Conductivity and strong liquid behavior of mixed oxy-sulfide nitride

glasses in the series Na4P2S7-6xO4.62xN0.92x ; 0<x<0.5

Madison Olson, Dr. Steven Kmiec, and Dr. Steve W. Martin

July 27th, 2021

Outline
 Introduction into glassy solid electrolytes (GSEs)
 High conductivity glasses

 Thin film processing and how it can be achieved

 Strong viscosity behavior

 MOSN phosphate glass that balances these properties

 Processing of this MOSN composition and how it could be done

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Components to optimize glassy solid-state electrolyte materials
 Glassy solid-state electrolytes
 Don’t have grain boundaries
 Highly tunable chemistry compared to Crystalline Electrolyte
crystals, which have defined crystal structures
 Able to be processed uniquely, such as film
drawing Na - metal
 High conductivity leads to a need for
highly modified glasses
 High modifier invert glasses
 Short-chain length structures, which can be Glassy Electrolyte
susceptible to crystallization
 High amount of secondary bonding opposed
to primary bonding along chains Na - metal
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Thin-film glass processing for use in GSE – why thin films?
 To draw thin film, a glassy preform must be Hot
placed in the draw tower, heated and slowly Furnace
drawn through
 The film to the right is of a low modifier sodium
borosilicate oxide glass
 The glass must be able to withstand long
isothermal holds in the furnace above its Tg
without crystallizing
 How can thin film drawing be achieved in
highly modified conductive glasses, which
have lower structural integrity compared to
oxide chemistries?
Cold

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 Achieving high conductivity, strong viscosity GSE materials
 Strategy to optimize GSE chemical composition:
 Mixing the high conductivity of sulfide chemistries with the strong durability of oxide glass
 Dopant strategy by incorporating nitrogen
 Nitrogen in the form of NaPO3-(3/2)yNy : y=0.46 (NaPON)
P2S5
Na2S NaPON
 Nitrogen has been shown to improve: O

 Thermal and chemical stability O P O-

O O
 Ionic conductivity P
N
P
O O-
O- O O
O

A purely sulfide chemistry made of Na2S and P O-

 -
-
O
-
O P O
O O N P O O
O O N

P2S5 can be doped with NaPON to form: -

P
N
P

-
P
O
O
-
O
P

-
P
O
O O O O O

 xNa4P2S7+(1-x)NaPON → Na4P2S7-6xO4.62xN0.92x -
O P O Na4P2S7-6xO4.62xN0.92x
O

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Na2S, P2S5, and NaPON can be mixed to form
 Structural characterization of Na4P2S7-6xO4.62xN0.92x using FT-IR: x=0.2
FT-IR Spectra Na4P2S7-6xO4.62xN0.92x
 High distribution of structural units
 Particularly beginning at x = 0.2
 Overall exchange of species

Normalized Absorbance [a.u.]

 Spectra showing P1 sulfide units exchanging x=0.5

to P0 units x=0.4
 Mixed anion species growing in with
x=0.3
increasing x
 Species in the form of PO2S24- and PSO34- x=0.2

 Oxide species growing in between 800- x=0.1

1400 cm-1
x=0.05
 Increased variety of structural species
incorporating into the structure x=0

600 800 1000 1200 1400

Wavenumber [cm-1]
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Conductivity and activation energy in the series Na4P2S7-6xO4.62xN0.92x
Conductivity and Activation Energy at T = 60°C
 Decrease in conductivity and increase in
activation energy with increasing x -5.0

 Conductivity, s(60 °C) = 4.9 x 10-6 56

Activation Energy [kJ/mol]

 Although there is an increase in nitrogen -5.2

the increase in oxygen dominates the 54

log(s) [Ωcm-1]
properties -5.4
 Decrease attributed to increase in oxygen 52
species in the glass
-5.6
 Decrease in conductivity worth the 50
increase in strong viscosity behavior of
the x=0.2 MOSN chemistry -5.8
48
 Na4P2S7-6xO4.62xN0.92x Na4P2S5.8O0.92N0.18
0.0 0.1 0.2 0.3 0.4 0.5
x-value

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Thermal cyclability of Na4P2S5.8O0.92N0.18 without observed crystallization
 The MOSN glass was thermally Thermal Cycleability of Na4P2S5.8O0.92N0.18

cycled passed its Tg using a DSC Heating Rate (°C/min)

Normalized Heat Flow [W/g] (endo up)

40
 Heating rates varied between 5 and 40
30
°C/min
20
 Tg’s are consistent: an increase in Tg
15
and signal is observed with
10
increasing heating rate
5
 Tg (20 °C/min) = 212 °C
 No evidence of an onset of
crystallization suggesting a good
glass for scaling-up and film drawing
 These curves were used to model
the temperature dependent viscosity 200 220 240 260 280 300 320
Temperature [°C]
of the glass
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Visualizing the strong viscosity and thermal cyclability of
Na4P2S5.8O0.92N0.18
 Shows an annealing T = 270-300°C
mold held at ~300°C
 No crystallization
 T > T
draw = 220°C
 Viable for small-
scale drawability
 Recyclable

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Temperature dependent viscosity and fragility index compared to MOS
glass Modeled Temperature-Dependent Viscosity
 Fragility index taken from the slope of 12

the experimental curve close to Tg Experimental data

Best fit line
 mNaPSON = 46 10
mSiO2 = 20

log(Viscosity, h [Pa-s])


 mEthanol = 55
8
 Model shows the temperature
dependent viscosity
6
 Mold temperature: h (275°C) ~ 107 Pa-s
 Model does not consider the shear-
thinning behavior of our glasses 4

 Shear thinning based on the short chain-

length structures present in the glass 2
 Draw temperature can be forecasted to be 200 250 300 350 400 450

~250°C or below Temperature, T [°C]

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First ever sodium MOSN thin film
 MOSN glassy preform
 ~200g of glass
 Thin film of Na4P2S5.8O0.92N0.18
 As shown, the pulled thin film is highly
transparent showing no signs of
crystallization
 Draw temperature was found to be 220°C
 Large thermal gradient in drawing furnace
 Weight of the preform aids drawing based on
shear thinning effect

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Conclusion
 Glassy solid-state electrolytes are advantageous compared to crystalline
electrolytes due to the lack of grain boundaries
 The chemistries must be optimized to balance the conductivity and the
thermal stability needed to draw film
 The glasses in the series Na4P2S7-6xO4.62xN0.92x were shown to balance these
needed properties at the x=0.2 composition
 Na4P2S5.8O0.92N0.18 was shown to be thermally cyclable making it a great
candidate for film drawing
 As shown in the figure, the first ever MOSN glass was pulled into a film
 Our future work will be to further characterized the thin film understand the
electrochemical properties its battery performance

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 Thank you for your time!
FT-IR Spectra Na4P2S7-6xO4.62xN0.92x

Normalized Absorbance [a.u.]

x=0.5

x=0.4

x=0.3

x=0.2

x=0.1

x=0.05

x=0

Questions?
600 800 1000 1200 1400
Wavenumber [cm-1]

Thermal Cycleability of Na4P2S5.8O0.92N0.18

Heating Rate (°C/min)
Normalized Heat Flow [W/g] (endo up)

40

30

20

15

10

200 220 240 260 280 300 320

Temperature [°C]

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