Electrical properties of K2Ni(SO4)2 ionic crystals for applications in solid-state

batteries
Vctor M. Snchez-Fajardo, Antonio D. Lozano-Gorrn, Sergio F. Len-Luis.
Type: POSTER

Area: Engineering and Technology

Electrical properties of K2Ni(SO4)2 ionic crystals as a function of frequency (from 100

Hz to 1 MHz) and temperature (300-900 K) have been measured.
The crystals of Tuttons salt family [1] have been investigated in order to understand
their physical and chemical properties as well as their potential technological
applications. Crystals of this family are used in the manufacture of electrodes for
solid-state batteries. An advantage of this family of crystals can be obtained easily
by thermal treatment of corresponding Tuttons salts A2B(SO4)26H2O.
A solid-state battery is a battery that has both solid electrodes and solid electrolytes.
These materials are very efficient conductors of ions, which is necessary for good
electrolyte and electrode performance. The high ionic conductivity minimizes the
internal resistance of the battery, and therefore permits high power densities, while
the high electronic resistance minimizes its self-discharge rate, enhancing its charge
retention.
Materials and methods
Tuttons salts K2Ni(SO4)26H2O crystals were synthesized by slow evaporation method
(Fig. 1a). Powder X-ray diffraction (XRD) was carried out in a PANalytical XPert PRO
diffractometer with temperature chamber that allows XRD measurements at
different temperature. The electrical measurements were carried out using a
HewlettPackard 4192 impedance analyzer, during a heating cycle in a frequency
range from 5 to 107 Hz over a temperature range from 300 to 900 K. Thermal analysis
was performed with a Perkin-Elmer Pyris Diamond instrument under dynamic regime,
in a heating and cooling cycle from 25 to 800C (2981073 K), with a step
temperature of 10C/min.

Figure 1. (a) K2Ni(SO4)26H2O crystals; (b) diffraction patterns before and after
heating.
Results
Fig. 1b shows both XRD patterns for the Tuttons salt synthetized by the slow
evaporation method and for the K2Ni(SO4)2 crystals obtained from it by thermal
treatment. Cell parameter values and agreement factors obtained from Rietveld
method [2] using the FULLPROF program [3] are shown in Table 1.

Space
group
P213

a ()

Rp

Rwp

Rexp

9.9228(4)

4.22

13.4

20.7

3.18

Table 1. Rietveld refinement parameters.

Dielectric measurements show that the real part of the complex conductivity (Fig.
2a) increases as the temperature increases, with an increment of more than 4 orders
of magnitude [4].
120

853 K

-4

50 KHz
100 KHz
500 KHz

130

803 K

10

753 K
-5

703 K

10

120

653 K

1 MHz
5 MHz
10 MHz

115

110

-6

10

603 K
553 K

-7

10

Real part of conductivity , (S/cm)

-3

10

105

110

503 K
-8

10

453 K

-9

10

100

413 K
2

10

100
3

10

10

10

10

10

450 500 550 600 650 700 750

Frequency, (Hz)

95

450

500

550

600

650

Figure 2. (a) Conductivity spectra; (b) permitivitty versus temperature.

The curve of the real part of the permittivity shows a raise around 600 K (Fig. 2b)
which suggests a possible phase transition. In order to understand the permittivity
change, XRD measurements were carried out at 600 K (heated), 800 K (heated) and
600 K (cooling).
10

20

30

40

50

K2Ni2(SO4)3
600 K
Cooling

100

K2Ni(SO4)2
600 K
Heated

10

20

30

Angle (2Q)

40

50

-20
90

-40
80

-60

70
300

450

600

750

900

Temperature, T (K)

1050

-80

DTA

Weight loss (%)

Intensity (a.u.)

K2Ni2(SO4)3
800 K
Heated

700

Temperature (K)

Temperature (K)

750

Figure 3. (a) Diffraction patterns over temperature; (b) Thermogravimetric spectra.

Fig. 3a shows the diffraction patterns obtained. A non-reversible decomposition
suffered by the crystal structure can be observed:
2K2Ni(SO4)2 K2Ni2(SO4)3 + K2SO4
The thermogravimetric spectra obtained for the Tuttons salt in the temperature
range from 25 to 800C (298 - 1073 K) are shown in Fig. 3b The peak observed at 628
K matches with the temperature where the real part of the permittivity shows the
sudden change, and within the temperature in which the diffraction pattern presents
the two-phase decomposition.
Conclusions
Electrical measurements show that
increment with temperature, which
solid state batteries. However,
decomposition above 600 K, so it is
high temperature environments.

this compound has a progressive conductivity

makes it attractive for use as a component in
this ionic crystal suffers a non-reversible
not suitable as electrical component for use in

References
[1] Housecroft, C.E.; Sharpe, A.G., Inorganic Chemistry (3rd ed.). Prentice Hall. p.
699 (2008).
[2] Rietveld, H.M., J. Appl. Cryst., 2, 65 (1969).
[3] Rodrguez-Carvajal, J. Physica B, 192, 55 (1993).
[4] R.H. Chen et al. Journal of Physics and Chemistry of Solids 61 (2000) 519527.