NASICON电位计Cl2传感器：结合NASICON与Cr2O3电极
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"这篇研究文章探讨了一种基于NASICON（Na超级离子导体）的电位计Cl2（氯气）传感器，该传感器结合了NASICON和Cr2O3（铬酸盐）感应电极。研究发现，在检测的八种单一氧化物中，Cr2O3在300℃时对空气中氯气的敏感度最高。传感器的电动势（EMF）值随着Cl2浓度的对数线性变化，表明其在5-50 ppm范围内的灵敏度。通过使用不同温度烧结的Cr2O3电极，验证了传感器的可靠性和灵敏度。600℃烧结的Cr2O3电极在300℃下对Cl2表现出最大敏感性。此外，通过将参考电极埋入NASICON层的中间并减小其面积，能显著提高传感器对Cl2的灵敏度。最后，文章提出了一种基于NASICON和氧化物电极的混合电位感应机制来解释传感器的工作原理。"
本文的核心知识点包括：
1. **NASICON材料**：NASICON（Na超级离子导体）是一种具有优异离子传导性的陶瓷材料，常用于制造气体传感器，因为它允许离子快速移动，从而在电极间形成电位差。
2. **Cr2O3感应电极**：Cr2O3被发现在300℃下对氯气有最高的敏感度，这使得它成为构建氯气传感器的理想材料。其在不同浓度的Cl2中表现出电动势的对数线性响应，证明了其作为感应电极的高效性能。
3. **烧结温度的影响**：研究显示，烧结温度对Cr2O3电极的性能有显著影响。600℃烧结的Cr2O3在300℃时对Cl2的敏感度最高，表明烧结条件对传感器的性能至关重要。
4. **埋藏参考电极**：通过将参考电极嵌入到NASICON层的中间，并减小其表面积，可以显著提高传感器对氯气的响应灵敏度。这种方法优化了传感器设计，增强了其对目标气体的探测能力。
5. **混合电位感应机制**：文中提出的感应机制是基于NASICON和氧化物电极的混合电位，这种机制解释了传感器如何通过电位变化来检测氯气的存在和浓度。
该研究为开发高性能氯气传感器提供了新的视角和方法，特别是在环境监测、工业安全以及可能的能源应用中，对于氯气泄漏的快速准确检测具有重要意义。
Please
cite
this
article
in
press
as:
H.
Zhang,
et
al.,
NASICON-based
potentiometric
Cl
2
sensor
combining
NASICON
with
Cr
2
O
3
sensing
electrode,
Sens.
Actuators
B:
Chem.
(2012),
doi:10.1016/j.snb.2012.03.024
ARTICLE IN PRESS
G
Model
SNB-13976;
No.
of
Pages
5
Sensors
and
Actuators
B
xxx (2012) xxx–
xxx
Contents
lists
available
at
SciVerse
ScienceDirect
Sensors
and
Actuators
B:
Chemical
journa
l
h
o
mepage:
www.elsevier.com/locate/snb
NASICON-based
potentiometric
Cl
2
sensor
combining
NASICON
with
Cr
2
O
3
sensing
electrode
Zhang
Han,
Li
Jianguo,
Zhang
Houbo,
Liang
Xishuang
∗
,
Yin
Chengguo,
Diao
Quan,
Zheng
Jie,
Lu
Geyu
∗∗
State
Key
Laboratory
on
Integrated
Optoelectronics,
College
of
Electronic
Science
and
Engineering,
Jilin
University,
2699
Qianjin
Street,
Changchun
130012,
China
a
r
t
i
c
l
e
i
n
f
o
Article
history:
Available online xxx
Keywords:
NASICON
Oxide
electrode
Cl
2
sensor
Buried
reference
electrode
Mixed
potential
a
b
s
t
r
a
c
t
This
work
focuses
on
the
sensing
performance
of
the
sensor
to
chlorine
(Cl
2
)
gas
in
air
based
on
sodium
super
ionic
conductor
(NASICON)
and
oxide
electrode.
Among
eight
single
oxides
examined,
Cr
2
O
3
exhib-
ited
the
highest
sensitivity
to
Cl
2
gas
in
air
at
300
◦
C.
EMF
values
of
the
sensing
device
attached
with
Cr
2
O
3
changed
linearly
with
the
logarithm
of
Cl
2
concentration
in
the
range
of
5–50
ppm.
The
sensitivity
of
the
sensors
was
testified
by
using
Cr
2
O
3
electrode
sintered
with
different
temperature.
The
sensor
using
Cr
2
O
3
sintered
at
600
◦
C
showed
the
largest
sensitivity
to
Cl
2
at
300
◦
C.
Through
burying
the
ref-
erence
electrode
in
middle
of
the
NASICON
layer
and
decreasing
the
area
of
the
reference
electrode,
the
sensitivity
of
the
sensor
to
Cl
2
can
be
greatly
improved.
Finally,
a
sensing
mechanism
related
to
the
mixed
potential
was
proposed
for
the
sensor
based
on
NASICON
and
oxide
electrode.
© 2012 Elsevier B.V. All rights reserved.
1.
Introduction
Chlorine
widely
used
in
industrial
processes
is
strongly
harmful
and
toxic
when
emitting
into
air,
so
high-performance
Cl
2
sensors
have
been
urgently
desired
for
detecting
chlorine
in
the
atmo-
sphere.
Up
to
now,
various
kinds
of
chlorine
sensors
based
on
semiconductor
oxide
[1],
organic
thin
film
[2]
and
solid
electrolytes
[3–6]
have
been
developed.
Among
them,
the
solid
electrolyte
type
sensors
exhibit
excellent
sensing
performance,
such
as
high
sensitivity,
rapid
response
kinetics,
outstanding
selectivity
and
reproducibility.
For
the
solid
electrolyte
sensors,
most
researches
focused
on
the
sensors
based
on
yttria
stabilized
zirconia
(YSZ)
and
sodium
super
ionic
conductor
(NASICON).
In
general,
the
YSZ-
based
sensor
was
operated
at
high
temperature
(600–800
◦
C),
so
it
seems
to
be
inappropriate
for
detecting
the
gases
in
atmospheric
environment
because
of
its
high
power
consumption.
Contrary
to
the
YSZ-based
sensors,
the
mixed
potential
type
sensors
based
on
NASICON
are
generally
operated
at
the
intermediate
temper-
atures
(300–500
◦
C),
so
they
are
more
suitable
for
detecting
the
toxic
gases
in
the
atmospheric
environment.
In
recent
years,
more
and
more
researches
have
been
reported
about
choosing
suitable
oxide
electrodes
for
improving
the
sensing
characteristics
of
mixed
potential
type
sensors.
For
example,
Miura
et
al.
reported
that
the
YSZ
based
sensors
using
ZnCr
2
O
4
,
ZnFe
2
O
4
,
NiO
or
Cr
2
O
3
+
NiO
as
sensing
electrode
showed
excellent
sensing
properties
to
NO
x
at
elevated
temperatures
[7–9].
Park
et
al.
also
examined
that
NiO
∗
Corresponding
author.
Tel.:
+86
431
85168384;
fax:
+86
431
85167808.
∗∗
Corresponding
author.
Tel.:
+86
431
85167808;
fax:
+86
431
85167808.
E-mail
addresses:
liangxs@jlu.edu.cn
(X.
Liang),
lugy@jlu.edu.cn
(G.
Lu).
and
CuO
were
suitable
as
the
sensing
electrode
for
NO
2
sensor
[10].
In
addition,
Miura
et
al.
developed
high
performance
CO
and
H
2
sensors
combining
stabilized
zirconia
and
CdO/SnO
2
sensing
electrode
[11].
Liang
et
al.
investigated
the
sensing
properties
of
the
sensor
using
NASICON
and
V
2
O
5
-doped
TiO
2
electrode
to
SO
2
[12].
Another
approach
to
improve
the
performance
of
this
type
of
sensor
is
to
optimize
the
sensor
structure.
Miura
et
al.
designed
a
tubular
mixed-potential
sensor
which
can
effectively
prevented
the
reactions
between
the
target
gas
and
the
reference
electrode,
how-
ever
the
fabrication
processes
were
rather
complex
and
the
devices
are
easily
damaged
[11].
Except
for
the
tubular
ones,
Elumalai
and
Miura
reported
a
planar
NO
2
sensor
using
stabilized
zirconia
and
NiO
as
sensing
electrode
at
high
temperature
with
simple
fabri-
cation
processes
[13].
Nevertheless,
the
reference
electrode
was
exposed
to
the
sample
gases
that
could
reduce
the
sensitivities
of
the
sensor.
Among
the
solid
electrolyte
sensors
reported,
the
sensor
for
detecting
chlorine
is
rarely
studied.
Recently,
we
have
designed
a
compact
tubular
potentiometric
Cl
2
sensor
and
the
structure
has
been
described
in
our
previous
paper
[14].
This
paper
presents
the
fabrication
and
the
sensing
properties
of
the
Cl
2
sensor
based
on
NASICON
and
oxide
sensing
electrodes.
The
influence
of
the
sin-
tering
temperature
of
Cr
2
O
3
on
the
performance
of
the
sensor
is
discussed.
Special
structures
of
the
sensor
devices
have
been
designed
too.
2.
Experimental
The
NASICON
was
prepared
from
ZrO(NO
3
)
2
,
NaNO
3
,
(NH
4
)
2
HPO
4
and
Si(C
2
H
5
O)
4
by
sol–gel
process
and
sintered
at
1000
◦
C
for
12
h
[14].
Eight
kinds
of
single
metal
oxides
(Cr
2
O
3
,
0925-4005/$
–
see
front
matter ©
2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2012.03.024
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