High power all-solid-state batteries using sulphide ... · High power all-solid-state batteries...

SUPPLEMENTARY INFORMATIONARTICLE NUMBER: 16030 | DOI: 10.1038/NENERGY.2016.30

NATURE ENERGY | www.nature.com/natureenergy 1

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Supplementary Information

High power all-solid-state batteries using sulphide superionic conductors

Yuki Kato1,2,3* Satoshi Hori,2 Toshiya Saito,1 Kota Suzuki,2 Masaaki Hirayama,2 Akio Mitsui4, Masao

Yonemura5, Hideki Iba1, and Ryoji Kanno2*

1Battery Research Div., Higashifuji Technical Center, Toyota Motor Corporation, 1200 Mishuku, Susono,

Shizuoka 410-1193, Japan

2Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo

Institute of Technology, 4259 Nagatsuta, Midori, Yokohama 226-8502, Japan

3Battery AT, Advanced Technology 1, Toyota Motor Europe NV/SA, Hoge Wei 33A B-1930, Zaventem,

Belgium

4Material analysis Department, Material engineering Div., Toyota Motor Corporation, 1 Toyota-cho, Toyota,

Aichi 471-8572, Japan

5Institute of Materials Structure Science (IMSS), High Energy Accelerator Research Organization (KEK),

Shirakata, Tokai, Ibaraki 319-1106, Japan

* Email:

Ryoji Kanno [email protected] Yuki Kato [email protected]

http://dx.doi.org/10.1038/nenergy.2016.30

2 NATURE ENERGY | www.nature.com/natureenergy

SUPPLEMENTARY INFORMATION DOI: 10.1038/NENERGY.2016.30

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Supplementary Figure 1| Calculation of the volume efficiency of bi-polar stacking cells. (a)

Thickness of the single cell stacked battery system. The thickness of the total battery system, Tss,

was calculated according to the following equation: Tss = N × (Tsc + 2Tpw), where N, Tsc, and Tpw

are the stacking number, single cell thickness, and package wall thickness, respectively. Tsc was

calculated by summing the thicknesses of the layers (cathode, separator, and anode) of the

lithium ion battery prepared in this study (see methods) and the thickness of the current collector

(Tcc = 20 μm). Two values of Tpw were assumed herein: 100 μm for the thin package (aluminium

laminating bag) and 300 μm for the thick package (stainless steel can). (b) Thickness of the bi-

polar stacked battery system. The thickness of the total battery system, Tbps, was calculated



SUPPLEMENTARY INFORMATIONDOI: 10.1038/NENERGY.2016.30

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according to the following equation: Tbps = N × (Tsc –Tcc) + Tcc + 2Tpw, where Tcc is the thickness

of the current collector (20 μm). For bi-polar stacking, only the thick package (Tpw =300 μm) was

assumed. The value of Tsc for single cell stacking was used in the calculation. (c) Dependence of

the thickness of the battery system on the voltage. The voltage was calculated using the average

voltage of the lithium ion battery prepared herein (2 V) with a stacking number N. The thickness

of the battery system can be reduced by bi-polar stacking. (d) The volume efficiency of the bi-

polar stacking system. The volumes for single cell stacking (Vss) and bi-polar stacking (Vbps)

were compared. Equal electrode areas were selected for both the systems and the following

equation was used: Vss/Vbps = Tss/Tbps. For calculating Tbps, only Tpw = 300 μm was used. The total

volume of the battery system can be significantly improved using the bi-polar stacking system at

voltages where typical electric vehicle motors operate. In addition, bi-polar stacking can

optimize the volume efficiency of high voltage systems. Note that the actual battery system is

more complicated than that depicted here.




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Supplementary Figure 2| Neutron Rietveld refinement of Li9.54Si1.74P1.44S11.7Cl0.3. Diffraction

data were obtained using neutron radiation at 25 ºC. Red: observed intensities; light blue:

calculated intensities; blue: difference plot; green and yellow markers indicate the positions of

the diffraction lines of the Li9.54Si1.74P1.44S11.7Cl0.3 and Argyrodite phases, respectively. Some

data was excluded from the refinement cycles because of the presence of very small amounts of

unknown impurity phases.

During Reitveld refinement for this material, several models were considered as follows: (I) Si

and P substitution at Li sites (II) Li substitution at the Si/P sites, (III) Si/P mixed at the 2b site,

(IV) chlorine substitution only at either S(1), S(2), or S(3), (V) chlorine substitution at all the

sulfur sites. Based on the refinement results, no Si and P ions were found at the Li sites. In

addition, no Li ions occupied the Si/P sites. The neutron diffraction data suggested the possibility

that the Si partially replaced P at the 2b sites. However, NMR measurements did not support the

existence of two different sites for Si in this material. Therefore, ultimately, it was determined




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that only P existed at the 2b sites. Additionally, P and Si were located at the same 4d sites. A

small amount of chlorine was present at the Cl(1) site. An insubstantial amount of chlorine ions

also occupied the Cl(2) and Cl(3) sites.




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Supplementary Figure 3| Neutron Rietveld refinement of Li9.6P3S12. Red: observed

intensities; light blue: calculated intensities; blue: difference plot; green and yellow markers

indicate the positions of the diffraction lines of the Li9.6P3S12 and -Li3PS4 phases, respectively.

Data in the d range of 2.0-2.4 Å was excluded from the refinement cycles because of the

presence of unknown impurity phases.

The structural parameters of Li10GeP2S12

1,2 were used in the initial structural model, which

consisted of four Li atoms occupying the 16h(Li1), 4c(Li2), 8f(Li3), and 4d(Li4) sites, three S

atoms occupying three 8g sites, and three P atoms occupying the 4d and 2b sites.




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Supplementary Figure 4| Charge–discharge curves of an all-solid-state cell of Li/Li9.6P3S12/

LiNbO3-coated LiCoO2 at 25 °C. Charge-discharge current was 0.045 mA cm−2. The cell with

Li anode and Li9.6P3S12 electrolyte shows good coulombic efficiency of over 95% during cycling.




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Supplementary Figure 5| Schematic diagram of the all-solid-state electrochemical cell

prepared herein, along with SEM images of the electrode layers.




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Supplementary Figure 6| Applied current vs initial voltage drop curves for the all-solid-

state and lithium ion cells at −30 °C, 25 °C and 100 °C. The internal resistance of the cells

were estimated from the initial potential drop of the discharge curves3.

□ = Lithium ion cell.

● = All-solid-state cell with the [Li4Ti5O12 + Li10GeP2S12/Li10GeP2S12/LiNbO3-coated LiCoO2 +

Li10GeP2S12] configuration (normal type cell).

■ = All-solid-state cell with the [graphite + Li9.6P3S12/Li9.6P3S12|Li10GeP2S12/LiNbO3-coated

LiCoO2 + Li10GeP2S12] configuration (high voltage type cell).

▲ = All-solid-state cell with the [Li4Ti5O12 + Li9.54Si1.74P1.44S11.7Cl0.3/Li9.54Si1.74P1.44S11.7Cl0.3/

LiNbO3-coated LiCoO2 + Li9.54Si1.74P1.44S11.7Cl0.3] configuration (large current type cell).




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Supplementary Figure 7| Rate characteristics of all-solid-state cells. (a), (b) Rate capability

of all-solid-state (Normal type) cells using Li10GeP2S12 with the [Li4Ti5O12 +

Li10GeP2S12/Li10GeP2S12/LiNbO3-coated LiCoO2 + Li10GeP2S12] configuration at operating

temperatures of 25 °C and 100 °C. (c), (d) Rate capability of all-solid-state (Large current type)

cells using Li9.54Si1.74P1.44S11.7Cl0.3 (LSiPSCl) with the [Li4Ti5O12 + LSiPSCl/LSiPSCl/LiNbO3-

coated LiCoO2 + LSiPSCl] configuration at operating temperatures of 25 °C and 100 °C. (e), (f)

Rate capability of all-solid-state (High voltage type) cells using Li9.6P3S12 with the [graphite +

Li9.6P3S12/Li9.6P3S12|Li10GeP2S12/LiNbO3-coated LiCoO2 + Li10GeP2S12] configuration at

operating temperatures of 25 °C and 100 °C. (g) Rate capability of a lithium ion cell prepared

herein employing 1 M LiPF6-ethylene carbonate (EC)/diethyl carbonate (DEC) (50:50, v/v) as

electrolyte with the [Li4Ti5O12/LiNbO3-coated LiCoO2] configuration at an operating

temperature of 25 °C. (h) Rate capability of a lithium ion cell (grey dashed line) and a Normal

type all-solid-state (blue solid line) cell at an operating temperature of −30 °C.

The dependence of the discharge profiles on the rate were measured after the cells were charged

at 2.6 V in the constant current charging mode [0.03 mA cm−2 (0.045 C) to 2.6 V] and constant

voltage charging mode [the cell voltage held constant until the charging current reached

0.001 mA cm−2 (0.015 C)].

The discharging current conditions in this Figure are listed below.

25 °C: 0.1C, 1C, 1.8C, 4.5C, 7.2C, 9C, 18C, 30C, 45C, 60C, 75C, 90C, 105C, 120C, 135C and

150C (1C = 0.667 mA cm−2).

100 °C: 0.1 C, 2C, 4.5C, 9C, 18C, 30C, 45C, 60C, 75C, 90C, 105C, 120C, 135C, 150C, 225C,

300C, 450C, 600C, 750C, 900C, 1050C, 1350C and 1500C (1C = 0.667 mA cm−2).

−30 °C: 0.05C, 0.09C and 0.9C (1C = 0.667 mA cm−2).




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Supplementary Figure 8| Stability test for the Li9.54Si1.74P1.44S11.7Cl0.3 electrolyte.

(a) Charge and discharge curves at 25 ºC at the constant current density of 1.8C (1C = 0.667 mA

cm−2). The cell with Li9.54Si1.74P1.44S11.7Cl0.3 shows good cyclability. (b) Impedance spectra of the

cell at the 1st cycle and after the 1000th cycle. Slightly increased resistance was observed during

the cycling test. (c), (e) TEM image of the interface between LiNbO3-coated LiCoO2 and

Li9.54Si1.74P1.44S11.7Cl0.3 after cycling. (d) EDX line spectrum. None of the elements in

Li9.54Si1.74P1.44S11.7Cl0.3 diffused into LiCoO2. (f) TEM image of the interface between Li4Ti5O12

and Li9.54Si1.74P1.44S11.7Cl0.3. The interface and crystal structure of Li4Ti5O12 does not greatly

deteriorate after cycling.




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Supplementary Figure 9| Cross-sectional SEM images of the electrode layers in the all-

solid-state and lithium ion cells. (a), (b) Cathode and anode layers of the all-solid-state cell,

respectively. (c), (d) Cathode and anode layers of the lithium ion cell, respectively. These

pictures indicate that the distributions and densities of the electrode materials are comparable in

both of the electrochemical systems, thereby minimizing the electrochemical effects of the

electrode materials between the solid and liquid electrolyte systems. Therefore, the rate-

determining step originated from the electrolyte.




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Supplementary Figure 10| Nyquist plots and equivalent circuit for the all-solid-state

(Normal type) cell of [Li4Ti5O12 + Li10GeP2S12/Li10GeP2S12/LiNbO3-coated LiCoO2 +

Li10GeP2S12] configuration and lithium ion cell at 25 ºC. (a) Equivalent circuit model4. (b)

Nyquist plot for the all-solid-state cell at 2.6 V. (c) Nyquist plot for the lithium ion cell at 2.6 V.

Open symbols indicate experimental data, while the lines represent fitted data. Two semicircles

are observed in the low and high frequency regions, which correspond to the cathode and anode

reactions, respectively. The component R0 corresponds to the resistance of the separator, while R1

and R2 indicate charge transfer resistances at the cathode and anode interfaces, respectively.

CPE1 and CPE2 indicate the double-layer capacitances at the cathode and anode interfaces,

respectively. W1 and W2 are the Warburg elements given by W = WR×tanh{(jWT)n}/(j)n. The

values obtained by fitting the impedance data are listed in Supplementary Table 5.




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Supplementary Figure 11| Nyquist plots of the all-solid-state (Normal type) cell with

[Li4Ti5O12 + Li10GeP2S12/Li10GeP2S12/LiNbO3-coated LiCoO2 + Li10GeP2S12] configuration

and lithium ion cell at 0 and −30 ºC. (a), Nyquist plots at 0 °C. (b), Nyquist plots at −30 °C.

The open symbols indicate experimental data, while the lines are fits based on the equivalent

circuit shown in Supplementary Figure 9a. (blue circles with blue line: all-solid-state cell; gray

squares with gray line: lithium ion cell.) At −30 °C, the resistances R0, R1, and R2 corresponding

to the all-solid-state cell were 41.0, 14.2, and 157.4 respectively, and those of the lithium ion

cell were 44.4, 42.4, and 708.4 respectively. Temperature dependence of resistance of (c) R0,

(d) R1, and (e) R2 for the all-solid-state cell (blue circle) and lithium ion cell (gray square). The




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activation energies (Ea) for lithium diffusion in the electrolyte were comparable for both the all-

solid-state cell and lithium ion cell. In contrast, charge transfer at the electrolyte/electrode

interface of the all-solid-state cell was lower than that of the lithium ion cell; Ea values of R1 and

R2 of the all-solid-state cell were 21.9 and 45.6 kJ mol−1, respectively, and those of the lithium

ion cell were 46.4 and 56.4 kJ mol−1, respectively.




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Supplementary Figure 12| Discharge curves of the all-solid-state cells with the electrode

configurations for high energy density at 25°C. (a) Cell with high active material content

(LiNbO3-coated LiCoO2 = 70 wt% and graphite = 60 wt%) electrode. 1C = 0.93 mA cm−2. (b)

Cell with the high ultra-thick (cathode layer = 308 m and anode layer = 321 m) electrode. 1C

= 8 mA cm−2. Both of the cells exhibited good rate capability of the discharging current density

of over 10 C at 25°C.




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Supplementary Table 1| Rietveld refinement results for Li9.54Si1.74P1.44S11.7Cl0.3 at 25 ºC. Atom Site g x y z Li(1) 16h 0.5 0.2610(3) 0.2676(3) 0.1923(2) Li(2) 4d 1 0 1/2 −0.05255(11) Li(3) 8f 0.972(9) 0.24384(10) = x(Li(3)) 0 Li(4) 4c 0.765(8) 0 0 0.24598(15) Si(1) 4d 1−g(P(1)) = x(P(1)) = y(P(1)) = z(P(1)) P(1) 4d 0.108(13) 0 1/2 0.69234(5) Si(2) 2b 1−g(P(2)) = x(P(2)) = y(P(2)) = z(P(2)) P(2) 2b 1 0 0 1/2 S(1) 8g 0.9590(11) 0 0.19056(8) 0.40707(6) Cl(1) 8g 1−g(S(1)) 0 = y(S(1)) = z(S(1)) S(2) 8g 0.9827(12) 0 0.29836(8) 0.09736(6) Cl(2) 8g 1−g(S(2)) 0 = y(S(2)) = z(S(2)) S(3) 8g 0.9817(13) 0 0.69572(9) 0.79183(6) Cl(3) 8g 1−g(S(3)) 0 = y(S(3)) = z(S(3)) Atom U11 U22 U33 U12 U13 U23 Li(1) 0.117(3) 0.0161(19) 0.301(7) 0.0053(13) 0.109(3) −0.060(2) Li(2) 0.0476(11) 0.0549(11) 0.0004(8) 0 0 0 Li(3) 0.0896(18) =U11(Li(2)) 0.406(5) −0.0276(13) 0.1093(14) =−U13(Li(3)) Li(4) 0.066(3) 0.188(4) 0.022(2) 0 0 0 Si(1) =U11(P(1)) =U22(P(1)) =U33(P(1)) =U12(P(1)) =U13(P(1)) =U23(P(1)) P(1) 0.0090(3) 0.0090(3) 0.0090(3) 0 0 0 Si(2) =U11(P(2)) =U22(P(2)) =U33(P(2)) =U12(P(2)) =U13(P(2)) =U23(P(2)) P(2) 0.0090(3) 0.0090(3) 0.0090(3) 0 0 0 S(1) 0.0380(4) 0.0380(4) 0.0380(4) 0 0 0 Cl(1) =U11(S(1)) =U22(S(1)) =U33(S(1)) =U12(S(1)) =U13(S(1)) =U23(S(1)) S(2) 0.0246(3) 0.0246(3) 0.0246(3) 0 0 0 Cl(2) =U11(S(2)) =U22(S(2)) =U33(S(2)) =U12(S(2)) =U13(S(2)) =U23(S(2)) S(3) 0.0201(3) 0.0201(3) 0.0201(3) 0 0 0 Cl(3) =U11(S(3)) =U22(S(3)) =U33(S(3)) =U12(S(3)) =U13(S(3)) =U23(S(3)) Unit cell: tetragonal P42/nmc (137); a = 8.709652(12) Å, c = 12.56907(3) Å Rwp = 4.45, Re = 1.98, goodness of fit S = 2.25, Rb = 3.04, Rf = 6.78 Weight ratio LGPS/Argyrodite phases = 0.8108 : 0.1892




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Supplementary Table 2| Rietveld refinement results for Li9.6P3S12 at 25 ºC. Atom Site g x y z U /Å2 Li(1) 16h 0.51(3) 0.2270(13) 0.312(2) −0.0286(15) 0.073(11) Li(2) 4d 0.55(7) 0 0.5 0.969(4) 0.13(3) Li(3) 8f 0.35(3) 0.276(4) 0.269(3) 0.128(3) 0.14(2) Li(4) 4c 0.79(7) 0 0 0.239(3) 0.15(2) P(1) 4d 1 0 0.5 0.7031(4) 0.0313(15) P(2) 2b 1 0 0 0.5 0.0379(19) S(1) 8g 1 0 0.1827(5) 0.4197(5) 0.0105(15) S(2) 8g 1 0 0.3059(7) 0.1050(6) 0.041(2) S(3) 8g 1 0 0.7103(5) 0.7836(5) 0.028(2) Unit cell: tetragonal P42/nmc (137); a = 8.7144 (4) Å, c = 12.4677 (7) Å Rwp = 2.88, Rp = 2.44, goodness of fit S = Rwp / Re = 2.42, Rb = 3.614, Rf = 3.54 Weight ratio of the LGPS/-Li3PS4 phases = 0.6411: 0.3589




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Supplementary Table 3| List of lithium superionic conductors with an LGPS-type structure

Chemical composition Ionic conductivity Activation

energy 1st charge/discharge

efficiency Reference Pellet density (%) 25 °C / S cm−1 100 °C / S cm−1 Ea / kJ mol−1 (%)

Li9.42Si1.02P2.1S9.96O2.04 76 1.10×10−4 8.62×10−4 23 87 Present study

Li9.6P3S12 76 1.20×10−3 5.90×10−3 25 90 Present study

Li9.54Si1.74P1.44S11.7Cl0.3 90 2.53×10−2 – 23 39 Present study (75)§ (1.40×10−2)§ (5.80×10−2)§ (23)§

Li9.81Sn0.81P2.19S12 75 5.50×10−3 2.43×10−2 25 51 5

Li10.35Si1.35P1.65S12 73 6.70×10−3 2.80×10−2 26 81 5

Li10GeP2S12 95 1.20×10−2 6.94×10−2 26 61 1

Li10GeP2S11.7O0.3 83 1.15×10−2 3.07×10−2 15 42 Present study

Li9P3S9O3 74 4.27×10−5 5.27×10−4 30 – 6

Li10.35Ge1.35P1.65S12 93 1.44×10−2 7.20×10−2 27 – 2

Li10(Ge0.5Si0.5)P2S12 78 4.20×10−3 – 26 – 7

Li10(Ge0.5Sn0.5) P2S12 81 6.17×10−3 – 24 – 7

Li10(Si0.5Sn0.5)P2S12 79 4.28×10−3 – 28 – Present study

§Value for compressed powder state.




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Supplementary Table 4| Characteristics of the all-solid-state cells and lithium ion cell constructed herein

a Calculated from the initial potential drop of the discharge curve3 (see Supplementary Figure5). b EC/DEC; ethylene carbonate/diethyl carbonate (50:50, v/v) c PP | PE | PP; polypropylene | polyethylene | polypropylene

When the laboratory cells are treated as “devices”, the energy density is still low, owing to the

very thick separator and low active material content. However, the energy density could be

improved by employing certain technical strategies. Therefore, fabricating a thin separator and

well-homogenized electrode layer are important in an actual device. These concerns still remain

critical and have to be solved with further developments in the electrode fabrication process.

Cell type All-solid-state cell

Large current type High voltage type Normal type Lithium ion cell

Indication

Figure 4a ––––––––– --------- - -

Figure 6 ▲ ■ ● ■

Cathode layer

Active material LiNbO3-coated LiCoO2 LiNbO3-coated LiCoO2 LiNbO3-coated LiCoO2 LiNbO3-coated LiCoO2

Electrolyte Li9.54Si1.74P1.44S11.7Cl0.3 Li10GeP2S12 Li10GeP2S12 1M LiPF6 in EC:DEC b

Separator Li9.54Si1.74P1.44S11.7Cl0.3 Li10GeP2S12 | Li9.6P3S12

(cathode | anode side) Li10GeP2S12 PP | PE | PP c

Anode layer

Active material Li4Ti5O12 Graphite Li4Ti5O12 Li4Ti5O12

Electrolyte Li9.54Si1.74P1.44S11.7Cl0.3 Li9.6P3S12 Li10GeP2S12 1M LiPF6 in EC:DEC b

Internal resistance a

R / cm2

−30ºC - - 257.2 1752.4

25ºC 4.5 14.0 8.4 13.2

100ºC 0.70 1.49 0.97 -

Specific energy

E / Wh kg−1 Based on mass of LiCoO2 319.6 430.9 297.7 302.4

Based on mass of cell 17.6 32.8 16.4 73.2




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Supplementary Table. 5| Equivalent circuit parameters of cells at 25 ºC

All-solid-state cell Lithium ion cell

R0 / 3.68 3.37

R1 / 1.94 0.62 C

PE1

T1 / F sp−1 3.20×10−5 2.26×10−5

P1 0.89 0.97

Cdl1 / F 9.68×10−6 1.64×10−5

W1

WR1 / 22.7 21.3

WT2 / F 118.5 39.7

n1 0.31 0.12

R2 / 2.43 4.16

CPE

2

T2 / F sp−1 4.13×10−2 4.13×10−3

P2 0.57 0.73

Cdl2 / F 7.58×10−3 9.11×10−4

W2

WR2 / 126240 84117

WT2 / F 110530 110540

n2 0.99 0.99




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Supplementary Table. 6| Specification of the cells used in Supplementary Figure 11. (a) High active material content electrode. (b) Ultra-thick electrode.

The energy density of the cell was not significantly improved in the case of high active material

content cell. It is due to the very thick separator layer (240m). If a thin separator layer of 25m

could be fabricated, the specific energy of the high active material content cell would be 152 Wh

kg−1. This indicates the importance of thin separator preparation technique.

Interestingly, the energy density of cell has been significantly improved by increasing the

thickness of cathode and anode layer in spite of the low content of active materials and thick

separator. The mass of active materials was up to the 40wt% in the cell due to the thicker

electrode layers than the separator layer. Such thick electrode configuration is difficult to realise

in conventional liquid electrolyte system due to diffusion limitation phenomena8. However, in

the case of the all-solid-state configuration, this diffusion limitation was not seen, as shown in

Figure 5 in the text. Therefore such thick electrode configuration can be realised.

Cathode layer Thickness 25 m

Active material LiNbO3-coated LiCoO2 (70 wt%) Solid electrolyte LGPS (27 wt%)

Electron conductor Acetylene black (3 wt%)

Separator

Thickness 240 m Solid electrolyte Li10GeP2S12 | Li9.2P3S12

Anode layer

Thickness 28 m Active material Graphite (60 wt%) Solid electrolyte Li9.2P3S12 (40 wt%)

Specific energy 45.6 Wh kg−1 (Cell based)

Cathode layer Thickness 308 m

Active material LiNbO3-coated LiCoO2 (61 wt%) Solid electrolyte LGPS (36 wt%)

Electron conductor Acetylene black (3 wt%)

Separator

Thickness 240 m Solid electrolyte Li10GeP2S12 | Li9.2P3S12

Anode layer

Thickness 321 m Active material Graphite (40 wt%) Solid electrolyte Li9.6P3S12 (60 wt%)

Specific energy 133 Wh kg−1 (Cell based)




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Supplementary Methods

Transmission electron microscopy (TEM) images of the interface between

Li9.54Si1.74P1.44S11.7Cl0.3 and the active materials were obtained using a scanning transmission

electron microscope (JEOL, JEM-ARM200F). Additionally, EDX spectra were also obtained.

Samples for the TEM observations were prepared using focused ion beam treatment (Hitachi,

FB200A).

Cross-sectional images of the cells were obtained using scanning electron microscopy (SEM;

JSM-6610A, JEOL). Cross-sections of the cells were prepared using an ion milling system

employing an Ar ion beam (E-3500; Hitachi High-Technologies).

Impedance measurements were conducted at a cell voltage of 2.6 V at −30, 0, and 25 ºC by

applying a constant AC voltage of 5 mV in the frequency range of 106-10−1 Hz, using a

frequency response analyser (Solartron 1260). Cell circuit parameters were estimated by fitting

the impedance measurements to an equivalent circuit using the ZView software (Scribner

Associates).




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Supplementary References

1. Kamaya, N. et al. A lithium superionic conductor. Nat. Mater. 10, 682-686 (2011).

2. Kwon, O. et al. Synthesis, structure, and conduction mechanism of the lithium

superionic conductor Li10+Ge1+P2-S12. J. Mater. Chem. A 3, 438-446 (2015).

3. Zhang, Y. & Harb, J., N. Performance characteristics of lithium coin cells for use in

wireless sensing systems: Transient behavior during pulse discharge. J. Power Sources.

229, 299-307 (2013).

4. Barsoukov, E & Macdonald, J.R. Impedance Spectroscopy: Experiment and

Applications Second Edition. John Wiley & Sons, Inc., Hoboken, New Jersey (2005).

5. Hori, S. et al. Synthesis, structure, and ionic conductivity of solid solution,

Li10+M1+P2-S12 (M = Si, Sn). Faraday Discuss. 176, 83-94 (2014).

6. Takada, K. et al. Lithium ion conductive oxysulfide, Li3PO4–Li3PS4. Solid State Ionics.

176, 2355-2359 (2005).

7. Kato, Y. et al. Synthesis, structure and lithium ionic conductivity of solid solutions of

Li10(Ge1-xMx)P2S12 (M = Si, Sn). J. Power Sources. 271, 60-64 (2014).

8. Fuller, T.F., Doyle, M. & Newman, J. Simulation and optimization of the dual lithium

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