Process Scale-up for Pilot Scale

Production of Lithium-ion electrode

materials
NanoInnovation Conference, Roma 17-09-2020

C.Paoletti, A. Aurora / TERIN-PSU-ABI

Accordo di Programma 2019-2021
WP1-Accumulo elettrochimico
Obiettivi: Modellizzazione, sintesi e caratterizzazione di materiali per batterie litio-
ione, sodio-ione e post litio-ione e realizzazione moduli per second life.
Targets: Modeling, synthesis and material characterization for lithium, sodium and
post lithium batteries; Second life modules realization

WP1 Linea Attività 10 WP1 Linea Attività 11

Scale-up di processi produttivi Realizzazione di celle complete su
Process scale up linea pilota
Full cell manifacturing on pilot scale

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 Scale-up and Pilot Plant
SCALE-UP : design a prototype using data obtained from a model pilot plant

From LABORATORY SCALE…

the idea borns in the laboratories, with
typical methods and tools …to PILOT SCALE
ü reproduces the idea by studying
transport phenomena (thermal,
mass)
ü a small industrial system that
provides information to be used in
the large scale
ü uses smaller but similar equipment
in operation
ü g enerally batch or semi-batch
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 I Case : Process scheme for the production of 2 kg of LiFePO4

Methodology:
- Identify the phases (4) and unitary operations of the production process
- Identify and acquire the equipment to carry out the operations
- Experimentally verify the single phases with PARALLEL QUALITY CONTROL

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 Phase I: Mixing - Filtration

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 Phase II: Digestion in H3PO4

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 Phase III and IV: Grinding - Cooking

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II Case: Process scheme for the production of 2 Kg of LNMO2

The synthesis involves two

fundamental phases: 1- a first
mixing and solubilization of the
salts in water and 2- a subsequent
heat treatment in an oven at
800°C.
The presence of a reagent
classified as potentially
carcinogenic has directed the
study of the wet synthesis process
thus reducing the handling time of
products in the form of powders

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 Scale-up strategy and issues
The experimentation basically followed two stages:
- In test I-IV we focused on fine-tuning the process on a small scale, with
determination of the amount of water necessary for the solubilization of the salts:
using the minimum amount of water required to obtain a clear and transparent
solution. The reduction of the quantity of solubilization water has the great advantage
of reducing the evaporation times for the formation of the gel.

-  In test VI and VII, attempts were made to improve

the process in order to a scale-up particularly focused on the heat treatment phase in
terms of the thickness of the layer to be treated and the operating conditions of
the heating and stasis ramp.

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 Cell manufacturing process:
Phase V and Phase VI

Mixing and Filtration Digestion Grinding and Cooking Coating Assembling

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 WP1-Accumulo elettrochimico
LA11

Targets
ü Improve the mechanical properties of the electrode tapes with the aim of giving further plasticity,
compactness and homogeneity

ü increase the load of active material

ü modifying the relative composition of the constituents, the type of mixing and the
physical and chemical properties of the ink.
ü Varying thickness and calendering conditions with the aim of improving the adhesion of
the deposit and its compactness.

ü Electrodes of 26 cm2 area

ü Complete water based Lithium-ion batteries of 26 cm2 area and evaluation of specific capacity as a
function of the discharge rate, relating it to the final mixing.

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 Water based electrode optimization

An experimental
Different routes have been
activity has been
approached
carried out in order
ü  sequence of ingredients
to produce water
ü  relative composition
based electrodes
ü  substrate
in the perspective
ü  mixing conditions
of a “total green
process”

J. Li, Y. Lu, T. Yang, D. Ge, D.L.Wood III, Z. Li, iScience, 23,101081 (2020)

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Phase V: Electrode Sheet Preparation

MIXING COATING DRYING CALENDERING

Active material, binder

and conductive agent
are mixed together in
mass specific ratios
and sequence

CRITICAL POINT:
HOMOGENEITY
DEGRADATION

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 Phase V: Electrode Sheet Preparation

MIXING COATING DRYING CALENDERING

•  areal coating 15x25 cm •  T: +/- 1°C,up to 200°C

•  2 µm -10 mm thickness •  Dry room
•  0 a 100 mm/sec rate •  Vacuum
CRITICAL POINT:
By tape-casting VISCOSITY
SLIDING PHENOMENA
procedure the NO ADESION
electrode slurry TOO FAST DRYING
is coated on the
current collector

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Phase V: Electrode Sheet Preparation

MIXING COATING HEATING CALENDERING

•  10 cm width
•  0 ÷ 1,2 mm distance
•  T up to 80°C (+/- 5°C)

During calendaring
the porous electrodes
are compressed by
driving them trough
CRITICAL POINT: two massive cylinders
COMPACTNESS
DEGRADATION

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 Quality Control
5:1 7:1 9:1
Limited carbon content of
positive electrode drastically
reduce the cracking
phenomenon without
compromise performances.

4,5 4,5

4,0 4,0
150

]
-1
3,5 3,5

Voltage [V]
Voltage [V]

Specific Capacity [mAhg

3,0 3,0
100

2,5 2,5

2,0 2,0 7:1 2015

5C 50
2C C C/2 C/5 C/10 5C 2C C C/2 C/5 C/10 7:1 KD24
9:1 2015
-20 0 20 40 60 80 100 120 140 -20 0 20 40 60 80 100 120 140 160
Specific Capacity [mAhg-1] Specific Capacity [mAhg -1
] 0 2 4 6 8 10 12
# of cycle

Different carbon content Different carbon/disperdant content

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Full coin cell water based

2,1
C/10
Charge Capacity
2,0
Discharge Capacity

Charge Capacity (mAhg-1)

1,9

1,8 LFP/Graphite
1,7

1,6

1,5

0 20 40 60 80 100

cycle
4,0

3,5
Voltage (V)

3,0

2,5

2,0

0 5 10 15 20 25 30 35
Capacity (mAhg-1)

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Phase VI: Pouch Cell Assembly
US WELDING
DISK CUTTER MACHINE STACK ASSEMBLING VACUUM WELDER

• Anode • set for Al and Cu foil

• 58mm(L) x 45mm(W) • welding area 4mm x 4mm.
• Cathode • Frequency up to 40K Hz The electrodes are
CRITICAL POINT:
• 57mm(L) x 44mm(W)
WELDING SOLIDITY cut or pounched into
• Tab
• 10mm x 10mm
ELECTRICAL CONDUCTIVITY stips of desired shape

Half coin cell for quality check

18
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 Phase VI: Pouch Cell Assembly
SEALER
US WELDING STACK
DISK CUTTER VACUUM
MACHINE ASSEMBLING
MACHINE

The electrodes are CRITICAL POINT:

wounded together with ADESION BETWEEN COMPONENT
ELECTROLYTE PENETRATION
separator. VACUUM
The electrolyte is injected NO CONTAMINATION

welding tab

electrolyte

vacuum

anode cathode

separator
19
NanoInnovation, 17 settembre 2020
Conclusions
WHAT WE HAVE DONE
ü  Synthesis of active materials in kg scale
ü  Realization of semi-automatic process for electrode
ü  Full pouch cell manufacturing

WHAT WE WILL DO
ü  Development and tuning of a pilot line for Lithium and post
Lithium batteries manufacturing
ü  Sodium-ion batteries

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 claudia.paoletti@enea.it
annalisa.aurora@enea.it

NanoInnovation, 17 settembre 2020

 LiFePO4 kilo lab production
Nel grafico sono riportate le prestazioni elettrochimiche in termini di capacità specifica (mAh/g) di un elettrodo
realizzato con LiFePO4 prodotto su larga scala nei laboratori ENEA. Come si può vedere, l’elettrodo ha una capacità
specifica compresa tra i 160 e i 165 mAh/g, vicino alle massime prestazioni teoriche del materiale (170 mAh/g a C/10).
4.2
4.15 175
4.1 170
4.05
V of 2103-1144-2019.001
4
165
3.95 160 CC of 2103-1144-2019.001
3.9 DC of 2103-1144-2019.001
155
3.85
3.8 150
3.75
145
3.7
3.65 140
3.6 135
3.55
3.5
130
125

Capacity/mAh
3.45
3.4
120
Voltage/V

3.35
3.3 115
3.25
110
3.2
3.15 105
3.1 100
3.05
95
3
2.95 90
2.9
85
2.85
2.8 80
2.75
75
2.7
2.65 70
2.6 65
2.55
60
2.5
0 1 2 3 4 5 6 7 8 9 10 11
2.45
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 Cycle no.
Capacity/mAh

Profili di carica e scarica di 10 cicli a C/10 per le batterie Andamento della capacità specifica per 10
con il LiFePO4 prodotto in laboratorio. cicli a C/10 rate per LiFePO4.

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