Elements Strategy Initiative for
Catalysts and Batteries (ESICB)学」及び「Kyoto University」を図案化した文字をさす。

PANTONE 281 C（CMYK 参考値：C100, M75, Y5, K35）
※スクールカラーの色指定は、一定条件下における参考値
であるため、表示媒体、使用環境等を考慮の上、使用上のルールその他諸規定に合わせ、数値を調整すること。

AIM of ESICB◆Development of high performance
TWC
catalysts with less use of and without useof critical-elements◆Development of critical-elements-freerechargeable batteries of high performance
CO
HC
NOx

candidates

Contribution to the realization of sustainable society◆Elucidation of guidance principles anddescription of processes during catalysis
and battery operation

Deepening the science of interface and surface of complex
and composite systems◆Development of human resources for next
generation

キをモチーフとした標章・記章をさす。

CO2
N2

H2O

Machida GL

Komaba GL

Okada GL

NIMS
Tateyama

YokohamaNat. Univ.
Dokko

Osaka
Univ.

AIST

Otani

TanakaDirector
Nagoya
Univ.

Ohta M

Hokkaido
Univ.
Sato

Satsuma

キをモチーフとした標章・記章をさす。

Morikawa Yamashita

Hagiwara

Shimizu Taketsugu

YamadaCo-Director
Tsukuda GL

Ehara GL

別図第１ 本学のエンブレムは、クスノキをモチーフとした標章・記章をさす。

ESICB Organization
エンブレム

Kyoto University Emblem

Kyoto University

別図第２ 本学のロゴタイプは、「京都大学」及び「Kyoto University」を図案化した文字をさす。

T. Tanaka
Director
Catalysts(Kyoto U.)

A. Yamada
Co-Director
Batteries(U. Tokyo)

Labs:40
Researchers : 120

K. Ohta
Project
Manager
ロゴタイプ縦組み (Kyoto U.)
Kanji Logotype (Vertical)

Kyoto U., U.Tokyo
Inst. Mol. Sci.,
Kyushu U.,
Kumamoto U. ,Tokyo U. Sci.,

Group leaders
Fundamental
M. Ehara
Electronic Theory(Inst. Mol. Sci.)

Material Synthesis
ロゴタイプ横組み

Kanji Logotype (Horizontal)

S. Okada
Post LIB(Kyushu U.)

M. Machida
TW Catalysts(Kumamoto U.)
英文ロゴタイプ
Logotype (English)

T. Tsukuda
Analysis & Evaluation(U. Tokyo)

S. Komaba
Na Batteries(Tokyo U. Sci.)

Hokkaido U., NIMS,
Nagoya U., AIST,
Tohoku U., Osaka U.
Waseda U., Kobe U. ,Nagoya Inst.Technol.,Tokyo Metropolitan U.,
Yokohama Nat. U., etc.

別図第３ スクールカラー
スクールカラー
University Color

PANTONE 281 C（CMYK 参考値：C100, M75, Y5, K35）
※スクールカラーの色指定は、一定条件下における参考値
であるため、表示媒体、使用環境等を考慮の上、使用上のルールその他諸規定に合わせ、数値を調整すること。

Target elements
in catalysts and batteries

PGM (Platinum Group Metals) in automotive catalyst

3/32

Consumption of PGM for automotive
catalyst（2012）
Demand for
Mining Demand
Automobile (％)
/ ton
/ ton
/ ton

Pt
Pd
Rh

190
205
23

240
300
30

100
210
25

(42)
(70)
(83)

Consumed PGM per a vehicle（Amount in 2000＝100）

100

PGM is essential for automotive
catalyst for purification of
exhaust gas- A natural resources issue

・Severe regulation
・Low temperature of exhaust gas
Present
Technology

・Resulting in an increase in PGM
use

Element strategy

Technology of less useof PGM or replacement
is desired.

50

0
２０００

２０２０

２０４０

IEA forecast of stock-base vehicles -2060

Million vehicles

in 2017

Number of cars will double by 2060
Rapid growth of battery cars.
Does Li production follow the growth?
Cars with Internal Combustion Engine FCV(ICE) still increase.
Catalysts with less PGM is needed.
EV

PHV

77%
Battery

Diesel
HV

73
%
ICE

Gasoline

2015

2060
Energy Technology Perspectives in 2017, International Energy Agency

リチウム資源需給構造
4Lithium Production
リチウム資源需給構造
4Classified by useof Li tLCE：炭酸リチウム換算ttLCE：炭酸リチウム換算tEstimated reserves of Li
Australia

Argentina

China

Chile

Metallugy additive
polymer
Metal greaseothersLIB (45%)
Glass
Ceramics

217 k ton as LCE in 201784.6埋蔵量（84,600千tLCE）
million ton as LCE 生産量（217千tLCE）－原料ベース

埋蔵量（84,600千tLCE）

用途別消費量（197千tLCE）
LCE: lithium carbonate
equivalent
Lithium element is uneven
distributed.
生産量（217千tLCE）－原料ベース
2017年に豪州がチリを逆転 用途別消費量（197千tLCE）
2017年に豪州がチリを逆転
Ref. USGS, Industrial Minerals
埋蔵量・生産量ともに偏在化合物ベース
埋蔵量・生産量ともに偏在
ただし中国以外はカントリー
化合物ベース
・国別消費量（炭酸リチウムなど）では？
・World productionoflithiummay
notfollowtheestimated
increase
ただし中国以外はカントリー・国別消費量 中国5割、EU・日本・韓国1割（炭酸リチウムなど）では？
リスク低い

ofリスク低い
battery cars although the lithium production 中国5割、EU・日本・韓国1割
will also increase.

2013年市場規模160千tLCE
市場規模：
二次電池向け：30%
2013年市場規模160千tLCE
2020年には？
市場規模：- Production of 5 millions
of battery
electric EV向け需cars二次電池向け：30%
is estimated in 2025,
2025年には？
2020年には？
要に大きく2006年の市場規模70千tLCE
EV向け需corresponding to the2025年には？
use of 150-250
k ton Li依存
as LCE.
二次電池向け：わずか5%
要に大きく2006年の市場規模70千tLCE
依存
二次電池向け：わずか5%主要生産企業：Albemarle,
SQM,Tianqi,FMC（7割のシェア）
And priceof lithium remarkably rises
up, more than twice during last two years

主要生産企業：Albemarle, SQM,Tianqi,FMC（7割のシェア）

出典：USGS,
Industrial Minerals等

出典：USGS,
Rechargeable Battery composed of abundant
Industrial Minerals等
elements, alternative to LIB is desired.

Main research themes in ESICBCatalyst• Reduction of PGM use in TWC (three-waycatalyst) working at low temperature• Realization of PGM-free TWC comparable topresent PGM TWCs
Rechargeable battery• Establishment of Na battery comparable to
LIB• Proposal of future rechargeable batteries

To save PGM in Three-Way-Catalysts
Purification of exhaust gas from gasoline engine
HC (Hydrocarbon)

O2

CO

O2

45
Rh

46
Pd

H2O + CO2CO2HC, CO✔ deNOx takes place on PGM surface.
General policy to save PGM✔ Stabilization of ﬁne PGM nanoparticles
and prevention of sintering of particles
to maintain high speciﬁc surface area
have been the way to save PGM.

N2

NO

diss
o
adso ciative
rpti
on

rec
& d omb
eso inat
rpt ion
ion

NO

78
Pt

N2

N N
Rh

CO2

O O

CO

metal oxide support

Prevention of sintering growth

supportsupportFine particles: active

Large particles: less active

Rh nanoﬁlm catalyst– enhancement of activity of Rh metal
Collaboration between activity measurement and DFT calculations suggested that
Rh(111) plane is the most active for NO reduction rather than nanoparticle withvarious planes.
Light-off Temp. lowered by 50℃

1-s2.0-S0169433217319657-fx1_lrg.jpg 2,213×886ピクセル

2019/09/27 12(25Rh nanofilm
catalyst Rh 60.5 µg
Rh nanoparMcle
catalyst (Rh/ZrO2)
Rh 200 µg

Pulsed AP deposition of Rh
onto an SUS foil to create
Rh(111) nanofilm

1,000 shots of AP pulses
Al

SEM
Zr

Al
Rh

Miniature metal
honeycomb fabrication

3 nm thickness

Rh

Rh (111) nanofilm
1 μm

SUS
https://ars.els-cdn.com/content/image/1-s2.0-S0169433217319657-fx1_lrg.jpg

üNanofilm catalyst with 1/3 lower Rh
amount shows higher activity at low
temperature than conventional Rh catalyst.
H. Yoshida, K. Koizumi, M. Ehara, J. Ohyama, M. Machida et al.,
JPCC 2019, 123, 6080. JP2015-166264
1 / 1 ページ

Pd/Mn-modiﬁed h-YbFeO3– Activating MvK-type NO reduction

Hexagonal YbFeO3(YFO)

1/2 N2

MvK-type NO reduction
N

Pd

O

CO + OL → CO2 + VO

Mn-YbFeO3
Oxygen vacancy site

NO conversion to N 2 (%)

HC, CO, NO, O2

Pd works as a promoter
1 1wt%
wt%Pd/Mn-YbFeO
Pd/Mn-YbFeO33

100

N2, CO2, H2O

2NO + 2VO → N2 + 2OL

1 wt% Pd/Al2O3

80

60

40

Mn-YbFeO
Mn-YbFeO
3(ST)
3
20

Mn-YbFeO30100

Mn(III), Mn(IV)

YbFeO3 is covered with Mn species
in Mn-YbFeO3

200
300
400
Reaction temperature / °C

500

üBy utilizing MvK-type NO reduction mechanism overcatalyst support (Mn-YbFeO3), PGM use can be
reduced to 1/10.
S. Hosokawa, K. Teramura, T. Tanaka et al, Catal. Sci.
Technol. 2016, 6, 7868. PCT/JP2016/057771

equipped
with
MS-5A
and
PoraPLOT
Realization of PGM-free tandem catalyst:
detector)for N2O and C3H6. De
ZnCr2O4 + CuCo2O4, ZnCr2O4+Cu/CeO
2
described in our previous reports.11,1
NO-CO-O2

CuCo2O4

Additionof C3H6.
NO-C3H6-CO-O2

B) CO conversion of chromium
composition 1000 ppm of NO,
CO, NO6000
ppm of O2NO, COandArOCO C H O
CuCo O
ZnCr Ootal ﬂow rate = 60 mL/min;or Cu/CeO
H O CO gas
HC .)
PROX:
714 mL g−1 ChH−1
NO-CO-O
removal by
3 6

2

2

3 6

4

2

2

preferential oxidation

22

N2 CO2 H2O

4

2

2

üTo avoid site-poisoning, base metal oxide catalyst
Figure3. Temperature-dependent
for preferential
oxidation of C H was placed at (A) N
Whereas an incorporation of
upstreamof
Cu/CeO ,catalysts
resulting in (ZnCrhigh activity
yieldof
tandem
2O4 + CuC
17
comparable to Rh benchmarking catalyst.
al (Cu, Co) into chromium
CeO2), upstream and downstream catalyst
Ohyama, A. Satsuma et al., ACS Catal., 2019, 9, 2866. JP2018-098843
sired J. CO
oxidation, that of
catalyst during NO−C3H6−CO−O2 react
3

2

6

Positive electrode for sodium ion battery
ナトリウムイオン電池： 年間の発表論文数（全世界）Yearly publications related to Na battery

1400

Ref.) Chem. Rec., 18, 459 (2018).

Number of scientific papers

1200

2012 – ESICB

1000
Positive E.
Negative E.
Electrolyte
Review articles
Others (solid‐state, Na‐S...)

800

TUSの実験ノウハウ
Æ 多くの設備⾒学者受⼊

600
400

Whittingham
LixTiS2

Delmas200

operation by Komaba

NaTi2(PO4)3

Abraham Tarascon
NaxMo2O4
DelmasNaxCoO2 Delmas
NaCrO2
Exxon

Mar.
2019

@ TUS of full cellFirst 駒場G
verification
Æ 全電池の初実証

Sony’s LIB

20
20

20
15

20
10

20
05

20
00

19
95

19
90

19
85

19
80

0

19
75

Na/TiS2

Year

Discovering and searching for cathode materialsRef.) Our group, Adv. Funct. Mater. (2011), Chem. Rev. (2014), Electrochem. (2019).

3

as well as development of ionic liquid for electrolyte

Na: disadvantage against Li:
Heavier atomic weight and more positive redox potential
駒場グループ： 年間の引用数
Na: advantage:
High natural abundance and larger ionic radius

Here, the energy density was estimated by calculation with theassumption of 300 mAh g−1 for hard carbon as a negative
Varietyof cathodes for Na battery
electrode material as full cells, as further discussed in the next
section. Combined with hard carbon, the estimated energy

NaxMnFe(CN)6,
permission frompermission frombH&Co. KGaA,
239. Copyright

Effective cathode materials reported till 2015
Energy Density / Wh (kg-1 of positive & negative)

P2-Na2/3Ni11/36Mn23/36Al1/16O2

ons. Recently,
ar framework
P2-Na Mg Mn O
ure 24b, have
The iron ande2(CN)6 and: layered oxide
thout alkaline−1: phosphate/sulfate saltof reversible
s. Polarization−1
ESICBʼs listof cathodematerials
at thelevel of international database.
Figure26. Averagevoltageis(Vave) and energy density (Wh kg )h smaller thanFig. 26 in Yabuuchi,
Kubota, Dahbi,
selectedof positiveelectrodeversus gravimetric capacity (mAh g−1) for Revision
Komaba, Chem. Rev., 2014, 114, 11636
Goodenough’smaterials for NIBs. Energy density was calculatedwith the hard carbon
2/3

0.28

0.72

2

peculiar frontier orbitals, is the origin of the enhanced reductive
stability of a superconcentrated solution that allows for reversible
lithium intercalation into a graphite electrode without EC solvents.
This work ensures the practical validity of superconcentrated organic solutions as a promising electrolyte for advanced batteries.

Unusual behavior of superconcentrated electrolytes- The second start of highly concentrated
electrolytes
In the future, our superconcentrating strategy will open a newresearch avenue in a functional electrolyte for advanced electrochemical technologies. In particular, the present breakthroughbased on the superconcentrated AN electrolyte will be an important step toward high-voltage Li-ion batteries utilizing graphite
ournal of the American Chemical Society
Articlenegative electrode and 5 V-class positive electrode, since the electrolyte allows for a reversible graphite negative-electrode reaction
with retaining high oxidation potential over 5 V inherent to AN.
Furthermore, the superconcentrated organic electrolyte can contribute to fast-charging lithium-ion batteries which are urgently
required for automobile application. However, there are several
problems to be overcome before consideration to practical applications. First, the coulombic efficiency and cycle performance of agraphite electrode should be further improved. However, it should
be noted that the present results are obtained under a severe condition; we used as-received natural graphite without any surface
treatment,29 functional binder,30 or electrolyte additive.31-33 Relying
on these techniques facilitating reversible lithium intercalation will
Figure 4. Raman spectra of LiTFSA/AN solutions in (a) 2230−2310 cm−1 (CN stretching mode of AN molecules) and (b) 720−780 cm−1 (S−N
remarkably improve thecoulombic
efficiency
and spectra
cycleanions
perforfree
solvents
Points andsolid lines
denote experimental or
and ﬁtting curves, respectively. (c)stretching, C−S stretching, and CF3 bending mode of TFSA−).No+−3
in a conventional(i.e., ∼1) and a salt-superconcentrated
Representative environment of Limance.
Second,dilutethe solution
corrosionof molan dmaluminum
current collectorsolutionby (i.e., 4.2 mol dm−3).
a LiTFSA salt might be a problem. This side reaction will easily be
suppressed by simple addition of a small amount of another salt
5042be a long way dx.doi.org/10.1021/ja412807w| J. Am. Chem. Soc. 2014, 136, 5039−5046
such as LiPF6.2 Although it will
to realize a superconHigh rate and stable operation
centrated electrolyte in practical application after resolving all
Figure 6 a) Discharge curves of a natural graphite / lithium metal half
above problems and also the issue of cost, we believe that the pecu3
cell with superconcentrated 4.5 mol dm LiFSA/AN and commercial
liar electrochemical feature and its detailed mechanism presented
1.0 mol dm 3 LiPF6/EC:DMC (dimethyl carbonate) (1:1 by vol.) elecJournal of the American Chemical Society
herein will be of great value not only in the development of nexto
trolytes at various C-rates (C/10, C/2, 1C, and 2C) at 25 C. b) Regeneration advanced batteries but also in the fundamental researchversible capacity of natural graphite in the two electrolytes at various Co
in electrochemistry and solution chemistry.
rates and 25 C. Charge and discharge were conducted at the same C-

4.5 M LiFSA/AN (acetonitrile)/ Li - Graphite anode
Molar ratio: Li/AN= 1/2
Performance of Li-graphite
CP-DFT-MD simulation
anode half cell

PDOS of superconcentrated solution−

Reactivity of Li and LiFSA/AN solutions−

Articlerate without using a constant-voltage mode at both ends of charge anddischarge, and the charge (lithium de-intercalation) capacity was plotted.

ASSOCIATED CONTENT

Supporting Information. Total energy profiles of DFT-MD simulation step, lithium metal deposition/dissolution, oxidative stability, N 1s
sequential formation of several stage structures of lithiumsuperconcentrated solution overcomes the inherent poorand O 1s spectra, PDOS of different DFT-MD trajectories or different
graphite intercalation compound (Li-GIC).
The obtained
reductive stability of AN solvent to exhibit enhanced tolerance
Conclusions
andperspective
,
which
is
close
to
the
reversible
capacity
was
ca.
330
mAh
g
toward reduction. The unusual reductive stability was
Enhancement
offurtherreductive
stability initialSEI
configuration
rate-performance,
physicochemicalﬁlm convergence,isformedby decompositionof anions
theoretical capacity (372 mAh g ) based on fully lithiatedproved by reversible lithium−metal deposition/dissolution
gure 5. SupercellsInused
densitystates(PDOS)
obtainedinquantummechanical
DFT-MD
simulations
on
(a
and
b)
dilute
(1. These results
clearly indicate
the reversible lithium(Figure of LiC
reaction in and
4.2 mol projected
dm LiTFSA/AN electrolyte
propertiesof
LiFSA/AN,
andcharge-discharge
curvesin
LiFSA/AN.
we ishavefound
reductive
stability
andWithout
intercalation
reaction at the naturalgraphite electrode.
S2).summary,Althoughthe reversibility
not good enough,this isenhanced
the
−3
−3
of
solvent
relying on(c)any techniqueto facilitate lithium intercalation, we,(10-LiTFSA/20-AN
spuerconcentrated
corresponding
dmChem.
) LiTFSA/AN
TFSA/43-AN ultrafast-charging
corresponding
to
0.4
ﬁrst to enable lithium metal
to functionasmol
a reversibledm
electrode ) andThis material
is available
free of tochargevia
theInternet
at 2014, 136, 5039.
Y.
Sodeyama,
Y. Tateyama,
A. Yamadaet4.2al.,mol
J. Am.
Soc.,
characterinis athoroughly
superconcentratedorganic
electrofor the ﬁrst time, observed
a Yamada,
reversible operationof K.
a graphite
in an AN-based electrolyte.
Since the reaction
negative
electrodein an AN-based electrolyte.
The successful(FigureS3), theunusualirreversiblestructuresin 3.0 mol dm solution
lutions. The illustratedarethesnapshotsinequilibrium
trajectories.
Foradilutesolution,
bothsituationsof
LiTFSA
salt(i.e.,(a) full
http://pubs.acs.org.
lithium intercalation
into graphite in one of the most reductionreductive
stability is uniquebatteries.
to such superconcentrated
lyte forlithium-ion
As an example,
a superconcentrated
Figure 1. Reactivity of lithium metal foil and LiTFSA/AN solutions at 1.0 and 4.2 mol dm−3 concentrations at room temperature.
34,35

−1

−1

−3

−3

6

Superconcentrated electrolytes
REVIEW ARTICLE

NATURE ENERGYHigh stability

C
/2
0

2C

200
Graphite|Li
4.5 M LiFSA/AN
1.0 M LiPF6/EC:DMC

100
0

0

5

10

15

Elimination of side reactions
20

25

Saltderiv

Cycle number

C/5

1

5.3 M LiFSA/TMP

7th·

1,000th

·

2

300

400

Voltage (V)

5.0

LNMO|graphite

100th

nt

lv e

so

ag

Stable 5 V full-cell

Capacity (mAh g−1)

e

re

e

200

t

100

ol

0

High voltage operation

ev

0

win

dow ·

f
No

0M

High level of safety

2M 4M

7M

Li2S8 dissolution in
LiTFSA/DME:DOL

Fire-extinguishing,
non-volatile

2nd

4.5

40 °C

4.0

C/5

5.5 M LiFSA/DMC
3.5

0

30

60

90

−1

1.0 M
3.3 M
NaFSA/TMP NaPF6/EC:
DEC

120

Capacity (mAh g )bAnti-corrosion,
shuttle prevention· High tran
EI
sp
S
or
ed

W id

Voltage (V)

5C

300

ber
um
tn

Graphite|Li

Metal anode reality

Dendrite suppression

400

Long calender life, wide
operating temperature range
3

High rate

Small polarization
at graphite
C
/2
0
C
/1
0
C
/5
C
/2
1C

Capacity (mAh g−1)a.

Advanced batteriesMultiple functionality of superconcentrated electrolytes applicable. to both Na and Li batteriesMultiple functionalities.

LiFSA/TEP:BTFE 106

2019
2018

NaFSA/DME:BTFE 104
LiFSA/SL60
LiFSA/TMP 21

LiFSA/SL:HFE62
LiFSA/DMC:BTFE 64
LiFSA/FEC 84

LiFSA/SL 60
LiFSA/SL:HFE62

LiFSA/DMC:BTFE 64
NaFSA/DME:BTFE 104

LiFSA/TEP:BTFE 106

ZnTFSA:LiTFSA/H2O 105

LiFSA/FEC 84

LiFSA/TEP 45

LiFSA/SL 60

LiFSA/TMP 21

LiFSA/SL:HFE62

LiFSA/SL60
LiFSA/TEP 45
ZnTFSA:LiTFSA/H2O 105
NaFSA/DME:BTFE 104

Publications and Patent Applications
Original papers

Patent applications

2012

Total
publications
18

5＜I.F.＜10

10＜I.F.

6

0

2012

2

InterNational
0

2013

97

20

4

2013

5

1

2014

272

57

14

2014

4

1

2015

200

41

16

2015

4

6

2016

204

54

12

2016

6

1

2017

245

58

11

2017

9

3

2018

254

44

27

2018

4

5

Domestic

Summary and vision for the future
Achievement
Catalysis
・Establishment of methodologies for reduction of PGM use in TWC
・Design of PGM-free TWC

Battery
・Proposal of sodium ion battery comparable to lithium ion battery
・Discovery of multiple functionality of superconcentrated electrolytes

Social implementation
Testing stage for practical use
・ 6 for catalyst and 7 for battery materials and technologies

Final stage of commercialization
・ 5 for catalyst and 4 for battery materials and technologies, and 4 softwares

Projects in the final term
Catalysis
・Realization of PGM-free TWC
・Development of TWC operatable at very low temperature

Battery
・Development of cathodes for high energy density
・Development of future battery; solid state Na battery, battery with aqueous electrolytes, etc.

Electrocatalysis
・Development of PGM-free/PGM less used cathodes of fuel cell・Development of PGM-free OER and ORR electrocatalysts

Future vision of ESICB center at Kyoto University
・11ESICB unit will be continued after finishing the project. Upgrading the unit to independent
center is planned.
・Strengthening the association among catalyst center at Kyoto and battery center at Tokyo
tightly bound with the group of electronic theory at IMS