Osaka Prefecture University, Japan 1
Kiyoharu TADANAGA, Akitoshi HAYASHI and Masahiro TATSUMISAGODepartment of Applied Chemistry, Graduate School of Engineering,
Osaka Prefecture University, Japan
Mario Aparicio, Alicia Durán, Yolanda Castro, and Francisco MuñozInstituto de Cerámica y Vidrio (ICV), Consejo Superior de Investigaciones
Científicas (CSIC), Spain
Development of New Electrolyte and Electrode Materials for All-Solid-State Thin Film Lithium
Batteries through Solution Process
SJ-nano symposium, Tsukuba, March 5, 2013
Osaka Prefecture University, Japan 2
Members of the projectOsaka Prefecture University
Professor Masahiro Tatsumisago (Leader)Associate Professor Kiyoharu TadanagaAssistant Professor Akitoshi Hayashi1 Post-Doc, 2 Ph-D students, 1 Master course student 1 Research assistant
Consejo Superior de Investigaciones Científicas (CSIC), Instituto de Cerámica y Vidrio (ICV)
Dr. Mario Aparicio (Leader)Professor Alicia DuránDr. Yolanda CastroDr. Francisco Muñoz1 Post-doc, 1 Ph-D student,
Osaka Prefecture University, Japan 3
Solid Electrolyte
Substrate
Negative Electrode
Positive Electrode
Thin-film battery
10 μm
Thin film lithium batteries will be used in things like smart cards, RFID tags, and other low power portable devices.
Possible application of thin film lithium batteries
Osaka Prefecture University, Japan 4
Large area and good quality, or nano-structured thin films can be prepared
Chemical compositions of thin films can be controlled.Rather thick films are easily obtained.
Examples of preparation of thin film batteries by physical processesSputtering・・・LiCoO2, LiMnO2, LiPON(lithium phosphate oxynitride)…Pulse Laser Deposition・・・ LiCoO2, LiMnO2, Li-V-Si-O amorphous thin film
Advantages of solution processes
Electrode and electrolyte thin films for all-solid-state lithium rechargeable batteries
Solution processes are very attractive for the development of thin film batteries.
Thin film battery is an important element in realizing next-generation sheet devices, as it needs to be formed as a small, thin-film device.
Osaka Prefecture University, Japan 5
Our project attempts to develop electrolyte and electrode materials for all-solid-state thin film lithium batteries using solution processes, as a clean and efficient energy production and storage device.
Safe, thin-film lithium secondary cells which are free from such hazards as liquid leakage and/or fires will be developed by employing electrolytes prepared from inorganic or inorganic-organic hybrid solid-state materials by using solution processes.
Purpose of our project
Osaka Prefecture University, Japan 6
Positive electrodesOPU: LiMn2O4
Solid electrolyteOPU: Li7La3Zr2O12
Li1.5Al0.5Ge1.5(PO4)3CSIC: organic-inorganic hybrid
Negative electrodesOPU: Li4Ti5O12CSIC: Li4Ti5O12
Current collector: Au
Current collector: AuSubstratePt, Au, Ti, Pt/Si,SiO2 glass, , etc.
Conceptual schematic of this project
Multi layered battery
Further development
Micro patterning
Osaka Prefecture University, Japan 7
Solution-based processes used in OPU, for the preparation of electrode and electrolyte thin films
・Sol-gel process・Mist-CVD process・Electrophoretic deposition of particles prepared by sol-gel・Aerosol deposition of particles prepared by sol-gel
Solution-based processes used in OPU, for the preparation of electrode and electrolyte thin films
・Sol-gel process・Mist-CVD process・Electrophoretic deposition of particles prepared by sol-gel・Aerosol deposition of particles prepared by sol-gel
Solution-based processes
Osaka Prefecture University, Japan 8
Mist CVD processMist CVD process
Features1. This process does not need vacuum systems because it is operated at atmospheric conditions. 2. Various precursor solutions can be used for the source, including innocuous and nonpoisonous ones.3. This process possesses various advantages such as: safety, cost-effectiveness, environmentally friendly, and the ability to apply to various types of materials.
In the mist CVD process, aqueous solution of starting material is ultrasonically atomized to form mist particles with a size of about 3 μm, and mists are transferred by a carrier gas to the substrate to form thin films.
MassFlowmeter
Gas
PrecursorSolution
Water
Ultrasonic transducer
Liner source nozzle
SubstrateStage and heater
Osaka Prefecture University, Japan 9
Preparation of LiMn2O4 thin films by mist-CVD processPreparation of LiMn2O4 thin films by mist-CVD process0.06M Mn(OCOCH3) 2.4H2O+ 0.033M Li( OCOCH3)
Molar ratio (Li : Mn=1.1:2)
Heat-treated at 500-800oC for 1h
Flow rates 8 L/minSubstrate temperature 200-400oC
Substrates
LiMn2O4 has advantages of low-cost, environmental friendliness, and high abundance.LiMn2O4 thin films
Osaka Prefecture University, Japan 10
LiMn2O4 thin films (substrate temperature: 200oC)LiMn2O4 thin films (substrate temperature: 200oC)
As prepared
10 20 30 40 50 60 70 80
After heat treatment at 700℃
Inte
nsity
( arb
.uni
t
2 θ / o (CuKα)
750 nm
5 μm
As prepared by mist-CVD process
After the heat treatment at 700oC
1 μm
750 nm
JCPDS LiMn2O4Au/SiO2 substrate
Spinel type LiMn2O4 single-phase thin film was obtained.
Osaka Prefecture University, Japan 11
Electrochemical behavior of heat-treated LiMn2O4 thin filmElectrochemical behavior of heat-treated LiMn2O4 thin film
0 20 40 60 80 1002.5
3
3.5
4
4.5
Capacity/mAhg-1
25 C, 0.05 mA cm-2
Cel
l vol
tage
/V( L
i+ /Li
)
1st~10th
1st~10th
beaker cell with three electrodes
W.E. LiMn2O4Film
R. E. Li film
C.E .Li film
electrolyte1 M LiPF6 (EC+DEC)
The LiMn2O4 thin-film electrode produced with the mist CVD method- Capacity is 80 mAhg-1
- Good cycle performance
Osaka Prefecture University, Japan 12
0.5
1
1.5
2
2.5
3
0 20 40 60 80 100 120
Charge-discharge behavior of Li4Ti5O12 thin films prepared by the mist-CVD
Capacity / mAh g-1
25 ℃, 0.1 mA cm-2
Cell
pote
ntial
vs . L
i / V
10 th←1 st
1 st10 th←2 nd
500 nm
Substrate temperature :400 oC + Heat-treatment at 700 oC for 1 h
[Li] = 0.02 M, [Ti] = 0.025 M
Thick film with cracks showed good cycle performance.
beaker cell with three electrodes
W.E. Li4Ti5O12Film
R. E. Li film
C.E .Li film
electrolyte1 M LiPF6 (EC+DEC)
Osaka Prefecture University, Japan 13
Solid electrolyte for thin film battery
Li1.5Al0.5Ge1.5(PO4)3 (LAGP) electrolyte can be prepared with a rather low sintering temperature.
Preparation of Li1.5Al0.5Ge1.5(PO4)3 thin films by mist-CVD processPreparation of Li1.5Al0.5Ge1.5(PO4)3 thin films by mist-CVD process
Electrolyte thin films are formed on electrode thin films => low temperature synthesis is expected.
Osaka Prefecture University, Japan 14
XRD pattern of the LAGP thin films
10 20 30 40 50 60 70 80
Sintering at 800oCfor 2 h
Inten
sity(
arb.u
nit
As-prepared
2 θ/° (CuKα)
LAGP
Sintering at 700oCfor 2 h
Sintering at 600oCfor 2 h
( Stage temperature:400 oC)- Peaks due to LAGP were observed in the as-prepared thin film.
- crystallinity increases with an increase in heat treatment temperature.
- LAGP phase was obtained as single-phase.
Osaka Prefecture University, Japan 15
1000T-1K-1
Cond
uctiv
ity /
S cm
-1
2 2.5 3 3 .5
Heat treatment temperature600oC
Ionic conductivity of the LAGP thin film
Conductivity in room temperature: about 2x10-6 S cm-1
Activation energy of conduction: About 40 kJ mol-1
10-6
10-5
10-4
10-3
Osaka Prefecture University, Japan 16
Osaka Prefecture University, Japan 17
Osaka Prefecture University, Japan 18
ConclusionsConclusions
・ LiMn2O4 cathode thin films, Li4Ti5O12 anode thin films, and Li1.5Al0.5Ge1.5(PO4)3(LAGP) solid electrolyte thin films were prepared by the mist CVD process.
・ Li4Ti5O12 anode thin films were prepared by a sol-gel process.
・New lithium ion conductive inorganic-organic hybrid was developed.
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