CN202423497U

CN202423497U - Box used for containing sodium and sodium-sulfur (NaS) battery

Info

Publication number: CN202423497U
Application number: CN2011205269783U
Authority: CN
Inventors: 尾藤章博
Original assignee: NGK Insulators Ltd
Current assignee: NGK Insulators Ltd
Priority date: 2011-12-16
Filing date: 2011-12-16
Publication date: 2012-09-05
Anticipated expiration: 2021-12-16

Abstract

The utility model provides a box (6) of a sodium-sulfur (Nas) battery (1). The box is made of metal and is arranged on the inner side of a solid electrolyte tube (3) and used for containing sodium. The box is characterized in that the box is divided into an upper space (71) and a lower space (72) by a separating wall (7), gases serving as producing sources of cathode side pressure are filled in the upper space (71), the sodium (5) is filled in the lower space (72), a communicating hole (73) is formed on the separating wall (7), the communicating hole is sealed by a component made of resin, the component made of resin melts or cracks at the temperature between 230 DEG C and 300 DEG C and is not subjected to chemical reaction with the sodium (5), a through hole (64) is formed at the bottom of the box (6), and the cathode side pressure formed by the gases is lower than anode side pressure formed by nitrogen all the time. Therefore, stop of electric discharge and increase of resistance caused by leakage of the gases from the box (6) can be prevented effectively.

Description

Sodium holds with box and sodium-sulphur battery

Technical field

The utility model relates to sodium in the sodium-sulphur battery (below be called " NaS battery ") and holds with box and the NaS battery that possesses this box.

Background technology

In the prior art; Known sodium-sulphur battery have the metallic box that is used to hold said sodium in; Above-mentioned sodium-sulphur battery is meant; Dispose the sodium azide in the source that produces as anode-side pressure in the outside of the solid electrolyte tube that the round-ended cylinder shape is arranged, it is used to produce anode active material sulphur and nitrogen, and disposes the sodium as cathode active material in said solid electrolyte tube inboard.

But in the once also not heated initial condition of NaS battery, the sodium in the box is solid.Therefore,, need the sodium of heating and melting be supplied with from the space of cassette interior between box and solid electrolyte tube, sodium is contacted with cathodic metal spare with solid electrolyte tube for causing exoelectrical reaction.For this reason; Expect following mode: configuration produces the gases such as argon gas (below be also referred to as inert gas) in source as cathode-side pressure in box, utilizes the pressure of this inert gas that the sodium of fusion is supplied with from the space of cassette interior between box and solid electrolyte tube.

But because when the NaS battery was heated, the fusion of sodium started near the box inwall, therefore when extruding molten sodium, inert gas also passes through between the sodium of box inwall and curing, and leaks from the space between box and the solid electrolyte tube.On the other hand, owing to the gas pressure in the box along with the minimizing that discharge dissolves sodium reduces, so the volume of the inert gas that leaks increases along with the minimizing of the volume of sodium in the box, begin to cover solid electrolyte inside pipe wall and cathodic metal spare.

If inert gas contacts with the solid electrolyte inside pipe wall, will hinder sodium ion to see through, so resistance increases from this part.In addition,, will hinder transceiver electronics between sodium and the cathodic metal spare, thereby discharge is stopped if inert gas covered cathode metalwork is whole.

The utility model content

The utility model is made in view of such problem, and its purpose is to provide a kind of gas that can prevent reliably to leak and can be with the cathode structure of the NaS battery of implemented with low cost from box.

Be used to realize the box of above-mentioned purpose the utility model; In sodium-sulphur battery, be used to hold sodium and be made of metal; Said sodium-sulphur battery is meant, disposes the sodium azide in the source that produces as anode-side pressure in the outside of the solid electrolyte tube that the round-ended cylinder shape is arranged, and said sodium azide is used to produce sulphur and the nitrogen as anode active material; And dispose sodium-sulphur battery as the said sodium of cathode active material in the inboard of said solid electrolyte tube; It is characterized in that this box is divided into upper space and lower space by the next door, in said upper space, dispose the gas in the source that produces as cathode-side pressure; In said lower space, dispose said sodium; Be formed with on the said next door and be used to intercommunicating pore that upper space and lower space are connected, and this intercommunicating pore sealed by resinous member, this resinous member is at fusion or cracking below 300 ℃ more than 230 ℃; And not with sodium generation chemical reaction; Be formed with through hole in this cartridge bottom, this through hole is used for by the pressure of said gas the said sodium of fusion from internal feed to the box of this box and the space between the said solid electrolyte tube, and the formed cathode-side pressure of said gas is lower than the formed anode-side pressure of said nitrogen all the time.

Here, preferably, box possesses tubular metastomium and the bottom that is installed on this tubular metastomium, and these tubular metastomiums and bottom have: make these tubular metastomiums and bottom chimeric fitting portion mutually through being pressed into; The portion that is soldered that these tubular metastomiums and bottom are welded under chimeric state.

In addition, preferred box is made up of the stainless steel that contains the Cr below the 16.5 weight % more than the 10 weight %.

In addition, the sodium-sulphur battery of the utility model possesses above-mentioned box.

If adopt the sodium of the utility model to hold, just can effectively prevent to stop the phenomenon with the resistance increase owing to leak caused discharge from box as the gas in cathode-side pressure generation source with box and the NaS battery that possesses this box.In addition, use and be used as the good resin of zygosity of the stainless steel etc. of box material, so can avoid the reduction of rate of finished products of leakage, the bonding processing of hermetic unit.

Description of drawings

Fig. 1 is the profile of the NaS battery of the utility model.

Fig. 2 is near the profile of upper space of the box of above-mentioned NaS battery.

Fig. 3 is near the profile of upper space of the box of above-mentioned NaS battery.

Fig. 4 is near the profile of bottom of the box of above-mentioned NaS battery.

Description of reference numerals

1 NaS battery

2 anode metal spares

3 solid electrolyte tubes

6 boxes

61 tubular metastomiums

62 bottoms

63 are soldered portion

64 through holes

71 upper spaces

72 lower space

73 intercommunicating pores

74,75 resinous members

Embodiment

Below, with reference to accompanying drawing, the sodium of the utility model held with box and the NaS battery that possesses this box describing.As shown in Figure 1; With regard to NaS battery 1; In male receptacle 2, dispose the solid electrolyte tube 3 of round-ended cylinder shape, dispose the sodium azide (sodium azide) in the source that produces as anode-side pressure in the outside of this solid electrolyte tube 3, it is used to produce sulphur 4 and the nitrogen as anode active material; And, dispose sodium 5 as cathode active material in the inboard of solid electrolyte tube 3.In addition, sodium 5 is contained in the box 6 that is made of metal.

The bottom 22 that male receptacle 2 has tube cylindraceous portion 21 and stops up these 21 bottoms.Upper periphery face in tube portion 21 is equipped with anode terminal 11.In addition, male receptacle 2 is formed by soft metals such as aluminum or aluminum alloy.

Solid electrolyte tube 3 is formed by beta-alumina, and through combining with male receptacle 2 with anode metal spare 13 by the alpha-oxidation aluminum dead ring 12 of glass bond at its openend.In addition, hot press has cathodic metal spare 14 on dead ring 12, on this cathodic metal spare 14, is welded with negative electrode lid 15.

Box 6 is divided into upper space 71 and lower space 72 by next door 7.In upper space 71, dispose the gas in the source that produces as cathode-side pressure, in lower space 72, dispose sodium 5.As shown in Figure 2; Be formed with the intercommunicating pore 73 that is used to be communicated with upper space 71 and lower space 72 on the next door 7; And use resinous member 74 to seal this intercommunicating pore 73, this resinous member 74 is at fusion or cracking below 300 ℃ more than 230 ℃, and with sodium 5 chemical reactions do not take place.In addition, as shown in Figure 3, also can use resinous member 75 to stick metallic film 76 from lower space 72 1 sides, thus sealing intercommunicating pore 73.That is, in the utility model, as long as use resinous member 74,75 seal intercommunicating pore 73 just can, these resinous members 74,75 are at least at fusion or cracking below 300 ℃ more than 230 ℃, and not with sodium 5 generation chemical reactions.In addition, about resinous member 74,75 employed concrete materials, narration more after a while.In addition, metallic film 76 for example use with after the same material (stainless steel etc.) of material of the box 6 stated.

In addition, like Fig. 1 and shown in Figure 4, box 6 possesses tubular metastomium 61 and the bottom 62 that is installed on tubular metastomium 61, and these tubular metastomiums 61 have with bottom 62: through being pressed into chimeric each

other fitting portion

61a, 62a; The portion that is soldered 63 that these tubular metastomiums 61 and bottom 62 are welded under chimeric state.In addition, in Fig. 4, illustrated tubular metastomium 61 has been pressed into the example in the bottom 62, but also can bottom 62 be pressed in the tubular metastomium 61.Make on the basis that tubular metastomium 61 and bottom 62 engage through being pressed into like this; Also tubular metastomium 61 and bottom 62 are engaged through welding; Leak from this junction surface so can prevent gas, therefore can more effectively prevent the external leaks of gas to box 6.

In addition, be formed with through hole 64 in the bottom of box 6 (that is, bottom 62), this through hole 64 is used to utilize the pressure of gas that the sodium 5 of fusion is supplied with in the space between box 6 and solid electrolyte tube 3 30 from box 6 inside.In addition, space 30 keeps vacuum down in initial condition (state before battery uses).

Box 6 uses metal, the preferred stainless steel that contains the Cr below the above 16.5 weight % of 10 weight % that uses.If the amount of Cr surpasses 16.5 weight %, then nitrogen absorption quantitative change is big, just can't keep to be used for sodium 5 is extruded into outside required pressure.On the other hand, if Cr amount less than 10 weight % can impair corrosion resistance, thereby not can be used as preference.In addition, so-called here stainless steel is meant the ferrous alloy of the Cr that has added 12-32 weight %, and the total amount of the element beyond the iron is no more than 50%.

In addition, in the utility model,, need to use not the gas with the material generation chemical reaction of sodium 5 and box 6, preferably use inert gas or nitrogen such as argon gas, helium as the gas in the upper space that is filled in box 6 71.In addition, in the utility model, the amount of adjustment gas and sodium azide is so that the formed cathode-side pressure of gas is lower than the formed anode-side pressure of nitrogen that is produced by the anode-side sodium azide all the time.Like this, cathode-side pressure is adjusted to and is lower than anode-side pressure all the time, so even solid electrolyte tube 3 is damaged in intensification, can prevents that also sodium 5 from flowing to anode-side sharp from solid electrolyte tube 3, thereby can improve the fail safe of battery.

In the utility model,, can use resin at fusion or cracking more than 230 ℃, below 300 ℃ as being used as in the resin of resinous member 74,75.This be because; When anode-side is used sodium azide; Consider its decomposition temperature (about 280 ℃) and heat conduction transmission, and by to make gas the cathode-side pressure that produces of formation be lower than the anode-side pressure of nitrogen institute formation generation all the time at ordinary times, fusion or the Cracking Temperature that then need make resin are at least more than 230 ℃; In addition, also need make resin fusion or cracking below 300-350 ℃ as the working temperature of NaS battery 1.In addition, for avoiding the danger of violent burning, heating, need to adopt the resin that chemical reaction does not take place with sodium 5.

As the resin that is used for above-mentioned resinous member 74,75; Particularly; Preferred use that the UV curable is acrylic resin modified, anaerobic is acrylic resin modified, response type acrylic resin, room temperature curing type silicon rubber, polyimides, nylon, polyvinyl formal/phenol, acrylonitrile-butadiene rubber/phenol, neoprene/phenol, epoxy/phenol, ethylene acetal/phenol, epoxy resin, nylon/epoxy, acrylonitrile-butadiene rubber/epoxy, epoxy/polyamide, polyurethane etc.; But the angle that need not to heat from resin-sealed intercommunicating pore 73 time adopts more preferably that the UV curable is acrylic resin modified, anaerobic is acrylic resin modified, response type acrylic resin, epoxy/polyamide etc.That is, owing to use these resins, so need not to be provided with firing equipment, cooling device.

Prevent just need after sodium 5 complete fusions, make the pressure of gas be applied to sodium 5 outside gas leakage to the box 6 in the box 6.In the utility model; If NaS battery 1 is heated in battery operated; Then at first sodium 5 fusions; Then resin component element 74,75 fusion or crackings are communicated with upper space 71 and lower space 72, and the sodium 5 of fusion comes to flow out from through hole 64 by the pressure that produces the gas in source as cathode-side pressure.

In addition, for example fill inert gas and sodium 5 to box 6 as follows.At first, under inert gas environment, upper space 71 inert gas injectings of the box 6 before bottom 62 is installed, and seal intercommunicating pore 73 with resin component element 74.Then, fill sodium 5, and be pressed into bottom 62 and weld to tubular metastomium 61 to lower space 72.This box in 6 up and down the other way around and with shown in Figure 1 mode be disposed at it solid electrolyte tube 3 in thereafter.

If adopt the sodium of the utility model to hold, just can effectively prevent because the gas that produces the source as cathode-side pressure stops the phenomenon with the resistance increase from the caused discharge of box 6 leakages with box 6 and the NaS battery 1 that possesses this box.In addition, utilize resin component element 74,75 to seal intercommunicating pore 73, therefore, because resin is good with the zygosity of the stainless steel etc. of the material that is used as box 6, so can prevent the reduction of rate of finished products of leakage, the bonding processing of hermetic unit.

Claims

1. box; In sodium-sulphur battery, be used to hold sodium and be made of metal, said sodium-sulphur battery is meant, disposes the sodium azide in the source that produces as anode-side pressure in the outside of the solid electrolyte tube that the round-ended cylinder shape is arranged; Said sodium azide is used to produce sulphur and the nitrogen as anode active material; And dispose sodium-sulphur battery in the inboard of said solid electrolyte tube, it is characterized in that as the said sodium of cathode active material

This box is divided into upper space and lower space by the next door, in said upper space, disposes the gas in the source that produces as cathode-side pressure, in said lower space, disposes said sodium,

Be formed with on the said next door and be used to intercommunicating pore that upper space and lower space are connected, and this intercommunicating pore sealed by resinous member, this resinous member is at fusion or cracking below 300 ℃ more than 230 ℃, and not with sodium generation chemical reaction,

Be formed with through hole in this cartridge bottom, this through hole is used for by the pressure of said gas the said sodium of fusion from internal feed to the box of this box and the space between the said solid electrolyte tube,

The formed cathode-side pressure of said gas is lower than the formed anode-side pressure of said nitrogen all the time.

2. box according to claim 1 is characterized in that,

Possess tubular metastomium and the bottom that is installed on this tubular metastomium,

These tubular metastomiums and bottom have:

Make these tubular metastomiums and bottom chimeric fitting portion mutually through being pressed into;

The portion that is soldered that these tubular metastomiums and bottom are welded under chimeric state.

3. box according to claim 2 is characterized in that, is made up of the stainless steel that contains the Cr below the 16.5 weight % more than the 10 weight %.

4. a sodium-sulphur battery is characterized in that, possesses each described box among the claim 1-3.