Development of a Sodium Ion Secondary Battery Sumitomo Chemical Co., Ltd. Tsukuba Material Development Laboratory Satoru KUZE Jun-ichi KAGEURA S

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1 Development of a Sodium Ion Secondary Battery Sumitomo Chemical Co., Ltd. Tsukuba Material Development Laboratory Satoru KUZE Jun-ichi KAGEURA Shingo MATSUMOTO Tetsuri NAKAYAMA Masami MAKIDERA Maiko SAKA Takitaro YAMAGUCHI Taketsugu YAMAMOTO Kenji NAKANE Recently, the demand for large storage batteries for electricity supply has been increasing remarkably. We have been developing a sodium ion secondary battery which has large storage capacity and which can work at ambient temperature without using rare elements. In this paper, we introduce the trends in the development of the anode and cathode materials for sodium ion secondary batteries. Moreover we report on the electrical and safety properties of the sodium ion secondary batteries which contain our anode and cathode materials. 1 kwh 213

2 1), 2) 3 Table 1.3 V 23 3) 4), 5) 2 6) Table 1 Comparison with lithium and sodium 3) ratio of reserves cost (for carbonate) atomic weight ionic volume theoretical capacity normal electrode potential vs. SHE lithium sodium 1 1, $ 5,/t $ 15/t 6.9 g/mol 23 g/mol 1.84 Å Å 3 3,829 mah/g 1,165 mah/g 3.45 V V 198 Delmas Na 7) Na Na 98 Na Na NAS NaNa Na198 Na 8) Na 2 9) 5 mah/g 1) Na 4), 5) Fig. 1 PVdF Na EC DMC =1 1 NaClO4 1mol/L 1M NaClO4/EC-DMC R232 Ar 3) Na Na 213

1.5 Fig. 1 5 1 15 2 Charge and discharge curves of graphite vs. Na metal 3) 2 Dahn Na 3 mah/g 6) 2 11) 15 2 1 OCV Na NaOCV OCV Na PC NaPF6 1mol/L 1M NaPF6/PC 5C44 4 Fig.

3 1.5 Fig Charge and discharge curves of graphite vs. Na metal 3) 2 Dahn Na 3 mah/g 6) 2 11) OCV Na NaOCV OCV Na PC NaPF6 1mol/L 1M NaPF6/PC 5C44 4 Fig. 3 (a) 3) 3 5C2C A / Ah =C OCVNa Fig. 3 (b) 3) Na (a) 1.5 Fig. 2 3) 32 mah/g 12), 13) measure this voltage 4min rest 4h C(1cycle) 1.8 5C(1cycle) 1.6 5C(2cycle) 1.4 5C(2cycle) Fig. 2 Charge and discharge curves of the hard carbon heat-treated at 16 C vs. Na metal 3) (b) Fig C 16 C 2 C (a) Measurement of quasi-open-circuitvoltage (QOCV) and (b) the QOCV plots of hard-carbons 3) 213

4 2 NMR Na NMR Na 23 Na-NMR Fig. 4 2 mah/g(=.6 V) 4 mah/g (=.3 V) 7 mah/g (=.1 V)2 mah/g 3 mah/g 5 3) Bruker Avance3 WB(7 T)4 khz 23 Na-NMR Na ( ppm)nacl Fig Na-NMR 1 ppm 3) Na Na OCV Na 3 DSC Na DSC Na DSC DSC 14) Fig. 6 3) DSC 14) Graphite LiPF6 in EC-DMC 1.5 large change region in potential small change region in potential (plateau) discharge DSC (uw/mg) 8 Hard carbon NaClO4 in PC Hard carbon NaPF6 in PC Temperature ( C) Fig. 4 The measurement points of 23 Na-NMR for hard-carbon 3) Fig. 6 DSC profile of carbons stored Li and Na respectively 3) absence of Na metal peak Intensity (a.u.) Na stored electorde 5 mv ( 3 mah/g) 2 mah/g.1 V ( 7 mah/g).3 V ( 4 mah/g).6 V ( 2 mah/g) blank small change region in potential (plateau) large change region in potential (ppm) δ (ppm) Fig Na-NMR profile of various discharged hard-carbons 3) 213

5 NaClO4 NaPF6 198Delmas NaCoO2NaMnO2 NaNi.6Co.4O2 Na 7), 15) 17) LiCoO2 NaCoO2 NaMO2 M 18), 19) LiMn2O4 2 LiFePO4 NaFePO4 2) NaVPO4 21) Na2FePO4F 22), 23) Na3Fe3(PO4)4 24) Na3V2(PO4)2F3 25) 3 TiS2 26), 27) Li 2.2 V Na 1.8 V.4 V 4 28), 29) 4 NaFeO2 3.5 V 3) NaFeO2 NaMnO2 Na Na.7MnO V 213

6 NaNiO2 NaCoO2 Na(FeaMnbNic)O2 a + b + c = 1 a b c 1 XAFS XAFS NaMO2 M /3 Na(Fe1/3Mn1/3Ni1/3)O2 x NaFexMn1/2-x/2Ni1/2-x/2O2 31), 32) Fig. 7 Na V Table 2 NaFexMn1/2-x/2Ni1/2-x/2O2 x x.4 NaFe.4Mn.3Ni.3O Fig. 7 Table 2 Na.7MnO2 NaFeO2 Na.6CoO2 NaFe.2Mn.4Ni.4O2 NaFe.33Mn.33Ni.33O2 NaFe.4Mn.3Ni.3O2 x= x=.4 x=.2 Discharge curves of NaFexMn1/2 x/2ni1/2 x/2o2 vs. Na Capacity of layered oxide cathode materials in the range of V vs. Na metal theoretical capacity [mah/g] st charge capacity [mah/g] st discharge capacity [mah/g] NaFexMn1/2-x/2Ni1/2-x/2O2 NaOH FexMn1/2-x/2Ni1/2-x/2(OH)2NaOH NaFexMn1/2-x/2Ni1/2-x/2O2 X x PVdFn- NMP Na 1M NaPF6/PC 3 DSC Na Na1-yFe.4Mn.3Ni.3O2 DSC NaFe.4Mn.3Ni.3O2 Na 4. V NaFe.4Mn.3Ni.3O2 Na.4Fe.4Mn.3Ni.3O2 DSC Fig. 8 DSC2 213

7 Fe.4NaClO4 in PC Fe.4NaPF6 in PC Fe nd 1 th 1 st DSC (μw/mg) exothermic onset temperature 23 C exothermic onset temperature 251 C 9.2 J/g 47.9 J/g st 1 th J/g Temperature ( C) Fig. 8 DSC profile of charged Na1 yfe.4mn.3ni.3o2 Fig Charge and discharge curves of the sodium ion battery consisting of NaFe.4Mn.3Ni.3O2 and hard-carbon 3) NaClO4 NaPF6 Na Na 2 Na Na 27 1), 33) 2) NaFe.4Mn.3Ni.3O2 1M NaPF6/PC PE 2cm R232 Fig. 9 3) V.1C 12 mah/g 32) C 1 2.1C Fig. 1.1C 3) Fig Cycle Number Discharge capacity of the sodium ion battery consisting of NaFe.4Mn.3Ni.3O2 and hard carbon at a rate of.1c 3) 2C.1C 213

76 3 4.1C 25.1C52 PC EC Temperature ( C) 4 35 3 25 2 15 1 5 self-heating 5 1 15 2 25 3 35 4 Time (min) sodium lithium 4 4. V 4. V V 4. V V 5 PEPP ARC Fig.

8 C 25.1C52 PC EC Temperature ( C) self-heating Time (min) sodium lithium 4 4. V 4. V V 4. V V 5 PEPP ARC Fig cathode anode electrolyte separator Fig. 11 sodium NFMN HC 1M-NaPF6 / PC PP Accelerated-reaction-calorimetry (ARC) profile of charged coin cell for sodium and lithium ion secondary battery respectively 5cm ) 1 lithium LNCM Graphite 1M-LiPF6 / EC : DMC : EMC (16/1/74) PP 25 4.V.1C 12 mah/g 1 3 mah Fig. 12 Photo of the 2 layered sodium ion secondary battery with 5yen coin for the comparison 213

4.5 at 13 C heated 4. 3.5 3. Capacity (mah) 2.5 1.5 Fig.

layered sodium ion secondary battery 4.5 4. 3.5 3. 2.5 1.5 Voltage Surface temperature 2 4 6 8 1 12 Time (s) Fig.

V charged Temperature ( C) 1 5 discharge capacity Fig. 14 5 1 15 2 2Fig. 12 Fig.

9 4.5 at 13 C heated Capacity (mah) Fig degas 1st charge-discharge 2nd charge-discharge 5th charge-discharge Capacity (mah) Charge-discharge curves of the 2 layered sodium ion secondary battery Voltage Surface temperature Time (s) Fig. 15 Heating test profile of the charged 2 layered sodium ion secondary battery at 4.7V charged at 5.V charged Temperature ( C) 1 5 discharge capacity Fig Fig. 12 Fig. 13 Cycle Number Cycle behavior of the 1 layered sodium ion secondary battery 2 CO 37CO2 62 Fig Voltage surface temp. room temp full charge for.1c Capacity (mah) 2% charge Fig. 16 Over-charging test profile of the 2 layered sodium ion secondary battery Temperature ( C) 2 4. V 2 6 mah 5 K/min Fig V 212 V Fig

10 1),,,,,,, 51, 3G12 (21). 2) S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama, A. Ogata, K. Gotoh and K. Fujiwara, Adv. Funct. Mater., 21 (2), 3859 (211). 3),,,,,, (213), p.1. 4) E. Zhecheva, R. Stoyanova, J. M. Jiménez-Mateos, R. Alcántara, P. Lavela and J. L. Tirado, Carbon, 4, 231 (22). 5) M. S. Dresselhaus and G. Dresselhaus, Adv. Phys., 3 (2), 139 (1981). 6) D. A. Stevens and J. R. Dahn, J. Electrochem. Soc., 147 (4), 1271 (2). 7) J. Braconnier, C. Delmas, C. Fouassier and P. Hagenmuller, Mater. Res. Bull., 15 (12), 1797 (198). 8), (1989) 9), (26) 1) S. Komaba, Y. Matsuura, T. Ishikawa, N. Yabuuchi, W. Murata and S. Kuze, Electrochem. Comm., 21, 65 (212). 11) R. Alcántara, P. Lavela, G. F. Ortiz, and J. L. Tirado, Electrochem. Solid-State Lett., 8 (4), A222 (25). 12), (29) 13),,, 79, 3D29 (212). 14),, 3 (1), 3 (23). 15) C. Delmas, J. Braconnier, C. Fouassier and P. Hagenmuller, Solid State Ionics, 3-4, 165 (1981). 16) A. Mendiboure, C. Delmas and P. Hagenmuller, J. Solid State Chemistry, 57 (3), 323 (1985). 17) I. Saadoune, A. Maazaz, M. Ménétrier and C. Delmas, J. Solid State Chemistry, 122 (1), 111 (1996). 18) S. Okada and J. Yamaki, Lithium Ion Rechargeable Batteries, K. Ozawa Editor, WILEY-VCH, Weinheim (29), p ) S. Komaba, C. Takei, T. Nakayama, A. Ogata and N. Yabuuchi, Electrochemistry Communications, 12 (3), 355 (21). 2), (21). 21) J. Barker, M. Saidi and J. Swoyer, Electrochemical and Solid-State Letters, 6 (1) A1 (23). 22) N. Recham, J. Chotard, L. Dupont, K. Djellab, M. Armand and J. Tarascon, J. Electrochem. Soc, 156, A993, (29). 23) Y. Kawabe, N. Yabuuchi, M. Kajiyama, N. Fukuhara, T. Inamasu, R. Okuyama, I. Nakai and S. Komaba, Electrochem. Commun. 13, 1225, (211). 24) K. Trad, D. Carlier, L. Croguennec, A. Wattiaux, B. Lajmi, M. Amara and C. Delmas, J. Phys. Chem. C, 114, 134, (21). 25),, I. Gocheva,,, 52, 4E16 (211). 26) G. H. Newman and L. P. Klemann, J. Electrochem. Soc., 127, 297 (198). 27) K. M. Abraham, Solid State Ionics, 7, 199 (1982). 28),,,,,, 79, 3D27 (212). 29),,,,,, 53, 2E9 (212). 3),,,,, 45, 3B23 (24). 31), (29). 32),,, 79, 3D33 (212). 33), (29). 34),,, 53, 2E3 (212). 213

11 PROFILE Satoru KUZE Maiko SAKA Jun-ichi KAGEURA Takitaro YAMAGUCHI Shingo MATSUMOTO Taketsugu YAMAMOTO Tetsuri NAKAYAMA Kenji NAKANE Masami MAKIDERA 213

SPring8菅野印刷.PDF

SPring8菅野印刷.PDF 20021219Spring-8 Ah/kg Ah/dm 3 Li -3.01 540 3860 2090 Na -2.71 970 1160 1140 Al -1.66 2690 2980 8100 Zn -0.76 7140 820 5800 Fe -0.44 7850 960 7500 Cd -0.40 8650 480 4100 Pb -0.13 11340 260 2900 H 2 0