called “dead Li”. This

dead Li is electrochemically inert and reduces the Coulombic efficiency additionally.

(4) Increased cell polarization: Li metal anode with dendrites has a porous and

non-uniform structure composing of numerous dead Li. These porous structure lead

to huge polarization and decreases the Coulombic efficiency due to the increased

large resistance of Li ions and electrons.

(5) Large volume change: Li metal anode has the large volume change during

each deposition/stripping process due to infinite Li ion source. Li dendrite growth

and porous Li deposition result in the volume change issue more severe due to the

porous Li deposits. These porous deposits prompt more volume expansion during

Li deposition /stripping.

Briefly, Li dendrite growth not only occurs the safety problems of LMBs, but also

low Coulombic efficiency and cycle life.

-8-
3. Experimental procudure

3.1. Electrolyte preparations

Bis(trifluoromethane sulfonyl)imide lithium salts (LiTFSI, Aldrich 99.95%) and

tetraethylene glycol dimethyl ether (TEGDME, Aldrich 99%), and urea (CH4N2O,

Aldrich 99%) were used without further purification. 1 M LiTFSI salt dissolved in

TEGDME solvent was used base electrolyte. In addition, the various concentration of

urea additive was added to base electrolyte ranging 0 to 1.0 M. To enhance the

solubility of urea in 1 M LiTFSI/TEGDME, urea was ball milled for 6 h.

3.2. Electrochemical measurement of Li metal cells

For electrochemical characterization, the Li metal foil with the thickness of 200 um

was used as the electrodes. The CR-2032 coin-type cells with the configuration of

symmetric Li/Separator/Li were assembled in the argon-filled glove box to evaluate

the cycle life of the Li electrode during cycles. Prior to assembling the cells,

Whatman® glass fiber separators were soaked in the electrolyte of 1 M

LiTFSI/TEGDME containing various concentration of urea. Preparations of the Li/Li

symmetric coin-type cells process are summarized in Fig. 3.1. Cyclic voltammetry

(CV) tests were conducted a three-electrode cell system using a Gamry potentiostat,

which was employed to use glassy carbon as a working electrode (WE), Li metal as
-9-
a counter electrode (CE) and a reference electrode (RE), respectively. Galvanostatic

tests were investigated using a Wonatech battery cycler under applied current

densities in the range of 0.5 to 2.0 mA cm-2 for 2h intervals of each discharge and

charge step. The electrochemical impedance spectra of the cells were measured

using an impedance analyzer (ZIVE SP2) in the frequency range of 100 mHz – 100

kHz with the voltage amplitude of 10 mV.

Fig. 3.1. Procedure of assembling the Li/Li symmetric 2032 coin-type cell.

- 10 -
 3.3. Electrochemical measurement of Li-O2 cells

The CR-2032 coin-type cells with the configuration of Li/Separtor/MnO2@Ni foam

were assembled in the argon-filled glove box. Preparations of the Li-O2 coin-type

cells process are summarized in Fig. 3.2.

Fig. 3.2. Procedure of assembling the Li-O2 2032 coin-type cell.

- 11 -
 The MnO2@Ni foam was used as the air cathode for Li-O2 cells, which was

synthesized through the hydrothermal method. The precursor solution was prepared

by 10 mM manganese sulfate monohydrate (MnSO4·H2O, Aldrich 99%) and 20 mM

potassium permanganate (KMnO4, Aldrich 99%) in 500 ml deionized (DI) water and

then 5 ml Ammonia solution (28 vol%, Aldrich) was added to resultant solution. After

stirring, the obtained homogeneous solution was transferred to Teflon-lined stainless

steel autoclave. After that, a clean Ni foam was input the vertically in the autoclave.

The autoclave was heated to 150 ℃ for 5 h. After the reaction, the obtained Ni foam

was rinsed 3 times with DI water and ethanol to remove impurities. Finally, the Ni

foam was annealed to 450 ℃ for 5 h. The discharge-charge behavior of Li-O2 cell was

conducted in pure O2 (99.995%) using Wonatech battery cycler under the limited

capacity mode of 1000 mA h g-1.

3.4. Materials characterization

After electrochemical tests, the cell was disassembled in an argon filled glove box.

The Li metal was rinsed 3 times with pure TEGDME, pure tetrahydrofuran (THF),

and transferred into vacuum chamber for drying. The samples were characterized

with a field-emission scanning electron microscope (FE-SEM; Hitachi S-4700/EX-

200), an X-ray photoelectron spectrometer (XPS; MultiLab 2000, VG), a Fourier

transform infrared spectrometer (FTIR, PerkinElmer Spectrum 400) with reflectance

mode, and an X-ray diffractometer (XRD; D/MAX Ultima Ⅲ, Rigaku).

- 12 -
 4. Results and discussion

4.1 Effects of urea additive in Li/Li symmetric cell

Fig. 4.1. (a) Cell potential profiles and (b) cycle life of Li symmetric cells containing

various concentration of urea. (c) Selected cell potential profiles showing the cycles;

the cells were cycled at a current density of 1.0 mA cm-2 for each discharge and

charge intervals of 2h.

Li symmetric cells were composed of Li/Separator/Li to investigate the effect

of a urea additive in electrolytes. 1 M LiTFSI in TEGDME was used base

electrolyte, which contains the various concentrations of the urea additive. The

cells were galvanostatically cycled under the limited areal capacity mode of 2.0

mA h cm-2 corresponding to 2 h intervals of each discharge and charge step at

applied current density of 1.0 mA cm -2 within the potential range from -5 to 5 V.

- 13 -
Fig. 4.1 (a) and (b) shows the cyclability of the Li symmetric cells, tested in

electrolytes with various concentrations of urea additive ranging from 0 to 1.0 M.

With increasing urea additive concentration, the cycle life of the Li symmetric c ell

increased up to 545 cycles corresponding to the urea additive concentration of 0.5

M. However, it decreased significantly with further increasing the amount of urea.

The maximum cycle life of 545 cycles corresponding to a lifespan of 2176 h

observed for the cell containing of 0.5 M urea was ~ 54 times longer than that of

the cell without urea additive. Fig. 4.1 (c) show the variation in the degree of

polarization with cycle number in selected cycles region. In the initial cycles, the

larger potential fluctuation was observed for the cells containing urea additive. In

addition, the fluctuation was larger and faster in electrolytes with high urea

concentration. However, the potential was soon stabilized in the following cycles.

In the presence of urea, the degree of polarization of the symmetric cell was in

the range of 100 ~ 400 mV. According to these results, the presence of urea in

the LiTFSI/TEGDME electrolyte was effective for enhancing the cell cycle life due

to formation of a stable SEI layer on the Li metal surface.

Furthermore, we monitored the polarization curves of the Li symmetric cells with

and without urea additive at various current densities in the range of 0.5 mA cm -

2
to 2.0 mA cm -2 (Fig. 4.2). The cells were cycled at 2 h interval of each discharge

and charge step. The overpotential of the cell without urea additive varied from

50 to 300 mV, when applied current density increased form 0.5 mA cm -2 to 2.0

mA cm-2. In the presence of urea additive, the overpotential of the cell was in the

range of 100 ~ 400 mV. With respect to the cyclability of the cells, the cells

- 14 -
containing urea additive showed a longer cycle life than without urea in each

current density. In particular, under the applied current density at 2.0 mA cm -2.

The symmetric cell without urea additive could operate only one cycle. In contrast,

the symmetric cell containing 0.5 M urea could survive up to 300 cycles under the

same condition (Fig. 4.2 (d)).

Fig. 4.2. Cell potential profiles of the Li symmetric cells with and without 0.5 M urea

additive. The cells were cycled at 2 h interval of each discharge and charge step

under the applied current densities of (a) 0.5, (b) 1.0, (c) 1.5 and (d) 2.0 mA cm -2.

- 15 -
 4.2 Surface morphology of the Lithium metal analysis

To investigate the effect of the urea additive on the morphology of Li electrode,

Fig. 3 shows the SEM images of the Li electrode obtained from the Li symmetric

cells after the tests for 2 h intervals each discharge and charge at the current

density of 1.0 mA cm-2. The pristine Li electrode had smooth interface (Fig. 4.3

(h)).

Fig. 4.3. Morphologies of Li electrode, obtained from the Li symmetric cells with

0.5 M and without urea after cyclic tests at a current density of 1 mA cm-2 for each

2h interval; (a and e) 1 cycle, (b and f) 5 cycles, (c and g) 10 cycles, (d) 50 cycles,

and (h) pristine Li metal.

- 16 -
 When the first cycle finished, the morphology of the Li electrode was similar

granular shape with and without urea additive (Fig. 4.3 (a) and (e)). When cycle

number increased, the morphology of the Li electrodes obtained from the cell with

0.5 M urea additive showed a smooth and granular shape. In particular, the

morphology of the Li electrode after 50 cycles finished was similar smooth shape

with pristine Li electrode (Fig. 4.3 (d)). However, the morphology of the Li

electrode obtained from the cell without the urea additive exhibited the mossy Li

dendrites and dead Li with increasing cycles (Fig. 4.3 (g), Fig. 4.4 (c)).

Further, Fig 4.4 shows the typical images of the Li electrode and separator from

the symmetric cell after 10 cycles at a current density of 1.0 mA cm -2 for 2 h

discharge and charge intervals. As shown in Fig. 4.4 (a), pristine Li electrodes

showed bright silver color of Li metal, and (d) the pristine separator was white

color. After 10 cycles, Li electrode and separator obtained the with urea additive

exhibited the similar silver color of pristine Li metal and white color of separator

(Fig. 4.4 (b) and (e)). In contrast, the color of the surface of the Li electrode and

separator without urea additive changed from white to black (Fig. 4.4 (c) and (f)).

This indicates that the LiTFSI/TEGDME electrolyte without urea highly react with

the Li dendrites and produces the dead Li. Therefore, the cyclability of the Li

symmetric cell could be significantly improved because the urea additive was

helpful to suppress the growth of the Li dendrites and make smooth SEI layer.

- 17 -
Fig. 4.4. Typical images of components from the Li symmetric cell: (a) pristine Li

metal; Li metals (b) with and (c) without 0.5 M urea additive; (d) bare separator;

the separators from the cell (e) with 0.5 M urea additive and (f) without urea additive.

The cells were cycled after 10 cycles at a current density of 1.0 mA cm -2 for 2h

each of discharge and charge steps.

- 18 -
 4.3 Electrochemical performance of Li/Li symmetric cells

Fig. 4.5. Electrochemical impedance spectra of the Li symmetric cells (a) with 0.5

M and (b) without urea electrolyte additive. The cells were cycled under the limited

capacity of 2.0 mA h cm-2 and current density of 1.0 mA cm-2.

To further elucidate the influence of the urea additive electrolyte, impedance

measurements were performed on the Li symmetric cells after each cycle. Fig. 4.5

displays the impedance spectra of the cells after various cycles, when the cells

were cycled at a current density of 1.0 mA cm -2 for 2h intervals each discharge

and charge step. The equivalent circuit model used for the data fitting is shown in

Fig. 4.6. Rs, indicates the electrolyte resistance, RSEI corresponding to the SEI layer

resistance originating from the reaction products formed on the surface of the Li

electrode, and Rct denotes the charge transfer resistance. CPESEI and CPEdl are the

corresponding constant phase elements. The fitting data of the symmetric cell with

and without urea additive was also shown in Table. 4.1 and Table. 4.2, respectively.
- 19 -
The impedance of the cell with 0.5 M urea additive exhibited the similar

phenomenon of the Li symmetric cell test (see Fig. 4.1 (c)). The impedance of the

cell with 0.5 M urea significantly increased after 1 cycle. However, the impedance

decreased and was stabilized from the following cycles. The impedance was

maintained around 30 Ω after 50 cycles (Fig. 4.5 (a)). In contrast, Fig. 4.5 (b) shows

the impedance of the cell without urea additive significantly increased after 10

cycles (cell failure). This indicates that the first formation of SEI layer with urea

additive was too resistive, which was induced high resistance. However, it can be

soon stabilized. In contrast, the cell without urea additive was gradually increased.

This increase of impedance was related to the dendrite formation of Li, break the

SEI layer and formation of dead Li. Therefore, urea additive electrolyte was

helpful to make stable SEI layer and prevent the formation of Li dendrite.

Fig. 4.6. Equivalent circuit for the impedance spectra of the Li symmetric cell.

- 20 -
 Table 4.1. Fitted parameters corresponding to equivalent circuit models for the

impedance of the Li symmetric cell with 0.5 M urea additive.

Sample Rs RSEI CPESEI Rct CPEdl

(Ω) (Ω) CSEI(F) nSEI (Ω) Cdl (F) ndl

After 1st cycle 7.52 1127.2 9.94 × 10-4 0.638 858.7 1.03 × 10-5 0.790

After 5th cycles 8.28 22.58 6.96 × 10-5 0.770 51.0 4.39 × 10-6 0.889

After 10th cycles 8.28 22.56 6.97 × 10-5 0.770 51.1 4.38 × 10-6 0.890

After 50th cycles 8.87 16.18 2.56 × 10-5 0.797 6.00 7.26 × 10-6 1.021

Table 4.2. Fitted parameters corresponding to equivalent circuit models for the

impedance of the Li symmetric cell without 0.5 M urea additive.

Sample Rs RSEI CPESEI Rct CPEdl

(Ω) (Ω) CSEI(F) nSEI (Ω) Cdl (F) ndl

After 1st cycle 10.08 19.66 3.37 × 10-2 0.448 19.86 2.18 × 10-5 0.829

After 5th cycles 6.46 22.48 1.99 × 10-4 0.545 9.60 5.92 × 10-2 0.736

After 10th cycles 64.62 867.0 8.59 × 10-6 0.445 834.11 2.96 × 10-2 0.157

- 21 -
 Fig. 4.7. Cyclic voltammograms of 1 M LiTFSI in TEGDME (a) with 0.5 M and (b)

without urea using a glassy carbon working electrode at a scan rate of 0.1 mV s -1

in potential range of -0.5 ~ 4.5 V vs. Li/Li+.

To investigate the effect of the urea additive in the electrolyte, Cyclic

voltammetry tests were measured in an electrolyte of 1 M LiTFSI/TEGDME

containing 0.5 M urea additive using a 3-electrode cell system. The cell system

was composed of a glassy carbon as a working electrode, Li metal as a reference

and counter electrode at a scan rate of 0.1 mV s -1 in a potential range of -0.5 ~

4.5 V vs. Li/Li +. During the first cathodic scan, a reduction peak was observed at

~ 0.3 V vs. Li/Li + in a condition with 0.5 M urea additive (Fig. 4.7 (a)), while no

reduction peak was detected at this potential region in a condition without urea

additive (Fig. 4.7 (b)) [34]. After increasing the cycles, the reduction current

density of the cell with 0.5 M urea additive was decreased (Fig. 4.7 (a)), while the

reduction current density of the cell without the additive was increased (Fig. 4.7

(b)). It is indicated that urea additive suppressed the electrolyte decomposition.

- 22 -
 4.4 Surface chemical composition analysis

Fig. 4.8 displays the XPS spectra of the Li electrodes obtained from the Li

symmetric cells after specific cycles. The chemical components estimated based

on the corresponding binding energies are listed in Table 4.3. The decomposition

products of the LiTFSI salt such as LiF (at 685.9 eV in XPS F 1s spectrum), Li 2SO4

(at 169.7 eV in XPS S 2p spectrum), Li 2S2O4 (at 166.2 eV in XPS S 2p spectrum),

Li3N (at 397 eV in XPS N 1s spectrum) were detected in the XPS spectra for the

Li electrode obtained from the cell with 0.5 M urea additive (Fig. 4.8 (a)) and

without urea additive (Fig. 4.8 (b)). In addition, the relative intensity of these

decomposition products gradually increased with the increased number of cycles.

However, the relative intensity of these decomposition products was shown to be

smaller for the Li electrode obtained from the electrolyte with urea under same

conditions. For example, Li electrode obtained from the cell with 0.5 M urea

additive, the LiTFSI salt was detected by presence of the C 1s peaks at 292.6 eV,

the F 1s peaks at 688.6 eV, the N 1s peaks at 399.4 eV, and the S 2p peaks at

168.7 eV after 10 cycles and even after 50 cycles (Fig. 4.8 (a)). Also, the urea

additive was detected by the presence of the N 1s peaks at 399.5 eV (Fig. 4.8 (a)).

In contrast, the Li electrode obtained from the cell without urea additive, the

LiTFSI salt was experienced serious decomposition [44-46]. As shown in Fig. 4.8

(b), the intensity of the peaks corresponding to LiF at 684.9 eV in the F 1s

spectrum was increased following cycles. Also, the peak of C-F bond was

observed after 10 cycles. Simultaneously, the intensity of the peaks corresponding

- 23 -
to other decomposition products of the LiTFSI salt such as Li 3N, Li2SO3, Li2S2O4

was increased following cycles.

This indicates that the urea additive effectively suppressed the decomposition of

the electrolyte especially LiTFSI salt.

Table 4.3. Binding energies corresponding to the fitted peaks for the surface of the Li

electrode of the Li symmetric cell.

Components Binding energy (eV)

C1s O1s F1s S2p3/2 N1s

Hydrocarbon 285

LiTFSI 292.6 688.5 168.7 399.4

Li2O 528.8

LiF 684.9

Li3N 397

Li2S 161.2

Li2S2O4 166.2

Li2SO4 169.7

Polysulfur 163.8

Li2CO3 290.3 531.8

-COO 287-288 532.3

C=O 286.1- 533.6

287.1

(NH2)2CO 288.7 535.0 399.5

- 24 -
Fig. 4.8. XPS spectra of the Li electrodes, obtained from the cells with and without 0.5

M urea. The cells were cycled at a current density of 1.0 mA cm-2 for each 2 h interval.

- 25 -
Fig. 4.9. FTIR spectra of the Li electrodes, obtained from the cells (a) with and (b)

without 0.5 M urea additive after cyclic tests at a current density of 1 mA cm-2 for 2h

interval. The reference spectra corresponding to HCOOLi, CH3COOLi, LiOH, Li2CO3,

Urea, LiTFSI, and TEGDME were also indicated.

To further investigate the effects of the urea additive, the surface analysis of the

tested Li electrode was examined by FTIR. The various groups such as –CH2, C=O,

C-O, SO2, S-N-S, S-S, Li-O was detected in the FTIR spectra (Fig. 4.9). These

peaks represent the decomposition products of the LiTFSI salt and TEGDME

solvent [4, 47-49]. Based on the XPS and FTIR data in this study, the mechanism

of the formation of the SEI layer on the surface of the Li electrode in the symmetric

cell is suggested as follows [50-53].

- 26 -
 Decomposition of the LiTFSI salt:

LiN(SO 2CF3)2 + n e- + n Li + → Li3N + Li2S2O4 + LiF + C2FxLiy (1)

LiN(SO 2CF3)2 + 2 e- + 2 Li + → Li2NSO2CF3 + CF3SO2Li (2)

Li2S2O4 + 10 e- + 10 Li + → 2 Li2S + 4 Li2O (3)

Li2S2O4 + 4 e- + 4 Li+ → Li2SO3 + Li2S + Li2O (4)

Decomposition of the TEGDME solvent:

R-O-R’ + e- + Li+ → ROLi + R’ * or R’OLi + R * (5)

R* + Li* → RLi (6)

R* + R* → R2 (7)

R* + H* → RH (8)

Where R and R’ are the hydrocarbon or etheric groups.

For the Li electrode obtained from the cell with urea additive, the mechanism for

decomposition of LiTFSI salt and TEGDME solvent was similar to the cell without

urea. However, the increased intensity of the NH 2, C=O, O-S-O, N-H peaks was

observed when increased following cycles (Fig. 4.9 (a)). Due to the effect of the

urea additive, urea has two functional groups which can interact with LiTFSI; the

C=O group can interact with the cation of the LiTFSI salt while the H atoms in the

NH2 groups can form the hydrogen bonding with the SO 2 groups of TFSI - anion

[34].

- 27 -
 Fig. 4.10 shows the FTIR spectra of the pure LiTFSI and urea [47, 55-59]. Also,

the vibrational frequencies and assignments for LiTFSI and urea as shown in Table.

4.4. As shown in Fig. 4.9 (a), the symmetric bending of the NH 2 related to urea

unchanged at 1675 cm -1. However, the asymmetric bending mode of NH2 and

symmetric stretching mode of C=O belonging to urea was shifted from 1621 cm -1

to 1661 cm -1 and 1591 cm -1 to 1629 cm -1 respectively [59]. Simultaneous, the

intensity of the symmetric bending mode of the O-S-O related to TFSI - anion was

increased. Furthermore, urea is known to be a hydrogen bond donor.

Fig. 4.10. FTIR spectra of the pure (a) LiTFSI and (b) urea.

- 28 -
 Urea gives to H atoms to LiTFSI salt and occurs the peak change. In the

frequency region from 3400 cm -1 to 3200 cm -1, The intensity of the symmetric

and asymmetric stretching mode of the N-H of the urea was increased and broad,

when increased following cycles [42 ,59-61]. However, the FTIR spectra of the

Li electrode obtained from the cell without urea was detected that the intensity

of the Li-O (at around 500 cm-1), S-S (at around 400 cm-1) increased when

increased cycles. This indicates the higher electrolyte decomposition and dead

Li on the surface of the Li electrode [50]. It is evident that urea additive interact

with LiTFSI salt and suppress the decomposition of LiTFSI salt.

- 29 -
 Table 4.4. Vibrational frequencies and assignments for LiTFSI and Urea.

LiTFSI Urea [(NH2)2CO]

Wavenumber Vibrational Wavenumber Vibrational

(cm-1) mode (cm-1) mode

2876 ϑ S-CF3 3430 ϑ N-H

1325 ϑ C-SO2-N 3332 ϑas NH2

1244 ϑas SO2 3256 ϑs NH2

1198 ϑas CF 1675 δs NH2

1141 ϑ C-SO2-N 1619 δas NH2

1061 ϑas S-N-S 1590 ϑs C=O

811 δs CF3 1458 ϑ C-N

747 ϑ S-N

635 δs O-S-O

572 δas CF3

512 δas O-S-O

- 30 -
 4.5 Effects of urea additive in Li-O2 cell

To investigate the applicability of the urea additive in Li metal-based batteries,

we fabricated a Li-O2 cell using 1 M LiTFSI/TEGDME electrolyte containing 0.5

M urea additive. For comparison, we also fabricated a Li-O2 cell without urea

additive. Herein, the MnO 2@ Ni oxygen electrode was prepared by a hydrothermal

method and annealed at 450 ℃ for 5 h [50, 51, 62, 63]. The XRD analysis on the

MnO2@Ni electrode confirmed the tetragonal structure of α-MnO2 (JCPDS card no.

00-044-0141) as shown in Fig. 4.11 and 4.12.

Fig. 4.11. XRD patterns of MnO2 catalyst formed on Ni foam (a) after annealing at
450 ℃ for 5 h, (b) before annealing, and (c) fresh Ni foam.

- 31 -
Fig. 4.12. XRD patterns of MnO2 powder obtained by hydrothermal method; (a) after
and (b) before annealing at 450 ℃ for 5 h.

Fig. 4.13. SEM images of fresh Ni foam: (a) low and (b) high magnification. SEM
images of the MnO2 catalyst formed on Ni foam: (c) low and (d) high magnification.
- 32 -
 Also, the morphology of MnO 2@Ni electrode was shown in Fig. 4.13. The

MnO2@Ni electrode exhibited a highly open and porous structure.

Fig. 4.14 (a) Variation of the end cell potential with cycle for the Li-O2 cells without
and with the electrolyte additive, tested under a limited capacity mode of 1000 mAh
g-1 at the current density of 0.1 mA cm-2 in a pure O2 atmosphere: relevant discharge-
charge cell potential profiles in conditions (b) with and (c) without 0.5 M urea additive.

- 33 -
 Fig. 4.14 shows the galvanostatic discharge-charge potential profiles and

cyclabiliy of Li-O2 cells with and without urea additive in electrolyte. The cells

were tested under the limited capacity mode of 1000 mAh g -1 at the current density

of 0.1 mA cm -2 within the cut-off potential range between 2.0 V and 4.5 V under

the 1 atm pure oxygen atmosphere. The capacity of the cell is indicated based on

the weight of MnO2.

For the cell with 0.5 M urea additive, the end cell potential of the first discharge

and charge state are located at 2.81 V and 4.10 V, respectively. Whereas the cell

without additive, the end cell potential of the first discharge and charge state are

located at 2.87 V and 4.04 V, respectively (Fig. 4.14 (a)). The first cycle

polarization of the cell with 0.5 M urea was slightly higher than the cell without

urea. However, the discharge state end cell potential of the cell with 0.5 M urea

was maintained at ~ 2.7 V up to 35 cycles, at ~ 2.6 V up to 128 cycles, at ~ 2.5

V up to 188 cycles and at ~2.4 V up to 195 cycles. After that discharge state end

cell potential of the cell with 0.5 M urea exhibited the rapid decay. In the 201 th

cycle of discharge. The cell potential was reached at cut-off potential at 2.0 V.

However, the discharge state end cell potential of the cell without urea was

maintained only at ~ 2.7 V up to 25 cycles, at ~ 2.6 V up to 46 cycles, at ~ 2.5 V

up to 47 cycles and at ~2.4 V up to 48 cycles. In the 49th cycle of discharge, the

cell potential was reached at cut-off potential at 2.0 V. In case of the charge state,

the end cell potential of the cell with and without urea additive was sustained at

~ 4.0 V up to cell failure. This result showed that the Li metal electrode with 0.5

M urea additive was more stable due to interact with LiTFSI salt and urea additive.

- 34 -
This interaction was helpful to make stable SEI layer formation and suppressed

electrolyte decomposition and evaporation.

- 35 -
 5. Conclusion

The effect of urea as an electrolyte additive for Li-metal based batteries such as

Li-O2 batteries is reported for the first time. The urea additive clearly contributed

to the suppression of the growth of Li dendrite and electrolyte decomposition

especially LiTFSI salt due to interact with LiTFSI and urea. Interaction between

urea and LiTFSI were found to use XPS and FTIR analysis. Accordingly, the Li

symmetric cell employing 0.5 M urea additive operated for 545 cycles

corresponding to a lifetime of 2176 h at a current density of 1.0 mA cm -2 for each

discharge and charge 2h intervals. Even at high current densities of 0.5, 1.5, 2.0

mA cm-2, the Li symmetric cell employing 0.5 M urea additive successfully

operated longer than 1200 h corresponding to cycle number of 300 cycles.

Furthermore, the Li-O2 cell containing the 0.5 M urea additive operated for 201

cycles under a limited capacity mode of 1000 mAh g -1. This cycle life was shown

to be 4 times higher than the cycle life of cell without additive.

- 36 -
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 리튬 금속 기반 전지에서 리튬 덴드라이트 성장 억제를

위한 유기 계 첨가제의 효과

김 희 상

전남대학교대학원 신소재공학과

(지도교수 : 박 찬 진)

(국문초록)

최근 에너지 수요가 급증함에 따라, 고 용량 및 고 에너지 밀도의 전지가

요구되고있다. 하지만, 현재 사용하고 있는 탄소 계 음극 물질의 용량 적 한계로

인하여 차세대 음극 물질이 요구되고 있다. 그 중 리튬 메탈은 가장 이상적인 음극

물질로 고려되고 있다. 리튬 메탈을 음극 물질로 사용 시 높은 이론 용량, 높은

전압 구현 등의 장점을 가지고 있지만, 충∙방전 시 국부적인 전류 집중으로 인해

SEI layer 가 깨지고 그 부분을 타고 Li dendrite 성장이라는 큰 문제점을 가지고

있다.

Li dendrite 성장 억제를 위해서 많은 방법으로 연구되고 있고, 인공적으로 SEI

layer 를 형성시켜 Li dendrite 성장을 억제하는 방법과 기존 SEI layer 에 첨가제

등을 이용하여 안정화 시키는 방법으로 크게 두가지로 나눌 수 있다. 본 연구는 그

중에서 전해질 내에 요소 첨가를 통해 안정한 SEI layer 를 형성시켜 Li dendrite

성장을 억제하는 연구를 진행했다. 고 전류밀도조건에서 리튬 대칭 셀 시험을 하여

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최적의 첨가제 함량을 도출했다. 최적 조건의 요소 첨가제가 첨가된 경우 1.0 mA

cm-2 의 전류 밀도 조건에서 2500 시간 이상 수명을 유지했고, 이 수치는 요소

첨가제가 없는 경우와 비교 시 50 배 이상의 수명이 증가했다. 그 후, 최적 첨가

조건에서 전류 밀도를 변화시키면서 첨가제인 요소의 성능을 파악했다. 요소

첨가제의 역할에 대한 정확한 분석을 위해 CV, EIS 등의 실험을 통해 전기화학적

분석을 진행하였고, XPS, FTIR 등의 실험을 통해서 리튬 메탈의 표면 분석을

진행했다. 리튬 대칭 셀에서 얻어진 결과를 토대로 요소 첨가제가 첨가된 전해질을

이용하여 리튬-공기 전지에 적용시켜, 실제 전지에서 적용 가능성을 평가했다.

리튬-공기 전지의 경우 양극 부분이 개방 구조를 가지므로, 액체 전해질의 분해 및

증발이 쉽게 일어난다는 단점을 가지고 있다. 하지만, 요소 첨가제가 적용된 경우

음극 물질인 리튬 메탈 부분에 안정한 SEI layer 를 형성되어, 액체 전해질의 분해

및 증발을 막아 리튬-공기 전지의 수명이 요소 첨가제가 없는 경우와 비교 시 약

4 배 이상 증가시키는 결과를 얻었다.

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