Page 13 - PERIODIC Magazine Issue 5

qweqwertyuiop[asdfghjkl;zxcvbnm,.QWERTYUI
12345678901234567QWERTYUIOP
OP[ASDFGHJKL;ZXCVB123ŒŒŒÂ
P[ASDFGHJKL;;;''\ASDF`ZXCVBNM,.,MNBVCXZNM,

Koichi Mizushima, a physicist, was to try cathodic extraction Allegro
of lithium from isostructural LiNiO and LiCoO where
2
2
sufficient electronic conductivity was anticipated: 1989, the phone rings - Keith Mansell on the other end
who had written the original Patents. A Japanese major
LiCoO - xLi - xe = Li CoO was trying to break the Patent but I was able to refute the
+
2 1-x 2
We knew that isostructural Na CoO had been synthesised allegations. I still didn’t think much about it – just wait till
0.9 2
conventionally at Bordeaux. By not attempting low it all catches fire on them! Then, a few years later, it’s Bill
temperature methods, later termed ‘chimie douce’, they Macklin, another solid state chemist from the department.
were one step from a breakthrough. I learn that Sony were manufacturing batteries; also,
they were claiming to have found a disclosure which, if
The figure below shows the cell Koichi used. The liquid true, would render the Harwell patents worthless. Out of
electrolyte was LiBF in propylene carbonate and the anode curiosity, I went out and bought a lithium-ion battery setting
4
initially lithium metal so all the work had to be done in a me back £50. I asked Bill how Sony had tackled the anode
glove box; an oil slick from the pump still stains the archway. problem and this confirmed an industrial stereotype. They
This was no overnight experiment. Koichi spent a wanted something solid and light which lithium would insert
painstaking year before being happy with his numbers. To into – coke! – which has graphitic elements:
get reproducible voltages, he used Li V O anodes. Lithium charge g LiCoO + C = Li CoO + Li C discharge
x
5
2
could be removed almost completely to CoO , a new oxide 2 1-x 2 x f
2
of cobalt, though above x=0.5 some degradation of the So sometimes in science simple is best. We basically
cathode occurred on repeated cycling. Unsurprisingly, adapted rock salt for the cathode while Sony adapted coke
with cobalt +4 in the mix, the voltage was huge, almost for the anode – and it worked.
twice that of the Whittingham cell with high energy and Sony’s second
current density; the absence of plateaus implied a topotactic attempt to break
the Patent centred
on a January 1979
conference in
Brussels where
I’d presented
our preliminary
battery work
for the first time
at a private meeting. Fortunately, after 15 years, I still had
video recall and was able to help Marcus Lofting, Head of
process. Phil Jones comes into the story as regards Patents. What transpired was that the talk I gave was used
analytical and X-ray proof of structure retention. Phil was by someone but only to pad out a later write-up of their
a Part II - or should I say ‘an established collaborator’. public talk. So Harwell’s royalties started to roll in. I’m not
By 1980, Koichi had returned to Tokyo, so I drafted the sure how many tens of millions they made but I did notice
paper which John submitted – just seven pages and never one year, the headline in the Business section of the Daily
refereed. There was voltage to burn. On page 6 we state, Telegraph was ‘Battery Powered’. Admittedly, when I did
‘the high voltages permit consideration of . . . an insertion eventually receive a consultancy fee, my balance sheet was
compound of low work function for the negative electrode’ transformed. I went from a Year 1 loss of £50 to a Year 1 plus
– a lithium-ion battery, Li rocking to and fro. Year 2 profit of £450. Welcome to the land of irony!
+
With ISIS Innovation in absentia, the intertwined grants But at least there was the Landmark Plaque. I had a
needed knot theory to disentangle them. There was EEC Physics master at school called Wally Evans who once,
sponsorship arranged by Bruce Tofield at Harwell despite Bunsenesquely, said, “You either go for the money or you
Koichi being supported by the US Air Force. In the ensuing go for the glory.” While Koichi was relatively easy to locate
kerfuffle, I walked with John to sign patent documents at for the presentation, Phil Jones had left chemistry for the
Wellington Square where he strode in and prophetically RAF after Part II. I tracked him down in France ten days
announced that, “Noone’s going to get rich out of this”! before the event. He wasn’t even aware his work had been
John’s main concern was the cost of cobalt, mine was the published, let alone its ramifications; unlike me, he did at
material’s tenuous ringfencing in phase space. A paling split least own a mobile phone.
one evening on scale-up and the fire brigade was called -
nowadays it’s politely called thermal runaway. And as for lithium-ion batteries - we’re now surrounded
by ’em. If in time superseded, their elegance will remain.
While further work was done in the lab, interest waned as In 1996 Peter Dickens retired. He never said anything, but
oil prices receded. John left for Texas in 1986, the year many one day I came in, and the cigar box of samples was in the
solid state chemists hitched a ride on the high temperature middle of my desk.
superconductivity bandwagon that rolled into town. All
quiet on the battery front.
13
Periodic
The Magazine of the Department of Chemistry