JPH05225962A - Manufacture of sodium-sulfur battery - Google Patents
Manufacture of sodium-sulfur batteryInfo
- Publication number
- JPH05225962A JPH05225962A JP4025320A JP2532092A JPH05225962A JP H05225962 A JPH05225962 A JP H05225962A JP 4025320 A JP4025320 A JP 4025320A JP 2532092 A JP2532092 A JP 2532092A JP H05225962 A JPH05225962 A JP H05225962A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- titanium nitride
- sulfur battery
- nitride layer
- anode
- 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 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 39
- 239000003513 alkali Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010936 titanium Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 12
- 238000007599 discharging Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- 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
-
- 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
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Vapour Deposition (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、アルカリイオン伝導性
を有する固体電解質を利用したナトリウム−硫黄電池の
製造方法に関するもので、特に、ナトリウム−硫黄電池
の陽極側金属容器の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a sodium-sulfur battery using a solid electrolyte having alkali ion conductivity, and more particularly to a method for manufacturing an anode side metal container of a sodium-sulfur battery.
【０００２】[0002]
【従来の技術】一般に、ナトリウム−硫黄電池は、陽極
室を構成する金属容器の表面が溶融硫黄化合物（多硫化
ナトリウム）により腐食されると、陽極活物質が腐食反
応生成物形成のために消費されるため、電池反応に必要
な陽極活物質量が減少して電池容量が低下したり、陽極
表面の金属硫化物の電気抵抗の影響で電池の内部抵抗が
増加して充電効率を低下させやすい。2. Description of the Related Art Generally, in a sodium-sulfur battery, when a surface of a metal container forming an anode chamber is corroded by a molten sulfur compound (sodium polysulfide), the anode active material is consumed for forming a corrosion reaction product. Therefore, the amount of the anode active material required for the battery reaction decreases and the battery capacity decreases, or the internal resistance of the battery increases due to the electric resistance of the metal sulfide on the anode surface, and the charging efficiency tends to decrease. ..
【０００３】従来より、この種のナトリウム−硫黄電池
の陽極室を構成する陽極容器としては、溶融多硫化ナト
リウムによる腐食を防止するため、陽極容器の表面に耐
食性の優れた窒化チタン層を形成するものが知られる。
例えば、特開昭６１−２６４６５９号公報には、容器表
面に低圧溶射により窒化チタン層を形成するものが開示
され、特開昭６２−２６８４０６９号公報には、チタン
製容器を窒化することにより表面に窒化チタン層を形成
するものが開示されている。また、特開昭６２−２９０
０６７号公報に示されるものは、窒素系ガス中で容器表
面を窒化処理した後、チタンまたはチタン化合物と添加
物との混合粉末を水素もしくは不活性ガスまたは真空中
で加熱して窒化チタン層を形成する。Conventionally, as an anode container constituting the anode chamber of this type of sodium-sulfur battery, a titanium nitride layer having excellent corrosion resistance is formed on the surface of the anode container in order to prevent corrosion due to molten sodium polysulfide. Things are known.
For example, Japanese Unexamined Patent Publication (Kokai) No. 61-264659 discloses a titanium nitride layer formed on the surface of a container by low pressure spraying, and Japanese Unexamined Patent Publication (Kokai) No. 62-2684069 discloses a surface formed by nitriding a titanium container. A method for forming a titanium nitride layer is disclosed. In addition, JP-A-62-290
No. 067 discloses a titanium nitride layer obtained by nitriding the surface of a container in a nitrogen-based gas and then heating a mixed powder of titanium or a titanium compound and an additive in hydrogen or an inert gas or in vacuum. Form.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな従来のナトリウム−硫黄電池の陽極容器の製造方法
によると、特開昭６１−２６４６５９号公報に示される
ようなものでは、溶射により形成した窒化チタン層中に
多数の気孔が生じやすく、溶融多硫化ナトリウムが該気
孔を通じて浸透し、容器基材が腐食されるという問題が
ある。However, according to such a conventional method for manufacturing an anode container for a sodium-sulfur battery, the conventional method for producing an anode container for a sodium-sulfur battery is such that the nitridation formed by thermal spraying is the same as that disclosed in JP-A-61-264659. There is a problem that a large number of pores are likely to be formed in the titanium layer, the molten sodium polysulfide penetrates through the pores, and the container base material is corroded.
【０００５】また、特開昭６２−２６８４０６９号公報
または特開昭６２−２９００６７号公報に示されるよう
なものでは、窒化チタン層形成時に電気炉等に容器基材
を長時間保持するため、生産効率が低下するという問題
がある。本発明が解決しようとする課題は、陽極容器の
表面に耐食性および信頼性の高い緻密な窒化チタン層を
比較的短時間で形成可能にしたナトリウム−硫黄電池の
製造方法を提供することにある。Further, in the case of the one disclosed in JP-A-62-2684069 or JP-A-62-290067, the container base material is held for a long time in an electric furnace or the like when the titanium nitride layer is formed, so that it is produced. There is a problem of reduced efficiency. The problem to be solved by the present invention is to provide a method for manufacturing a sodium-sulfur battery in which a dense titanium nitride layer having high corrosion resistance and high reliability can be formed on the surface of an anode container in a relatively short time.
【０００６】[0006]
【課題を解決するための手段】本発明のナトリウム−硫
黄電池の製造方法は、アルカリイオン伝導性を有する固
体電解質により陽極室と陰極室とを区画形成し、陽極室
内には溶融多硫化ナトリウムを収容し、陰極室内には溶
融ナトリウムを収容したナトリウム−硫黄電池の製造法
において、前記陽極室を形成する金属容器の少なくとも
溶融多硫化ナトリウムと接触する表面にＣＶＤ法を用い
て窒化チタンを付着させることにより窒化チタン層を形
成することを特徴とする。The method for producing a sodium-sulfur battery of the present invention comprises an anode chamber and a cathode chamber defined by a solid electrolyte having alkali ion conductivity, and molten sodium polysulfide is stored in the anode chamber. In a method for manufacturing a sodium-sulfur battery that contains molten sodium in the cathode chamber, titanium nitride is attached to at least the surface of the metal container forming the anode chamber in contact with molten sodium polysulfide by the CVD method. Thus, a titanium nitride layer is formed.
【０００７】前記窒化チタン層の層厚を２．５〜１５μ
ｍにしたことを特徴とする。前記金属容器は、比較的強
度が高く、窒化チタンとの結合性が良いアルミニウム合
金、ステンレス等の材質のものを用いるとよい。前記Ｃ
ＶＤ法は、原料ガスによる反応速度が比較的大きい熱Ｃ
ＶＤ法を用いるのが望ましい。熱ＣＶＤ法を用いた場
合、例えば、電気炉内に金属容器を配置し、四塩化チタ
ンガス、窒素ガス、および水素ガスを流通させながら９
５０℃程度で約３時間反応させると、比較的良質な窒化
チタン層を得ることができる。金属容器がＡｌ合金から
なる場合にはＣＶＤ法として、プラズマＣＶＤ法、真空
ＣＶＤ法等を用いてもよい。The thickness of the titanium nitride layer is 2.5 to 15 μm.
It is characterized in that it is m. The metal container is preferably made of a material such as aluminum alloy or stainless steel, which has a relatively high strength and has a good bondability with titanium nitride. The C
The VD method uses heat C, which has a relatively high reaction rate due to the source gas.
It is desirable to use the VD method. When the thermal CVD method is used, for example, a metal container is placed in an electric furnace, and titanium tetrachloride gas, nitrogen gas, and hydrogen gas are circulated while flowing.
A relatively good titanium nitride layer can be obtained by reacting at about 50 ° C. for about 3 hours. When the metal container is made of an Al alloy, a plasma CVD method, a vacuum CVD method or the like may be used as the CVD method.
【０００８】前記窒化チタン層の層厚を２．５μｍ以上
としたのは、２．５μｍ未満であると、ナトリウム−硫
黄電池の耐用期間中に溶融多硫化ナトリウムが窒化チタ
ン層を腐食し容器基材に達しやすくなるからであり、１
５μｍ以下としたのは、１５μｍを超えると、窒化チタ
ン層の形成時にＣＶＤ法による反応時間が比較的長時間
になるからである。The reason why the thickness of the titanium nitride layer is 2.5 μm or more is that if the thickness is less than 2.5 μm, molten sodium polysulfide corrodes the titanium nitride layer during the service life of the sodium-sulfur battery and the container substrate Because it is easier to reach the material, 1
The reason for setting the thickness to 5 μm or less is that if the thickness exceeds 15 μm, the reaction time by the CVD method at the time of forming the titanium nitride layer becomes relatively long.
【０００９】[0009]
【実施例】以下、本発明の実施例を説明する。ナトリウ
ム−硫黄電池の陽極容器として用いるステンレス製容器
の表面に次に示すように熱ＣＶＤ法により窒化チタン層
を形成した。まず、熱ＣＶＤ装置内にステンレス製容器
（ＳＵＳ４３０製）を配置し、９５０℃に昇温し、次い
で、反応ガスとして四塩化チタンガス、窒素ガスおよび
水素ガスを導入し、所定時間反応させた。反応ガスの流
量比は、（水素ガス＋四塩化チタンガス）：窒素ガス＝
７：１に設定した。熱ＣＶＤ装置内で１時間反応させた
ものを実施例１とし、３時間反応させたものを実施例２
とした。窒化チタン層の層厚は、実施例１が１μｍ、実
施例２が３μｍであった。EXAMPLES Examples of the present invention will be described below. A titanium nitride layer was formed on the surface of a stainless steel container used as an anode container of a sodium-sulfur battery by a thermal CVD method as shown below. First, a stainless steel container (made of SUS430) was placed in a thermal CVD apparatus, the temperature was raised to 950 ° C., and then titanium tetrachloride gas, nitrogen gas and hydrogen gas were introduced as reaction gases and reacted for a predetermined time. The flow rate ratio of the reaction gas is (hydrogen gas + titanium tetrachloride gas): nitrogen gas =
It was set to 7: 1. Example 1 was the one reacted for 1 hour in the thermal CVD apparatus, and Example 2 was the one reacted for 3 hours.
And The layer thickness of the titanium nitride layer was 1 μm in Example 1 and 3 μm in Example 2.
【００１０】耐食性試験１（耐多硫化ナトリウム性） 次に、実施例１および実施例２について、多硫化ナトリ
ウムに対する窒化チタン層の耐食性を調査するため、溶
融多硫化ナトリウム（Ｎａ2 Ｓ4 ）中で浸漬試験を行な
った。試験条件は、浴槽温度：３３０℃、浸漬時間：９
６０時間に設定した。なお、比較例１としてステンレス
製容器（ＳＵＳ４３０製）の表面に低圧溶射により窒化
チタン層を５０μｍ形成したものと、比較例２としてチ
タン製容器の表面を窒化することにより窒化チタン層を
１０μｍ形成したものについても、同様な条件で試験を
行なった。結果を表１に示す。Corrosion Resistance Test 1 (Sodium Polysulfide Resistance) Next, in order to investigate the corrosion resistance of the titanium nitride layer with respect to sodium polysulfide in Examples 1 and 2, in molten sodium polysulfide (Na 2 S 4 ). The immersion test was carried out. The test conditions are bath temperature: 330 ° C., immersion time: 9
It was set to 60 hours. In Comparative Example 1, a titanium nitride layer having a thickness of 50 μm was formed on the surface of a stainless steel container (SUS430) by low pressure spraying, and as Comparative Example 2, the surface of a titanium container was nitrided to form a titanium nitride layer of 10 μm. The thing was also tested under the same conditions. The results are shown in Table 1.
【００１１】[0011]
【表１】 [Table 1]
【００１２】実施例１および実施例２による窒化チタン
層は、比較例１および比較例２に比べて層厚が小さく、
特に比較例２に対しては窒化チタン層の作成時間が大幅
に短縮されているにもかかわらず、窒化チタン層の表面
がほとんど腐食されなかった。これに対し、比較例１
は、低圧溶射時に窒化チタン層に生じた気孔を通じて基
材のステンレス製容器が腐食され、比較例２は、窒化チ
タン層の表面が２〜３μｍ程度腐食され、硫化物が形成
された。すなわち、熱ＣＶＤ法により窒化チタン層を形
成した実施例１および実施例２は、耐多硫化ナトリウム
性に優れることが判明した。The titanium nitride layers according to Examples 1 and 2 have a smaller layer thickness than Comparative Examples 1 and 2,
Especially for Comparative Example 2, the surface of the titanium nitride layer was scarcely corroded although the time for forming the titanium nitride layer was significantly shortened. On the other hand, Comparative Example 1
In the comparative example 2, the stainless steel container of the base material was corroded through the pores formed in the titanium nitride layer during low pressure spraying, and in Comparative Example 2, the surface of the titanium nitride layer was corroded by about 2 to 3 μm, and sulfide was formed. That is, it was found that Examples 1 and 2 in which the titanium nitride layer was formed by the thermal CVD method had excellent sodium polysulfide resistance.
【００１３】耐食性試験２（充放電時の窒化チタン層の
腐食） 次に、実施例１について、充放電時の窒化チタン層の腐
食量を調査するため、実施例１の条件で作製した陽極容
器を使用して製作した試験用のナトリウム−硫黄電池に
ついて充放電試験を行なった。充放電試験は、試験時間
を短縮するため、通常の約３倍の電流密度１６５ｍＡ／
ｃｍ2 で充放電を繰返し、所定サイクル経過後に解体し
たナトリウム−硫黄電池について、陽極容器内面の窒化
チタン層の存在の有無を確認することにより行なった。
結果を表２に示す。Corrosion Resistance Test 2 (Corrosion of Titanium Nitride Layer During Charging / Discharging) Next, in Example 1, in order to investigate the amount of corrosion of the titanium nitride layer during charging / discharging, an anode container manufactured under the conditions of Example 1 A charge-discharge test was conducted on a test sodium-sulfur battery manufactured using In the charge / discharge test, in order to reduce the test time, the current density is about 3 times the normal current density of 165 mA /
The charging / discharging was repeated at cm 2 , and the sodium-sulfur battery dismantled after the lapse of a predetermined cycle was confirmed by checking the presence or absence of the titanium nitride layer on the inner surface of the anode container.
The results are shown in Table 2.
【００１４】[0014]
【表２】 [Table 2]
【００１５】表２から判るように、実施例１は、２００
サイクルの充放電で１μｍの窒化チタン層が消失した。
これにより、通常の充放電時の電流密度に換算した場
合、実施例１の窒化チタン層は、６００サイクルの充放
電に対し１μｍ程度損失すると考えられるため、充放電
における総通電電気量に相当する１５００サイクルまで
容器基材の耐食性を保持するには、窒化チタン層の層厚
が２．５μｍ以上必要とされることが判明した。As can be seen from Table 2, the first embodiment has 200
The titanium nitride layer with a thickness of 1 μm disappeared due to the charge and discharge of the cycle.
As a result, when converted to a current density during normal charge / discharge, the titanium nitride layer of Example 1 is considered to lose about 1 μm after 600 cycles of charge / discharge, which corresponds to the total amount of electricity supplied during charge / discharge. It has been found that the titanium nitride layer needs to have a thickness of 2.5 μm or more in order to maintain the corrosion resistance of the container substrate up to 1500 cycles.
【００１６】耐食性試験３（充放電時の内部抵抗および
電池容量の変化） 次に、実施例２について、充放電の内部抵抗および電池
容量の変化量を調査するため、実施例２を用いて製作し
たナトリウム−硫黄電池の充放電試験を行なった。充放
電時の電流密度は、前記耐食性試験２と同様１６５ｍＡ
／ｃｍ2 に設定した。結果を図１に示す。Corrosion resistance test 3 (changes in internal resistance and battery capacity during charging / discharging) Next, Example 2 was manufactured to investigate the amount of change in internal resistance during charging / discharging and battery capacity. The charge-discharge test of the sodium-sulfur battery was performed. The current density during charging / discharging was 165 mA, the same as in the above corrosion resistance test 2.
/ Cm 2 was set. The results are shown in Figure 1.
【００１７】図１に示すように、実施例２は、５００サ
イクルの充放電後も内部抵抗および電池容量に電池性能
を劣化させるような変化は見られなかった。すなわち、
実施例２の窒化チタン層によると、溶融硫黄化合物によ
る容器基材の腐食が防止されるとともに、電池性能が確
実に維持されることが確認された。本発明を適用するナ
トリウム−硫黄電池の模式的構造は、例えば図１に示す
とおりである。As shown in FIG. 1, in Example 2, no change that deteriorates the battery performance was observed in the internal resistance and the battery capacity even after 500 cycles of charging and discharging. That is,
It was confirmed that according to the titanium nitride layer of Example 2, corrosion of the container base material by the molten sulfur compound was prevented and the battery performance was reliably maintained. A schematic structure of a sodium-sulfur battery to which the present invention is applied is as shown in FIG. 1, for example.
【００１８】ナトリウム−硫黄電池１０は、陽極活物質
である溶融硫黄Ｓを含浸したカーボンマットなどの陽極
用導電材Ｍを収納する円筒状の陽極容器１と、この陽極
容器１の上端部に対し、α−アルミナ製の絶縁リング２
および中間部材５を介して連結された陰極容器３と、前
記絶縁リング２の内周部に固着され、かつ、陰極活物質
である溶融金属ナトリウムＮａを貯留し、ナトリウムイ
オンＮａ+ を選択的に浸透させる機能を有した下方へ延
びる多結晶β−アルミナ製の有底円筒状をなす固体電解
質管４とから構成される。陽極容器１の内壁面には、陽
極用伝導材Ｍの頂面より高い位置まで窒化チタン層７が
形成されている。The sodium-sulfur battery 10 has a cylindrical anode container 1 containing a conductive material M for the anode such as carbon mat impregnated with molten sulfur S as an anode active material, and an upper end portion of the anode container 1. , Α-alumina insulation ring 2
And a cathode container 3 connected via an intermediate member 5, and is fixed to the inner peripheral portion of the insulating ring 2 and stores molten metal sodium Na which is a cathode active material and selectively selects sodium ions Na +. The solid electrolyte tube 4 has a bottomed cylindrical shape and is made of polycrystalline β-alumina and has a function of permeating downward. The titanium nitride layer 7 is formed on the inner wall surface of the anode container 1 to a position higher than the top surface of the conductive material M for anode.
【００１９】放電時には陰極室Ｒ１からナトリムイオン
Ｎａ+ が固体電解質管４を透過して陽極室Ｒ２内の硫黄
Ｓと次のように反応し、多硫化ナトリウムを生成する。 ２Ｎａ＋ＸＳ→Ｎａ2 Ｓｘ また、充電時には放電時とは逆の反応が起こり、多硫化
ナトリウムがナトリウムＮａおよび硫黄Ｓに分解する。During discharge, sodium ion Na + from the cathode chamber R1 passes through the solid electrolyte tube 4 and reacts with the sulfur S in the anode chamber R2 as follows to produce sodium polysulfide. 2Na + XS → Na 2 Sx When charging, the reaction opposite to that during discharging occurs, and sodium polysulfide is decomposed into sodium Na and sulfur S.
【００２０】本発明の方法によるナトリウム−硫黄電池
１０は、耐食性に優れた均質で緻密な窒化チタン層を有
するため、長期間に渡って使用しても陽極容器１の基材
が腐食されず、電池性能が低下しにくい。Since the sodium-sulfur battery 10 according to the method of the present invention has a uniform and dense titanium nitride layer having excellent corrosion resistance, the base material of the anode container 1 is not corroded even when used for a long period of time. Battery performance does not easily deteriorate.
【００２１】[0021]
【発明の効果】以上説明したように、本発明のナトリウ
ム−硫黄電池の製造方法によると、陽極容器の表面に比
較的短時間で耐食性の高い緻密な窒化チタン層を形成す
ることができるため、耐久性および信頼性の高いナトリ
ウム−硫黄電池を効率よく生産することができるという
効果がある。As described above, according to the method of manufacturing a sodium-sulfur battery of the present invention, a dense titanium nitride layer having high corrosion resistance can be formed on the surface of the anode container in a relatively short time. There is an effect that a highly durable and highly reliable sodium-sulfur battery can be efficiently produced.
【図１】充放電サイクル数とナトリウム−硫黄電池の比
内部抵抗および比電池容量との関係を示す特性図であ
る。FIG. 1 is a characteristic diagram showing the relationship between the number of charge / discharge cycles and the specific internal resistance and specific battery capacity of a sodium-sulfur battery.
【図２】本発明の実施例によるナトリウム−硫黄電池を
示す模式図である。FIG. 2 is a schematic diagram showing a sodium-sulfur battery according to an embodiment of the present invention.
１ 陽極容器 ３ 陰極容器 ４ 固体電解質管 ７ 窒化チタン層 １０ ナトリウム−硫黄電池 1 Anode Container 3 Cathode Container 4 Solid Electrolyte Tube 7 Titanium Nitride Layer 10 Sodium-Sulfur Battery
Claims (2)
質により陽極室と陰極室とを区画形成し、陽極室内には
溶融硫黄化合物を収容し、陰極室内には溶融ナトリウム
を収容したナトリウム−硫黄電池の製造法において、 前記陽極室を形成する金属容器の少なくとも溶融硫黄化
合物と接触する表面にＣＶＤ法を用いて窒化チタンを付
着させることにより窒化チタン層を形成することを特徴
とするナトリウム−硫黄電池の製造方法。1. A sodium-sulfur battery in which an anode chamber and a cathode chamber are partitioned and formed by a solid electrolyte having alkali ion conductivity, a molten sulfur compound is contained in the anode chamber, and molten sodium is contained in the cathode chamber. In the manufacturing method, a titanium nitride layer is formed by depositing titanium nitride using a CVD method on at least a surface of the metal container forming the anode chamber, the surface being in contact with the molten sulfur compound. Production method.
μｍにしたことを特徴とする請求項１記載のナトリウム
−硫黄電池の製造方法。2. The layer thickness of the titanium nitride layer is 2.5 to 15
The method for producing a sodium-sulfur battery according to claim 1, wherein the sodium-sulfur battery has a thickness of μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4025320A JPH05225962A (en) | 1992-02-12 | 1992-02-12 | Manufacture of sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4025320A JPH05225962A (en) | 1992-02-12 | 1992-02-12 | Manufacture of sodium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05225962A true JPH05225962A (en) | 1993-09-03 |
Family
ID=12162692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4025320A Pending JPH05225962A (en) | 1992-02-12 | 1992-02-12 | Manufacture of sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05225962A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100294467B1 (en) * | 1994-06-07 | 2001-10-24 | 남창우 | Process for producing solid electrolyte for sodium-sulfur battery |
-
1992
- 1992-02-12 JP JP4025320A patent/JPH05225962A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100294467B1 (en) * | 1994-06-07 | 2001-10-24 | 남창우 | Process for producing solid electrolyte for sodium-sulfur battery |
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