JP2020153733A - Automatic electrochemical measuring system and automatic measurement method of electrochemical property - Google Patents

Abstract

To provide an automatic electrochemical measuring system for measuring simultaneously, electrochemical property of a test solution being formed of two or more mother liquids in a limited space, and an automatic measurement method for automatically measuring simultaneously, the electrochemical property thereof.SOLUTION: A system of the invention comprises: a plate stacker on which a mother liquid plate and an evaluation plate are installed; transport means for transporting them; dispensation means for extracting a mother liquid from the mother liquid plate, and then preparing a test solution on the evaluation plate; a measurement stage on which the evaluation plate is mounted; an electrochemical measuring device for measuring simultaneously, an electrochemical property; and control means for controlling operations of other parts. The control means controls the operation of the dispensation means so that the dispensation means performs as basic operations, extraction of a fixed amount v of the mother liquid from a well of the mother liquid plate, and dispensation of the mother liquid plate to a well of the evaluation plate, repeatedly for all mother liquids stored in the mother liquid plate, and adjusts the test liquid to a number of evaluation plates, the number being corresponding to an integer part n of a solution obtained by dividing a capacity V of the mother liquid by a fixed amount v, for each mother liquid plate.SELECTED DRAWING: Figure 1

Description

The present invention relates to an automatic electrochemical measurement system that simultaneously measures the electrochemical characteristics of a plurality of test solutions, and a method that automatically measures the electrochemical characteristics of a plurality of test solutions at the same time. This application incorporates all the contents described in Japanese Patent Application No. 2018-58785, which is a Japanese patent application filed on March 26, 2018.

An automation system using a microplate having a plurality of wells containing a plurality of types of samples in which a plurality of mother liquors are mixed at different ratios is known in the field of biotechnology (see, for example, Patent Documents 1 to 4). ). This system is a screening system that has been established on the premise that an optical measurement system that optically measures a plurality of types of samples is adopted as a detection system.

Many trials and errors are required when searching for electrolytes (compositions, additives) for new applications. However, the conventional electrolyte search relies on experience, and there is a demand for tacit knowledge algorithms based on that experience.

For this algorithmization, a large data group that is the basis of the algorithmization is required. However, a high-throughput electrochemical measurement system for acquiring such a large data group has not existed in the past.

Since the system described in Patent Documents 1 to 4 described above is based on the premise that an optical measurement system for optically measuring a plurality of types of samples is adopted as a detection system, it is necessary to measure the electrical characteristics of the electrolytic solution. I have a problem that I can't do it. It is desired to develop a more compact and high-throughput electrochemical measurement system in a limited space, and further, a high-throughput electrochemical measurement system capable of long-term operation.

Japanese Patent No. 5930961 U.S. Pat. No. 8222048 U.S. Pat. No. 7,169,362 International Publication No. 2007/038521

Based on the above, the subject of the present invention is an automatic electrochemical measurement system that simultaneously measures a plurality of test solutions in which a plurality of electrolytic solutions are mixed at different ratios in a limited space according to electrochemical characteristics, and a plurality of test solutions. It is to provide a method for automatically measuring the electrochemical characteristics of all at once.

The automatic electrochemical measurement system for simultaneously measuring the electrochemical characteristics of a test solution obtained by mixing two or more mother liquors according to the present invention includes one or more mother liquor plates having a plurality of wells containing each of a plurality of mother liquors. , A plate stacker for installing one or more evaluation plates provided with a plurality of wells for accommodating a plurality of test solutions, and each of the plurality of wells provided with the one or more evaluation plates A plate stacker and one or more mother liquors, wherein a pair of electrodes and a separator located between the pair of electrodes are arranged, and one electrode of the pair of electrodes is located at the bottom of each of the plurality of wells. The mother liquor is extracted from each of the plate, the transport means for conveying the one or more evaluation plates, and the plurality of wells of the one or more mother liquor plates, and the extracted mother liquor is used in the one or more evaluation plates. It is a measurement stage in which a dispensing means for injecting liquid into the plurality of wells and preparing the plurality of test solutions and an evaluation plate having the plurality of wells containing each of the plurality of test solutions are placed. The measurement stage includes a first probe group consisting of a plurality of probes electrically connected to one of the pair of electrodes arranged in each of the plurality of wells, and the other of the pair of electrodes, respectively. An electric measurement stage comprising a second probe group consisting of a plurality of electrically connected probes, and an electric electrode of each of the plurality of test solutions electrically connected to the first probe group and the second probe group. The control means includes an electrochemical measuring device for simultaneously measuring chemical characteristics, a control means for controlling the operation of the transport means, the dispensing means, the measuring stage, and the electrochemical measuring device, and the control means is the same. Note:
(A) A fixed amount v of a mother liquor from one well of one of the one or more mother liquor plates (however, the fixed amount v is a mother liquor contained in the one well of the one mother liquor plate. The volume of V or less) is extracted, and the extracted mother liquor is poured into the wells of one evaluation plate.
(B) The fixed amount v of the mother liquor is extracted from another well of the one mother liquor plate, and the extracted mother liquor is poured into the well of the one evaluation plate.
(C) The above (A) and the above (B) are repeated to prepare the plurality of test solutions on the one evaluation plate.
(D) For each of the one or more mother liquor plates, the plurality of test solutions are prepared in a number of evaluation plates corresponding to the integer portion n of the solution obtained by dividing the volume V by the fixed amount v. The operation of the dispensing means is controlled so as to repeat (A), (B) and (C), thereby solving the above-mentioned problem.
The control means interlocks with the operation of the dispensing means, and the transporting means separates each of the one or more mother liquor plates and each of the one or more evaluation plates from the plate stacker to the dispensing means. Transport to the dispensing position and transport the evaluation plate with the plurality of wells containing each of the plurality of test solutions prepared by the dispensing means from the dispensing position to the measuring stage. The operation of the transport means may be controlled.
The control means is interlocked with the operation of the transport means, and when the measurement stage has the evaluation plate provided with the plurality of wells containing each of the plurality of test solutions, the evaluation plate is placed on the measurement stage. At least one of the first probe group and the second probe group is movable, and the first probe group is electrically connected to one of the pair of electrodes arranged in each of the plurality of wells. The second probe group is electrically connected to the other of the pair of electrodes, and the first probe group and the second probe group are electrically connected to the electrochemical measuring device. When the measurement by the electrochemical measuring device is completed, at least one of the first probe group and the second probe group is movable, and the first probe group and the second probe group are paired. The operation of the measurement stage may be controlled so as to be separated from the electrodes.
In the control means, when the electrochemical measuring device electrically connects the first probe group and the second probe group to the pair of electrodes, the electrochemical measuring device conducts electricity of the plurality of test solutions. The operation of the electrochemical measuring device may be controlled so as to measure the chemical characteristics.
Further display means may be provided.
The control means may control the operation of the display means so that the display means displays the measurement result by the electrochemical measuring device.
The control means causes the display means to cause the user to input a dispensing condition including at least the fixed amount v, the composition of the plurality of mother liquors, and the composition of the plurality of test solutions, and / or an electrochemical measurement. The operation of the display means may be controlled so as to display a user interface for inputting conditions.
Based on the dispensing conditions, the control means calculates the total amount of each of the plurality of mother solutions used from the compositions of the plurality of test solutions for each of the one or more evaluation plates, and the plurality of test solutions. The total amount of each of the mother liquors used is compared with the fixed amount v, and when at least one of the total amounts of each of the plurality of mother liquors used exceeds the fixed amount v, the above 1 or more. For each of the mother liquor plates, it is determined that the plurality of test solutions cannot be prepared in a number of evaluation plates corresponding to the integer portion n of the solution obtained by dividing the volume V by the fixed amount v, and a warning is given to the display means. It may be displayed and the user may be prompted to reset the dispensing conditions.
Each of the plurality of wells included in the one or more evaluation plates may have a common electrolytic solution which is a lithium salt.
In the dispensing means, the height of the test liquid contained in each of the plurality of wells provided in the evaluation plate from the bottom of the well is the other side facing one electrode located at the bottom. The plurality of test solutions may be prepared so as to be lower than the height of the electrodes.
The plate stacker, the transport means, the dispensing means, and a glove box accommodating the measurement stage may be further provided.
The atmosphere inside the glove box may be an inert gas atmosphere.
The first probe group and the second probe group may pressurize the pair of electrodes with a force in the range of 200 gf or more and 10 kgf or less.
A waste liquid unit for discarding the waste liquid and a disposal unit for discarding the waste are further provided, and the control means is such that the dispensing means is provided with the plurality of wells provided in the mother liquid plate of one or more mother liquid plates. The mother liquor of the fixed amount v is extracted from one of the wells, and each time the injection into the plurality of wells provided in the one evaluation plate is completed, the remaining mother liquor of the fixed amount v is added to the waste liquid portion. The operation of the dispensing means is controlled so as to be discarded, and the dispensing means obtains the fixed amount v of the mother liquor from all of the plurality of wells included in the one mother liquor plate among the one or more mother liquor plates. Each time the number of the integer portion n is extracted and / or each time the electrochemical measuring device finishes the measurement of the electrochemical characteristics of the plurality of test solutions of the one evaluation plate, the transport means. However, the operation of the transport means may be controlled so that the one mother solution plate and / or the one evaluation plate is discarded in the disposal unit.
The control means may store in the memory the information of the plurality of test solutions of the plurality of wells provided in each of the one or more evaluation plates and the measurement results corresponding to the plurality of test solutions.
The plate stacker includes the one or more mother liquor plates and the first one or more so that the number of the one or more evaluation plates corresponds to the number obtained by multiplying the number of the one or more mother liquor plates by the integer portion n. The above evaluation plate may be installed.
The method of automatically measuring the electrochemical characteristics of a test solution obtained by mixing two or more mother liquors according to the present invention is one of one or more mother liquor plates having a plurality of wells containing each of a plurality of mother liquors. A step of moving the mother liquor plate to the dispensing position and a step of moving one of one or more evaluation plates having a plurality of wells for accommodating each of a plurality of test solutions to the dispensing position. A pair of electrodes and a separator located between the pair of electrodes are arranged in each of the plurality of wells included in the one or more evaluation plates, and one electrode of the pair of electrodes is the plurality of electrodes. A step located at the bottom of each of the wells and a step of preparing a plurality of test solutions in the one evaluation plate, wherein a fixed amount v of the mother liquor from one well of the one mother liquor plate (provided, said The fixed amount v is equal to or less than the volume V of the mother liquor contained in the one well provided by the one mother liquor plate), and the extracted mother liquor is injected into the well of the one evaluation plate. Step (a), a step (b) of extracting a fixed amount of mother liquor from another well of the one mother liquor plate and injecting the extracted mother liquor into a well of the one evaluation plate, and the above-mentioned A step and the plurality of wells included in the one evaluation plate include a step (c) in which the step (a) and the step (b) are repeated to prepare the plurality of test solutions in the one evaluation plate. The step of electrically connecting the pair of electrodes and the electrochemical measuring device of each of the above, and the electrochemical characteristics of each of the plurality of test solutions of the one evaluation plate are simultaneously measured by the electrochemical measuring device. The step of causing the measurement, the step of discarding the measured one evaluation plate, and the integer of the solution in which the number of the one or more evaluation plates is 2 or more and the capacity V is divided by the fixed amount v. When the portion n is 2 or more, the one evaluation plate is taken out so as to measure the electrochemical characteristics of a plurality of test solutions for the number of evaluation plates corresponding to the integer portion n with respect to the one mother liquor plate. The above-mentioned problems are solved by including a step of preparing the plurality of test solutions, a step of electrically connecting the test solution, a step of measuring the measurement, and a step of repeating the discarding step n-1 times.
Following the step of repeating the n-1 times, a step of further repeating the step of moving the one mother liquor plate and subsequent steps may be further included.
The step of preparing the plurality of test solutions may be based on a dispensing condition input by the user, which includes at least the fixed amount v, the composition of the plurality of mother liquors, and the composition of the plurality of test solutions.
The step to be measured may be based on the electrochemical measurement condition input by the user.

As described above, the automatic electrochemical measurement system for simultaneously measuring the electrochemical characteristics of a plurality of test solutions according to the present invention is a plate stacker for installing a mother liquor plate and an evaluation plate, and a transport for transporting the mother liquor plate and the evaluation plate. Means, a dispensing means that extracts the mother liquor from the mother liquor plate, injects it into the evaluation plate, and prepares a plurality of test solutions, a measurement stage on which the evaluation plates are placed, and the electrochemical of the plurality of test solutions. It is provided with an electrochemical measuring device for simultaneously measuring the characteristics and a control means for controlling each of these operations. In the control means, the dispensing means extracted a fixed amount v of the mother liquor from the mother liquor plate (however, the fixed amount v is equal to or less than the volume V of the mother liquor contained in each well of the mother liquor plate) and extracted the liquid. Since the operation of the dispensing means is controlled so that the mother liquor having a fixed amount v or less is injected into the evaluation plate, the liquid level sensor when the dispensing means prepares the mother liquor can be eliminated. As a result, the system of the present invention can be realized even in a limited space.

Further, the control means dispenses a plurality of test solutions so as to be injected into an evaluation plate having a number corresponding to the number obtained by multiplying the integer portion n of the solution obtained by dividing the volume V by the fixed amount v by the number of mother liquor plates. In order to control the operation of the means, the end of the extraction from all the mother liquor plates installed in the plate stackers and the end of the injection into all the evaluation plates are always constant, and it is only necessary to replace each plate stacker. , Enables efficient long-term operation.

It is a schematic diagram which shows the automatic electrochemical measurement system of this invention. It is a schematic diagram which shows the mother liquor plate of this invention. It is a schematic diagram which shows the evaluation plate of this invention. It is a figure which shows typically the 1st probe group. It is a figure which shows typically the 2nd probe group. It is a schematic diagram which shows another automatic electrochemical measurement system of this invention. It is a figure which shows an exemplary user interface. It is a figure which shows the exemplary dispensing condition setting screen. It is a figure which shows an exemplary mother liquor plate recipe which is composition of a plurality of mother liquors to be uploaded. It is a figure which shows the exemplary evaluation plate recipe which is the composition of a plurality of test liquids to be uploaded. It is a figure which shows an exemplary warning message. It is a figure which shows the exemplary electrochemical measurement condition setting screen. It is a figure which shows the exemplary measurement result. It is a figure which shows the flow which automatically measured the electrochemical property of the test liquid of this invention all at once. FIG. 14 is a diagram showing a flow for automatically measuring the electrochemical characteristics of the test solution of the present invention following FIG. It is a schematic diagram which shows the automatic electrochemical measurement system used in an Example. It is a figure which shows the appearance of the evaluation plate.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The same elements are given the same numbers, and the description thereof will be omitted.

FIG. 1 is a schematic diagram showing an automatic electrochemical measurement system of the present invention.

The automatic electrochemical measurement system 100 of the present invention is a system for simultaneously measuring the electrochemical characteristics of a test solution obtained by mixing two or more mother solutions. The automatic electrochemical measurement system 100 of the present invention includes a plate stacker 130 in which one or more mother liquor plates 110 containing two or more mother liquors and one or more evaluation plates 120 containing test solutions are installed, and one or more. A test solution is prepared, a transport means 140 for transporting the mother liquor plate 110 and one or more evaluation plates 120, a dispensing means 150 for preparing a test solution by dispensing the mother liquor extracted from the mother liquor plate into the evaluation plate. Controls the operation of the measurement stage 160 on which the evaluation plate is placed, the electrochemical measurement device 170 that measures the electrochemical characteristics of the test solution, the transport means 140, the dispensing means 150, the measurement stage 160, and the electrochemical measurement device 170. The control means 180 is provided.

The automated electrochemical measurement system 100 of the present invention preferably further includes a glove box 190 that houses a plate stacker 130, a transport means 140, a dispensing means 150, and a measurement stage 160. As a result, the internal atmosphere can be controlled, the chemical change of the prepared test solution can be suppressed, and the measurement conditions of the test solution can be made constant, so that the measurement accuracy can be improved.

The atmosphere inside the glove box 190 is preferably an inert gas atmosphere. The inert gas can be, for example, a rare gas such as dry nitrogen, helium, neon, or argon.

Each component will be described in detail.
FIG. 2 is a schematic view showing a mother liquor plate of the present invention.

FIG. 2 schematically shows a mother liquor plate 200 of one or more mother liquor plates 110. The mother liquor plate 200 includes a plurality of wells 210, and the mother liquor 220 is housed in each of the plurality of wells 210. The amount of the contained mother liquor 220 is represented by the volume V. In FIG. 2, 96 wells 210 are shown in a matrix of 8 rows × 12 columns in the mother liquor plate 200, but the number and arrangement of the wells 210 are not limited to this.

The mother liquor is intended as a solution that can constitute an electrolytic solution of a battery, and corresponds to an electrolyte, a solvent, or the like. All wells 210 may contain the mother liquor 220, or some wells 210 may contain the mother liquor, but two or more different mother liquors are contained. Further, the mother liquor plate 200 is preferably made of a material having low reactivity with the mother liquor (for example, polypropylene).

FIG. 3 is a schematic view showing the evaluation plate of the present invention.

FIG. 3 schematically shows an evaluation plate 300 of one or more evaluation plates 110. The evaluation plate 300 includes a plurality of wells 310, and a test solution 360 (that is, an electrolytic solution) is prepared and contained in each of the plurality of wells 310. In FIG. 3A, the evaluation plate 300 shows 96 wells 310 in a matrix of 8 rows × 12 columns, but the number and arrangement of the wells 310 are not limited to this.

As shown in FIG. 3B, a pair of electrodes 330, 340 and a separator 350 located between the pair of electrodes 330 and 340 are arranged in advance in each of the wells 310. One of the pair of electrodes 330 and 340, the electrode 340, is arranged so as to be located at the bottom of the well 310. FIG. 3B also shows how the test solution 360 prepared in the well 310 is stored.

For example, the electrode 330 is a positive electrode, and the electrode 340 functions as a negative electrode. In the case of evaluation of the electrolytic solution used for the lithium battery, nickel foil, stainless steel, copper, alloys thereof and the like can be used for the electrode 330, and metallic lithium or magnesium, titanium, tin and lead can be used for the electrode 340. , Aluminum, indium, silicon, zinc, antimony, bismuth, gallium, germanium, yttrium, etc. and lithium alloy can be used.

When evaluating the electrolytic solution used in the sodium battery using the automatic electrochemical measurement system 100 of the present invention, the electrode 340 may be formed of metallic sodium or magnesium, titanium, tin, lead, aluminum, indium, or the like. Sodium alloys of sodium, silicon, zinc, antimony, bismuth, gallium, germanium, ittrium, etc. can be used. As described above, the electrode 340 can be appropriately changed depending on the type of battery.

Further, in FIG. 3, the electrode 330 is shown as a positive electrode and the electrode 340 is shown as a negative electrode, but the opposite may be true.

The separator 350 is not particularly limited as long as it allows alkali metal ions and / or alkaline earth metal ions to pass through and is made of an insulating material having a porous structure, and is used for existing metal batteries. The separator to be applied can be applied. Illustratively, examples of the separator 350 include a porous film made of polyolefin such as polyethylene and polypropylene, and a non-woven fabric made of glass fiber.

The test solution 360 may be contained in all wells 310, or the test solution 360 may be contained in some wells 310, but from the viewpoint of long-term efficient automatic electrochemical measurement, the well 310 may be contained. It is desirable that all test solutions 360 be prepared and contained. Here, too, the evaluation plate 300 is preferably made of a material having low reactivity with the electrolytic solution (for example, polypropylene).

The common electrolytic solution may be stored in all the wells 310 in advance. As a result, when the test solution 360 is prepared therein, it can be easily mixed, and the pair of electrodes 330, 340 and the separator 350 and the test solution 360 are well compatible with each other, and the measurement accuracy can be improved. In the case of a lithium ion battery, any electrolytic solution containing a lithium salt can be used as such a common electrolytic solution, and typically, ethylene carbonate (EC), diethyl carbonate (DEC), and propylene carbonate (PC). ) And Lithium salts such as LiPF ₆ and LiBF ₄ are dissolved in a solvent selected from at least one selected from the group consisting of dimethyl carbonate (DMC) (concentration is, for example, 1M). Similarly, a common electrolyte can be used for other batteries.

The common electrolyte is preferably contained so that the volume ratio of the prepared test solution 360 to the common electrolyte is test solution: common electrolyte = 2: 1 to 1: 1. Thereby, the measurement accuracy can be improved.

As shown in FIG. 3C, in the well 310, one electrode 330 of the pair of electrodes 330 and 340 and the probe 370 are electrically connected to each other, and the other electrode 340 and the probe 380 are electrically connected to each other. Connect to the electrochemical measuring device to enable measurement.

One or more mother liquor plates 110 made of such a mother liquor plate 200 and one or more evaluation plates 120 made of an evaluation plate 300 are installed in a plate stacker 130 prior to measurement.

Return to FIG. 1 again.
The transport means 140 takes out one or more mother liquor plates 110 and one or more evaluation plates 120 from the plate stacker 130 and transports them. From this point of view, the transport means 140 preferably includes a robot arm.

The dispensing means 150 extracts the mother liquor extracted from each of the plurality of wells 210 of one mother liquor plate 110 ′ of one or more mother liquor plates 110, and one evaluation plate 120 ′ of one or more evaluation plates 120. A plurality of test solutions are prepared on an evaluation plate by injecting a solution into a plurality of wells 310. The extracted mother liquor does not necessarily have to be dispensed into all of the plurality of wells 310 of the evaluation plate 120', and may be dispensed according to the composition of the test solution described later. As such a dispensing means, a dispensing system capable of extracting and injecting a predetermined amount of liquid can be adopted.

The measurement stage 160 mounts an evaluation plate 120 ”with a plurality of wells 310 containing each of the plurality of test solutions prepared by the dispensing means 150. The measurement stage 160 is placed on each of the plurality of wells 310. A first probe group 161 composed of a plurality of probes (for example, probe 370 of FIG. 3C) electrically connected to one of the arranged pair of electrodes 330 and 340, and the other electrode. It includes a second probe group 162 composed of a plurality of probes electrically connected to the 340 (for example, the probe 380 in FIG. 3C). At least one of the first probe group 161 and the second probe group 162. If one is movable, it is preferable because it enables electrical connection with the pair of electrodes 330 and 340 of the well 310.

FIG. 4 is a diagram schematically showing a first probe group.
FIG. 5 is a diagram schematically showing a second probe group.

FIG. 4A is a plan view of the first probe group 161 and FIG. 4B is a side view of the first probe group 161. The first probe group 161 includes a plate 410 having a hole 420 and a plurality of probes 430 press-fitted into the hole 420. The holes 420 formed in the plate 410 correspond to the number of plurality of wells 310 in the evaluation plate 300. Each of the plurality of probes 370 of the first probe group 161 is configured to be electrically connected to the respective electrodes 330 of the plurality of wells 310.

FIG. 5 (A) is a plan view of the second probe group 162, and FIG. 5 (B) is a side view of the second probe group 162. The second probe group 162 includes a plate 510 having a hole 520 and a plurality of probes 530 press-fitted into the hole 520. Again, the holes 520 formed in the plate 510 correspond to the number of plurality of wells 310 in the evaluation plate 300. Similar to FIG. 4, but each of the plurality of probes 380 in the second probe group 162 is configured to be electrically connected to the respective electrodes 340 of the plurality of wells 310.

Return to FIG. 1 again.
The electrochemical measuring device 170 is electrically connected to the first probe group 161 and the second probe group 162, and has the electrochemical characteristics of each of the plurality of test solutions contained in the plurality of wells 310 of the evaluation plate 120 ”. It is preferable that such an electrochemical measuring device 170 includes a charge / discharge tester and an impedance measuring machine.

The control means 180 controls the operations of the above-mentioned transport means 140, dispensing means 150, measurement stage 160, and electrochemical measuring device 170, respectively. Such a control means 180 preferably includes, for example, a central processing unit (CPU), a memory for storing data, and, if necessary, a communication means. Such a control means 180 may be a personal computer or the like.

The control means 180 will be described in more detail.
According to the present invention, the control means 180 controls the operation of the dispensing means 150 so that the dispensing means 150 performs the following steps (A) to (D).

Step (A): A fixed amount v of the mother liquor from one well of the mother liquor plate 110'of one or more mother liquor plates 110 (however, the fixed amount v is contained in the well 210 provided by one mother liquor plate 110'. (The volume of the mother liquor is V or less) is extracted, and the extracted mother liquor is poured into the well 310 of one evaluation plate 120'. Again, the extracted mother liquor does not necessarily have to be dispensed into all of the plurality of wells 310 of the evaluation plate 120'. The volume V of the mother liquor is assumed to be the same volume for all the wells containing the mother liquor.

Step (B): A fixed amount of mother liquor v is drawn from another well of one mother liquor plate 110', and the extracted mother liquor is poured into well 310 of one evaluation plate 120'.

Step (C): Repeat step (A) and step (B) to prepare a plurality of test solutions on one evaluation plate 120'. The total number of repetitions may be as many as the number of mother liquors contained in one mother liquor plate 110'. That is, it may be repeated for all the wells 210 containing the mother liquor. As a result, a plurality of test solutions are prepared on one evaluation plate 120'. As described above, in steps (A) to (C), since the fixed amount v is always extracted, the liquid level sensor when the dispensing means 150 extracts the mother liquor can be eliminated. As a result, the system of the present invention can save space.

Further, the evaluation plate 120' thus obtained is conveyed to the measurement stage 160 by the conveying means 140, and the electrochemical characteristics of each of the plurality of test solutions are simultaneously measured by the electrochemical measuring device 170. ..

Step (D): The dispensing means 150 has steps (A) to (C) as basic operations, and for each of one or more mother liquor plates 110, the integer portion n of the solution obtained by dividing the volume V by a fixed amount v. Steps (A) to (C) are repeated so as to prepare a plurality of test solutions on the number of evaluation plates corresponding to. When n is 1, step (D) repeats steps (A) to (C) 0 times (step (D) is not performed).

Since the control means 180 controls the operation of the dispensing means 150 so that the dispensing by the dispensing means 150 performs the above steps (A) to (D), the integer of the solution obtained by dividing the capacitance V by the fixed amount v. A plurality of test solutions can be prepared in a number of evaluation plates corresponding to the number of portions n multiplied by the number of mother liquor plates. For example, when the volume V is 1 mL (= 1000 μL) and the fixed amount v is 150 μL, n is 6, and when the number of mother liquor plates is 2, the number of evaluation plates is 12.

In this way, one or more mother liquor plates 110 and one or more evaluation plates 120 having a number obtained by multiplying the number of one or more mother liquor plates 110 by n are simply installed on the plate stacker 130. The end of the extraction from 110 and the end of injection of one or more evaluation plates 120 into all the evaluation plates are performed at the same time. As a result, efficient long-term operation is possible only by replacing each plate stacker 130.

The control means 180 preferably has the dispensing means 150 height above the bottom of the well 310 of the test solution 360 housed in each of the plurality of wells 310 included in the evaluation plate 300, as shown in FIG. 3 (B). The test solution 360 is controlled so that the height is lower than the height of the other electrode 330 on the side facing the one electrode 340 located at the bottom. As a result, the probe 370 does not come into contact with the test solution 360, so that the test solutions 360 do not mix with each other, and the measurement accuracy can be improved. The same applies when the common electrolytic solution is stored in the well 310 in advance. The control means 180 is preferably performed based on dispensing conditions including setting the amount of test solution 360 input by the user, which will be described later.

The control means 180 preferably takes out each of one or more mother liquor plates 110 and each of one or more evaluation plates 120 from the plate stacker 130 and conveys them to the dispensing position of the dispensing means 150. Then, the operation of the transport means 140 is controlled so that the evaluation plate having the plurality of wells 310 containing each of the plurality of test solutions 360 prepared by the dispensing means 150 is transported from the dispensing position to the measurement stage 160. To do.

Illustratively, by the control means 180, the transport means 140 takes out one mother liquor plate 110'from one or more mother liquor plates 110 of the plate stacker 130, transports it to the dispensing position of the dispensing means 150, and then 1 One evaluation plate 120'is taken out from the above evaluation plate 120 and conveyed to the dispensing position of the dispensing means 150. Further, by the control means 180, the transport means 140 transports the evaluation plate 120 ”containing the plurality of test liquids 360 prepared by the dispensing means 150 from the dispensing position to the measurement stage 160 in this way. The means 180 controls the operation of the transport means 140 in conjunction with the operation of the dispensing means 150 to enable long-term operation.

The control means 180 preferably allows the measurement stage 160 to move at least one of the first probe group 161 and the second probe group 162 when the evaluation plate 120 ”is placed on the measurement stage. One probe group 161 is electrically connected to one electrode 330 of a pair of electrodes 330 and 340 arranged in each of a plurality of wells 310, and a second probe group 162 is electrically connected to the other electrode 340. The first probe group 161 and the second probe group 162 are electrically connected to the electrochemical measuring device 170, and then when the measurement by the electrochemical measuring device 170 is completed, the first probe group 161 and the first probe group 161 and The operation of the measurement stage 160 is controlled so that at least one of the second probe group 162 is movable and the first probe group 161 and the second probe group 162 are separated from the pair of electrodes 330 and 340. As described above, the control means 180 controls the operation of the measurement stage 160 in conjunction with the operation of the transport means 140 to enable long-term operation. The first probe group 161 and / or the second probe group. The 162 is movable so as to move up and down, for example.

The first probe group 161 and the second probe 162 of the measurement stage 160 hold down the pair of electrodes 330 and 340 in the plurality of wells 310 from above and below to establish an electrical connection with the electrochemical measuring device 170. It is possible, but more preferably, the first probe group 161 and the second probe group 162 pressurize each pair of electrodes 330, 340 of the plurality of wells 310 with a value of 200 gf or more. This can maintain electrical connectivity and improve measurement accuracy. More preferably, the pressurizing force is in the range of 400 gf or more and 10 kgf or less. As a result, the measurement accuracy is improved and the reproducibility is excellent.

The control means 180 preferably has a plurality of electrochemical measuring devices 170 when the electrochemical measuring device 170 electrically connects the first probe group 161 and the second probe group 162 to the pair of electrodes 330 and 340. The operation of the electrochemical measuring device 170 is controlled so that the electrochemical characteristics of the test solution 360 are measured all at once. The electrical connection is, for example, by the first probe group 161 and the second probe group 162 reaching a predetermined position on the measurement stage 160, i.e., the probe at a predetermined position on each of the plurality of wells 310. When 370 and 380 are reached, it can be considered to be electrically connected. In this way, the control means 180 controls the operation of the electrochemical measuring device 170 in conjunction with the operation of the measuring stage 160, thereby enabling long-term operation.

Here, the operation of the automatic electrochemical measurement system 100 will be described.

The automatic electrochemical measurement system 100 operates as follows. The transport means 140 takes out one mother liquor plate 110'and one evaluation plate 120' from the plate stacker 130, respectively, and moves them to the dispensing position of the dispensing means 150. Next, the dispensing means 150 repeats drawing and injecting the liquid from the mother liquor plate 110'to the evaluation plate 120' to prepare a plurality of test solutions on the evaluation plate 120'. The transport means 140 moves the evaluation plate 120 "in which a plurality of test solutions are prepared to the measurement stage 160.

The measurement stage 160 electrically connects the pair of electrodes 330, 340 of the evaluation plate 120 ”, the first probe group 161 and the second probe group 162, and the first probe group 161 and the second probe group When the 162 and the electrochemical measuring device 170 are electrically connected, the electrochemical measuring device 170 simultaneously measures the electrochemical characteristics of the plurality of test solutions on the evaluation plate 120 ”. The control means 180 controls the operations of the transport means 140, the dispensing means 150, the measurement stage 160, and the electrochemical measuring device 170. In this way, the electrochemical properties of a plurality of test solutions can be measured with high throughput.

Further, the automatic electrochemical measurement system 100 of the present invention completes extraction from one or more mother liquor plates 110 installed in the plate stacker 130 and injects liquid into all evaluation plates of one or more evaluation plates 120. The measurement can be repeated so that the end and the end are simultaneous.

FIG. 6 is a schematic diagram showing another automated electrochemical measurement system of the present invention.

The same components as those in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted. Another automatic electrochemical measurement system 600 is provided with, in addition to the automatic electrochemical measurement system 100 of FIG. 1, a waste liquid unit 610 for discarding waste liquid, a disposal unit 620 for discarding waste, and a display means 630. Is similar.

Hereinafter, the automatic electrochemical measurement system 600 of FIG. 6 will be described as including all of the waste liquid unit 610, the waste unit 620, and the display means 630, but the automatic electrochemical measurement system 100 of FIG. 1 includes the waste liquid unit 610, Needless to say, any one or more of the disposal unit 620 and the display means 630 may be provided arbitrarily.

The control means 640 preferably extracts a fixed amount v of the mother liquor from one of the plurality of wells 210 included in the mother liquor plate 110'one of the one or more mother liquor plates 110. The operation of the dispensing means 150 is controlled so that the remaining mother liquor of the fixed amount v is discarded in the waste liquid section 610 each time the liquid is injected into the plurality of wells 310 provided in one evaluation plate 120'. As a result, in the dispensing means 150, mixing of the mother liquor is suppressed, so that the measurement accuracy is improved and the reproducibility is excellent. By providing such a waste liquid portion 610, it is not always necessary to dispense the extracted mother liquor into all of the plurality of wells 310 of the evaluation plate 120', so that the degree of freedom in designing the test liquid is increased.

The control means 640 preferably has a fixed amount v of the mother liquor from all the wells 210 containing the mother liquor among the plurality of wells 210 included in one mother liquor plate 110'by the number of integer portions n. Each time the liquid is drawn and / or the electrochemical measuring device 170 finishes measuring the electrochemical characteristics of the plurality of test solutions 360 of one evaluation plate 120, the transport means 140 uses one mother liquor plate. The operation of the transport means 140 is controlled so that the 110'and / or one evaluation plate'is disposed of in the disposal unit 620. In this way, the control means 640 disposes of the mother liquor and the mother liquor plate and the evaluation plate, so that long-term operation is possible.

The display means 630 is preferably an image display monitor such as a display. This improves user operability. The control means 640 may be integrated with the display means 630.

The control means 640 preferably controls the operation of the display means 630 so that the display means 630 displays the measurement result by the electrochemical measuring device 170. As a result, the user can visually confirm the measurement result.

The control means 640 preferably causes the display means 630 to allow the user to enter a dispensing condition that includes at least a fixed amount v, a plurality of mother liquor compositions and a plurality of test liquor compositions, and / or electrochemical measurements. The operation of the display means 630 is controlled so as to display the user interface for inputting the conditions. Based on the dispensing conditions and the electrochemical measurement conditions input by the user, the control means 640 can control the operations of the transport means 140, the dispensing means 150, the measurement stage 160, and the electrochemical measuring device 170 described above. ..

The control means 640 preferably calculates the total amount of each of the plurality of mother liquors used from the composition of the plurality of test solutions based on the dispensing conditions, compares each total amount with the fixed amount v, and of each total amount. When at least one of them exceeds the fixed amount v, n evaluation plates 120 (n is a fixed amount v of the capacity V of the well 210 of the mother liquor plate 200) for each of one or more mother liquor plates 110. It is possible to determine that a plurality of test solutions cannot be prepared (corresponding to the integer part of the solution divided by), display a warning on the display means 630, and prompt the user to reset the dispensing conditions. Since the error can be checked before the measurement in this way, the automatic measurement does not stop due to the error after the measurement starts.

The control means 640 preferably stores in the memory the information of the plurality of test solutions of the plurality of wells 310 included in each of the one or more evaluation plates 120 and the measurement results corresponding to the plurality of test solutions. it can. This facilitates the management of information.

FIG. 7 is a diagram showing an exemplary user interface.
FIG. 8 is a diagram showing an exemplary dispensing condition setting screen.

The user interface 700 includes at least a dispensing condition setting button 710, an electrochemical measurement condition setting button 720, an execution button 730, a result button 740, and an end button 750.

When the user presses the dispensing condition setting button 710, the screen moves to the dispensing condition setting screen 800 including at least the fixed amount v, the composition of the plurality of mother liquors, and the composition of the plurality of test solutions.

Here, on the mother liquor tab, the user selects the amount of the mother liquor extract corresponding to the fixed amount v, selects the number of the plurality of wells 210 of the mother liquor plate 200 to be used, uploads the composition of the plurality of mother liquors, and the plate stacker. Input the number of mother liquor plates to be installed in 130. In addition, the user can input the volume of the mother liquor (corresponding to the volume V of the mother liquor) contained in the well 210 of the mother liquor plate 200. When the same mother liquor plate 200 is always used, the volume V can be fixed.

FIG. 9 is a diagram showing an exemplary mother liquor plate recipe which is the composition of the plurality of mother liquors uploaded.

As shown in FIG. 9, in the mother liquor plate recipe, the well number and the corresponding mother liquor type and concentration are controlled by a sheet for each mother liquor plate. If the mother liquor plate recipe is stored in the memory of the control means 180 or the like in advance, it suffices to read it.

Return to FIG. 8 again. Subsequently, in the test solution tab, the user selects the amount of test solution prepared in each of the plurality of wells 310 of the evaluation plate 300, uploads the composition of the plurality of test solutions, and evaluates the test solution to be placed in the plate stacker 130. Enter the number of plates. Since the number of evaluation plates is the number obtained by multiplying the number of mother liquor plates by n (n is the integer part of the solution obtained by dividing the volume V of the mother liquor of the mother liquor plate by the fixed amount v) as described above, it is automatically calculated. It may be entered.

FIG. 10 is a diagram showing an exemplary evaluation plate recipe which is the composition of a plurality of uploaded test solutions.

As shown in FIG. 10, in the evaluation plate recipe, the positions of the plurality of wells 310 of the evaluation plate 300 are associated with each other by columns (vertical) and rows (horizontal), and the numbers of the stock solutions to be mixed (FIG. 9). (Corresponding to No.), the amount of mother liquor, and their combination are controlled by a sheet for each evaluation plate.

In FIG. 10, each of the plurality of wells 310 of the evaluation plate 300 is an evaluation plate recipe in which 5 μL of each of five types of mother liquor (solution 1 to solution 5) is mixed to prepare a test solution. For example, the test solution prepared in the well 310 (FIG. 3) of vertical A and horizontal 1 is the solution 1 of No. 9 in FIG. 1. As solution 2, No. 9 in FIG. 18. No. 9 in FIG. 9 as solution 3. 20. As solution 4, No. 9 in FIG. No. 21 and solution 5 in FIG. It means that 5 μL of each of the 32 mother solutions is mixed.

FIG. 11 is a diagram showing an exemplary warning message.

Returning to FIG. 8 again, when the user presses the confirmation button after inputting the predetermined information, the control means 180 is based on the dispensing conditions, for example, from the composition of the plurality of test solutions shown in FIG. Calculate the total amount used for each and compare each total amount with the fixed amount v. As a result, when the control means 180 determines that at least one total amount of each total amount exceeds the fixed amount v (there is an error), for example, as shown in FIG. 11, a warning is given to the display means 630. Can be displayed to prompt the user to reset the dispensing conditions. In addition, detailed error information may be displayed on the display means 630. This facilitates the user to reset the dispensing conditions.

FIG. 12 is a diagram showing an exemplary electrochemical measurement condition setting screen.

Returning to FIG. 7 again, if there is no error in the dispensing conditions, the user presses the electrochemical measurement condition setting button 720 to move to the electrochemical measurement condition setting screen 1200.

Here, the user inputs an electrochemical measurement condition for measuring the Coulomb efficiency (also referred to as charge / discharge efficiency). Specifically, on the electrochemical measurement condition setting screen 1200, the user selects a sequence related to the number of repeated measurements (number of cycles) of charge / discharge, and selects a pattern for setting the amount of charge electricity during charging and the discharge capacity during discharge. And do.

For example, in FIG. 12, the user can see the sequence number on the sequence tab. 1 is selected, and the sequence No. 1 is the pattern No. Using 2, it can be seen that the number of cycles consists of a sequence of 20 times. Further, the user can display the sequence No. on the sequence tab. Pattern No. 1 cited in 1. Set the details of 2 (current density, control time, data storage time interval, cutoff (target) voltage if necessary). In FIG. 12, the pattern No. 2 is a combination of 10-hour discharge (step No. 1), 30-minute reset (step No. 2), 10-hour charge (step No. 3), and 30-minute reset (step No. 4), and has a cutoff voltage. It can be seen that is 2V to 4V.

If various sequences and various patterns are stored in the memory of the control means 180 or the like in advance, it is sufficient to read them.

Returning to FIG. 7 again, when the electrochemical setting condition is set and the user presses the execute button 730, the control means 180 controls the dispensing means 140 and the dispensing means 150 based on the dispensing condition and the electrochemical setting condition. , Control the operation of the measurement stage 160 and the electrochemical measuring device 170, respectively, and perform automatic electrochemical measurement.

FIG. 13 is a diagram showing an exemplary measurement result.

When the measurement is completed, the result button 740 of FIG. 7 becomes active, and when the user presses the result button 740, the measurement result as shown in FIG. 13 is displayed. In FIG. 13, information on a plurality of wells and a plurality of test solutions (column (vertical) and row (horizontal), test solution number) provided in the evaluation plate, and coulombs of each cycle (1st to 20th) corresponding to each. The efficiency result is displayed for each sheet of the evaluation plate. The user can also rearrange the Coulomb efficiency from the top. The user can also show the measurement result as a graph (capacity-voltage). In this way, the user can simultaneously measure the electrochemical characteristics of the test solution obtained by mixing two or more mother solutions, and enable a high-throughput search for a plurality of test solutions. When the end button 750 is pressed after all the measurements are completed, the interface 700 of FIG. 7 is terminated.

Here, the operation of the automatic electrochemical measurement system 600 will be described.

The automatic electrochemical measurement system 600 is the same as the operation of the automatic electrochemical measurement system 100 except for the following points. The point that the dispensing means 150 draws liquid from one well 210 of the mother liquor plate 110'and drains the mother liquor remaining in the syringe or the like each time the liquid is injected into the plurality of wells 310 of the evaluation plate 120', the mother liquor plate 110. Dispose of the mother liquor plate / evaluation plate, dispensing conditions, and electrochemical setting conditions each time the extraction from all wells 210 of'is completed, and each time the evaluation of the electrochemical properties of the evaluation plate 120'is completed. The difference is that it is set and the measurement results are displayed.

Next, a method of automatically measuring the electrochemical characteristics of a test solution obtained by mixing two or more mother solutions of the present invention will be described.
FIG. 14 is a diagram showing a flow for automatically measuring the electrochemical characteristics of the test solution of the present invention all at once.
FIG. 15 is a diagram showing a flow for automatically measuring the electrochemical characteristics of the test solution of the present invention following FIG. 14 all at once.

Step S1410: The mother liquor plate 110'of one or more mother liquor plates 110 having a plurality of wells 210 containing each of the plurality of mother liquors is moved to the dispensing position.

Step S1420: One evaluation plate 120'of one or more evaluation plates 120 provided with a plurality of wells 310 for accommodating each of the plurality of test solutions is moved to the dispensing position. Here, the evaluation plate 120'is similar to the evaluation plate 130 described with reference to FIG. 3, and each of the plurality of wells 310 has a pair of electrodes 330, 340, and a separator 350 located between them. Arranged, one electrode 340 is located at the bottom of each of the plurality of wells 310.

Step S1430: Prepare multiple test solutions on one evaluation plate 120'. Here, the preparation of a plurality of test solutions comprises the following three steps.
Step (a): A fixed amount v of the mother liquor from one well 210 of the one mother liquor plate 110'(where the fixed amount v is the volume V of the mother liquor contained in one well 210 of the one evaluation plate 110'. The following) is drawn and poured into the wells of one evaluation plate 120'. The volume V of the mother liquor is assumed to be the same volume for all the wells containing the mother liquor.
Step (b): A fixed amount of mother liquor v is drawn from another well 210 of one mother liquor plate 110'and poured into the well of one evaluation plate 120'.
Step (c): Repeat steps (a) and (b) to prepare multiple test solutions on one evaluation plate 120'. The total number of repetitions may be as many as the number of mother liquors contained in one mother liquor plate 110'. That is, it is repeated for all the mother liquors contained in one mother liquor plate 110'. For example, if there are 96 wells 210 of one mother liquor plate 110'and 36 of them contain the mother liquor, the process may be repeated 36 times in total. In this way, one evaluation plate 120 "containing a plurality of test solutions is obtained.

Step S1430 is preferably performed based on a dispensing condition entered by the user, including at least a fixed amount v, a plurality of mother liquor compositions and a plurality of test liquor compositions. Since such dispensing conditions are as described with reference to FIGS. 7 to 11, they are omitted. Note that you may call the dispensing conditions stored in the memory or the like in advance and perform step S1430 based on the calling conditions.

Step S1440: The pair of electrodes 330 and 340 of each of the plurality of wells 310 included in the one evaluation plate 120 "obtained in step S1430 and the electrochemical measuring device (electrochemical measuring device 170 in FIG. 1) are electrically connected. Connect to.

Step S1450: The electrochemical measuring device is made to measure the electrochemical characteristics of each of the plurality of test solutions of one evaluation plate 120 "at the same time. In this way, the electrochemical characteristics of the plurality of test solutions can be measured at high throughput. ..

Step S1450 is preferably performed based on the electrochemical measurement conditions input by the user. Such electrochemical measurement conditions are as described with reference to FIGS. 7 and 12, and are therefore omitted. Note that you may call up the electrochemical measurement conditions stored in the memory or the like in advance and perform step S1430 based on the electrochemical measurement conditions.

Step S1460: When the measurement is completed in step S1450, one measured evaluation plate 120 ”is discarded.

Step S1510: If there is one or more unused evaluation plates 120 and the integer part n of the solution obtained by dividing the capacitance V by the fixed amount v is 2 or more, the process proceeds to step S1520. If there is no one or more unused evaluation plates 120, or if the integer portion n of the solution obtained by dividing the capacitance V by a fixed amount v is 1, the measurement ends here.

Step S1520: Step S1420 to step S1460 are repeated n-1 times. Here, n is an integer part of the solution obtained by dividing the capacitance V by a fixed quantity v. In this way, for one mother liquor plate 110', a plurality of test solutions can be prepared for each of n evaluation plates, and their electrochemical characteristics can be evaluated with high throughput.

Step S1530: If there is one or more unused mother liquor plates 110 and one or more unused evaluation plates 120 following step S1520, the process may be further advanced to step S1540. If there is no unused one or more mother liquor plates 110, or no unused one or more evaluation plates 120, the measurement ends here.

Step S1540: Steps S141-10 are repeated. The number of repetitions may be repeated until one or more unused mother liquor plates 110 are exhausted or one or more unused evaluation plates 120 are exhausted. Thereby, at least a plurality of test solutions can be prepared for each of the number of evaluation plates corresponding to the number of mother liquor plates multiplied by n, and their electrochemical properties can be evaluated with high throughput. Since the end of the extraction from the mother liquor plate and the end of the injection into all the evaluation plates can be kept constant, efficient long-term operation is possible.

Next, the present invention will be described in detail with reference to specific examples, but it should be noted that the present invention is not limited to these examples.

[Example 1]
In Example 1, the electrical characteristics of various electrolytic solutions were measured all at once using the automatic electrochemical measurement system shown in FIG.

FIG. 16 is a schematic diagram showing an automatic electrochemical measurement system used in the examples.

The automatic electrochemical measurement system 1600 shown in FIG. 16 includes a plate stacker 1630 equipped with six mother liquor plates 1610 and 36 evaluation plates 1620, a robot arm 1640 that conveys them, and a non-contact dispensing system 1650. A measurement stage 1660 equipped with a first probe group and a second probe group, a charge / discharge tester 1670, a robot arm 1640, a non-contact dispensing system 1650, a measurement stage 1660, and a charge / discharge tester 1670. It was equipped with a computer 180 equipped with a display for controlling the operation. Further, the automatic electrochemical measurement system 1600 further includes a waste liquid container 1601 for discarding the waste liquid and a waste container 1602 for discarding the plate.

Elements other than the charge / discharge tester 1670 and the computer 1680 were housed in the glove box 1690, and the inside of the glove box was controlled to an argon atmosphere.

FIG. 17 is a diagram showing the appearance of the evaluation plate.

The evaluation plate has 96 wells in a matrix of 8 rows (A to H) x 12 columns (1 to 12), and each well has a pair of electrodes (nickel foil and lithium metal foil) and their wells. An electrode member made of glass fiber paper (Whatman®, GF / A) was placed between the electrodes. In addition, 25 μL of DMA (dimethylacetamide) in which 1 M of LiNO ₃ was dissolved was previously stored in each well as a common electrolytic solution.

Like the evaluation plate, the mother liquor plate also had 96 wells in a matrix of 8 rows × 12 rows, and the volume of the mother liquor contained in each well was 1 mL.

The dispensing condition setting button was selected from the interface shown in FIG. 7, and 1 mL was input to the well volume (corresponding to the volume V) of the mother solution plate and 6 was input to the number of mother solution plates on the mother solution tab of the dispensing condition setting screen. Next, 150 μL was selected as the amount of the mother liquor extract (corresponding to the fixed amount v), 32 was selected as the number of wells used in the mother liquor plate, and Tables 1 and 2 were uploaded as the mother liquor plate recipe. It should be understood that Tables 1 and 2 are actually one continuous table.

Subsequently, in the test solution tab, 25 μL was selected as the amount of test solution prepared in each well of the evaluation plate, Tables 3 to 6 were uploaded as the evaluation plate recipe, and 36 was entered as the number of evaluation plates. The confirmation button was pressed on the dispensing condition setting screen, and it was confirmed that there was no problem with the dispensing condition. Tables 3 to 6 show only the evaluation plate recipe corresponding to the first evaluation plate out of the 36 evaluation plates. It should be noted that Tables 3 to 6 are actually one continuous table, and it should be understood that 96 recipes are described on the first evaluation plate.

Select the electrochemical measurement condition setting button from the interface shown in FIG. 7, and in the sequence tab of the electrochemical measurement condition setting screen, the sequence No. Select 3 (Pattern No. 1, number of cycles 3), and in the Pattern tab, select Pattern No. 1. The charge / discharge condition of 1 was set. Pattern No. 1 is shown in Table 7.

The interface was returned to that shown in FIG. 7, and the execute button was pressed. The test solution was prepared on all 36 evaluation plates and the electrochemical characteristics were measured without stopping the system 1600 due to an error. The measurement time was 144 hours (about 6 days). After the measurement was completed, it was confirmed that the plate stacker 1630 had neither a mother liquor plate nor an evaluation plate and was empty.

Since the volume V of the wells of the mother liquor plate is 1 mL and the fixed amount v is 150 μL, the integer portion n of the solution obtained by dividing the volume V (1 mL = 1000 μL) by the fixed amount v (150 μL) is 6, and the mother liquor plate It was confirmed that a plurality of test solutions were prepared for each of the 36 evaluation plates corresponding to the number (6) multiplied by 6 (= n), and the electrochemical characteristics were measured. The end of extraction from all mother liquor plates installed on the plate stackers and the end of injection of liquor into all evaluation plates are always constant, and efficient long-term operation is possible simply by replacing each plate stacker. Was shown to be.

After the measurement, when the result button of the interface shown in FIG. 7 was pressed, the results shown in Tables 8 to 11 were displayed. Tables 3 to 6 show only the evaluation plate recipe corresponding to the first evaluation plate out of the 36 evaluation plates, while Tables 8 to 11 show the plurality of wells and the plurality of test solutions provided in the evaluation plates. The information (column (vertical) and row (horizontal), test solution number) and the corresponding Coulomb efficiency results for each cycle (1st to 3rd) were displayed for each sheet of the evaluation plate. It should be understood that Tables 8 to 11 are actually one continuous table, and 96 results are described on the first evaluation plate.

By using the automatic electrochemical measurement system of the present invention, the electrochemical characteristics of a plurality of test solutions can be evaluated at the same time, which is particularly advantageous for acquiring a data group for algorithmizing a battery electrolyte.

100, 600, 1600 Automatic electrochemical measurement system 110, 1610 1 or more mother liquor plates 110', 200 1 mother liquor plate 120, 16201 1 or more evaluation plates 120', 300 1 evaluation plate 120 ”Contains multiple test solutions Evaluation plate 130, 1630 Plate stacker 140 Transport means 150 Dispensing means 160, 1660 Measurement stage 161 First probe group 162 Second probe group 170 Electrochemical measuring device 180, 640 Control means 190, 1690 Globe box 210, 310 Well 220 Mother's solution 330, 340 Pair of electrodes 350 Separator 360 Test solution 370, 380 Probe 410, 510 Plate 420, 520 Hole 610 Waste liquid part 620 Disposal part 630 Display means 700 User interface 710 Dispensing condition setting button 720 Electrochemical measurement condition setting Button 730 Execute button 740 Result button 750 End button 800 Dispensing condition setting screen 1200 Electrochemical measurement condition setting screen 1640 Robot arm 1650 Non-contact dispensing system 1670 Charging / discharging tester 1680 Computer

Claims (20)

It is an automatic electrochemical measurement system that simultaneously measures the electrochemical characteristics of a test solution made by mixing two or more mother liquors.
A plate stacker in which one or more mother liquor plates having a plurality of wells containing each of a plurality of mother liquors and one or more evaluation plates having a plurality of wells containing each of a plurality of test solutions are installed. A pair of electrodes and a separator located between the pair of electrodes are arranged in each of the plurality of wells included in the one or more evaluation plates, and one electrode of the pair of electrodes is the said. Plate stackers, located at the bottom of each of the multiple wells,
A transport means for transporting the one or more mother liquor plates and the one or more evaluation plates.
The mother liquor is extracted from each of the plurality of wells of the one or more mother liquor plates, and the extracted mother liquor is injected into the plurality of wells of the one or more evaluation plates to prepare the plurality of test solutions. Dispensing means and
A measurement stage on which an evaluation plate having the plurality of wells containing each of the plurality of test solutions is placed, and the measurement stage is one of the pair of electrodes arranged in each of the plurality of wells. A measurement stage comprising a first probe group consisting of a plurality of probes electrically connected to each other and a second probe group consisting of a plurality of probes electrically connected to the other of the pair of electrodes.
An electrochemical measuring device that is electrically connected to the first probe group and the second probe group and simultaneously measures the electrochemical characteristics of each of the plurality of test solutions.
The transport means, the dispensing means, the measuring stage, and the control means for controlling the operation of the electrochemical measuring device are provided.
The control means
The dispensing means
(A) A fixed amount v of a mother liquor from one well of one of the one or more mother liquor plates (however, the fixed amount v is a mother liquor contained in the one well of the one mother liquor plate. The volume of V or less) is extracted, and the extracted mother liquor is poured into the wells of one evaluation plate.
(B) The fixed amount v of the mother liquor is extracted from another well of the one mother liquor plate, and the extracted mother liquor is poured into the well of the one evaluation plate.
(C) The above (A) and the above (B) are repeated to prepare the plurality of test solutions on the one evaluation plate.
(D) For each of the one or more mother liquor plates, the plurality of test solutions are prepared in a number of evaluation plates corresponding to the integer portion n of the solution obtained by dividing the volume V by the fixed amount v. Repeat (A), (B) and (C).
An automated electrochemical measurement system that controls the operation of the dispensing means. The control means interlocks with the operation of the dispensing means, and the transport means
Each of the one or more mother liquor plates and each of the one or more evaluation plates are transported from the plate stacker to the dispensing position of the dispensing means.
The evaluation plate having the plurality of wells containing each of the plurality of test solutions prepared by the dispensing means is transported from the dispensing position to the measuring stage.
The automatic electrochemical measurement system according to claim 1, which controls the operation of the transport means. The control means is interlocked with the operation of the transport means, and the measurement stage is
When the evaluation plate having the plurality of wells containing each of the plurality of test solutions is placed on the measurement stage, at least one of the first probe group and the second probe group is placed. Movable, the first probe group is electrically connected to one of the pair of electrodes arranged in each of the plurality of wells, and the second probe group is electrically connected to the other of the pair of electrodes. The first probe group and the second probe group are electrically connected to the electrochemical measuring device.
When the measurement by the electrochemical measuring device is completed, at least one of the first probe group and the second probe group is movable, and the first probe group and the second probe group are paired. To keep away from the electrodes
The automated electrochemical measurement system according to claim 1 or 2, which controls the operation of the measurement stage. In the control means, when the electrochemical measuring device electrically connects the first probe group and the second probe group to the pair of electrodes, the electrochemical measuring device conducts electricity of the plurality of test solutions. The automated electrochemical measurement system according to claim 3, which controls the operation of the electrochemical measuring device so as to measure chemical characteristics. The automated electrochemical measurement system according to any one of claims 1 to 4, further comprising a display means. The automatic electrochemical measurement system according to claim 5, wherein the control means controls the operation of the display means so that the display means displays the measurement result by the electrochemical measurement device. The control means causes the display means to cause the user to input a dispensing condition including at least the fixed amount v, the composition of the plurality of mother liquors, and the composition of the plurality of test solutions, and / or an electrochemical measurement. The automated electrochemical measurement system according to claim 5 or 6, which controls the operation of the display means so as to display a user interface for inputting conditions. Based on the dispensing conditions, the control means calculates the total amount of each of the plurality of mother solutions used from the compositions of the plurality of test solutions for each of the one or more evaluation plates, and the plurality of test solutions. The total amount of each of the mother liquors used is compared with the fixed amount v, and when at least one of the total amounts of each of the plurality of mother liquors used exceeds the fixed amount v, the above 1 or more. For each of the mother liquor plates, it is determined that the plurality of test solutions cannot be prepared in a number of evaluation plates corresponding to the integer portion n of the solution obtained by dividing the volume V by the fixed amount v, and a warning is given to the display means. The automatic electrochemical measurement system according to claim 7, which is displayed and prompts the user to reset the dispensing conditions. The automated electrochemical measurement system according to any one of claims 1 to 8, wherein each of the plurality of wells included in the one or more evaluation plates has a common electrolytic solution which is a lithium salt. In the dispensing means, the height of the test liquid contained in each of the plurality of wells provided in the evaluation plate from the bottom of the well is the other side facing one electrode located at the bottom. The automated electrochemical measurement system according to claim 9, wherein the plurality of test solutions are prepared so as to be lower than the height of the electrodes. The automated electrochemical measurement system according to any one of claims 1 to 10, further comprising the plate stacker, the transport means, the dispensing means, and a glove box accommodating the measurement stage. The automatic electrochemical measurement system according to claim 11, wherein the atmosphere in the glove box is an inert gas atmosphere. The automatic electrochemical measurement system according to any one of claims 1 to 12, wherein the first probe group and the second probe group pressurize the pair of electrodes with a force in the range of 200 gf or more and 10 kgf or less. The waste liquid part that discards the waste liquid and
It also has a disposal department that disposes of waste.
The control means
The dispensing means extracts the fixed amount v of the mother liquor from one of the plurality of wells included in the mother liquor plate of one or more mother liquor plates, and the one evaluation plate comprises the said. Every time the liquid is injected into the plurality of wells, the operation of the dispensing means is controlled so that the remaining mother liquor of the fixed amount v is discarded in the waste liquid portion.
Each time the dispensing means extracts the fixed amount v of the mother liquor from all of the plurality of wells of the one mother liquor plate among the one or more mother liquor plates by the number of the integer portion n, and. / Or, each time the electrochemical measuring device finishes measuring the electrochemical characteristics of the plurality of test solutions on the one evaluation plate, the transport means transfers the one mother solution plate and / or the one. The automated electrochemical measurement system according to any one of claims 1 to 13, which controls the operation of the transport means so that one evaluation plate is disposed of in the disposal unit. The control means claims that the information of a plurality of test solutions in the plurality of wells provided in each of the one or more evaluation plates and the measurement results corresponding to the plurality of test solutions are stored in a memory together. The automated electrochemical measurement system according to any of 14. The plate stacker includes the one or more mother liquor plates and the first one or more so that the number of the one or more evaluation plates corresponds to the number obtained by multiplying the number of the one or more mother liquor plates by the integer portion n. The automatic electrochemical measurement system according to any one of claims 1 to 15, wherein the above evaluation plate is installed. It is a method of automatically measuring the electrochemical characteristics of a test solution obtained by mixing two or more mother solutions at the same time.
A step of moving one of one or more stock solutions plates having multiple wells containing each of the stock solutions to the dispensing position.
A step of moving one of one or more evaluation plates having a plurality of wells for accommodating each of a plurality of test solutions to a dispensing position, wherein the plurality of evaluation plates included in the one or more evaluation plates are provided. A pair of electrodes and a separator located between the pair of electrodes are arranged in each of the wells, and one electrode of the pair of electrodes is located at the bottom of each of the plurality of wells. ,
This is a step of preparing a plurality of test solutions on the one evaluation plate.
A fixed amount v of the mother liquor (wherein the fixed amount v is equal to or less than the volume V of the mother liquor contained in the one well of the one mother liquor plate) is extracted from one well of the one mother liquor plate. Then, in the step (a) of injecting the extracted mother liquor into the well of the one evaluation plate,
In step (b), a fixed amount v of the mother liquor is extracted from another well of the one mother liquor plate, and the extracted mother liquor is injected into the well of the one evaluation plate.
A step that repeats the step (a) and the step (b) to prepare the plurality of test solutions on the one evaluation plate, and the step (c).
A step of electrically connecting the pair of electrodes of each of the plurality of wells included in the one evaluation plate and the electrochemical measuring device,
A step of causing the electrochemical measuring device to simultaneously measure the electrochemical characteristics of each of the plurality of test solutions on the one evaluation plate.
The step of discarding the measured evaluation plate and
When the number of the evaluation plates of 1 or more is 2 or more and the integer portion n of the solution obtained by dividing the volume V by the fixed amount v is 2 or more, the integer is the integer for the one mother liquor plate. A step of taking out the one evaluation plate, a step of preparing the plurality of test solutions, and a step of electrically connecting the test solutions so as to measure the electrochemical characteristics of the plurality of test solutions for the number of evaluation plates corresponding to the portion n. A method comprising the step of repeating the step of measuring and the step of discarding n-1 times. 17. The method of claim 17, further comprising the step of repeating the n-1 times, followed by the step of moving the one mother liquor plate and subsequent steps. The step of preparing the plurality of test solutions is according to claim 17 or 18, based on a dispensing condition input by the user, which comprises at least the fixed amount v, the composition of the plurality of mother liquors, and the composition of the plurality of test solutions. The method described. The method according to any one of claims 17 to 19, wherein the step to be measured is based on an electrochemical measurement condition input by a user.