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Electrochemical Dilatometer
ECD-nano-DL
User Manual
© 2008 - 2015
EL-Cell GmbH
Release: 1.8
2015-02-26
PCB: ECD-nano-DL-4.2 (TVS)
The information in this manual has been carefully checked and believed to be
accurate; however, no responsibility is assumed for inaccuracies.
EL-Cell GmbH maintains the right to make changes without further notice to
products described in this manual to improve reliability, function, or design.
EL-Cell GmbH does not assume any liability arising from the use or
application of this product.
EL-Cell GmbH
Tempowerkring 8
D-21079 Hamburg
Germany
phone:+49 (0)40 790 12 733
fax: +49 (0)40 790 12 736
e-mail: [email protected]
web: http://el-cell.com
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Contents
1
Product Description .................................................................................... 4
2
Technical Specifications .............................................................................. 5
3
Safety Precautions ...................................................................................... 6
4
Unpacking.................................................................................................. 7
5
Dilatometer Assembly ................................................................................. 8
6
EC-LINK Software Installation ................................................................... 19
7
Settings and Calibration ............................................................................ 19
8
Recording the Displacement Signal with an External Potentiostat ................ 20
9
Dilatometer Disassembly ........................................................................... 21
10
Using the Reference Electrode .................................................................. 22
11
Using an Auxiliary Electrode ...................................................................... 22
12
Using Single Crystals or Grains as the Working Electrode (option) ............... 23
13
Spare Parts .............................................................................................. 25
14
Connector and Cable Pin-out ..................................................................... 29
15
Technical Support .................................................................................... 30
16
Warranty ................................................................................................. 31
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1
Product Description
The ECD-nano-DL electrochemical dilatometer is dedicated to the measurement of
charge-induced strain (expansion and shrinkage) of electrodes down to the
nanometer range. The ECD-nano-DL has been particularly developed for the
investigation of Li-ion battery and other insertion-type electrodes. It may, however,
also be used for many other electrochemical systems utilizing organic as well as
aqueous electrolyte solutions. The electrode materials used can either be bound
films or single crystals/grains (e.g. HOPG or graphite flakes). The maximum sample
size is 10 mm x 1 mm (diameter x thickness).
The heart of the ECD-nano-DL is an electrochemical cell, hermetically sealed against
ambient atmosphere. The two electrodes inside are separated by a stiff glass frit that
is fixed in position. The upper working electrode (WE) is sealed by means of a thin
metal foil, through which any charge-induced height change is transmitted towards
the sensor/load unit above. This working principle allows determining the height
change of the working electrode without any interference from that of the counter
electrode (CE).
A high-resolution capacitive displacement transducer detects dimensional changes of
the WE ranging from a few nanometers up to 250 micrometers, during one and the
same experiment that may last between a few minutes to many days.
The ECD-nano-DL features an integrated USB data logger for recording the
electrode displacement, temperature, cell potentials and current. Analog outputs of
displacement and temperature are provided for integration with external instruments.
For best accuracy and drift stability, the dilatometer is to be operated inside a
temperature controlled chamber.
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Friction-free flexure guide
Sensor plunger
Weight load on WE
(not exchangeable)
Spacer disc for
height adjustment
Valve assembly
for vacuum filling
via syringe
Metal membrane
Auxiliary port
Reference electrode
assembly
Glas T-frit
Separates WE test
Specimen on top
from CE below
Spring-loaded
CE plunger
2
Gas filled dead
Volume to suppress
changes in hydrostatic
pressure inside cell
Technical Specifications









High resolution capacitive sensor system with <5 nm resolution, drift
stability of < 20 nm/hour (sample-free instrument at constant temperature),
and 250 µm full range.
Conditioning electronics with analog output signals (-10 to 10 V) for
displacement and temperature.
Integrated USB data logger for recording of displacement, temperature,
cell potentials and current.
3-electrode electrochemical cell
Sample (working electrode):
bound electrode film or single crystal / grain
max. sample size 10 mm x 1 mm (diameter x thickness)
Load on working electrode: 1 N
Electrolyte volume: approx. 2 mL
Materials in contact with electrolyte: PEEK, borosilicate glass, EPDM
rubber, stainless steel 316L for aprotic, gold for aqueous electrolytes
Operating temperature range
Cell and sensor: -20 to +70 °C
Conditioning electronics and data logger: 0 to +40 °C
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Minimum dimensions for
antechamber-transfer to glove
box (stand detached)
Dimensions in mm
(ECD-nano completely
assembled on stand)
3
Safety Precautions
Use proper safety precautions when using hazardous electrolytes. Wear protective
glasses and gloves to protect you against electrolyte that may accidentally spill out of
the instrument during filling, operation, and disassembly.
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4
Unpacking
Check the contents of the packages against the list given below to verify that you
have received all of the components. Contact the factory if anything is missing or
damaged.
NOTE: Damaged shipments must remain with the original packaging for freight
company inspection.
List of Components
1.
ECD-nano dilatometer (in the assembled state) equipped for use with aprotic
electrolytes
2. Signal conditioning electronics (controller box) with integrated USB data
logger for recording the displacement, temperature, cell potentials and
current
3. USB data acquisition software, Windows drivers and operating manual on
CD
4. Cell cable (connects dilatometer cell with controller box)
5. Sensor cable (connects dilatometer sensor unit with controller box)
6. Sensor GND cable (connects the sensor target at the sensor unit to the
sensor GND socket at the controller box)
7. 3 tubing assemblies for interconnection between cell, valves and syringe port
8. 20 ml syringe for filling the dilatometer cell with electrolyte
9. Vacuum pipette and tweezers for electrode handling
10. Hex wrenches for assembly and maintenance
11. Activated carbon electrodes (5 pcs) for reference measurements
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5
Dilatometer Assembly
The following photographs refer to the use of the dilatometer with aprotic electrolytes.
For aqueous electrolytes, the assembly differs slightly as indicated in the respective
figure captions.
1
Insert o-rings into cell body
(21.95 x 1.78 and 41 x 1.78)
2
Insert glass frit (T frit 10/20 mm dia) into cell body
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3
Place CE (dia <= 20 mm) on top of the glass frit
4
Insert the central CE piston into the cell bottom
(O-ring size 9.75 x 1.78 mm)
NOTE: For aqueous electrolytes, additionally place
the gold current collector on top of the CE, and use
the optional gold pin piston instead of the stainless
steel piston
5
Stack cell bottom (with central CE piston inserted)
on top of the cell bottom
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6
Put base flange (with valve support attached) on
top, hold the assembly tightly together, and turn it
upside down
7
Screw the assembly together by means of the 3
hex socket screws M4x25
8
Screw in the CE spring load from below to its
uppermost position, then release it slightly by
turning the screw back (ccw) by approx 45°
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3
9
Attach the three transfer lines following the
numbering on the cell parts
10
Attach the cell to the stand by means of the two
knurled screws
11
Insert the membrane O-ring seal
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12
Put the working electrode with its active layer
downside on top of the T-frit
13
Place the appropriate spacer disc on top of the WE
(SS 316L for aprotic, gold for aqueous
electrolytes).
NOTE: Three different spacer discs (thickness 2.1,
2.2 and 2.3 mm) are provided to initially adjust the
membrane for a given WE thickness close to its
neutral (flat) position (see sketch below). Use the
2.3 mm disc for a sample thickness between 0 and
150 µm.
WE
Spacer disc
Metal membrane
T-frit
CE
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14
Place the metal membrane on top
15
Attach the flange..
16
..and tighten the screws
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17
Plug the auxiliary port
18
Load the reference pin with the appropriate
reference material (e.g. by picking up lithium
metal) and attach the reference assembly to the
cell.
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Dead volume
valve (red)
19
Syringe valve
(yellow)
Fill the cell with electrolyte according to the
following procedure
1. Charge a 20 ml syringe with approx. 3 ml of electrolyte. We recommend
one-time use PP plastic syringes with low friction polysiloxane pistons.
2. Connect the syringe to the Luer adapter of the inner (syringe) valve
3. Open the syringe valve, and close the outer (dead volume) valve
4. Pull the syringe piston back to evacuate the cell. Hold the piston a few
seconds in the strained position.
5. Release the piston so that the electrolyte from the syringe replaces
deliberately the previously removed gas. NOTE: Never pressurize the cell
by pushing the syringe piston.
6. Repeat the two previous steps to complete filling.
7. Close the syringe valve, and open the dead volume valve
NOTE: The cell is now filled and hermetically tight. Up to this point, for airsensitive systems, assembly and filling has to be done in a glove box. All
subsequent steps may be carried out in ambient atmosphere.
20
Securing screw
Release the carriage securing screw, then move
the carriage into the uppermost position by turning
the micrometer screw clockwise
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21
Attach the sensor/load unit to the cell
22
Fasten the sensor/load unit by the two Allen head
screws
23
Place the dilatometer inside a temperature
controlled chamber. Connect the sensor cable and
the sensor GND cables to the controller and to the
dilatometer. Turn on the sensor electronics by
connecting the controller box to the power supply.
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24
Unlock the flexure guide by turning the locking
screw 90° counter clockwise
25
Adjust the sensor target by turning the micrometer
screw counter clockwise until the bar graph
indicator at the controller box is approximately in
mid position.
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26
Fasten the carriage securing screw
Finally, connect your potentiostat or battery tester to the 4 mm jacks on the front
panel of the controller box. The rightmost column in the table below refers to the
terminology used for the lead connections of Biologic potentiostats (MPG-2, SP, VSP
and VMP series). http://www.bio-logic.info/electrochemistry-ec-lab/instruments/
Controller
Box
I1
V1
REF
V2
I2
GND
Potentiostat
WE Current
WE Sense
Reference
CE
GND (if available)
Biologic Potentiostat
VSP, VMP3 etc.
WE
Ref1
Ref2
Ref3
CE
GND
Before starting the electrochemical cycle we recommend holding the cell at constant
potential (or open-circuit) for several hours to allow for baseline stabilization. The
initial rest period helps to discern charging induced dimensional changes from the
initial creeping.
Note that all materials display a more or less pronounced creeping. They tend to
shrink when applying a load, and to swell when removing this load. A mayor
contribution to the initial creeping seen right after cell assembly is to be assigned to
the construction materials of the dilatometer. Creeping of the working electrode is
induced each time the mechanical properties of the working electrode are altered by
charging. Therefore, each charge induced height change is followed by some
creeping. The charge induced creeping effects are real and not artefacts of the
measurement.
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6
EC-LINK Software Installation
In order to record the displacement signal together with the cell voltage, cell current,
electrode potential and dilatometer’s temperature, the software of the integrated USB
data logger needs to be installed on a Windows® PC.
a. You must be logged into an account with Administrator privileges.
b. Save your work and close down all active programs.
c. On the installation CD, run X:\Driver_CDM20814_Setup (where X refers to
the CD drive). This will install the FTDI driver required to establish the USB
connection with the data logger.
d. On the installation CD, run X:\setup. This will install the data logger
software. Follow any instructions that may appear on your screen.
e. Once installation is finished plug in the provided USB cable into both the
host PC and the ECD-nano-DL controller box.
f. Launch the data logger software if not already done.
g. After a few seconds, the data logger software should report a valid
connection and you are ready to start the measurement.
Additional information on the EC-LINK software can be found in the EC-LINK Quick
Start Guide.
7
Settings and Calibration
Calibration of the instrument has been carried out at the factory. The corresponding
settings of the EC-LINK software are stored in the file settings.txt in the installation
directory on the local hard drive and on the installation CD. If the default settings
have been changed for any reason, the original settings can be restored by copying
settings.txt from the CD into the installation directory of the EC-LINK software. The
settings affect only the data logger readings.
The DIP switches at the controller box affect both the displacement readings of the
USB data logger and the analog output signal. Leave the switches in their default
position as shown in the screenshot below.
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8 Recording the Displacement Signal
with an External Potentiostat
Many of today’s battery testers and potentiostats provide additional analog inputs
that may be used to record sensor signals along with cell current and potential.
In the following, connection of the ECD-nano-DL to a Biologic potentiostat (MPG-2,
SP, VSP and VMP series) is described as an example. The Biologic potentiostats
feature two analog inputs that are used here to record both displacement and
temperature.
1. Connect the 9-pin Sub-D connector of the optional analog output cable to the
analog input of the respective VMP3 channel.
2. In the Biologic EC-Lab software, load the experiment settings ECD-nano.mps
provided on the ECD-nano-DL documentation CD. NOTE: Don’t use the default
settings given in the EC-Lab software.
3. Adapt the Parameter Settings of the charge/ discharge protocol to your particular
experiment.
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9
Dilatometer Disassembly
When disassembling the dilatometer cell, wear protective gloves and goggles. Collect
parts that have been in contact with electrolyte on a separate tray for subsequent
cleaning.
a) In the following order, disconnect the cell cable from the dilatometer cell, the
power supply from the controller box, and the sensor cable from the dilatometer
cell.
b) Remove the dilatometer from the temperature chamber.
c) Lock the flexure guide and lift the sensor tip by turning the locking screw 90°
clockwise
d) Detach the sensor/load unit from the dilatometer cell.
e) Detach the cell from the bracket.
f) Unscrew the counter electrode spring load.
g) Detach the reference electrode.
h) Remove the tubing
i) Remove the cover flange, the metal membrane, the spacer disc, and the working
electrode.
j) Unfasten the cell body, and remove the T-frit from the cell body.
Clean all wetted parts right after disassembly. Ultrasonic cleaning with water and/or
detergent wash is recommended. Valves and tubing may clog if not properly purged
with water or other solvent. After cleaning, dry all parts in vacuum at 80°C overnight.
Additionally, dry the cell body and the cell bottom in vacuum at 120°C for at least 12
hours. Absorbed moisture may otherwise adversely affect test results.
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10 Using the Reference Electrode
The reference electrode assembly is comprised of the reference pin (1), the set collar
(2) attached to the pin by means of a set screw (3), the fitting (6), the spring (4), and
the hollow screw (5). The hollow screw serves to apply the spring pressure on the set
collar, thereby gently pushing the reference pin against the glass frit. The blind bore
on the tip of the reference pin is intended for taking up the reference electrode
material. For most lithium ion chemistries the reference material may be a small
piece of lithium metal picked up by the reference pin. For other aprotic electrolytes,
and also for some aqueous systems, a piece of PTFE bound activated carbon may
serve as the (pseudo) reference material. The optional gold reference pin is
recommended for use in aqueous electrolytes only. It must not be used with lithium
metal.
11 Using an Auxiliary Electrode
As an option, the ECD-nano-DL may be equipped with an additional electrode face to
face with the reference electrode. This auxiliary electrode may be a second reference
electrode, or simply a bare metal wire. For instance, in aqueous solutions, a platinum
wire auxiliary electrode may be cycled against the counter electrode to determine the
actual electrode potential of a simultaneously attached pseudo reference electrode.
The auxiliary electrode assembly is virtually identical with the reference electrode
assembly, except that the reference pin is replaced by a metal wire with 1.6 mm
diameter.
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12 Using Single Crystals or Grains as
the Working Electrode (option)
With the optionally available Crystal/Grain Test Kit (part-# ECD1-00-0018-B), the
ECD-nano may be loaded with a single crystal or grain as the working electrode.
Operating Instructions
a) Exchange the standard ball-tip at the sensor unit with the provided flat tip. The tip
is connected to the sensor plunger by means of a thread M2.5. For assembly and
disassembly, the sensor tip must only be turned with your fingertips. Never use
pliers or other tools as this may damage the sensor unit.
b) For cell assembly, refer to the instructions given in chapter 5 starting on page 8.
In the following, only those points are addressed where the assembly differs from
the standard procedure. Reference is made to the picture (step) numbers.
c) At step 2, account for the height of your sample by placing the provided distance
washers into the cell body before inserting the T-frit. The upper thickness value in
the table below refers to the neutral (straight) position of the membrane. The
membrane may be distorted by at least 0.3 mm into vertical direction without
causing excessive forces.
# of washers Sample thickness
0
<0.1 mm
1
0.1 to 0.4 mm
2
0.4 to 0.7 mm
3
0.7 to 1.0 mm
d) At step 12, place one of the provided holed glass fiber separators on top of the
glass frit. The thickness of the separator must not exceed the sample thickness.
Then put the sample (e.g. a graphite flake) into the separator hole. No spacer disc
is to be used, i.e., leave out step 13. The holed glass fiber separator may help to
improve the wetting of the sample with electrolyte. Its use is optional.
e) At step 15, place the provided modified cover flange on top.
f) After fastening the cover flange (step 16), place the provided isolation foil on top
of the metal membrane.
The remaining assembly steps and the dilatometer operation are identical with the
standard procedure described in chapter 5.
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Cover flange
Flat sensor tip
Cranked membrane
Crystal (sample)
Distance washers
Holed GF separator
T-frit
Part Kit for Testing Single Crystals Packing List
Order No.
VOR9050
ECC1-00-0041-A
ECC1-00-0179-A
ECC1-00-0016-S
ECC1-01-0021-E/X
ECC1-01-0021-D/X
ECC1-01-0021-C/X
ECC1-00-0019-G
ECC1-00-0019-F
ECC1-01-0025-A
Page 24 of 31
Description
Flat sensor tip (1 piece)
T-frit, borosilicate glass (1 piece)
Adjusting washer, 1.4404 (3 pieces)
Cover flange (single crystal), 1.4301 (1 piece)
Holed glass fiber separator, 10 mm x 0.65 mm (10 pieces)
Holed glass fiber separator, 10 mm x 1.0 mm (10 pieces)
Holed glass fiber separator, 10 mm x 1.55 mm (10 pieces)
Membrane cranked, copper (3 pieces)
Membrane cranked, aluminum (3 pieces)
Insulation foil (1 piece)
ECD-nano_manual / 27/02/2015
13 Spare Parts
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Note: This unit must not be disassembled by the user.
For repair, always send back the whole sensor/load unit.
Single spare parts for this unit are not available.
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14 Connector and Cable Pin-out
Cell Cable (4 x 2 x 0.25 mm2, TP, shielded)
Part-# ECE1-00-0033-E
One end of the cable is terminated with a Sub-D HD M15 connector (to box); the
other end is terminated with 2 mm banana connectors. A Pt100 sensor is located
beneath the black shrink tube at the end of the cable pointing to the dilatometer. The
cable shield is connected to GND.
Pin #
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Signal
V1
V2
REF
I2
AUX
I1
Pt100(1)
Pt100(2)
-
Cable Color Color of 2mm Plug
Red
Red
Blue
Blue
Grey
Grey
Yellow
Yellow
Pink
Black
Green
Green
Brown
White
-
Biologic Auxiliary Cable
(IEEE 1394 Cable)
Part-# ECE1-00-0039-D
Both connector housings are tied to the cable shield. The cable shield is connected
to GND.
IEEE 1394 to Box
Signal
Pin #
Signal
GND
Black
7
GND
Temperature
Blue
6
Analog IN 2
-10..10V; 8°C/V
Displacement
Green
1
Analog IN 1
-10..+10V; -12.5 µm/V (250 µm FR)
or -5 µm/V (100 µm FR)
Pin #
1
2
3
4
5
6
Sub-D M9 to Biologic AUX Input
Cable
Color
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Comments
15 Technical Support
Technical support for this product is exclusively handled by EL-Cell GmbH.
The following procedure must be followed when the ECD-nano-DL or any part of it is
returned to EL-Cell GmbH for repair:
1.
2.
3.
4.
5.
Send an e-mail to [email protected] to obtain a return authorization
number and a decontamination report form.
Sign the decontamination report asserting that the instrument has been
decontaminated and is safe for technicians to work on it.
Describe in detail what is wrong.
Include a contact name, address, telephone number, and email
address.
Return the instrument to
EL-Cell GmbH
Tempowerkring 8
D-21079 Hamburg
Germany
Email [email protected]
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16 Warranty
For a period of one year from the date of shipment, EL-Cell GmbH (hereinafter
Seller) warrants the goods to be free from defect in material and workmanship to the
original purchaser. During the warranty period, Seller agrees to repair or replace
defective and/or nonconforming goods or parts without charge for material or labour,
or, at the Seller’s option, demand return of the goods and tender repayment of the
price. Buyer’s exclusive remedy is repair or replacement of defective and
nonconforming goods, or, at Seller’s option, the repayment of the price.
Seller excludes and disclaims any liability for lost profits, personal injury, interruption
of service, or for consequential incidental or special damages arising out of, resulting
from, or relating in any manner to these goods.
This Limited Warranty does not cover defects, damage, or nonconformity resulting
from abuse, misuse, neglect, lack of reasonable care, modification, or the attachment
of improper devices to the goods. This Limited Warranty does not cover expendable
items. This warranty is void when repairs are performed by a non-authorized person
or service center. At Seller’s option, repairs or replacements will be made on site or
at the factory. If repairs or replacements are to be made at the factory, Buyer shall
return the goods prepaid and bear all the risks of loss until delivered to the factory. If
Seller returns the goods, they will be delivered prepaid and Seller will bear all risks of
loss until delivery to Buyer. Buyer and Seller agree that this Limited Warranty shall be
governed by and construed in accordance with the laws of Germany.
The warranties contained in this agreement are in lieu of all other warranties
expressed or implied, including the warranties of merchantability and fitness for a
particular purpose.
This Limited Warranty supersedes all prior proposals or representations oral or
written and constitutes the entire understanding regarding the warranties made by
Seller to Buyer. This Limited Warranty may not be expanded or modified except in
writing signed by the parties hereto.
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