WO2011092936A1 - 電源システム及び、その電源システムを搭載する医療用カプセル装置 - Google Patents
電源システム及び、その電源システムを搭載する医療用カプセル装置 Download PDFInfo
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- WO2011092936A1 WO2011092936A1 PCT/JP2010/071732 JP2010071732W WO2011092936A1 WO 2011092936 A1 WO2011092936 A1 WO 2011092936A1 JP 2010071732 W JP2010071732 W JP 2010071732W WO 2011092936 A1 WO2011092936 A1 WO 2011092936A1
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- power supply
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/07—Endoradiosondes
- A61B5/073—Intestinal transmitters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
- A61B1/00002—Operational features of endoscopes
- A61B1/00025—Operational features of endoscopes characterised by power management
- A61B1/00027—Operational features of endoscopes characterised by power management characterised by power supply
- A61B1/00032—Operational features of endoscopes characterised by power management characterised by power supply internally powered
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
- A61B1/04—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor combined with photographic or television appliances
- A61B1/041—Capsule endoscopes for imaging
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6846—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be brought in contact with an internal body part, i.e. invasive
- A61B5/6847—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be brought in contact with an internal body part, i.e. invasive mounted on an invasive device
- A61B5/6861—Capsules, e.g. for swallowing or implanting
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2560/00—Constructional details of operational features of apparatus; Accessories for medical measuring apparatus
- A61B2560/02—Operational features
- A61B2560/0204—Operational features of power management
- A61B2560/0214—Operational features of power management of power generation or supply
Definitions
- the present invention relates to a swallowing medical capsule device that is equipped with a power supply system that generates power using digestive organ contents present in a living body and detects surrounding information and performs medical treatment when flowing down the living body.
- a typical capsule endoscope mounts an imaging mechanism and a battery in a capsule and drives the imaging mechanism with the battery to perform imaging.
- the number of shots is limited by the capacity of the built-in battery, and the introduction of a drive mechanism is also limited.
- a generally used small battery cannot be discarded as mere non-burnable garbage, after being discharged and collected outside the body, the battery is taken out from the capsule endoscope, separated, and discarded.
- a power generation system or power feeding system is installed in the capsule device, and after administration, light, radio waves, electromagnetic waves, etc. are transmitted from outside the living body to generate electric energy in the capsule device and drive it.
- a configuration is also proposed.
- Japanese Patent Application Laid-Open No. 2001-231187 proposes a system for supplying power by irradiating a medical capsule device with infrared light from outside the body.
- Japanese Patent Laid-Open No. 9-327447 also proposes a configuration in which a generator is mounted in a capsule device.
- Japanese Patent Application Laid-Open No. 2007-200249 has also proposed a technique for generating electricity by using the gastric internal solution as an electrolytic solution (electrolyte).
- the conventional power supply system that generates power by receiving light or electrical energy from outside the body stays within the irradiation range of the light source or the range in which the magnetic field acts until the patient completes the examination. And the movement of the patient is severely limited.
- Patent Document 3 proposes a gastric acid battery using an intragastric solution as an electrolyte, but the disclosed technology is limited to power generation in the stomach.
- the inspection by the medical capsule device is in high demand not only for the stomach but also for the duodenum and the small intestine.
- the present invention provides a swallowable medical capsule device that has a built-in battery that can generate a sufficient amount of power generation in the flowing stomach of the living body, or in the duodenum, large intestine and small intestine.
- the purpose is to provide.
- a power supply system includes a water-tight capsule having acid resistance and a different member having a difference in standard electrode potential provided to be exposed on the outer wall surface of the capsule.
- a voltaic battery comprising: at least one electrode pair; and a power supply unit disposed in the capsule and connected to the electrode pair to extract and supply power generated by the electrolysis. Constitute.
- the medical capsule device in which the power supply system according to the embodiment is mounted includes a water-tight capsule having acid resistance and two different members having a difference in standard electrode potential provided so as to be exposed on the outer wall surface of the capsule.
- At least one electrode pair a power supply system that supplies and outputs power generated by connecting to the electrode pair, a lens that forms an image of an object to be imaged, and a plurality of light sources for illuminating the field of view
- a light-emitting element, an optical image formed on the lens, photoelectrically converted to generate an image signal, and an image signal generated by the optical sensor is corrected to be converted into an information signal for wireless communication.
- a swallowable medical capsule device that has a built-in battery capable of obtaining a sufficient amount of power generation in the stomach, large intestine, and small intestine of a living body, and is disposable and can be collected after use. be able to.
- FIG. 1A is a diagram showing an external configuration of a medical capsule device according to the first embodiment of the present invention.
- FIG. 1B is a diagram showing a cross-sectional configuration of the capsule device in the AA direction of FIG.
- FIG. 2 is a diagram illustrating a conceptual configuration of a power supply system mounted on the capsule device.
- FIG. 3 is a diagram showing a cross-sectional shape of the electrode of the first modification of the first embodiment in the AA direction of FIG. 1A.
- FIG. 4 is a diagram showing a cross-sectional shape of the electrode of the second modification of the first embodiment in the AA direction of FIG. 1A.
- FIG. 5A is a diagram illustrating an external configuration of a capsule device according to a third modification example of the first embodiment.
- FIG. 1B is a diagram showing a cross-sectional configuration of the capsule device in the AA direction of FIG.
- FIG. 2 is a diagram illustrating a conceptual configuration of a power supply system mounted on the capsule device.
- FIG. 5B is a diagram showing a cross-sectional configuration of the electrode in the BB direction of FIG. 5A.
- FIG. 6 is a diagram illustrating a cross-sectional configuration of the power supply system in the capsule device according to the fourth modification example of the first embodiment.
- FIG. 7 is a diagram illustrating a configuration in which a temperature sensor is provided on an electrode of a power supply system according to a fifth modification example of the first embodiment.
- FIG. 8 is a diagram illustrating an external configuration of a capsule device in which the power supply system according to the second embodiment is mounted.
- FIG. 9 is a diagram illustrating a cross-sectional configuration of a capsule device in which the power supply system according to the third embodiment is mounted.
- FIG. 10 is a diagram illustrating an internal configuration of a capsule device in which the power supply system according to the fourth embodiment is mounted.
- FIG. 11 is a diagram illustrating an internal configuration of a capsule device in which the power supply system according to the fifth embodiment is mounted.
- FIG. 12 is a diagram illustrating an internal configuration of a capsule device in which the power supply system according to the sixth embodiment is mounted.
- FIG. 13 is a diagram illustrating characteristics of the generated current with respect to elapsed time by the power supply system of the seventh embodiment.
- FIG. 14 is a diagram illustrating a characteristic of the generated voltage with respect to elapsed time by the power supply system of the seventh embodiment.
- FIG. 15 is a diagram illustrating the relationship between the electrode area and the generated current in the power supply system according to the seventh embodiment.
- FIG. 16 is a diagram showing a characteristic of the generated current with respect to elapsed time in an electrode pair of an aluminum electrode and a Pt electrode as a comparative example.
- FIG. 17 is a diagram showing characteristics of the generated voltage with respect to elapsed time in an electrode pair of an aluminum electrode and a Pt electrode as a comparative example.
- FIG. 18 is a diagram illustrating characteristics of the generated current with respect to elapsed time by the power supply system of the eighth embodiment.
- FIG. 19 is a diagram illustrating characteristics of the generated current with respect to elapsed time by the power supply system according to the modified example of the eighth embodiment.
- FIG. 20 is a diagram illustrating characteristics of the generated current with respect to elapsed time by the power supply system of the ninth embodiment.
- FIG. 21 is a diagram illustrating characteristics of the generated current with respect to elapsed time by the power supply system of the tenth embodiment.
- FIG. 22 is a diagram illustrating characteristics of the generated current with respect to elapsed time by the power supply system of the eleventh embodiment.
- FIG. 23 is a diagram illustrating an internal configuration of a capsule device in which the power supply system according to the twelfth embodiment is mounted.
- FIG. 24A is a diagram illustrating an example of a manufacturing process of a stacked structure electrode formed on a capsule body in the power supply system of the twelfth embodiment.
- FIG. 24B is a diagram illustrating an example of a manufacturing process of the stacked structure electrode following FIG. 24A.
- FIG. 24C is a diagram illustrating an example of a manufacturing process of the stacked structure electrode following FIG. 24B.
- FIG. 24D is a diagram illustrating an example of a manufacturing process of the stacked structure electrode following FIG. 24C.
- FIG. 25A is a diagram illustrating another example of the manufacturing process of the stacked structure electrode in the power supply system according to the twelfth embodiment.
- FIG. 25B is a diagram showing another example of the manufacturing process of the stacked structure electrode following FIG. 25A.
- FIG. 25C is a diagram showing another example of the manufacturing process of the stacked structure electrode subsequent to FIG. 25B.
- FIG. 25D is a diagram showing another example of the manufacturing process of the stacked structure electrode following FIG. 25C.
- FIG. 25A is a diagram illustrating another example of the manufacturing process of the stacked structure electrode in the power supply system according to the twelfth embodiment.
- FIG. 25B is a diagram showing another example of the manufacturing process of the stacked structure electrode following FIG. 25A
- FIG. 25E is a diagram showing another example of the manufacturing process of the stacked structure electrode following FIG. 25D.
- FIG. 25F is a diagram showing another example of the manufacturing process of the stacked structure electrode subsequent to FIG. 25E.
- FIG. 25G is a diagram showing another example of the manufacturing process of the stacked structure electrode subsequent to FIG. 25F.
- FIG. 26 is a diagram showing the characteristics of the power generation amount with respect to time in the battery using the artificial gastric juice as the electrolytic solution in the first embodiment.
- FIG. 27 is a diagram showing the characteristics of the amount of power generation with respect to time in the battery using the artificial intestinal fluid as the electrolytic solution in the first embodiment.
- FIG. 1A is a diagram showing an external configuration of a swallowable medical capsule device (hereinafter referred to as a capsule device) in a state of being administered into a living body according to the first embodiment of the present invention.
- FIG. 1B is a diagram showing a cross-sectional configuration of the capsule device in the AA direction of FIG. 1A.
- FIG. 2 is a diagram showing a conceptual configuration of the power supply system.
- FIG. 3 shows a cross-sectional shape of the electrode of the first modification in the AA direction of FIG. 1A.
- the digestive organ contents indicate all substances contained in the digestive organ that function as an electrolyte or an electrolytic solution. Specifically, it is a mixture of digestive organ secretions such as saliva and gastric juice secreted from the mouth, stomach and intestines, etc., or waste products from the digestive organs and substances taken from the mouth and nose.
- the capsule device 1 shown in FIG. 1A only needs to have a shape that can be easily swallowed when administered into the living body 8.
- a wrinkle shape with rounded front and back is assumed, such as capsule medication including a drug.
- other shapes such as a spherical shape and a disk shape, can be easily applied depending on the apparatus to be incorporated therein.
- the capsule body 5 is divided into two parts, a front capsule 5a and a rear capsule 5b, and these are bonded and configured to be watertight.
- At least the front capsule 5a is formed of a transparent material that serves as a window.
- a resin material having resistance to acids such as digestive secretion 7 is used for these capsule portions.
- the power supply system is preliminarily formed from at least two electrodes 2 and 3 made of metal of different materials, which will be described later, provided on the outer wall surface of the capsule body 5 and the electromotive force generated by these electrodes 2 and 3. And a power source unit 6 that generates a power source having a predetermined constant voltage. If these electrodes 2 and 3 and the surrounding digestive contents 7 are used as an electrolytic solution, a known battery configuration called a voltaic battery is obtained. Using the electromotive force generated between the electrodes 2 and 3 using this voltaic battery, the power supply unit 6 supplies each drive unit (not shown) of the capsule device 1 as a power source.
- the electromotive force of a voltaic battery is determined by the difference between the standard electrode potentials of electrodes made of these two different metals.
- the amphoteric metal aluminum (including an aluminum alloy) is selected as the electrode 2 serving as the cathode. This is because alkali metals and alkaline earth metals are suitable as the cathode, but since they are administered into the body, the influence on the living body must be small, and even in the acidic stomach, the duodenum is basic. It is better to have an electrode that can generate electricity inside.
- the material of the electrode 3 serving as the anode is not particularly limited as long as the standard electrode potential is higher than that of hydrogen.
- a noble metal such as platinum, gold, silver, or a carbon electrode is preferable.
- the carbon material used for the carbon electrode is not particularly limited as long as it has high conductivity. Specific examples include conductive carbon black and carbon black represented by acetylene black and ketjen black (trade name: Lion). Amorphous carbon composites, graphite, carbon fibers, carbon nanotubes, or mixtures thereof may be employed.
- the areas of the electrode 2 and the electrode 3 are not necessarily the same.
- the electrode 2 may have a larger area than the electrode 3.
- the shape of the electrodes 2 and 3 viewed from above is rectangular in FIG. 1A, but of course is not limited, and may be a circle, an ellipse, a track, a polygon, or a triangle. Any of these may be used, and these may be combined.
- the electrodes 2 and 3 may be formed in a comb shape so that a certain pattern, for example, the comb teeth engage with each other with a space therebetween.
- the manufacturing method of these electrodes 2 and 3 can use a general film forming technique.
- vapor deposition film formation, sputtering film formation, ECR film formation, or CVD film formation can be easily applied as a dry film formation technique used in semiconductor manufacturing technology.
- plating film formation can be applied as a wet film formation technique.
- the electrode is a carbon electrode, for example, it can be formed by printing using conductive carbon black ink.
- an electrode may be separately formed and then adhered to the outer wall surface of the capsule body 5.
- the adhesive those used in medicine are preferable.
- the voltaic battery has a decrease in electromotive force due to polarization, that is, hydrogen bubbles generated at the anode.
- polarization that is, hydrogen bubbles generated at the anode.
- the embodiment according to the present invention by adopting a structure in which the electrodes 2 and 3 are formed on the outer wall surface of the capsule device 1 as shown in FIG. The retention of the solution is prevented, and hydrogen bubbles adhering to the electrode surface are quickly removed.
- a method of spraying a depolarizer on the electrode 3 or a method of using platinum which hardly causes polarization is known.
- the polarization preventing effect of the platinum electrode is not sufficient.
- the power supply unit 6 is an integrated circuit in which a general circuit configuration, for example, an amplifier circuit and a constant voltage circuit (or a constant current circuit) are integrated and formed on one chip. In order to stabilize the output, a capacitor (charge storage element) functioning as a buffer may be arranged on the input side.
- the actual power generation amount was verified using artificial gastric juice and artificial intestinal fluid.
- a glass beaker and put artificial gastric juice and artificial intestinal fluid 10 m immersing the Pt electrode of aluminum electrode and 0.02 cm 2 area of 1 cm 2, was examined power generation amount (generation current and generated voltage).
- a 48 ⁇ resistor was connected as a battery load.
- the maximum generated current was 0.7 mA
- the power generation amount after 8 hours was 0.06 mA.
- the generated voltage was 1.25 V, and no deterioration occurred after 8 hours.
- the maximum current generation was 0.12 mA
- the power generation amount after 8 hours was 0.02 mA.
- the generated voltage was 1.2 V, and almost no deterioration occurred after 8 hours.
- the capsule device of the present embodiment is a power supply system for mainly operating in the stomach, and has the same configuration as shown in FIG. 1B.
- This power supply system forms on the outer wall surface of the capsule device 1 an electrode pair composed of an electrode 2 made of aluminum that acts as a cathode and an electrode 3 made of carbon that acts as an anode.
- a voltaic battery as an electrolyte (electrolytic solution) is configured.
- a power supply unit 6 is disposed inside the capsule device, and the electrodes 2 and 3 are connected to each other by wires 4a and 4b.
- the power supply unit 6 is an integrated circuit in which a general circuit configuration, for example, an amplifier circuit and a constant voltage circuit (or a constant current circuit) are integrated on one chip.
- a capacitor charge storage element functioning as a buffer may be arranged on the input side.
- the exposed portion on the inner surface side of the electrode can expose the capsule 5b by making a hole from the inside.
- a hole (bottomed hole) or groove is cut in advance from the outside in the electrode formation region of the capsule 5b, and an electrode is formed by sputtering film formation so as to fill the hole.
- the electrodes 2 and 3 are each formed with a size of about 10 ⁇ 10 mm. Then, it can expose easily by scraping off the thin bottom part from the inner side of the capsule 5b.
- a mold that fits inside the capsule 5b without a gap is created. After forming at least one through hole in an area where electrodes are to be formed when the capsule 5b is formed, the mold is fitted inside the capsule. Thereafter, an electrode is formed so that the hole is filled from the outside, and the mold is pulled out, so that the electrode is exposed inside the capsule.
- the stomach is one of the digestive organ contents 7 and the stomach contents are acidic.
- An oxidation reaction of Al 3+ + 3e ⁇ occurs, and an electromotive force is generated at the electrode 3 due to a reduction reaction.
- Electrodes 2 and 3 may be exposed to the outer surface of the capsule body 5 and immersed in the digestive organ contents, and various modifications and changes are possible.
- the electrodes 2 and 3 are embedded in a depression or protrusion formed on the outer surface of the capsule body 5, there is no particular limitation as long as the electrodes 2 and 3 are formed so as to be exposed on the surface.
- the electrode 3 may be formed of platinum or other various noble metals.
- Electrodes 2 and 3 What is necessary is just to design the surface area of these electrodes 2 and 3 with the quantity of the electric current which the capsule apparatus 1 requires. In the case of power consumption using a capsule device currently in practical use as an example, an electrode area of 0.25 to 2 cm 2 is sufficient. Furthermore, if a large amount of current is required, the electrode surface area may be increased. If the capsule device is put into practical use, it is possible to form electrodes having a total area of up to about 6 cm 2 in total.
- a power supply system having electrodes with different cross-sectional shapes will be described as a first modification of the first embodiment.
- the configuration of the power supply system in the first embodiment described above is the same as that of the first embodiment except for the electrodes.
- the stripe electrode 11 of the first modified example is formed in a stripe shape in which rectangular convex portions directed in the front-rear direction of the capsule 5 are formed as a plurality of stages of lines.
- this formation method after forming into a thick film, it may be mechanically scraped, or may be removed by anisotropic etching after masking.
- the rectangular stripe electrode 11 By forming the rectangular stripe electrode 11 in this way, not only the surface area in contact with the digestive organ contents is enlarged, but also the stripe groove portion on the electrode surface is in close contact with the stomach wall when contacting the stomach wall (intestinal wall). Without this, an area that contacts the digestive organ contents is secured. Thereby, the fall of an electromotive force can be prevented. Furthermore, as the capsule flows down, the digester contents move rearward along the rectangular fin, so that the generated hydrogen bubbles are more efficiently separated.
- the stripe electrode 11 can also function as a heat sink. That is, it also has a function of radiating heat generated by each driving part of the capsule device from the electrode. Therefore, the increase in the surface area of the electrode is the same as the increase in the area for heat dissipation, and the performance related to cooling is improved.
- FIG. 4 shows the cross-sectional shape of the electrode of the second modification in the AA direction of FIG. 1A.
- the stripe electrode 12 of the second modification example has a curved cross section with respect to the stripe electrode 11 having the rectangular cross section of the first modification example described above.
- a forming method after forming a thick film, it is formed into a curved surface by isotropic etching such as wet etching.
- isotropic etching such as wet etching.
- it does not necessarily have to be a curved surface, and may have a shape obtained by scraping the side surface of the stripe into a taper.
- This 2nd modification can obtain the same operation effect as the 1st modification mentioned above.
- FIG. 5A is a diagram illustrating an external configuration of a capsule device according to a third modification.
- FIG. 5B is a diagram showing a cross-sectional configuration of the electrode in the BB direction of FIG. 5A.
- This third modification is a configuration in which mesh covers 13 and 14 are provided with a space 15 of an arbitrary distance from electrodes 2 and 3. These mesh covers 13 and 14 are shaped to cover the electrodes 2 and 3, and are provided with an opening of a separation space 15 in the front-rear direction (short side of the electrode shown in FIG. 4), and on the side (electrode shown in FIG. 4) Connected on the long side).
- the mesh covers 13 and 14 hold the digestive organ contents 7 so that the electrodes 2 and 3 are always immersed in the digestive organ contents (or digestive organ solution) 7 when staying in the living body.
- the space 15 that opens in the front-rear direction is provided so that new digestive contents 7 always enter the space 15 when flowing down the living body.
- the digestive organ contents 7 flow through the separation space 15 from the front to the rear, the bubbles generated on the electrodes can be pushed backward.
- the mesh covers 13 and 14 can be appropriately selected for the size of the eyes.
- a mesh with fine eyes is adopted so that it can easily hold the digestive contents 7 entered in the front, and a mesh with coarse eyes is adopted in the rear so that bubbles can easily flow out.
- Different mesh sizes may be combined.
- the opening area on the inlet side of the digestive contents 7 ahead larger than the opening area on the outlet side, the digestive contents 7 can be easily sucked and pushed out from the outlet. Also good.
- a mesh cover is used to hold the digestive contents 7, but the present invention is not limited to this, and a punch board having a large number of holes having an arbitrary diameter may be used.
- the mesh covers 13 and 14 may be made of the same material as that of a metal (conductive) member, for example, an electrode, if it contributes to electromotive force.
- a resin material may be used.
- the electrodes 2 and 3 can be always immersed in the digestive organ contents when staying in the living body. Can be stably generated. Further, by forming the mesh covers 13 and 14 with the same metal material as the electrodes 2 and 3, the amount of current to be generated can be increased without increasing the electrode formation occupation area in the capsule body 5.
- FIG. 6 is a diagram illustrating a cross-sectional configuration of the power supply system in the capsule device 1 according to the fourth modification.
- a plurality of electrodes (cathodes) 16 and electrodes (anodes) 17 are alternately formed so as to surround the outer periphery of the capsule body 5.
- the outer electrodes 16 a and 17 a provided on the outer wall surface side of the capsule body 5 and the inner electrodes 16 b and 17 b provided on the inner wall surface side are integrated through the holes or grooves.
- Bobbin shape is formed.
- the outer shape of the electrodes 16 and 17 can be selected as appropriate.
- these inner electrodes 16a and 17b have a certain area, they can be easily connected to the power source 6 by the wiring 4 (4a1, 4a2, 4a3, 4a4). Furthermore, the heat generated by the components provided in the capsule body 5 is received by the inner electrodes 16a and 17b, transferred to the outer electrodes 16b and 17b through the holes or grooves, and further radiated from the outer electrodes 16b and 17b. Is done.
- a temperature sensor is provided on the electrode of the power supply system as a fifth modification example of the first embodiment with reference to FIG.
- the electrodes 2 and 3 have a function of radiating heat.
- a sensor for measuring temperature for example, a thermocouple sensor 18 is provided so as to protrude or be exposed from the surface of one electrode 2 (3), and a temperature measuring unit 19 is disposed in the capsule body 5. is there.
- thermocouple sensor 18 When the thermocouple sensor 18 is provided on the electrode 2 (3), it is provided so as to surround the sensor with a heat insulating material so as to eliminate the influence of heat from the electrode 2 (3) (heat generated by driving the components). It is desirable to do. According to this modification, it is possible to inspect the temperature in the visceral tube, which is the deep body temperature of a living body that cannot be measured in a normal state.
- FIG. 8 shows an external configuration example of a capsule device for mainly operating in the duodenum and the small intestine.
- the same parts as those of the first embodiment described above are denoted by the same reference numerals, and description thereof is omitted.
- an electrode 22 made of aluminum that acts as a cathode and an electrode 23 made of carbon that acts as an anode are formed on the wall surface of the capsule body 5.
- a voltaic battery using an electrolyte as an electrolyte is constructed.
- the above-described power supply unit 6 is disposed in the capsule body 5 and connected by wiring. Furthermore, the entire surface of the electrode 21 is covered with a thin film (gelatin film) 24 made of a gelatin material.
- the capsule device 21 prevents gastric juice and the like from adhering to the electrode 21 until the gelatin film 24 is dissolved when administered into the living body.
- the capsule device 21 can reach the duodenum and the small intestine before the electrode 22 contacts the gastric juice, and can start power generation.
- the time until the gelatin film 24 at this time is dissolved and the electrode 22 is exposed can be adjusted by increasing or decreasing the thickness of the film based on information obtained through experience or experiment. Therefore, power can be supplied to the capsule device 21 at the timing when it reaches the duodenum or small intestine after administration.
- the duodenum is weakly basic with a pH of about 8-9 because trypsin, a digestive enzyme, works effectively.
- the amphoteric metal aluminum is oxidized even if the electrode 22 is made of aluminum under such weakly basic conditions. Accordingly, the electrodes 22 and 23 operate as a battery and can supply power to the capsule device 21.
- gelatin film 24 of the present embodiment can be substituted with other materials.
- a thin film made of starch, agar, sugar or the like may be used, and any thin film that dissolves or decomposes inside the digestive organ can be used without limitation.
- the surface of the aluminum of the electrode 22 is coated, it is not directly exposed to air (oxygen). For this reason, the oxidation of the electrode at the time of storage can be prevented, and an electromotive force that outputs a normal value immediately after the thin film is dissolved can be performed. Furthermore, since the electrode can be formed of aluminum, the cost can be reduced as compared with a noble metal material. Also in this embodiment, the electrodes and mesh covers according to the first to third modifications described above can be applied.
- FIG. 9 shows a cross-sectional configuration of a capsule device that mainly operates in the large intestine.
- a power supply unit 6 (not shown) of the power supply system in the capsule device 1 has the same configuration as that of the first embodiment described above.
- the capsule device 1 of the present embodiment forms an electrode 22 made of aluminum acting as a cathode and an electrode 23 made of carbon acting as an anode on the outer surface of the capsule body 5 to electrolyze the digestive organ contents.
- a voltaic battery is formed as a liquid. This is equivalent to the electrode in the second embodiment described above.
- These electrodes 22 and 23 are covered with a porous thin film 25 for holding a solution, and further covered with a gelatin film 24.
- the gelatin film 24 prevents gastric juice and substances in the small intestine from adhering to the electrodes 22 and 23 without being dissolved until it reaches the large intestine after administration. Then, when reaching the large intestine, the gelatin film 24 dissolves and the digestive organ contents come into contact with the electrodes 22 and 23 to start power generation. At this time, the porous thin film 25 is held so that the electrodes 22 and 23 are immersed in the electrolytic solution, and even in a state where the water content of the electrolytic solution in the digestive organ contents is reduced in the large intestine, the electrodes 2 and 3 are used. Can always be immersed in the digestive organ contents, and can stably generate electricity.
- FIG. 10 shows an example of the internal configuration of the capsule endoscope 31.
- the same parts as those of the first embodiment described above are denoted by the same reference numerals, and description thereof is omitted.
- the power supply system mounted on the capsule endoscope 31 includes the electrodes 2 and 3 and the power supply unit 6, and is equivalent to the power supply system in the first to third embodiments and the first to fourth modifications described above.
- the electrodes 2 and 3 are assumed to have a size of about 10 mm ⁇ 10 mm, for example.
- the capsule endoscope 31 is inserted into a living body, and then a lens 32 for forming an image of a photographing object (subject) in the digestive organ and a plurality of light emitting elements (for example, LEDs) 33 for illuminating the photographing field of view.
- a lens holder 34 that holds the lens 32 and the light emitting element 33, a CMOS sensor 35 that photoelectrically converts an optical image formed on the lens 32 to generate an image signal, an image processing unit, and a wireless signal conversion unit (ASIC) ) 36 and an antenna 37.
- ASIC wireless signal conversion unit
- the captured image signal is subjected to various correction processes related to noise removal and image quality, is generated as image data together with information related to imaging, is converted into an information signal for wireless communication, and is disposed outside the living body. 20 is transmitted.
- the captured image may be transmitted at all times during the imaging period, or may be transmitted when the amount of image that has been temporarily stocked with the memory mounted is reached. Alternatively, it may be transmitted at a predetermined time interval.
- the capsule endoscope 31 equipped with this power supply system is immersed in artificial gastric fluid (adjusted to PH 3.0 by containing 0.2% NaCl, 0.04% pepsin and 1M HCl) installed in a constant temperature bath at 36 ° C.
- Each component of the capsule endoscope 31 is driven by a power source generated by a power source system immersed in the artificial gastric juice to perform imaging.
- the captured image was transmitted from the antenna 37 and displayed on the monitor (viewer) of the external device, thereby confirming the shooting and transmission of the image.
- the power supply system of the present invention can be mounted on a capsule endoscope to supply power in place of a conventional battery such as a silver oxide button battery.
- FIG. 11 shows an example of the internal configuration of the capsule endoscope 41.
- the same reference numerals are given to those that function in the same manner as the constituent parts shown in FIG. 10 of the fourth embodiment described above, and the description thereof is omitted.
- the power supply system mounted on the capsule endoscope 41 includes electrodes and a power supply unit, and is equivalent to the power supply system in the first to third embodiments and the first to fourth modifications described above.
- the capsule endoscope 41 includes a lens 32, a plurality of light emitting elements (LEDs) 33, a lens holder 34, a CCD 38 that photoelectrically converts an optical image formed on the lens 32 and generates an image signal, and an image signal.
- the digital signal processor (DSP) 39 that performs noise removal and various correction processes on the radio, the radio transmission module 40 that converts the processed image data into radio signals, and the antenna 37 are configured.
- the captured image is generated as image data together with information related to shooting in the DSP 39, converted into a wireless signal (information signal for wireless communication) by the wireless transmission module 40, and placed outside the living body using the antenna 37. Sent to the image receiving device 20.
- the capsule endoscope 41 similarly to the above-described fourth embodiment, the capsule endoscope 41 is immersed in the artificial gastric fluid and a power source is generated from the power supply system to drive the capsule endoscope 41 to perform imaging.
- the captured image was transmitted from the antenna 37 and displayed on the monitor of the external device (image receiving apparatus), thereby confirming the shooting and transmission of the image.
- the power supply system of the present invention is mounted on a capsule endoscope and can supply power in place of a conventional battery such as a silver oxide button battery. Further, the capsule endoscope of the present embodiment can be further reduced in size because a space is removed from the battery as compared with a capsule endoscope having a conventional configuration.
- the capsule device according to the present embodiment includes a drug delivery function unit that injects a drug solution at a target location or a sampling function unit that samples a gas and a liquid around an observation target and an endoscope function unit in the capsule body. Capsule device.
- FIG. 12 shows an example of the internal configuration of the capsule device.
- the power supply system mounted on the capsule device 51 includes the electrodes 2 and 3 and the power supply unit 6 and is equivalent to the power supply system in the first to third embodiments and the first to fourth modifications described above.
- the endoscope functional unit of the capsule device 51 is equipped with a configuration equivalent to that of the above-described fourth embodiment. That is, the endoscope function unit includes a lens 32, a light emitting element (LED) 33, a lens holder 34, a CMOS sensor 35, an ASIC 36, and an antenna 37.
- the endoscope function unit includes a lens 32, a light emitting element (LED) 33, a lens holder 34, a CMOS sensor 35, an ASIC 36, and an antenna 37.
- the drug delivery function unit includes a chemical cylinder 52 that stores an arbitrary chemical, an electromagnetic valve 53, a compressed carbon dioxide tank 54, and a chemical injection nozzle 55.
- the electromagnetic valve 53 is opened and closed by an instruction from a control unit (not shown) provided in the ASIC 36 described above.
- a capsule device 51 including an endoscope function unit and a drug delivery function unit observes an arbitrary image taken in a living body from the outside, and determines a target target portion.
- an instruction is given to open the electromagnetic valve 53 from outside while confirming the image.
- the electromagnetic valve 53 is opened, the compressed carbon dioxide gas pushes out the chemical solution stored in the chemical solution cylinder 52 to the chemical solution injection nozzle 55.
- the chemical liquid is ejected from the chemical liquid injection nozzle 55 toward the target target portion displayed on the monitor of the image receiving device 2 and is dispersed.
- the drug solution adapted to this embodiment can be applied not only to a drug for healing, but also to various drugs such as a contrast agent for MRI diagnosis and an anticancer agent.
- the capsule body 5 is provided with a pH sensor or a chemical sensor. Using these sensors, not only the determination based on the image, but also the timing of supplying the chemical solution may be achieved based on the detection result of the pH sensor or the chemical sensor.
- the charging timing can be automatically set by setting a determination value in advance for the detection result of the pH sensor or the chemical sensor. For example, when a pH sensor is used, when the capsule device 51 moves from the stomach where the pH of the digestive organ contents is low to the duodenum where the pH is high, if the detected pH value exceeds the judgment value, the drug solution is injected. It is also possible to do.
- the sampling function unit can use the configuration of the drug delivery function unit. That is, the sampling function unit can collect the gas in the digestive tract and the gastrointestinal contents liquid by emptying the chemical liquid cylinder 52 and evacuating the compressed carbon dioxide gas tank 54.
- the capsule device 51 including the endoscope function unit and the sampling function unit observes an arbitrary image captured in the living body from the outside, and instructs to open the electromagnetic valve 53 from the outside at the target position.
- the electromagnetic valve 53 When the electromagnetic valve 53 is opened, the gas and liquid in the digestive apparatus are drawn into the chemical cylinder 52 from the chemical solution injection nozzle 55 and stored so as to eliminate the negative pressure due to the vacuum state of the compressed carbon dioxide gas tank 21.
- the endoscope function unit of the capsule device 51 is operated to acquire an image.
- the image may be discharged out of the body as it is without acquiring the subsequent image.
- the capsule device of the sixth embodiment after being administered to the living body, while observing the image acquired by the endoscope function unit, when facing the desired target region, By opening the electromagnetic valve 53, the chemical solution can be ejected to the target site. Further, in the same configuration, the compressed carbon dioxide gas tank 21 is evacuated and the chemical cylinder 52 is emptied, so that when the electromagnetic valve 53 is opened at a desired position, the gas and liquid in the surrounding digestive organs are transferred to the capsule body. As a result, the gas and solution in the digestive organ can be collected in the chemical cylinder.
- the drug delivery function unit uses the power supply system of this embodiment, so that the battery storage space in the capsule device of the conventional configuration is vacant, so that the size of the capsule device is not changed by mounting in the space. Can be realized.
- the configuration in which any one of the sampling function unit and the drag delivery function unit is mounted has been described, but a configuration in which both of them are mounted may be employed.
- the drug delivery function unit is configured to eject the chemical solution, but may be configured to eject powder medicine.
- the chemical injection nozzle 55 of the drug delivery function unit is shown in an open state.
- a thin film that is crushed by vacuum suction may be provided, or a lid that opens and closes may be provided.
- the sampling function unit of the sixth embodiment is minimally invasive and samples the gas inside the digestive organ directly at the imaging location.
- the gas inside the digestive organ cannot be sampled directly at the photographing site with minimal invasiveness.
- the composition may change when the gas in the digestive organ moves through the digestive organ. Therefore, the new sampling method by the capsule device of the present embodiment can take out the most appropriate subject without damaging the living body at all, and can provide a new diagnostic method.
- the power supply system of the present invention described above can be easily implemented by appropriately combining the configurations of the above-described embodiments and modifications, including the exclusion or modification of some components.
- the capsule device of the present embodiment is not limited to being used alone, and can be used in combination with other inspection devices or medical devices.
- an X-ray device or the like may be used in combination, and the imaging position of an image obtained by the capsule device may be specified as necessary.
- the electrodes (electrode pairs) formed on the outer wall surface of the capsule body are formed with the electrode surfaces exposed to the outside.
- the electrode is not opposed to be housed in the case, and the arrangement in which the electrode surfaces face each other is not included in the main body and the outer wall of the capsule.
- This power supply system has the same configuration as that of the capsule body 5 shown in FIG. 1B in the first embodiment described above.
- the electrode material is different, and the intestinal juice is used as the digestive organ contents around the electrode. It is a system that generates electricity.
- a power supply unit 6 for generating a power supply.
- a known battery called a voltaic battery as shown in FIG. 2 is used if the electrodes 2 and 3 and the digestive organ contents (intestinal fluid) 7 around the electrodes are used as the electrolyte. It becomes composition.
- the power supply unit 6 uses the electromotive force generated between the electrodes 2 and 3 using this voltaic battery, the power supply unit 6 supplies each component in the capsule device 1 as a power source.
- the electromotive force of a voltaic battery is determined by the difference between the standard electrode potentials of electrodes made of these two different metals.
- aluminum including an aluminum alloy
- an amphoteric metal is selected for the electrode 2 serving as a cathode. This is because an alkali metal or alkaline earth metal is suitable as the cathode, but it must have a small effect on the administered living body, and it can generate power even in the acidic stomach or in the basic duodenum. It must be possible.
- the present embodiment proposes a power generation unit that generates power by using an electrode and a substance in the intestinal fluid as a bio-voltaic battery.
- the intestinal substance is reduced by hydrogen on the electrode 3 by catalytic action using hydrogen ions.
- a larger generated current can be obtained than in the reduction reaction of hydrogen ions.
- the electrode In order to perform this reaction efficiently, it is desirable that the electrode has a large surface area and must be safe for a living body.
- the carbon electrode is the most suitable electrode that meets these requirements.
- the carbon material used for the carbon electrode is not particularly limited as long as it has high conductivity. Specific examples include conductive carbon black and carbon black represented by acetylene black and ketjen black (trade name: Lion).
- Amorphous carbon composites, graphite, carbon fibers, carbon nanotubes, carbon nanohorns, or a mixture thereof or those dispersed on a conductive substrate such as carbon paper or carbon cloth can be employed.
- a noble metal is supported on the carbon electrode.
- gold, platinum, palladium, rhodium, and silver are preferable in consideration of safety to an administered living body and reaction characteristics.
- the capsule device of the present embodiment is equipped with a power supply system for operating mainly in the intestine.
- a power supply system for operating mainly in the intestine.
- an electrode pair is formed on the outer wall surface of the capsule device 1 by an electrode 2 made of aluminum that acts as a cathode and a Pt-supported carbon electrode 3 that acts as an anode, and the contents of the digestive organs are used as an electrolyte.
- a voltaic battery electrolyte
- a power supply unit 6 is disposed, and the electrodes 2 and 3 are connected to each other by wires 4a and 4b. These wirings 4a and 4b are connected by welding (or soldering) to a part of the electrodes 2 and 3 exposed on the inner wall of the capsule device.
- the power supply unit 6 is an integrated circuit in which a general circuit configuration, for example, an amplifier circuit and a constant voltage circuit (or a constant current circuit) are integrated on one chip.
- a capacitor (charge storage element) functioning as a buffer may be arranged on the input side.
- the exposed portion on the inner surface side of the electrode can expose the capsule 5b by making a hole from the inside.
- a hole (bottomed hole) or groove is cut in advance from the outside in the electrode formation region of the capsule 5b, and an electrode is formed by sputtering film formation so as to fill the hole.
- the electrodes 2 and 3 are each formed with a size of about 10 ⁇ 10 mm. Then, it can expose easily by scraping off the thin bottom part from the inner side of the capsule 5b.
- a mold that fits inside the capsule 5b without a gap is created. After forming at least one through hole in an area where electrodes are to be formed when the capsule 5b is formed, the mold is fitted inside the capsule. Thereafter, an electrode is formed so that the hole is filled from the outside, and the mold is pulled out, so that the electrode is exposed inside the capsule.
- the power supply system having such a configuration constitutes a bio-voltaic battery using the digestive organ contents 7 as an electrolyte, and the electrode 2 undergoes an oxidation reaction of Al ⁇ Al 3 + + 3e ⁇ . If the biological substance contained in A is A, an electromotive force is generated by the catalytic reduction of the digestive contents 7 as H + + A + e ⁇ ⁇ HA. Examples of the substance that undergoes a reduction reaction at the electrode 3 include substances that are contained in a large amount in the intestinal fluid such as taurocholic acid.
- Electrodes 2 and 3 may be exposed on the outer wall surface of the capsule body 5 and immersed in the contents of the digestive organ, and can be variously modified and changed.
- the electrodes 2 and 3 are embedded in a depression or protrusion formed on the outer surface of the capsule body 5, there is no particular limitation as long as the electrodes 2 and 3 are formed so as to be exposed on the surface.
- the surface areas of the electrodes 2 and 3 may be designed according to the amount of current required by the capsule device 1. In the case of power consumption using a capsule device currently in practical use as an example, an electrode area of 0.25 to 2 cm 2 is sufficient. Furthermore, if a large amount of current is required, the electrode surface area may be increased. If the capsule device is put into practical use, it is possible to form electrodes having a total area of up to about 6 cm 2 in total. Furthermore, the electrode 2 can provide a larger area by providing irregularities on the surface or using porous aluminum such as foamed aluminum.
- Such an electrode 2 made of an aluminum electrode and an electrode 3 made of a Pt-supported carbon electrode according to the present embodiment will be described in terms of power generation amount and power generation durability.
- the electrodes 2 and 3 are immersed in the artificial intestinal fluid, for example, a load of 48 ⁇ is applied, and the power generation amount for 8 hours is measured.
- the load 48 ⁇ is a numerical value according to the load at the time of quality confirmation in the manufacturing process of the dry battery.
- the measurement time is set to 8 hours, which is an estimated time from when the capsule device is swallowed until it passes through the intestine and is discharged from the body.
- FIG. 13 is a diagram showing the generated current with respect to the elapsed time by the electrodes 2 and 3 of this embodiment
- FIG. 14 is a diagram showing the characteristics of the generated voltage with respect to the elapsed time by the electrodes 2 and 3. As shown in FIG. 13, it decreases suddenly for 2 hours from the beginning of power generation, but after that, power generation with a current amount of 1 mA per 1 cm 2 of Al electrode area is stably performed until 8 hours have passed. Further, as shown in FIG. 14, the generated voltage is not deteriorated after 8 hours and is maintained at a voltage of 1.5V.
- FIG. 15 shows the relationship between the electrode areas of the electrodes 2 and 3 and the generated current. From this result, the electrode area and the generated current are in a proportional relationship, and when the electrode area is increased, the generated current is also increased in proportion thereto. Therefore, the amount of generated current can be increased by increasing the electrode area according to the required amount of current.
- FIG. 16 and 17 show the characteristics of the generated current and the generated voltage with respect to the elapsed time of the comparative example for the electrodes 2 and 3 of the present embodiment.
- FIG. 16 shows a generated current with respect to elapsed time in a comparative example in which an aluminum electrode is applied to the electrode corresponding to the electrode 2 of the present embodiment and a Pt electrode is applied to the electrode corresponding to the electrode 3.
- FIG. 17 shows the generated voltage with respect to the elapsed time in the comparative example.
- the aluminum electrode and the Pt electrode of this comparative example are immersed in an artificial intestinal fluid, a load of 48 ⁇ is applied as described above, and the amount of power generation up to 8 hours is measured.
- the measured power generation current gradually decreases until about 3 hours from the beginning of power generation, and thereafter, stable power generation with a current amount of 2 ⁇ A per 1 cm 2 of Al electrode area is performed until 8 hours elapse.
- the voltage is less deteriorated after 8 hours and the voltage of 1.5V is maintained.
- the generated voltage by the electrode pair composed of the aluminum electrode 2 and the Pt-supported carbon electrode according to the present embodiment is between 2V to 1.5V, both of the generated voltage by the electrode pair composed of the aluminum electrode and the Pt electrode in the comparative example. is there.
- the generated current according to the present embodiment can obtain a current value three orders of magnitude greater than the generated current of the comparative example. That is, this embodiment is in a more practical stage by securing the electrode area.
- the electrode 2 in the power supply system includes an electrode 2 made of an aluminum electrode and an electrode 3 made of an AuPt-supported carbon electrode.
- the power generation amount and power generation durability in this electrode configuration will be described below.
- These electrodes 2 and 3 are immersed in artificial intestinal fluid, a load of 48 ⁇ is applied, and the amount of power generation from the initial power generation to 8 hours is measured.
- FIG. 18 is a diagram showing the characteristics of the generated current with respect to the elapsed time by the electrodes 2 and 3 of the present embodiment.
- the current decreases from 4 mA to 2 mA per 1 cm 2 of Al electrode area by about 3 hours from the initial stage of power generation, and thereafter, stable power generation with a current amount of 0.5 mA or more is performed until 8 hours. It is.
- the maximum generated current was 4 mA.
- the decrease in the generated current is assumed to be due to a bubble generated at the anode or the oxidation of the surface of the Al electrode, which actually contributes to the power generation.
- the electrodes 2 and 3 are inserted and immersed in the artificial intestinal fluid in the container. For this reason, it is not administered to an actual living body and is not always in contact with the new digestive contents 7 due to flow. Further, even when bubbles or oxide films are generated on the electrode, the operation for removing them is not performed.
- aluminum electrode area of the power generation early is 0.5 cm 2, after 8 hours are increased to 2 cm 2.
- the generated current returns to the current value at the initial stage of power generation.
- the amount of current stably supplies an output of 3 mA as an average value from the beginning of power generation until 8 hours have passed. Therefore, by periodically adding electrodes after the start of power generation, the current value at the initial stage of power generation can be restored, and a power generation current of a certain value or more can be continuously obtained.
- the electrode surface is covered with a thin film (gelatin film) made of gelatin materials having different thicknesses.
- the gelatin film dissolves with a time lag in the intestine, and new electrode surfaces can be periodically exposed to the electrolyte solution of the digestive organ contents 7.
- FIG. 20 is a diagram showing the characteristics of the generated current with respect to the elapsed time by the electrodes 2 and 3 of the present embodiment.
- the electrode in the power supply system includes an electrode 2 made of an aluminum electrode and an electrode 3 made of a PdPt-supported carbon electrode.
- the power generation amount and power generation durability in this electrode configuration will be described below.
- This PdPt-supported carbon electrode has not been used as a fuel cell electrode until now, but it contributes to longer electromotive force and battery life by using two kinds of precious metals for bio-voltaic cells. The performance is improved.
- a combination of Pd and Pt is preferable.
- FIG. 21 is a diagram showing the characteristics of the generated current with respect to the elapsed time by the electrodes 2 and 3 of the present embodiment.
- FIG. 22 is a diagram showing the characteristics of the generated current with respect to the elapsed time by the electrodes 2 and 3 of the present embodiment.
- the electrode pair (electrodes 2 and 3) formed on the outer surface of the capsule body 5 is always electrolyzed with new digestive contents 7. It is assumed that it comes into contact with the liquid. Therefore, the electrode pair does not cause a problem because the flow of the digestive organ contents 7 with respect to the electrolytic solution occurs.
- the electrode pair of this embodiment has laminated structure electrodes 61 and 62 having the same structure as shown in FIG.
- the electrode material forming the laminated structure electrodes 61 and 62 uses a combination of materials described in the seventh to eleventh embodiments.
- the laminated structure electrode 62 has a laminated structure of a plurality of electrode pieces 63a to 63e and thin films (gelatin films) 64a to 64e made of an extremely thin gelatin material interposed between these electrode pieces.
- the plurality of electrode pieces 63a to 63e are formed in a thin film or mesh shape having a large number of small holes so that the intervening gelatin films 64a to 64e are dissolved by the electrolytic solution of the digestive organ contents 7. Therefore, in order to obtain the electrode surface area, the electrode pieces 63a to 63e do not have to be flat.
- the electrode pieces 63a to 63e are electrically connected by a common wiring 65.
- the common wiring 65 is led out into the capsule body, connected to the power supply unit 6 by the wiring 67, and the generated current (voltage) is input to the power supply unit 6. Further, in this embodiment, there is a concern that the electrode area exposed by the remaining gelatin film is reduced until the gelatin films 64a to 64e of the respective layers are completely dissolved, and the power generation amount is reduced.
- Providing the capacitor 66 functions to supply power stably during the decrease period.
- the laminated structure electrodes 61 and 62 configured in this way are formed on the outer wall surface of the capsule body 5 as shown in FIGS. 24A to 24D.
- the first electrode piece 63a having a uniform film thickness is formed on the outer wall surface on which the mask 68 is formed.
- the first electrode piece 63a is formed so as to embed a hole opened in the capsule body 5, and a portion formed in the hole becomes a lead wire for a lower electrode (not shown).
- the first gelatin film 64a is formed by making a space for the common wiring 65.
- the first gelatin film 64a can be formed, for example, by printing using a printing technique and then curing. In the same manner, stacking is performed in the procedure of FIGS. 24C and 24D.
- the formed laminated structure electrodes 61 and 62 may be separately manufactured and attached to the capsule body 5 as described later, or may be directly formed on the outer wall surface. Further, the film thickness of the uppermost gelatin film is adjusted so that power generation is started from the time when it reaches the intestines. By adjusting the gelatin film, the capsule device 1 can start power generation when the laminated structure electrodes 61 and 62 reach the duodenum or the small intestine without contacting the gastric juice.
- the lowermost gelatin film 64d is dissolved after a certain period of time after the uppermost electrode piece 63e is exposed and the power generation is started when flowing down the intestine. To do.
- the electrode piece 63e is lifted and separated from the common wiring 65, and the next electrode piece 63c is exposed to start power generation.
- the separated electrode piece 63e is a small solid and is then discharged outside the body, so there is no influence on the surroundings due to the residue.
- the gelatin film 64 under the exposed electrode piece 63 is dissolved, the exposed electrode is separated at that time, and new electrode surfaces are sequentially exposed. As shown in FIG. 19, the operation is equivalent to that of adding a new electrode, and a decrease in the amount of power generation can be prevented, and a practical level output close to the power generation amount at the initial stage of power generation can be obtained.
- FIG. 25A to 25G are diagrams showing an example of the manufacturing process of the laminated structure electrodes 61 and 62.
- FIG. In this example, a single electrode film (for example, a Pd-supporting carbon film) is formed, cut and stacked to form a laminated structure electrode, and an example of bonding to a capsule body is shown.
- a combination of the aluminum electrode 61 and the Pd-supporting carbon electrode 62 in the seventh embodiment described above is taken as an example.
- a large Pd-supporting carbon thin film 63 corresponding to the area of a plurality of electrodes is formed by a known manufacturing technique.
- a gelatin film 64 having a predetermined thickness is formed, leaving both ends of the Pd-supporting carbon thin film 63 exposed. Then, it cut
- the surfaces of the gelatin films 64a to 64d are melted and then solidified again in a state where both side ends of the stacked electrode pieces 63a to 63e are sandwiched from above and below.
- the pieces 63a to 63e are adhered to each other.
- the common electrode 65 is formed so as to include both ends of the electrode pieces by using a method such as plating at both ends, and cut at the center indicated by the dotted line A.
- the electrode pieces 63a to 63e are bonded to the base electrode 68 formed in the capsule body 5 and connected to the power supply unit 6 by the wiring 67 so as to be electrically connected.
- at least the common wiring 65 may be electrically connected to the base electrode 69.
- the thickness of the gelatin film 70 is a thickness at which power generation is started immediately after reaching the duodenum or the small intestine without contacting the gastric juice, and can be obtained empirically.
- the laminated structure electrode 61 made of aluminum or a known semiconductor film forming technique such as vapor deposition or CVD may be used.
- the gelatin film of the present embodiment can be substituted with another material.
- starch, agar, or a thin film made of sugar or the like may be used, as long as it is harmless (non-toxic) to a test subject such as a living body and is dissolved or decomposed inside the digestive organs. It can be used without particular limitation.
- disconnected may be sufficient. That is, a hierarchical structure is formed in which each layer of the electrode pieces is connected to each other by a plurality of support columns, and the interlayer is filled with gelatin to form a hierarchical structure electrode in which gelatin is exposed on the side surface. In the intestine, the gelatin may be dissolved away from the side of the hierarchical structure electrode, and the surface area of the electrode may increase with time. With this hierarchical structure, the back side of the electrode piece of each layer also serves as an electrode surface that contributes to power generation.
- Each embodiment described above includes the following inventions.
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Abstract
Description
更に、特開2007-200739号公報においては、胃内部溶液を電解液(電解質)として利用して発電する技術も提案されている。
[第1の実施形態]
まず、本発明の電源システムの概念について説明する。図1Aには、本発明の第1の実施形態に係る、生体内に投与された状態の体内飲み込み型医療用カプセル装置(以下、カプセル装置と称する)の外観構成を示す図である。図1Bは、図1AのA-A方向におけるカプセル装置の断面構成を示す図である。また、図2は、電源システムの概念的な構成を示す図である。図3は、図1AのA-A方向における第1の変形例の電極の断面形状を示している。
電源システムは、カプセル本体5の外壁面に設けられて全てが露呈する、後述する材質の異なる金属からなる少なくとも2つの電極2,3と、これらの電極2,3が発生させた起電力から予め定めた定電圧の電源を生成する電源部6と、で構成される。これらの電極2,3と、周囲にある消化器内容物7を電解液として用いれば、ボルタ電池と称される公知な電池構成となる。このボルタ電池を利用する電極2,3の間に発生した起電力を用いて、電源部6がカプセル装置1の図示してない各駆動部に電源として供給する。
また、電源部6は、一般的な回路構成、例えば、増幅回路及び定電圧回路(又は、定電流回路)が1チップ上に集積形成された集積回路である。尚、出力を安定させるために、入力側にバッファとして機能するキャパシタ(電荷蓄積素子)を配置してもよい。
人工胃液では最大発電流が0.12mAであり、8時間経過後の発電量は0.02mAでたった。発電電圧は1.2Vであり8時間経過後もほとんど劣化は起こらなかった。
本実施形態のカプセル装置は、主に胃で作動するための電源システムであり、図1Bに示した構成と同様である。
この電源システムは、カプセル装置1の外壁面に、陰極として作用するアルミニウムで構成された電極2と、陽極として作用する炭素で構成された電極3とによる電極対を形成し、消化器内容物を電解物(電解液)とするボルタ電池を構成する。カプセル装置内部には、電源部6が配置され、それぞれの電極2,3とは、配線4a,4bにより接続されている。これらの配線4a,4bは、カプセル装置の内壁に露呈する電極2,3の一部分に溶着(又は、半田付け)して接続する。電源部6は、一般的な回路構成、例えば、増幅回路及び定電圧回路(又は、定電流回路)が1チップ上に集積形成された集積回路である。尚、出力を安定させるために、入力側にバッファとして機能するキャパシタ(電荷蓄積素子)を配置してもよい。
第1の変形例のストライプ電極11は、カプセル5の前後方向に向かう矩形の凸部が複数段のラインとして形成されたストライプ形状に形成されている。この形成方法としては、厚膜に形成した後、機械的に削り取ってもよいし、又はマスクした後、異方性エッチングにより除去してもよい。
次に、第1の実施形態における第2の変形例として、断面形状を変えた電極を有する電源システムについて説明する。この変形例では、電極を除き、前述した第1の実施形態における電源システムの構成と同等である。図4は、図1AのA-A方向における第2の変形例の電極の断面形状を示している。
この第2の変形例は、前述した第1の変形例と同等の作用効果を得ることができる。
次に、第1の実施形態における第3の変形例として、消化器内容物を保持する機能を備えた電極を有する電源システムについて説明する。この変形例では、電極を除き、前述した第1の実施形態における電源システムの構成と同等である。図5Aは、第3の変形例に係るカプセル装置の外観構成を示す図である。図5Bは、図5AのB-B方向における電極の断面構成を示す図である。
尚、メッシュカバー13,14は、起電に寄与させるならば、金属(導電)部材例えば、電極と同じ材料を用いればよい。一方、消化器内容物7を保持するのみであれば、他の部材、例えば樹脂材料により形成してもよい。
次に、第1の実施形態における第4の変形例として、陰極及び陽極がそれぞれ複数の電極を有する電源システムについて説明する。この変形例では、電極を除き、前述した第1の実施形態における電源システムの構成と同等である。
第4の変形例は、カプセル本体5の外周を囲むように、複数の電極(陰極)16と電極(陽極)17が交互に形成される。電極16,17は、カプセル本体5の外壁面側に設けられた外電極16a,17aと、内壁面側に設けられた内電極16b,17bと、が孔又は溝を貫通して一体的になったボビン形状に形成される。勿論、電極16,17の外形形状は、適宜選択できる。
次に図7を参照して、第1の実施形態における第5の変形例として、電源システムの電極に温度センサを設けた構成例について説明する。
前述した第1乃至4の変形例においては、電極2,3が放熱する機能を持つことについて説明した。本変形例は、温度を測定するセンサ、例えば熱電対センサ18を1つの電極2(3)の表面から突出又は、露呈するように設け、カプセル本体5内に温度測定部19を配置した構成である。熱電対センサ18を電極2(3)に設ける場合には、センサ周囲を断熱材で囲うように設けて、電極2(3)からの熱(構成部位の駆動により発生した熱)の影響を排除することが望ましい。
本変形例によれば、通常状態では、測定できない生体の深部体温である内臓管内の温度を検査することができる。
次に、第2の実施形態に係る電源システムを搭載するカプセル装置について説明する。
図8は、主に十二指腸や小腸で作動するためのカプセル装置の外観構成例を示している。ここで、本実施形態の構成部位については、前述した第1の実施形態の構成部位と同等のものには同じ参照符号を付して、その説明を省略する。
次に、第3の実施形態に係る電源システムを搭載するカプセル装置について説明する。
図9は、主に大腸で作動するカプセル装置の断面構成を示している。ここで、本実施形態の構成部位については、前述した第1の実施形態の構成部位と同等のものには同じ参照符号を付して、その説明を省略する。
このカプセル装置1における電源システムの電源部6(図示せず)は、前述した第1の実施形態と同じ構成である。
次に、第4の実施形態に係る電源システムを搭載するカプセル装置について説明する。
本実施形態は、本発明の電源システムを小腸で作動するカプセル内視鏡に適用した例である。図10は、カプセル内視鏡31の内部構成の一例を示す。ここで、本実施形態の構成部位については、前述した第1の実施形態の構成部位と同等のものには同じ参照符号を付して、その説明を省略する。
以上のように、本発明の電源システムは、カプセル内視鏡に搭載して、これまでの酸化銀ボタン電池等の電池に変わって電源供給を行うことができる。
次に、第5の実施形態に係る電源システムを搭載するカプセル装置について説明する。
本実施形態は、本発明の電源システムを小腸で作動するカプセル内視鏡に適用した例である。図11は、カプセル内視鏡41の内部構成の一例を示す。ここで、本実施形態の構成部位については、前述した第4の実施形態の図10に示す構成部位と同等に機能するものには同じ参照符号を付して、その説明を省略する。
カプセル内視鏡41は、レンズ32と、複数の発光素子(LED)33と、レンズホルダ34と、レンズ32に結像された光学像を光電変換して画像信号を生成するCCD38と、画像信号に対してノイズ除去及び種々の補正処理を施すDSP(Digital signal processor)39と、処理された画像データを無線信号に変換する無線送信モジュール40と、アンテナ37と構成される。
次に、第6の実施形態に係る電源システムを搭載するカプセル装置について説明する。
本実施形態のカプセル装置は、カプセル本体内に、対象箇所に薬液を噴射するドラッグデリバリ機能部又は観察対象周囲の気体及び液体をサンプリングするサンプリング機能部と、内視鏡機能部と、を搭載するカプセル装置である。
このカプセル装置51に搭載する電源システムは、電極2,3及び電源部6で構成され、前述した第1乃至3の実施形態及び第1乃至4の変形例における電源システムと同等である。
本実施形態に適応する薬液は、治癒するための薬剤だけではなく、例えば、MRI診断用の造影剤や抗がん剤など様々な薬品に対しても適用することができる。
尚、本実施形態においては、サンプリング機能部とドラッグデリバリ機能部のいずれか1つを搭載した形について説明したが、これらを共に搭載する構成であってもよい。また、実施形態では、ドラッグデリバリ機能部が薬液を噴出する構成であったが、粉薬を噴出する構成であってもよい。
次に、第7の実施形態に係るカプセル装置1に設けられる電源システムについて説明する。
この電源システムは、前述した第1の実施形態における図1Bに示すカプセル本体5と同等の構成を成し、電極材料が異なり、電極の周囲にある消化器内容物として、腸液を電解液に用いて、発電するシステムである。
この電源システムは、カプセル装置1の外壁面に、陰極として作用するアルミニウムで構成された電極2と、陽極として作用するPt担持カーボン電極3とによる電極対を形成し、消化器内容物を電解物(電解液)とするボルタ電池を構成する。
まず、発電量と発電耐久性を調べるため、人工腸液に電極2,3を浸漬し、例えば、48Ωの負荷をかけ、8時間の発電量の測定を行なう。尚、この負荷48Ωは、乾電池の製造工程における品質確認を行なう際の負荷に準じる数値である。また、測定時間を8時間と設定したのは、カプセル装置を飲み込んだ後、胃から腸を通過して体外に排出されるまでの想定時間である。
図13に示すように、発電初期から2時間までは、急に減少するが、以降8時間経過までは、Al電極面積1cm2あたり1mAの電流量の発電が安定して行なわれている。また、図14に示すように、発電電圧も8時間経過で劣化は無く、1.5Vの電圧を維持している。
図16及び図17は、本実施形態の電極2,3に対する比較例の経過時間に対する発電電流と発電電圧の特性を示している。図16は、本実施形態の電極2に相当する電極にアルミニウム電極を適用し、電極3に相当する電極にPt電極を適用した比較例における経過時間に対する発電電流を示している。また、図17は、その比較例における経過時間に対する発電電圧を示している。
第2の実施形態における電源システムについて説明する。
本実施形態は、電源システムにおける電極として、アルミニウム電極からなる電極2と、AuPt担持カーボン電極からなる電極3による構成を成す。以下に、この電極構成における発電量と発電耐久性について説明する。
これらの電極2,3を人工腸液に浸漬し、負荷48Ωをかけ、発電初期から8時間までの発電量の測定を行なう。図18は、本実施形態の電極2,3による経過時間に対する発電電流の特性を示す図である。
本実施形態の電源システムによれば、電極面積を確保することにより、実用段階にある。
また、この構成において、発電電流の減少は、陽極に生じた気泡又は、Al電極表面の酸化等の何らかの原因により、実際に発電に寄与する電極面積の減少が想定される。尚、図13乃至15及び図18に示した測定においては、容器内の人工腸液に電極2,3を差し入れて浸漬している。そのため、実際の生体に投与されて、流下による常に新たな消化器内容物7と接しているものではない。また、電極に気泡や酸化膜が生じた場合でも、それらを除去する動作は行われていない。
図19は、発電初期時のアルミニウム電極面積が0.5cm2であった場合に、発電開始から2時間毎に0.5cm2のアルミニウム電極を追加して、発電を行なった時の発電電流の特性を示す図である。
第9の実施形態における電源システムについて説明する。
本実施形態は、電源システムにおける電極として、アルミニウム電極からなる電極2と、Au担持カーボン電極からなる電極3による構成を成す。以下に、この電極構成における発電量と発電耐久性について説明する。
これらの電極2,3を人工腸液に浸漬し、負荷48Ωをかけ、発電初期から8時間までの発電量の測定を行なう。図20は、本実施形態の電極2,3による経過時間に対する発電電流の特性を示す図である。
第10の実施形態における電源システムについて説明する。
本実施形態は、電源システムにおける電極として、アルミニウム電極からなる電極2と、PdPt担持カーボン電極からなる電極3による構成を成す。以下に、この電極構成における発電量と発電耐久性について説明する。
このPdPt担持カーボン電極は、これまで燃料電池の電極として略利用されていないが、バイオ・ボルタ電池に対して、2種類の貴金属を利用することで、起電力や電池寿命の長寿化に寄与して、性能が改善される。特に、2種類の貴金属の組み合わせにおいては、PdとPtとの組み合わせが好適する。
第11の実施形態における電源システムについて説明する。
本実施形態は、電源システムにおける電極として、アルミニウム電極からなる電極2と、Pd担持カーボン電極からなる電極3による構成を成す。以下に、この電極構成における発電量と発電耐久性について説明する。
これらの電極2,3を人工腸液に浸漬し、負荷48Ωをかけ、発電初期から8時間までの発電量の測定を行なう。図22は、本実施形態の電極2,3による経過時間に対する発電電流の特性を示す図である。
前述した第7乃至第11の実施形態の電源システムの電極の構造において、発電初期は、実用レベルにある発電電流を得ることができるが、時間の経過と共に、その発電電流値が小さくなる傾向がある。その原因は、消化器内容物7の電解液に接する電極表面が変化し、発電に寄与していない状態になっている場合と、電極に接している消化器内容物7の電解液が流動せず停留し、同じ電解液が接した状態となっているため、適正な発電が行われていない場合が考えられる。
(1)耐酸性を有する水密なカプセルと、
カプセル外壁面に露呈するように設けられた、標準電極電位の差を有する2種類の異なる部材からなる少なくとも1つの電極対と、
前記電極対と任意の距離を離間して該電極対を覆い、前記消化器内容物を保持する保持部材(13,14)と、
前記カプセル内に配置され、前記電極対と接続して起電した電源を取り出し出力する電源部と、を備えて、
前記消化器内容物を電解質溶液としたボルタ電池として構成されていることを特徴とする電源システム。
Claims (17)
- 耐酸性を有する水密なカプセルと、
前記カプセルの外壁面に露呈するように設けられた、標準電極電位の差を有する異なる部材からなる少なくとも1つの電極対と、
前記カプセル内に配置され、前記電極対と接続して起電した電源を取り出し供給する電源部と、を備えて、
消化器内容物を電解質溶液としたボルタ電池として構成されていることを特徴とする電源システム。 - 前記電極対において、
陰極となる第1の電極が、アルミニウムにより形成され、
陽極となる第2の電極が、白金、金、銀及び炭素を含む金属材料又は炭素材料のうちのいずれかにより形成されることを特徴とする請求項1に記載の電源システム。 - 前記電極対において、
それぞれの電極が、複数段の凸部ラインを有するストライプ形状に形成されていることを特徴とする請求項1に記載の電源システム。 - 前記電極対において、
電極が前記消化器内容物に対して非耐性の両性金属で形成された場合に、前記電極を覆うように、前記消化器内容物に対して溶解性を有する材料により任意の厚さに形成された薄膜を有することを特徴とする請求項1に記載の電源システム。 - 前記電極対において、
前記消化器内容物を保持する多孔体薄膜により前記電極対が覆われていることを特徴とする請求項1に記載の電源システム。 - 陰極となる第1の電極が、アルミニウム電極であり
陽極となる第2の電極が、触媒担炭素電極である電極対を備え、
腸液からなる電解質溶液に前記電極対を浸漬して、発電する発電部を構成することを特徴とする請求項1に記載の電源システム。 - 耐酸性を有する水密なカプセルと、
前記カプセルの外壁面に露呈するように設けられた、アルミニウム電極と、触媒担炭素電極とからなる少なくとも1つの電極対と、
前記カプセル内に配置され、前記電極対と接続して起電された電源を取り出し供給する電源部と、を備えて、
消化器内容物を電解質溶液としたボルタ電池として構成されていることを特徴とする電源システム。 - 前記電極対において、陽極となる触媒担持炭素電極は、導電性炭素材料上に貴金属微粒子を担持した物質であることを特徴とする請求項6に記載の電源システム。
- 前記触媒担持炭素電極の炭素電極に用いる材料は、導電性カーボンブラック、カーボンブラック及びアモルファスカーボンのコンポシット、グラファイト、カーボンファイバー、カーボンナノチューブ、カーボンナノホーン、これらの混合物及び、これらをカーボンペーパーやカーボンクロスからなる導電性を有する基材に散布したもののいずれかであることを特徴とする請求項8に記載の電源システム。
- 前記貴金属微粒子は、金、白金、パラジウム、ロジウム及び、銀のうちのいずれかであることを特徴とする請求項8に記載の電源システム。
- 前記触媒担炭素電極が、Pt担持カーボン電極、AuPt担持カーボン電極、Au担持カーボン電極、PdPt担持カーボン電極及び、Pd担持カーボン電極のうちのいずれかからなることを特徴とする請求項6又は7に記載の電源システム。
- 前記アルミニウム電極及び前記触媒担炭素電極は、
積み重ねられた複数の電極片と、
前記電極片の間に介在し、前記消化器内容物により溶解する部材からなる複数の介在膜と、
前記複数の電極片の一端を電気的に接続する共通配線と、
で構成される積層構造電極を成し、
上層からの前記介在膜の溶解により、露呈する電極片より前記共通配線から切り離されることを特徴とする請求項6又は7に記載の電源システム。 - 耐酸性を有する水密なカプセルと、
カプセル外壁面に露呈するように設けられた、標準電極電位の差を有する2種類の異なる部材からなる少なくとも1つの電極対を備えて、消化器内容物内で起電した電源を取り出し供給を行う電源システムと、
撮影対象を結像するレンズと、
撮影視野を照明するための複数の発光素子と、
前記レンズに結像された光学像を光電変換し、画像信号を生成する撮像センサと、
前記光学センサにより生成された画像信号の補正処理を施し無線通信用の情報信号に変換する処理部と、
前記処理部からの情報信号を外部に発信するアンテナと、
を備えることを特徴とする医療用カプセル装置。 - 前記医療用カプセル装置は、更に、
任意の薬液を貯留する薬液シリンダと、
ガスを圧縮して収容するタンクと、
前記薬液を外部に向けて噴出するノズルと、
前記タンクと前記薬液シリンダとを連結する通路に設けられた第1のバルブと、
前記薬液シリンダと前記ノズルとを連結する通路に設けられた第2のバルブと、で構成され、
前記撮像センサにより撮像された画像に従うタイミングにより前記前記第1,第2のバルブを開放し、前記ガスが前記薬液シリンダ内に貯留された薬液を前記ノズルから噴出させるドラッグデリバリ機能部を具備することを特徴とする請求項13に記載の医療用カプセル装置。 - 前記医療用カプセル装置は、更に、
内部が空の前記薬液シリンダと、
内部が真空状態の前記タンクと、を具備し、
前記撮像センサにより撮像された画像に従うタイミングにより前記第1,第2のバルブを開放し、前記タンクの真空状態による負圧により、前記ノズルの周囲に存在する気体及び液体の両方いずれか又は両方を前記シリンダ内に引き込み貯留するサンプリング機能部を具備することを特徴とする請求項14に記載の医療用カプセル装置。 - 耐酸性を有する水密なカプセルと、
前記カプセルの外壁面に露呈するように設けられた、アルミニウム電極と、触媒担炭素電極とからなる電極対を備え、腸液からなる電解質溶液に前記電極対を浸漬して、発電した電源を取り出し供給を行なう電源システムと、
撮影対象を結像するレンズと、
撮影視野を照明するための複数の発光素子と、
前記レンズに結像された光学像を光電変換し、画像信号を生成する撮像センサと、
前記光学センサにより生成された画像信号の補正処理を施し無線通信用の情報信号に変換する処理部と、
前記処理部からの情報信号を外部に発信するアンテナと、
を備えることを特徴とする医療用カプセル装置。 - 前記カプセルの外壁面に露呈するように設けられた前記アルミニウム電極及び前記触媒担炭素電極は、
前記外壁面から積み重ねられた複数の電極片と、
前記電極片の間に介在し、前記消化器内容物により溶解する部材からなる複数の介在膜と、
前記複数の電極片の一端を電気的に接続し、発電した電源を供給するための共通配線と、
で構成される積層構造電極を成し、
上層からの前記介在膜の溶解により、露呈する電極片より前記共通配線から切り離されることを特徴とする請求項16に記載の医療用カプセル装置。
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CN110167451A (zh) * | 2016-09-28 | 2019-08-23 | Biome牛津有限公司 | 用于胃肠材料采样的装置 |
CN110167451B (zh) * | 2016-09-28 | 2023-10-20 | Biome牛津有限公司 | 用于胃肠材料采样的装置 |
JP2020523123A (ja) * | 2017-06-12 | 2020-08-06 | インキューブ ラブズ, エルエルシー | 胃内容排出パラメータを測定するための嚥下可能カプセル、システム、および方法 |
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WO2019244639A1 (ja) * | 2018-06-20 | 2019-12-26 | 国立大学法人東北大学 | 発電池用の負極、胃酸電池、金属イオン二次電池、システム、及び、電池の使用方法 |
JP2020004700A (ja) * | 2018-06-20 | 2020-01-09 | 国立大学法人東北大学 | 発電池用の負極、胃酸電池、金属イオン二次電池、システム、及び、電池の使用方法 |
KR102239695B1 (ko) * | 2019-10-10 | 2021-04-13 | 울산대학교 산학협력단 | 인체내장형 유체마찰 발전기 |
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US20120289775A1 (en) | 2012-11-15 |
JP5276184B2 (ja) | 2013-08-28 |
JPWO2011092936A1 (ja) | 2013-05-30 |
CN102724907A (zh) | 2012-10-10 |
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