Page 12 - PERIODIC Magazine Issue 5

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refused to gain any financial reward from his burner and – few cared then about the environment but they did care
there was even a Bunsen battery that belched out NO . The about finding alternatives for oil. Stan cleverly combined this
X
Bunsen philosophy still pervaded most of the department. with his earlier work and in summer 1976 announced a room
Whenever Peter was asked about his interests he would temperature, rechargeable lithium titanium disulfide battery.
always reply, “Oh, they’re as pure as the driven snow.’’ This battery had a respectable 2 volts plus and with lithium
being light, small and electropositive had a good energy and
I was very briefly under the wing of Rod Hurditch who,
on paper, was doing a Post Doc with JS. I was told that if Rod current density. Room temperature allowed a liquid, non-
had been active at the weekend, you could come in on a aqueous electrolyte to be used; discharge and recharge
Monday morning and not recognise the place. These were involved a fast, non-disruptive intercalation/de-intercalation
pioneering days in the lab both for solid state chemistry and of the cathode (0 ≤ x ≤1):
powder diffraction. JS had brought in Brian Fender with his discharge g xLi+TiS = Li TiS charge
2 f
x
2

stable of St Catz thoroughbreds, most notably Allan Jacobson
and Bruce Tofield. Years later, I overheard Prof Malcolm Despite it providing the foundation for later developments,
Green correctly inform a visitor that, “This department has the battery would be abandoned before the end of the
filled the world with solid state chemists.” decade. Later, when Allan Jacobson, now at Exxon, visited
the lab, he said to me, “You won’t do it with lithium.” On
Our main competitor in the bronze field was Hagenmuller’s recycling, dendrites grew on the lithium anode and internally
Bordeaux group who were exhaustively exploring high short-circuited the cell.
temperature syntheses in sealed gold tubes. Peter Larkham
was dispatched there for training. Apparently, tea came
round on spotless trolleys; using a glove box while stood on a Fugue
pile of Dexion wasn’t a common sight either.
So this was the situation when John Goodenough arrived
A hidden facet of solid state chemistry was gradually being in September 1976. The first thing he ever said to me was
exposed – new, often metastable, solids could be made at that he was ‘riding loose’, a phrase I’ve never heard here
low temperature by kinetic control, partial ionic mobility before or since. I was also exposed to the Goodenough
permitting. That significant electron and proton mobility in laugh, the decibels of which were out of all proportion to
H WO , coupled to its colour changes, found application in the quality of joke that induced it. With no qualifications
X 3
electrochromic display devices we noted only in passing; in chemistry, perhaps an unusual choice for Professor, but
possibly, the MnO ‘depolariser’ in the Leclanché cell might his recent work at MIT designing new solid electrolytes
2
+
be H MnO . While the Na ions in cubic Na WO were was sure to get funding. When Peter learnt of John’s grant
X 2 X 3
imprisoned in their perovskite cells, an oddball electrical success, he quipped, “I’ll give you four years before you’re
insulator called sodium beta-alumina was found in 1967 to rumbled.” The ‘JBG group’ occupied a room adjoining the
have a Na ion mobility similar to that of a liquid, the first of Abbots Kitchen which John called ‘the rats nest’ and avoided
+
the ‘superionic conductors’. This found use as the electrolyte at all costs. Instead, ‘strategy sessions’ took place at his
in the rechargeable sodium sulfur battery operating around blackboard where you took great care not to tread chalk into
350C and also hampered by aggressive electrodes and slow the Professorial carpet. During one of these, I queried what
secondary phase formation: would happen if you took a known lithiated oxide, LiMO ,
n
and then tried to extract lithium electrochemically. How
2Na + xS = Na S
2 x many lithium props could you remove before the oxide roof
Stan wanted to make Na ionic caved in? This was an inversion of the Whittingham theme –
+
conductivity measurements a new metastable phase would
on beta-alumina and, with now be produced in the charge
his Oxford training, tried rather than the discharge cycle.
Na WO electrodes choosing
X
3
the structure opposite with Bill England, a former Part II of
larger channels. He found the Allan’s, was investigating low
electrodes reversible to Na . temperature ion-exchange, a
+
Despite the tiny current, it footprint of potential fast-ion
was another indication that bronzes might play a role in the conductors. Surprisingly, even
battery scene. spinel phases exchanged and
later they’d be used as cathode
Stan moved to the mighty Exxon Corporation in New Jersey materials. Crucially, so did
where researchers were working on the superconducting LiCrO , an ordered rock salt
2
properties of lithiated layered transition metal sulfides structure whose layers emerge -
synthesised at room temperature using nBuLi. We’re now when you looked down the body
in the energy crisis of the early 70s with rocketing oil prices diagonal of the cube.

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Periodic The Magazine of the Department of Chemistry