Electroanalytical Chemistry and Interracial Electrochemistry, 53 (1974) 329-333 329

© Elsevier Seouoia S.A., Lausanne - Printed in The Netherlands

PRELIMINARY NOTE

C a t h o d i c r e d u c t i o n o f g r a p h i t e in organic s o l u t i o n s o f alkali a n d NR4 + salts

J.O. BESENHARD and H.P. FRITZ

Inorganic Chemistry Laboratory o f the Technical University o f Munich, Arcisstrasse 21, D-8000 Munich 2
(G.F.R.)
(Received 25th April 1974)

Introduction
Graphite cathodes are chemically rather inert in aqueous electrolytes but may be
attacked in aprotic solutions which are cathodically sufficiently stable to allow the electro-
chemical reduction of graphite itself.
The reason for this corrosion is the formation of lamellar intercalation com-
pounds, e.g. ammonium-graphites, which have already been prepared electrochemically in
liquid NH3 and amines 1'2.
Our investigations on graphite foil electrodes in different organic solutions of NR4 ÷
and alkali salts show up to date that in every case alkylammonium- or alkali metal-
graphites, respectively, are formed as primary reduction product of graphite. This type of
reaction is a very general one and to a first approximation independent of the solvent, the
cation as well as of the anion. It is characterized by a nearly ideal electrochemical revers-
ibility and by the swelling of graphite in the direction of the c-axis on cathodic load.
The reduction of graphite in organic solutions of alkali salts is a process closely
related to the electrochemical alloying of solid metal cathodes which is well known z'4 in
electrolytes containing Li+. The potentials of alkali metal-graphites as well as those of
alkali metal alloys are significantly positive versus the standard potentials of the free alkali
metals.
The knowledge of the reactivity of graphite is important for the interpretation of
the electrochemical domain of organic electrolytes which i_sfrequently limited by reactions
of graphite not only in the anodic s, but also in the cathodic region.
Furthermore there is every indication to believe that alkali metal-graphites act as
highly reactive intermediates in the reduction of organic products at graphite cathodes: an
example for this is the reduction of propylene carbonate (PC) in the presence of Li+.

Experimental
The investigations were made by means of cyclic voltammetry and by recording
the potential of the graphite electrode in the course of quantitative galvanostatic reductions.
330 PRELIMINARY NOTE

The electrodes consisted of graphite foil ("Sigraflex", SIGRI Elektrographit, Meitingen,

G.F.R., thickness 0.2 mm) which was sandwiched between porous glass for the long-time
galvanostatic measurements to avoid losses of material on account of scaling of the
expanding graphite. The working electrode was faced by two counter electrodes in a
diaphragm cell of the double H-type; the potential was taken near the surface by a Luggin
capillary. An aqueous SCE, separated from the compartment of the working electrode by
two-diaphragm vessels filled with working electrolyte, was used as reference electrode.
Solvents and supporting electrolytes were dried carefully and handled continuously under
protective atmosphere (N2, or if remarked specially Ar).

Results
Cyclic voltarnrnetry. The stability range of graphite cathodes in comparison with
that of inert metals as well as the reversibility of the reduction was verified in different
aprotic organic solutions of alkali and NR4 ÷ salts.
In solvents stable to reduction, such as dimethyl sulphoxide (DMSO), 1,2-di-
methoxyethane (DME) or PC, a reversible reduction of graphite was observed without
exception at potentials considerably more positive than those necessary for the deposition
of alkali metals or for the discharge of NR4 + at inert electrodes.

30
f~
E

15
8 5
,i
E
15
6 i
4

-15
'-' 5 U

0
-30
-2

-4 -45

-6

-8
F't]

-3 -2 -1 -3 -2 -I 0

E l V vs. SCE E l V vs. SCE

Fig. 1. Cyclic vol~ammograms at graphite foil and Pt in satd. LiCIOJDME (Ar atmosphere); scan rate
50 mV s -~ .
Fig. 2. Cyclic voltammograms at graphite foil and Pt in satd. NMe4CI/DMSO; scan rate 50 mV s -~
PRELIMINARY NOTE 331

Fig. 1 and Fig. 2 show this for the typical examples of a solution of Li ÷ (reversible
reaction at graphite and Pt) and a solution of NMe4 ÷ (reversible reaction at graphite, nearly
irreversible reaction at Pt). An interpretation of the currents as caused by adsorption
phenomena can be eliminated by reason of the large current-time products, which are
explicable only by a faradaic process. The formation of real compounds of graphite is also
demonstrable by quantitative reactions (see below).
The reduction of graphite is always associated with its swelling up, this beginning
fan-like from the edges. The swelling is to some extent macroscopic disintegration, as the
increase in volume in general exceeds an increase which might be referred only to growing
distances between the carbon layers in consequence of intercalations. It must be noticed,
that current densities may be fixed only approximately under these conditions.
Compared to the voltammograms of the Li-deposition on Pt, less steep slopes of
the corresponding curves at graphite are observed. This may be attributed to a favoured
beginning of the intercalation at the edges of carbon layers or at lattice disorders - in this
case only parts of the graphite surface would be effective.
The electrochemical reactivity of graphite is extremely dependent - as expected -
on the state of its surface; if it is smooth the deposition of free alkali metals is possible even
at low current densities. Vitreous material is completely inert, at least on short-time
cathodic load in solutions of Li÷, Na +, K ÷, NEt4 ÷ and NBu4 + in PC 6
Quantitative galvanostatic reductions. The evidence for the total reduction of pure
graphite to defined, stoichiometric graphite compounds was furnished by quantitative
cathodic reductions at very low current densities; under these conditions the potential/time
curves of graphite electrodes show characteristic, reproducible stages.
Weighed graphite foil, pressed between two disks of porous sintered glass and
contacted with a Pt wire was used as electrode. Fig. 3 shows as a typical example the reduc-
tion in NMe4CI/DMSO; a nearly identical curve is to be obtained in KPFJDMSO.

-3

UJ
f
~-2 J
f
24
W -1

0 I I I
5O0 100 50 30 20 (n)

I I I I I , I
o I00 20() 3oo 400 500

C h a r ~ tr~ansterred l mAs. rr~ -1

Fig. 3. Galvanostatic reduction o f graphite foil in satd. NMe,;CI/DMSO; current density 250 ,uA c m - 2 ;
n = n u m b e r o f carbon a t o m s per electron transferred.
 332 PRELIMINARY NOTE

From the step-wise course of the curve it can be concluded that the quantity of
one reduced speciesdoesnotincrease continually. Rather, and this is evidence for defined,
stoichiometric structures being formed one after another, only after the termination of a
preceding stage the succeeding, thermodynamically less stable one is formed.
The reactions of vapours of alkah metals (M) with graphite, in general lead to CaM
as a final product; C24M and C4aM are assumed to be "ideal" intermediate stages 7. In
analogy to the intercalation compounds formed by the elements, the compounds C4a M and
C24M (M = NMe4, K) are suggested by the steps in potential in NMe4CI/DMSO and
KPF6/DMSO. Nevertheless, it must be concluded from these similarities, that the
electrochemically formed products are identical with those formed by reacting the elements.
Firstly, it is to be considered, that supporting electrolyte or solvent may be incorporated in
the graphite lattice; alkali metal-graphites formed by the reaction of naphthalene-alkali
metal in DME or tetrahydrofuran are known to be solvent-containing ternary phases 8.
Secondly, it is to be supposed - mainly from the graphite reduction in NMe4CI/DMSO at
room temperature that uecomposition possibly does not necessitate an influence on the
progress of the reduction, since decomposition products may still block up their place in
the graphite lattice and guard it against further reaction.
Chemical reactions of electrochemically generated graphite compounds. The
chemical properties of alkali metal-graphites are rather similar to those of free alkali metals,
e.g. the reaction with water leads to strongly basic solutions under evolution of hydrogen.
Electrochemically formed alkali metal-graphite intermediates undergoing a
secondary chemical reaction may simulate a direct electroreduction at unusual potentials;

I/L
30 12
o

20
v

q~
5

/-
E E
0

-10

-20 -8

-30

I
-3
Graphite)

-2

El V vs. SCE
I
-1
t
o
-12

-16

Fig. 4. Cyclic voltammograms at graphite foil and Pt in 1 M LiCI04/PC; scan rate 50 mV s -~ .

PRELIMINARY NOTE 333

an example for this is the reduction of PC at graphite cathodes in LiCIO4/PC.

The reduction o f PC by free Li is to be expected on account o f thermodynamic
data 9 , but occurs very slowly because of passivating films I°'1' . However, the reaction is
fast with Li activated by amalgamation'2 and yields Li2 CO3 and propene as main products.
These products are formed also at graphite cathodes in LiC104/PC at potentials from +0.6
to +1 V vs. Li; the coulombic efficiency is about 100% and the cathodes disintegrate slowly ~3
Cyclic voltammograms in LiCIO4/PC clearly show the usual reversible reaction o f graphite
known from other solutions containing Li ÷.
An interpretation of the anodic current as oxidation of cathodically formed
propene can be eliminated; in agreement with results o f the alkene oxidation in aceto-
nitrile 14 this reaction was found to occur in LiC104/PC at Pt only at a potential very close
to that of the oxidation of PC.
Cyclic voltammograms show a considerable decrease in the ratio of anodic to
cathodic c u r r e n t - t i m e product with a decrease in scan rate. This proves that a fast reaction
of L i - g r a p h i t e with PC compared to the reaction o f pure Li with PC, is taking place.
As was to be expected, no steps in the p o t e n t i a l - t i m e curves were to be obtained
during galvanostatic reaction at graphite cathodes in LiCIO4/PC; this stands in contrast to
the results in LiCIO4/DME and LiCIO4/DMSO.

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