U.S. patent number 3,753,110 [Application Number 05/211,022] was granted by the patent office on 1973-08-14 for timing apparatus using electrochemical memory device.
This patent grant is currently assigned to Sanyo Electric Co., Ltd.. Invention is credited to Hironosuke Ikeda, Yosio Ooe.
United States Patent |
3,753,110 |
Ikeda , et al. |
August 14, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
TIMING APPARATUS USING ELECTROCHEMICAL MEMORY DEVICE
Abstract
An electrochemical potential memory device comprising a cathode
mainly comprising silver, an anode mainly comprising silver
chalcogenide, and a silver ion conductive solid state electrolyte
sandwiched therebetween is connected to a current source for
selectively driving the device in a charging state or discharging
state and to a high input impedance direct current amplifier
responsive to the terminal voltage of the device, and a timing
operation signal proportional to the lapse of the charging or
discharging time is obtained from the amplifier. In a preferred
embodiment, the potential memory device comprises a main cathode
for supply of the charging or discharging current and an auxiliary
cathode for detecting the terminal voltage of the device, the
latter being connected to the high input impedance amplifier. The
timing apparatus employing such device eliminates disadvantageous
influence caused by an overvoltage as occurs at the time of current
conduction in the device.
Inventors: |
Ikeda; Hironosuke
(Hirakata-shi, Osaka-fu, JA), Ooe; Yosio
(Hirakata-shi, Osaka-fu, JA) |
Assignee: |
Sanyo Electric Co., Ltd.
(Osaka-fu, JA)
|
Family
ID: |
27306819 |
Appl.
No.: |
05/211,022 |
Filed: |
December 22, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Dec 24, 1970 [JA] |
|
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45/127566 |
Dec 24, 1970 [JA] |
|
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45/127567 |
Nov 16, 1971 [JA] |
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46/91713 |
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Current U.S.
Class: |
368/114;
361/434 |
Current CPC
Class: |
H03K
17/28 (20130101); H01H 43/32 (20130101) |
Current International
Class: |
H01H
43/00 (20060101); H01H 43/32 (20060101); H03K
17/28 (20060101); G04f 009/00 (); H01g
009/00 () |
Field of
Search: |
;324/182,94
;317/230,231 |
Other References
Kennedy et al., Journ. Elec. Chem. Soc.; pp. 263-267, Feb.
1970..
|
Primary Examiner: Smith; Alfred E.
Claims
What is claimed is:
1. A timing apparatus comprising:
a solid state electrochemical potential memory device
comprising:
a main cathode including an active metal,
an auxiliary cathode including an active metal,
an anode comprising an alloy including said metal, and
a solid state electrolyte having high ion conductivity sandwiched
between said cathodes and said anode,
said device exhibiting a terminal voltage between said anode and
said cathodes linearly changing as a function of the charging or
discharging quantity of electricity fed to said device in
accordance with the anode being positive or negative,
respectively,
means connected to said main cathode for providing a substantially
constant current therethrough to said device in a selected
direction, thereby selectively charging or discharging said
device,
a direct current amplifier having a high impedance input connected
to said auxiliary cathode and responsive to the voltage between the
anode and auxiliary cathode of said device, and
an output means coupled to said direct current amplifier for
providing a timing operation signal, said signal being proportional
to the lapse of time of, selectively, the charging or discharging
operation of said device.
2. A timing apparatus in accordance with claim 1, in which said
current providing means comprises
a means for relatively quickly charging said device in a charging
cycle, and
a means for relatively slowly discharging said device in a
discharging cycle,
said charging cycle being used for time setting and said
discharging cycle being used for the timing operation.
3. A timing apparatus in accordance with claim 2, in which said
current providing means further includes means selectively operable
for relatively quickly discharging said device in a quick discharge
cycle, said quick discharge cycle being used for resetting the time
theretofore set in a charging cycle.
4. A timing apparatus in accordance with claim 1, in which said
output means comprises an indicator.
5. A timing apparatus in accordance with claim 4, in which said
indicator provides visual indication of the voltage of said device
as a function of the time.
6. A timing apparatus in accordance with claim 1, in which said
direct current amplifier comprises a field effect transistor.
7. A timing apparatus in accordance with claim 1, in which said
direct current amplifier comprises a differential amplifier.
8. A timing apparatus in accordance with claim 1, in which the
cathode of said device includes Ag and the anode thereof includes
an alloy of Ag and a chalcogen element.
9. A timing apparatus in accordance with claim 8, in which the
anode of said device includes an Ag-Te alloy.
10. A timing apparatus in accordance with claim 9, in which the
anode of said device includes an alloy of Ag and a chalcogen
element, graphite and a solid state electrolyte.
11. A timing apparatus in accordance with claim 10, in which said
alloy of Ag and a chalcogen element is an Ag-Te alloy.
12. A timing apparatus in accordance with claim 11, in which the
anode of said device is less than 1 mm in thickness.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a solid state timing apparatus using an
electrochemical potential memory device. More specifically, this
invention relates to such a solid state timing apparatus that can
provide visual indication of the passing of any preset time.
2. Description of the Prior Art
A timing apparatus or a timer has been widely used to control the
operation of any given apparatus after a preset time interval. One
such type timer is of a mechanical structure. Such a mechanically
built timer usually comprises a timing mechanism driven by motor,
spring or the like. However, such a mechanical timer is
disadvantageous in that a reduction gear mechanism inevitably
employed in the timer for this purpose is complicated, with the
result that miniaturization is difficult, the mechanism is readily
vulnerable to troubles and furthermore the motor, if employed, must
be of relatively high power.
A solid state type timer was also proposed and has already been
commercially employed. The typical type of such existing solid
state timer usually uses the charging or discharging time constant
of an RC circuit, or the resistor-capacitor circuit. In more
detail, a timing output signal is provided as a function of the
charged or discharged voltage of the capacitor present in such RC
circuit. It is apparent that such capcitor voltage changes
exponentially and therefore is unsuitable for any prolonged timing
operation. Usually, such capacitor voltage is merely applicable to
a short timing operation that cannot exceed a few minutes at most.
Accordingly, it is highly desirable to provide such solid state
timing apparatus that can precisely set to any given time to
relatively longer duration.
Professor Takehiko Takahashi and Assistant Professor Osamu
Yamamoto, Technological Department of Nagoya University, announced
their study on the electrochemical potential memory by the use of a
solid state electrolyte at the b 22nd annual assembly of Japan
Chemical Association held on Apr. 5th to 7th, 1969. Briefly stated,
this device comprises an Ag electrode as a cathode, an Ag-Te alloy
electrode as an anode, and a solid state electrolyte having high
ion conductivity, such as RbAg.sub.4 I.sub.5 sandwiched between
both electrodes. When a DC voltage is applied to the device so that
the Ag electrode may be negative, a portion of Ag contained in the
Ag-Te alloy electrode migrates over to the Ag electrode, resulting
in a decreased activity of Ag in the Ag-Te alloy, and thus an
increased potential difference between both electrodes. The
inventors of this device termed this state of operation as
"charging." When the polarity of the applied DC voltage is reversed
relatively to that of the former case, Ag is refilled into the
Ag-Te alloy, resulting in a decreased potential difference and
return to the initial value eventually. The inventors of this
device termed this state of operation as "discharging." Study
disclosed by the inventors of this device indicates that the
electromotive force generated by the aforementioned charging or
discharging current can cause linear change to some extent with
respect to the charging or discharging time. Thus, this device
makes it possible as an outstanding characteristic to do write-in
and non-destructive read-out operation while preserving relatively
linear relation between the charging or dischrging time and
terminal voltage, and in addition, it can hold the memory condition
for a relatively longer period of time. These advantages mean that
this device has opened a way for its potential use as an analogue
memory device.
In view of these advantageous characteristics of the aforementioned
memory device, it may be possible to utilize this device as an
essential component of solid state timing apparatus. The invention
described in this application has been thus accomplished by the
inventors in order that such possibility may be realized.
Accordingly, details of the aforementioned memory device which is
the foundation of this invention will be further described in the
subsequent section of Description of the Preferred Embodiment.
SUMMARY OF THE INVENTION
Briefly stated, this invention comprises a solid state
electrochemical potential memory device comprising a cathode
including an active metal, an anode including an alloy including
said metal, and a solid state electrolyte having high ion
conductivity sandwiched therebetween, said device showing a voltage
between said anode and cathode linearly changing as a function of
the charging or discharging quantity of electricity supplied to
said device in a direction of the anode being positive or the anode
being negative, respectively; a means for charging or discharging
said device by substantially a constant current flowing
therethrough in a selected direction; and a means for providing a
signal that is proportional to the lapse of the time of charging or
discharging operation of said device in response to the terminal
voltage of said device. As mentioned in the section of the
Description of the Prior Art and also as described hereinafter in
detail, substantially a constant current flows through the
aforementioned electrochemical potential memory device when a given
voltage is applied in a charging or discharging manner, and the
terminal voltage or electromotive force of this device increases or
decreases in proportion to the flowing time. Accordingly, such
signal proportional to said charging or discharging time is
practically applicable to the purpose of timing operation such as
performed by a timer, sequence programmer or the like. This signal
is also available for the energization of such indicator that is
provided with a timing scale along with the aforementioned
operation and provides visual indication of the lapse of time.
Quite clearly, such timing apparatus of the invention is of a solid
state type and thus may be built in small dimensions and is
economical in power consumption, and makes the timing operation
possible for a relatively longer period of time.
In a preferred embodiment, the terminal voltage of the potential
memory device is sensed by means of an amplifier having a high
impedance input, such as a field effect transistor. In a more
preferred embodiment, the memory device comprises a main cathode
for the charging and discharging operation and an auxiliary cathode
available for the sensing of terminal voltage, both being discrete
to each other. Such embodiment enables more precise timing
operation of such timing apparatus.
In a more preferred embodiment, charging cycle of the device is
rapidly carried out for the purpose of time setting, whereas the
discharging cycle of the device is slowly carried out for the
purpose of timing operation.
Therefore, an object of this invention is to provide an improved
solid state timing apparatus.
Other object of this invention is to provide a solid state timing
apparatus that is capable of performing timing operation for a
relatively longer period of time.
Another object of this invention is to provide a solid state timing
apparatus that provides visual indication of the lapse of time.
A further object of this invention is to provide a timing apparatus
incorporating a solid state potential memory device that generates
a terminal voltage proportional to the quantity of electricity
passing therethrough.
Still a further object of this invention is to enable precise
timing operation of the timing apparatus using a solid state
potential memory device.
It is a further object of this invention to provide an improved
solid state potential memory device using a solid state electrolyte
suitable for use in a timing apparatus.
It is still a further object of this invention to provide an
improved solid state potential memory device using a solid state
electrolyte suitable for use in a timing apparatus, said device
avoiding unfavorable influence caused by the overvoltage of the
device.
It is a further object of this invention to enable rapid time
setting of the timing apparatus using a solid state potential
memory device.
These objects and other objects and features of the present
invention will become apparent from the following detailed
description of the preferred embodiments taken in conjunction with
the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a schematic sectional view of an electrochemical
potential memory device for use in a timing apparatus of this
invention,
FIG. 2 illustrates a graph showing characteristics between the
terminal voltage and the charging or discharging time of the device
shown in FIG. 1,
FIG. 3 illustrates the basic concept of an embodiment of this
invention in a block form,
FIG. 4 illustrates a more detailed schematic diagram of the
embodiment shown in FIG. 3,
FIG. 5 illustrates another embodiment of this invention that has
been developed, based in part on the embodiment shown in FIG.
4,
FIG. 6 illustrates a schematic sectional view of another embodiment
of the electrochemical potential memory device whcich is
particularly suitable for the embodiment of this invention,
FIG. 7 illustrates, partially in a block form, a schematic diagram
of an embodiment of this invention that incorporates the device
shown in FIG. 6,
FIG. 8 illustrates a graph showing voltage holding characteristics
after the cutting of the current of the device shown in FIG. 6,
FIG. 9 illustrates a graph showing voltage holding characteristics
after the cutting of the current of a similar structural and yet
more preferred embodiment of the device shown in FIG. 6,
FIG. 10 illustrates a schematic diagram of the timing apparatus of
another embodiment of this invention, and
FIG. 11 illustrates a graph for explaining the operations of the
embodiment shown in FIG. 10.
In the drawings, like parts are indicated by like reference
characters.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As described in the foregoing section of Description of the Prior
Art, this invention utilizes the prior art electrochemical
potential memory device including a solid state electrolyte. As
described already, this device has a significant characteristic of
the terminal voltage or electromotive force changing in an
approximately linear way with respect to the charging or discharing
quantity of electricity passing therethrough. Accordingly, prior to
a detailed description of this invention, it would be appropriate
to give a more detailed description of such electrochemical
potential memory device.
FIG. 1 illustrates a schematic sectional view of an electrochemical
potential memory device 1 which is used in the apparatus of this
invention. It may be considered that this device is a kind of cell
which comprises a solid state electrolyte 4 of high ion
conductivity, such as RbAg.sub.4 I.sub.5 or Ag.sub.3 SI, sandwiched
between a cathode 2 mainly including silver (Ag) and an anode 3
mainly including an alloy of silver and a member selected from the
group consisting of sulfur (S), selenium (Se) and tellurium (Te),
preferably an Ag-Te alloy. When a DC voltage is applied between
both electrodes of this device 1 in such way that the anode 3 of
this device may be positive and the cathode 2 may be negative,
silver contained in the Ag-Te alloy in the anode 3 is ionized to be
dissolved into the solid state electrolyte 4 and is deposited on
the cathode 2. In this specification, such state of operation is
referred to as "charging" hereinafter. When a DC voltage is applied
to the aforementioned device in the directly opposite polarity to
the above case, silver deposited over the cathode 2 migrates onto
the anode 3 and is deposited thereupon. In this specification, such
state of operation is referred to as "discharging" hereinafter.
FIG. 2 is a graph which indicates the relation between the charging
or discharging time and the electromotive force of the
aforementioned device by taking the current for charging or
discharging the device as a parameter. As illustrated in the FIG.
2, the following facts of function have been clarified; that the
electromotive force of this device as a cell indicates the value
dependent upon the activity of silver contained in the Ag-Te alloy
of cathode 3, that the activity of silver varies to a large measure
by any slight charging or discharging performance when the atomic
composition ratio of silver and tellurium contained in the Ag-Te
alloy approximates to a value of 2, and that the relation between
the aforementioned electromotive force and the charging or
discharging quantity of electricity i.sup.. t, where i is a current
value and t is time, generally indicates a linear relation during
the charging or discharging period in case of the electromotive
force of relatively low voltage range (from 0 (zero) to 100mV. as
per the embodiment illustrated in the FIG. 2) and also in case of
the current density of relatively low order (less than 100
.mu.A/cm.sup.2 as per the embodiment illustrated in the FIG. 2). In
this connection, it is to be pointed out that application of a
given voltage to the device in either charging or discharging
manner causes substantially a constant current to flow therethrough
and therefore the said linear relation is also applicable to the
characteristic between the terminal voltage of the device and the
charging or discharging time.
It has further been known that this device has an additional
characteristic capable of holding the potential established
immediately before cutting the current even after the cutting of
the current supplied to this device for the aforementioned voltage
range (from 0 (zero) to 100mV. as per the embodiment illustrated in
the FIG. 2).
Accordingly, this invention is directed to providing such timing
apparatus as to function to indicate the passing of the preset time
by detecting the terminal voltage of the device by the use of the
advantageous linear characteristic in a preselected region
obtainable between the supplied quantity of electricity i.sup.. t,
where t is the lapse of time and the terminal voltage of this
device.
FIG. 3 illustrates a block diagram that indicates the most
fundamental structure of the timing apparatus of this invention.
The timing apparatus illustrated in the FIG. 3 basically comprises
the aforementioned electrochemical memory device 1, a power source
and switching circuit 11 for switching the polarity of the voltage
being applied to the device 1 for the charging or discharging
performance, a high input impedance initial step amplifier 12,
preferably a differential amplifier comprising a pair of field
effect transistors, a latter step amplifier 13, such as a
differential amplifier comprised of a pair of bipolar transistors,
and an indicating device 14 like an analogue indicating device such
as ammeter or like an appropriate digital indicating device.
The initial amplifier 12 apparently functions to detect the voltage
of the device 1. It is preferable to use an amplifying device of
high input impedance, such as a field effect device, so as to
prevent the drop of potential in this device caused by formation of
a closed circuit with respect to the potential of this device
through the attached circuit.
FIG. 4 illustrates a schematic diagram of an embodiment of this
invention for implementation of the block diagram shown in FIG. 3.
In the FIG. 4, portions corresponding to those of a block form in
FIG. 3 are designated by the same reference characters.
Referring to FIGS. 3 and 4, the following description covers the
structure of an embodiment of this invention and its operation. The
potential memory device 1 has its anode 3 connected to the ground
and the cathode 2 connected to the negative voltage bus -Vcc
through a charge contact 21c of a switch 21 (as shown)
alternatively connected to the positive voltage bus +Vcc through a
discharge contact 21d, thereby allowing the switch to be switched
to the charge, discharge or open (at a contact 21n) position. A
variable resistor 22 is provided in the charge/discharge circuit
for setting a value of the constant current fed to the device
during the charging or discharging period. Adjustment of the
variable resistor 22, for example by means of a rotatable knob or
push button, permits the selective setting of the operation time
range in the graph shown in FIG. 2.
First, the charging operation of the device 1 will be considered.
When the switch 21 is turned from the open position 21n to the
charge position 21c and at the same time an apparatus being
controlled (not shown) is caused to start its operation, the
voltage of the device 1 increases linearly as illustrated in FIG.
2. This potential is then fed to the input of the initial stage
differential amplifier comprising field effect transistors TR1 and
TR2 through the resistor 23. This potential is detected by the gate
of said transistor TR1, while the gate of the other FET TR2 is
connected to the ground through the high value resistor 24. These
two transistors TR1 and TR2 are so connected as to function as a
differential amplifier for effecting impedance conversion and
voltage amplification. Outputs at both drains of the transistors
TR1 and TR2 are fed to bases of bipolar transistors TR3 and TR4,
respectively, of the succeeding stage differential amplifier
13.
An ammeter 14 is inserted between the collectors of said
transistors TR3 and TR4 through the regulating resistors 25 for
regulating the balance so as to amplify the device voltage
linearly. Accordingly, passing of the operating time can be
indicated by the ammeter 14. As an alternative embodiment of such
indicator means 14, a number of indicating lamps may be used in
place of said ammeter for indicating the operating time in a
digital manner by flickering these lamps in successive order in
response to the device voltage.
The collector of one transistor TR3 of both transistors in the
latter stage amplifier 13 is connected to an output transistor TR5
through an appropriate base bias resistor so as to provide a
single-ended output, which is then taken out through the output OUT
as an output for load driving or for program controlling.
If the charging is discontinued by switching the switch 21 to a
position 21n, the device 1 holds a potential proportional to the
charging quantity of electricity so far fed to the device and
accordingly, it is possible to retain the indication of the
indicator means 14, or to keep a needle of ammeter or indicating
lamps for digital indication in the indicated position or
state.
If the switch is turned to the discharging position after the
required charging operation, the voltage of the device 1 linearly
decreases contrary to the preceding case along the characteristic
curve as illustrated in FIG. 2, and accordingly, it is also
feasible to operate the indicator means 14 so as to indicate the
detected voltage of the device, as in the preceding case.
FIG. 5 illustrates a circuit of another embodiment of this
invention, in which the embodiment shown in FIG. 4 has been
partially modified or developed. More specifically, the embodiment
of FIG. 5 additionally comprises a circuit for effecting DC
amplification of the output of said transistor TR5 by means of
transistors TR6 and TR7 arranged in successive order so as to
control a transistor TR8 for driving a relay 26. Other portions are
the same as those of FIG. 4 and the same portions are indicated by
the same reference characters. Operating level of transistors TR5,
TR6, TR7 and TR8 are so selected that the relay 26 may be operated
by any optionally preset voltage in the device 1. Accordingly, it
is possible to control the equipment being controlled (not shown),
or to effect on/off operation of energization of such equipment at
any preset time by using the contact of said relay. If a plurality
of output circuits each comprising such transistor amplifying
circuit and relay are provided so that the operating level of
respective output circuits may be different from each other, it
would be possible to effect the programming control of such
equipment in any required timing sequence.
The embodiment of FIG. 5 shows an example in which such relay is
utilized for a specific purpose. More specifically, a normally
closed switch 27 engageable with said relay 26 is inserted in the
charging circuit as shown in FIG. 5 in order that the charging may
be effected only within a range in which the voltage characteristic
of the device 1 is substantially linear. The above-mentioned relay
26 is so adjusted that the aforementioned normally closed switch 27
may be opened when the device voltage exceeds the voltage range
that indicates relatively desirable linear character as mentioned
with reference to FIG. 2, for example, when the device voltage
reaches a range between 100 to 120 mV. Thus, regulation is
effective to permit the charging operation only within a range in
which the voltage characteristic of the device 1 is linear, and
prevents the device 1 from excessive charging thereupon.
It is understood that each of the embodiments described with
reference to FIGS. 1, 4, and 5 includes a common terminal
corresponding to a single cathode by means of which the charging or
discharging current is supplied and also the terminal voltage of
the device 1 is detected. In this connection it is recalled that
the device shown in FIG. 1 can be considered as a cell, as
mentioned previously. Therefore, in case of such device as
comprising the common cathode for supply of the current and for
detection of the terminal voltage, the detected output voltage is a
total of an electromotive force of the device and of an overvoltage
of the device as a cell. This results in the fact that the start or
the stop of the electric current conduction into the device 1
causes influence of the overvoltage on the detected voltage and
therefore the output voltages detected at each device 1 immediately
before and after the change to a different electrical current
conduction state. This means that the voltage holding
characteristic of the device is degraded. For example, when the
switch 21 is opened or turned to the open position 21n in the
course of charging or discharging the device 1, indication by the
indicating means 14 varies from such indication that should
correspond to the time in which charging or discharging was
actually done. It has been found that the said degradation of the
voltage holding characteristic is aggravated by the fact that an
increased current for charging or discharging the device causes a
greater overvoltage, resulting in more inaccurate indication. Thus
it is desired to provide an improved potential memory device that
eliminates the abovementioned problem.
The overvoltage as occurs in the electrochemical potential memory
device causing a voltage drop after the cutting of the current
conduction into the device may be classified as follows:
1. A voltage drop caused by the current flowing through the
resistance involved in the solid state electrolyte of the device
(or an IR drop across the resistance in the electrolyte).
2. An overvoltage caused by dissolution or deposition of Ag at an
interface between the electrolyte and the anode or cathode.
3. An overvoltage caused by diffusion of Ag ion into the anode.
FIG. 6 shows a schematic sectional view of an improved
electrochemical potential memory device 30 for eliminating the IR
drop across the resistance in the electrolyte as described in the
above subsection (1) and the overvoltage caused by dissolution or
deposition of Ag as described in the above subsection (2). The
device 30 shown in FIG. 6 is basically characterized by the
provision of an auxiliary cathode that comprises an output terminal
for detecting the potential separately from the aforementioned
cathode available for the input terminal for the current
conduction. More specifically, the device 30 shown in FIG. 6
essentially comprises a solid state electrolyte 31 composed of
Ag.sub.3 SI, an anode 33 composed of an Ag-Te alloy, a cathode
composed of Ag, and an auxiliary cathode 34 composed also of
Ag.
FIG. 7 illustrates a block diagram that describes the basic concept
of the timing apparatus of this invention using an electrochemical
memory device that has such auxiliary cathode 34 as described
above. The cathode 32 of the device 30 is connected to the switch
21 through a variable resistor 22, while the auxiliary cathode 34
is connected to the first stage amplifier 12, and the anode 33 is
connected to the ground. Circuit connections of FIG. 7 are
basically the same as those which are described with reference to
FIGS. 4 and 5, and the same or corresponding portions are
designated by the same or corresponding reference characters.
Operation of the timing apparatus using said memory device that has
an auxiliary electrode will be described in more detail later with
reference to a specific embodiment of such circuit shown in FIG.
10.
Returning to FIG. 6, a more detailed description is given with
respect to an embodiment of the memory device that has the
aforementioned auxiliary electrode. 70 mg and 20 mg of silver
powder of 200 mesh each are weighed out, which are then pressed by
approximately 5 tons/cm.sup.2 pressure generated by metal mold jig
of 70 and 30, respectively, followed by forming into silver pellets
for the main cathode and the auxiliary cathode. The prepared two
silver pellets are then laid over the metal mold jig of 120 so as
not to be in contact with each other, and then 1,000 mg of Ag.sub.3
SI powder of 200 mesh is put upon the metal mold to plane the
surface, and further 200 mg of Ag.sub.2 Te alloy of 200 mesh grain
is put on it, followed by pressing and molding with approximately 2
tons/cm.sup.2 pressure.
FIG. 8 illustrates a graph that indicates the potential holding
characteristic of the device of FIG. 6 in comparison with that of
the device of FIG. 1, and the curve (a) therein shown indicates the
case of FIG. 1 embodiment and the curve (b) therein shown indicates
the case of FIG. 6 embodiment, respectively. The reason why the
characteristic of the device may be improved by practicing the
embodiment of FIG. 6 as mentioned above is that no deposition of Ag
on the auxiliary cathode from the opposite electrode during the
charging period and no dissolution of Ag from the auxiliary cathode
towards the opposite electrode during the discharging period take
place because the auxiliary cathode is not used as a terminal for
current conduction of the device, and consequently, an overvoltage
that might arise at the interface between the electrolyte and the
auxiliary cathode (that is, an overvoltage caused by deposition of
Ag ion onto the metal Ag at the charging cycle as well as an
overvoltage caused by the dissolution of Ag ion into the
electrolyte at the discharging cycle) and the resistive
polarization in the electrolyte are removed from the detected
voltage. By taking the output voltage of this auxiliary cathode,
accurate detection of the electromotive force of the device is thus
possible without being affected by the aforementioned
over-voltage.
Another solution of avoiding the disadvantageous influence by the
overvoltages may be directed to the overvoltage caused by diffusion
of Ag ion into the anode, as mentioned in the previous subsection
(3). It has been found that the charging or discharging by an
increased current fed to the device gives rise to a
disadvantageously increased overvoltage, resulting in more
aggravated degradation of the voltage holding characteristic of the
device. Thus, it is also desired to provide such an electrochemical
potential memory device as satisfactory in the potential holding
characteristic even in case of charging or discharging the device
by a greater current in a shorter period of time.
The following is a description of preferred embodiment for
implementing such an improved voltage holding characteristic. This
embodiment will be hereinafter described as embodied in a device of
such structure as shown in FIG. 6, though this should not be
construed by way of limitation. The inventors knew that the
degradation of said characteristic affected by the above-mentioned
overvoltage was solved by selecting the thickness of anode
comprising three members, namely, Ag-Te alloy, graphite, and solid
state electrolyte, in other words, a fact that the diffusive
migration of the silver ion present in the anode 33 could affect
the aforementioned degradation strongly. They followed up
experiments repeatedly by varying the thickness of the anode 33 in
various way. As a result, they reached a conclusion that the
degradation of said characteristic under the influence of
overvoltage could take place noticeably if the thickness of the
anode 33 exceeds 1 mm as the borderline. The embodiment hereinafter
described utilizes such conclusion thus obtained.
The following describes one of the fabrication examples as regards
the device of such preferred embodiment. 100 mg and 20 mg of silver
powder of 200 mesh each are weighed out and then preliminary
pressing is given to the both lots with pressure of approximately
0.5 ton/cm.sup.2 by means of metal mold jig of 70 and 30,
respectively, so as to form silver pellets available for the
cathode and also for the auxiliary cathode. Then, the
above-mentioned two silver pellets are laid upon a metal mold jig
of 120 so as not to be in contact with each other. Then 500 mg of
Ag.sub.3 SI powder of 200 mesh is put on them to plane the surface.
The 500 mg of anode material comprising a mixture of Ag.sub.2 Te
powder of 200 mesh (as the main), graphite and Ag.sub.3 SI powder
is put onto the abovementioned planed material to plane the surface
thereof, followed by pressing with approximately 2 tons/cm.sup.2
pressure for molding.
FIG. 9 illustrates a graph that indicates the correlation between
the thickness of the anode 33 and the potential holding
characteristic of the device 30 prepared in accordance with the
above-mentioned process. Curve (a) shown in the graph indicates the
characteristic of the device of the embodiment just described and
the curve (b) indicates that of the device described in connection
with FIG. 1. Table 1 indicates the correlation between the
thickness and the weight of the embodiment shown as a parameter in
FIG. 9.
TABLE 1
Weight of anode (mg) 300 450 600 750 900 Thickness of anode (mm)
0.5 0.75 1.0 1.25 1.5
As seen from FIG. 9, when thickness of the anode 33 is reduced to
less than 1 mm, the characteristic of the device is remarkably
improved. One possible reason may be considered as follows. As soon
as the electric current starts to flow through the device, activity
of silver at the anode portion in contact with the solid state
electrolyte starts to change in the first step and then the silver
activity becomes uniform by diffusive migration of the silver ion.
However, in case of a greater current flowing through the device,
stronger influence can be caused by the migrative diffusion, or
diffusive migration, of silver ions because the charging is
completed within a shorter time by the greater current. It is
considered that the distance or width of said migrative diffusion
would be about 1.00 mm. Thus, in accordance with the embodiment
just described, by employment of the anode less than 1 mm in
thickness including an Ag-Te alloy, graphite and a solid state
electrolyte, it is possible to provide electrochemical potential
memory device showing a linear change in the output voltage with
respect to the supplied quantity of electricity wherein even such a
great current as 1 mA per cell only causes an overvoltage less than
one fifth of that of FIG. 1 embodiment, for example. This
considerable improvement in the potential holding characteristic of
such device would apparently be a great contribution to the
applications of such device.
A detailed circuit diagram of a preferred embodiment of the timing
apparatus in accordance with this invention is illustrated in FIG.
10, wherein some blockes constituting this apparatus are
encompassed by dot-dash lines. The embodiment shown in FIG. 10
comprises the timing apparatus 40 that functions to make off-delay
control, i.e., delayed turn-on of the load 48, such as electronic
equipment energized by the source 49, or to turn off such equipment
after a preset period of time. The load 48 is connected to the
source 49 through the main source switch SW5 and a manual-automatic
switch SW1. When the off-delay control of the load 48 is not
desired, in other words, when manual control of energization of the
load 48 is desired, switch SW1 may be turned over to the manual
contact "MAN," thereby allowing the energization of the load 48 to
be controlled by manual opening or closing of the switch SW5 as
desired. When automatic off-delay control of the load 48 is
desired, switch SW1 may be turned over to the "AUTO" contact. The
following is a description of the structure of the timing apparatus
40 and such off-delay control operation thereof.
The timing apparatus 40 of the embodiment shown in FIG. 10
comprises a switching circuit 47 for switching energization of the
timing apparatus 40, a charging/discharging circuit 41 for charging
or discharging the potential memory device 30, an amplifying
circuit 42 for amplifying the terminal potential of the device 30,
a reference voltage source 44 for providing the reference voltage
to make comparison with the output of the amplifying circuit 42, an
indicator circuit 43 for providing visual indication of a time to
be preset and also visual analog indication of the passing state of
the preset time by comparing the output of the aforementioned
amplifying circuit 42 and the reference voltage of the reference
voltage source 44, a control circuit 45 for enabling or disabling a
load switching circuit 46 after the lapse of a preset time, to be
explained later, and power switching circuit 47 for switching
control of the load 48.
The embodiment of FIG. 10 utilizes the charging/discharging circuit
41, a potential memory device 30 that employs such auxiliary
cathode as described with reference to FIGS. 6, 7, 8 and 9, though
this should not be construed by way of limitation. The anode 33 of
the device 30 is connected through the resistor 50 to, and the
cathode 32 is connected through the resistor 52 to and also through
the resistor 53 and the switch SW4 to the positive potential bus
+Vcc. The anode 33 is also connected through the discharge contact
CD of the charging/discharging switch SW3 and the cathode 32 is
also connected through the charge contact CC of the switch SW3 to
the negative potential bus -Vcc. The auxiliary cathode 34 is
connected to the input electrode of a field effect transistor TR11.
The amplifying circuit 42 comprises transistor TR11 and TR12. A
high input impedance transistor, preferably a field effect
transistor is appropriate for the transistor TR11 for the reason
mentioned previously. The reference voltage source 44 comprises a
potential divider comprising resistors 57 and 58. A variable
resistor 59 and an ammeter 14 are connected in series between the
junction E of the output load resistor 55 of the amplifying circuit
42 and the resistor junction F of the reference voltage source 44.
The control circuit 45 comprises transistors TR13 and TR14. The
switching circuit 46 comprises a switching transistor TR15 which is
connected to the load 48 in series and also to the switch SW1 in
parallel. The energization switch circuit 47 comprises a transistor
TR17 which is connected in series with the positive voltage bus
+Vcc and a transistor TR16 which is connected between the input
electrode of the transistor TR17 and the negative voltage bus -Vcc,
and the transistor TR16 is shunted by the switch SW2 which is
provided to start the operation of the timing circuit 40.
FIG. 11 illustrates the relation between the terminal voltage of
the device during the charging and discharging operation of the
potential memory device 30 used in the embodiment illustrated in
FIG. 10 and the charging and discharging operation time. This graph
will be referred to in conjunction with the following description
of the operation of the timing apparatus.
The following is a description as regards the operation of the
timing apparatus 40. The switch SW1 is turned to the "AUTO" contact
position so as to place the timing apparatus in the operating
state. The switch SW5 is kept as being closed. The timing apparatus
is at first so controlled as to drive the device 30 in the charging
condition. For this purpose, the starting switch SW2 is at first
depressed. The source switching transistor TR17 becomes conductive
due to a short circuit formed between the emitter and the collector
of the transistor TR16, thereby energizing or supplying the power
to the timing apparatus 40. Such energizing state is self-held in
an electronic manner in response to the subsequent switching of the
switch SW3 over to the contact CC, the detail of which will be
described later on. For the purpose of setting to the charging
state, the switch SW3 is also depressed to close the charging
contact CC. The device 30 is supplied with the current flowing
through the resistor 50 in a direction of the anode 33 being
positive , in other words, the device 30 is charged. The terminal
voltage of the device 30 varies from the point a to the point b
along the curve illustrated in FIG. 11 in proportion to the
charging quantity of electricity i.sup.. t as supplied to the
device 30. The variation of the potential is detected by the
cathode 34 for driving the transistors TR11 and TR12, resulting in
indication by means of the ammeter 14 of a value that is
proportional to such voltage variation. This ammeter is provided
with the timing scale to indicate the timing operation of the
timing apparatus 40. Accordingly, when the ammeter or the time
meter 14 reaches a voltage indication level corresponding to the
time T.sub.1 (time required to reach the point c from the point b
for discharging) to be preset, depression of the switch SW3 is
released to complete the desired charging, or setting of the
desired time.
In the circuit of the embodiment, resistance of the resistors 56,
55, 57 and 58 is selected so that the potential difference between
the junctions E and F becomes zero volt and so that the needle of
the ammeter 14 can indicate zero and thus the transistor TR13 can
be turned on, when the voltage of the detecting electrode 34 of the
device 30 is 0 (zero). Accordingly, while the starting switch SW2
is depressed with the terminal voltage of the device 30 at OV,
transistors TR13 and TR14 remain on and the transistor TR16 remains
off. It is thus apparent that the opening of the switch SW2 will
turn the transistor TR17 off and discontinue the supply of the
source. Once the time-setting switch SW3 is turned to the charge
contact CC after the starting switch SW2 is closed, the circuit
functions to self-hold the transistor TR17 on, irrespective of the
subsequent opening of the switch SW2. More specifically, the
potential at the junction E becomes higher than that of the
junction F simultaneously with the starting of the charging of the
device 30 to cause the needle of the indicator to move by influence
of the current flow produced by the potential difference between E
and F, and to turn off the transistors TR13 and TR14 in the
switching circuit 45 and also to turn on the transistor TR16, and
consequently, the transistor TR17 remains on even after the circuit
of the starting switch SW2 is opened, and thus power continues to
be supplied to the apparatus 40. The transistor TR15 in the load
control circuit 46 also remains on at the same time and load 48
continues to be supplied with the power. While the time-setting
switch SW3 is kept turned to the charge contact CC after the
starting switch SW2 is closed, the device 30 is charged, and the
negative potential develops at the detecting auxiliary cathode 34
in proportion to the quantity of electricity passing through the
device 30. The said negative potential is fed to the gate of the
transistor TR11. As described above, since the potential at the
junction E rises in proportion to the terminal voltage of the
device 30 as the voltage is amplified by the transistors TR11 and
TR12, the needle of the time indicator 14 comprised of an ammeter
moves in accordance with the current that flows between the
junctions E and F, and accordingly, the charging quantity of
electricity can be selected based on the indication of the
indicator 14, thereby permitting any desired time setting
easily.
It is important in the embodiment of FIG. 10 that the charging
operation for the device 30 is completed within a short time. It is
to be pointed out that for this purpose the resistor 50 has been
selected to be of a negligible value. As the transistor TR13 is
subjected to a reverse bias simultaneously with the start of
charging the device 30, the transistor TR13, and thus the
transistor TR14 are turned off, and accordingly, the transistors
TR15 and TR16 are turned on to set out the load 48 in operation.
However, as the setting of any desired time by means of depressing
the above mentioned switch SW3 is carried out by rapid charging as
described above, which is effected within 10 seconds, preferably
within a period of 3 to 4 seconds, and therefore, the required time
for charging may be negligible as compared with the discharging
time of the device 30.
Now, the following is a description of the discharging operation of
the device 30, in other words, timing operation of the apparatus
40. Simultaneously with the release of the depression of the switch
SW3, the device 30 conducts the current in a direction of the anode
33 being negative through the discharge resistor 52, and the timing
operation begins simultaneously with the starting of the
discharging operation. Through the discharging process, the
potential of the device 30 gradually decreases towards the point c
from the point b along the curve illustrated in FIG. 11 along with
the decrease of the quantity of electricity (i.sup.. t) stored in
the device 30. Accordingly, the needle of the indicator 14 swings
from an indication point T.sub.1 to an indication point 0 in
proportion to the above-mentioned decrease. In such manner, the
needle of the ammeter or of the time indicator 14 moves towards the
0 point of the scale, thereby indicating the passing of time. As
soon as the potential of the device 30 detected by the auxiliary
cathode 34 reaches OV upon completion of the discharging of the
potential memory device 30, the needle of the indicator 14
indicates the completion of the passed time previously set by
returning to the 0 point. At that time, the transistor TR13 turns
on as a function of the forward bias given by the resistor 56, and
accordingly, the transistor TR14 also turns on, so that the
transistor TR15 turns off to discontinue the energization of the
load 48, and likewise, the transistor TR16 also turns off to turn
the transistor TR17 off, and consequently, supply of the electric
power to the apparatus 40 is discontinued.
It is thus understood that the discharging time and thus the delay
operation time of the apparatus 40 may be determined by a value of
the resistor 52. It is desirable that the discharging may be
effected at a relatively slow rate so that the device 30 in the
apparatus 40 may be rapidly charged in order that the preparation
for the timing operation may be quickly completed and also any
desired prolonged timing operation may be provided. In such
understanding, the resistor 50 of a small value and the resistor 52
of a large value have been selected.
The embodiment illustrated in FIG. 10 further provides an
additional means that facilitates resetting of the required timing
rapidly within a shorter period than the timing operation time left
after the lapse of a given time in the course of passing of a given
preset time for the timing operation or for the delaying operation.
It is readily understood that such means is often necessary in the
practical use of the apparatus. If any change is desired as regards
the preset time after the timing once has been set in such manner
as described above by the use of the aforementioned switch SW3, or
in the course of the timing process, such change may be attained by
operating the second operating switch SW4 that is connected to the
discharge resistor 52 in parallel through the resistor 53. More
specifically, if it is desired to change the preset time to a value
T.sub.0 after the lapse of time T' from the start of the timing
operation as based on the initially set time T.sub.1, as shown in
FIG. 11, such a change is attainable by depressing the rapid
discharge switch SW4 to close the circuit of the resistor 53 so as
to effect rapid discharging of the device 30 through the
parallelled resistors 52 and 53 and transfer the terminal voltage
from the point f to point g, and then opening the switch SW4 as
soon as the needle of the indicator reaches a point of the scale
corresponding to the voltage g. Thereafter, the potential of the
device 30 again gradually decreases towards the point h from the
point g as affected by normal discharging, and thus, timing
operation for the newly set time that has been already changed is
effected. It is needless to emphcsize that the aforementioned rapid
discharge switch SW4 may also be used to bring back the preset time
to the desired time rapidly in case the time has been set in excess
of the said desired value.
While specific preferred embodiments of the present invention have
been described, it will be apparent that obvious variations and
modifications of the invention will occur to those of ordinary
skill in the art from a consideration of the foregoing description.
It is, therefore, desired that the present invention be limited
only by the appended claims.
* * * * *