JP4701450B2 - Battery characteristic evaluation apparatus and battery characteristic evaluation method - Google Patents

Description

  The present invention relates to an apparatus for measuring battery characteristics of a sealed battery and a measuring method thereof.

Conventionally, in order to evaluate battery characteristics such as electromotive force and discharge characteristics of a battery, the battery is discharged under a predetermined condition, and the voltage between the positive and negative electrodes every time and the voltage between the positive and negative electrodes every discharge capacity are changed. Has been measured and evaluated.
In addition, when evaluating each single electrode of the positive and negative electrodes, the evaluation is performed by reproducing the state of the single electrode using a simple cell, a reference electrode, etc., and measuring the voltage of the cell or the like. I have been. (See Non-Patent Document 1)
Akira Fujishima, Masuo Aizawa, Tohru Inoue, Electrochemical Measurement Method, Gihodo Publishing, Chapters 3-4, Experiment Chart 3.1, Figure-3.2, etc.

  The method of measuring the voltage between the positive and negative electrodes for each time and the voltage change between the positive and negative electrodes for each discharge capacity for judging the battery characteristics is for evaluating the battery voltage that appears as the difference between the positive electrode potential and the negative electrode potential. It is difficult to determine whether the obtained voltage and battery characteristics are due to the positive electrode material or the negative electrode material, and it is difficult to obtain useful information for developing the positive electrode material and negative electrode material. was there. For example, even when the battery voltage is 1.5V, the positive electrode potential may be 1.2V and the negative electrode potential -0.3V, and the positive electrode potential may be 0.3V and the negative electrode potential may be -1.2V.

On the other hand, for example, when evaluating each single electrode of the positive electrode material and the negative electrode material using a simple cell, a reference electrode, etc., the positive electrode, the negative electrode can be obtained by installing the reference electrode in the vicinity of the electrode to be measured. Each potential and battery characteristics can be measured. However, the evaluation results obtained from these measurement methods are measurements using simple cells in which the electrode structure and the battery structure etc. are significantly different from those of the actual batteries. There were various problems when applied to manganese batteries.
Therefore, the present invention is capable of measuring the potential of the positive electrode material and the negative electrode material separately and with high accuracy, without greatly destroying the original battery shape, for example, in a sealed battery such as a sealed alkaline manganese battery. A battery characteristic evaluation apparatus and a battery characteristic evaluation method are provided.

That is, the first means for solving the above problem is as follows.
An apparatus for evaluating battery characteristics of a sealed battery,
The sealed battery with perforations that do not impair the battery characteristics is provided in the battery can body,
An electrolyte outside the sealed battery in contact with the electrolyte contained in the sealed battery through the perforations ;
An electrode immersed in an electrolyte outside the sealed battery;
A load for discharging the sealed battery under desired conditions;
Voltage between the positive and negative electrodes of the sealed battery, the voltage between the hermetic being said immersion and cathode materials constituting the positive electrode of the battery, is the negative electrode material constituting the anode immersed in said sealed battery Measuring means for measuring at least two voltages selected from among the voltages between the two electrodes,
The battery characteristic evaluation apparatus is characterized by measuring a potential difference between a positive electrode material and a negative electrode material with respect to an electrode immersed in an electrolyte outside the sealed battery from the voltage value .

The second means is a battery characteristic evaluation device for a sealed battery,
An electrolyte outside the sealed battery in contact with the electrolyte contained in the sealed battery;
An electrode immersed in an electrolyte outside the sealed battery;
A load for discharging the sealed battery under desired conditions;
Voltage between the positive and negative electrodes of the sealed battery, the voltage between the hermetic being said immersion and cathode materials constituting the positive electrode of the battery, is the negative electrode material constituting the anode immersed in said sealed battery And a measuring means for measuring at least two voltages selected from among the voltages between the two electrodes.

The third means is a battery characteristic evaluation device for a sealed battery,
A load for discharging the sealed battery under a predetermined condition; a voltage measuring unit; an electrolyte solution outside the sealed battery; and an electrode immersed in the electrolyte solution outside the sealed battery. And
The voltage measuring means, the voltage between the positive and negative electrodes of the sealed battery, the voltage between the electrode on the can body side of the sealed battery and the electrode immersed in the electrolyte, accompanying the discharge, Is to measure
In the battery characteristic evaluation apparatus, an electrode immersed in an electrolytic solution outside the sealed battery is installed in the vicinity of the can of the sealed battery.

The fourth means is a battery characteristic evaluation method of a sealed battery,
Contacting the electrolyte contained in the sealed battery with the electrolyte outside the sealed battery;
While discharging the sealed battery under predetermined conditions, it is immersed in the voltage between the positive and negative electrodes of the sealed battery, the positive electrode material constituting the positive electrode of the sealed battery and the electrolyte outside the sealed battery. Selected from among three voltages: the voltage between the electrode and the electrode between the negative electrode material constituting the negative electrode of the sealed battery and the electrode immersed in the electrolyte outside the sealed battery The battery characteristic evaluation method is characterized in that at least two voltages are measured.

The fifth means is a battery characteristic evaluation method for a sealed battery,
In the sealed battery can body, a perforation that does not impair the battery characteristics of the sealed battery is provided,
Via the perforations, the electrolyte contained in the sealed battery is brought into contact with an electrolyte outside the sealed battery having the same composition and concentration as the electrolyte, and outside the sealed battery. Immerse the electrode in a certain electrolyte,
While discharging the sealed battery under predetermined conditions, the voltage between the electrode on the can body provided with the perforations of the sealed battery and the electrode immersed in the electrolytic solution is measured, and the sealed battery It is a battery characteristic evaluation method characterized by measuring a potential difference between an electrode material of a can body side electrode provided with a battery perforation and an electrode immersed in the electrolytic solution.

The sixth means is a method for evaluating battery characteristics of a sealed battery,
In the sealed battery can body, a perforation that does not impair the battery characteristics of the sealed battery is provided,
Via the perforations, the electrolyte contained in the sealed battery is brought into contact with an electrolyte outside the sealed battery having the same composition and concentration as the electrolyte, and outside the sealed battery. Immerse the electrode in a certain electrolyte,
While discharging the sealed battery under predetermined conditions, a voltage between the positive and negative electrodes of the sealed battery, a can body provided with a perforation of the sealed battery, and an electrode immersed in the electrolyte A voltage between the electrode material of the electrode that is not on the can body provided with the perforations of the sealed battery and an electrode immersed in the electrolytic solution is calculated from the two voltages. This is a battery characteristic evaluation method.

The seventh means is a battery characteristic evaluation method for a sealed battery,
In the sealed battery can body, a perforation that does not impair the battery characteristics of the sealed battery is provided,
Via the perforations, the electrolyte contained in the sealed battery is brought into contact with an electrolyte outside the sealed battery having the same composition and concentration as the electrolyte, and outside the sealed battery. Immerse the electrode in a certain electrolyte,
While discharging the sealed battery under predetermined conditions, a voltage between the positive and negative electrodes of the sealed battery, a can body provided with a perforation of the sealed battery, and an electrode immersed in the electrolyte The voltage difference between the electrode material of the can body side electrode provided with perforations in the sealed battery and the electrode immersed in the electrolytic solution, the can provided with perforations It is a battery characteristic evaluation method characterized by measuring a potential difference between an electrode material of an electrode that is not on the body side and an electrode immersed in the electrolytic solution, and a voltage between positive and negative electrodes.

  The battery characteristic evaluation apparatus according to the first means for solving the problem is immersed in an electrolyte outside the sealed battery in a form close to an actual battery without greatly losing the sealed battery being evaluated. The potential difference between the positive electrode material and the negative electrode material with respect to the formed electrode can be obtained.

  The battery characteristic evaluation apparatus according to the second means is configured such that the voltage between the positive and negative electrodes of the sealed battery, the positive electrode of the sealed battery, in a form close to an actual battery, without greatly destroying the sealed battery to be evaluated. Between the positive electrode material constituting the electrode and the electrode immersed in the electrolyte outside the sealed battery, the negative electrode material constituting the negative electrode of the sealed battery and the electrolyte outside the sealed battery By measuring at least two voltages selected from the voltages between the positive electrode material and the negative electrode material, the positive electrode material and the negative electrode material for the electrode immersed in the electrolyte outside the sealed battery are measured based on these values. The potential difference can be obtained.

  The battery characteristic evaluation apparatus according to the third means is immersed in the electrode on the can body and the electrolyte outside the sealed battery in a form close to a real battery without greatly losing the sealed battery to be evaluated. Since the voltage between the electrodes and the voltage between the positive and negative electrodes can be measured, the positive electrode material and the negative electrode material with respect to the electrode immersed in the electrolyte outside the sealed battery can be measured from these values. The potential difference can be obtained.

  According to the battery characteristic evaluation method according to the fourth means, the voltage between the positive and negative electrodes of the sealed battery, the sealed battery in a form close to an actual battery without greatly losing the sealed battery to be evaluated. The voltage between the positive electrode material constituting the positive electrode and the electrode immersed in the electrolyte solution outside the sealed battery, the negative electrode material constituting the negative electrode of the sealed battery and the electrolyte solution outside the sealed battery By measuring at least two voltages selected from among three voltages, the voltage between the immersed electrode and the electrode, the positive electrode for the electrode immersed in the electrolyte outside the sealed battery from these values The potential difference between the material and the negative electrode material can be determined.

  According to the battery characteristic evaluation method according to the fifth means, outside the sealed battery and the can-side electrode provided with perforations in a form close to an actual battery, without greatly losing the sealed battery to be evaluated. Measuring the voltage between the electrode immersed in an electrolyte and determining the potential difference of the electrode material of the can-side electrode provided with perforations relative to the electrode immersed in the electrolyte outside the sealed battery it can.

  According to the battery characteristic evaluation method according to the sixth means, the sealed battery which is not the can body side provided with the perforations and the sealed battery in a form close to an actual battery without greatly breaking the sealed battery to be evaluated The voltage between the electrode immersed in the electrolyte solution outside can be obtained, and the electrode material of the electrode that is not on the can body side provided with the perforations with respect to the electrode immersed in the electrolyte solution outside the sealed battery Can be obtained.

  According to the battery characteristic evaluation method according to the seventh means, the can-side electrode provided with a voltage between the positive and negative electrodes and a perforation in a form close to an actual battery without greatly losing the sealed battery to be evaluated. The voltage between the electrode immersed in the electrolytic solution outside the sealed battery and the electrode immersed in the electrolytic solution outside the sealed battery can be measured simultaneously. The potential difference of the negative electrode material can be obtained.

The present inventor has conducted extensive research to solve the above-described problems. Then, after providing a hole in one or both of the cans in contact with the positive electrode material or the negative electrode material of the sealed battery to be measured, the battery is electrolyzed having the same composition and concentration as the electrolyte solution of the battery. It is installed in a new battery characteristic evaluation apparatus that can be immersed in the liquid, and the electrolyte inside and outside the battery is brought into contact. Next, the voltage between the positive and negative electrodes of the battery, an electrode immersed in an electrolyte outside the sealed battery provided near the outside of the perforation (hereinafter, may be referred to as a reference electrode) and the perforation. The voltage between the positive electrode near the inner side of the hole (provided that the perforation is provided in the can on the positive electrode side), the voltage between the reference electrode provided near the outer side of the perforation and the negative electrode near the inner side of the perforation ( However, when the perforation is provided in the can on the negative electrode material side.), The battery is discharged under desired conditions while measuring at least two voltages selected from the three voltage values of Let Then, it came to the idea that the potential difference between the reference electrode and the electrode material inside the perforation can be measured while the sealed battery as the measurement object is still configured as a battery.
On the other hand, since the total potential difference between the positive electrode material and the negative electrode material with respect to the reference electrode becomes the voltage between the positive and negative electrodes of the battery, it is possible to measure at least two voltages selected from the three voltages. The remaining voltage can be easily calculated.

Each voltage obtained by measuring the battery voltage, the positive electrode material potential, and the negative electrode material potential while discharging the battery under predetermined conditions, and the correlation between the potential and the discharge time are battery characteristics, positive electrode material, and The present inventors have found that there is a relationship with each characteristic of the negative electrode material, and have arrived at a novel battery characteristic evaluation apparatus and battery characteristic evaluation method.
Here, embodiments of the present invention will be described with reference to the drawings.
In the description, a cylindrical alkaline manganese battery is used as an example of a sealed battery, and a perforation is provided in a can on the negative electrode side, a voltage between the positive and negative electrodes of the battery, and a reference electrode and the inside of the perforation. An example of measuring the voltage with the negative electrode material will be described. In the embodiment of the present invention, an Hg / HgO reference electrode (hereinafter sometimes referred to as a reference electrode) was used as a reference electrode.
Here, FIG. 1 is a schematic cross-sectional view of a battery characteristic evaluation apparatus according to the present invention and a block diagram of a measurement circuit.

First, the battery characteristic evaluation apparatus 1 according to the present invention will be described.
The battery characteristic evaluation apparatus 1 according to the present invention includes a measurement cell 10, a voltage measuring device 50, and a discharge device 60. The measurement cell 10 is filled with the electrolytic solution 11 outside the alkaline manganese battery 30 which is an example of a sealed battery, and the reference is immersed in the electrolytic solution 11 as an alkaline manganese battery 30 to be evaluated and a reference electrode. The electrode 20 is supported and installed by appropriate support means (not shown).

  The alkaline manganese battery 30 has a positive electrode 31 and a negative electrode 32, and the can body 33 is provided with perforations 40. The internal structure of the alkaline manganese battery 30 will be described later. On the other hand, as for the reference electrode 20, the Hg / HgO electrode 22 is installed in the lugin tube 21, and the tip 23 of the lugin tube 21 is 2-20 mm in the vicinity of the perforation 40 by a support means such as a clamp, more preferably 2-10 mm. Is installed.

  The electrolytic solution 11 in the measurement cell 10 immerses the perforations 40 of the alkaline manganese battery 30 and the Hg / HgO electrode 22. However, the negative electrode 32 to which the measurement lead wire is connected is previously sealed with a sealing material 45 such as a resin so as not to come into contact with the electrolytic solution 11. And the electrolyte solution 11 has the same composition and the same density | concentration as the electrolyte solution 38 in the alkali manganese battery 30 mentioned later. Instead of sealing the negative electrode 32 with the sealing material 45, this may be configured to protrude above the liquid surface of the electrolytic solution 11, but the negative electrode 32 is sealed with the sealing material 45 and the entire alkaline manganese battery 30 is electrolyted. 11, the temperature of the alkaline manganese battery 30 can be easily controlled by controlling the temperature of the electrolytic solution 11. Therefore, the immersion of the entire alkaline manganese battery 30 is a preferable configuration.

The voltage measuring device 50 measures the voltage between the positive electrode 31 and the reference electrode 20.
The discharge device 60 is provided with a voltage measuring device 61, a load (variable current device) 62 and a switch 63 that can discharge the battery to be evaluated under predetermined conditions (current value, ON-OFF timing, etc.). Has been.

Next, the structure of the alkaline manganese battery 30 and the perforations 40 will be described.
The alkaline manganese battery 30 includes, for example, manganese dioxide as a positive electrode material 34, a separator 35, zinc powder as a negative electrode material 36, and a negative electrode current collector 37 in an iron can 33 whose surfaces are nickel-plated in order from the outside. For example, a tin-plated brass bar is provided. The can body 33 comes into contact with the positive electrode material 34 to become a positive electrode, and is joined to the positive electrode 31 to also serve as a positive electrode side lid portion of the can body 33. The negative electrode current collector 37 comes into contact with the negative electrode material 36 to become a negative electrode, and is bonded to the negative electrode 32. The negative electrode 32 also serves as a negative electrode side lid of the can 33 together with a sealing material 39 made of resin or the like. The positive electrode material 34, the separator 35, and the negative electrode material 36 are immersed in the electrolytic solution 38. The electrolytic solution 38 of the alkaline manganese battery 30 is, for example, a KOH aqueous solution.

  Here, the perforation 40 provided in the can 33 will be described. The perforations 40 contact the electrolytic solution 38 in the alkaline manganese battery 30 and the electrolytic solution 11 in the measurement cell 10 described with reference to FIG. 1, and serve as a measurement window for measuring the characteristics of the battery described later. It is. Specifically, the molded body of the positive electrode material 34 filled in the can body 33 is broken by perforations having a diameter of about 1 to 2 mm and a depth of about 0.5 to 1 mm provided at a substantially central portion of the can body 33. There is no. As will be described later, the potential of the positive electrode material 34 is measured by the reference electrode 20 through the perforations 40. However, the structural limitations of the reference electrode 20 (for accurate measurement, the Hg / HgO electrode 22 is almost the same). The whole is preferably immersed in the electrolytic solution.) Therefore, the alkaline manganese battery 30 is immersed in the electrolytic solution 11 having the same composition as the electrolytic solution 38 in the battery, and the tip 23 of the lugin tube 21 is brought close to the perforation 40. The measurement is performed. In addition, since the perforations 40 are minute as compared with the whole of the alkaline manganese battery 30, the measurement can be performed while maintaining almost the same state as the battery before drilling.

Next, a method for measuring the characteristics of the alkaline manganese battery 30 using the battery characteristic evaluation apparatus 1 according to the present invention will be described.
First, the voltage measuring device 50 measures a voltage between the electrode on the can body 33 side and the reference electrode 20 (this is E2), and the voltage measuring device 61 in the discharge device 60 includes the positive electrode 31 and the negative electrode. 32 is measured (this is referred to as E1). Further, the discharge device 60 applies a predetermined load to the alkaline manganese battery 30 by the load 62 and the switch 63, and the E1 and E2 of the alkaline manganese battery 30 to which this load is applied are measured.
Here, it is difficult to directly measure the voltage between the electrode that is not on the can body 33 and the reference electrode 20 (referred to as E3), but E1 and E2 using the relationship of E1 = E2 + E3. From the value of E3, the value of E3 can be calculated as appropriate.

  As a result, with the load 62 and the switch 63 in the discharge device 60, the alkaline manganese battery 30 is subjected to a predetermined load (for example, constant current continuous discharge while applying a predetermined load, or pulse discharge while applying a predetermined load. The potential difference between the positive electrode material 34 and the negative electrode material 36 with respect to the reference electrode 20 can be accurately measured, and the time change of each potential difference can be measured. Since the time change of the potential difference between each of the positive electrode material 34 and the negative electrode material 36 can be measured with high accuracy, the polarization state of each electrode material and the resistance component are almost the same as in the actual battery. I was able to grasp the condition. As a result, it is possible to evaluate and select the positive electrode material 34 and the negative electrode material 36 that are preferable as an actual battery.

  That is, according to the battery characteristic evaluation apparatus and the battery characteristic evaluation method according to the present invention, the battery characteristic can be measured while maintaining a form close to an actual battery sealed in a can, which has been difficult in the past. It can be said that the potential difference between the positive electrode material and the negative electrode material with respect to the reference electrode can be clearly separated and measured with high accuracy, and so on.

  As described above, a cylindrical alkaline manganese battery is used as the sealed battery, and the can on the negative electrode side is perforated, and the voltage between the positive and negative electrodes of the battery, the electrolyte near the outside of the perforation, and the negative electrode material near the inside of the perforation The battery characteristic evaluation apparatus and the battery characteristic evaluation method according to the present invention have been described using the case of measuring the voltage as an example.

Next, modifications 1 to 3 of the battery characteristic evaluation apparatus and the battery characteristic evaluation method according to the present invention will be described with reference to FIGS.
In the description of the first to third modifications, a button-type alkaline manganese battery is used as an example of the sealed battery, and a case in which perforations are provided in the positive electrode side and / or the negative electrode side can is taken as an example.
Further, in the description of the first to third modifications, portions overlapping with the description of the embodiment described with reference to FIG. 1 are denoted by the same reference numerals as in FIG. May be omitted.

  Here, FIG. 8 is a schematic cross-sectional view of a battery characteristic evaluation apparatus according to Modification 1, and a block diagram of a measurement circuit.

  First, in the battery characteristic evaluation device 2 according to the first modification, the measurement cell 10, the voltage measuring device 50, the discharge device 60, and the reference electrode 20 are the same as those of the battery characteristic evaluation device 1 described in FIG. Yes, a button-type alkaline manganese battery 70 is used as the sealed battery.

Next, the structure of the button-type alkaline manganese battery 70 and the perforations 80 will be described.
The button-type alkaline manganese battery 70 includes, for example, manganese dioxide, which is a positive electrode material 74, a separator 75, and a negative electrode material 76 in order from the right in the drawing in an iron positive electrode body 73B that is nickel-plated on both sides. Zinc powder is filled, and the negative electrode side can body 73A is covered. The positive electrode side can body 73 </ b> B comes into contact with the positive electrode material 74 to become the positive electrode 71, and the negative electrode side can body 73 </ b> A comes into contact with the negative electrode material 76 to become the negative electrode 72. Further, the negative electrode side can body 73A becomes a lid portion while being electrically insulated from the positive electrode side can body 73B by the sealing material 79 made of resin or the like. The positive electrode material 74, the separator 75, and the negative electrode material 76 are immersed in the electrolytic solution 78. The electrolyte solution 78 of the button-type alkaline manganese battery 70 is, for example, a KOH aqueous solution.

  Here, the perforation 80 provided in the substantially central portion of the positive electrode side can body 73B has the same configuration as the perforation described in FIG. 1, but when the size of the button-type alkaline manganese battery 70 is small. In addition, it is preferable to appropriately reduce both the diameter of the hole and the depth of the hole.

Next, a method for measuring the characteristics of the button-type alkaline manganese battery 70 using the battery characteristic evaluation apparatus 2 according to the present invention will be described.
First, as described with reference to FIG. 1, the distal end 23 of the Luggin tube 21 is set in the vicinity of the perforation 80 by 2 to 20 mm, more preferably 2 to 10 mm by a support means such as a clamp.
The electrolyte 111 outside the button-type alkaline manganese battery 70, which is an example of a sealed battery in the measurement cell 10, immerses the perforation 80 and the Hg / HgO electrode 22 of the button-type alkaline manganese battery 70. However, the negative electrode 72 to which the measurement lead wire is connected is previously sealed with a sealing material 85 such as a resin so as not to come into contact with the electrolytic solution 111. The electrolytic solution 111 has the same composition and the same concentration as the electrolytic solution 78 contained in the button type alkaline manganese battery 70.

On the other hand, the voltage measuring device 50 measures the voltage between the positive electrode side can body 73B and the reference electrode 20 (referred to as E2), and the voltage measuring device 61 in the discharge device 60 includes the positive electrode 71 and the negative electrode 72. (This is referred to as E1). Further, the discharge device 60 applies a predetermined load to the button-type alkaline manganese battery 70 by the load 62 and the switch 63, and E1 and E2 of the button-type alkaline manganese battery 70 to which this load is applied are measured.
Here, the voltage between the negative electrode side can body 73A and the reference electrode 20 (referred to as E3) is appropriately calculated from the values of E1 and E2, using the relationship of E1 = E2 + E3. can do.

  As a result, the load 62 and the switch 63 in the discharge device 60 give the button-type alkaline manganese battery 70 a predetermined load similar to that in the embodiment described with reference to FIG. Each potential difference of the negative electrode material 76 with respect to the reference electrode 20 could be accurately measured, and the time change of each potential difference could be measured. As a result, the positive electrode material 74 and the negative electrode material 76, which are preferable as an actual battery, can be evaluated and selected as described with reference to FIG.

Next, a different modification 2 will be described with reference to FIG. FIG. 9 is a schematic cross-sectional view of a battery characteristic evaluation device according to a different modification 2 and a block diagram of a measurement circuit.
The battery characteristic evaluation apparatus 2 according to the second modification has the same configuration as the battery characteristic evaluation apparatus 2 described in the first modification. The button-type alkaline manganese battery 70 itself, which is a sealed battery, has the same configuration as the button-type alkaline manganese battery 70 described in the first modification.

Here, the perforation 81 and the sealing material 86 provided in the button type alkaline manganese battery 70 will be described.
In the second modification, the perforations 81 are provided in the substantially central portion of the negative electrode side can body 73A, and the diameter and the like thereof are the same as those of the perforations 80 described in the first modification. And the positive electrode side can body 73B is sealed with the sealing material 86, and even if the button type alkaline manganese battery 70 is immersed in the electrolyte solution 111, it does not contact this.

As in the first modification, the button-type alkaline manganese battery 70 is connected to the discharge device 60 and immersed in the electrolytic solution 111. And the front-end | tip 23 of the Lugin tube 21 is installed 2-20 mm in the vicinity of the perforation 81, More preferably, it is 2-10 mm.

Next, a method for measuring characteristics of the button-type alkaline manganese battery 70 according to Modification 2 will be described.
First, the voltage measuring device 50 measures the voltage (referred to as E3) between the electrode on the negative electrode side can body 73A side and the reference electrode 20, and the voltage measuring device 61 in the discharge device 60 is a positive electrode 71. And the negative electrode 72 (this is referred to as E1). Furthermore, the discharge device 60 applies a predetermined load to the alkaline manganese battery 70 as in the first modification, and the E1 and E3 of the button-type alkaline manganese battery 70 to which this load is applied are measured.
Here, the voltage (referred to as E2) between the positive electrode side can body 73B and the reference electrode 20 can be calculated from the values of E1 and E3 using the relationship of E1 = E2 + E3.

  As a result, the load 62 and the switch 63 in the discharge device 60 give the button-type alkaline manganese battery 70 a predetermined load similar to that in the embodiment described with reference to FIG. Each potential difference of the negative electrode material 76 with respect to the reference electrode 20 could be accurately measured, and the time change of each potential difference could be measured. As a result, the positive electrode material 74 and the negative electrode material 76, which are preferable as an actual battery, can be evaluated and selected as described with reference to FIG.

Next, a different modification 3 will be described with reference to FIG. FIG. 10 is a schematic cross-sectional view of a battery characteristic evaluation device according to a different modification 3 and a block diagram of a measurement circuit.
The battery characteristic evaluation apparatus 3 according to the modified example 3 includes the second reference electrode 120 and the voltage measurement unit 51 in addition to the first reference electrode 20 and the voltage measurement unit 50, except that the battery described above. It has the same configuration as the characteristic evaluation device 2.
On the other hand, the button-type alkaline manganese battery 70 according to the third modification is the same as that described in the first modification, but the first perforation provided in the positive electrode can body 73B described in the first modification. 80 and the second perforation 81 provided in the negative electrode side can body 73A described in the second modification. The positive electrode 71 and the negative electrode 72 of the button-type alkaline manganese battery 70 are connected to the discharge device 60 as in the first modification. In the case of the modification 3, the can body sealing by the sealing material performed in the modifications 1 and 2 is not necessary.

Here, as in the first modification, the distal end 23 of the Lugin tube 21 of the reference electrode 20 is installed in the vicinity of the perforation 80 2 to 20 mm, more preferably 2 to 10 mm. In addition to this, in Modification 3, the tip 123 of the Lugin tube 121 of the reference electrode 120 is installed in the vicinity of 2 to 20 mm, more preferably 2 to 10 mm in the vicinity of the perforation 81, and the button type alkaline manganese battery 70, The reference electrodes 20 and 120 are immersed in the electrolytic solution 111.

Next, a method for measuring characteristics of the button-type alkaline manganese battery 70 which is a sealed battery according to Modification 3 will be described.
First, the voltage measuring device 50 measures the voltage (this is referred to as E2) between the positive electrode side can body 73B and the reference electrode 20, while the voltage measuring device 51 is connected to the negative electrode side can body 73A and the reference electrode. The voltage between 120 (this is set to E3) is measured.
Further, the discharge device 60 applies a predetermined load to the alkaline manganese battery 70 as in the first modification, and measures E2 and E3 of the button-type alkaline manganese battery 70 to which this load is applied.

  As a result, the potential difference of the positive electrode material 74 with respect to the reference electrode 20 and the potential difference of the negative electrode material 76 with respect to the reference electrode 120 can be measured, and the time change of each potential difference can be measured. As a result, the positive electrode material 74 and the negative electrode material 76, which are preferable as an actual battery, can be evaluated and selected as described with reference to FIG.

  As mentioned above, although embodiment which concerns on this invention, and its modifications 1-3 were demonstrated, furthermore, this invention is limited to the cylindrical alkaline manganese battery and button-type alkaline manganese battery which can measure further this invention. The positive and negative electrode materials, such as a cylindrical manganese battery, button-type silver oxide battery, button-type silver oxide battery, and button-type lithium battery, are stacked in a concentric or flat shape without adopting a spiral structure. Any sealed battery can be used. Further, in the embodiment and its modification according to the present invention, the reference electrode having the Hg / HgO electrode is used as the reference electrode. However, as the reference electrode, in addition to this, a calomel electrode, various kinds of electrodes can be used. A metal electrode or the like can be used.

Next, the present invention will be described in more detail using examples.
(Example 1)
An AA-type alkaline manganese battery sample 501 was prepared, and a drill having a diameter of 1 mm and a depth of 0.5 mm was provided in a substantially central portion on the side surface of the can body. Next, lead wires were provided on the positive electrode and the negative electrode of the battery sample 501, and a resin sealing material was applied thereto so that the negative electrode was not in contact with the electrolyte. And the battery sample 501 was installed in the cell for a measurement satisfy | filled with the electrolyte solution of the battery characteristic evaluation apparatus.
At this time, the electrolytic solution in the measurement cell was a 40% -KOH aqueous solution having the same composition and the same concentration as the electrolytic solution in the battery sample 501, and the electrolytic solution temperature (measurement temperature) was 20 ° C.
Next, the reference electrode in which the Hg / HgO electrode was installed in the Lugin tube was installed so that the tip of the Lugin tube was approximately 10 mm from the perforation provided in the battery sample 501.
Then, the discharge device is set so as to give a predetermined load for 1 A continuous discharge to the battery sample 501, and the voltage between the positive electrode and the negative electrode and the voltage between the positive electrode and the reference electrode are measured every discharge time. did. And the voltage between a negative electrode and a reference electrode was computed from these values. The measurement results are shown by thick solid lines in FIGS.
2 to 4 are graphs in which the vertical axis represents the measured or calculated voltage and the horizontal axis represents the discharge time. FIG. 2 shows the voltage between the positive electrode and the negative electrode for each discharge time, FIG. 3 shows the voltage between the positive electrode and the reference electrode for each discharge time, and FIG. 4 shows the voltage for each discharge time. The voltage between a negative electrode and a reference electrode is shown.

(Example 2)
A single-cylinder alkaline manganese battery sample 502 of a brand different from that of the battery sample 501 was prepared, and the same test as in Example 1 was performed. The measurement results are shown by solid lines in FIGS.

(Example 3)
A single-cylinder alkaline manganese battery sample 503 of a brand different from the battery samples 501 and 502 was prepared, and the same test as in Example 1 was performed. The measurement results are shown by broken lines in FIGS.

(Analysis of Examples 1 to 3)
1) From FIG. 2, it was found that the discharge capacity of the battery sample 501 was the largest, and in the following order, the battery sample 502 and the battery sample 503.
When the reason why the discharge capacity of the battery sample 501 is large is read from FIG. 3 and FIG. 4, the battery sample 501 is found from FIG. 4 although the polarization of the positive electrode material is large as can be seen from FIG. 3. It has been found that the negative electrode material has a large discharge capacity due to the small polarization.
On the other hand, when the reason why the discharge capacity of the battery sample 503 is the smallest is read from FIG. 3 and FIG. 4, the battery sample 503 has a positive electrode material whose polarization is not so large as shown in FIG. As can be seen from the above, it was found that the discharge capacity was small due to the large polarization of the negative electrode material.

  2) From FIG. 2, the voltage between the positive electrode and the negative electrode of the battery sample 502 is the highest until 30 minutes of discharge, but has dropped significantly thereafter. The reason for this is read from FIGS. 3 and 4, as can be seen from FIG. 3, the polarization of the positive electrode material is not so large, but as can be seen from FIG. It has been found that this is caused by an increase in polarization.

  As described above, from the analysis examples 1) and 2), it is understood that the present battery characteristic evaluation method is effective in evaluating positive and negative electrode materials of a battery sample.

Example 4
An AA alkaline manganese battery sample 504 was prepared, and the same test as in Example 1 was performed except that the discharge conditions for the battery sample 504 were set to 2A-2 seconds and 0A-28 seconds of pulse discharge. Carried out. The measurement results are shown by broken lines in FIGS.
5 to 7 are graphs in which the vertical axis represents the measured or calculated voltage and the horizontal axis represents the discharge time. FIG. 5 shows the voltage between the positive electrode and the negative electrode for each discharge time, FIG. 6 shows the voltage between the positive electrode and the reference electrode for each discharge time, and FIG. 7 shows the voltage for each discharge time. The voltage between a negative electrode and a reference electrode is shown. Then, the upper limit value and the lower limit value of the data relating to the pulse discharge of the battery sample 504 are respectively connected by an envelope.

(Example 5)
An AA-type alkaline manganese battery sample 505 of a brand different from the battery sample 504 was prepared, and the same test as in Example 4 was performed. The measurement results are shown by solid lines in FIGS.

(Analysis of Examples 4 to 5)
1) From FIG. 5, the discharge voltage of the battery sample 504 is always higher than that of the battery sample 505, and the discharge capacity is also large.
The reason why the battery sample 504 has a high discharge voltage and a large discharge capacity is read from FIG. 6 and FIG. 7. As can be seen from FIG. 6, the polarization of the positive electrode material is smaller in the battery sample 505. Thus, the polarization of the negative electrode material is smaller in the battery sample 504.
That is, the difference in discharge voltage and the difference in capacity between the battery samples 504 and 505 are such that the polarization of the negative electrode material of the battery sample 504 is sufficiently smaller than that of the battery sample 505, and the polarization of the positive electrode material of the battery sample 504 is the positive electrode material of the battery sample 505. It is interpreted that the preferable battery characteristics are maintained while compensating for the higher polarization.

  2) It was found from FIG. 6 that the difference between the open circuit voltage (hereinafter referred to as OCV) and the closed circuit voltage (hereinafter referred to as CCV) at the positive electrode of the battery sample 505 was small. Here, since the difference between the OCV and the CCV can be read as a resistance component (IR component) of the electrode, it can be said that the electrical resistance of the positive electrode of the battery sample 505 is low and is in a good state as an electrode.

1) From the analysis example in 2), if a battery sample combining the negative electrode of the battery sample 504 and the positive electrode of the battery sample 505 can be produced, it is very good for pulse discharge of 2A-2 seconds and 0A-28 seconds. It has been found that a battery that exhibits excellent characteristics can be constructed.
Also from this example, it is understood that this battery characteristic evaluation method is effective in evaluating positive and negative electrode materials of a battery sample.

It is typical sectional drawing of the battery characteristic evaluation apparatus which concerns on this invention, and the block diagram of a measurement circuit. It is the graph which showed the voltage between the positive electrode and the negative electrode for every discharge time in the battery sample which concerns on an Example. It is the graph which showed the voltage between a positive electrode and a reference electrode for every discharge time in the battery sample which concerns on an Example. It is the graph which showed the voltage between the negative electrode and the reference electrode for every discharge time in the battery sample which concerns on an Example. It is the graph which showed the voltage between a positive electrode and a negative electrode for every pulse discharge time in the battery sample which concerns on an Example. It is the graph which showed the voltage between a positive electrode and a reference electrode for every pulse discharge time in the battery sample which concerns on an Example. It is the graph which showed the voltage between a negative electrode and a reference electrode for every pulse discharge time in the battery sample which concerns on an Example. FIG. 6 is a schematic cross-sectional view of a battery characteristic evaluation device according to Modification 1 and a block diagram of a measurement circuit. FIG. 10 is a schematic cross-sectional view of a battery characteristic evaluation device according to Modification 2 and a block diagram of a measurement circuit. 10 is a schematic cross-sectional view of a battery characteristic evaluation device according to Modification 3 and a block diagram of a measurement circuit. FIG.

Explanation of symbols

1.2.3. Battery characteristic evaluation apparatus 10. Measurement cell 11. Electrolytic solution 20.120. Reference electrode 21.121. Lugin tube 22.122. Hg / HgO electrode 23.123. Tip 30 (of Lugin tube) 30. (Cylindrical) alkaline manganese battery 31. Positive electrode 32. Negative electrode 33. Can body 34. Positive electrode material 35. Separator 36. Negative electrode material 37. Negative electrode current collector 38. Electrolyte (contained in cylindrical alkaline manganese battery) 39. Sealing material 40. Perforation 45. Sealing material 50.51. Voltage measuring instrument 60. Discharge device 61. Voltage measuring instrument 62. Load (variable current source)
63. Switch 70. Button-type alkaline manganese battery 71. Positive electrode 72. Negative electrode 73A. Negative electrode side can body 73B. Positive electrode side can body 74. Positive electrode material 75. Separator 76. Negative electrode material 78. Electrolyte solution 79 (contained in button-type alkaline manganese battery) Sealing material 80.81. Perforation 85.86. Sealing material 111. Electrolyte

Claims (5)

An apparatus for evaluating battery characteristics of a sealed battery,
The sealed battery with perforations that do not impair the battery characteristics is provided in the battery can body,
An electrolyte outside the sealed battery in contact with the electrolyte contained in the sealed battery through the perforations ;
An electrode immersed in an electrolyte outside the sealed battery;
A load for discharging the sealed battery under desired conditions;
Voltage between the positive and negative electrodes of the sealed battery, the voltage between the hermetic being said immersion and cathode materials constituting the positive electrode of the battery, is the negative electrode material constituting the anode immersed in said sealed battery Measuring means for measuring at least two voltages selected from among the voltages between the two electrodes,
An apparatus for evaluating battery characteristics , wherein a potential difference between a positive electrode material and a negative electrode material with respect to an electrode immersed in an electrolyte outside the sealed battery is measured from the voltage value . The battery characteristic evaluation apparatus according to claim 1, wherein an electrode immersed in an electrolyte outside the sealed battery is installed in the vicinity of the can of the sealed battery. A battery characteristic evaluation method for a sealed battery using the battery characteristic evaluation device according to claim 1,
In the sealed battery can body, a perforation that does not impair the battery characteristics of the sealed battery is provided,
Via the perforations, the electrolyte contained in the sealed battery is brought into contact with an electrolyte outside the sealed battery having the same composition and concentration as the electrolyte, and outside the sealed battery. Immerse the electrode in a certain electrolyte,
While discharging the sealed battery under predetermined conditions, the voltage between the electrode on the can body provided with the perforations of the sealed battery and the electrode immersed in the electrolytic solution is measured, and the sealed battery A method for evaluating battery characteristics, comprising measuring a potential difference between an electrode material of a can body side electrode provided with a battery perforation and an electrode immersed in the electrolytic solution. Measure the voltage between the positive and negative electrodes of the sealed battery and the voltage between the can body provided with the perforations of the sealed battery and the electrode immersed in the electrolyte, from both the voltages, 4. The battery characteristic evaluation method according to claim 3, wherein a potential difference between an electrode material of an electrode that is not on a can body provided with perforations of the sealed battery and an electrode immersed in the electrolytic solution is calculated. Measure the voltage between the positive and negative electrodes of the sealed battery and the voltage between the can body provided with the perforations of the sealed battery and the electrode immersed in the electrolyte, from both the voltages, immersing the potential difference between the perforations in the sealed battery is immersed in the electrolytic solution and the electrode material of the can body side electrode provided electrode, the electrolyte and the electrode material of the perforations is not a can body side provided electrodes The battery characteristic evaluation method according to claim 3, wherein a potential difference with respect to the applied electrode and a voltage between positive and negative electrodes are measured.

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