Background
Battery Time Line
My Batteries
Instructions on glass jar
Gravity (Crow's foot) Battery (pre dated Leclanché)
Fuller Cell
Patents
Battery Patent
Flashlight
Telegraph Sounder
Links
Telegraph Equipment - seperate web page
Telephones - seperate web page
Telephone patents - seperate web page
Background
The Voltaic cell was invented about
1800 and consisted of two dissimilar metals immersed in an acid
solution. The same chemistry as a lemon battery using a
galvanized nail and copper penny. This cell has a very feeble
output and uses acid that's not human friendly. When the
telegraph system was the primary means of communication in the 1830 to
1880
time frame batteries
were needed at every telegraph station. The Leclanché
Battery offered a more powerful battery and at the same time a more
user friendly battery. Although it uses a primary chemistry it
could be charged by replacing the electrolyte for a small cost.
So millions of them were made.
Later
when the telephone required a local battery these same cells were used
until they were replaced with a different physical form of the same
chemistry called the
No. 6. The No. 6 was a "dry cell" and was
more convenient than the Leclanché wet cell. When the dry
cell goes dead it can not be reused and is thrown in the trash.
A primary battery is one where the chemistry only works one way.
You can not put electricity back into a primary battery to recharge
it. A secondary battery is one where the chemistry works both
ways and so it can be recharged using electricity.
The Leclanché Battery is a primary chemistry type, but was made
in an open glass jar (called a wet cell) so that when the battery was
dead the electrolyte
could be dumped out and fresh electrolyte put back in thus chemically
recharging the battery.
Georges Lionel Leclanché (1839-1882) pioneered a battery that
did not use acid but instead used Sal Ammoniac (ammonium chloride)
electrolyte along with a metallic zinc rod anode and a carbon and
natural
manganese dioxide cathode. He is the father of
the modern AA, C, D and 9 volt batteries that are so common today.
Eveready in the UK was making wet cell batteries of this design into the 1957 time frame.
Woodhouse & Rawson was also making them up until ___?___ and they
were sued by Edison and the court ruled that his electric light patent
was valid. They went out of business shortly thereafter (189?).
In their 1960 battery handbook Eveready had a few pages about
Leclanché cells. Not wet cells but the same chemistry in
flashlight battery form. It mentions that there's a tradeoff in
how much carbon is mixed with the MnO
2. More carbon
gives higher currents but lower capacity. Photoflash batteries
use more carbon so that they can supply higher peak currents, but
flashlight batteries use more MnO
2 so that they last longer.
Note that the Zinc rod may corrode and to prevent that it can be
amalgamated with Mercury. This was done in Zinc-Carbon
(Leclanché) flashlight batteries and later in Alkaline
flashlight batteries. But when Mercury was removed from all
batteries for environmental reasons there was a need for a complete
redesign of Alkaline batteries. Many of the patent numbers you
see on batteries relate to how this was done.
Materials can be listed in what's called Galvanic order. See the
Galvanic Table
at On Line Metals for an example. When designing a machine it's
bad practice to place two metals together that have a big separation in
the table. Doing so leads to corrosion and/or electrical
offsets. But for making a battery it's good to do. Notice
that Graphite is third from the top of the list and that Zinc is third
from the bottom of the list.
Battery Time Line
Year
|
Name
|
Comment
|
1800
|
Volta
|
Pile of copper & zinc seperated by electrolyte
|
1821
|
Seebeck |
called a thermopile (based on the "pile" name by Volta
used by Simon Ohm 1825 to develop Ohms law
|
1836
|
Daniell
|
porous cup seperates copper and zinc
|
1859
|
Planté |
Lead Acid cell
|
1860
|
Callaud
|
Gravity cell eliminates the porous cup from Daniell cell
|
1866 -1880
|
Leclanché |
Zinc & carbon porous cup and later without cup
|
1887
|
Gassner |
Zinc carbon dry battery
|
The sulfuric acid in lead acid batteries is much more a problem that
the milder electrolytes used in all the above batteries. So they
were not used for telegraph and/or telephone circuits.
My Batteries
On order are a couple of NEW wet
cell batteries. These are intended for use in chemistry/physics
classrooms. We'll see if they have any specifications and how
they compart to the 100+ year batteries.
12 Dec 2006 - I got a couple of Peerless wet batteries on eBay.
They do not use a porous cup for the manganese dioxide and instead have
it combined with the carbon like in the
Leclanché patent 165452 . The Zinc rod was missing and goes
through a hole in the center of the carbon block. A white
porcelain insulator, like was used in early electrical wiring, is used
to keep the Zinc rod from shorting to the carbon block.
The glass jar is about 110 mm square and 160mm tall. The complete battery with electrolyte weighs about 5.5 pounds.
A local electrician is on the lookout for a couple of the porcelain insulators to replace the missing one and the broken one.
I've added to the photo a catalog drawing of the "Pencil Zinc" that was
meant to be used but have some Zinc wire and rod stock on order.
There are two slots in the carbon block that allow you to see the Zinc
rod in the center. Maybe this is so you can see when the Zinc rod
has been consumed and needs to be replaced? Also there is a 3/8
to 3/4" gap between the bottom of the carbon block and the bottom of
the glass jar, maybe to allow some zinc compound to settle to the
bottom without effecting battery operation.
Note that the top cap overlaps the top of the jar. The top
surface of the jar has been ground on a flat surface so it mates to the
bottom of the cap in an almost air tight way. By applying a small
amount of "battery oil" to the joint between the jar and cap it becomes
an air tight seal. I may also be the case that the insulator and
zinc rod are a close fit and can also be sealed using a small amount of
"battery oil". The air tight seal prevents the water from
evaporating allowing the battery to work until the zinc is consumed.
A battery looking just like the one above on eBay has a paper label saying:
DIRECTIONS
FOR CLEANING CARBON
CYLINDER BATTERIES.
Remove the carbon cylinder and hold it
in a gas flame for a few moments, turning it
to apply the flame to all parts. Scrape off
the white matter that will appear on the sur-
face. Wet the carbon and repeat the oper-
ation two to three times till no white matter
appears and the carbon becomes coated with
soot from the gas flame.
Dissolve a charge of sal ammoniac un the
solution in the jar, replace the carbon and
the
battery will be ready for immediate use.
The Peerless batteries may by circa 1905, well after the
Leclanché patent 165452.
14 Dec. 2006 - 1 liter of water and 6 level tablespoons of Ammonium
Chloride mixed well and micro waved a little to warm it up.
Open Circuit Voltage about 1 and rising and short circuit current of about 500 ma.
Instead of a 1.4" dia. Zinc rod I'm using a piece of 0.091" dia Zinc
wire. It has a problem in that it can tilt and touch the
carbon/magnesium dioxide block. A rod would be better
centered. The 3/8" zinc rod is too large to fit inside the white
porcelain insulator.
Roto Metals has Zinc rods and wire
There are a number of sellers on eBay tha have
Ammonium
Chloride
Using 3 Zinc wires and warping the top part with scotch tape to make
the diameter fit the porcelain insulator the wires stay centered.
OCV is not about 1.2 volts and SCC is about 600 ma.
When I measured the current I didn't think is was real, but I now do. This came about after working with the
Toy Motor Kit
that was designed to be powered by a single No. 6 Dry Cell. The
motor will attempt to draw 17 amps from the 1.5 volt No. 6 Dry
Cell. I expect that the 600 ma was the current limit caused by
the test leads and internal resistance of the Fluke 87 Digital
Multimeter used to make the measurement and that a much higher current
would be produced by a lower resistance circuit.
Note that this battery is over 100 years old. It's made from an 1875 patent.
Date
|
Time
|
OCV
V
|
SCC
ma
| 100
Ohms
|
14 Dec 06
|
16:00
|
1.26
|
900
|
|
14 Dec 06
|
20:00
|
1.374
|
900->800->700
| 1.145 v
|
15 Dec 061
|
10:45
|
1.40
|
700
| 1.25
|
15 Dec 062
|
14:00
|
|
| .75v @ 11 Ohms
|
15 Dec 06
|
17:30
|
|
| .74v @ 11 Ohms
|
16 Dec 06
|
10:30
|
|
|
.74v @ 11 Ohms
|
Note
1 - After sitting overnight the water is now clear, not
the foggy appearance when first mixed. There are crystals of
Ammonium Chloride on the bottom of the jar. So maybe 6 level
tablespoons was a little too much Ammonium Chloride, but it's good to
have a saturated solution.
Note
2 - After leaving the 11 Ohm load on for many hours the
voltage across the load is stable at 0.75. But the No. 6 battery
is specified to power this load for 380 hours and is at >= 0.9 Volts at
the end of that time. The current would start at 1.5/10
= 150 ma and end at 0.9/10 = 90 ma, but my wet cell is only delivering
about 75 ma. So if the No. 6 battery replaced the wet cell then
the output should be about the same. But so far I have not found
any specifications for wet cell batteries.
It may help to use sandpaper to clean the surface of the carbon block
or maybe use water that has had the oxygen boiled out. Or maybe
this is the performance of the battery when it was new?
New Battery
1 Dec 2006 - Activated one of the new batteries. Uses 500 ml of distilled water and 7 level tablespoons of NH
4Cl. I'm just guessing on the NH
4Cl. This is half the volume of the older battery.
This is twice as concentrated as what I used for the old battery (1
liter & 6 level tbl spoons). After adding the NH
4Cl
and the Zinc rod the liquid level is at the bottom of the black band
around the top of the porous cup.
This new battery is missing the air tight seal to prevent
evaporation. That's consistent with the idea it was made for a
school class demonstration rather for use in a working
environment.
Just after activating the new
battery it had an Open Circuit Voltage of 1.688 V and a Short Circuit
Current of 200 ma. The new battery will dimly light an LED but
the old battery will not.
After a day or two will try swapping various parts to see which is the key factor.
Note that the new battery comes with a white plastic jar that has a
place for the Zinc rod in one corner. And a pre-assembled porus
cup that's 1 7/8" diameter (similar to a No. 6 dry battery).
If you know where the new batteries are made let me know.
2
Jan 2007 - Connecting the old and new batteries in series with an LED
and 27 Ohm resistor lights the LED. Since the capacity of a No. 6
dry cell Leclanché
Battery is about 52 Amp Hours I expect this setup would light the LED
for about 4.5 months. The current is about 16 ma and the LED
voltage is about 2 Volts.
9 Jan 2007 - LED has been on 24/7.
15 Jan 2007 - When walking near the batteries the LED flickers.
It's because the zinc wires I put in the old battery are getting eaten
up and only a small area remains below the electrolyte. I expect
the LED to turn off shortly when all the zinc has been consumed.
18 Jan 2007 - the LED is on but very weak, I think the zinc must be almost gone.
21 Jan 2007 - the LED has turned off.
The starting zinc was 3 wires each 0.091" dia by 9 inches long.
Now there are 3 wires each 4.25" long. The relative position of
the wires and insulator in the photo is slightly off. The bottom
end of the wires are about 1 inch up from the bottom of the
insulator. Capillary action has pulled the electrolyte up into
the insulator and that column of liquid has eaten the bottom end of the
wires. So 3 wires 4.75" long have been consumed by 17 ma for 19
days.
The zinc rod in the new battery, although black, looks about the same
as when new. I don't know if the new zinc has been amalgated with
a mercury coating or if the small amount of use is because of it's
larger 0.478" diameter.
The new zinc rod for the old battery is 8.1" long x 0.37' dia.
scotch tape used to make an insulator to keep it from touching the
carbon block. Installed 21 Jan 2007 13:20. It's resting on
the bottom of the glass jar. Not good since as it's used up it
will fall down. Should be suspended from the top.
4 April 2007 - 75 % of the water in the modern cell has
evaporated (there's a 1/2" gap outside the porous pot and the jar's top
lip. But the old glass cell has 100% of it's water (the carbon
block sits on top of the lip like a lid & there's only a 1/8" gap
between the Zinc rod and the hole in the carbon block).
Although a little dimmer than at the start the LED was still glowing
and was on a 24/7 basis until today when my wife ran into the
stack holding these and spilled some electrolyte when the new cell fell
to the floor. stop test
Photo and instructions from
Fred Coady.
“OUR OWN” DISQUE LECLANCHE BATTERY
DIRECTIONS FOR SETTING UP AND USING
First – Put the contents of paper bag (Sal Ammoniac) in the glass jar, fill one third full of warm water, and stir well.
Second – Insert the Porous Cup and Zinc, being careful that the mixture
does not rise within 1 1\2 inches of the top, or quite up to the line
of paraffine.
Third – Pour a little water into the air holes of Porous Cups and let
the cells stand a few hours before connecting the poles, so that the
solution may saturate the contents of the Cups.
Note – If immediate work is required, use HOT WATER.
The battery should not be set to work, however, until the Porous Cup and its contents are well soaked.
Fourth – Set the Battery in a dry, cool place. See that the connections
are clean and firmly made, and that the connecting wires are properly
insulated.
Fifth – When adding water or Sal Ammoniac to supply the loss by
evaporation, be careful to keep the top of the Porous Cup and Jar
entirely dry and clean.
Sixth –
When the Battery fails to work satisfactorily, throw out the solution and substitute a fresh charge of Sal Ammoniac and Water
THE ELECTRIC GAS LIGHTING CO.
195 Devonshire Street, - 56 Arch Street
BOSTON, MASS.
Note: Since this was
not made by the Leclanché Battery Co. of N.Y. it probably was
made after the Leclanché Patents had run out.
This may be an early Leclanché type cell, but before any of the Leclanché patents, so has a different name.
4 Ohm sounders are for local loops
(under say 100 feet). 20 Ohm sounders are for up to 15 mile
lines. Higher Ohm sounders are for very long lines.
In most cases a relay is used on a long line and then 4 Ohm sounders
can be used in the local loop. Battery was typically supplied at
each end of a line by either Gravity and later Leclanché
cells. The number of cells goes up like one cell per mile of line
and per sounder.