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2. Electrochemistry Overview
When an external circuit is connected, the electron flow, the ion flow
and the discharge reactions proceed spontaneously and
simultaneously, releasing the chemically stored energy as
electricity. The ions flow mainly by diffusion through the electrolyte,
spreading because like charges repel, and by attraction to the
opposite electrode as they reach it. The current capacity of the
battery depends partly on how fast the ions diffuse through the
electrolyte. Potassium chloride salt is supposed to be very fast.
The discharging reactions release chemically stored energy
electrically. The recharging reactions require electrical energy from
the external circuit - the battery charger. Charging restores the
'spent' lower energy substances to their higher energy oxidation
states and valences.
There are many solutions and some solids that can pass ions, but
the best - fastest - solvent is a polar liquid such as water, with an
acid, salt or alkali electrolyte dissolved in it. There is, however, one
serious limitation to using water as an electrolyte, as mentioned
previously:
"The use of aqueous battery electrolytes theoretically limits the
choice of electrode reactants to those with decomposition voltages
less than that of water, 1.23 V at 25 C, although because of the
high "overvoltage" potential normally associated with the
decomposition of water, the practical limit is some 2.0 V. The liquid
state offers very good contacts with the electrodes and high ionic
conductivities." Lead-acid batteries are theoretically 2.05 open
circuit volts, and many earlier cells were about 2 volts.
The voltage delivered to a load circuit is somewhat lower than the
open circuit voltage, depending on the internal resistances of the
battery relative to the amount of current flowing. Hence batteries
are given a "nominal" voltage rating which might be expected in
typical heavier use, such as "1.2 volts" for Ni-Fe, Ni-Cd, and Ni-MH,
which read more typically 1.33 to 1.43 volts with no load. Heavy
loads may drop the output even more, eg to 1.0 volts. If such loads
are expected, it's usually best to add more batteries in parallel to
reduce the load on each one, or to use bigger cells, which is
effectively about the same thing.
[-0.72 V]
Ni(O)Mn2O4. It'll probably get a bit more mileage out of the nickel because of the high conductivity, it would probably discharge down
to nickel valence 2.0, whereas nickel hydroxide pretty much stops
supplying current when the average valence is down to 2.25 owing
to increasingly poor conductivity.
I made three small (1/4" square) cylinder electrodes from it. They
worked well, and seemed to be much more conductive than simple
nickel hydroxide.
The approximate formula was:
11g NiMn2O4
5 g graphite powder
.4 g Sunlight dishsoap
I meant to put in a little neodymium oxide (maybe 1/2 a gram?),
to raise the oxygen overvoltage either for better higher temperature
performance or in case the higher voltage permanganate reaction
applied, but I forgot.
I couldn't find nickel manganate to buy. I tried making it
chemically, but it was messy and smelly. Then I mixed appropriate
amounts of dry NiO and MnO2 powders (both from the pottery
supply) in a stainless steel pot and simply heated them red hot with
a propane torch (outdoors, with a respirator). This gave a lower
resistance product and was fast and pretty simple to do. I only got
15 grams, so I guess the torch blew 7 or 8 grams of powder out of
the pot. This is what made the successful electrodes above. Later I
made another batch and 'only' lost 25% of the mass.
Vanadium
I 2011 I made a battery with a vanadium electrode. It was
supposed to be the negatrode, but it didn't seem to work unexpectedly, the vanadium seemed to become soluble and to
migrate. (This was also the first cell I'd made with transparent
plexiglass sides, and I could see the vanadium pentoxide yellow
color appearing on the other electrode.) I reversed the charges, and
found that the cell charged to about 2.2 volts. The vanadium
positrode side would have made up around 3/4 of that, and it seems
surprising that it didn't just bubble oxygen and spontaneously
discharge itself to a lower oxide. It seemed to charge and discharge
well, but at the time I hadn't made the grafpoxy yet and it
deteriorated like my other cells of that period, as the graphite
backing sheet swelled and lost conductivity and good contact with
the electrode and the carbon terminal post. Judging by the voltage
and the chart, the likely half-reaction was:
V2O5 + H2O + 2e- <==> V2O4 + 2 OH- [+1.6? V]
Unlike the case for either alkali or acid solution, and unlike it's
unexpected behavior as a negatrode, the oxides appeared to me to
remain in solid form, not dissolve, in the salt electrolyte. This
appears to make it a good positrode, moving one electron per
vanadium atom, hopefully with good stability from the double
vanadium molecular center.
Taking the average of the acid and alkali voltages as being the
approximate salt voltage, the voltage obtained in the cell indicates
the single valence change to V2O4 seems to apply. (average of
(1.0V [acid] + 2.19V [base]) / 2 = 1.6V [salt])
The table shows that vanadium's higher oxides are "amphoteric", that is, they'll dissolve in either
acid or alkali.
However, they don't seem to dissolve or break down in neutral pH salty solution even with a
valence of +5.
I don't see the common V2O5 form (or VO for that matter)
anywhere in the pourbaix diagram, and the voltages don't match
the table above, nor do they appear to jibe with my experimental
results.
Vanadium probably deserves more research in salt electrolyte for
use as a positrode (and maybe in alkali as a negatrode), but I have
no present plans for doing it myself. After I found the vanadium
Pourbaix diagram, I figured there's probably soluble ions
somewhere during charge or discharge, which might make for
limited cycle life. If I'm going to stick with 'tried and true', that's
nickel, and if I'm going to experiment, I'll try for a bigger prize:
perchlorate or permanganate.
Perchlorate
Chlorine ion, Cl-, oxidizes to perchlorate, ClO4-, moving 8
electrons with its very own electrochemical reactions regardless of
the metal+ ion it's attached to. I once tried to make a positrode of
lanthanum perchlorate, La(ClO4)3, which would reduce on discharge
to lanthanum chloride, LaCl3. The lanthanum was (my intent,
anyway) chelated into the substance of the electrode so that, even
being in dissolved form, the heavy La+++ ions wouldn't be mobile.
(There is precident for this last, the article saying chelated dissolved
lanthanum behaved about the same as undissolved, tho I can't
remember where I read of it.) In addition, perchlorate is often much
less soluble than chloride, as with only slightly soluble potassium
perchlorate versus potassium chloride salt.
As I've said, if heavier elements were used, they'd have to move
more electrons to attain the same energy density. Lanthanum
perchlorate, potentially with 12 O-- ions forming 24 OH- ions on
contact with water, is a super example: 24 electrons per reaction
where nickel moves one or two. That much more than makes up for
the atomic weight of La(ClO4)3 being almost five times that of
Ni(OH)2, and suggests the theoretical possibility of a much higher
energy density electrode than nickel hydroxide.
There may be reasons I'm unaware of that this can't work. I am
after all only an amateur chemist. However in the absence of any
[+0.15 V]
[~+0.5 V]
Although cell A has the highest voltage, and although the positive
electrode has about the same watt-hours as cell B, cell B has twice
the amp-hours, providing 1.5 times the energy density
(theoretically 393 WH/Kg) with only slightly more weight.
Furthermore, manganese dioxide can discharge to two lower
oxide states after discharging to MnOOH (or Mn2O3), for 1.5x or 2x
the amp-hours if the equipment being powered can tolerate a lower
cell voltage.
In this case, one or two more high energy negative electrodes can
be added to the battery to utilize these additional amp-hours,
depending on acceptable voltage. (Cell C) The drooping voltages as
the cell is 1/2 discharged and then 3/4 discharged will provide good
warning that recharging is required.
So for a while, I thought Mn-Mn would be the outstanding choice.
And the main materials for Mn-Mn cells are essentially the same and hence the same price - as those for throw-away dry cells.
But when I made a cell, it charged right up to (potassium)
manganate or permanganate, which are slightly soluble. I suspect it
Th
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NiZn alkaline cells is best seen in the Zinc Pourbaix diagram. Here it
is revealed that this ion probably won't form below about pH 13.5,
and it's the pH 14 electrolyte that's the problem: it would be fine at
about pH 8 to 13.
Evidently, adding some manganese oxide to the zinc to lower the
pH to 13, as the manganese negatrode does for itself, should stop
zincate from forming and allow long life zinc negatrodes.
The question then is, is there any point to making zinc negatrodes
when manganese ones have more energy and are just as cheap?
One possible reason is to get close to a specific battery voltage. For
example, if NiMn cells are 1.7 volts, 6 volts is hard to attain:
1.7 * 3 = 5.1
1.7 * 4 = 6.8
whereas four NiZn is closer:
1.6 * 4 = 6.4
or to get very close, use 3 NiZn and one NiMH:
1.6 * 3 + 1.2 = 6.0
Thus it would seem that NiZn could have uses in specific
situations.
For general application however, including 12 volts, the NiMn would
seem to be the winner, needing only 7 cells for 11.9 volts, while
zinc is way off at 11.2 or 12.8 with 7 or 8 cells. NiMH takes 10 cells.
"Active" high surface
area zinc oxide
(ZnOxide.org)
An issue with
zinc in salt
solution is that
zinc powder
and zinc oxide
powder both
absorb CO2 out
of the air and
form zinc
electrolyte. The surface area of a sheet of metal is small, and all but
the very surface atoms of the sheet are wasted, out of contact with
the electrolyte. A vast multiplication of minute particles to make a
porous substance is required in order that the battery electrodes
need not span a gymnasium to supply much current or store much
energy.
On the other hand, these many minute particles must all be in
electrical contact with each other and they can't physically fall
apart. To achieve this, they must be "glued" and compacted from
loose powder into something more like a dense piece of sandstone
or brick - a porous electrode "briquette". The briquette must be well
compacted so the particles electronically connect, and yet consist of
open pores so they all also contact the electrolyte. And the binder
'glue' can't interfere or coat the particles.
Since connections are generally still poor though the maze of
particles over much distance (and increasingly poor with oxidation
level), some sort of continuous metal or carbon conductor spans the
entire area of the electrode, the "current collector". The briquette is
compacted around this for good contact throughout. None of the
grains are more than the electrode thickness away from this plate,
mesh or metallic sponge that is connected straight to the battery
terminal.
Obviously there's an optimum compacting pressure to achieve the
best compromise between electronic conductivity and pores for ionic
conductivity. Doubtless this varies with the ingredients in the
electrode mix. An electrode with fluffy nickel hydroxide and
considerable graphite powder may have a different optimum
pressure than a dense zinc electrode with few additives.
The only figure I've seen for compacting pressure was in one
research paper where the authors mentioned an "optimum"
pressure of 675 Kg/sq.cm - 9600 pounds per square inch - for an
iron oxide electrode. For the chosen 1.5" x 3" electrode size, that
would be 21.5 tons. I trust this may be taken as a maximum
pressure requirement. I describe some electrode compactors and
ways to get sufficient pressure in the appendices. (I hope to offer a
good compactor press with a "steering wheel" type tightening
handle - but it can be done by tightening some bolts with a wrench,
(especially nickel hydroxide), and if they are able to do so, they lose
their conductivity and become pretty much useless. This was a
major problem through most of my battery research. The best
solution appears to be the perforated rigid plastic pocket electrodes,
which hold the substance in and can take the pressure.
There are at least 3 types of electrode construction: Pocket,
Sintered Plate, and Paste Electrodes. All of them use powders of the
active material, usually with additives mixed in.
Pocket electrodes consisting of thin perforated metal enclosures,
"pockets", to hold the electrode briquettes, were invented in the
1890s. These work great and are highly conductive but with metal
pouches holding the electrode materials they're expensive to
manufacture and heavier, with low energy densities by weight.
Nevertheless nickel-iron alkaline pocket batteries were better than
lead-acid and Edison's best version was in common use in early
electric cars by 1910 or so. They had to be nickel plated (at least in
the positive electrode) to avoid dissolving away. Since all common
metals including nickel dissolve in salty electrolyte, metal pocket
cells would be impractical for them.
However, having dismissed pocket electrodes for most of the
duration of the battery project, I ended up adopting perforated rigid
plastic pocket electrodes as the best choice for homemade DIY
batteries. The extra weight of the electrode and battery case
structures is compensated and more by better, higher energy
chemistries.
Sintered electrodes were invented in the late 1920's as a better
way, but their manufacture and use only spread gradually. The
carbonyl or a powder of the metal, usually nickel and cadmium for
Ni-Cd's, would be sintered (heated until it softens and flows a bit,
and the particles just barely melt together where they touch) into a
porous "metal sponge" structure full of minute open cavities -- 80 95 % empty space. The electrode active particles would be
impregnated into these spaces, then the whole thing compacted. As
the conductive metal permeates every little recess of the entire
electrode, these are highly conductive and have great current
capacity from small cells, eg ~20 amps from ~"AA" sizes. The
but with rather low conductivity, this will be a bigger focus in future
development.
The manganese standard dry cell "+" electrode occupies almost
the whole diameter of the cell - the construction does work, but is
generally for low current rates.
Of course, the taller the cylinder is, the more electrode cylinders
there are in the cell, and the more cells that are in parallel, the
lower the overall resistance will be and the higher the current that
can be driven, but they will still charge and discharge at about the
same rate.
Another aspect to this problem is the speed of ion diffusion
through the electrolyte. If an electrolyte diffuses ions twice as
quickly, the electrodes may be considerably thicker and still have
the same current capacity. Potassium chloride is, I believe, about
the fastest electrolyte. Potassium compounds (KCl, KOH) are known
to be faster than their sodium equivalents (NaCl, NaOH).
Battery Layouts
One common type of battery construction is wrapped, spiral
electrodes, common in "AAA" to "D" NiMH dry cells. A "V" of
separator paper encloses one electrode.
Another common type is "prismatic", where alternate positive and
negative flat plates, separated by sheets, are connected together in
parallel to each terminal. This is usually used in flooded cells such
as lead-acid.
These constructions have the advantage of providing the
maximum interface area between electrodes, each plate being
adjacent on both sides through separators to an opposite electrode,
except of course for the two end plates, or the outside of the spiral.
An older construction is "pocket electrodes", wherein a minutely
perforated, nickel plated shell of thin metal holds the electrode
chemicals compacted. (Nickel is the only metal that doesn't corrode
away in the positrode in KOH or NaOH alkaline electrolyte.)
Typically there's a wall every 1 to 2 cm, dividing the pocket plates
up into rows or columns - they would bulge out if wider. These
harkens back to the early days of batteries - but they didn't have
plastic back then. A number of previous ideas came together, and a
couple of new ones were soon developed, to make this work. A
battery of any size could be assembled from easy to make, square
cylinder plastic pocket electrodes, layed out checkerboard style.
Each electrode was a separate unit, individually compacted and held
that way. Initially the biggest problems were bursting of the
perforated cylinders and high internal electrode resistance.
The first plastic cylinders were 1/2" square inside. This made
electrodes that were just too fat, and the conductivity was very
poor. So this electrode size was changed to 1/4" square, more in
keeping with the electrochemical requirements (see "Electrodes
Overview", next section), and it increased conductivity an order of
magnitude. The cost was making four times as many electrodes. I
may try 5/16" and see how that works, but they'll probably be
pretty low rate cells. At that point, I decided a special jig to help
compact the powders into the small tubes was needed to speed
things up.
Right jig: channel for folding the plastic around a 1/4" steel rod, after heating it in an oven (rod
shown is 5/16")
Left jig: electrode stuffing jig. Powder is dropped/brushed into slot,
1/4" rod pushes it in, and then tamps it down (not too hard).
After the top is glued on, a zinced nail is driven in.
Right electrode is the original 1/2" size, replaced by four 1/4" size.
The sides of the first square tubes were made from .063" ABS
sheet plastic. Next will be tougher .020" styrene plastic to cut waste
space, weight, and the distance between electrodes. They are
perforated with a heavy-duty sewing machine.
The perforated plastic is cut into sections about 25 x 65 mm. This
is heated in a kitchen oven on an unwanted cookie sheet or shallow
baking pan to 350 degrees F, for about 3 minutes if the oven is
preheated. (The longer it's left in, the more it shrinks.) In 3
minutes, it should be pretty much limp and can be formed into any
desired shape. That shape is a four walled cylinder of 1/4" square
inside dimensions, by 60mm tall, formed around a 1/4" square steel
rod with a jig. A bottom and a top end cap close the ends. The top
cap has a hole for the connection wire. The overlapped seam and
the end caps are glued with methylene chloride, a solvent which
dissolves the plastic, thus making the plastic its own glue as it
evaporates.
Filling the electrode is to be done with an "Electrode Stuffing Jig"
having a slot for electrode powder mix to fall into place for a 1/4"
square steel plunger rod to stuff it into the cylinder and tamp it
down. Once it's filled, the end caps are glued on.
The straight connection wire runs right through the cylinder from
top to bottom, and sticks out the top far enough to poke through
the top of the battery to solder to. At the roof of the battery, it's
sealed with RTV cement, or epoxy.
For the negatrode, the connection wire is a galvanized box nail,
pounded into the electrode after both caps are glued on. The zinc
coating on the nail has the required hydrogen overvoltage.
For the positrode, a nail is used to make a hole, then a grafpoxy
(or "nimangapoxy"?) wire (too fragile for pounding) is stuffed into
the hole.
Like the carbon rod in the manganese center of a "carbon"-zinc dry
cell, a single grafpoxy coated wire sticks out the center of the top of
the electrode for connection, for both polarity of electrodes, of any
chemistry. The electrode chemical mix is compacted by tamping it
directly into the plastic shell with a hammer and a punch. (The
punch has a center hole to fit around the wire.) Once the bottom is
glued on, there's nowhere the chemicals can expand except by
bulging the stiff plastic sides. (A bit of expansion ability is vital for
most pocket electrodes, depending on the chemistry, temperature,
etc.)
Separator Sheets
Separator sheets up until the 1970s were
pretty simple: any insulator to keep the two
electrodes from touching. Recently there have
been developments of interest.
The first is the zircon (ZrSiO4) or zirconia
goes between the wide sides as the internal width, and your cuts
won't have to be perfect or sanded down to exact uniform
thickness, except the bottom ends of the two side pieces should
contact the edge of the bottom piece well. The chief place to watch
for leaks is the bottom corners.
I would LOVE to have injection molded cases and lids, and I hope
I can make the molds some day, or perhaps two or three of them of
different thicknesses. (January 11th 2012 note: I've just acquired a
milling machine and ordered a kit to make it into a CNC milling
machine - the vital tool for making injection molds.)
Molded ABS (or other plastic) boxes would eliminate the seams
except around the lid. A molded ABS lid with a lip made to fit over
would solve that. They'd be my ideal for production - sealed or
vented - when the visual inspection aspect loses its meaning.
A possible way to do seamless rectangular boxes without injection
molds would be to make a simple mold from a solid block of
polyethylene, wrap polypropylene fabric ("landscaping fabric")
around it, and epoxy it. When it sets, add more layers if needed to
get to the desired thickness. Spray the mold block with wax to help
release the finished box from around it. I would think making the
block taller than required and putting in a handle hole to pull on
would be the way to go.
Grafpoxy Current Collector Grills and Terminal Leeds
The first thing needed is a compatible metal. Nickel is suitable but
for some reason seems harder to get than gold. Copper seems to
work, but is very hard to tack-weld. Stainless steel mesh doesn't
seem to work.
The grafpoxy is a one to one mixture of epoxy resin and graphite.
It's rather thick with West System epoxy, so I'm going to try
diluting it. Evidently acetone is a common solvent, also MEK,
xylene... Let's see... I have toluene. I guess I'll try that.
Electrode Current Collector Grills & Terminal Leeds
Current collectors first and foremost must not corrode away in the
electrolyte during charging and discharging. Since every common
metal corrodes away in salty electrolyte (very quickly in the
positrode), only conductive carbon substances such as graphite can
be used. This is why the standard dry cell has a conductive carbon
rod for a terminal. But these rods are hard to make and brittle, and
graphite isn't as conductive as one might wish. Graphite sheets or
even flakes tend to degrade in the cell during charging. Fine
graphite powder fares better, also as demonstrated by the standard
dry cell.
In 2011 I invented 'grafpoxy', simply a 50-50 (by weight) mixture
of epoxy resin and graphite powder. The resin makes it impervious
to the electrolyte, and the graphite makes it at least somewhat
conductive. This could possibly be used and molded by itself, but
metal is still a much better conductor. So the grafpoxy is used to
coat a metal current collector and the parts of the terminal inside
the cell.
The best current collectors are those that provide the best
conductance to every bit of the electrode, yet allow electrolyte to
pass though so they can be in the middle of the thickness, and to
which the electrode substance will remain affixed. A fine grill, eg, 20
to 40 wires per inch, is ideal. Compatible metals include (at least)
copper, brass, nickel-brass (AKA "nickel-silver"), monel or other
copper-nickel alloy, and nickel. Pure copper is so conductive it's
hard to tack weld. My ersatz tack welder won't make any sort of join
to copper.
Rivetted copper grills before grafpoxy coating,
and electrode compactor revised to work with book (or hydraulic) press.
Left electrode grill has one installed rivet,
one not yet spread with center punch and hammer,
and one empty 1/8" hole
I
got
so
me
exp
and
ed
cop
per
me
sh
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pro
tot
ype
s at
an art supply store, but it's only about 10 x 15 'wires' per inch,
which is rather coarse, and I'm riveting it to copper foil for the
terminal leed. I'm still looking for something better. Here I
scrunched up the mesh somewhat (and then hammered it flat
again) to get a few more wires per unit area. The small rivets, 'post
and cap' (IIRC) rivets, are available from leather supply stores (i.e.
Tandy Leatherword). I only use the posts, spreading the thin end
with a center punch and then hammering it flat (see foto - the fat
'head' end of all the rivets is underneath).
With this third batch of electrodes, I went back to using a wire for
the terminal instead of the foil, and I made the slot in the
compactor for wires only. The inner end is flattened and runs the
length of the electrode inside the foil.
If the electrolyte gets through the grafpoxy and inside the foil, it'll
spread along the wire and it'll all dissolve from the inside. I did two
coats of grafpoxy, and touched up some spots with a third.
I used some toluene solvent to thin the grafpoxy. It seemed
about right at first, but it gradually became thicker as I worked, as
the solvent evaporated.
I would very much like to automate production of the grills, as
making and coating them is very tedious. With nickel or perhaps
brass alloys, one could at least tack-weld the wire and mesh
together and skip the foil and rivets.
one size smaller than the mortar ("8 oz") was helpful.)
5. Add the liquid ingredients and mix thoroughly. The mix should
seem barely damp. If there is too much liquid, it will simply ooze
out the cracks instead of compacting. You should be able to tamp it
down in the mortar and check electrical conductivity with an ohm
meter. If it's above 100 ohms, you might want to let it dry a bit
until you can tamp it down harder, or if it seems dry enough, add
more graphite. If it's too dry of 'diesel kleen', the graphite won't
process properly in the compactor.
6. Put about 1/2 of the mix into the compactor. Try to get it evenly
spread around in the box. Put in the current collector grill on top of
it, putting the terminal leed through its slot in a corner of the box.
(Instructions for making the grills are .)
7. Put a 1.5" x 3" sheet of polyethylene plastic over top, then put
the die in over that.
8. Put the lid on and do up the bolts (or clamp the box in a heavy
book press or 20+ ton hydraulic press) to compact the electrode
into a "briquette". Leave it in with the top tightened for 1/2 an hour
or more. During this time, the graphite will dissolve in the diesel
kleen (probably the methyl benzene is the active ingredient) and
form lamillae - random linear formations that connect the active
elements randomly across the electrode for the best short circuit
conductivity throughout.
9. Remove the briquette from the compactor.
The next steps show what fun you miss by using perforated plastic
pocket electrodes. Skip to step 13.
10. For positrodes only, paint calcium oxide on the surface. (Making
calcium oxide from calcium carbonate is in the appendix.)
11. Dry it in a toaster oven outdoors (not indoors - the diesel kleen
reeks) for over an hour at about 100C/212F.
12. Play a propane torch over the surface for about 5 seconds to
sinter and hence harden the surface layer. The battery will last
longer. If the electrode isn't wholly dry, it may suddenly pop apart
from steam pressure - hence the oven step above.
13. Drip some toluene onto the briquette. This will absorb in and
dissolve a bit of graphite, which will (theoretically) form into carbon
nano-tubes as the toluene (or turpentine) evaporates, creating the
best connections.
Naturally, you'll save considerable effort by making multiple
identical electrodes at a time. (It wouldn't hurt to have two, or even
three, compactor boxes.) If some of this seems rather intricate and
involved, it's because it is. It's more than has traditionally been
done to create electrodes, but they should (I hope) be the best they
can be and extremely long lasting.
I caution however that some of the steps are just my own ideas
which aren't all verified as to their efficacy or even their actual
effect. It should be realized that I have created these things on my
own on a very low budget with very minimal equipment,
concurrently with other inventive projects. In no case am I certain
all the ingredients are given in optimum proportions - many are just
fair guesses. The amount of compaction is just whatever the box
can do - it's probably below optimum pressure in most cases.
Sintering with a torch to toughen the surface is a theoretical idea.
The diesel kleen and toluene do appear to improve conductivity. But
to verify fine scale graphite lamillae surely needs at least a
microscope, and to verify carbon nanotubes would require an
electron microscope. A calcium layer has also been used by others
to help with toughness and oxygen overvoltage, but whether oxide
(lime) is the best form I can't verify. (It's likely to turn into calcium
carbonate if left exposed to the air too long. This must be what
happens to bags of cement.) Torched barium carbonate (turns to
oxide on heating) might be better. Thiamin to chelate the rare earth
and ions is experimental, as is the specific choice of antimony
sulfide, to raise hydrogen overvoltage.
Nickel Manganate Positrode
I presently think this is the best choice. It has high voltage and I
believe should have very long life, and the high amp hours of
manganese.
I won't try to give a formula this time - instead a principle.
Measure out 'X' amount of NiMnO4(?), then add some graphite
powder. Add 1 or 2% Sunlight dishsoap, a few % rare earth oxide
or hydroxide, and a bit of water.
Mix it well then tamp it down. Measure the resistance. If it's well
tamped down and the resistance is over tens of ohms, add more
graphite and try again. If it doesn't tamp down well, add more
water or let some evaporate to get a better consistency.
Manganese Positrode
The ideal powder mix for Mn positive electrodes is the positive
electrode powder salvaged from throw-away dry cells.
To this, add perhaps about 1% Sunlight dishsoap added to help
permanently glue the powder together, and enough Diesel Kleen to
dampen it to a dry paste. The paste becomes more moist as it is
compacted into the electrode cylinder since liquid doesn't compress.
If it oozes out the cracks, it has too much liquid. Best to wait for
some to evaporate off. Diesel kleen evaporates more slowly than
water (despite the smell). Methylbenzene (in the Diesel Kleen and in
toluene) dissolves graphite. As it evaporates, the graphite forms
into random lamilar nanotube structures that are more conductive,
improving current capacity. Another way of doing this might be to
add toluene after and let it soak in... if that doesn't hurt the plastic
enclosure.
Since the voltage is lower than nickel, there should be no need to
add oxygen or chlorine overvoltage raising ingredients.
Come to think of it, with the graphite forming conductive
nanotubes, it might be worth experimenting with lesser amounts of
graphite in the mix, eg by adding a percentage of pure MnO2 to it to
dilute the graphite.
Since I've already written instructions for making some nickel
electrode types, I'll leave them in here. But I no longer recommend
them.
Nickel Positrode
The main dry ingredients, except for the graphite powder, each
can take more than one form. See the list of supply sources to find
each form of each metallic element.
Nickel can be had as fine nickel powder, nickel oxide (NiO), nickel
hydroxide (Ni(OH)2, nickel sulfate, or nickel carbonate. The
recommended form is NiO, followed by Ni(OH)2. The sulfate or
carbonate have to be converted to Ni(OH)2 in alkali. Unless you
have a pre-existing stash, why bother? Ni(OH)2 can be converted to
the charged form, NiOOH with bleach, and back again with
hydrogen peroxide. (see appendix)
In the salty battery it's not clear (to me) whether the nickel will
take the typical alkaline forms above or: NiO, Ni2O3 and NiO2 for
valence states 2, 3 and 4. I suspect NiO is the discharged form, and
NiO2 is most likely the valence four form. For valence 3, toss a coin.
Remember these various oxide and hydroxide forms only affect
the consumption and release of water during charge and discharge.
It's probably relevant in a 'dry' cell, but not really in a flooded cell.
The manganese is best added as potassium permanganate, which
is likely what it'll become when the cell is charged anyway. That
way, it already has its potassium and there's no chlorine left over
from charging with the potassium form the potassium chloride
electrolyte. But if that's too hard to obtain (owing to bizarre
substance laws or local supply) it can also be added as manganese
dioxide. That will charge to KMnO4, but in the process use up some
of the KCl salt electrolyte, releasing a bit of chlorine gas. (doubtless
undesirable in a sealed cell.)
Many of the rare earth oxides (REO) might work fine. I'd say the
order of preference is: samarium, neodymium or lanthanum.
Cerium is one that should probably be avoided, owing to a possible
charging reaction from valence 3 to 4 (Ce(OH)3 <-> CeO2).
Mischmetal (unseparated blend of rare earth metals) oxides should
be avoided because they'd contain cerium.
Dry ingredients:
30g - NiO (or 37g Ni(OH)2)
20g - KMnO4 (= 9g MnO2)
22g - fine graphite powder
1g - Sm(OH)3 (or other rare earth oxide/hydroxide)
Liquid ingredients:
2.5g - Diesel Kleen
.5g - Lemon Fresh Sunlight dishsoap - no other dishsoap (or PVA or
teflon powder)
Monel Positrode
The monel positrode is still somewhat experimental as to
ingredients and proportions. It is essentially a nickel positrode in
which the nickel and manganese mix is replaced by nickel and
copper oxides in solid solution. In order to attain the solid solution
state, the nickel and copper are purchased as fine monel alloy
powder. A typical monel alloy is about 2/3 nickel. The powder I
obtained contains: Ni 67%, Cu 28%, Fe 3%, Mn 2%.
All of these metals will oxidize/hydroxidize when the battery is
charged. The copper oxide in solid solution improves the
conductivity of the nickel oxide, hence less graphite is added. The
manganese is at worst benign. (Perhaps one should add more.) The
iron is probably benign as well.
The only form to obtain the substance in is as metal alloy powder.
As with the other nickel electrode formulations, a rare earth
oxide/hydroxide is added to increase the oxygen overvoltage, in the
same order of preference as to element. Some thiamin (bean sauce)
is added to chelate the ingredients and make the electrode very
long lasting.
Dry ingredients:
40g - fine monel powder
Liquid ingredients:
1.5g - Diesel Kleen
1g - Lemon Fresh Sunlight dishsoap - no other dishsoap (or PVA or
teflon powder)
Vary the diesel kleen as required to get the best amount of
dampness. Add graphite if required to get lower resistance readings
on tamped-down mix or finished electrodes. Make electrode as per
instructions in chapter 5.
After putting the electrode together, it is wrapped in zircon painted
separator paper (next chapter). Then it's immersed for several
hours in a solution of calcium hydroxide (slaked lime). (Calcium
carbonate can be purchased at a pottery supply. Making lime from
calcium carbonate in a kiln and dissolving it is detailed in an
appendix.) Then the Ca(OH)2 is rinsed or diluted out. The alkali
removes passivating carbonate from the zinc oxide, purifying it.
Some Ca(OH)2 absorbs the carbonate from the zinc and becomes
calcium carbonate, CaCO3 - limestone. If it doesn't rinse out, this
probably will, if anything, contribute a bit of strength to the fragile
electrode.
Manganese Negatrode
This is (if it works) one of my major battery making coups. No
one has been able to make a manganese negatrode before, because
its voltage is just a little over the hydrogen generation voltage.
Thus, hydrogen bubbles up as it charges, and continues to do so
until the electrode has discharged itself to Mn(OH)2 or MnO.
Hydrogen generation voltage varies with electrode ingredients (as
well as pH). Zinc is "improved" by ingredients to raise the hydrogen
generation voltage. Manganese is "enabled" only by ingredients that
sufficiently raise the hydrogen generation voltage to where it will
charge effectively and stay charged without excessive self
discharge.
If it works, manganese makes a better electrode all round: it
doesn't form a soluble ion, it's higher voltage (-1.37 vs -1.05),
7. Electrode Separators
The electrode separator consist of three layers:
separator paper
Paste: zirconium oxide ("zirconia", 8 parts) and ferric oxide ("rust",
1 part) powders,
in "Sunlight".
separator paper
Sheets
Chemicals
Fabrication
dd
9. Working it up
dd
Discharge cycle. Held > 1.5 volts for ___ seconds/minutes, and 1.0
volts for ___ with 25 load, then after discharge continued to .9
volts, recovered to ___ volts.
1. 60 s, ?, 1.4 v
2. 90 s, ?, 1.45 v
3. 2 m, 6m, 1.5 v
4. 5 m, 10 m, 1.6 v
5. 6 m, 12 m, 1.63 v (and only 1-1/2 hours after test 5.)
Electrodes are pretty soft when made, but they harden up with
forming. They might not even need the plastic enclosures, tho I
suspect they'd gradually fall apart without them. Evidently it's
common to replace the electrolyte after the electrodes are formed,
or even to form a bunch of electrodes in a bath before putting them
into a battery cell. This seems like especially good advice for DIY
with chemicals that might not be completely clean by the time
they're in an electrode.
11. Appendices
"Acetal Polyester" Electrode Binder
Once the electrode powders are mixed, they need a binder, "glue"
to help hold them together and also to prevent migration of the
"solid" chemicals during charge and discharge cycles.
Various binders have been used: PTFE (teflon) powder and CMC
(sodium carboxy methyl cellulose gum) among others. PTFE is the
preferred choice.
But these are insulators. A conductive, or perhaps even a
semiconductive, binder would not only help hold things together,
but improve the current handling capacity of the electrode.
A great advantage of the sintered type of electrode was that the
sintered metal conductor ran through the whole electrode. Thus we
would find old Ni-Cd cells for portable power tools, in the "AA" size
range, that would put out 25 amps. A modern high capacity Ni-MH
"AA" cell may hold over twice the energy, but it won't put out 10
amps.
A conductive binder would be a great replacement for the sintered
metal "sponge".
I decided to try polymerizing acetal ester hoping to gain this
effect. This is the real "chemistry lab" part of making the battery.
It's a four step process:
1. Convert potassium dichromate (AKA potassium bichromate) into
potassium chlorochromate (AKA "chromic acid") with hydrochloric
acid (AKA "muriatic acid").
2. Convert alcohol (AKA "ethanol", AKA "triple distilled vodka") into
acetaldehyde (AKA "ethanal") with the potassium chlorochromate.
3. Convert the acetaldehyde into acetal ester (monomer solvent)
with hydrochloric acid.
4. Use the acetal ester as the liquid to mix the electrode powders
together with.
5. Compact the electrode.
6. Cook the electrode at 110c (225f) to polymerize the acetal
ester into acetal polyester. Also freeze it. (One of these must do
it...)
(You were going to mix the electrode powders with some liquid and
compact the electrode anyway, so it's only four additional steps, not
six.)
Making the Potassium Chlorochromate
It's hard to buy "ethanal" because it's evidently an explosion risk
during shipping. To make the unavailable "ethanal" (CH3CHO) from
available though pricey ethanol (CH3CH2OH) without accidentally
reducing it all the way to acetic acid (vinegar, CH3CHOOH) we need
another unavailable chemical: KClCrO3 (AKA KCrO3Cl).
Web info for reducing alcohols to aldehydes invariably says to use
pyridinium chlorochromate, but that's pricey and also considered
Engineers. However, if it's not well mixed with anitmony sulfate, it's
likely to discharge to Mn(OH)2 or MnO anyway when it gets damp.
Not only considering the expense of the metal powder but the
particle size (the oxide is doubtless finer), and the likelihood of it
becoming an oxide anyway, it's probably best just to use the dry
cell or pottery store manganese.
This is not an exhaustive list. It's just where I got my stuff plus a few other sources I know of.
[applicable to Victoria BC]
Ceramics Supply Store [Victoria Clay Arts; gets stuff from Seattle Pottery Supply] - good source
of many powdered chemicals: mostly oxides, carbonates, sulfates.
cobalt tetraoxide (a.k.a. cobalt oxide) - small qty (1/4#, 125 g)
cobalt carbonate - small qty
potassium dichromate (a.k.a. potassium bichromate) - small qty
nickel oxide
Arts Supply Store [Opus Framing]
Arches Watercolour paper 90#, electrode separator paper
expanded copper grill (used for modelling)
Plastics Supply Store [Industrial Plastics & Paints]
ABS plastic sheets, 1/4 inch thickness to make battery case from
(Prefer white for "+" end, black for "-" end. Choice of Bk or Wh for middle parts.)
Methylene Chloride solvent to melt/glue the ABS
Methyl Ethyl Ketone (solvent): a small amount is used in the electrolyte.
(it also seems to glue ABS - I used some by accident,
so maybe you could skip the methylene chloride?)
Syringe
methylene chloride dispenser (has a very fine syringe-like metal tube. Careful not to get any
plastic in it or it'll clog.)
Hardware Store [Baywest Rona, Capital Iron, Canadian Tire...]
Brass bolts, 5/16" x 1.5" hex or flat head for battery terminal posts.
Brass or stainless steel nuts and washers.
Hydrochloric Acid (a.k.a. "Muriatic" acid)
Hygrometer
HEFA Rare Earths (Richmond BC Canada)
Lanthanum (2 Kg Ingots)
Zirconium Oxide (a.k.a. zirconia. powder, small qty or 1 Kg.)
(Or try "yttria stabilized zirconia" - might give better high temperature performance.)
B. Equipment & Supplies
(This equipment is all supplied for the workshops)
Chemical
Voltage AH/Kg WH/Kg Density*
NiOOH <-> Ni(OH)2 +0.52
289
150
1.3 - 2.2
Ni(OH)2 <-> Ni
-0.72
578
Fe(OH)3 <-> Fe
-0.9
Cd(OH)2 <-> Cd
Metal <-> Metal-Hydride -0.83
Zn(OH)2 <-> Zn
-1.24
Ca(OH)2.Zn(OH)2 <-> ? -1.69
416
1.3 - 2.2
* The density of powders in pastes depends on several things, especially how hard the particles
are crammed together. The higher the density, the better they conduct electrons, so higher
density is best unless it doesn't provide room for any expansion that may be necessary. The most
densely packed beta nickel hydroxide can cause trouble as some changes into alpha nickel
hydroxide. This crystalline form is said to occupy 44% more space than the beta form. Big
Edison cells have no problem with it, but a tightly packed dry cell can burst and leak.
Any metal hydroxide that conducts electrons, can be reduced to the metal in an alkaline e
Incidental Chemical Processes
Tables
Energies of Common Negatrode Materials ( /Kg of metal
element only)
Element
Voltage (in
alkali)
Amp-Hours /
Kg
Watt-Hours /
Kg
Cd
0.82
477
391
H (as in
MH)
0.83
500-1000
830 (max)
Fe
0.93
961
894
Zn
1.24
820
1017
Mn
1.56
976
1523
Notes:
Cd - toxic, grows crystals that short out the cells giving poor cycle
life.
MH - metal hydrides store a lot of hydrogen at low pressure - the
voltage is the same as for 'H' alone. The batteries work very well
with long to exceptional life.
Fe - grows into larger clumps, reducing surface area, hence it has
less available energy density than the figure indicates. Otherwise,
the chemistry works very well with exceptional cycle life. Mixing
with cadmium reduces clumping.
Zn - grows crystal "tentacles" (dendrites) that short out the cells
giving poor cycle life.
Mn - any long-term issues with manganese are undetermined so
far, but it looks like it might well be as close to "perfect" as it gets.
Some Overvoltage Potentials
The table below, while describing acid solution and a limited
selection of materials, illustrates the differing overvoltage
("overpotential") of different substances. So while the theoretical
voltage of hydrogen (the reference for all other electrochemical
voltages) is 0.00 volts, it takes different voltages to actually
generate it depending on the material of the electrode. Although the
alkaline voltages in which zinc with mercury have been used aren't
shown, one can see why mercury would be an additive to a zinc
electrode, which charges to -.79 volts (in acid), to raise the
hydrogen overvoltage from -.77 volts to -.85 volts. The zinc would
discharge itself without such an additive.
Activation overpotential for the evolution of selected gases
on various electrode materials at 25 C in acid solution. (from wikipedia)
Material of the electrode
Platinum (platinized)
Palladium
Gold
Iron
Platinum (shiny)
Hydrogen
0.07 V
0.07 V
0.09 V
0.15 V
0.16 V
Oxygen Chlorine
+0.77 V +0.08 V
+0.93 V
+1.02 V
+0.75 V
+0.95 V +0.10 V
Silver
Nickel
Graphite
Lead
Zinc
Mercury
0.22 V
0.28 V
0.62 V
0.71 V
0.77 V
0.85 V
+0.91 V
+0.56 V
+0.95 V +0.12 V
+0.81 V
MISC NOTES
Mn Negatrodes
I looked at and became very excited by manganese as a highest
energy potential negatrode, and it appeared that sealed Ni-Mn, like
sealed Ni-Fe cells (first made experimentally in 2003/2004), could
be maintenance free and last virtually indefinitely. Wow! The chief
difference between -Fe and -Mn seems to be the metal to metalhydroxide reaction energy, manganese being an extra 2/3 of a volt.
This would make for cells of over two volts instead of 1.2.
But no one had previously been able to use manganese in this
capacity. To enable the higher voltage manganese reactions to
work, I employed a previously unused 1964 discovery that organic
amines and especially egg albumin, even in minute concentrations,
significantly raises hydrogen overvoltage, allowing the higher
(if anywhere) with the negative voltage rather than the positive.
Lanthanum is what gives flint its spark, and its fiery oxidation gives
a demonstration of the energy potential hidden within!
I prefer to buy some chemicals from ceramics supply stores than
from chemical companies as it's local and the cost is much less.
Cobalt carbonate ("cobalt blue" pottery glaze, powder) is available
at ceramics supply stores but not cobalt chloride. The carbonate
may be converted to chloride simply by placing it in hydrochloric
acid. (Cobalt is poisonous, acid is acid: rubber gloves, goggles, at a
sink!) Hydrochloric acid is available at hardware or building supply
stores under the confusing code name "muriatic acid". It fizzes until
the carbonate (or the acid) is used up. Refrigerate and pour the acid
off the from the precipitated cobalt chloride. Rinse the sink - acid is
hard on stainless steel. Use jars with plastic lids. LABEL
EVERYTHING. If you don't you will soon start running across things
that you can't remember what they are, or which jar is which.
After it's "dry", it's a hydrated crimson powder, CoCl2:6H2O. Get
rid of the latter (or at least four of them) by heating the powder in
an oven above about 70C for an hour or two. It will then be a blue
powder. Put a lid on it or it will soon reabsorb 4 H2O's back out of
the air.
Sintering Procedure
The monel and lanthanum hydroxide are mixed in a ratio of about 3
to 1 by volume. About 1% cobalt chloride is added. To the powder is
added enough "glue", tinned beans in their sauce, to make it all into
a paste. This is rolled (rolling pin - grocery store etc.) into thin (12mm) sheets on thin pieces of aluminum sheet (eg, pieces of
roofing flashing - building supplies store) and dried.
The sheets are then placed in an oven and heated until the bean
sauce catches fire and burns off. Do it outside - the smoke is thick
and unpleasant. The whole procedure should take less than about
90 seconds. Sometimes you don't see the blue flame, more often
you do. Longer than a couple of minutes will oxidize the chemicals
too much. When it cools, the crusty powder is scraped into a
container. Dumping in powders with an 80cc scoop, I find I usually
have around 8 sheets to burn in a "session".
The "oven" I use uses a 1500 watt electric barbecue (Value Village doubtless available new somewhere, though I confess I've never
seen another one) built up with pottery kiln bricks (Victoria Clay
Arts) sliced into shapes with an abrasive cutting wheel on the radial
arm saw (hardware store - kiln bricks cut like butter) to form a floor
under the burner, walls, and removable roof pieces. Leave some air
gaps for ventilation.
Fabrication
The powder is mixed with just enough "Lemon Fresh Sunlight"
dishsoap (grocery) to make a paste. Acetaldehyde (a.k.a. ethanal,
ethyl aldehyde, aldehyde, "the hangover chemical", ALcohol
DEHYDrogenated) is poured in. Add a little HCl (Eye Protection,
Rubber Gloves) and churn vigorously to turn the aldehyde into
acetal ester. This is then dished into the battery.
Making the Acetaldehyde
Putting the electrode together is easy enough, but where do you get
this "aldehyde" stuff? Turns out it's not very stable, so it doesn't
keep very well and it's considered a hazardous substance to ship.
(What, just because it can explode?!?) It's better to make your own.
That doesn't mean it's especially easy or cheap to do so. This is the
real "chemistry lab" part of making the battery.
Put 20 parts (by volume) of Alberta "triple distilled" Vodka (40%
told that the last person to buy some was a high school student
making rocket fuel a few years previously, proving that ceramics
supplies are the right place to get the cool chemicals. He was
planning to hit the stratosphere with his next rocket.) Now, where
do we get the chlorine, and how do we put it in? Turns out
hydrochloric acid, HCl, has chlorine and works well. Since the
dichromate is losing some oxygen and stealing the chlorine from the
acid, the obvious byproduct with the hydrogen from the acid is H2O,
so according to my reckoning we're left with the desired product
and water. Of course, some acid will be left over... or potassium
dichromate if there wasn't enough HCl. (Actually, one could
probably calculate the correct proportions. According to the
hygrometer, the HCl from Rona is about 33% strength, and the
K2Cr2O7 is 100%. Figure out what atomic weights of the active
ingredients per gram that gives.)
It's made just about the same way as the aldehyde: Pour a little HCl
(RUBBER GLOVES, GOGGLES, do it in the sink; avert your nose!)
into a jar and add K2Cr2O7 crystals. Heat it, stirring gently, in a
shallow pot of water on the stove until the solids dissolve. This
takes quite hot water. If the crystals don't completely dissolve, that
probably means the acid is used up and there'll be some dichromate
left over. Add more acid. At some point in the process, put the lid
on. Then label it and put it in a safe fridge. The KClCrO3 will
precipitate out and the acidy water can be gently drained off and
flushed down the sink. Label it, let it dry out, and put it in your
secure chemical cupboard.
Making the Acetal Ester
This is made from the acetaldehyde in the presence of the negative
electrode mix, which include lanthanum hydroxide. Pour some
acetaldehyde into the mix. Then pour in a little HCl (RUBBER
GLOVES, EYE PROTECTION). Some lanthanum chloride is formed,
and this substance is called "a mild lewis acid, able to convert
aldehydes to acetals in a neutral [non acidic] environment". Herein
lies the unique advantage of using lanthanum over other possible
metals with similar valences.
Making Monel-Lanthanum Aspic
Okay, having thrown all these ingredients into the negative
electrode, there's one more thing to do: gel it. The positive
electrode became a paste with the addition of the Sunlight, but that
doesn't work for the negative mixture. Agar agar [a.k.a. "agar";
natural foods stores] is a white powder or flakes made from some
kinds of red seaweed. It's used for a neutral microscope slide
culture gel base... and for aspics and jellies that are stable at and
above room temperature. This second use is of interest. The battery
won't charge if the lanthanum hydroxide molecules are free to
migrate. A cheesy gel holds them in place.
Take a dish. Put in ____ cc of the negative electrode mix with the
acetal ester solvent in it, and add ____ grams of agar. Stir in ____
cc of water. (A lot of experimentation is due here to determine
optimum proportions.) Stir or whip vigorously for a few minutes to
dissolve the agar. Heat a shallow pot of water to about boiling on
the stove in put the dish in it. Stir. Once it's hot, pour it into a flat
tray about 6mm (1/4") deep and put it in the chemical fridge. Let it
cool and gel.
Cut it into squares that fit in the battery and use a spatula to put
them in. One possibility, especially for larger cell sizes, is to use
trays the size of the electrodes, eg, 6" x 12", and put a cell wall
sheet in the bottom. Then the gel is already on the cell wall plate,
which will be easy to remove intact from the tray. Or, make the
trays from the wall plates with ABS or other insulating edges, ready
to pull out and stick into the battery without removing the gel at all.