JP2002151063A - Electrode reaction characteristic measurement equipment and method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide electrode reaction characteristic measurement equipment, which can evaluate in high efficiency diversified and a large number of electrode materials by easy control. SOLUTION: In a recessed part 2 of a substrate 1, in which two or more recessed parts 2 containing a sample 3 under evaluation, and consists of material, which has electronic conductivity and does not show ion conductivity, electrolyte dispenser 6, which pours an electrolyte 7, and measurement equipment 16, which has an electrode 17 inserted into each of the recessed parts and measures voltage-current characteristic between the substrate 1 and the electrode 17.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode reaction characteristic measuring apparatus and an electrode capable of efficiently measuring and evaluating the characteristics of various kinds of products synthesized using, for example, a combinatorial technique as an electrode material. The present invention relates to a method for measuring reaction characteristics.

[0002]

2. Description of the Related Art In recent years, with the rapid spread of various portable devices such as portable telephones and portable information terminals, batteries as power sources have become increasingly important. Basically, a battery is composed of an electrolyte in which ions move, and an electrode active material that generates energy by an electrochemical reaction. In order to cope with an increase in power consumption due to multifunctionalization, electrode active materials having higher functions with higher energy density are being vigorously developed in various fields.

[0003] As a main power supply for portable equipment at present, lithium ion batteries have been widely used. LiCoO ₂ is currently used as a positive electrode active material for lithium ion batteries.
LiNiO ₂ is expected as an active material having a higher capacity, and LiMn ₂ O ₄ is expected as an active material having a lower cost and excellent thermal stability as a next-generation positive electrode active material. I have. However, there are still problems to be solved when these materials are used as a positive electrode active material, and they have not been put to practical use.

Here, among the above substances, LiNiO₂of
One of the challenges in use is thermal stability. sand
That is, with charging, LiNiO₂From lithium ion
Desorbed, Li1-xNiO₂Of nickel-nickel
Part of the ON state is in a +4 valence electronic state. Nickel ion
+4 is a very unstable valence, increasing the temperature
When the nickel ion becomes stable +2 state,
Li1-xNiO ₂Desorbs oxygen. This
The resulting oxygen is in a very active state
Reacts with the organic solvents used in the electrolyte,
In such a case, the possibility of firing the battery cannot be denied.

Moreover, LiMn ₂ O ₄ is, Mn 3 ₊ ions Ya - down Terra - ions distortion is likely to occur in the crystal in order to be, it has been reported poor result charge-discharge cycle life.

In order to solve these problems, LiNi
In O ₂ , part of Ni 3+ for improving high temperature stability is replaced with C
Consideration has been given to replacement with a replacement element such as o3 +.
Also, for LiMn ₂ O ₄ , a part of Mn 3+ was replaced with Cr.
By replacing with various cations such as 3+, Yan Terra
Attempts have been made to eliminate distortion and improve charge / discharge cycle characteristics.

As mentioned above, the importance of substitution elements in the recent development of lithium ion batteries has been described. In nickel / metal hydride batteries, part of nickel of nickel hydroxide, which is a positive electrode active material, is replaced by cobalt or zinc. The charging efficiency has been improved by substituting or adding calcium fluoride or ytterbium.In lead-acid batteries, the improvement of the life performance by adding various elements to the alloy lattice used for the electrodes has been studied. I have.

Conventionally, evaluation of electrode materials such as an electrode active material and a current collector, which are the constituent materials of these electrodes, has been performed by the following method.

First, the synthesized electrode material is mixed with a binder such as polytetrafluoroethylene, polyvinylidene fluoride, or synthetic rubber, and molded into a sheet, or coated on a metal foil or porous. An electrode is manufactured by embedding in a metal body. An electrode (for example, a metal lithium foil in the case of a lithium battery) serving as a counter electrode for measurement and a battery (for example, a battery case) via a separator (a porous film or a woven or non-woven fabric of resin fibers). After being put inside, an electrolyte is injected and the whole is sealed to prepare a battery for measurement. Using this battery for measurement, polarization characteristics, charge / discharge characteristics,
Electrochemical characteristics such as impedance measurement are evaluated.

[0010]

However, when searching for such a substitution element or an additional element, it is necessary to add various elements in various ratios. However, the method of examining the electrode characteristics not only requires enormous time to reach the target substance material, but also may be extremely unlikely to lead to accidental discoveries beyond intuition and experience. . That is, a key point in searching for a new electrode material is how to synthesize and evaluate various combinations of various kinds of raw materials while systematically controlling them.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides an electrode reaction characteristic measuring apparatus and a method thereof capable of evaluating various electrode materials with high efficiency by easy control. The purpose is to do so.

[0012]

According to a first main aspect of the present invention, there is provided an electrode reaction characteristic measuring apparatus for measuring an electrode reaction characteristic of a sample, the apparatus holding the sample. A substrate having a plurality of recesses, and an electrolyte supply means for supplying an electrolyte into the recesses of the substrate holding the sample,
An electrode reaction characteristic measuring device for measuring an electrode reaction characteristic of the sample in the concave portion.

According to such a configuration, for example, the electrode reaction characteristics of a large number of various samples synthesized by the combinatorial method can be evaluated at once with high efficiency.

According to one embodiment of the present invention, the substrate has a plurality of recesses for holding a sample, and is made of a material having electron conductivity and not exhibiting ion conductivity, for example, platinum,
It is made of either gold or carbon.

According to such a configuration, the synthesis of the sample itself can be performed using the substrate.

According to a different embodiment, the apparatus further comprises electrolyte dispensing means and degassing means for degassing the substrate after injecting the electrolyte into the recess of the substrate.

According to such a configuration, air bubbles and the like remaining in the sample after the injection of the electrolyte can be removed, and a good electrochemical reaction interface can be formed at the interface between the sample and the electrolyte.

According to a further different embodiment, the device comprises a plurality of electrodes.

According to such a configuration, a plurality of samples can be evaluated at the same time, and the evaluation can be performed with higher efficiency.

According to still another embodiment, the electrode reaction characteristic measuring device includes either or both of the electrode moving means and the substrate moving means.

According to such a configuration, by moving the electrode and the substrate relatively, a large number of various samples synthesized by, for example, a combinatorial method can be evaluated with high efficiency.

According to another embodiment, a solution or a slurry containing an element for synthesizing the sample is injected into the recess, and the substrate is cooled to a synthesis temperature of the sample to be measured. Is synthesized by heating.

According to such a configuration, a sample excellent in electrical bonding with the substrate can be obtained by using a solution or slurry as a starting material, and a highly accurate electrode reaction evaluation can be performed.

According to still another embodiment, the electrode comprises an electrode body made of a substance which causes an electrochemical oxidation-reduction reaction in an electrolyte used for evaluation, and a container accommodating the electrode body and the electrolyte. And a part of the container is made of an insulating porous material.

According to such a configuration, it is possible to obtain an electrode having no electronic short circuit with the sample or the substrate.

According to a further different embodiment, the electrode serves as a reference electrode during measurement,
An electrode having an electrode body acting as a counter electrode is used.

According to such a configuration, a three-electrode measurement can be performed, a measurement without polarization on the electrode side can be performed, and the degree of freedom in selecting an electrode material is increased.

According to a second main aspect of the present invention, there is provided an electrode reaction characteristic measuring method for measuring an electrode reaction characteristic of a sample, comprising: a plurality of recesses for holding the sample; And a substrate supply step of supplying a substrate made of a material having no ion conductivity; a sample synthesis step of synthesizing a sample in a concave portion of the substrate; an electrolyte supply step of supplying an electrolyte into the concave portion; An electrode reaction characteristic measuring step of measuring an electrode reaction characteristic of a sample in the concave portion by inserting an electrode into the electrode and measuring a voltage-current characteristic between the substrate and the electrode. A measuring method is provided.

According to such a method, there is provided an electrode reaction characteristic measuring method capable of evaluating the electrode reaction characteristics of various electrode materials with high efficiency by easy control.

The other features and remarkable effects of the present invention will be clearly understood by those skilled in the art by referring to the following embodiments of the present invention and the accompanying drawings.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below with reference to the drawings.

(Basic Configuration) First, the basic configuration of this embodiment will be described with reference to FIG. In addition, S1 in each figure
What is indicated by S4 corresponds to the step numbers (steps S1 to S4) referred to below.

FIG. 1 is a diagram for explaining the outline of the measurement procedure according to this embodiment.

As shown in this figure, this procedure is roughly divided into a sample synthesizing step (step S1) for synthesizing a sample to be evaluated by a combinatorial method, and an electrolyte dispensing step for supplying an electrolyte onto each of the samples. (Step S2), a degassing step for degassing the electrolytic solution (Step S3), and a measurement / evaluation step (Step S4) for measuring and evaluating the electrode reaction characteristics of each sample.

In step S1, as shown in FIG. 2, a plurality of types of samples 3 to be evaluated are simultaneously synthesized using the substrate 1 having a large number of concave portions 2 on the upper surface. This method is called a combinatorial method, in which various starting materials for synthesizing the sample to be evaluated 3 are supplied at different mixing ratios for each of the concave portions 2, and the entire substrate 1 is heated in a heating furnace 5. Thus, many kinds of samples 3 are synthesized at the same time. In addition,
As will be described in detail later, the substrate 1 is integrally formed of an electron conductive material and a material having no ion conductivity. In this embodiment, a substrate formed of platinum is used.

In step S 2, as shown in FIG. 3, the dispensing device 6 dispenses the electrolyte 7 into each recess 2 of the substrate 1 by using, for example, a dispensing nozzle 8. At this time, it is important that the dispensed amount is optimized so that the electrolytes 7 filled in the recesses 2 do not contact each other.

In step S3, the atmosphere around the substrate 1 is reduced by the deaerator 12 shown in FIG. 4 so that the electrolyte 7 is sufficiently impregnated between the particles constituting the sample 3 to be evaluated. Degas. As a result, the minute gas between the particles of the sample 3 expands and appears, and is drawn out into the electrolyte 7 and degassed.

In step S4, the measuring device 1 shown in FIG.
6 in each recess 2 filled with the electrolyte 7 in FIG.
By inserting an electrode indicated by a symbol, a voltage-current characteristic between the substrate 1 and the electrolyte 7 is measured by a voltage-current characteristic measuring device 19, and a computer 22 evaluates an electrode reaction characteristic of the sample 3 to be evaluated. . Here, since the substrate 1 is formed from an electronic conductive material, the sample 3 to be evaluated and the electrode 1
It is possible to measure the voltage between 7 and the current flowing between them. Further, since the substrate 1 is made of a material having no ion conductivity, no ion conductivity occurs between the concave portions 2. Therefore, the electrochemical cell is independently formed by the concave portions 2 and the electrodes 17, and does not cause interference.

According to such an embodiment, the electrode reaction characteristics of each of the plurality of samples 3 can be independently evaluated, and the characteristics of each of the samples 3 as electrodes can be effectively examined.

Hereinafter, the above components will be described in more detail.

(Substrate) First, as shown in FIG. 6, the substrate 1 has a large number of concave portions 2 on the upper surface in order to hold the sample 3 to be evaluated. Further, the substrate 1 has electronic conductivity,
It is made of a material that does not exhibit an electrochemical reaction in the measurement potential range. Further, it is preferable to use a material having no ion conductivity as a material of the substrate 1.

For example, when a potential region of 4 V is evaluated on the basis of a lithium electrode, a passive layer is formed on the surface of an electrochemically inactive material such as platinum or carbon material or aluminum or the like, and an electrochemical reaction occurs. Metal materials not shown can be used. On the other hand, when evaluating the intercalation of lithium ions into carbon, copper or stainless steel can be used.

When a noble metal material such as platinum is used for the substrate 1, a plurality of samples 3 can be simultaneously synthesized as in this embodiment, and the synthesized samples 3 can be simultaneously measured. That is, the synthesized various samples 3 are
It is possible to apply the electrode reaction evaluation process (steps S2 to S4) and evaluate without removing the sample from the sample, so that the evaluation efficiency for a large number of samples 3 can be increased. For this reason, as a material of the substrate 1, a noble metal capable of responding to the synthesis of various materials, that is, platinum, gold, or the like is preferably used. When the synthesis of the sample 3 is performed in a deoxygenated atmosphere, a carbon material is used. It is also possible.

When a material having no ion conductivity is used as the material of the substrate 1, when a material having ion conductivity is used, an ionic current flows between the concave portions 2 via the substrate 1, and a common This is because the electrode reaction characteristics of each sample 3 cannot be independently evaluated due to the electrolyte effect.

However, for example, when aluminum described above is alloyed with lithium or when lithium ions are intercalated into a carbon material, ion conductivity occurs. However, the potential range in which aluminum forms an alloy with lithium is 0.4 V or less based on the lithium-lithium electrode, and when evaluating electrode reaction characteristics in a potential range noble than this potential, aluminum exhibits ionic conductivity. There is no problem to act as no material. Similarly, the carbon material also functions as a material that does not exhibit ionic conductivity in a range noble than the potential range in which lithium ions intercalate. In other words, even if the substance has a possibility of exhibiting ionic conductivity, a substance which does not exhibit ionic conductivity at the time of measurement can be used as the material of the substrate 1.

In order to prevent the electrolytes 7 injected into the respective recesses 2 from coming into contact with each other, as shown in FIG. 6B, partition walls separating the respective recesses 2 are provided on each substrate 1 ′. 4 may be provided. In order to further increase the electrical contact between the sample 3 to be evaluated and the substrates 1 and 1 ', it is preferable to roughen the inner surface of the concave portion 2.

(Sample Synthesizing Step) In the sample synthesizing step (step S 1) using the substrate 1, as shown in FIG. 2, a starting material is put into the concave portion 2 of the substrate 1 and heated by the heating furnace 5. Done in As the starting material, a mixture of the starting material solid powder, a slurry in which the starting material solid fine powder is dispersed in a liquid, or a desired sample 3
A solution containing an element for synthesizing the compound can be used. In particular, when a slurry or a solution is used as a starting material, the sample 3 to be evaluated can be obtained in a state where the sample 3 is particularly densely sintered in the concave portion 2. As a result, the evaluated sample 3
The electrical contact between the particles in the sample and the sample 3 to be evaluated and the substrate 1 can be increased, and the electrode reaction characteristics can be more accurately evaluated. Therefore, when synthesizing the sample 3 to be evaluated in the concave portion 2, it is preferable to use a slurry or a solution as a starting material.

Here, for example, when examining the effect of an additive element on LiCoO ₂ , a slurry-like aqueous solution of cobalt oxide or an aqueous solution of cobalt acetate contains an aqueous solution of lithium hydroxide and further contains various additive elements. The aqueous solution or slurry is mixed at various ratios, and the mixture is injected into the recess 2. Then, after removing and drying the water at 100 to 200 ° C., and heating at 600 to 900 ° C., the LiCoO ₂ sintered body containing various additive elements in the concave portion 2 at various ratios (sample 3 to be evaluated) ) Can be obtained.

(Electrolyte Dispensing Step) In the dispensing step of the electrolyte 7 (step S2), as shown in FIG. 3, the dispensing device 6 moves the dispensing nozzle 8 to the substrate 1 in the XY directions. It is performed by relatively and intermittently moving. The dispensing nozzle 8 is positioned to face each of the recesses 2 by being driven by a dispensing nozzle driving mechanism indicated by 9 in FIG. The dispensing nozzle 8 is connected to an electrolyte supply mechanism 10 so that a predetermined amount of the electrolyte 7 can be sequentially injected into each recess 2. At this time, even if the electrode 17 is inserted into the recess 2 in a later step, the amount of each electrolyte 7 is
Optimized to not overflow from

The dispensing nozzle 8 may be singular or plural. The number of dispensing nozzles 8 is
The number may be the same as the number. Further, the substrate 1 may be driven, or the nozzle 8 may be driven. Alternatively, both of them may be driven.

(Deaeration Step) This deaeration step (Step S)
3) is performed using, for example, a deaerator 12 as shown in FIG. The deaerator 12 includes a bell jar 14 that hermetically covers the substrate 1, and a vacuum pump 15 that reduces the pressure inside the bell jar 14.

After supplying the substrate 1 in which the electrolyte 7 is dispensed into each of the concave portions 2 into the deaerator 12,
The substrate 1 is covered with the bell jar 14. By operating the vacuum pump 15 for a predetermined time, the reduced pressure state in the bell jar 14 is maintained for a certain time. With this,
The gas between the particles of the sample 3 is degassed.

The deaerator 12 is provided with the electrolyte 7
May be integrated with the dispensing device 6. In this case, there is no need to transfer the substrate 1.

(Evaluation step) Measuring device 16 for performing this measurement
As shown in FIG. 5, for example, the electrode 17, an electrode driving mechanism 18 for driving the electrode 17,
And a voltage-current characteristic measuring device 19 connected to the electrode 17 via signal lines 20 and 21 for measuring the voltage-current characteristic of the sample 3 to be evaluated, and a result measured by the voltage-current characteristic measuring device 19. It consists of a computer 22 for evaluating and displaying.

The number of the electrodes 17 may be singular or plural, and may be the same as the number of the concave portions 2. In an electrode reaction characteristic measuring device having a single electrode 17, a single electrode 17 is inserted into each concave portion 2 sequentially, and the electrode reaction characteristics of each sample 3 are sequentially measured and evaluated. Alternatively, when a plurality of electrodes 17 are provided, the electrodes 17 can be simultaneously inserted into each of the recesses 2 and the sample 3 to be evaluated in the plurality of recesses 2 can be simultaneously measured and evaluated. Further, a group of the plurality of recesses 2 provided on the substrate 1 may be evaluated at the same time, and by repeating the evaluation, all the samples 3 in the recesses 2 may be evaluated. When a plurality of electrodes 17 are provided, the arrangement of the plurality of electrodes 17 is adjusted so that each electrode 17 is inserted into each recess 2.
Is desirably the same as the arrangement. In addition, in order to make the electrode 17 face each concave portion 2, only the electrode 17 or only the substrate 1 may be driven, or both may be driven.

Next, the configuration of the electrode 17 will be described.

FIG. 7 shows a detailed configuration of the electrode 17. The electrode 17 includes a container 26 holding an electrolyte 25 and an electrode body 24 immersed in the electrolyte 25 in the container 26. With such a configuration, the electrode body 24 and the electrolyte (7, 2) are compared with a case where the electrode body 24 is directly immersed in the electrolyte 7 injected into the concave portion 2.
5) The contact area can be increased. as a result,
The polarization of the electrode body 24 can be reduced when the electrode reaction characteristics of the sample 3 are evaluated, and the change in the surface state of the electrode body 24 due to the current flowing during the measurement can be reduced. Thereby, the electrode reaction characteristics of the sample 3 to be evaluated can be more accurately evaluated. It is preferable that the container 26 holding the electrolyte 25 be made of an insulating material so that no current flows in contact with the substrate 1 or the sample 3 to be evaluated. Here, the electrode body 24 indicates a portion where an electrochemical reaction occurs on the surface thereof.

Further, the electrode 17 has an ion conductive layer 27 having ion conductivity at the bottom of the container 26. By providing such an ion conductive layer 27, it is possible to eliminate the possibility that the electrode body 24 and the sample 3 to be evaluated are electrically short-circuited. As the ion conductive layer 27, for example, an electronic insulating material such as porous glass or a porous resin film can be used. By using these, the electrolyte 7 penetrates into the pores and exhibits ion conductivity.

The electrode 17 may be constituted by an electrode body 24 which also serves as a reference electrode and a counter electrode as shown in FIG. 7 (a bipolar electrode 17). Alternatively, as shown in FIG. It is also possible to adopt a configuration in which the body 31 and the electrode body 32 acting as a counter electrode are combined (a three-electrode 17 ′). When the electrode 17 shown in FIG. 7 is used, only the bipolar electrochemical measurement is possible, and the electrode 1 shown in FIG.
When 7 'is used, a three-electrode electrochemical measurement can also be performed. When the electrode 17 shown in FIG. 7 is used, the configuration of the electrode can be simplified. When the electrode 17 'shown in FIG. 8 is used, an evaluation result without the influence of polarization can be obtained, and the reference electrode and the counter electrode can be selected from various materials.

In the electrode 17 shown in FIG. 7, the electrode body 24 which also serves as a reference electrode and a counter electrode is made of a material appropriately selected according to the sample 3 to be evaluated or the electrolytes 7 and 25 to be used. Since the electrode body 24 also serves as a reference electrode, a material that has a small change in potential even when an electrode reaction occurs is preferable.

When an electrode material for a lithium battery is used as the sample 3 to be evaluated, metallic lithium, a metal such as aluminum, indium or silicon alloyed with lithium or lithium such as Li ₄ Ti ₅ O ₁₂ is used. It is preferable to use an intercalation material having a small change in potential in the ion intercalation / deintercalation reaction.

When an electrode material of an alkaline electrolyte battery such as a nickel-cadmium battery, a nickel-metal hydride battery, or an alkaline storage battery is used as the sample 3 to be evaluated, a metal such as silver or mercury, or a metal such as silver or mercury is used. Mixtures of chlorides of these metals are preferably used.

Further, in the electrode 17 'shown in FIG. 8, the electrode body 31 acting as a reference electrode is made of an aqueous electrolyte such as an alkaline electrolyte in addition to the material used for the electrode body 24 shown in FIG. Alternatively, a platinum electrode having platinum black formed on the surface may be used, and a hydrogen electrode through which hydrogen gas is passed around the platinum wire may be used.

On the other hand, as a material for the electrode body 32 acting as a counter electrode, in addition to the material used for the electrode body 24 in FIG.
-xCoO ₂ , Li1-xNiO ₂ , Li1-xMn ₂ O
₄ , LixV ₂ O ₅ , LixTiS _{2 and} other lithium intercalation materials can also be used. When evaluating an electrode material for a battery using an aqueous electrolyte, a metal such as zinc, or an oxyhydroxide or hydroxide of nickel or manganese can be used.
Further, even when an electrochemically inactive material such as a platinum foil or a carbon rod is used, an electric current can be flowed by an electrochemical decomposition reaction of the electrolyte, and these materials can also be used.

When the material of the electrode bodies 24, 31, 32 is a metal foil or a metal wire, the lead wires 28, 33, 34
Can be directly connected using welding or a conductive adhesive. On the other hand, when the material of the electrode bodies 24, 31, and 32 is a powder, the lead wire 2 is made of resin or the like.
8, 33 or 34, or may be mixed with a resin or the like and then embedded in a metal mesh or the like, and this metal mesh may be welded to the lead wires 28, 33, 34.

The electrolytes 7 and 25 are appropriately selected according to the sample 3 to be evaluated, and may be the same or different.

When the sample 3 to be evaluated is an electrode material for a lithium battery, the electrolytes 7 and 25 are each prepared by dissolving a lithium salt in an organic solvent. As the organic solvent, ethylene carbonate, propylene carbonate,
Diethyl ether, 1,2-dimethoxyethane, dimethyl sulfoxide, 1,3-dioxolan, 2-methyltetrahydrofuran, γ-butyrolactone, and the like are used, and lithium salts include LiOlO ₄ , LiBF ₄ , and LiP.
F ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (CF
₃ SO ₂ ) ₂ or the like can be used.

When the sample 3 to be evaluated is an alkaline electrolyte electrode material, an aqueous solution of potassium hydroxide, sodium hydroxide or the like is used.

Next, a measuring instrument 1 for measuring voltage-current characteristics
9 will be described.

The measuring device 19 is for performing an electrochemical measurement on the sample 3 to be evaluated, and can use a potentiostat, a galvanostat, an electrometer, a charge / discharge device, and an impedance measuring device. It is also possible to combine these as needed. By using these measuring means and using a potentiostatic electrolysis method, a galvanostatic electrolysis method, a pulse electrolysis method, a potential sweep method, an AC impedance method, or the like, the potential, polarization characteristics, current or voltage transients of the sample 3 to be evaluated, Electrode characteristics such as charge / discharge characteristics and impedance characteristics can be evaluated.

As means for measuring the voltage-current characteristics, the function of connecting the sample 3 to be evaluated (substrate 1) to the sample 3 to be evaluated (substrate 1) in the present invention is a state in which the sample 3 to be evaluated is all electronically short-circuited. It is preferable that the pole terminal side be grounded.

FIG. 9 shows a voltage-voltage in one embodiment of the present invention.
The multi-channel potentiostat used as the measuring instrument 19 for measuring current characteristics is shown. One input terminal of the operational amplifier 37 is connected to a working electrode terminal 39 via a potential setting power supply 38, and this input terminal is connected to a working electrode terminal 39 via a current detecting resistor 40.
9 is connected to a signal line 20 from the substrate 1. The input terminal of the operational amplifier 37 is grounded 41. On the other hand, the other input terminal of the operational amplifier 37 is connected to the reference electrode terminal 42, and the output terminal of the operational amplifier 37 is connected to the counter electrode terminal 43. When performing a two-electrode electrochemical measurement, the reference electrode terminal 42 and the counter electrode terminal 43 are connected to the electrode body 24 in the electrode 17 described above. When performing a three-electrode electrochemical measurement, the electrode 1 described above is connected to the reference electrode terminal 42.
7 ', the counter electrode terminal 43 is connected to the electrode body 31 acting as a reference electrode, and the counter electrode terminal 43 is connected to the electrode body 32 acting as a counter electrode. When the electrode reaction characteristic measuring device of this embodiment includes a plurality of electrodes 17, a plurality of samples 3 to be evaluated are measured simultaneously by using a multi-channel potentiostat including a plurality of circuits. In this case, there is no interference between the channels, and an accurate measurement result can be obtained.

Although the multi-channel potentiostat has been described as the measuring instrument 19 for measuring the voltage-current characteristic, the working electrode is similarly grounded when a means for measuring the voltage-current characteristic such as a galvanostat is used. Is preferred. However, in the charging / discharging device, although the term of the working electrode is not used, it is preferable that the terminal connecting the sample 3 to be evaluated (substrate 1) is grounded.

Further, as shown in FIG. 5, the measured value measured by the voltage-current characteristic measuring device 19 is evaluated by the computer 22, and the result is displayed.

(Other Embodiments) The present invention is not limited to the above embodiments, but can be variously modified without changing the gist of the invention.

For example, in the above embodiment, an example in which the sample 3 to be evaluated is synthesized in the concave portion 2 of the substrate 1 and the electrode characteristics are evaluated has been described, but the present invention is not limited to this. When evaluating only the electrode characteristics without combining the sample 3 to be evaluated in the recess 2 of the substrate 1, the sample 3 to be evaluated may be inserted into the recess 2 of the substrate 1. Further, in order to prevent the sample 3 to be evaluated from dissipating into the electrolyte 7, the sample 3 to be evaluated may be mixed with a binder such as a fluororesin or a synthetic rubber. In order to improve the electrical connection, a conductive material may be mixed. Further, the sample 3 to be evaluated may be bonded with a conductive adhesive or the like having both a binding action and a conductive action. Further, a solid polymer electrolyte can be used as having both a binding action and an ion conduction action.

Further, in order to improve the bonding property between the sample 3 to be evaluated and the substrate 1 and to improve the moldability of the sample 3 to be evaluated and to prevent the sample 3 from being dissipated, the sample 3 to be evaluated is
May be pressed by a method such as a uniaxial pressing method.

Further, the electrode 17 may be pressed against the sample 3 to be evaluated to prevent the sample 3 from being dissipated. More preferably, after arranging the porous film 44 on the sample 3 to be evaluated as shown in FIG.
According to this method, the porous film 44 prevents the sample 3 to be evaluated from dissipating, and when sequentially evaluating a plurality of samples 3 to be evaluated with the same electrode 17, the sample 3 to be evaluated adheres to the electrode 17 and becomes an impurity. It can be prevented from being mixed into another sample 3 to be evaluated.

[0079]

As described above, according to the present invention, it is possible to provide an electrode reaction characteristic measuring device and a method thereof capable of evaluating various electrode materials with high efficiency by easy control.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a procedure for measuring an electrode reaction characteristic by an electrode reaction characteristic measuring apparatus according to an embodiment of the present invention.

FIG. 2 is a schematic configuration diagram showing a heating furnace for synthesizing a sample.

FIG. 3 is a schematic configuration diagram showing a dispensing device for dispensing an electrolyte.

FIG. 4 is a schematic configuration diagram showing a deaerator for performing deaeration.

FIG. 5 is a schematic configuration diagram showing a measurement device for measuring electrode reaction characteristics.

FIG. 6 is a perspective view showing a substrate.

FIG. 7 is a schematic configuration diagram showing a bipolar electrode.

FIG. 8 is a schematic configuration diagram showing a three-electrode electrode.

FIG. 9 is a diagram showing a circuit example of a potentiostat as a voltage-current characteristic measuring device.

FIG. 10 is a schematic configuration diagram showing an example in which a porous film is arranged on a sample to be evaluated.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Concave part 3 ... Sample to be evaluated 4 ... Partition wall 5 ... Heating furnace 6 ... Dispensing device 7 ... Electrolyte 8 ... Dispensing nozzle 10 ... Electrolyte supply mechanism 12 ... Degassing device 14 ... Bell jar 15 ... Vacuum pump 16 ... Voltage-current characteristics measuring device 17: two-electrode 17 ': three-electrode 18: electrode drive mechanism 19: current characteristic measuring device 20, 21, signal line 22: computer 24: electrode body 25: electrolyte 26: container 27 ... Ion conductive layer 28, 33 ... Lead wire 31 ... Electrode body acting as a reference electrode 32 ... Electrode body acting as a counter electrode 35 ... Electrode terminal 36 ... Electrode terminal 37 ... Operational amplifier 38 ... Potential setting power supply 39 ... Working extreme Element 40: resistance 41: ground 42: reference electrode terminal 43: counter electrode terminal

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ikuo Yanase 1-1, Namiki, Tsukuba, Ibaraki Pref., Japan Science and Technology Agency (72) Inventor Kazunori Takada 1-1-1, Namiki, Tsukuba, Ibaraki Pref. (72) Inventor Takuo Otaki 1-24-24 Nishi-Shimbashi, Minato-ku, Tokyo Nissan Industrial Co., Ltd. F-term (reference) 5H050 AA19 BA17 CA08 CA09 GA28

Claims (23)

[Claims] 1. An electrode reaction characteristic measuring device for measuring an electrode reaction characteristic of a sample, comprising: a substrate having a plurality of recesses for holding a sample; an electrolyte supply means for supplying an electrolyte into the recesses of the substrate; An electrode reaction characteristic measuring device for measuring an electrode reaction characteristic of the sample in the concave portion. 2. The electrode reaction characteristic measuring device according to claim 1, wherein the substrate is made of a material having electronic conductivity and not exhibiting ionic conductivity. 3. The electrode reaction characteristic measuring device according to claim 2, wherein the substrate is made of any one of platinum, gold, and carbon. 4. The electrode reaction characteristic measuring device according to claim 1, wherein the substrate has a partition partitioning between the concave portions. 5. The apparatus according to claim 1, wherein the electrolyte supply means comprises: an electrolyte dispensing means for dispensing an electrolyte into a concave portion of the substrate holding the sample; and an electrolyte injecting the electrolyte into the concave portion of the substrate. And a degassing means for degassing the substrate after decomposing the substrate. 6. The electrode reaction characteristic measuring device according to claim 1, wherein the sample is synthesized in a concave portion of the substrate. 7. The apparatus according to claim 6, wherein a solution or a slurry containing an element for synthesizing the sample is dispensed into the recess, and the substrate is heated to a predetermined synthesis temperature. An electrode reaction characteristic measuring device characterized by being synthesized by: 8. The apparatus according to claim 1, wherein the electrode reaction characteristic measuring means inserts an electrode into each concave portion of the substrate, and measures a voltage-current characteristic between the substrate and the electrode, thereby measuring the sample. An electrode reaction characteristic measuring apparatus for measuring the electrode reaction characteristic of the electrode. 9. An apparatus according to claim 1, wherein said electrode reaction characteristic measuring means comprises a plurality of said electrodes. 10. The electrode reaction characteristic measuring device according to claim 1, wherein said electrode reaction characteristic evaluation means includes one or both of an electrode moving means and a substrate moving means. apparatus. 11. The device according to claim 1, wherein the electrode comprises: a container for holding an electrolyte; and an electrode body made of a substance which is immersed in the electrolyte in the container and causes an electrochemical redox reaction. An electrode reaction characteristic measuring device, wherein a part of the container is made of an insulating porous material. 12. The device according to claim 11, wherein the electrode body comprises a first electrode body acting as a reference electrode when measuring the characteristics of the sample, and a second electrode body acting as a counter electrode. An electrode reaction characteristic measuring device, characterized in that: 13. An electrode reaction characteristic measuring method for measuring an electrode reaction characteristic of a sample, comprising: a material having a plurality of recesses for holding the sample, having electron conductivity and not exhibiting ionic conductivity. A substrate supplying step of supplying a substrate, a sample synthesizing step of synthesizing a sample in a concave portion of the substrate, an electrolyte supplying step of supplying an electrolyte into the concave portion, inserting an electrode into each concave portion, and An electrode reaction characteristic measuring step of measuring an electrode reaction characteristic of the sample in the concave portion by measuring a voltage-current characteristic between the electrodes. 14. The method according to claim 13, further comprising a degassing step of degassing the substrate after the electrolyte supply step. 15. The method according to claim 13, wherein in the substrate supplying step, the substrate is made of any one of platinum, gold, and carbon. 16. The method according to claim 13, wherein the sample synthesizing step is to synthesize the sample in a concave portion of the substrate. 17. The method according to claim 16, wherein a solution or a slurry containing an element for synthesizing the sample is injected into the recess, and the substrate is brought to a synthesis temperature of the sample to be measured. A method for measuring electrode reaction characteristics, characterized in that the electrode reaction characteristics are synthesized by heating. 18. The method according to claim 13, wherein the electrode reaction characteristic measuring step comprises: inserting an electrode into each concave portion of the substrate, and measuring a voltage-current characteristic between the substrate and the electrode. A method for measuring electrode reaction characteristics, characterized in that the electrode reaction characteristics are measured. 19. The method according to claim 13, wherein the step of measuring the electrode reaction characteristics comprises performing the measurement using a plurality of electrodes. 20. The method according to claim 13, wherein the electrode reaction characteristic evaluation step comprises inserting the electrode into the plurality of recesses sequentially by relatively moving the electrode and the substrate. A method for measuring electrode reaction characteristics, comprising: 21. The method according to claim 19, further comprising a driving unit for relatively inserting the electrode into the plurality of recesses by relatively moving the electrode and the substrate. Electrode reaction characteristics measurement method. 22. The method according to claim 19, wherein the electrode comprises: a container for holding an electrolyte; and an electrode body made of a substance which is immersed in the electrolyte in the container and causes an electrochemical redox reaction. A method for measuring electrode reaction characteristics, wherein a part of the container is made of a porous material. 23. The method according to claim 19, wherein the electrode body is composed of a first electrode body acting as a reference electrode and a second electrode body acting as a counter electrode when measuring the characteristics of the sample. A method for measuring electrode reaction characteristics, characterized in that: