JPH04115154A - Hydrogen gas sensor - Google Patents
Hydrogen gas sensorInfo
- Publication number
- JPH04115154A JPH04115154A JP2235035A JP23503590A JPH04115154A JP H04115154 A JPH04115154 A JP H04115154A JP 2235035 A JP2235035 A JP 2235035A JP 23503590 A JP23503590 A JP 23503590A JP H04115154 A JPH04115154 A JP H04115154A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- gas
- laf3
- hydrogen gas
- reference electrode
- 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.)
- Granted
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 16
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 32
- 229910002319 LaF3 Inorganic materials 0.000 abstract description 7
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004544 sputter deposition Methods 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 2
- 230000008020 evaporation Effects 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は水素ガスを検出するセンサに関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a sensor for detecting hydrogen gas.
（従来の技術）
水素ガスを検出するセンサとして、特開昭６０−２１１
３４７号、特開昭６１−２２３６４２号及び特開昭６２
−２０４１４８号公報に開示されるものがある。(Prior art) As a sensor for detecting hydrogen gas, Japanese Patent Application Laid-Open No. 60-211
No. 347, JP-A-61-223642 and JP-A-62
There is one disclosed in JP-204148.
特開昭６０−２１１３４７号公報に開示される水素ガス
センサは第１の電極上に充填密度の低いアモルファス酸
化タングステン層を設け、このアモルファス酸化タング
ステン層の上に第２の電極を形成したものであり、特開
昭６１−２２３６４２号公報に開示される水素ガスセン
サはＳｎＯ□上にＰｔ及びｓｂを所定割合で分散せしめ
、更にこれをシラン系ガス雰囲気で処理することでセン
サ上にＳｉ酸化物を分散せしめたものであり、特開昭６
２−２０４１４８号公報に開示される水素ガスセンサは
５ｎｏ２等の金属酸化物半導体の表面にバナジウム等の
金属酸化物を担持した触媒層を設けたものである。The hydrogen gas sensor disclosed in JP-A-60-211347 has an amorphous tungsten oxide layer with a low packing density provided on a first electrode, and a second electrode formed on this amorphous tungsten oxide layer. , the hydrogen gas sensor disclosed in Japanese Unexamined Patent Publication No. 61-223642 has Pt and sb dispersed in a predetermined ratio on SnO□, and this is further treated in a silane gas atmosphere to disperse Si oxide on the sensor. This is a result of the Japanese Unexamined Patent Application Publication No. 6
The hydrogen gas sensor disclosed in Japanese Patent No. 2-204148 has a catalyst layer supporting a metal oxide such as vanadium on the surface of a metal oxide semiconductor such as 5no2.
（発明が解決しようとする課題）
上述した従来の水素ガスセンサは、水素ガスに対する選
択性は多少改善されているが十分ではなく、特に低濃度
の水素ガスに対する感度が劣る。(Problems to be Solved by the Invention) The conventional hydrogen gas sensor described above has somewhat improved selectivity to hydrogen gas, but is not sufficient, and particularly has poor sensitivity to low concentration hydrogen gas.
また水素ガス以外のイソブタンやプロパン等の可燃性ガ
スも検知しやすい。In addition to hydrogen gas, flammable gases such as isobutane and propane are also easily detected.
（課題を解決するための手段）
上記課題を解決すべく本発明は、ＬａＦｓからなる固体
電解質の表面にＳｎ＋ＳｎＦ２又はＡｕからなる参照電
極と、ｐｔ又はＰｄからなる検知電極を形成した。(Means for Solving the Problems) In order to solve the above problems, the present invention forms a reference electrode made of Sn+SnF2 or Au and a detection electrode made of PT or Pd on the surface of a solid electrolyte made of LaFs.
（作用）
ＬａＦｓはフッ素イオンを導電種とする固体電解質であ
り、検知電極とＬａＦａの界面に水素ガスが接触するこ
とにより、界面近傍のイオン活量に変化が生じる。この
ため、ＬａＦ、上に形成した参照電極と検知電極との間
の電位差（起電力）に変化を生じ、応答信号として取り
出せる。(Function) LaFs is a solid electrolyte that uses fluorine ions as a conductive species, and when hydrogen gas comes into contact with the interface between the sensing electrode and LaFa, the ionic activity near the interface changes. Therefore, a change occurs in the potential difference (electromotive force) between the reference electrode and the sensing electrode formed on LaF, which can be taken out as a response signal.
（実施例） 以下に本発明の実施例を添付図面に基いて説明する。(Example) Embodiments of the present invention will be described below with reference to the accompanying drawings.
第１図は本発明に係る酸素ガスセンサとしての平面型セ
ンサの断面図、第２図は積層型センサの断面図であり、
平面型センサ１は固体電解質２の一面側に検知電極３及
び参照電極（対極）４を離間して形成し、これら検知電
極３及び参照電極４にＰｔ線５，５を接続している。ま
た、積層型センサ１１は固体電解質１２の一面側にエポ
キシ樹脂１６によってガラスチューブ１７の一端を当て
、このガラスチューブ１７にて固体電解質１２の一面側
に形成した参照電極１４を囲み、参照電極１４を被検ガ
ス雰囲気から遮断し、更に固体電解質１２の他面側に検
知電極１３を形成し、これら参照電極１４及び検知電極
１３にＰｔ線１５を接続している。FIG. 1 is a sectional view of a planar sensor as an oxygen gas sensor according to the present invention, and FIG. 2 is a sectional view of a laminated sensor.
The planar sensor 1 has a sensing electrode 3 and a reference electrode (counter electrode) 4 spaced apart from each other on one side of a solid electrolyte 2, and Pt wires 5, 5 are connected to the sensing electrode 3 and the reference electrode 4. In addition, in the stacked sensor 11, one end of a glass tube 17 is applied to one side of the solid electrolyte 12 using an epoxy resin 16, and the reference electrode 14 formed on the one side of the solid electrolyte 12 is surrounded by this glass tube 17. A detection electrode 13 is formed on the other side of the solid electrolyte 12, and a Pt wire 15 is connected to the reference electrode 14 and the detection electrode 13.
ここで本発明にあっては、固体電解質２，１２としては
ＬａＦ、（フッ化ランタン）の単結晶を用い、参照電極
４．１４としてはＳｎ（スズ）＋５ｎＦ２（フッ化スズ
）又はＡｕ（金）を用い、検知電極３．１３としてはｐ
ｔ（プラチナ）、Ｐｄ（パラジウム）を用いる。In the present invention, single crystals of LaF (lanthanum fluoride) are used as the solid electrolytes 2 and 12, and Sn (tin) + 5nF2 (tin fluoride) or Au (gold) is used as the reference electrode 4.14. ), and p as the sensing electrode 3.13.
t (platinum) and Pd (palladium) are used.
そして、固体電解質２．１２としては板状ＬａＦ３を所
定寸法に切断するか、参照電極１４又は別の基板にスパ
ッタリング等によってＬａＦ、の薄膜を形成してもよい
。また参照電極１４は例えばＳｎとＳｎＦ２の混合粉末
をＬａＦｓの表面に載せ、約２３０℃で加熱溶融するこ
とにより形成し、参照電極４はＡｕを蒸着またはスパッ
タリングにより形成する。一方検知電極３．１３は例え
ばＬａＦ３の表面にＰｔ又はＰｄの薄膜を蒸着またはス
パッタリングにより形成する。The solid electrolyte 2.12 may be formed by cutting a plate-shaped LaF3 into a predetermined size, or by forming a thin film of LaF on the reference electrode 14 or another substrate by sputtering or the like. The reference electrode 14 is formed by placing, for example, a mixed powder of Sn and SnF2 on the surface of LaFs and heating and melting it at about 230° C., and the reference electrode 4 is formed by depositing or sputtering Au. On the other hand, the detection electrode 3.13 is formed by forming a thin film of Pt or Pd on the surface of LaF3, for example, by vapor deposition or sputtering.
次に、検知電極をｐｔ及びＰｄとし、参照電極をＡｕ又
はＳｎ＋５ｎＦｚとした場合のＨ２ガス、ＣＯガス、Ｃ
Ｈ，ガス、イソブタンガス及びエタノールガス濃度と起
電力変化との関係について実験した結果を第３図乃至第
７図に示す。なお、測定は全て室温（２７℃）で行なっ
た。Next, H2 gas, CO gas, C
The results of experiments regarding the relationship between the concentrations of H, gas, isobutane gas, and ethanol gas and changes in electromotive force are shown in FIGS. 3 to 7. Note that all measurements were performed at room temperature (27°C).
先ず、Ｈ２ガス濃度と起電力変化との関係を示す第３図
について考察すると、Ｈ２ガス濃度の増加につれて起電
力変化が負の側に大きくなる。First, considering FIG. 3 showing the relationship between the H2 gas concentration and the electromotive force change, as the H2 gas concentration increases, the electromotive force change becomes larger on the negative side.
一方第４図乃至第７図について考察すると、ＣＯガス、
ＣＨ４ガス、イソブタンガス及びエタノールガスについ
ては、ガス濃度の増加につれて起電力変化は殆どないか
若干圧の側に現れる。On the other hand, considering FIGS. 4 to 7, CO gas,
For CH4 gas, isobutane gas, and ethanol gas, as the gas concentration increases, there is almost no change in the electromotive force or the change appears on the pressure side.
以上の関係をＰｄを検知電極としＡｕを参照電極とした
場合についての起電力変化Ｉｔ（ｍＶ）を以下の［表］
に示す。Based on the above relationship, the electromotive force change It (mV) when Pd is used as the sensing electrode and Au is used as the reference electrode is shown in the table below.
Shown below.
［表］
また、第８図（Ａ）は検知電極をＰｔ１参照電極をＳｎ
十ＳｎＦ２とし、第８図（Ｂ）は検知電極をＰｄ、参照
電極をＳｎ＋ＳｎＦ２とし、第８図（Ｃ）は検知電極を
Ｐｄ、参照電極をＡｕとした場合の１０ｐｐｍ及び１０
１００ｐｐ ２ガスに対する応答曲線を表わしたもので
ある。この図から本発明に係るセンサはＨ２ガス用のセ
ンサとして十分に使用でき、特に検知電極をＰｄ、参照
電極をＳ ｎ＋ Ｓ ｎＦ ２とするか検知電極をＰｄ
、参照電極をＡｕとするとその効果が大きいことが分る
。[Table] In addition, Fig. 8 (A) shows that the detection electrode is Pt, the reference electrode is Sn
10 ppm and 10 SnF2, Fig. 8 (B) shows the detection electrode as Pd and the reference electrode as Sn+SnF2, and Fig. 8 (C) shows the detection electrode as Pd and the reference electrode as Au.
It shows a response curve to 100pp2 gas. From this figure, the sensor according to the present invention can be fully used as a sensor for H2 gas, especially when the sensing electrode is Pd and the reference electrode is S n + S nF 2 or the sensing electrode is Pd.
, it can be seen that the effect is large when the reference electrode is made of Au.
（効果）
以上に説明したように本発明によれば、Ｌａ５ｓからな
る固体電解質の表面にＳｎ＋ＳｎＦ２又はＡｕからなる
参照電極と、Ｐｔ又はＰｄからなる検知電極を形成した
ので、検知電極とＬａＦ、の界面に水素ガスが接触する
と、界面近傍のイオン活量に変化が生じ、ＬａＦ、上に
形成した参照電極と検知電極との間の電位差（起電力）
に変化を生じる。そして、この電位差変化（起電力変化
）は他の可燃性ガスの場合と異なり負（マイナス）側に
発生するので水素ガスと他のガスとを峻別することがで
きる。(Effects) As explained above, according to the present invention, the reference electrode made of Sn+SnF2 or Au and the detection electrode made of Pt or Pd are formed on the surface of the solid electrolyte made of La5s, so that the detection electrode and the LaF, When hydrogen gas comes into contact with the interface, a change occurs in the ion activity near the interface, causing a potential difference (electromotive force) between the reference electrode and the sensing electrode formed on LaF.
cause a change in Since this change in potential difference (change in electromotive force) occurs on the negative side unlike in the case of other combustible gases, hydrogen gas can be clearly distinguished from other gases.
第１図は本発明に係る水素ガスセンサのうち平面型セン
サの断面図、第２図は本発明に係る水素ガスセンサのう
ち積層型センサの断面図、第３図は本発明に係るガスセ
ンサのＨ２ガス濃度と起電力変化との関係を示すグラフ
、第４図は本発明に係るガスセンサのＣＯガス濃度と起
電力変化との関係を示すグラフ、第５図は本発明に係る
ガスセンサのＣＨ４ガス濃度と起電力変化との関係を示
すグラフ、第６図は本発明に係るガスセンサのイソブタ
ンガス濃度と起電力変化との関係を示すグラフ、第７図
は本発明に係るガスセンサのエタノール濃度と起電力変
化との関係を示すグラフ、第８図（Ａ）乃至（Ｃ）は本
発明に係るガスセンサのＨ２ガスに対する応答曲線を示
すグラフである。
尚、図面中１．１１はＨ２ガスセンサ、２，１２は固体
電解質、３．１３は検知電極、４，１４は参照電極、５
．１５はｐｔ線である。FIG. 1 is a cross-sectional view of a flat type sensor among the hydrogen gas sensors according to the present invention, FIG. 2 is a cross-sectional view of a stacked type sensor among the hydrogen gas sensors according to the present invention, and FIG. FIG. 4 is a graph showing the relationship between concentration and electromotive force change, FIG. 4 is a graph showing the relationship between CO gas concentration and electromotive force change in the gas sensor according to the present invention, and FIG. 5 is a graph showing the relationship between CH4 gas concentration and electromotive force change in the gas sensor according to the present invention. A graph showing the relationship between the electromotive force change and FIG. 6 a graph showing the relationship between the isobutane gas concentration and the electromotive force change of the gas sensor according to the present invention, and FIG. 7 a graph showing the relationship between the ethanol concentration and the electromotive force change of the gas sensor according to the present invention. FIGS. 8(A) to 8(C) are graphs showing the response curves of the gas sensor according to the present invention to H2 gas. In addition, in the drawing, 1.11 is an H2 gas sensor, 2 and 12 are solid electrolytes, 3.13 is a detection electrode, 4 and 14 are reference electrodes, and 5
．． 15 is a pt line.
Claims (1)
面にＳｎ（スズ）＋ＳｎＦ＿２（フッ化スズ）又はＡｕ
（金）からなる参照電極と、Ｐｔ（プラチナ）又はＰｄ
（パラジウム）からなる検知電極を形成したことを特徴
とする水素ガスセンサ。Sn (tin) + SnF_2 (tin fluoride) or Au on the surface of a solid electrolyte made of LaF_3 (lanthanum fluoride)
(gold), Pt (platinum) or Pd
A hydrogen gas sensor characterized by forming a detection electrode made of (palladium).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2235035A JP2841795B2 (en) | 1990-09-05 | 1990-09-05 | Hydrogen gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2235035A JP2841795B2 (en) | 1990-09-05 | 1990-09-05 | Hydrogen gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04115154A true JPH04115154A (en) | 1992-04-16 |
| JP2841795B2 JP2841795B2 (en) | 1998-12-24 |
Family
ID=16980123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2235035A Expired - Lifetime JP2841795B2 (en) | 1990-09-05 | 1990-09-05 | Hydrogen gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841795B2 (en) |
-
1990
- 1990-09-05 JP JP2235035A patent/JP2841795B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2841795B2 (en) | 1998-12-24 |
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