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1. 发明专利

JPH01279577A SODIUM-SULFUR BATTERY 失效
公开(公告)号：JPH01279577A
公开(公告)日：1989-11-09
申请号：JP10902488
申请日：1988-05-06
申请人： HITACHI LTD , TOKYO ELECTRIC POWER CO
发明人： WADA HAJIME , NAKAMURA MASAAKI , KOBAYASHI AKIRA
IPC分类号： H01M10/39
摘要： PURPOSE:To cause the solid layer of sodium sulfide to be formed rapidly when a solid electrolyte is broken and minimize the heating value of the battery by covering all over the surface of the solid electrolyte with a porous material and causing the negative electrode side space to be more negative in pressure than the positive electrode side space. CONSTITUTION:Surfaces on both sides of a wall of a solid electrolyte 7 are covered closely by a porous material 5 filled with an active material of each electrode and the negative electrode side space storing sodium is kept to be more negative in pressure than the positive electrode side space. When the solid electrolyte is broken, very small cracks are produced on the solid electrolyte 7 at the beginning of the breakage and active materials of positive and negative electrodes move into opposite side region through these cracks. The speed of the positive electrode active material flowing into the negative electrode side becomes small because the porous material suppresses the motion of the fluid for the liquid active material. The heating value of the active material can be held small because the amount of the flow is small, and the sodium sulfide produced by a reaction in the negative electrode side is solidified rapidly to seal the further flow of the positive active material into the negative electrode side so that the battery will never generate heat any more.

2. 发明专利

JPS6288281A SODIUM-SULFUR CELL 失效
公开(公告)号：JPS6288281A
公开(公告)日：1987-04-22
申请号：JP22929585
申请日：1985-10-15
申请人： TOKYO ELECTRIC POWER CO , HITACHI LTD
发明人： MORI SADAO , WATANABE EIJI , WADA HAJIME
IPC分类号： H01M10/39
摘要： PURPOSE:To increase the charge/discharge capacity and to improve the energy efficiency by making such that at least one of the volume resistivity, the surface area per unit volume or the surface polarization resistance factor will have specific characteristic from the cathode section toward the depth direction of the anode section. CONSTITUTION:It is constituted such that the volume resistivity will decrease from the cathode section toward the depth direction of the anode section while the surface area per unit volume will increase and the surface polarization resistance factor will also increase. In order to set the resistivity of porous electron conductive members 4, 5, for example, the quantity of electrochemical reaction at each section of anode is integrated within a charge/discharge range of cell to determine such that the sulfur mol. ratio in sodium polysulfide will be uniform between completion of discharge and stopping time of charge/ discharge. Consequently, the cell reaction in the anode can be uniformed resulting in improvement of the charge/discharge capacity and the energy efficiency.

3. 发明专利

JPS61239570A SODIUM-SULFUR CELL 失效
公开(公告)号：JPS61239570A
公开(公告)日：1986-10-24
申请号：JP8017885
申请日：1985-04-17
申请人： TOKYO ELECTRIC POWER CO , HITACHI LTD
发明人： MORI SADAO , OSHIMA KISHIO , KUSAKABE KOJI , WADA HAJIME
IPC分类号： H01M10/39
摘要： PURPOSE:To enable to eliminate non-uniformity in cell reaction caused by the effect of gravity and to prevent the accompanying ineffective use of an active material, by making a porus electrically conductive material to have different electric resistances along the direction of the acceleration of gravity. CONSTITUTION:A positive electrode is made to have different values of electric conductivity at its upper part A and lower part B respectively. That is, the lower part B of the positive electrode includes more molten sulfur than the upper part A of the positive electrode due to the effect of gravity. This is because the molten sulfur fills the voids of the porus electrically conductive material and moves upward because of surface tension. This causes a bias to the branch of current at the onset, resulting lower current density in the upper part of the positive electrode and higher current density in the lower part of the positive electrode. As a result, the difference between x values of the upper and lower parts of the positive electrode approaches zero at the end of discharging, and sodium polysulfide with mole ratio of sulfur to sodium uniform over the entire positive electrode is obtained. In this state, the cell can discharge further and active material can be utilized effectively.

4. 发明专利

JPS6155871A Natrium-sulphur battery 失效
标题翻译： NATRUM-SULFUR电池
公开(公告)号：JPS6155871A
公开(公告)日：1986-03-20
申请号：JP17876384
申请日：1984-08-28
申请人： Hitachi Ltd , Tokyo Electric Power Co Inc:The
发明人： WADA HAJIME
IPC分类号： H01M10/39
CPC分类号： H01M10/3909
摘要： PURPOSE:To enlarge effective capacity of a battery by making an anode active material consisting of molten sulphur and molten natrium polysulfide to circulate a circulation flow path formed inside an anode container housing said material by thermal convection. CONSTITUTION:A cylindrical inner anode 14 and an inner heater 15 inserted into the inside of said inner anode are attached to the inside of an anode container 5. In a battery reaction region A, heat due to an electric resistance loss is generated both in the charging and discharging time while the temperature of an anode active material at said part rises reducing its specific gravity due to expansion for traveling to the upper part of the anode container 5 because of a connection effect. The expanded anode material collected in the upper part is cooled by the wall surface of the anode container 5 while going down through the space between the anode container 5 and the inner anode electrode 14 in the direction of gravity for entering the space inside the inner anode electrode 14 in the part of the container bottom and returning again to the battery reaction region A. The inner heater 15 is used for assisting in the convection circulation.
摘要翻译：目的：通过制造由熔融硫和熔融的纳米多硫化物组成的负极活性物质来扩大电池的有效容量，以循环形成在通过热对流容纳所述材料的阳极容器内形成的循环流路。构成：插入到内阳极内侧的圆柱形内阳极14和内加热器15附接到阳极容器5的内部。在电池反应区域A中，由于电阻损失而产生热量充电和放电时间，同时由于连接效应，所述部分的阳极活性材料的温度升高，由于膨胀而向阳极容器5的上部行进而降低其比重。收集在上部的膨胀的阳极材料被阳极容器5的壁面冷却，同时在重力方向向下通过阳极容器5和内阳极电极14之间的空间，以进入内阳极内的空间电极14在容器底部的一部分中并再次返回到电池反应区域A.内部加热器15用于辅助对流循环。

5. 发明专利

JPH0240866A SODIUM-SULFUR BATTERY 失效
公开(公告)号：JPH0240866A
公开(公告)日：1990-02-09
申请号：JP18976288
申请日：1988-07-29
申请人： HITACHI LTD , TOKYO ELECTRIC POWER CO
发明人： WADA HAJIME , NAKAMURA MASAAKI , KOBAYASHI AKIRA
IPC分类号： H01M10/39
摘要： PURPOSE:To improve the corrosion-resistance of a safety tube by providing within a cylindrical bladder tube form solid electrolyte a safety tube having a pore on the bottom part and holding a fused metal sodium therein, and filling an outer fluid resistance member and an inner fluid resistance member in the gap between the safety tube and the solid electrolyte and within the safety tube. CONSTITUTION:A bladder tube type safety tuber 9 is provided in the inside of a solid electrolyte tube 3, and further an inner fluid resistance member 10 and an outer fluid resistance member 11 are disposed in the inside of the safety tube 9 and in the space between the safety tube 9 and the solid electrolyte tube 3, respectively. Sodium 1 stored within the safety tube 9 flows to the outside of the safety tube 9 through a pore 12 opened in the safety tube 9 bottom part. The sodium 1 is supplied to the whole area of the solid electrolyte tube 3 by the capillary phenomenon or vacuum suction in the space between the safety tube 9 and the solid electrolyte tube 3. Here, no presence of bubbles within the outer fluid resistance member 11 is particularly important. Hence, the corrosion resistance of the safety tube is improved.

6. 发明专利

JPS6362164A MANUFACTURE OF MOLDED SULFUR ELECTRODE FOR SODIUM-SULFUR BATTERY 失效
公开(公告)号：JPS6362164A
公开(公告)日：1988-03-18
申请号：JP20382386
申请日：1986-09-01
申请人： HITACHI LTD , TOKYO ELECTRIC POWER CO
发明人： HATOU HISAMITSU , KAWAMOTO HIROYUKI , WADA HAJIME , KUSAKABE KOJI , SUGAWARA HITOSHI , MORI SADAO , OGINO MASAO
IPC分类号： H01M10/39
摘要： PURPOSE:To achieve high performance and a long life with suppression of an increase in internal resistance by impregnating a porous electron conductive material, which is beforehand calcined in the oxygen atmosphere then furthermore calcined in vacuum to activate the surface, with molten sulfur in vacuum not to be exposed to the air. CONSTITUTION:To remove impurities adsorbed in a porous electron conductive material, it is calcined in the oxygen atmosphere and then atmospheric gas is evacuated to dehydrate it completely, while the temperature is kept as it is. Sulfur is put in an airtight vessel and it is evacuated. Then sulfur is heated to melt and dehydrated. These processes are carried out in a airtight loop so that the processed porous electron conductive material is impregnated with sulfur, without being exposed to the air, and a molded sulfur electrode is taken out after cooling. Carbon and graphite fiber substance and the like are used for the porous electron conductive material. With the arrangement, impurities contained in the molded sulfur electrode are removed as far as possible and deterioration of the solid electrolyte can be suppressed, which results in an improvement of the life.

7. 发明专利

JPS6226768A SODIUM-SULFUR BATTERY 失效
公开(公告)号：JPS6226768A
公开(公告)日：1987-02-04
申请号：JP16580085
申请日：1985-07-29
申请人： TOKYO ELECTRIC POWER CO , HITACHI LTD
发明人： MORI SADAO , WATANABE EIJI , SAKURADA TETSUO , KAWAMOTO HIROYUKI , HATOU HISAMITSU , WADA HAJIME
IPC分类号： H01M10/39
摘要： PURPOSE:To prevent any breakage of the electrolyte tube of a sodium-sulfur battery which might occur during the initial temperature increase of the battery by placing a positive body, which consists of sectoral sections each having slits on its inner surface, outside an electrolyte tube packed with a negative active material. CONSTITUTION:After molten sodium 2 used as the negative active material is packed inside an electrolyte tube 1, a positive body 12 which is made of carbon fiber impregnated with molten sulfur and packed in a case 5 is placed outside the electrolyte tube 1 to produce a sodium-sulfur battery. The positive body consists of, for example, four sections each having a sectoral cross section perpendicular to the axis and having several slits 13 parallel to the axis and several slits 14 perpendicular to the axis are formed on the inner surface of each of these sections. Due to the above structure, the stress applied to the electrolyte tube 1 due to the thermal expansion of the positive body 12 during the initial temperature increase of the battery can be effectually absorbed. Consequently, the yield of the battery can be increased by preventing any breakage of the electrolyte tube 1.

8. 发明专利

JPS61245473A SODIUM-SULFUR CELL 失效
公开(公告)号：JPS61245473A
公开(公告)日：1986-10-31
申请号：JP8724685
申请日：1985-04-23
申请人： TOKYO ELECTRIC POWER CO , HITACHI LTD
发明人： OOYAMA TAKESHI , WATANABE EIJI , WADA HAJIME
IPC分类号： H01M10/39
摘要： PURPOSE:To lengthen the service life of cell by providing a gap for preventing concentration of current density on the surface of solid electrolytic tube between said tube and porous conductive material. CONSTITUTION:Negative electrode active material or sodium 2 is encapsulated in a negative electrode container 1 while filling a tubular bag type solid catalytic tube 4. The container 1 is connected through a ring 3 insulative against the sodium ions and electrons with positive electrode container 9 where positive electrode active material or sulfur or sodium sulfide is encapsulated in the container 9 while immersing porous carbon conductors 6-8 for conducting electrons. A gap section 5 where the conductive member 6 will never contact directly against the tube 4 and region A where the tube 4 will contact against a conductive member 8 at the bottom of cell in the direction of gravity (g) are provided. The gap section 5 is formed approximately in parallel where the ion reaction on the surface of tube 4 will provide uniform distribution of current over the entire length of tube 4 while the current densities in central area of positive electrode B and the bottom area A of positive electrode are approximately equalized.

9. 发明专利

JPH0256868A SODIUM-SULFUR BATTERY 失效
公开(公告)号：JPH0256868A
公开(公告)日：1990-02-26
申请号：JP20924388
申请日：1988-08-23
申请人： HITACHI LTD , TOKYO ELECTRIC POWER CO
发明人： SHIMOYASHIKI SHIGEHIRO , TOKOI HIROMI , YAMAMOTO HAJIME , TAKAHASHI KAZUO , SOMA HISASHI , WADA HAJIME , SUGAWARA HITOSHI , NAKAMURA MASAAKI , OSHIMA MASAAKI
IPC分类号： H01M4/58 , H01M10/38 , H01M10/39
摘要： PURPOSE:To improve the safety of a battery when an electrolyte is broken by limiting the sodium quantity participating in the reaction with sulfur at a battery reaction section to the minimum and suppressing the direct reaction between sodium and sulfur when the solid electrolyte is broken. CONSTITUTION:An alpha alumina plate 4 electrically insulates an upper container 1 from a lower container 2, a bulkhead 17 is provided on the alpha alumina plate 4, and it forms a sodium storage tank 21 together with the upper container 1. This bulkhead 17 is inserted into a solid electrolyte 3, the upper end of a suction pipe 19 having a blind lower end is fitted, and the suction pipe 19 damps the pressure when the direct reaction between sodium 7 and sulfur 8 is generated by the breakage of the solid electrolyte 3. Even if the solid electrolyte 3 is broken due to deterioration or the like, the quantity of the sodium 7 participating in the direct reaction with sulfur 8 can be limited to the minimum, the direction reaction between sodium and sulfur can be suppressed, and the temperature rise and pressure rise can be suppressed to the minimum. Even if the temperature and pressure in a battery rise, the suction pipe 19 is solved or broken to absorb the pressure, as a result the outermost battery container is not broken.

10. 发明专利

JPS634570A DIAGNOSIS OF ABNORMALITY FOR SODIUM-SULFUR BATTERY 失效
公开(公告)号：JPS634570A
公开(公告)日：1988-01-09
申请号：JP14706986
申请日：1986-06-25
申请人： HITACHI LTD , TOKYO ELECTRIC POWER CO
发明人： ISHIDA YASUMASA , KAWAMOTO HIROYUKI , WADA HAJIME , HATOU HISAMITSU , MIYATAKE YOSHITERU , MORI SADAO , TAKAHASHI EIJI
IPC分类号： H01M10/39 , G01R31/36 , H01M10/48
摘要： PURPOSE:To enable to find an abnormality as a forecast of a final breakage of a Na/S battery which occurs due to wear after repeated charge and discharge by judging that a final breakage is close at hand when fine ripples appear in a working voltage in charging and discharging where the ripples are more apparent in charging than in discharging and the amplitude and the frequency of occurrence of ripples increase as charge and discharge are repeated. CONSTITUTION:In the obserration of a working voltage in charging and discharging of a sodium-sulfur battery, if fine ripples appear in the voltage and moreover if they are more apparent in charging than in discharging, and furthermore if the amplitude and the frequency of occurrence of ripples increase as charge and discharge are repeated, it is judged that a final breakage is close at hand because of wear in the battery. Thus a final breakage of a Na/S battery can be forecast before it occurs (before a few charge/discharge cycles, for example), and proper meassures can be taken in advance.

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