U.S. patent number 3,615,829 [Application Number 04/471,097] was granted by the patent office on 1971-10-26 for novel carbon compositions, methods of production, and use.
This patent grant is currently assigned to The Standard Oil Company. Invention is credited to James W. Sprague.
United States Patent |
3,615,829 |
Sprague |
October 26, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
NOVEL CARBON COMPOSITIONS, METHODS OF PRODUCTION, AND USE
Abstract
An improved electrode material for electrical energy storage
devices is provided by heating a carbonaceous material to provide a
charred residue, then treating this charred residue in a fused salt
bath under reducing and oxidizing (in the absence of oxygen)
conditions. The resulting material contains occluded salts and
these may, in a preferred embodiment, be removed.
Inventors: |
Sprague; James W. (Streetsboro,
OH) |
Assignee: |
The Standard Oil Company
(Cleveland, OH)
|
Family
ID: |
23870239 |
Appl.
No.: |
04/471,097 |
Filed: |
July 12, 1965 |
Current U.S.
Class: |
429/103; 429/199;
252/509; 429/209; 205/768; 423/445R |
Current CPC
Class: |
H01M
4/96 (20130101); H01M 4/00 (20130101); H01G
9/155 (20130101); Y02E 60/50 (20130101); Y02E
60/13 (20130101) |
Current International
Class: |
H01G
9/00 (20060101); H01M 4/00 (20060101); H01M
4/96 (20060101); C14c 003/34 (); H01m 013/02 ();
H01m 035/00 () |
Field of
Search: |
;136/86,6,120,121,122,34,22,155 ;204/130,294,39,131
;252/425,445,502,503,506,509 ;23/209.1,209.2,209.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Dellmarskii et al. - Electrochemistry of Fused Salts Translated
from Russian by Peiperl Sigma Press, Washington D.C., 1961, pp.
123, 251, 275, and 284 relied upon QD553 Dy - copy in Scientific
Library.
|
Primary Examiner: Douglas; Winston A.
Assistant Examiner: Andrews; M. J.
Claims
What is claimed is:
1. A porous, electrically conductive, carbon polymer char body
having a zero point of charge at about -0.7 volt, a maximum cation
storage capacity in the range of about -1.8 to about -2 volts, a
strong adsorption for both alkali metal ions and electron storage
at about -2.7 volts, said char containing electrochemically
associated therewith at least one cationic component selected from
the group consisting of alkali metals, alkaline earth metals, rare
earth metals and mixtures of at least two thereof and at least one
anionic halogen selected from the group consisting of chlorine,
bromine and fluorine, said electrochemically associated char being
characterized by its ability to reversibly collect high-capacity
charges over a broad electrical potential.
2. An electrical energy storage cell comprising a container for a
fused metal salt electrolyte, a fused metal halide salt electrolyte
maintained at a temperature ranging from about 350.degree. C. to
about 1,000.degree. C. said halide selected from the group
consisting of chlorine, bromine and fluorine, means for maintaining
said temperature, and a plurality of electrodes immersed in said
electrolyte at least one of said electrodes comprising a porous,
electrically conductive polymer char body according to claim 1.
3. A char body as in claim 1 wherein said cationic component
includes alkali metal.
4. A char body as in claim 3 wherein said halogen is chlorine.
5. A char body as in claim 3 wherein said cationic component is
alkali metal.
6. A char body as in claim 5 wherein a plurality of alkali metal
cationic components are associated with said char.
7. A char body as in claim 6 wherein said alkali metal cationic
components are sodium and potassium.
8. A char body as in claim 7 having the following approximate
concentration of components:
9. A char body as in claim 6 wherein said alkali metal components
are lithium and potassium.
10. A char body as in claim 9 wherein said halogen is chlorine.
11. A char body as in claim 10 having the following approximate
concentration of components.
12. A method of making a porous, electrically conductive, carbon
polymer char body comprising heating a substantially carbonaceous
material at temperatures ranging between about 500.degree. C. and
about 1,250.degree. C. to convert said material to a porous
polymeric carbon char body having diffuse x-ray diffraction bands
and low-crystallite concentration and then in any order
electrochemically reducing and electrochemically oxidizing said
char body, said oxidation being conducted in a nonoxygen-containing
medium, by immersing said body in molten salt of halogen anion
selected from the group consisting of chlorine, bromine and
fluorine and at least one cation selected from the group consisting
of alkali metals, alkaline earth metals, rare earth metals and
mixtures thereof, said salt being maintained at temperatures of
about 350.degree. C. to about 850.degree. C. and electrically
charging said immersed body to at least -2 volts in the negative
direction relative to chlorine evolution to effect said reduction
and charging said immersed body to at least -0.3 volt in the
positive direction relative to chlorine evolution to effect said
oxidation.
13. A method as in claim 12 wherein said salt is comprised of the
chloride of a plurality of alkali metals including potassium.
14. A method as in claim 12 wherein said charging in the negative
direction is to from -2 to -3 volts relative to chlorine
evolution.
15. A method as in claim 12 including removing a substantial
proportion of said cations by desalting the resulting char body.
Description
This invention relates to novel carbon compositions; and to methods
of production. Also, this invention relates to an energy storage
device utilizing one of the novel carbon compositions of the
present invention as an important component thereof.
CARBON COMPOSITIONS DEFINED
Carbonaceous or carbonizable materials are plentiful in natural
form. When these materials are heated in the absence of air,
several products can be formed depending upon the conditions such
as temperature, pressure and the like that are used. The products
that can be produced include diamond, graphite, cokes and
chars.
The carbon compositions of this invention are prepared from those
of the above several products which have had a thermal history
within the range of about 500.degree. C. to about 1,250.degree. C.
Particularly useful precursors are chars prepared by heating
carbonaceous or carbonizable materials to a temperature in the
range from about 500.degree. C. to about 1,250.degree. C.
Carbonaceous or carbonizable materials occur in many forms
including wood, coal, petroleum, pitch, and the like. However,
low-temperature-produced chars prepared from these plentiful
substances contain many undesirable impurities, introduced either
by absorption, absorption, chemical occlusion or other, which
render them relatively useless for many applications including
those hereinafter described.
Therefore, these low-temperature carbon chars must be refined and
treated to remove the impurities, and/or have materials added to
them either after on concomitantly with purification, to thereby
convert them to a more highly useful form. The resulting, unique
carbon compositions and a method for their formation constitute an
important part of the present invention and provide a substantial
advance to the art.
APPLICATIONS - ENERGY STORAGE DEVICES
The novel carbon compositions contemplated by the present invention
contain many potential applications including chemical reaction
catalysts, sensing elements for electrical control units for both
industrial and home utility, and as electrodes in energy storage
systems, batteries, capacitors, fuel cells, and the like.
One especially interesting and important use for novel carbon
compositions produced in accordance with the present invention is
as an ion absorber and electron conductor in an electrical energy
storage device where carbon electrodes have heretofore been
used.
In accordance with the present invention, a particular application
of the novel carbon compositions is as electrodes in novel single
and multicell capacitor-battery energy storage devices.
The novel capacitor-battery storage device possesses the known
functional advantages of conventional chemical storage batteries
and conventional capacitors but not of their disadvantages.
Specifically, a conventional capacitor is able to store energy
quickly -- on the order of seconds or at most minutes for charging,
but suffers the disadvantage that it stores very little energy per
unit size. Conversely, a chemical battery is able to store larger
amounts of energy per unit size, but suffers the disadvantage of a
relatively slow charging rate.
The capacitor-batteries, as contemplated by the present invention,
provide both the quick energy storage characteristic of the
conventional capacitor, and the high-level energy storage
characteristic of the conventional chemical storage battery. Thus,
capacitor-batteries have the advantageous characteristics of both
conventional capacitors and conventional chemical storage batteries
but none of the major defects of these devices. Accordingly, the
capacitor-battery device is quickly rechargeable to high levels of
energy storage for greater utility than either the conventional
capacitor or the conventional chemical storage battery.
CONTRIBUTION TO THE ART
Therefore, a unique electrode for use in capacitor-battery storage
devices and a novel capacitor-battery energy storage device
utilizing such electrode as a component part thereof would also
provide a substantial advance to the art.
Accordingly, it is an important object of the present invention to
provide novel carbon compositions.
A further object is to provide a method for producing novel carbon
compositions, wherein precursor, activatable chars are converted to
"modified" structures having unexpected utility in the modified
state.
A further object is to provide novel electrodes for electrical
energy storage devices.
A further object is to provide a novel capacitor-battery energy
storage device.
A further object is to provide a novel electrical capacitor-battery
utilizing as an electrode or electron-conducting component, a novel
carbon composition of invention.
A further object is to provide a method for producing novel carbon
compositions involving oxidation and reduction of precursor,
activatable chars in molten salt electrolytes, whereby materials
from the molten salt electrolytes are adsorbed into the carbon
structures to render them more highly useful than activatable chars
not so treated.
A further object is to provide a novel electrical capacitor-battery
storage device utilizing an electron conductor of novel carbon
composition in combination with a fused salt electrolyte wherein
the novel carbon composition is partially produced by pre-use
cycling in the cell to cause the occlusion therein of certain
elements of the molten salt to produce unexpectedly active electron
storage members, surpassing in capacity the prior art analagous
members of carbon, wherein it was postulated that surface area was
the principal factor contributing to high levels of energy
storage.
Other objects of this invention will appear in the following
description and appended claims, reference being had to the
accompanying drawings forming a part of this specification wherein
like reference characters designate corresponding parts in the
several views.
FIG. 1 is a graph illustrating electrode capacity phenomena that
have been discovered in accordance with the present invention;
FIG. 2 is an isometric view, partly broken away in section, of
capacitor-battery storage cell made according to the present
invention;
FIG. 3 is an isometric view of a bipolar electrode unit, usable in
a cell of the type shown in FIG. 2;
FIG. 4 is a graph illustrating electrode capacity phenomena
obtained in the run of example 6;
FIG. 5 is a graph illustrating electrode capacity phenomena
observed in the preconditioning of a carbon material to produce
products within the scope of the present invention in accordance
with example 7, wherein the sweep was made first in the more
negative direction;
FIG. 6 is a graph illustrating electrode capacity phenomena
observed in the preconditioning of a carbon material in accordance
with example 7a wherein the sweep was made first in the more
positive direction; and
FIG. 7 is a graph illustrating electrode capacity phenomena
observed in the preconditioning of a carbon material in accordance
with example 7b, wherein the carbon was previously treated by vapor
phase chlorination.
Before explaining the present invention in detail it is to be
understood that the invention is not limited in its application to
the particular construction and arrangement of parts illustrated in
the accompanying drawings, since the invention is capable of other
embodiments and of being practiced and carried on in various ways.
Also, it is to be understood that the phraseology or terminology
employed herein is for the purpose of description and not of
limitation.
THE NOVEL CARBON COMPOSITION AND ITS PRODUCTION
The novel carbon compositions of the present invention can be
characterized by the terminology "selected carbon polymers".
Further, the novel carbon compositions of the present invention can
be identified by chemical analysis, and also perhaps equally
importantly, as will be discussed hereafter, by the method of
production inasmuch as the chemical analysis and method of
production seem to be inextricably intertwined with one
another.
Still further, it should be pointed out that the novel carbon
compositions of the present invention exist in two forms:
1. The form in which it has electrochemically associated with it
certain ingredients from a molten salt bath produced by cycling at
a predetermined voltage range in such bath. This cycling converts
the carbon into an unexpectedly easily reversible charge collector
of unusually high capacity over an unexpectedly broad potential
span as the result of the electrochemical association with it of
certain constituents from the molten bath.
2. The form wherein the carbon compositions has been desalted
following the electrochemical-cycling treatment, with the resultant
retention of the unique carbon structure that has been developed
during the cycling, irrespective of the occlusion therein of
component parts of the salt.
Chemical analysis. The quantitative chemical analysis of the
electrochemically reacted material, with salt from a molten bath of
sodium chloride and potassium chloride, is as follows:
PERCENT
__________________________________________________________________________
CONSTITUENT BROAD SPECIFIC
__________________________________________________________________________
Na 10-13 11.7 K 18-21 19.6 Cl 29-31 29.0 C Balance
The quantitative chemical analysis of the carbon material of
invention, made by desalting the above material, is as follows:
CONSTITUENT PERCENT
__________________________________________________________________________
C 87.56 H <0.10 Cl 5.51 Ash 1.52 O 5.31 (by difference) Surface
Area 256 square meters per gram.
DEFINITIONS
Oxidation: In the present invention, oxidation is used in the broad
sense to denote the increase in positive valence or decrease in
negative valence of any element in a substance. On the basis of the
electron theory, oxidation is a process in which an element loses
electrons. In a narrower sense, oxidation means the chemical
addition of oxygen to a substance.
Reduction: In the broad sense, reduction is the decrease in
positive valence or the increase in negative valence of an element.
In the narrow sense, reduction means the decrease in the oxygen
content, or the increase in the hydrogen content, of a
substance.
Definitions taken from Handbook of Chemistry, Lange, 10th edition,
1961, McGraw-Hill Book Company, Inc.
THE METHOD OF PRODUCTION
Basically, the steps involved in the method are as follows:
Step I. Heating a carbonaceous or carbonizable material in a
nonoxidizing atmosphere at a temperature in the range of about
500.degree. to about 1,250.degree. C. to form a char.
It has been found that carbons in accordance with the present
invention can be made of activated petroleum coke, wood char,
activated sodium lignosulfonate char, activated bituminous coal,
polyvinylidene chloride char, polyacrylonitrile char and the like.
The feature which is common to all of these materials is their low
temperature of preparation. None of these carbons has been heated
above about 1,100.degree. C.
A lower limit can be set on the temperature of preparation because
the carbon must be conducting. Conductivity in chars or carbonized
materials ordinarily begins around 600.degree. or 700.degree. C.,
although in certain specific instances, for example polyvinylidene
chloride char, conductivity becomes appreciable at temperatures
around 500.degree. C. In a definitive sense then, any polymer
carbon that has been prepared between the temperatures of about
500.degree. C. and about 1,250.degree. C. is to be included within
the scope of the present invention.
In general, these carbons can be characterized by their X-ray
diffraction patterns, which are distinctly different from graphite.
Graphite is characterized by very sharp diffraction lines, while
the low-temperature polymer carbons are characterized by very
diffuse diffraction bands. In fact, in many instances, very flat
diffraction patterns which indicated very low crystallite
concentration are obtained. Upon heat treatment, the flat patterns
of the low-temperature carbons are gradually converted in stages to
the crystalline graphite type of diffraction pattern.
Slightly higher temperature carbons, which begin to show a
substantial organization as evidenced by their diffraction patterns
do not exhibit sufficient capacity to be economically attractive
and could not compete with low-temperature carbons.
Step II. The selected charcarbon is next pressed and bonded into
electrode form.
Step III. The charcarbon is then treated by both oxidation and
reduction to remove therefrom certain occluded impurities such as
ash, oxygen, nitrogen, etc. to produce a selected carbon polymer.
This can be done by:
A. oxidizing first, reducing, and then reoxidizing to produce the
selected carbon polymer; or
B. reducing first and then oxidizing to produce the selected carbon
polymer.
Oxidizing as contemplated above is to be understood as a reaction
conducted in a nonoxygen-containing atmosphere, such as a chlorine
gas treatment of the charcarbon in a closed chamber.
In accordance with the present invention, the oxidation-reduction
operation can be conducted by cycling the charcarbon electrode in
an electrochemical cell or equivalent environment. Although a cell
containing a LiCl--KCl eutectic melt has given good results, other
molten salt electrolytes can be used. This cycling accomplishes a
two-fold effect on the carbon material as follows:
1. It modifies the structure of the porous carbon material in an
unexpected, and as yet unexplained way to produce a novel material
of high electrical charge-holding capacity.
2. It produces an electrochemical reaction between the carbon and
the fused eutectic in which the electrical conditioning is
effected.
It is to be noted with respect to this exemplary step of the method
that a selected voltage range is chosen to produce the unexpected
structure. Therefore, in detail, step III of the exemplary method
is as follows:
The carbon from step II is immersed in a fused lithium
chloride-potassium chloride eutectic melt or equivalent
electrolyte, at a temperature in the range of about 350.degree. C.
to about 850.degree. C.
The carbon is for this purpose connected to a source of electrical
current and is thus made an electrode in a circuit, another
electrode also being immersed in the electrolyte to provide a
complete circuit.
Thereafter, the electrode is charged in both positive and negative
directions. In the positive direction, the carbon is charged to at
least - 0.3 volt with respect to chlorine evolution. From a
practical point of view this can be extended to the point at which
halogen evolution becomes prohibitive. Then in the negative
direction, the carbon is charged to at least -2 volts with respect
to chlorine evolution. The negative side can be extended to the
-3-volt level.
The order in which these reactions are carried out is not to be
considered limiting.
Charging the carbon in the positive direction apparently removes
oxygen from the polymer as carbon oxides, both carbon monoxide and
carbon dioxide. Hydrogen would also be stripped from the electrode
as HCl in a chloride melt or as HBr in a bromide melt.
It is not certain what the effect is when taking the carbon in the
negative direction, but an electrochemical reaction does occur
between the melt and the chlorinated carbon at some point between
about -1.5 and -2.3 volts. Subsequent reoxidation, when
accomplished, puts the carbon in condition for use as an
electrode.
These steps amount to electrochemical oxidation and reduction of
the carbon and are effective to remove all of the oxygen and most
of the ash, leaving a novel carbon polymer structure.
Both oxidation and reduction must be accomplished in order to put
the carbon into the unique compositional form. Thus, oxidation
alone, as by charging the electrode in one direction, still
requires reduction by charging the electrode in the reverse
direction.
Relative to the foregoing electrochemically treated product, it is
to be clearly understood that the product is distinctly different
from simple mixtures of the melt and the carbon.
When conditioned in this way, electrodes having characteristic
capacities are obtained. Although the detailed characteristics of
the capacity curve depend upon the source of the char, the general
characteristics of the curve are common, as shown in FIG. 1. Thus,
there is a zero point of charge which appears somewhere in the
vicinity of - 0.7 volt, a maximum capacity in the neighborhood of -
1.8 to -2 volts, and frequently, with a shoulder in the
neighborhood of -1 to -1.5 volts.
Between zero volts and the zero point of charge, the charge storage
is probably as an electrical double layer, involving primarily
adsorption of the anions. From the zero point of charge to more
negative potentials, the adsorptions appear to be specific. The
shoulder between -1 and -1.5 volts may correspond to removal of
covalently bound chlorine, and the maximum at about -1.8 to about
-2 volts would correspond to the specific adsorption of alkali
metal ions.
EXAMPLES
The following examples relate to specific runs made in accordance
with the present invention.
EXAMPLE I
Petroleum Coke
6 to 14 mesh activated petroleum coke, obtained from the Matheson
Coleman Bell Company was pulverized to 200-320 mesh and 200
milliliters of the powdered coke was mixed with 75 milliliters of
Durez resin No. 16470 (obtained from the Durez Plastics Division of
Hooker Chemical Company). The mixture was cast into a block and
dried overnight in an oven at a temperature of 40.degree. C. The
oven temperature was the raised to 60.degree. C. for an additional
24 hour period. The dried block was then packed in a granular coke
in an electric furnace and baked in an atmosphere of argon for a
period of 20 hours. The temperature program for this 20-hour period
was 2 hours at 245.degree. C., then 81/2 hours at 245.degree. C.,
then 2 hours up to 845.degree. C., then 3 hours at 845.degree. C.,
and finally 4 1/2 hours to below 235.degree. C.
The baked block subsequently was removed from the furnace. A
rectangular piece of carbon 1 .times.1/2 .times.1/4 inch was cut
from the block and used as a test electrode in an electrochemical
cell. The electrolyte in the cell was molten lithium chloride -
potassium chloride eutectic. Other electrodes in the cell included
a graphite tube, bubbling chlorine, used as a chlorine reference
electrode, and a lithium-10percent aluminum electrode used as the
working electrode or anode.
The temperature of the cell was maintained at 500.degree. C.
The carbon polymer electrode was initially charged to 0 volta and
maintained there for a period of 2 hours. The electrode potential
was then adjusted to -3 volts over a period of 1 hour and then
brought again to 0 volt over a similar period.
The electrical properties of the novel carbon material so formed
were characterized using a potentiostatic sweep method with the
results shown in FIG. 1 and table I.
---------------------------------------------------------------------------
TABLE I
---------------------------------------------------------------------------
PETROLEUM COKE CAPACITY
Electrode Capacity within Zone
__________________________________________________________________________
Zone (meq./cc.)
__________________________________________________________________________
I 0.4 II 0.06 III 0.4 IV 2.2 V 2.8 d=0.785 g./c.c.
__________________________________________________________________________
The general characteristics of the capacity curve based on these
data are typical of the polymeric carbon charge exchange electrodes
produced and conditioned in this manner in accordance with the
present invention.
The test results of several runs proved that a maximum energy
storage of nearly 20-watt minute from a cell using electrodes made
from activated petroleum coke can be obtained when:
1. The carbon electrode is charged in the positive direction
first;
2. The conditioning is carried out at the comparatively high
temperature (525.degree. C.); and
3. The conditioning is carried out over approximately a 2.8-volt
range.
Typical data are set forth in the following table:
Direction Energy Temperature of Delivery at 250 .degree. C. First
Charge (Watt Min.)
__________________________________________________________________________
450 + 19.0 - 17.1 525 + 19.9 - 18.8
__________________________________________________________________________
EXAMPLE II
Sodium Lignosulfonate Char
One hundred milliliters of Green Label Brer Rabbit Molasses was
placed in a No. 3-AUS 1-quart Baker-Perkins dough mixer and the
mixer heated by means of the steam jacket until the molasses flowed
freely. Small amounts of N-BC4567 Filtchar (a sodium lignosulfonate
char obtained from the West Virginia Pulp and Paper Company) were
added and mixed with the molasses until the mixture was not sticky
to the touch and did not cling tenaciously to the sides of the
mixer. The temperature of the mixer was raised to drive off sulfur
dioxide and more Filtchar added to maintain the desired
consistency. Water was evaporated from the mixture until a semidry
rubbery mixture was obtained.
This mixture was further dried in the Baker-Perkins dough mixer
until it broke up into fairly small granular particles. The mixture
was then transferred to a drying oven and dried for a period of 2
days at a temperature of 230.degree. F. The dried particles were
then pulverized in a hammermill (running at 16,000 r.p.m. using a
fine (0.02-inch diameter) round hole screen. The resulting powder
was mixed with one-quarter of its weight of additional filtchar and
this mixture was compressed into a block at a temperature of
150.degree. F. and a die pressure of 8 tons per square inch. The
dried block was packed in granular coke in an electric furnace and
heated in an atmosphere of argon gas for a period of 45 hours. The
heating-cooling cycle was on an automatic 30.degree. curve program
with a maximum temperature of 780.degree. C.
A pair of electrodes measuring 1 .times. 1/2.times. 1/4inch were
cut from the baked block and inserted in a cell similar to that
described in example 1.
One of the carbon electrodes was used to produce a composition of
the present invention while the other was used as a working
electrode.
The test electrode was charged initially to 0 volt for a period of
2 hours and subsequently to -3 volts and back to 0 volt over a
period of 2 hours.
Then, the capacitance of this polymeric carbon electrode was
measured by the potentiostatic sweep method with results similar to
those shown in FIG. 1. The results are listed in table II below.
---------------------------------------------------------------------------
TABLE II
---------------------------------------------------------------------------
SODIUM LIGNOSULFONATE CHAR CAPACITY
Electrode Capacity within Zone
__________________________________________________________________________
Zone (meq./cc.)
__________________________________________________________________________
I 0.7 II 0.4 III 0.9 IV 2.6 V 2.5 d=0.56 g./cc.
__________________________________________________________________________
The general characteristics of the specific capacitance curve of
the sodium lignosulfonate char are similar to those obtained with
the petroleum coke polymeric carbon electrode of example 1. The
curve is subject to substantially the same theoretical
interpretations.
EXAMPLE III
Bituminous Coal Char
30-S Coal Tar Pitch (obtained from the Barrett Division of Allied
Chemical Company) was mixed with dry ice and pulverized to a fine
powder, mixed with more dry ice and screened to give a 200 to 320
mesh powder pitch. This was mixed with an equal amount of
Bituminous Coal Char (obtained from the Pittsburg Chemical Company)
and compressed to a block at a temperature of 90.degree. C. at a
pressure of less than 300 pounds per square inch to give a block
volume of 80 percent of the loose mixture volume.
The block was packed in granular coke in an electric furnace and
heated at a temperature of 500.degree. C. for a period of 36 hours,
then at a temperature of 1,000.degree. C. for a period of 18 hours
and finally cooled from 1,000.degree. C. to room temperature over
an 18 hour period.
A rectangular piece measuring 1 .times.1/2 .times. 1/4 inch was cut
from the baked block and used as a test electrode in an
electrochemical cell similar to that described in example 1.
However, both the reference electrode and the working electrode
were graphite tubes contained in a larger Pyrex tube.
Bottled chlorine gas was bubbled through the graphite tube of the
reference electrode.
The electrolyte was potassium chloride - lithium chloride eutectic.
The temperature of the eutectic was maintained at 450.degree.
C.
After initial charging of the last electrode to 0 volt and
maintaining it there for 2 hours, the electrode was subsequently
returned to -3 volts, and then back to 0 volt over a period of 2
hours. Thereafter, the capacity of the resulting carbon composition
was determined by the potentiostatic sweep method and the results,
again, were substantially as shown in FIG. 1 of the drawings. The
actual capacity figures are listed in table III following.
---------------------------------------------------------------------------
TABLE III
---------------------------------------------------------------------------
BITUMINOUS COAL CHAR CAPACITY
Electrode Capacity within Zone
__________________________________________________________________________
Zone (meq./cc.)
__________________________________________________________________________
I 0.3 II 0.2 III 0.3 IV 1.3 V 2.2 d=0.82 g./cc.
__________________________________________________________________________
EXAMPLE IV
Cocoanut Char
An electrochemical cell was constructed using a block of carbon
obtained from the Pure Carbon Co., St. Mary's, Pa., and designated
as Purebon FC--13, having an average particle size of about 30
microns. The block of carbon was 1/2 .times. 1/8 .times. 1 inch and
was used as a test electrode in an electrochemical cell.
A second electrode of equivalent size was fabricated from
lithium-18 percent aluminum alloy.
The two electrodes were placed in lithium chloride - potassium
chloride eutectic and connected through an external circuit such
that the cell could be charged to maximum voltage and discharged at
constant current. The cell was operated with the eutectic
maintained at a temperature of 425.degree. C.
The lithium-18 percent aluminum electrode has a potential of -3.36
volts at the 425.degree. C. temperature of the eutectic. Thus, when
a cell comprising carbon and aluminum-lithium electrodes is charged
to 3.36 volts, the carbon electrode will be at 0 volt. When the
cell is discharged to 0.36 volt across the cell, the carbon
electrode will be at -3 volts.
Accordingly, after this cell was assembled, it was discharged from
its initial voltage of 1.8 volts to 0.36 volts. Thereafter, the
cell was reversed and charged to 3.36 volts. The current at which
this operation was conducted was 500 milliamperes.
The cell was operated for approximately 15 hours, or approximately
30 cycles.
Thereafter, a chlorine reference electrode was inserted into the
system and the electrical properties of the carbon material formed
by the electrical cycling were characterized using the
potentiostatic sweep method as in the prior examples. The results
were again similar to those presented in FIG. 1. The results are
tabulated in table IV following.
---------------------------------------------------------------------------
TABLE IV
---------------------------------------------------------------------------
PUREBON FC-13 CAPACITY
Electrode Capacity within Zone
__________________________________________________________________________
Zone (meq./cc.)
__________________________________________________________________________
I 0.7 II 0.4 III 0.8 IV 3.0 V 4.0 d=0.90 g./cc.
__________________________________________________________________________
EXAMPLE 5
Cocoanut Char
A series was run in which six cells were constructed. Each cell
consisted of a chlorine reference electrode and two carbon
electrodes fabricated from Purebon FC-13 having the dimensions 1/2
.times. 1/4 .times. 1 inch.
The temperature of operation was 450.degree. C.
The electrolyte was lithium chloride - potassium chloride
eutectic.
The cells were each operated for about 15 hours on a cycling
schedule which consisted of charging to 3 volts across the cell
under constant voltage and then discharging to 1 volt across the
cell at a constant current of 500 milliamperes.
At the end of the 15 hour schedule, each of the cells was charged
fully. Thereafter, each cell was discharged to a predetermined
voltage across the cell. Different cells were discharged to
different voltage levels to provide a spread over a range
corresponding to substantially the full working potential range of
the electrodes.
The exact potential of each electrode was then measured with
respect to the chlorine reference electrode. The two test
electrodes were withdrawn from each cell and analyzed for lithium,
potassium, and chloride ion content, using extraction and
precipitation techniques. The balance was assumed to be carbon. The
analytical results are set forth in table V following. ##SPC1##
The data set forth in table V shows that over the entire range of
potential of the electrodes, the occluded components from the
molten eutectic electrolyte are present in substantially the same
ratio at all times. However, the total amount of occluded materials
in the electrodes from the eutectic, increases slightly with
decreasing potential of the electrode.
EXAMPLE 6
Hardwood Char
A cell was assembled using a test electrode prepared from a
commercial carbon obtained from the Purebon Carbon Company, St.
Mary's, Pa., designated Purebon FC-50, having an average particle
size of about 75 microns. The electrode was 1/2 .times. 1/4 .times.
1 inch. The cell also included a working electrode of lithium-18
percent aluminum, and a chlorine reference electrode. Lithium
chloride - potassium chloride eutectic was used as the electrolyte
and was maintained at a temperature of 450.degree. C.
The test carbon electrode was first charged to -3 volts and
subsequently taken to 0 volt over a period of 21/2 hours on a sweep
potentiostat.
On the fifth cycle the data of table VI were obtained.
---------------------------------------------------------------------------
TABLE VI
---------------------------------------------------------------------------
PUREBONS FC-50 CAPACITY
Electrode capacity within Zone
__________________________________________________________________________
Zone (meq./cc.)
__________________________________________________________________________
I 1.5 II 0.6 III 0.9 IV 4.6 V 4.7 d.times.0.84 g./cc.
__________________________________________________________________________
The capacity versus potential data obtained during the fifth cycle
are plotted in graph form in FIG. 4 of the drawings. As shown in
FIG. 4, the forward sweep from 0 volt to -3 volts on the test
carbon electrode is represented by the solid line. The reverse
sweep from -3 volts to 0 volt is represented by the dotted
line.
The graph demonstrates the complete reversability of a reaction
which occurs at -1.8 volts on the forward sweep. Thus, the capacity
increases sharply at this point on both the forward and reverse
sweeps.
A similar reaction occurs at -2.8 volts. However, the peak at that
point is not sufficiently sharp to be observed on the reverse
sweep.
THE METHOD OF PRODUCTION-- FURTHER INSIGHT
Insight into the method of production has been obtained by carrying
out the preconditioning steps on the raw carbon with a controlled
potential sweep apparatus. Results of several experiments show
clearly that the carbon compositions of the invention are clearly
different from either the starting materials or simple mixtures
thereof. These conclusions are demonstrated conclusively by the
following examples.
EXAMPLE 7
SWEEP FIRST IN MORE NEGATIVE DIRECTION
A cell was constructed as in example 6, using a test electrode of
Purebon FC-50 carbon, obtained from the Pure Carbon Company, St.
Mary's, Pa. The cell also included a lithium-18 percent aluminum
working electrode and a chlorine reference electrode. Lithium
chloride - potassium chloride eutectic was the electrolyte, and the
temperature of operation was 450.degree. C.
The carbon test electrode was operated on the potentiostatic sweep
apparatus at a rate of 10 millivolts/minute starting at 1.3 volts
which was the initial potential of the cell. The sweep was made
first in the more negative direction.
The results of this run are shown in FIG. 5 where the potential of
the electrode is plotted as the abscissia, and the instantaneous
amount of reaction is plotted on the ordinate as capacity in
milliequivalents per gram of original carbon material per volt of
sweep.
At the onset of the sweep, no reaction occurs. However, at a
potential slightly more positive than -2 volts, a reaction begins
which increases sharply at -2.5 volts and passes through its
maximum rate at -2.7 volts.
On reversal, a slowly diminishing reaction is observed which causes
the current to increase in magnitude, maximizing at -1.85 volts.
The amount of reaction then decreases to near zero and begins to
rise sharply again at -0.8 volt. Between this potential and 0 volt
a gas was evolved from the test electrode.
The gas was collected, analyzed on infrared apparatus, and found to
be composed of substantially equal amounts of carbon monoxide and
carbon dioxide.
Upon discharging this electrode, there is a rapidly diminishing
reaction passing through a minimum at -0.6 volt and then rising
slowly, showing appreciable reaction in the -1 to -1.5-volt region,
zone III.
A larger reaction occurs in the region -1.5 to -2.3 volts, zone
IV.
A small peak occurs in the region of about -2.7 volts, zone V.
Subsequent cycling of this electrode was constant, and essentially
the same as shown in FIG. 4.
EXAMPLE 7a
SWEEP FIRST IN MORE POSITIVE DIRECTION
FIG. 6 illustrates the results of a run on the order of that
conducted in example 7, but with the exception that the sweep was
made first in the more positive direction.
In this run, no reaction occurred until the carbon electrode
reached the potential of -0.3 volts, at which point an abrupt
reaction began. During this abrupt reaction, a gas was also evolved
that was analyzed and found to be made up of approximately equal
parts of carbon monoxide and carbon dioxide.
This reaction is essentially irreversible as evidenced by the
reverse sweep of FIG. 6, where the current drops rapidly to zero.
Nothing happened until the electrode potential had reached -1.6
volts. At this point a slow reaction began which accelerated at
about -2.2 volts and reached a maximum at -2.35 volts. This
reaction then dropped rapidly and a second maximum occurred at -2.8
volts.
The reverse sweep was very similar to the reverse sweep of example
7, as shown in FIG. 5, but showed a slightly larger reaction in the
-1.75-volt region and slightly less reaction in the -0.8-volt
region.
EXAMPLE 7b
CHLORINE TREATMENT
Further insight into the method of production can be obtained by
treating a raw carbon electrode in an atmosphere of chlorine gas
for a period of 1 hour at room temperature. The carbon used was
Purebon FC-50.
The results obtained from a cell constructed using this material as
a test electrode are shown in FIG. 7.
In this run the reaction was similar to that of example 7, as shown
in FIG. 5, except that the peak which occurred at -2 volts in
example 7, FIG. 5, is shifted to -2.35 volts and is substantially
enhanced.
The peak that occurred at -2.8 volts in example 7, FIG. 5, is
virtually nonexistent in this run, FIG. 7.
In toto, these results show that this portion of the carbon
composition synthesis, i.e. taking the raw carbon to 0-volt results
in the removal of oxygen from the carbon polymer structure and the
replacement of the oxygen with a chlorine structure. This reaction
may be represented by the following equations.
1. A-O+Cl.sup.- CO, CO.sub.2 +ACl wherein A represents a raw carbon
material.
where B represents a new carbon structure.
Apparently this reaction proceeds with near perfect stoichiometry,
i.e., two atoms of chlorine replace one atom of oxygen.
Either the chlorine structure or the oxygen structure can be
reduced at sufficiently negative potential to produce a totally new
material. The chlorine structures are reduced at -2.35 volts while
the oxygen structures are reduced at -2.8 volts. These reductions
are essentially irreversible. At no time during subsequent cycling
are reaction maxima observed that could correspond to these same
reactions.
Apparently it does not matter whether the chlorine structure is
reduced or the oxygen structure is reduced, because in the end, the
same novel carbon material is produced.
This may be restated as follows: Thus, the carbon can be reduced
electrochemically by charging it to -3 volts; and then oxidizing it
by charging it to 0 volt. Alternatively, it may be oxidized by
charging to 0 volt and then reduced by charging it to -3 volts.
As a further alternative, if desired, the carbon can first be
oxidized in a chlorine atmosphere and then reduced in an
electrochemical cell. Presumably this could be extrapolated to a
process taking place entirely outside a cell as long as proper
energetics for the reactions could be maintained.
Novel carbon structure B, in the equation above, must still be
oxidized to 0 volt or greater, preferably in an electrochemical
cell, to produce the final compositions of the present invention.
After such treatment, the novel product produced is then reversible
on continued cycling, as in an electrochemical storage
application.
THE POSSIBILITY OF OTHER SALT COMPOSITIONS AS REDUCTANTS FOR THE
CARBON POLYMER
The electrochemical treatment as described in the foregoing
examples can be carried out in electrolytes other than lithium
chloride - potassium chloride eutectic. However, for reasons that
will become apparent, this particular electrolyte is preferred. The
primary requirement for the electrolyte is that it must support a
wide potential span. Furthermore, the range between about -0.2 volt
and about -2.0 volts with respect to chlorine evolution must be
readily attainable in the electrolytes under consideration.
At least in principle, the electrolyte need not be a fused salt.
Thus, although particular solvents have not been discovered to
date, the reactions of the present invention can conceivably be
carried out in a nonaqueous solvent containing dissolved lithium or
potassium chlorides, for example.
Further, the electrolytes may be other than the eutectic
compositions. For example, novel carbon compositions within the
scope of the present invention have been prepared successfully in
molten potassium chloride as well as molten lithium chloride. In
each of these cases, similar reactions were observed and similar
products were obtained.
Within the extended scope of the invention the reaction may be
carried out, at least to a degree, in fluoride and bromide melts,
in addition to chloride melts. Iodide melts do not at present
appear to be operable.
The chloride electrolyte is preferred for two reasons:
1. The carbon electrode is not attacked at an appreciable rate at
the most positive potentials attainable; and
2. The attainable positive voltage in chloride melts is sufficient
to oxidize the carbon structure.
Fluoride melts can be used to oxidize the carbon, but at potentials
near -0.3 volts, perfluorocarbons begin to be evolved.
Bromide melts, on the other hand, do not allow a sufficient degree
of oxidation of the carbon structures to give the highest yields of
the desired products.
The cationic components of the melt may be any or all of the alkali
metals (Group Ia of the Periodic Table), the alkaline earth metals
(Group IIA) or the members of Group IIIb including the members of
the rare earth and actinide contraction series. These materials
have in common the property that the cation will not be discharged
at an iron or other inert cathode at potentials greater than -2
volts with respect to chlorine. Thus, salts containing these
cations will not be decomposed under the conditions of operation of
the present invention.
These conclusions are substantiated by the following examples:
EXAMPLE 8
An electrochemical cell was constructed using two electrodes made
from Purebon FC-13 carbon of 1/2 .times. 1/4 .times. 1
inch-dimension. The cell also included a chlorine reference
electrode.
The electrolyte was molten potassium chloride.
The temperature of operation was 850.degree. C.
The cell was operated on a 0 to -3.3-volt span across the cell on a
schedule consisting of a constant voltage charge and constant
current at 500 milliamps discharge over a 15 hour period
(overnight).
At the end of this schedule, the carbon electrode that had been
maintained positive throughout the cycling was connected as a test
electrode to the sweep potentiostat while the electrode that had
been maintained most negative was connected as the working
electrode.
The cell was then cycled between 0 and -2.5 volts at a rate of 20
millivolts per minute. The results are presented in composite table
VII, presented below example 14.
EXAMPLE 9
A cell as in example 8 was constructed and cycled in the same
manner.
The electrolyte was lithium chloride and the operating temperature
was 700.degree. C.
The results are recorded in composite table VII.
EXAMPLE 10
A cell as in example 8 was constructed and cycled in the same
manner.
The electrolyte was lithium chloride - barium chloride eutectic and
the operating temperature was 650.degree. C.
The results are recorded in composite table VII.
EXAMPLE 11
A cell as in example 6 was constructed. This comprised a test
electrode of Purebon FC-13 carbon 1/2 .times. 1/4 .times. 1 inch,
an anode of lithium - 18 percent aluminum and a chlorine reference
electrode.
The electrolyte was 32 weight percent lithium chloride, 17 weight
percent cesium chloride, and the balance potassium chloride.
The operating temperature was 450.degree. C.
The cycling was the same as in example 8.
The results are presented in composite table VII.
EXAMPLE 12
A cell as in example 8 was constructed and cycled in the same
manner.
The electrolyte was lithium chloride-- potassium chloride
eutectic.
The operating temperature was 700.degree. C.
The results are presented in composite table VII.
EXAMPLE 13
A cell was constructed as in example 6, see example 11.
This comprised a test electrode of Purebon FC-13 carbon 1/2 .times.
1/4 .times. 1 inch.
The electrolyte was 31 weight percent lithium chloride, 51 weight
percent potassium chloride, and the balance was rubidium
chloride.
The operating temperature was 450.degree. C.
The cycling was carried out as in example 8.
The results are presented in composite table VII.
EXAMPLE 14
This is a comparison to example 12.
A cell as in example 8 was constructed and cycled in the same
manner.
The electrolyte was 50 percent lithium chloride - 50 percent
potassium chloride instead of a lithium chloride - potassium
chloride eutectic, as in example 12.
The operating temperature was 700.degree. C.
The results are presented in composite table VII. ##SPC2##
SUMMARY OF THE RESULTS SHOWN IN TABLE VII
Table VII affirms the point made above that a broad range of
cationic components can be used in the electrolyte to provide
practical and similar operation.
The following examples relate to further extensions relative to the
salt compositions. Example 15 shows that the carbon can be cycled
first in a chloride eutectic and then transferred to a bromide
eutectic with analogous results. Example 16 shows that an operation
performed entirely in a bromide eutectic produced an electrode
having the same capacity as in the chloride then bromide operation
of Example 15.
EXAMPLE 15
An electrochemical cell was constructed using Purebon FC-13 carbon
as a test electrode of 1/2 inch.times. 1/4 inch.times. 1
inch-dimensions. The anode was fabricated of lithium-18 percent
aluminum alloy.
The electrolyte was lithium chloride - potassium chloride eutectic
and the operating temperature was 450.degree. C.
The electrodes were connected through an external circuit such that
the cell could be charged to maximum voltage and discharged at a
constant current. The cell was operated on a constant voltage
charge to 3.36 volts across the cell and discharged at a constant
current of 500 milliamperes down to a level of 0.5 volt across the
cell.
The cell was cycled for 15 hours (overnight) approximately 30
cycles. Then the discharge for record purpose was taken at 500
milliamperes.
The electrodes were then withdrawn from the electrolyte and
transferred to fresh electrolyte consisting of a lithium bromide -
potassium bromide eutectic. Note that this is an all bromide
eutectic.
The cell was then cycled according to the same schedule. However
the charging voltage was reduced to 3.0 volts.
After cycling for 4 hours, a trace of voltage versus time was made
for the record.
The results are shown in composite table VIII.
The capacities as reported in table VIII for zones II, III and IV
were obtained by integrating the area beneath the discharge curve,
using as reference, the potential of the lithium-aluminum working
electrode.
The capacities of the test electrode were similar in both
electrolytes but values were somewhat lower in the bromide
electrolyte.
It was observed that the distribution within specific zones was
somewhat different. In the bromide electrolyte, zone II gained
capacity at the expense of zone III. This could have certain
advantages in some applications particularly in an energy storage
device. ##SPC3##
EXAMPLE 16
A cell was constructed essentially as in example 15 bromide--that
the entire operations was carried out in lithium bromide potassium
bromide eutectic. The cycling range was between 0 and -3 volts at
450.degree. C.
The cell was cycled for about 15 hours and then a discharge curve
was taken for record.
The results are shown in table VIII, above.
The capacity in zone IV was the same as for the electrode of
example 15. Thus, an electrode prepared and operated in lithium
bromide - potassium bromide eutectic, had the same capacity as an
electrode prepared in lithium chloride-- potassium chloride
eutectic but operated in lithium bromide-- potassium bromide
eutectic.
It will be noted that the capacity in zones II and III was however
significantly reduced by comparison.
Even with these minor differences however, the similarity is
clearly evident.
CONCLUSIONS
The foregoing runs comprise part of a substantial series.
Temperature Range
The results show that the temperature at which the reactions of the
present invention can be conducted extend over a substantial range.
Similar products have been produced at temperatures from about
400.degree. C. to about 850.degree. C. Temperatures of about
400.degree. C. to about 500.degree. C. are generally preferred for
reasons of economy.
Also, the results show that best energy storage results are
produced by first charging in the positive direction to about -0.3
volt relative to chlorine evolution, and subsequently cycling
between about 0 volts and about -2.8 volts relative to chlorine
evolution.
After about 5 to 6 cycles, the carbon reaches a steady state.
Ash content of the carbon does not appear to have either an
advantageous or detrimental effect on the energy storage
capacity.
THE NATURE OF THE CHARGED CARBON IN VIEW OF THE EXAMPLES
The method which is most useful for the study of a carbon structure
in a fused salt is a potentiostatic sweep method in which the
voltage impressed across the electrode with respect to a reference
is continuously and linearly changed as a function of time. The
current required to bring the system to the instantaneous potential
is a direct measure of the differential capacitance of the test
electrode.
The capacity measured includes the double-layer capacity along with
any pseudocapacity due to reactions which occur either in the
carbon surface which could be considered as a part of the double
layer, or between constituents of the melt and the electrode
surface.
In the carbon structures of the present invention, the primary
reactions involve ions of the melt with the carbon substrate in the
region of the electrical double layer.
At the extreme end of the stability range of the melt, reactions do
occur at carbon electrodes which result in loss of adsorbed
material from the electrode into the melt. In this region, the
double-layer concept of material storage does not apply.
In FIG. 1 of the drawings accompanying this application, there is
illustrated the capacity curve obtained with a pressed activated
petroleum coke material according to example I. This particular
carbon shows to some degree all of the possible regions of
appreciable variation in the capacity curve as a function of
electrode potential.
The units of the vertical or capacity axis of FIG. 1 are farads per
milliliter of electrode.
The horizontal or potential axis varies from the chlorine evolution
point at 0 volts to -3 volts relative to chlorine evolution.
The vertical dotted lines in FIG. 1 divide the curve into five
regions, the exact nature of which are at present unknown. However,
reasonable speculation is believed possible as follows:
I. The first zone, at the left side of the curve probably
represents the pseudocapacity and double-layer capacity of chloride
ion on the electrode surface.
II. The second region conforms to published capacity values for
carbon in cryolite, i.e. about 15-20 microfarads per cm..sup.2 and
includes the zero point of charge. (from "Fused Salts", McGraw
Hill, 1964, H. A. Laitinen and R. A. Osteryoung, P. 271).
This area II is perhaps the only region in which truly pure
double-layer absorption is involved.
III. The third region involves a slight prominence in the curve and
may correspond to the desorption of covalently bound chloride.
IV. The fourth region is a region of significant alkali metal
adsorption occurring near -1.8 to -1.9 volts.
V. The fifth region shows another strong adsorption that occurs at
-2.7 volts.
If the assumption is valid that region III corresponds to chloride
desorption, then regions IV and V correspond to excess alkali on
the carbon surfaces - or electrochemically reacted and infused into
the actual carbon structure.
By integrating the area beneath the capacity curve for voltage
intervals from chloride desorption to the more negative regions,
the numbers of adsorbed ions can be calculated. These numbers then
can be related to the number of atoms present in the carbon
electrode to give a relative population of the carbon atoms per
adsorbed ion. This gives an indication of the surface density of
charge.
Calculated in the manner indicated, the -1.9-volt maximum in zone
IV corresponds to 46 carbon atoms per ion. At the -2.8 maximum of
zone V there is a correspondence to 12 carbon atoms per ion. In
terms of concentrations, these figures correspond to about 1.5 and
3.5 milliequivalents per cc. respectively.
The following general statements illustrate the unique aspects of
the present invention.
Not all carbons perform in the manner indicated to produce the
novel compositions of the present invention. For example, a
graphitic carbon fails to produce adsorption of the type shown in
FIG. 1 of the drawings. Source materials from which effective
electrodes are produced, if heated above 1,250.degree. C. are not
effective. Therefore, carbons produced by heat treatments not
exceeding about 1,250.degree. C. are necessary as starting
materials for the present invention.
These selected carbons all perform generally in accordance with the
showing of FIG. 1. Some of the carbons fail to show a pronounced
peak at 2.8 volts in region V; however, they all show substantially
similar adsorption.
The quantity of charge in the 1.9-volt region varies somewhat as
does the magnitude of the shoulder in the region of chloride
desorption.
From the foregoing, it will be observed that possible minor
variations in products falling within the scope of the present
invention are therefore possible. The variations appear to depend
upon the source of the carbon raw materials from which the novel
products are made.
USES FOR THE PRODUCTS OF INVENTION
One of the most important uses for the carbon materials of the
present invention is set forth in the latter part of this
specification, e.g., an electron conductor, functioning in the
nature of an electrode, for an electrical energy storage cell.
Extremely high storage capacities have been displayed by the novel
carbon products of the present invention in this type of use.
Further uses include: reagents in chemical reactions, catalysts for
chemical reactions, and the like. These materials would function in
chemical reactions as reducing agents and possibly as metallation
agents. Thus, the reduction of ketones, aldehydes, etc., should
occur in a highly specific fashion using these alkali-containing
carbons.
Transmetallation, or the formation of alkyl or aryl lithiums from
Grignard reagents or possibly by direct metallation, also seem
likely.
These materials are also eligible as catalysts for base-catalyzed
reactions particularly. Variation in basicity of these different
voltage regions is quite large. For example, the first would
correspond to roughly the pH of an alkoxide ion while the second
peak would be approaching the basicity expected from a phenyl
negative ion. From these latitudes of possible basicities, the
latitude of reactions and the selectivity of the reactions which
could be promoted are quite large.
Further applications for the novel carbon materials of the present
invention would include electrodes for use in systems other than
fused halides in which the pretreatment is conducted. This
contemplates that the fused salt residues be removed by simple
solvents. The desalted electrodes would be useful in other
electromechanical energy storage systems using nonaqueous solvents
or lower decomposition potential salt mixtures.
THE ENERGY STORAGE CELL ASPECT
In accordance with the present invention, use is made of the novel
carbon structures alluded to above as electron conductors in energy
storage cells. Thus, the use in accordance with the present
invention is that of forming an electron conductor and
ion-gathering surface for exposure in a nonconducting
electrolyte.
It is not proposed that the novel carbons of the present invention
function in accordance with the prior art theory of surface area.
At the present, it is not known what the phenomenon involved is.
However, it has been found that an unexpectedly high storage
capacity for electrical energy is provided by utilizing a novel
carbon of this invention as an electron conductor, with the carbon
forming an interface component with a nonelectron-conducting
medium, such as a fused salt electrolyte.
In accordance with the present invention, electrical energy is
stored to an unexpectedly high order of magnitude substantially
greater than that of conventional capacitors of comparable
size.
Further, in accordance with the present invention it has been
discovered that a greatly extended feedout of energy is provided --
as distinguished from the short, high-peak surge provided when a
capacitor substantially instantaneously discharges. Thus, useful
power output, of long duration, is provided by the present
invention, as distinguished from the quick-surge-type pulse
produced by the discharge of a capacitor.
By operating in accordance with the present invention, an
electrolyte is used that makes it possible to store high-current
densities and at the same time materially decrease the size of an
electrical energy storage device as compared to the size of a
capacitor necessary to store the same amount of energy.
THE NOVEL STORAGE CELL: FIGS. 2 and 3
Referring now more particularly to FIG. 2, there is shown an
electrical energy storage cell embodying an electrode made by the
present invention.
A container 10 provides a housing for the unit and serves as a
storage reservoir for the fused lithium chloride - potassium
chloride eutectic used as the electrolyte in the system. Suitable,
the container 10 is fabricated of a heat-resistant material capable
of withstanding the fused eutectic. This material must be inert
relative to the eutectic, of course, and materials such as a
nonporous graphite, sheet steel, sheet nickel, stainless steel
alloys, ceramics, alumina, etc., will function in this
application.
Since the cell illustrated operates at or above the fusion
temperature of the lithium chloride - potassium chloride eutectic,
means must be provided for maintaining the temperature at the
levels indicated. Any suitable heating means can be utilized, such
as immersion heaters or the like. For purposes of exemplary
illustration, there is shown in FIG. 2 a resistance heater,
designated by the reference numeral 12. If it be assumed that the
container 10 is made of an electrically conducting material, it
would be understood that the heater 12 must be spaced from it by an
insulator. Accordingly, a layer 14 of insulating cement is placed
over the outside surface of container 10 prior to the application
of the heater 12. Heater 12 suitable comprises a continuous
nichrome wire in coil form, wound about the container 10, over the
cement layer 14, and thereby spaced from contact with the container
10. It will be understood that the heater 12 could be comprised of
flat strip-type resistance units as well as the coiled wire
mentioned.
To conserve heat within the unit, there is conveniently and
preferably provided an external insulation sheath 16 of suitable
material, such as asbestos or the like.
In the embodiment of FIG. 2, there is provided a pair of electrodes
18 and 20. At least one of the members 18 and 20 is made from a
novel carbon composition of the present invention. The electrodes
18 and 20 are maintained in spaced relationship relative to one
another by means of a separator member 22. This separator member 22
is suitably formed of a porous nonconductor such as asbestos cloth.
Being porous, the member 22 is readily permeated by the
ion-containing and conducting medium 11, namely the lithium
chloride - potassium chloride molten eutectic. It is to be
understood that any nonconducting, inert spacing material that is
also pervious to the passage of the liquid eutectic can be used for
the function of the asbestos cloth unit discussed.
Electrical energy current collectors 24 are provided in intimate
contacting relationship with the electrodes 18 and 20. The current
collectors 14 suitably are formed from graphite compressed into
plates. Leads 26 and 28 are connected to and extend from the
current collectors 24. These are adapted to be connected either to
a charging circuit or to a load such as an electric motor or the
like to impart power thereto. It is to be understood that the
invention is not limited to the use of graphite in the current
collectors 24; accordingly, tantalum metal and the like can be used
to serve the current-collecting function.
The current 24 are intimately contacted with or joined to the
electrodes 18 and 20. This provides an ideal electrical connection
for proper functioning of the unit.
To provide an assembled unit, it will be understood that the
electrodes 18 and 20 and the separator member 22 can be fastened
together by any suitable means as nonconducting bolts extending
through the assembly.
THE ELECTROLYTE
As has been pointed out before, the novel carbon structures of the
present invention are derived by an electrochemical
oxidation-reduction reaction. This is done in an environment of the
energy storage cell illustrated in FIG. 2, which utilizes as one of
its components a suitable molten salt of the nature previously set
forth.
A particularly useful salt mixture is composed of lithium chloride
and potassium chloride with the lithium chloride being present at a
level of 58.5 mol percent and the potassium chloride being present
at a level of 41.5-mol percent. This is a eutectic composition and
is functionally operable in a temperature range of 350.degree. C.
to 1,000.degree. C. This material has a low specific resistivity,
0.6 ohm cm. at 450.degree. C., which produces a low internal
resistance of the cell.
THE NATURE OF THE ELECTRODES AND THEIR ULTIMATE PRODUCTION IN SITU
IN A STORAGE CELL
As has been indicated above relative to the unique carbon
compositions of the present invention, a step in their production
as regards the inclusion therein of at least portions of the molten
salt, comprises electrochemical charging or treatment of the
charcarbon composition after it has been fashioned into the shape
of an electrode and actually placed either in an environment
simulating an energy storage cell or in an actual storage cell.
The treatment comprises the cycling of the electrode over the
voltage range from about -0.3 volt relative to chlorine evolution
to about -3 volts relative to chlorine evolution. As has been
previously mentioned, this imparts a unique character to the carbon
material and at the -2.7-volt level a very strong adsorption
phenomenon for electron storage takes place. This region is the
region of significant alkali metal adsorption; and also a region
occurs near -1.8 to -1.9 volts, indicating a strongly adsorptive
phenomenon.
MULTIPLE COMPONENT STORAGE CELLS
FIG. 2 illustrates a single cell unit of the present invention. In
the extended scope of invention, these units lend themselves to
connection or association with other cells of similar construction
to produce higher capacity units. Within the scope of the
invention, these plural cells can be connected in parallel or in
series.
THE BIPOLAR CELL ASPECT
This is illustrated in FIG. 3 of the drawings.
In FIG. 3, a unit of the bipolar-electrode-type is illustrated in
its basic form. A number of cells constructed as shown in FIG. 3
may be further assembled, by repetition, to provide an electrical
storage device of high capacity, applicable to the propulsion of
stationary prime movers, or to vehicles of the automotive type, and
the like.
Referring further to FIG. 3, it will be noted that the bipolar
electrode 30 in the center of the unit is of greater thickness than
the spaced electrodes 32 and 34 that flank the center electrode.
The reason is that the center electrode 30 functions actually as a
dual electrode and its storage capacity in volumetric measurement
is therefore equivalent to the two electrodes 32 and 34.
The outer or flanking electrodes 32 and 34 are maintained in spaced
relationship away from the center electrode 30 by nonconducting
spacer elements 36. As indicated above, these may be formed from a
material such as asbestos cloth. An electrical tapoff is provided
from the central dual electrode 30 by means of a lug portion 38
that extends above the top edge, a marginal edge, thereto. A
graphite bolt 40 or equivalent is used to provide an electrical
connector.
Electrical infeed-outfeed to the flanking electrodes 32 is provided
by means of lug portions 42 that extend beyond the top edge, or one
marginal edge thereof. The lug portions 42 are interconnected
electrically by means of a graphite spacer or bridge member 44. A
graphite bolt 40 extends through aligned holes in the elements 42,
44, 42 to hold those parts in assembled relationship, providing
electrical connection.
From the foregoing it will be observed that an insert of the type
shown in FIG. 3 actually comprises two cells connected in parallel,
with the intermediate plate 30 functioning as a common
electrode.
It will be evident that any number of these inserts can be
assembled in either individual compartments or side-by-side
contacting relationship to produce higher energy storage units.
In this regard, a sandwich construction can be produced wherein all
of the intermediate electrodes are of the double-thickness type,
characterized by element 30 in FIG. 3. Only the outside units would
be singles. Thus, in the intermediate portion of a stacked
sandwich, all of the double-thickness units would function as
bipolar electrodes.
From the foregoing it will be understood that the cell units of the
present invention lend themselves to connection with cells of
similar construction either by connection of a number of cell units
in parallel or in series, or by utilization of a stack of electron
conductors where the individual electron conductors in the stack
are separated by nonconducting spacers, preferably of thin cross
section for maximum storage per unit volume. Thus the intermediate
electron conductors act in the bipolar capacity, cumulatively
adding their respective outputs as if connected in series.
* * * * *