TUGAS PENGANTAR KIMIA BAHAN BAKAR

RESUME JURNAL INTERNASIONAL

MANUFACTURING OF γ-LiAlO2 MATRIX FOR MOLTEN CARBONATE FUEL
CELL BY HIGH-ENERGY MILLING

Dosen Pengampu : Dr. Tety Sudiarti M.Si

Disusun oleh :
Kelompok 3
Ratna Lusiyana (1167040059)
Rizki Abdul Azis (1167040064)
Tri Bungsu Oktaria (1167040080)
Tyas Mega Legiastuti (1167040083)
Viranda Andria Yuninda (1167040084)

KIMIA 5 B
JURUSAN KIMIA
FAKULTAS SAINS DAN TEKNOLOGI
UNIVERSITAS ISLAM NEGERI SUNAN GUNUNG DJATI
BANDUNG
2018
MANUFACTURING OF γ-LiAlO2 MATRIX FOR MOLTEN CARBONATE
FUEL CELL BY HIGH-ENERGY MILLING

A. Abstract
MCFC in the process uses liquid electrolytes which must be mobilized in a porous
matrix. MCFC uses high temperatures to melt salt. The pulp material of (γ -LiAlO2) and
green matrix is made by tape casting method. Next to obtain the desired matrix structure,
(γ -LiAlO2) powder is ground in the planet's ball mill by mixing solvents, dispersants and
defoaming for 18 hours. The next step is to add a binder and plasticizer to obtain the optimal
rheology of the slurry. Cell tests show optimal performance of the Lithium aluminate
matrix. The burning matrix was characterized by (SEM) and laser diffraction to determine
the particle size and morphology of γ-LiAlO2 powder. The results show that high energy
milling will obtain a good pore structure and a high specific surface area of the matrix can
be obtained in a relatively short time. The results of the matrix structure obtained in this
study are suitable for high performance MCFC operations.
B. Introduction
MCFC is the most widely available efficient power generation device. MCFC is
more flexible in terms of refueling and does not require rare metal catalysts. For example
nickel metal has a low price showing strong catalytic activity at high working temperatures
of cells. MCFC uses liquid electrolytes consisting of lithium, potassium, sodium carbonate.
The electrolyte matrix is produced from lithium aluminate (γ -LiAlO2) by ceramic/
polymer slurry casting tape. Ceramic/polymer slurry is prepared by a grinding process
which takes a long time as long as the base material undergoes refinement. The γ -LiAlO2
powder is embedded in the polymeric PVB binder, which burns during the start-up
procedure (PVB decomposes at about 400 ⁰C. Thus leaving the porous structure to be filled
with melting electrolytes.
Translucent pressure (between the anode and cathode) corresponds to the pore
radius in the matrixcalculated from the Young-Laplace equation. Assuming a pressure
 difference of 105 Pa, the pore radius must be 3.96 mm. If the pore size is reduced, then the
electrolyte matrix can withstand greater pressure differences without the occurrence of a
gas crossover, so the grain size of the powder must be controlled to ensure adequate
capillary action.
Strengthening the Lithium aluminate matrix occurs when the addition of aluminum
and Li2CO3 particles to the γ -LiAlO2 matrix uses stainless steel wire (0.3 mm thick) and
aluminum foam. In this work, planetary grinding has been successfully used to improve
the particle size of γ -LiAlO2 for the MCFC Matrix during preparation of the slurry. Matrix
production is characterized by scanning electron microscopy (SEM) and laser diffraction.
Good pore structure and high specific surface area of the matrix are considered suitable for
high performance operations.
C. Experimental Procedure
Matrix fabrication
The matrix is made of ceramic tape casting or polymer slurry using a castor tape.
Caster tape is a mobile device with a high doctor blading that is set to 0.55 mm. The basic
material used is LiAlO2 powder which is subjected to laser scattering for particle size
analysis which will determine the particle size distribution of powder before it enters the
planetary ball mill. LiAlO2 powder was milled in sintered zirconia containers with 5 mm
zirconia balls in Retsch PM400 mill at 250 rpm for 18 h.
The first mill was carried out by adding ethanol purchased from APMP, adding
solsperse 2000 dispersants, and defoamer DF300 agitates. this composition produces low
viscosity and good powder dispersion. then, other ingredients such as PBB Mowital pvb
binder and dibutyl phthalate plasticizer (DBP) were added and milled for 3 hours vacuum
deaired to obtain homogeneous slurry. this step can be seen from the flow diagram in figure
2. This milling is done to reduce the particle size of LiAlO2 powder to produce a smaller
pore size than the matrix. in addition, this technique allows the slurry results obtained to
be homogeneous.
Characterization and testing
In order to investigate the structure of the matrix with scanning electron
microscopy, green tapes were heated slowly to 650 _C and kept at this temperature for 18
h in order to burn out the binder and other additives. This procedure mimics the start-up of
the fuel cell stack. A sample of the matrix was vacuum deposited with copper and observed
on a Hitachi SU8000 scanning electron microscope.
Quantitative image analysis was performed in order to study g-LiAlO2 particle size
distribution [15,16]. Burned out matrices were also subject to BET specific surface area
analysis. Porosity was evaluated by measuring the bulk volume of a series of samples from
each matrix tape.
In order to conduct a performance test of the single MCFC, a stack of two 7 _ 7 cm
green tapes was utilized as a matrix with reference Ni/NiO electrodes and eutectic
Li2CO3/K2CO3 (32/68) carbonate melt. For comparison purposes, a reference LiAlO2
matrix [5] was used, as the only variable in the cell assembly.
Testing was conducted at 650 _C for 1000 h and the working area of the cell was
20 cm2. The unit (see Fig. 3) was operated at atmospheric pressure with the same reference
point for gas compositions and flow rates. Fuel gas (H2)80(CO2)20 and oxidant gas
(Air)70(CO2)30 were used. All components were housed in 310 alloy stainless steel
endplates with 310 alloy current collectors. Cell voltage was directly measured at the
electrodes and its value processed by a National Instruments board. Currentevoltage
characteristics and area specific resistance measurements were made every 200 h. For load
demand, DC electronic load (SAE Electronic Conversion SRL) was used.

Fig. 1 e Particle size distribution of base g-LiAlO2 powder (Horiba LA-950 analyzer)
shows that raw powder is too coarse for capillary retention of electrolyte. Planetary ball
milled powder (after 18 h) has a mean size of under 0.5 mm.
Fig. 2 e Flowchart of the g-LiAlO2 matrix preparation.

Fig. 3 e Testing rig for the single MCFC unit used in this study.
 D. Results and Discussion
Greenmatrix tapes, without defects such as agglomerates and voids, were cast
on a smooth polyethylene surface. The resulting tapes were dried for 48 h at ambient
conditions and separated from the PE surface. Their thickness was measured at
0.30mme0.35mm. The aforementioned milling parameters (250rpm, 18þ3h)were found to
give optimal results in terms of particle and pore size of theburned out tape (see Figs. 4
and 5).A few coarse g-LiAlO2 grains were observed, but fine neighboring particles made
for a uniform pore size of under 1 mm, which is sufficient for capillary holding of
electrolyte melt.

SEM Analysis
Testing showed proper gas sealing of the electrodes and nosigns of fuel crossover (open-circuit
voltage was unaffected) after 120 h of operation. Gas sealing was confirmed by applying
differential pressure between the electrodes in order to check for the presence of cracks in the
matrix. Electrolyte impregnated matrix dismantled from the unit (after 1000 h) exhibited uniform
wetting with the electrolyte melt. This proves correct capillary action of the electrolyte due to the
pores being smaller than the pores of the electrodes, which were in direct contact with the matrix.

Table 1 Characteristics of γ-LiAlO2 Matrices

In table one it is shown that porosity and surface area of the matrix are higher than
the reference matrix. The results of higher porosity and smaller pore size on the matrix are
influenced by the grinding process with the planetary ball mill which results in better
performance than the reference results matrix. higher porosity will increase the electrolyte
work area which causes increased ionic conductivity of the layer and prevents gas
crossover.
 Figure 1 Current density/power density characteristics for the single MCFC show greater
efficiency than reference [5] matrix.

From the curve in Figure 6 it can be seen that the current density or the characteristic
of the power density in the matrix produced has efficiency greater than the matrix of the
reference results. cells of the matrix produced have a 23% increase in the yield of the
reference matrix.

Figure 2 Maximum power density and ASR (area specific resistance) for increasing operation
time (up to 1000 h) for the tested cells.
 Maximum power density for each cell and area specific resistance (ASR) measured
every 200 hours for 1000 hours in a period produces a performance without significant
degradation (stable).
E. Summary

In this research, the lithium aluminate for making the matriks is development by
method of planetary ball miling (grinding) ethanol dispersed and powder ceramic.From the
milling was resulted the slurry and then reacted with vpb binder (such as the adhesive) and
DBP plasticizer (that is the name of substances / substances added).

So the method of energy planetary ball miling it with high energy that helping the
produce of matrix ito a size submicron (so the size of the Matrix it's submicron) and to
prevent the slurry contaminated with metal due to conduction electron If contaminated
cause conductivity large from the matrix and efficiency of the stack is reduced.

The preparation method using this slurry method is better because the
consumption of time is less than what has been done by Silly, Coy, and Wang. So the
determining factor is high energy, the grinding strength is a factor that determines the
formation of good structure pores, and the surface area is specific so the structure produced
by this method is suitable for MCFC operations.

So internal resistance and the density of energy including the characteristics of

the matrix, so that the characteristics of the internal resistance matrix and energy density
measured for 1000 hours per view without perfomance degradation which means doesn't
happen degradation, does not show a reduction of resistance or power density, so that good
perfomance does not decrease on that matrix.