JPH06150965A - Battery jar for sodium-sulfur battery - Google Patents
Battery jar for sodium-sulfur batteryInfo
- Publication number
- JPH06150965A JPH06150965A JP4321316A JP32131692A JPH06150965A JP H06150965 A JPH06150965 A JP H06150965A JP 4321316 A JP4321316 A JP 4321316A JP 32131692 A JP32131692 A JP 32131692A JP H06150965 A JPH06150965 A JP H06150965A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- battery
- iron
- battery case
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010955 niobium Substances 0.000 claims abstract description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 6
- 238000005254 chromizing Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 3
- 229910000905 alloy phase Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 239000011651 chromium Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 3
- 229910003470 tongbaite Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はナトリウム−硫黄電池の
電槽に関するもので、さらに詳しく言えば、その陽極活
物質に対する耐腐食性の向上に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery cell of a sodium-sulfur battery, and more particularly to improvement of corrosion resistance of the anode active material.
【０００２】[0002]
【従来の技術】ナトリウムイオン伝導性の固体電解質管
の外部に陽極室を、内部に陰極室を形成してなるナトリ
ウム−硫黄電池には、陰極室を密閉する陰極蓋と陽極室
を密閉する電槽とが用いられている。2. Description of the Related Art A sodium-sulfur battery in which a sodium ion conductive solid electrolyte tube is provided with an anode chamber outside and a cathode chamber inside is provided with an electrode for sealing a cathode lid and an anode chamber. Tanks and are used.
【０００３】そして、前記電槽には、陽極活物質として
の硫黄や放電によって生成する多硫化ナトリウムに対す
る耐腐食性を有し、陽極集電体として作用しうる電導性
を有したものが用いられる。As the battery case, a battery having corrosion resistance against sulfur as an anode active material and sodium polysulfide generated by discharge and having conductivity capable of acting as an anode current collector is used. .
【０００４】上記した条件を満足する材料としては、炭
素鋼またはステンレスを母材として表面にクロムを熱拡
散させてクロム−鉄合金相を形成したもの、すなわちク
ロマイズ加工したものが知られている。As a material satisfying the above-mentioned conditions, there is known a material in which carbon steel or stainless is used as a base material and chromium is thermally diffused on the surface to form a chromium-iron alloy phase, that is, a material subjected to chromizing.
【０００５】[0005]
【発明が解決しようとする課題】上記した材料では、ク
ロム−鉄合金層の外側に、母材に含まれている炭素とク
ロムとが反応することによってＣｒ23Ｃ6 やＣｒ7 Ｃ3
のようなクロム炭化物を生成し、このクロム炭化物層に
よって母材へのクロムの拡散が妨げられ、陽極活物質に
対して耐腐食性を有するクロム−鉄合金層を厚くするこ
とができないという問題があった。In the above-mentioned materials, the carbon contained in the base material reacts with chromium on the outside of the chromium-iron alloy layer, so that Cr 23 C 6 or Cr 7 C 3 is produced.
However, there is a problem in that the chromium-carbide layer prevents the diffusion of chromium into the base material by the chromium-carbide layer, and the chromium-iron alloy layer having corrosion resistance to the anode active material cannot be thickened. there were.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するた
め、本発明は、ナトリウムイオン伝導性の固体電解質管
の内部に陰極室を、外部に陽極室を形成し、前記陰極室
を陰極蓋で密閉するとともに、前記陽極室を電槽で密閉
してなるナトリウム−硫黄電池の電槽において、前記電
槽が０．０５％以下の炭素と０．０５〜０．５％のチタ
ンとを含有する鉄からなり、この鉄の表面にクロマイズ
加工によってクロム−鉄合金の単一層が形成されてなる
ことを特徴とするものである。In order to solve the above-mentioned problems, the present invention forms a cathode chamber inside a sodium ion conductive solid electrolyte tube and an anode chamber outside and uses the cathode chamber as a cathode lid. In a battery case of a sodium-sulfur battery which is hermetically closed and the anode chamber is closed by a battery case, the battery case contains 0.05% or less of carbon and 0.05 to 0.5% of titanium. It is characterized in that it is made of iron, and a single layer of a chromium-iron alloy is formed on the surface of this iron by chromizing.
【０００７】[0007]
【作 用】従って、本発明は、炭素原子の半径ｒc に対
してチタン原子、ニオブ原子、ジルコニウム原子の半径
ｒTi，ｒNb，ｒZr が０．５９未満であるため、炭素原
子がチタン原子、ニオブ原子、ジルコニウム原子の結晶
格子間に侵入して優先的に安定性の高いＴｉＣ，Ｎｂ
Ｃ，ＺｒＣのような侵入型炭化物が多数形成されてクロ
ム炭化物の形成が抑制される。[Operation] Therefore, according to the present invention, since the radius r Ti , r Nb , and r Zr of the titanium atom, niobium atom, and zirconium atom is less than 0.59 with respect to the radius r c of the carbon atom, the carbon atom is titanium. TiC and Nb, which have high stability by penetrating between crystal lattices of atoms, niobium atoms, and zirconium atoms
A large number of interstitial carbides such as C and ZrC are formed to suppress the formation of chromium carbide.
【０００８】[0008]
【実施例】本発明の電槽用材料として、炭素の含有率が
０．０５％以下の鉄Ａ、同０．０８％の鉄Ｂ、同０．１
％の鉄Ｃを準備し、鉄Ａにはニオブを０．５％、ジルコ
ニウムを０．５％含有させるとともに、チタンを０％，
０．０３％，０．０５％，０．１％，０．５％含有させ
てから、重量比で１０〜６０％のクロム粉末、０．５〜
２．０％の塩化アンモニウム粉末および５０〜８０％の
アルミナ粉末とともに鉄箱内に封入し、約９５０℃の水
素雰囲気中で数時間加熱することによってクロマイズ加
工を行った後、Ｘ線と光学顕微鏡とで組織を調査したと
ころ、表１のような結果が得られた。EXAMPLE As the battery material of the present invention, iron A having a carbon content of 0.05% or less, iron B having a carbon content of 0.08%, and iron B having a carbon content of 0.1%
% Iron C is prepared, and iron A contains 0.5% niobium and 0.5% zirconium, and 0% titanium.
0.03%, 0.05%, 0.1%, 0.5%, and then 10 to 60% by weight of chromium powder, 0.5 to
After enclosing it in an iron box together with 2.0% ammonium chloride powder and 50-80% alumina powder, and heating it in a hydrogen atmosphere at about 950 ° C. for several hours to perform chromization, X-ray and an optical microscope were used. When the organization was investigated with and, the results shown in Table 1 were obtained.
【０００９】[0009]
【表１】 [Table 1]
【００１０】表１から、本発明の電槽用材料としては、
炭素の含有率が０．０５％以下、チタンの含有率が０．
０５〜０．５％であり、かつ少なくともニオブ、ジルコ
ニウムから選択された一種の金属を含有する鉄を用いれ
ばよいことがわかる。From Table 1, as the battery case material of the present invention,
The carbon content is 0.05% or less, and the titanium content is 0.
It is understood that iron having a content of 05 to 0.5% and containing at least one metal selected from niobium and zirconium may be used.
【００１１】また、本発明の電槽用材料としては、炭素
の含有率が０．０５％以下、チタンの含有率が０．０５
〜０．５％であっても、ほぼ同様の効果が得られること
がわかった。The battery case material of the present invention has a carbon content of 0.05% or less and a titanium content of 0.05%.
It was found that almost the same effect can be obtained even when the content is up to 0.5%.
【００１２】上記実施例ではチタンの含有率が０．０５
〜０．５％であればよいとしたが、ニオブ、ジルコニウ
ムについても含有率を０．０５〜１％とし、総添加量を
１％程度にして金属間化合物の生成を抑制し、材料の延
性、強度を確保する必要があることは言うまでもない。In the above embodiment, the titanium content is 0.05.
.About.0.5%, but niobium and zirconium have a content of 0.05 to 1% and a total addition amount of about 1% to suppress the formation of intermetallic compounds and to reduce the ductility of the material. Needless to say, it is necessary to secure strength.
【００１３】次に、上記のようにクロマイズ加工した電
槽用材料のうち、チタンを０．０５％含有する鉄Ａ、鉄
Ｂ、鉄Ｃを最も腐食性の強い多硫化ナトリウムＮａ2 Ｓ
3 が封入されたパイレックスガラス容器内に入れて３５
０℃に加熱し、一定期間ごとにその重量の減少割合を調
査し、結果を図１に示す。Next, among the battery case materials that have been chromized as described above, iron A, iron B, and iron C containing 0.05% titanium are the most corrosive sodium polysulfide Na 2 S.
Put it in a Pyrex glass container containing 3 and put it in 35
It was heated to 0 ° C., and the weight reduction rate was investigated at regular intervals, and the results are shown in FIG.
【００１４】図１から、チタンを０．０５％含有する鉄
Ａは重量の減少割合が最も小さく、多硫化ナトリウムＮ
ａ2 Ｓ3 に対して耐腐食性が高いことがわかる。このこ
とから、前記鉄Ａはナトリウム−硫黄電池の電槽に用い
るのに適していることがわかる。From FIG. 1, iron A containing 0.05% of titanium has the smallest weight reduction ratio, and sodium polysulfide N
It can be seen that the corrosion resistance is high with respect to a 2 S 3 . From this, it is understood that the iron A is suitable for use in the battery case of the sodium-sulfur battery.
【００１５】[0015]
【発明の効果】上記したとおりであるから、本発明のナ
トリウム−硫黄電池の電槽は多硫化ナトリウムに対する
耐腐食性が高いので、ナトリウム−硫黄電池の長寿命化
を図ることができる。As described above, since the battery case of the sodium-sulfur battery of the present invention has high corrosion resistance to sodium polysulfide, the life of the sodium-sulfur battery can be extended.
【図１】本発明のナトリウム−硫黄電池の電槽に用いる
鉄と従来のナトリウム−硫黄電池の電槽に用いる鉄との
多硫化ナトリウムに対する耐腐食性を調査した結果を示
す図である。FIG. 1 is a diagram showing the results of an examination of the corrosion resistance of iron used in the battery case of the sodium-sulfur battery of the present invention and iron used in the battery case of the conventional sodium-sulfur battery to sodium polysulfide.
Claims (3)
の内部に陰極室を、外部に陽極室を形成し、前記陰極室
を陰極蓋で密閉するとともに、前記陽極室を電槽で密閉
してなるナトリウム−硫黄電池の電槽において、前記電
槽が０．０５％以下の炭素と０．０５〜０．５％のチタ
ンとを含有する鉄からなり、この鉄の表面にクロマイズ
加工によってクロム−鉄合金相の単一層が形成されてな
ることを特徴とするナトリウム−硫黄電池の電槽。1. A sodium ion conductive solid electrolyte tube is provided with a cathode chamber inside and an anode chamber outside, the cathode chamber is sealed with a cathode lid, and the anode chamber is sealed with a battery case. In a battery case of a sodium-sulfur battery, the battery case is made of iron containing 0.05% or less of carbon and 0.05 to 0.5% of titanium, and the surface of the iron is chromium-iron by chromizing. A battery case for a sodium-sulfur battery, characterized in that a single layer of an alloy phase is formed.
の内部に陰極室を、外部に陽極室を形成し、前記陰極室
を陰極蓋で密閉するとともに、前記陽極室を電槽で密閉
してなるナトリウム−硫黄電池の電槽において、前記電
槽が０．０５％以下の炭素と０．０５〜０．５％のチタ
ンとを含有し、かつ少なくともニオブ、ジルコニウムか
ら選択された一種の金属を含有する鉄からなり、この鉄
の表面表面にクロマイズ加工によってクロム−鉄合金相
の単一層が形成されてなることを特徴とするナトリウム
−硫黄電池の電槽。2. A sodium ion conductive solid electrolyte tube is provided with a cathode chamber inside and an anode chamber outside, the cathode chamber is sealed with a cathode lid, and the anode chamber is sealed with a battery case. In a battery case of a sodium-sulfur battery, the battery case contains 0.05% or less of carbon and 0.05 to 0.5% of titanium, and contains at least one kind of metal selected from niobium and zirconium. A battery case for a sodium-sulfur battery, characterized in that a single layer of a chromium-iron alloy phase is formed on the surface of the iron by chromizing.
０５〜１％であることを特徴とする請求項第２項記載の
ナトリウム−硫黄電池の電槽。3. The content of niobium and zirconium is 0.
The battery case of a sodium-sulfur battery according to claim 2, characterized in that it is from 0 to 1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4321316A JPH06150965A (en) | 1992-11-04 | 1992-11-04 | Battery jar for sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4321316A JPH06150965A (en) | 1992-11-04 | 1992-11-04 | Battery jar for sodium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06150965A true JPH06150965A (en) | 1994-05-31 |
Family
ID=18131228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4321316A Pending JPH06150965A (en) | 1992-11-04 | 1992-11-04 | Battery jar for sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06150965A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100730262B1 (en) * | 2004-09-30 | 2007-06-20 | 산요덴키가부시키가이샤 | Latch clock generation circuit and serial-parallel conversion circuit |
-
1992
- 1992-11-04 JP JP4321316A patent/JPH06150965A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100730262B1 (en) * | 2004-09-30 | 2007-06-20 | 산요덴키가부시키가이샤 | Latch clock generation circuit and serial-parallel conversion circuit |
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