JP2014225373A - Liquid injection device and method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte injection device and a method which allow for visualization of the permeability and impregnation state of an electrolyte in the battery container of a secondary battery in the subsequent inspection process, without affecting the productivity or the performance of a product.SOLUTION: An electrolyte injection device 1 includes a sealed container (chamber 11), and a fixed base 21 arranged in the sealed container and holding a battery container (battery cell 12). Furthermore, the electrolyte injection device 1 includes electrolyte supply means for injecting the electrolyte into the battery container, a vacuum pump 15 for bringing the interior of the sealed container into high vacuum state, and rare gas introduction means for supplying rare gas into the sealed container.

Description

  The present invention relates to an injection apparatus and method for injecting an electrolytic solution.

  Secondary batteries with stacked electrodes, such as lithium ion secondary batteries, have a large electrical capacity per unit volume and unit mass, so they are widely used for electronic terminals that require portability such as laptop computers and mobile phones. ing. In recent years, secondary batteries have been applied to electric vehicles that can run only on batteries, PHVs (Plug in Hybrid Vehicles) that use batteries and engines, electric motorcycles, and the like. Furthermore, with the growing demand for renewable energy and increasing environmental awareness, the development of secondary batteries suitable for stationary storage batteries and the like used in large-capacity power storage systems has become active. Secondary batteries used in these large devices require a larger amount of electric power than secondary batteries used in electronic terminals that require portability, and thus are required to be increased in size. A large-sized secondary battery can store a large amount of electric power, but the size of the battery container (battery can) and electrodes increases, and the number of electrodes to be stacked also increases. It is difficult to sufficiently permeate the electrolyte in the meantime.

  An infusion device (electrolyte injection device) that injects electrolyte into a battery container of a secondary battery using a funnel-shaped auxiliary collecting means to continuously inject the electrolyte so as not to overflow from the battery container ) Is disclosed in Patent Document 1. By using the auxiliary collection means, it is possible to continuously inject the electrolyte into the battery container, so that air is less likely to enter the battery container than when the electrolyte is intermittently injected. It is easy to penetrate.

  A liquid injection method (electrolyte supply method) in which an electrolytic solution is injected into a battery container of a secondary battery under normal pressure, and then the pressure is reduced twice by a first vacuum pressure and a second vacuum pressure higher than the first vacuum pressure. ) Is disclosed in Patent Document 2. By performing the decompression process at the first vacuum pressure and the second vacuum pressure, overflow of the electrolyte from the battery container is suppressed, and impregnation of the electrolyte between the electrodes in the battery container is efficiently performed. .

  On the other hand, an inspection method for inspecting whether or not gas remains in a battery container of a secondary battery into which an electrolytic solution has been injected is desired. Generally, as shown in FIG. 8A, a flaw detection apparatus using ultrasonic waves such as NAUT21 (registered trademark) manufactured by Japan Probe Co., Ltd. is used. Since the flaw detection apparatus using ultrasonic waves forms a two-dimensional image as shown in FIG. 8B, the position of the gas in the battery container of a flat laminate-type (pouch-type) secondary battery. Suitable for checking.

  Patent Document 3 discloses a method for nondestructive inspection of the internal configuration of a secondary battery by X-ray CT (Computed Tomography). By using X-ray CT as a method for inspecting the remaining gas in the secondary battery, a three-dimensional stereoscopic image can be obtained, so that a specific place where the gas remains can be specified. . In addition, since a three-dimensional stereoscopic image can be obtained, the inspection method using X-ray CT can be applied to a cylindrical or wound large secondary battery in addition to a flat laminate-type secondary battery. The amount and position of the gas in the battery container can be confirmed.

JP-A-9-283114 JP 11-339770 A JP 2001-203003 A

  The inventions disclosed in Patent Documents 1 and 2 are effective in improving the permeability and impregnation of the electrolytic solution into the battery container of the secondary battery, but even if these inventions are used, the secondary battery When the electrolyte solution is injected into the battery container, gas may be mixed into the battery container. Therefore, at least in the first lot, it is necessary to inspect the presence or absence of gas in the battery container of the secondary battery after injecting the electrolytic solution. The flaw detection apparatus using ultrasonic waves described above and X disclosed in Patent Document 3 An inspection method using line CT is used.

  However, since the flaw detection apparatus using ultrasonic waves is configured to measure the transmission intensity of emitted ultrasonic waves, only a two-dimensional image image can be obtained, and the amount of gas and an accurate position cannot be measured. Furthermore, as described above, only the laminate type secondary battery can be adapted, and the presence or position of the gas remaining in the battery container of the cylindrical or wound large secondary battery cannot be measured.

  Moreover, since the injection of the electrolyte into the battery container of the secondary battery is usually performed in a dry room with extremely low moisture, the gas component when the gas remains in the battery container is included in the atmosphere. Nitrogen, oxygen, etc. Since X-ray absorption coefficients of nitrogen and oxygen are generally small, as disclosed in Patent Document 3, X-ray CT can be used to inspect the remaining gas in the battery container of the secondary battery. In the battery container of the secondary battery, the gas whose main component is nitrogen or oxygen does not appear as an image in the three-dimensional image. Therefore, the presence or position of gas remaining in the battery container of the secondary battery could not be measured.

  Accordingly, an object of the present invention is to solve the above-described problems, and to determine the permeability and impregnation state of the electrolytic solution in the battery container of the secondary battery in a later inspection process without affecting the productivity and product performance. An object of the present invention is to provide an electrolyte injection device and method that can be visualized.

  In order to achieve the above-described object, an electrolyte solution injection device according to the present invention includes a sealed container, a fixing base disposed inside the sealed container and holding the battery container, and the electrolyte solution in the battery container. An electrolyte supply means for injecting liquid into the container, a vacuum pump for making the inside of the sealed container into a high vacuum state, and a rare gas introducing means for supplying a rare gas to the inside of the sealed container. It is characterized by.

  In addition, the method for injecting an electrolyte of the present invention includes a step of fixing a battery container having at least one opening to a fixing base disposed inside the sealed container, and sealing the sealed container; And a step of supplying a rare gas to the inside of the sealed container, and a step of injecting and impregnating the electrolyte into the battery container from the opening.

  Further, the electrolyte solution injection device of the present invention includes a hermetically sealed container, a fixing base that is disposed inside the sealed container and holds the battery container, and for injecting the electrolyte solution into the battery container. Electrolyte supply means, vacuum pump for making the inside of the sealed container into a high vacuum state, nuclide introduction means for supplying the positron anti-β decay nuclide into the sealed container, and discharged from the inside of the sealed container A nuclide disposal container for discarding the nuclide, and a radiation detector provided inside the sealed container for measuring the radiation dose inside the sealed container.

  In addition, the method for injecting an electrolytic solution of the present invention includes a step of fixing a battery container having at least one opening to a fixing base disposed inside the sealed container, and sealing the sealed container; A step of bringing the inside into a high vacuum state, a step of supplying a nuclide capable of positron anti-β decay into the inside of the sealed vessel, a step of injecting and impregnating the electrolyte into the battery vessel from the opening, And a step of discharging the nuclide supplied to the inside.

  According to the present invention, it is possible to inject an electrolytic solution in a later inspection process so that the permeability of the electrolytic solution into the battery container of the secondary battery and the impregnation state can be easily visualized.

It is side surface perspective drawing which shows the injection apparatus of the electrolyte solution of the 1st Embodiment of this invention. It is a side view which shows the state which test | inspected the secondary battery manufactured using the liquid injection apparatus of 1st Embodiment by X-ray CT. It is the top view and sectional drawing which show the image image obtained when the secondary battery manufactured using the liquid injection apparatus of 1st Embodiment is test | inspected by X-ray CT. It is the top view and sectional drawing which show the other image image obtained when the secondary battery manufactured using the liquid injection apparatus of 1st Embodiment is test | inspected by X-ray CT. It is the top view and sectional drawing which show the further another image image obtained when the secondary battery manufactured using the liquid injection apparatus of 1st Embodiment is test | inspected by X-ray CT. It is side surface perspective drawing which shows the injection apparatus of the electrolyte solution of the 2nd Embodiment of this invention. (A) is a perspective view showing a wound-type secondary battery and a cross-sectional view showing an image image obtained by X-ray CT, (b) is a perspective view and an X-ray showing a laminate-type secondary battery. It is sectional drawing which shows the image image obtained by CT. (A) is a side view which shows the ultrasonic flaw detector which is a related technique, (b) is a top view which shows the image image obtained when test | inspecting a secondary battery with an ultrasonic flaw detector.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(First embodiment)
FIG. 1 is a side perspective view showing a liquid injection device for injecting an electrolytic solution into a battery cell (battery container) of a laminate type, cylindrical type or wound type secondary battery according to a first embodiment of the present invention. It is.

  The liquid injection apparatus 1 includes a chamber 11 (sealed container) having rigidity capable of withstanding a high vacuum state, a vacuum pump 15 for realizing a high vacuum state, and a rare gas introduction for supplying a rare gas into the chamber 11. Means, and electrolyte supply means for supplying the electrolyte. The liquid injection device 1 is generally installed in a dry room having a dew point of −30 degrees or less.

  The chamber 11 is made of a highly corrosion-resistant metal such as stainless steel so as not to be corroded by the electrolytic solution, and has high airtightness in order to realize a high vacuum state in a sealed state. Inside the chamber 11, there is provided a fixed base 21 having a function of holding the battery cell 12 having at least one liquid injection port (opening) for injecting the electrolyte and measuring the mass of the battery cell 12. It has been. The space inside the chamber 11 is preferably not too large for the battery cell 12 in order to shorten the time for creating a high vacuum state and the time for filling the chamber 11 with a rare gas. Further, in order to monitor the injection state of the electrolytic solution into the battery cell 12, the chamber 11 may be provided with a transparent window (not shown) made of pressure-resistant glass or the like.

  The battery cell 12 fixed to the fixing base 21 is configured such that a positive electrode and a negative electrode are stacked so that a separator is sandwiched between them, and is configured in a cylindrical shape or a laminate shape. It is placed vertically on the fixed base 21 so as to face. The battery cell 12 is used as a secondary battery such as a lithium ion battery.

  The noble gas introduction means may be configured to be able to introduce the noble gas into the chamber 11. In this embodiment, the noble gas introduction means includes the noble gas cylinder 13, the pressure adjustment valve, the noble gas introduction port 23, and the noble gas valve 14. Is configured. The rare gas cylinder 13 is a pressure cylinder and is connected to the chamber 11 via a pressure regulating valve (not shown). A noble gas introduction port 23 is formed at a connection portion between the chamber 11 and the noble gas cylinder 13, and a noble gas valve 14 that can be opened and closed by an external signal is provided between the chamber 11 and the noble gas cylinder 13. .

  The gas used as the rare gas is preferably krypton or xenon. Krypton and xenon are safe gases that have a higher atomic number than the main material of the battery cell 12 (for example, iron) and are not radioactive isotopes. The gas used is preferably xenon. However, since xenon is a rare gas and expensive, whether to use krypton or xenon is appropriately selected according to the configuration of the battery cell 12 and the manufacturing conditions of the secondary battery. It only has to be done. A plurality of rare gas cylinders 13 may be provided, such as a rare gas cylinder that supplies krypton and a rare gas cylinder that supplies xenon.

  As the vacuum pump 15, an oil rotary vacuum pump with a large displacement is used, and in order to realize a high vacuum, a turbo molecular pump or the like may be used as an auxiliary pump in addition to the oil rotary vacuum pump. An exhaust port 25 is formed at a connection portion between the chamber 11 and the vacuum pump 15, and an exhaust valve 16 that can be controlled to open and close by an external signal is provided between the chamber 11 and the vacuum pump 15. The vacuum pump 15 is connected to the outside of the dry room by piping so that the gas inside the chamber 11 is not exhausted into the dry room where the liquid injection device 1 is installed.

  The electrolyte supply means may be configured to be able to supply the electrolyte to the battery cells 12 arranged inside the chamber 11. In this embodiment, the electrolyte supply tank 17, the electrolyte supply port 22, the injection valve 18, Thus, an electrolyte supply means is configured. The electrolytic solution tank 17 stores an electrolytic solution composed of an organic solvent and a Li salt, and communicates with an electrolytic solution supply port 22 provided inside the chamber 11 so as to face the liquid injection port of the battery cell 12. Yes. Between the chamber 11 and the electrolytic solution tank 17, a liquid injection valve 18 that can be controlled to open and close by an external signal is provided.

  The chamber 11 includes a pressure gauge 19 for measuring the pressure inside the chamber 11, a communication port 24 for communicating the inside of the dry room and the chamber 11, and a vent valve 20 that can be opened and closed by an external signal. Is provided. The pressure gauge 19 has a function of measuring atmospheric pressure or higher and a function of measuring a high vacuum state, and the vent valve 20 is used when returning the interior of the chamber 11 to a dry room atmosphere.

  Below, the process which injects electrolyte solution to the battery cell 12 with the injection apparatus of this embodiment, and test | inspects the electrolyte solution impregnation state in the battery cell 12 is demonstrated.

  First, the battery cell 12 that accommodates a laminated body in which a plurality of positive electrodes, negative electrodes, and separators are stacked is fixed to a fixed base 21 disposed inside the chamber 11. At this time, the battery cell 12 is fixed so that the liquid injection port provided in the upper part of the battery cell 12 faces the electrolyte solution supply port 22.

  Next, when the chamber 11 is sealed, the vacuum pump 15 is operated, and the exhaust valve 16 is opened, the gas inside the chamber 11 is exhausted to the outside of the dry room, and the inside of the chamber 11 is It becomes a high vacuum state. At this time, the pressure in the chamber 11 needs to be 10 Pa or less, and the pressure in the chamber 11 is preferably 1 Pa or less in order to exhaust as much as possible so that no gas remains.

  After the inside of the chamber 11 is in a high vacuum state, the exhaust valve 16 is closed and the rare gas valve 14 is opened, so that the rare gas contained in the rare gas cylinder 13 is given into the chamber 11. Supplied until the pressure is reached. The predetermined pressure inside the chamber 11 depends on the structure of the battery cell 12 and the viscosity of the electrolytic solution, but a pressure reduced from atmospheric pressure to about 0.1 atm (about 10,000 Pa) is preferable. When the pressure inside the chamber 11 reaches a predetermined pressure, the rare gas valve 14 is closed.

  With the rare gas supplied into the chamber 11, the liquid injection valve 18 is opened, and the electrolytic solution is supplied from the electrolytic solution tank 17 toward the electrolytic solution supply port 22. At this time, the liquid injection valve 18 is controlled so that an amount of the electrolytic solution that matches the size of the battery cell 12 and the porosity in the battery cell 12 is supplied. In addition, you may monitor from the exterior whether the electrolyte solution overflows from the battery cell 12 with the window, camera, etc. which were provided in the chamber 11. FIG.

  When the battery cell 12 is filled with the electrolyte, a vacuum impregnation step is performed. Specifically, the gas in the battery cell 12 is changed by alternately changing the pressure inside the chamber 11 a plurality of times (preferably about three times) between a low pressure state of about 0.1 atmosphere and a high pressure state of about atmospheric pressure. Is removed. The interior of the chamber 11 is depressurized by opening the exhaust valve 16 and pressurized by opening the rare gas valve 14.

  After the vacuum impregnation step is completed, the liquid injection port of the battery cell 12 is sealed. When the battery cell 12 is sealed, the vent valve 20 is opened, the inside of the chamber 11 of the liquid injection device 1 is set in a dry room atmosphere, and the battery cell 12 is taken out from the liquid injection device 1. The battery cell 12 is preferably sealed in the liquid injection device 1, but the liquid injection port may be quickly sealed after being taken out of the liquid injection device 1.

  As shown in FIG. 2, the battery cell 12 taken out from the liquid injection device 1 is checked by an X-ray CT (Computed Tomography) device 2 (computer tomography) in order to confirm the impregnation state of the electrolyte inside the battery cell 12. (Photographing device). In the present embodiment, an industrial X-ray CT apparatus 2 is used, and the X-ray CT apparatus 2 includes an X-ray source 26, a rotary stage 28 (stage), and an X-ray detector 29. In order to prevent leakage, it is installed inside a highly airtight container (not shown). A high voltage (100 kV or more, output 100 W or more) is used for the X-ray source 26. When high energy X-rays are obtained, an acceleration voltage of 200 kV or higher is preferable. The rotary stage 28 holds and rotates the battery cell 12. The X-ray detector 29 is a detector for detecting the intensity of the X-ray 30 emitted from the X-ray source 26 and transmitted through the battery cell 12, and an imaging fire or the like is used as the X-ray detector 29.

  The battery cells 12 arranged on the rotary stage 28 of the X-ray CT apparatus 2 are irradiated with X-rays 30 emitted from the X-ray source 26 while being rotated in accordance with the direction of the image to be acquired. The X-ray 30 transmitted through the battery cell 12 is detected by the X-ray detector 29, and a three-dimensional image is formed from the amount of absorption of the X-ray 30 detected by the X-ray detector 29. The formed three-dimensional image is numerically analyzed, and an arbitrary cross section is displayed as an arbitrary multi-plane reconstruction (MPR) on a monitor such as a personal computer.

  3 to 5 are examples of results obtained when the X-ray CT apparatus 2 is used to measure the stacked planar type 20 Ah size battery cell 12 in order to confirm the impregnation state of the battery cell 12 with the electrolyte. It is the MPR image of the plane and cross section which show.

  In the MPR image, a portion where the amount of absorption of the X-ray 30 is large is depicted white, and a portion where the amount of absorption is small is depicted black. At the intermediate point from where the amount of absorption of X-ray 30 is small to large, it is depicted in any gray from dark gray to light gray according to the amount of absorption. In the portion that does not pass through the battery cell 12, the X-ray 30 passes through the atmosphere, and the air does not substantially absorb the X-ray 30, so the portion that does not pass through the battery cell 12 on the MPR image is displayed in black. ing. On the other hand, since the electrode main body 31 in the battery cell 12 and the positive electrode tab 32 and the negative electrode tab 34 which are the connection part with the exterior of the battery cell 12 are formed with metals, such as aluminum and nickel, they are X-rays 30. Is absorbed white and is displayed in white.

  Referring to FIG. 3, there are two extremely white portions in the battery cell 12 in the planar MPR image and three extremely white portions in the battery cell 12 in the cross-sectional MPR image. In FIG. 4, the planar MPR image includes one portion inside the battery cell 12, and the cross-sectional MPR image includes four portions displayed extremely white inside the battery cell 12. These portions are the portions where the rare gas remains, and the contrast between the rare gas and the electrode body 31 is clear because the amount of absorption of the X-ray 30 of the rare gas is larger than the amount of absorption of the X-ray 30 of the electrode body 31. It has become. FIG. 5 reflects the results obtained in FIGS. 3 and 4, and in order to further remove the gas inside the battery cell 12, the electrolytic solution is injected by setting the high vacuum state of the liquid injection device 1 to a lower pressure. The MPR image of the liquid battery cell 12 is shown. In FIG. 5, a small gas displayed in white remains in one place inside the battery cell 12 in the planar MPR image and in one place inside the battery cell 12 in the MPR image of the cross section.

  As described above, the amount of gas remaining in the battery cell 12 is repeated by repeatedly reviewing the pressure in the high vacuum state or the pressure in the vacuum impregnation step until the gas remaining in the battery cell 12 is reduced to an allowable amount. Is adjusted. In addition, since the reactivity of the rare gas used in the present embodiment is poor, even if some of the gas within the allowable value remains inside the battery cell 12, it is stable without reacting with the electrolytic solution, etc. The operation of the secondary battery is not hindered.

  However, if a gas exceeding the allowable value remains in the battery cell 12, the remaining portion of the gas does not contribute to charging / discharging of the secondary battery when used as a secondary battery. The capacity may vary. In addition, a film called a SEI (Solid Electrolyte Interface) layer is not formed on the portion of the electrode body 31 that is in contact with the gas during the initial charge. Therefore, Li is not sufficiently intercalated, and Li or a Li compound is deposited on the surface of the electrode body 31. As a result, there are concerns about variations in product life such as cycle characteristics and storage characteristics of the secondary battery, and rapid deterioration and safety deterioration due to deposition of Li or Li compounds in the electrolyte solution on the surface of the electrode body 31. Therefore, it is required to reduce the gas inside the battery cell 12 as much as possible. In recent years, electrolytes with high viscosity and volatility have been used, and gas tends to remain inside the battery cells 12, so an inspection method that clearly shows the impregnation state of the battery cells 12 is required. Yes.

  In this embodiment, before injecting the electrolyte into the battery cell 12, the injection device 1 is filled with a rare gas that absorbs a large amount of X-rays 30, thereby remaining in the battery cell 12. The component of the gas to become rare gas. Therefore, when the impregnation state of the battery cell 12 is inspected by the X-ray CT apparatus 2, the rare gas absorbs a lot of X-rays 30, and the remaining portion of the gas is clearly displayed in white in the MPR image. Therefore, the amount of gas remaining inside the battery cell 12 is known, and this is reflected in the high vacuum state pressure of the liquid injection device 1, whereby the battery cell 12 with less gas remaining is obtained.

  The liquid injection device 1 using the rare gas according to the present embodiment generally sets the high vacuum state pressure or the like of the liquid injection device 1 using the rare gas when changing the specifications of the battery cell or creating the first lot. Used when Thereafter, when production is performed with the same set value, it is better not to inspect with the X-ray CT apparatus 2 in order to improve production efficiency. Air may be used.

(Second Embodiment)
FIG. 6 is a side perspective view showing a liquid injection device for injecting an electrolytic solution into a battery cell (battery container) of a laminate type, cylindrical type or wound type secondary battery according to a second embodiment of the present invention. It is.

  The liquid injection device 1 includes a chamber 11, a vacuum pump 15, an exhaust gas primary storage tank 43 (nuclide disposal container) connected to the vacuum pump 15, and a nuclide introduction that supplies a nuclide that positron-anti-β decays into the chamber 11. Means, and electrolyte supply means.

  The chamber 11 is covered with a heavy metal such as lead so that gamma rays do not leak in order to accommodate a positron anti-β decay nuclide that is a radiation material described later. Further, the chamber 11 may be provided with a transparent window (not shown) made of pressure-resistant radiation-proof glass or the like in order to monitor the injection state of the electrolytic solution into the battery cell 12.

  The nuclide introduction means may be configured to be able to introduce a nuclide capable of positron anti-β decay into the chamber 11. In this embodiment, the nuclide primary storage tank 41, the nuclide introduction port 45, and the gas valve 42 are used to introduce the nuclide introduction means. Is configured. The nuclide primary storage tank 41 stores nuclides that undergo positron anti-β decay such as 15 oxygen, 13 nitrogen, and 18 fluorine. Since this nuclide has a very short half-life, it is preferable to use it immediately after it is produced by a cyclotron (not shown) or the like. A nuclide introduction port 45 is formed at a connection portion between the chamber 11 and the nuclide primary storage tank 41, and a gas valve 42 that can be controlled to open and close by an external signal is provided between the chamber 11 and the nuclide primary storage tank 41. Is provided.

  An exhaust gas primary storage tank 43 is connected to the vacuum pump 15 so that the nuclides inside the chamber 11 are not immediately exhausted into the dry room in which the liquid injection device 1 is installed. Immediately after the exhaust gas is stored in the exhaust gas primary storage tank 43, it has a high radiation dose and is very dangerous. Therefore, it is temporarily stored in the exhaust gas primary storage tank 43. Then, after confirming that the radiation dose of the exhaust gas has sufficiently decreased inside the exhaust gas primary storage tank 43, the exhaust gas is released from the exhaust gas primary storage tank 43 into the atmosphere.

  Further, the chamber 11 is provided with a radiation detector 44 such as a Geiger-Muller tube for measuring the radiation dose inside the chamber 11.

  Below, the process which inject | pours electrolyte solution into the battery cell 12 with the injection apparatus of this embodiment, and test | inspects the osmosis | permeability and impregnation property of the electrolyte solution in the battery cell 12 is demonstrated.

  After the battery cell 12 is fixed to the fixing base 21 disposed inside the chamber 11, the chamber 11 is sealed, the vacuum pump 15 is operated, and the inside of the chamber 11 is in a high vacuum state. After the inside of the chamber 11 is in a high vacuum state, the nuclide stored in the nuclide primary storage tank 41 is supplied to the inside of the chamber 11 until a predetermined pressure is reached, from the electrolyte tank 17 toward the electrolyte supply port 22. The electrolyte is supplied.

  After the battery cell 12 is filled with the electrolytic solution and the vacuum impregnation step is performed, the liquid injection port of the battery cell 12 is sealed. And the inside of the chamber 11 is made into a high vacuum state, the radiation dose is confirmed, and after the inside of the chamber 11 becomes a dry room atmosphere, the radiation dose from the battery cell 12 is measured. When the radiation dose from the battery cell 12 is high, the battery cell 12 is left as it is until the radiation dose becomes low. When the radiation dose from the battery cell 12 becomes a dose below the X-ray management area designation, the battery cell 12 is quickly taken out and photographed with a positron tomography apparatus (not shown) having a gamma ray detector. In the positron tomography apparatus, the exact position of the gas containing the nuclide remaining inside the battery cell 12 is specified using the property that gamma rays are then emitted in the opposite direction.

  Other configurations and processes are the same as those in the first embodiment, and are omitted.

  Even in the embodiment as described above, the same effect as that obtained in the first embodiment can be obtained.

(Example)
In accordance with the first embodiment of the present invention, an example will be described in which an electrolytic solution is injected into the 20 Ah winding type battery cell and a 10 Ah laminate type battery cell 12 by injecting an electrolytic solution with the liquid injection device 1. In this embodiment, the rare gas cylinder 13 is a 47 L container containing xenon gas with a purity of 99.9% or higher.

  After the pressure inside the chamber 11 is lowered to 1 Pa or less and xenon gas is introduced to return the pressure inside the chamber 11 to atmospheric pressure, the wound battery cell 12 has 100 g of electrolyte, a laminate type The battery cell 12 is supplied with 60 g of an electrolytic solution. Next, pressurization and depressurization are repeated so that the internal pressure of the chamber 11 alternately reaches a low pressure of 0.2 atm and a high pressure of 1 atm about three times. The gas is removed. After the liquid injection port of the battery cell 12 is sealed, the battery cell 12 is taken out from the liquid injection device 1 and placed in the X-ray CT apparatus 2 having a tungsten tube high-voltage X-ray source 26. . The X-ray 30 is irradiated to the battery cell 12 in the X-ray CT apparatus 2, and MPR images as shown in FIGS. 7A and 7B are obtained. In the MPR images shown in FIGS. 7A and 7B, the gas remaining in the battery cell 12 displayed in white is displayed, and the impregnation state of the battery cell 12 becomes clear.

(Appendix 1)
A hermetically sealed container, a fixing base arranged inside the sealed container and holding the battery container, an electrolyte supply means for injecting an electrolyte into the battery container, and an interior of the sealed container A liquid injection device for an electrolytic solution, comprising: a vacuum pump for bringing the gas into a high vacuum state; and a rare gas introducing means for supplying a rare gas to the inside of the sealed container.

(Appendix 2)
The liquid injection device according to appendix 1, wherein the rare gas is xenon or krypton.

(Appendix 3)
The liquid injection device according to appendix 1 or 2, a stage for holding a secondary battery formed by sealing the battery container after the electrolytic solution is injected by the liquid injection device, and the secondary battery A liquid injection and inspection apparatus comprising: a computed tomography apparatus comprising: an X-ray source for irradiating X-rays to the X-ray; and an X-ray detector for detecting the X-ray transmitted through the secondary battery.

(Appendix 4)
Fixing the battery container having at least one opening to a fixing base disposed inside the sealed container, and sealing the sealed container;
Placing the inside of the sealed container in a high vacuum state;
Supplying a rare gas into the sealed container;
Injecting an electrolytic solution from the opening into the battery container and impregnating the battery container.

(Appendix 5)
The liquid injection method according to appendix 4, wherein the rare gas is xenon or krypton.

(Appendix 6)
Each step of the injection method according to appendix 4 or 5, a step of sealing the battery container into which the electrolytic solution has been injected to form a secondary battery, and the secondary battery using computer tomography A step of inspecting the liquid, and a liquid injection and inspection method.

(Appendix 7)
An inspection method comprising a step of sealing a battery container containing a rare gas by injecting an electrolytic solution to form a secondary battery, and a step of inspecting the secondary battery using a computer tomography method.

(Appendix 8)
A hermetically sealed container, a fixing base arranged inside the sealed container and holding the battery container, an electrolyte supply means for injecting an electrolyte into the battery container, and an interior of the sealed container A vacuum pump for making a high vacuum state, a nuclide introducing means for supplying a nuclide that positron-anti-β decays into the sealed container, and a waste nuclide discharged from the sealed container An electrolyte injection device comprising: a nuclide disposal container; and a radiation detector that is provided inside the sealed container and measures a radiation dose inside the sealed container.

(Appendix 9)
The liquid injection device according to appendix 8, wherein the nuclide includes 15 oxygen, 13 nitrogen, and 18 fluorine.

(Appendix 10)
The liquid injection device according to appendix 8 or 9, and a gamma ray detector for detecting gamma rays emitted from a secondary battery formed by sealing the battery container after the electrolytic solution is injected by the liquid injection device A positron tomography apparatus having a liquid injection and inspection apparatus.

(Appendix 11)
Fixing the battery container having at least one opening to a fixing base disposed inside the sealed container, and sealing the sealed container;
Placing the inside of the sealed container in a high vacuum state;
Supplying a positron anti-β decay nuclide into the sealed container;
Injecting and impregnating an electrolytic solution from the opening into the battery container; and
Discharging the nuclide supplied to the inside of the sealed container.

(Appendix 12)
The liquid injection method according to appendix 12, wherein the nuclide includes 15 oxygen, 13 nitrogen, and 18 fluorine.

(Appendix 13)
Each step of the injection method according to appendix 11 or 12, a step of sealing the battery container into which the electrolytic solution has been injected to form a secondary battery, and the secondary battery using positron tomography A step of inspecting the liquid, and a liquid injection and inspection method.

(Appendix 14)
An inspection including a step of sealing a battery container containing a nuclide that positron-anti-β decays by injecting an electrolyte and forming a secondary battery, and a step of inspecting the secondary battery using positron tomography Method.

DESCRIPTION OF SYMBOLS 1 Injection apparatus 2 X-ray CT apparatus 11 Chamber 12 Battery cell 13 Noble gas cylinder 15 Vacuum pump 17 Electrolyte tank 21 Fixing base 26 X-ray source 28 Rotating stage 29 X-ray detector 30 X-ray

Claims (10)

  A hermetically sealed container, a fixing base arranged inside the sealed container and holding the battery container, an electrolyte supply means for injecting an electrolyte into the battery container, and an interior of the sealed container A liquid injection device for an electrolytic solution, comprising: a vacuum pump for bringing the gas into a high vacuum state; and a rare gas introducing means for supplying a rare gas to the inside of the sealed container.   The liquid injection device according to claim 1, wherein the rare gas is xenon or krypton. The liquid injection device according to claim 1 or 2,
A stage for holding a secondary battery formed by sealing the battery container after the electrolytic solution is injected by the liquid injection device; and an X-ray source for irradiating the secondary battery with X-rays; A liquid injection and inspection apparatus, comprising: a computed tomography apparatus comprising: an X-ray detector that detects the X-ray transmitted through the secondary battery. Fixing the battery container having at least one opening to a fixing base disposed inside the sealed container, and sealing the sealed container;
Placing the inside of the sealed container in a high vacuum state;
Supplying a rare gas into the sealed container;
Injecting the electrolyte from the opening into the battery container and impregnating the battery container.   5. The liquid injection method according to claim 4, wherein the rare gas is xenon or krypton.   Each step of the liquid injection method according to claim 4 or 5, a step of sealing the battery container into which the electrolytic solution has been injected to form a secondary battery, and the secondary using computer tomography A step of inspecting the battery, and a liquid injection and inspection method.   A hermetically sealed container, a fixing base arranged inside the sealed container and holding the battery container, an electrolyte supply means for injecting an electrolyte into the battery container, and an interior of the sealed container A vacuum pump for making a high vacuum state, a nuclide introducing means for supplying a nuclide that positron-anti-β decays into the sealed container, and a waste nuclide discharged from the sealed container An electrolyte injection device comprising: a nuclide disposal container; and a radiation detector that is provided inside the sealed container and measures a radiation dose inside the sealed container.   The liquid injection device according to claim 7, wherein the nuclide includes 15 oxygen, 13 nitrogen, and 18 fluorine. Fixing the battery container having at least one opening to a fixing base disposed inside the sealed container, and sealing the sealed container;
Placing the inside of the sealed container in a high vacuum state;
Supplying a positron anti-β decay nuclide into the sealed container;
Injecting and impregnating an electrolytic solution from the opening into the battery container; and
And a step of discharging the nuclide supplied to the inside of the sealed container.   The liquid injection method according to claim 9, wherein the nuclide contains 15 oxygen, 13 nitrogen, and 18 fluorine.